JP2023179402A - Method for reusing depolymerizable copolymer - Google Patents
Method for reusing depolymerizable copolymer Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title description 18
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 229920001519 homopolymer Polymers 0.000 claims abstract description 45
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 17
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 abstract description 32
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 239000004621 biodegradable polymer Substances 0.000 description 6
- 229920002988 biodegradable polymer Polymers 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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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)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
本発明は、熱や光によって重合体（ポリマー）が単量体（モノマー）に分解する解重合性を有する共重合ポリマーに関し、特に熱により解重合した際に残渣が残りにくい解重合性を有する共重合ポリマーに関する。 The present invention relates to a copolymer that has a depolymerizable property in which the polymer is decomposed into monomers by heat or light, and in particular has a depolymerizable property that hardly leaves a residue when depolymerized by heat. Regarding copolymer polymers.
近年、プラスチック（ポリマー）は耐久性や耐熱性に優れる素材としての技術開発が進み様々な素材が市場で使用されている。一方、これらプラスチック材料は環境では分解されないことから環境への影響が指摘されているが、再利用が難しく廃棄することも多い。特に金属とプラスチックが複合化された製品が多くなってきているが、このような複合材料は、それぞれに分離することが難しく埋め立て処理しかないのが現状である。 In recent years, the technology of plastic (polymer) as a material with excellent durability and heat resistance has been developed, and various materials are being used on the market. On the other hand, it has been pointed out that these plastic materials have an impact on the environment because they do not decompose in the environment, but they are difficult to reuse and are often discarded. In particular, there are an increasing number of products that are made of composite metals and plastics, but these composite materials are currently difficult to separate into their individual parts and can only be disposed of in landfills.
このため、生分解性ポリマーなどプラスチックを分解可能としたり、プラスチックを回収して再利用したりする様々な取り組みが進められている。 For this reason, various efforts are underway to make plastics degradable, such as biodegradable polymers, and to collect and reuse plastics.
しかしながら、生分解性ポリマーは、生分解途中の物質の環境における安全性や、分解途中の物質がマイクロプラスチックとなり、これらを環境生物・海洋生物が摂取した時の影響などが明確になっていない。さらに、生分解性ポリマーは、廃棄物削減に対しては一定の効果があるものの、再利用という課題に関しては、何ら解決するものではない。さらに、廃棄物削減に限ってみても、分解するまでの時間が数カ月以上かかる場合もある、という問題点がある。 However, it is not clear whether biodegradable polymers are safe in the environment as they are in the process of being biodegraded, or the effects of microplastics that are ingested by environmental and marine organisms. Furthermore, although biodegradable polymers have a certain effect on waste reduction, they do not solve the problem of reuse. Furthermore, even when looking only at reducing waste, there is a problem in that it can take several months or more for decomposition.
また、ペットボトルなどは、リサイクルして再利用されているが、再利用するためには特殊な化学薬品などを使用してモノマーにまで分解する必要があり、多大な手間とエネルギーを必要とする、という問題点がある。さらに再利用の用途も限定される、という問題点もある。 In addition, plastic bottles and other items are recycled and reused, but in order to be reused, they must be broken down into monomers using special chemicals, which requires a great deal of effort and energy. , there is a problem. Another problem is that the applications for reuse are also limited.
そこで、熱や光などの簡単な方法でプラスチックを分解し、再利用できる素材や方法が求められている。 Therefore, there is a need for materials and methods that can reuse plastics by decomposing them using simple methods such as heat and light.
本発明は、上記課題に鑑みてなされたものであり、熱や光によって重合体（ポリマー）が単量体（モノマー）に分解する解重合性を有し、再利用することが容易な共重合ポリマーを提供することを目的とする。 The present invention has been made in view of the above problems, and is a copolymer that has depolymerizability in which a polymer is decomposed into monomers by heat or light and is easy to reuse. The purpose is to provide polymers.
上記課題を解決するために本発明は、加熱や光などでモノマーに分解する解重合性ホモポリマーを構成するモノマーを２種又は３種以上共重合させた、解重合性共重合ポリマーを提供する（発明１）。 In order to solve the above problems, the present invention provides a depolymerizable copolymer obtained by copolymerizing two or more types of monomers constituting a depolymerizable homopolymer that decomposes into monomers by heating, light, etc. (Invention 1).
かかる発明（発明１）によれば、解重合性の高いホモポリマーを構成するモノマー同士を２成分以上で共重合させることにより、リサイクルしやすく、加熱時の残渣も少なく、利便性の高い解重合性共重合ポリマーとすることができる。これは以下のような理由による。すなわち、これまで解重合性を有するホモポリマーについては知られているが、解重合性を有するホモポリマーを構成するモノマー同士を共重合したポリマーについてはその特性が明らかではなかった。そこで、本発明者らが、解重合性を有するホモポリマーを構成するモノマー同士の共重合ポリマーについて、熱分解特性を確認した結果、これらの共重合ポリマーも解重合性を有し、さらに熱分解による残渣がほとんど残らないポリマーであることを確認した。しかも、解重合性を有するホモポリマーを構成するモノマー同士を共重合することにより、元となる各解重合性ホモポリマーの特性（解重合開始温度、柔軟性、機械的強度など）を調整することができることも見出したのである。 According to this invention (Invention 1), by copolymerizing two or more monomers constituting a highly depolymerizable homopolymer, the depolymerization process is easy to recycle, leaves little residue upon heating, and is highly convenient. It can be made into a polyester copolymer. This is due to the following reasons. That is, although homopolymers having depolymerizability have been known so far, the characteristics of polymers obtained by copolymerizing monomers constituting the homopolymer having depolymerizability have not been clarified. Therefore, the present inventors confirmed the thermal decomposition characteristics of copolymerized polymers of monomers that constitute homopolymers that have depolymerizability, and found that these copolymers also have depolymerizability and that they also have thermal decomposition characteristics. It was confirmed that the polymer leaves almost no residue. Furthermore, by copolymerizing the monomers constituting the depolymerizable homopolymer, the characteristics (depolymerization initiation temperature, flexibility, mechanical strength, etc.) of each depolymerizable homopolymer can be adjusted. They also discovered that it can be done.
上記発明（発明１）においては、前記解重合性共重合ポリマーの解重合後のモノマーの回収率が９０重量％以上であることが好ましい（発明２）。 In the above invention (Invention 1), it is preferable that the recovery rate of the monomer after depolymerization of the depolymerizable copolymer is 90% by weight or more (Invention 2).
かかる発明（発明２）によれば、解重合性の高いホモポリマーの解重合後のモノマーの回収率は９０％を超えることも多く、このようなホモポリマーのモノマー同士を２成分以上共重合させた共重合体においても、加熱などにより解重合させた際にそれぞれのモノマーを高い回収率で回収することが可能となる。 According to this invention (Invention 2), the recovery rate of monomers after depolymerization of highly depolymerizable homopolymers often exceeds 90%, and the monomers of such homopolymers are copolymerized with two or more components. Even in the case of a copolymer, it is possible to recover each monomer at a high recovery rate when depolymerized by heating or the like.
上記発明（発明１）においては、前記解重合性共重合ポリマーの加熱による残渣が、該解重合性共重合ポリマー全量に対して１０重量％以下であることが好ましい（発明３）。 In the above invention (Invention 1), it is preferable that the residue of the depolymerizable copolymer after heating is 10% by weight or less based on the total amount of the depolymerizable copolymer (Invention 3).
かかる発明（発明３）によれば、解重合性の高いホモポリマーを解重合した際の残渣は１０重量％以下となることも多く、このようなホモポリマーのモノマー同士を２成分以上共重合させた共重合体においても、加熱などにより解重合させた際の残渣を少なくすることができる。 According to this invention (Invention 3), when a highly depolymerizable homopolymer is depolymerized, the residue is often 10% by weight or less, and the monomers of such a homopolymer are copolymerized with two or more components. Even in the case of a copolymer, it is possible to reduce the amount of residue when depolymerized by heating or the like.
上記発明（発明１～３）においては、前記解重合性のホモポリマーが、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリα－メチルスチレン（ＰＡＭＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）から選ばれる２種以上であることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the depolymerizable homopolymer is two or more types selected from polymethyl methacrylate (PMMA), polyα-methylstyrene (PAMS), and polytetrafluoroethylene (PTFE). It is preferable that (Invention 4).
かかる発明（発明４）によれば、これらの解重合性のホモポリマーを構成するメタクリル酸メチル（ＭＭＡ）、α－メチルスチレン（ＡＭＳ）、テトラフルオロエチレン（ＴＦＥ）などのモノマーを組み合わせて共重合体とすることにより、解重合性のホモポリマーの有する各種性状を相互に調整して、所望の性状の解重合性共重合ポリマーとすることができる。 According to this invention (Invention 4), monomers such as methyl methacrylate (MMA), α-methylstyrene (AMS), and tetrafluoroethylene (TFE) constituting these depolymerizable homopolymers are combined and copolymerized. By combining them, the various properties of the depolymerizable homopolymers can be mutually adjusted to produce a depolymerizable copolymer with desired properties.
本発明は、解重合性の高いホモポリマーを構成するモノマー同士を２成分以上で共重合させた解重合性共重合ポリマーであり、加熱による簡単な方法でモノマーを高収率で回収できるので、リサイクルが容易となっている。また、加熱分解後の残渣が少ないため、金属などの異種材料とこのポリマーとを組み合わせて複合材料としても、加熱するだけでポリマーを分解してモノマーを回収できるため素材の分別回収が可能となる。 The present invention is a depolymerizable copolymer obtained by copolymerizing two or more monomers constituting a highly depolymerizable homopolymer, and the monomer can be recovered in high yield by a simple method by heating. It is easy to recycle. In addition, since there is little residue after thermal decomposition, it is possible to use composite materials by combining dissimilar materials such as metals with this polymer, as the polymer can be decomposed and the monomer recovered simply by heating, making it possible to separate and recover the material. .
以下の本発明の解重合性共重合ポリマーについて、詳細に説明する。 The depolymerizable copolymer of the present invention will be explained in detail below.
（解重合性ホモポリマー及びモノマー）
本発明においては、原材料として加熱や光などでモノマーに分解する解重合性ホモポリマーを構成するモノマーを用いる。
(Depolymerizable homopolymer and monomer)
In the present invention, monomers constituting a depolymerizable homopolymer that decomposes into monomers by heating, light, etc. are used as raw materials.
この解重合性ホモポリマーは、所定の単量体（モノマー）を単独で重合させたものであり、加熱や光などでモノマーに分解して、モノマー回収率９０％以上と極めて高い回収率を有するものが好ましい。このようなモノマー回収率の高い解重合性ホモポリマーとしては、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリα－メチルスチレン（ＰＡＭＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）などが知られている（例えば、大谷肇ら：「高分子の熱分解特性」 高分子， ４６， ３９４ （１９９７）、大澤善次郎ら：「高分子の熱劣化」 Ｍａｔｅｒｉａｌｓ Ｌｉｆｅ，８［４］， １６５ （１９９６）など）。これらのホモポリマーを構成するモノマー（単量体成分）は、メタクリル酸メチル（ＭＭＡ）、α－メチルスチレン（ＡＭＳ）、テトラフルオロエチレン（ＴＦＥ）である。 This depolymerizable homopolymer is made by polymerizing a specific monomer alone, and when it is decomposed into monomers by heating or light, it has an extremely high monomer recovery rate of 90% or more. Preferably. Polymethyl methacrylate (PMMA), polyα-methylstyrene (PAMS), and polytetrafluoroethylene (PTFE) are known as such depolymerizable homopolymers with a high monomer recovery rate (for example, Otani et al. Hajime et al.: “Thermal decomposition characteristics of polymers” Kobunshi, 46, 394 (1997), Zenjiro Osawa et al.: “Thermal deterioration of polymers” Materials Life, 8 [4], 165 (1996), etc.). The monomers (monomer components) constituting these homopolymers are methyl methacrylate (MMA), α-methylstyrene (AMS), and tetrafluoroethylene (TFE).
（解重合性共重合ポリマー）
本発明の解重合性共重合ポリマーは、上述したようなモノマー（単量体成分）を２種又は３種以上共重合したものである。
(Depolymerizable copolymer)
The depolymerizable copolymer of the present invention is a copolymer of two or more monomers (monomer components) as described above.
この解重合性共重合ポリマーにおけるモノマーの配合割合は特に制限はないが、例えば、解重合性共重合ポリマーが２種のモノマーからなる場合、第一のモノマー２０～８０重量部、好ましくは４０～６０重量部と、第二のモノマー８０～２０重量部、好ましくは６０～４０重量部とを配合して共重合させればよい。また、３種のモノマーからなる場合、第一のモノマー２０～８０重量部と、第二のモノマー２０～８０重量部と、第三のホモポリマー２０～８０重量部とを配合して共重合させればよい。 The blending ratio of monomers in this depolymerizable copolymer is not particularly limited, but for example, when the depolymerizable copolymer consists of two types of monomers, the first monomer is 20 to 80 parts by weight, preferably 40 to 80 parts by weight. 60 parts by weight and 80 to 20 parts by weight, preferably 60 to 40 parts by weight of the second monomer may be blended and copolymerized. In the case of three types of monomers, 20 to 80 parts by weight of the first monomer, 20 to 80 parts by weight of the second monomer, and 20 to 80 parts by weight of the third homopolymer are blended and copolymerized. That's fine.
このように２種又は３種以上の解重合性のホモポリマーを構成するモノマーを共重合させることにより、元となる各解重合性のホモポリマーの特性を調整することができる。この特性としては、例えば、解重合開始温度、柔軟性、機械的強度などであり、モノマーの配合比に応じて適宜調整することが可能となる。 By copolymerizing two or more types of monomers constituting a depolymerizable homopolymer in this way, the characteristics of each depolymerizable homopolymer as the base can be adjusted. These characteristics include, for example, depolymerization initiation temperature, flexibility, mechanical strength, etc., and can be adjusted as appropriate depending on the blending ratio of monomers.
この解重合性共重合ポリマーは、解重合により解重合性ホモポリマーを構成するモノマーの９０重量％以上と極めて高い回収率を有し、リサイクル効率に優れたものが好ましい。さらに、解重合性共重合ポリマーの加熱による残渣が、解重合性共重合ポリマー全量に対して１０重量％以下であり、取扱い性にも優れていることが好ましい。 The depolymerizable copolymer preferably has an extremely high recovery rate of 90% by weight or more of the monomers constituting the depolymerizable homopolymer upon depolymerization, and is excellent in recycling efficiency. Further, it is preferable that the amount of residue after heating of the depolymerizable copolymer is 10% by weight or less based on the total amount of the depolymerizable copolymer, and that the depolymerizable copolymer has excellent handling properties.
上述したような２種又は３種以上の解重合性のホモポリマーを構成するモノマーを共重合させた解重合性共重合ポリマーとしては、メタクリル酸メチル（ＭＭＡ）と、α－メチルスチレン（ＡＭＳ）とを共重合したものが好ましく、特にメタクリル酸メチル（ＭＭＡ）：α－メチルスチレン（ＡＭＳ）が２０：８０～８０：２０（重量比）、好ましくは４０：６０～６０：４０（重量比）で構成される共重合ポリマーが好ましい。この解重合性共重合ポリマーは、その配合割合により２００～３００℃程度の範囲で解重合開始温度を変動させることができるので、ポリマーの回収が容易である。さらに、その配合割合により得られる解重合性共重合ポリマーの柔軟性や機械的強度を調整することもできる。 Examples of the depolymerizable copolymer obtained by copolymerizing two or more types of monomers constituting the depolymerizable homopolymer as described above include methyl methacrylate (MMA) and α-methylstyrene (AMS). A copolymer of methyl methacrylate (MMA) and α-methylstyrene (AMS) is preferably 20:80 to 80:20 (weight ratio), preferably 40:60 to 60:40 (weight ratio). A copolymer composed of is preferred. The depolymerization start temperature of this depolymerizable copolymer can be varied within a range of about 200 to 300°C depending on the blending ratio, so the polymer can be easily recovered. Furthermore, the flexibility and mechanical strength of the resulting depolymerizable copolymer can be adjusted by changing the blending ratio.
上記解重合性共重合ポリマーには、必要に応じて、任意の適切な添加剤を配合してもよい。この添加剤としては、例えば、架橋剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤等）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 Any appropriate additives may be added to the depolymerizable copolymer, if necessary. These additives include, for example, crosslinking agents, tackifiers, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, and the like.
（解重合性共重合ポリマーの製造方法）
上記解重合性共重合ポリマーの製造方法に特に制限はないが、例えば、ラジカル重合反応により共重合させればよい。具体的には、原材料となるモノマーをラジカル重合開始剤、架橋剤などを混合した溶媒とともに不活性ガス雰囲気下に密封し、長時間攪拌を継続して共重合させ、貧溶媒に析出させて回収することにより製造することができる。
(Method for producing depolymerizable copolymer)
There is no particular restriction on the method for producing the above-mentioned depolymerizable copolymer, but for example, copolymerization may be carried out by a radical polymerization reaction. Specifically, the raw material monomer is sealed in an inert gas atmosphere with a solvent mixed with a radical polymerization initiator, a crosslinking agent, etc., copolymerized by continuous stirring for a long time, and recovered by precipitation in a poor solvent. It can be manufactured by
以上、本発明の解重合性共重合ポリマーについて説明してきたが、本発明は、２種以上の解重合性のホモポリマーを構成するモノマーを共重合させたものであり、高い解重合性を有していればよく、種々の解重合性のホモポリマーを原材料として用いることができる。上述したような解重合性共重合ポリマーは、従来はリサイクルが困難であった金属などの異種材料との成形体としても加熱により容易にモノマーを回収することができるので、リサイクル性に優れており、その産業上の利用性は極めて大きい。 The depolymerizable copolymer of the present invention has been explained above, but the present invention is a copolymerizable monomer constituting two or more types of depolymerizable homopolymer, and has high depolymerizability. Various depolymerizable homopolymers can be used as raw materials. The depolymerizable copolymer described above has excellent recyclability because the monomer can be easily recovered by heating even when molded with dissimilar materials such as metals, which were previously difficult to recycle. , its industrial applicability is extremely large.
以下の具体的な実施例に基づき本発明をさらに詳細に説明するが、本発明は下記の実施例に限定されるものではない。 The present invention will be explained in more detail based on the following specific examples, but the present invention is not limited to the following examples.
［実施例１］
（解重合性共重合ポリマーの合成）
５Ｌの４つ口フラスコにイオン交換水２１５２．９７ｇ、炭酸ナトリウム２．２０ｇ、ＫＳソープ（固形分９０％）を投入し、攪拌しながら溶解させた。溶解後、α－メチルスチレン（ＡＭＳ）７９５．０８ｇ、メタクリル酸メチル（ＭＭＡ）２７４．１２ｇを加えて１５０ｒｐｍで攪拌しながら系内をアルゴンガスで置換した。
[Example 1]
(Synthesis of depolymerizable copolymer)
2152.97 g of ion-exchanged water, 2.20 g of sodium carbonate, and KS soap (solid content 90%) were placed in a 5 L four-necked flask and dissolved with stirring. After dissolving, 795.08 g of α-methylstyrene (AMS) and 274.12 g of methyl methacrylate (MMA) were added, and the system was purged with argon gas while stirring at 150 rpm.
フラスコ内の温度が３～４℃になったことを確認したら、亜ニチオン酸ナトリウム０．６４３７ｇ、エチレンジアミン四酢酸鉄ナトリウム三水和物０．１１０７ｇ、エチレンジアミン四酢酸四ナトリウム四水和物０．２７５１ｇ、ナトリウムホルムアルデヒドスホキシレート０．４１７９ｇ、及びクメンハイドロパーオキサイド（８０％）２．１６１５ｇを順次添加して、３～４℃にフラスコ内の温度を保持しながら６３時間攪拌を行った。 After confirming that the temperature inside the flask has reached 3 to 4°C, add 0.6437 g of sodium dithionite, 0.1107 g of sodium iron ethylenediaminetetraacetate trihydrate, and 0.2751 g of tetrasodium ethylenediaminetetraacetate tetrahydrate. , 0.4179 g of sodium formaldehyde sulfoxylate, and 2.1615 g of cumene hydroperoxide (80%) were sequentially added, and the mixture was stirred for 63 hours while maintaining the temperature inside the flask at 3 to 4°C.
６３時間の攪拌後、２，６－ジ－ｔ－ブチル－４－メチルフェノール５．５０ｇを添加し、反応を停止させた。 After stirring for 63 hours, 5.50 g of 2,6-di-t-butyl-4-methylphenol was added to stop the reaction.
上記反応液を１５Ｌのメタノールに滴下し、析出した白色固体をろ過により回収した。得られた白色固体を簡易乾燥後、テトラヒドロフラン（ＴＨＦ）に溶解した（溶液総重量１５００ｇ）。この溶液を１７Ｌのメタノールに滴下し、析出した固体をろ過により回収した。得られた白色固体を５０℃で４８時間減圧乾燥し最終物を得た（収量：２５９．１６ｇ）。 The above reaction solution was added dropwise to 15 L of methanol, and the precipitated white solid was collected by filtration. The obtained white solid was briefly dried and then dissolved in tetrahydrofuran (THF) (total solution weight: 1500 g). This solution was added dropwise to 17 L of methanol, and the precipitated solid was collected by filtration. The obtained white solid was dried under reduced pressure at 50° C. for 48 hours to obtain the final product (yield: 259.16 g).
得られた共重合ポリマーのモノマー比をＮＭＲにより分析したところ、ＡＭＳ：ＭＭＡ＝５８：４２（モル比）であった。また、この共重合ポリマーに分子量をＧＰＣ分析したところ、数平均分子量（Ｍｎ）：１１６４２７、重量平均分子量（Ｍｗ）：２６２９０８、分子量分布（Ｍｗ／Ｍｎ）：２．３であった。さらに、得られた共重合ポリマーを画像観察可能な熱重量示差熱分析装置（ＴＧ－ＤＴＡ）で分析（Ｎ２環境、昇温速度１０℃／分）したところ、分解開始温度は約２００℃、分解終了温度は約３５０℃であった。一般的なポリマーは継続的な加熱により、ポリマー分子の末端から徐々に分解していくために変色が起こり最終的には黒色の残渣が残るが、実施例１の共重合ポリマーはそのような分解に伴う変色がなく、モノマーに完全に分解していく様子が確認され、解重合性が高いことが確認された。 When the monomer ratio of the obtained copolymer was analyzed by NMR, it was found that AMS:MMA=58:42 (molar ratio). Further, when the molecular weight of this copolymer was analyzed by GPC, it was found that the number average molecular weight (Mn): 116427, the weight average molecular weight (Mw): 262908, and the molecular weight distribution (Mw/Mn): 2.3. Furthermore, when the obtained copolymer was analyzed using a thermogravimetric differential thermal analyzer (TG-DTA) capable of image observation ( N2 environment, heating rate 10°C/min), the decomposition initiation temperature was approximately 200°C. The decomposition end temperature was about 350°C. Conventional polymers gradually decompose from the end of the polymer molecule due to continuous heating, causing discoloration and eventually leaving a black residue, but the copolymer of Example 1 does not undergo such decomposition. It was confirmed that there was no discoloration associated with the depolymerization, and that the monomer was completely decomposed, confirming that the depolymerization property was high.
［比較例１］
（ポリカーボネートのＴＧ－ＤＴＡ分析
解重合性が低いポリマーの一例として、ポリカーボネートのＴＧ－ＤＴＡ分析（Ｎ２環境、昇温速度１０℃／分）を行った結果、分解開始温度は約４００℃であり徐々に黒色に変化し、分解終了温度は約５５０℃で、分解は約７０％まで進むが約３０％は分解されずに残渣として残ることが観察された。
[Comparative example 1]
(TG-DTA analysis of polycarbonate As an example of a polymer with low depolymerizability, TG-DTA analysis of polycarbonate ( N2 environment, temperature increase rate 10°C/min) was performed, and the decomposition initiation temperature was approximately 400°C. It was observed that the color gradually changed to black, the decomposition end temperature was about 550° C., and decomposition progressed to about 70%, but about 30% remained as a residue without being decomposed.
［実施例２］
実施例１で得られたＡＭＳとＭＭＡの共重合ポリマーに対し、以下の条件で熱分解ガスクロマトグラフ質量分析（ＰＹ－ＧＣ／ＭＳ）を行った。その結果、加熱により気化する成分として、ＡＭＳとＭＭＡが主成分として検出された。以下、ＰＹ－ＧＣ／ＭＳ分析の条件を下記表１～３に示す。
[Example 2]
The copolymer of AMS and MMA obtained in Example 1 was subjected to pyrolysis gas chromatography mass spectrometry (PY-GC/MS) under the following conditions. As a result, AMS and MMA were detected as the main components that vaporize upon heating. The conditions for PY-GC/MS analysis are shown in Tables 1 to 3 below.
［実施例３］
実施例１で得られたＡＭＳとＭＭＡの共重合ポリマーを、Ｎ２環境下、昇温速度１０℃／分で４００℃まで温度上昇させ、気化した成分を室温に冷却して液体成分が得た。この液体成分を実施例１と同様にしてポリマー合成した結果、実施例１と同様のＡＭＳとＭＭＡの共重合ポリマーが得られ、反復利用が可能であることが確認できた。
[Example 3]
The copolymer of AMS and MMA obtained in Example 1 was heated to 400°C at a heating rate of 10°C/min in an N2 environment, and the vaporized component was cooled to room temperature to obtain a liquid component. . As a result of polymer synthesis using this liquid component in the same manner as in Example 1, a copolymer of AMS and MMA similar to that in Example 1 was obtained, and it was confirmed that repeated use was possible.
本発明は、熱によって重合体（ポリマー）が単量体（モノマー）に分解する解重合性を有する共重合ポリマーの再利用方法に関し、特に熱により解重合した際に残渣が残りにくい解重合性を有する共重合ポリマーの再利用方法に関する。 The present invention relates to a method for recycling a copolymer having a depolymerizable property in which the polymer is decomposed into monomers by heat , and in particular, a depolymerization method that does not leave a residue when depolymerized by heat. The present invention relates to a method for recycling a copolymer having properties.
近年、プラスチック（ポリマー）は耐久性や耐熱性に優れる素材としての技術開発が進み様々な素材が市場で使用されている。一方、これらプラスチック材料は環境では分解されないことから環境への影響が指摘されているが、再利用が難しく廃棄することも多い。特に金属とプラスチックが複合化された製品が多くなってきているが、このような複合材料は、それぞれに分離することが難しく埋め立て処理しかないのが現状である。 In recent years, the technology of plastic (polymer) as a material with excellent durability and heat resistance has been developed, and various materials are being used on the market. On the other hand, it has been pointed out that these plastic materials have an impact on the environment because they do not decompose in the environment, but they are difficult to reuse and are often discarded. In particular, there are an increasing number of products that are made of composite metals and plastics, but these composite materials are currently difficult to separate into their individual parts and can only be disposed of in landfills.
このため、生分解性ポリマーなどプラスチックを分解可能としたり、プラスチックを回収して再利用したりする様々な取り組みが進められている。 For this reason, various efforts are underway to make plastics degradable, such as biodegradable polymers, and to collect and reuse plastics.
しかしながら、生分解性ポリマーは、生分解途中の物質の環境における安全性や、分解途中の物質がマイクロプラスチックとなり、これらを環境生物・海洋生物が摂取した時の影響などが明確になっていない。さらに、生分解性ポリマーは、廃棄物削減に対しては一定の効果があるものの、再利用という課題に関しては、何ら解決するものではない。さらに、廃棄物削減に限ってみても、分解するまでの時間が数カ月以上かかる場合もある、という問題点がある。 However, it is not clear whether biodegradable polymers are safe in the environment as they are in the process of being biodegraded, or the effects of microplastics that are ingested by environmental and marine organisms. Furthermore, although biodegradable polymers have a certain effect on waste reduction, they do not solve the problem of reuse. Furthermore, even when looking only at reducing waste, there is a problem in that it can take several months or more for decomposition.
また、ペットボトルなどは、リサイクルして再利用されているが、再利用するためには特殊な化学薬品などを使用してモノマーにまで分解する必要があり、多大な手間とエネルギーを必要とする、という問題点がある。さらに再利用の用途も限定される、という問題点もある。 In addition, plastic bottles and other items are recycled and reused, but in order to be reused, they must be broken down into monomers using special chemicals, which requires a great deal of effort and energy. , there is a problem. Another problem is that the applications for reuse are also limited.
そこで、熱により簡単な方法でプラスチックを分解し、再利用できる素材や方法が求められている。 Therefore, there is a need for materials and methods that can easily decompose plastics using heat and reuse them.
本発明は、上記課題に鑑みてなされたものであり、熱によって重合体（ポリマー）が単量体（モノマー）に分解する解重合性を有し、再利用することが容易な解重合性共重合ポリマーの再利用方法を提供することを目的とする。 The present invention has been made in view of the above problems, and has a depolymerizable property in which a polymer is decomposed into monomers by heat , and can be easily reused. The purpose of this invention is to provide a method for reusing copolymerized polymers.
上記課題を解決するために本発明は、加熱によりモノマーに分解する解重合性ホモポリマーを構成するモノマー２種を共重合させた解重合性共重合ポリマーの再利用方法であって、前記２種のモノマーが、メタクリル酸メチル（ＭＭＡ）及びα－メチルスチレン（ＡＭＳ）で、前記メタクリル酸メチル（ＭＭＡ）及び前記α－メチルスチレン（ＡＭＳ）の重量比が２０：８０～８０：２０であり、前記解重合性のホモポリマーが、ポリメタクリル酸メチル（ＰＭＭＡ）、及びポリα－メチルスチレン（ＰＡＭＳ）であり、前記解重合性共重合ポリマーを２００～３００℃の解重合開始温度に加熱して解重合し、この解重合により得られる液体成分から前記解重合性共重合ポリマーを再度合成する、解重合性共重合ポリマーの再利用方法を提供する（発明１）。 In order to solve the above problems, the present invention provides a method for recycling a depolymerizable copolymer obtained by copolymerizing two types of monomers constituting a depolymerizable homopolymer that decomposes into monomers by heating, the method comprising: The monomers are methyl methacrylate (MMA) and α-methylstyrene (AMS), and the weight ratio of the methyl methacrylate (MMA) and the α-methylstyrene (AMS) is 20:80 to 80:20, The depolymerizable homopolymers are polymethyl methacrylate (PMMA) and polyα-methylstyrene (PAMS), and the depolymerizable copolymer is heated to a depolymerization initiation temperature of 200 to 300°C. Provided is a method for recycling a depolymerizable copolymer, which comprises depolymerizing and resynthesizing the depolymerizable copolymer from a liquid component obtained by this depolymerization (Invention 1).
上記発明（発明１）においては、前記解重合性共重合ポリマーの加熱による解重合における温度の上限が約３５０℃であり、この解重合性共重合ポリマーの加熱による残渣が、該解重合性共重合ポリマー全量に対して１０重量％以下であることが好ましい（発明２）。 In the above invention (invention 1) , the upper limit of the temperature in the depolymerization by heating of the depolymerizable copolymer is about 350°C, and the residue of the depolymerizable copolymer by heating is The amount is preferably 10% by weight or less based on the total amount of polymerized polymer (Invention 2).
本発明は、解重合性の高いホモポリマーを構成するモノマー同士を２成分以上で共重合させた解重合性共重合ポリマーであり、加熱による簡単な方法でモノマーを高収率で回収できるので、リサイクルが容易となっている。また、加熱分解後の残渣が少ないため、金属などの異種材料とこのポリマーとを組み合わせて複合材料としても、加熱するだけでポリマーを分解してモノマーを回収できるため素材の分別回収が可能となる。 The present invention is a depolymerizable copolymer obtained by copolymerizing two or more monomers constituting a highly depolymerizable homopolymer, and the monomer can be recovered in high yield by a simple method by heating. It is easy to recycle. In addition, since there is little residue after thermal decomposition, it is possible to use composite materials by combining dissimilar materials such as metals with this polymer, as the polymer can be decomposed and the monomer recovered simply by heating, making it possible to separate and recover the material. .
以下の本発明の解重合性共重合ポリマーの再利用方法について、詳細に説明する。 The method for recycling the depolymerizable copolymer of the present invention will be described in detail below.
（解重合性ホモポリマー及びモノマー）
本発明においては、原材料として加熱によりモノマーに分解する解重合性ホモポリマーを構成するモノマーを用いる。
(Depolymerizable homopolymer and monomer)
In the present invention, monomers constituting a depolymerizable homopolymer that decomposes into monomers by heating are used as raw materials.
この解重合性ホモポリマーは、所定の単量体（モノマー）を単独で重合させたものであり、加熱によりモノマーに分解して、モノマー回収率９０％以上と極めて高い回収率を有するものが好ましい。このようなモノマー回収率の高い解重合性ホモポリマーとしては、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリα－メチルスチレン（ＰＡＭＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）などが知られている（例えば、大谷肇ら：「高分子の熱分解特性」 高分子， ４６， ３９４ （１９９７）、大澤善次郎ら：「高分子の熱劣化」 Ｍａｔｅｒｉａｌｓ Ｌｉｆｅ，８［４］， １６５ （１９９６）など）。これらのホモポリマーを構成するモノマー（単量体成分）は、メタクリル酸メチル（ＭＭＡ）、α－メチルスチレン（ＡＭＳ）、テトラフルオロエチレン（ＴＦＥ）である。 This depolymerizable homopolymer is obtained by polymerizing a predetermined monomer alone, and preferably has an extremely high monomer recovery rate of 90% or more when it is decomposed into monomers by heating. . Polymethyl methacrylate (PMMA), polyα-methylstyrene (PAMS), and polytetrafluoroethylene (PTFE) are known as such depolymerizable homopolymers with a high monomer recovery rate (for example, Otani et al. Hajime et al.: “Thermal decomposition characteristics of polymers” Kobunshi, 46, 394 (1997), Zenjiro Osawa et al.: “Thermal deterioration of polymers” Materials Life, 8 [4], 165 (1996), etc.). The monomers (monomer components) constituting these homopolymers are methyl methacrylate (MMA), α-methylstyrene (AMS), and tetrafluoroethylene (TFE).
（解重合性共重合ポリマー）
本発明の解重合性共重合ポリマーは、上述したようなモノマー（単量体成分）を２種又は３種以上共重合したものである。
(Depolymerizable copolymer)
The depolymerizable copolymer of the present invention is a copolymer of two or more monomers (monomer components) as described above.
この解重合性共重合ポリマーにおけるモノマーの配合割合は特に制限はないが、例えば、解重合性共重合ポリマーが２種のモノマーからなる場合、第一のモノマー２０～８０重量部、好ましくは４０～６０重量部と、第二のモノマー８０～２０重量部、好ましくは６０～４０重量部とを配合して共重合させればよい。 The blending ratio of monomers in this depolymerizable copolymer is not particularly limited, but for example, when the depolymerizable copolymer consists of two types of monomers, the first monomer is 20 to 80 parts by weight, preferably 40 to 80 parts by weight. 60 parts by weight and 80 to 20 parts by weight, preferably 60 to 40 parts by weight of the second monomer may be blended and copolymerized .
このように２種の解重合性のホモポリマーを構成するモノマーを共重合させることにより、元となる各解重合性のホモポリマーの特性を調整することができる。この特性としては、例えば、解重合開始温度、柔軟性、機械的強度などであり、モノマーの配合比に応じて適宜調整することが可能となる。 By copolymerizing the monomers constituting two types of depolymerizable homopolymers in this way, the characteristics of each of the base depolymerizable homopolymers can be adjusted. These characteristics include, for example, depolymerization initiation temperature, flexibility, mechanical strength, etc., and can be adjusted as appropriate depending on the blending ratio of monomers.
この解重合性共重合ポリマーは、解重合により解重合性ホモポリマーを構成するモノマーの９０重量％以上と極めて高い回収率を有し、リサイクル効率に優れたものが好ましい。さらに、解重合性共重合ポリマーの加熱による残渣が、解重合性共重合ポリマー全量に対して１０重量％以下であり、取扱い性にも優れていることが好ましい。 The depolymerizable copolymer preferably has an extremely high recovery rate of 90% by weight or more of the monomers constituting the depolymerizable homopolymer upon depolymerization, and is excellent in recycling efficiency. Further, it is preferable that the amount of residue after heating of the depolymerizable copolymer is 10% by weight or less based on the total amount of the depolymerizable copolymer, and that the depolymerizable copolymer has excellent handling properties.
上述したような２種の解重合性のホモポリマーを構成するモノマーを共重合させた解重合性共重合ポリマーとしては、メタクリル酸メチル（ＭＭＡ）と、α－メチルスチレン（ＡＭＳ）とを共重合したものであり、好ましくはメタクリル酸メチル（ＭＭＡ）：α－メチルスチレン（ＡＭＳ）が２０：８０～８０：２０（重量比）、特に４０：６０～６０：４０（重量比）で構成される共重合ポリマーである。この解重合性共重合ポリマーは、その配合割合により２００～３００℃程度の範囲で解重合開始温度を変動させることができるので、ポリマーの回収が容易である。さらに、その配合割合により得られる解重合性共重合ポリマーの柔軟性や機械的強度を調整することもできる。 A depolymerizable copolymer obtained by copolymerizing the monomers constituting the two types of depolymerizable homopolymers described above is a copolymer of methyl methacrylate (MMA) and α-methylstyrene (AMS). It is preferably composed of methyl methacrylate (MMA):α-methylstyrene (AMS) in a ratio of 20:80 to 80:20 (weight ratio), particularly 40:60 to 60:40 (weight ratio). It is a copolymer. The depolymerization start temperature of this depolymerizable copolymer can be varied within a range of about 200 to 300°C depending on the blending ratio, so the polymer can be easily recovered. Furthermore, the flexibility and mechanical strength of the resulting depolymerizable copolymer can be adjusted by changing the blending ratio.
上記解重合性共重合ポリマーには、必要に応じて、任意の適切な添加剤を配合してもよい。この添加剤としては、例えば、架橋剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤等）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 Any appropriate additives may be added to the depolymerizable copolymer, if necessary. These additives include, for example, crosslinking agents, tackifiers, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, and the like.
（解重合性共重合ポリマーの製造方法）
上記解重合性共重合ポリマーの製造方法に特に制限はないが、例えば、ラジカル重合反応により共重合させればよい。具体的には、原材料となるモノマーをラジカル重合開始剤、架橋剤などを混合した溶媒とともに不活性ガス雰囲気下に密封し、長時間攪拌を継続して共重合させ、貧溶媒に析出させて回収することにより製造することができる。
(Method for producing depolymerizable copolymer)
There is no particular restriction on the method for producing the above-mentioned depolymerizable copolymer, but for example, copolymerization may be carried out by a radical polymerization reaction. Specifically, the raw material monomer is sealed in an inert gas atmosphere with a solvent mixed with a radical polymerization initiator, a crosslinking agent, etc., copolymerized by continuous stirring for a long time, and recovered by precipitation in a poor solvent. It can be manufactured by
以上、本発明の解重合性共重合ポリマーの再利用方法について説明してきたが、本発明は、特定の２種の解重合性のホモポリマーを構成するモノマーを共重合させたものである。上述したような解重合性共重合ポリマーは、従来はリサイクルが困難であった金属などの異種材料との成形体としても加熱により容易にモノマーを回収することができるので、リサイクル性に優れており、その産業上の利用性は極めて大きい。 The method for recycling the depolymerizable copolymer of the present invention has been described above, but the present invention involves copolymerizing monomers constituting two specific types of depolymerizable homopolymers . The depolymerizable copolymer described above has excellent recyclability because the monomer can be easily recovered by heating even when molded with dissimilar materials such as metals, which were previously difficult to recycle. , its industrial applicability is extremely large.
以下の具体的な実施例に基づき本発明をさらに詳細に説明するが、本発明は下記の実施例に限定されるものではない。 The present invention will be explained in more detail based on the following specific examples, but the present invention is not limited to the following examples.
［実施例１］
（解重合性共重合ポリマーの合成）
５Ｌの４つ口フラスコにイオン交換水２１５２．９７ｇ、炭酸ナトリウム２．２０ｇ、ＫＳソープ（固形分９０％）を投入し、攪拌しながら溶解させた。溶解後、α－メチルスチレン（ＡＭＳ）７９５．０８ｇ、メタクリル酸メチル（ＭＭＡ）２７４．１２ｇを加えて１５０ｒｐｍで攪拌しながら系内をアルゴンガスで置換した。
[Example 1]
(Synthesis of depolymerizable copolymer)
2152.97 g of ion-exchanged water, 2.20 g of sodium carbonate, and KS soap (solid content 90%) were placed in a 5 L four-necked flask and dissolved with stirring. After dissolving, 795.08 g of α-methylstyrene (AMS) and 274.12 g of methyl methacrylate (MMA) were added, and the system was purged with argon gas while stirring at 150 rpm.
フラスコ内の温度が３～４℃になったことを確認したら、亜ニチオン酸ナトリウム０．６４３７ｇ、エチレンジアミン四酢酸鉄ナトリウム三水和物０．１１０７ｇ、エチレンジアミン四酢酸四ナトリウム四水和物０．２７５１ｇ、ナトリウムホルムアルデヒドスホキシレート０．４１７９ｇ、及びクメンハイドロパーオキサイド（８０％）２．１６１５ｇを順次添加して、３～４℃にフラスコ内の温度を保持しながら６３時間攪拌を行った。 After confirming that the temperature inside the flask has reached 3 to 4°C, add 0.6437 g of sodium dithionite, 0.1107 g of sodium iron ethylenediaminetetraacetate trihydrate, and 0.2751 g of tetrasodium ethylenediaminetetraacetate tetrahydrate. , 0.4179 g of sodium formaldehyde sulfoxylate, and 2.1615 g of cumene hydroperoxide (80%) were sequentially added, and the mixture was stirred for 63 hours while maintaining the temperature inside the flask at 3 to 4°C.
６３時間の攪拌後、２，６－ジ－ｔ－ブチル－４－メチルフェノール５．５０ｇを添加し、反応を停止させた。 After stirring for 63 hours, 5.50 g of 2,6-di-t-butyl-4-methylphenol was added to stop the reaction.
上記反応液を１５Ｌのメタノールに滴下し、析出した白色固体をろ過により回収した。得られた白色固体を簡易乾燥後、テトラヒドロフラン（ＴＨＦ）に溶解した（溶液総重量１５００ｇ）。この溶液を１７Ｌのメタノールに滴下し、析出した固体をろ過により回収した。得られた白色固体を５０℃で４８時間減圧乾燥し最終物を得た（収量：２５９．１６ｇ）。 The above reaction solution was added dropwise to 15 L of methanol, and the precipitated white solid was collected by filtration. The obtained white solid was briefly dried and then dissolved in tetrahydrofuran (THF) (total solution weight: 1500 g). This solution was added dropwise to 17 L of methanol, and the precipitated solid was collected by filtration. The obtained white solid was dried under reduced pressure at 50° C. for 48 hours to obtain the final product (yield: 259.16 g).
得られた共重合ポリマーのモノマー比をＮＭＲにより分析したところ、ＡＭＳ：ＭＭＡ＝５８：４２（モル比）であった。また、この共重合ポリマーに分子量をＧＰＣ分析したところ、数平均分子量（Ｍｎ）：１１６４２７、重量平均分子量（Ｍｗ）：２６２９０８、分子量分布（Ｍｗ／Ｍｎ）：２．３であった。さらに、得られた共重合ポリマーを画像観察可能な熱重量示差熱分析装置（ＴＧ－ＤＴＡ）で分析（Ｎ２環境、昇温速度１０℃／分）したところ、分解開始温度は約２００℃、分解終了温度は約３５０℃であった。一般的なポリマーは継続的な加熱により、ポリマー分子の末端から徐々に分解していくために変色が起こり最終的には黒色の残渣が残るが、実施例１の共重合ポリマーはそのような分解に伴う変色がなく、モノマーに完全に分解していく様子が確認され、解重合性が高いことが確認された。 When the monomer ratio of the obtained copolymer was analyzed by NMR, it was found that AMS:MMA=58:42 (molar ratio). Further, when the molecular weight of this copolymer was analyzed by GPC, it was found that the number average molecular weight (Mn): 116427, the weight average molecular weight (Mw): 262908, and the molecular weight distribution (Mw/Mn): 2.3. Furthermore, when the obtained copolymer was analyzed using a thermogravimetric differential thermal analyzer (TG-DTA) capable of image observation ( N2 environment, heating rate 10°C/min), the decomposition initiation temperature was approximately 200°C, The decomposition end temperature was about 350°C. Conventional polymers gradually decompose from the end of the polymer molecule due to continuous heating, causing discoloration and eventually leaving a black residue, but the copolymer of Example 1 does not undergo such decomposition. It was confirmed that there was no discoloration associated with the depolymerization, and that the monomer was completely decomposed, confirming that the depolymerization property was high.
［比較例１］
（ポリカーボネートのＴＧ－ＤＴＡ分析
解重合性が低いポリマーの一例として、ポリカーボネートのＴＧ－ＤＴＡ分析（Ｎ２環境、昇温速度１０℃／分）を行った結果、分解開始温度は約４００℃であり徐々に黒色に変化し、分解終了温度は約５５０℃で、分解は約７０％まで進むが約３０％は分解されずに残渣として残ることが観察された。
[Comparative example 1]
(TG-DTA analysis of polycarbonate As an example of a polymer with low depolymerizability, TG-DTA analysis of polycarbonate ( N2 environment, temperature increase rate 10°C/min) was performed, and the decomposition initiation temperature was approximately 400°C. It was observed that the color gradually changed to black, the decomposition end temperature was about 550° C., and decomposition progressed to about 70%, but about 30% remained as a residue without being decomposed.
［実施例２］
実施例１で得られたＡＭＳとＭＭＡの共重合ポリマーに対し、以下の条件で熱分解ガスクロマトグラフ質量分析（ＰＹ－ＧＣ／ＭＳ）を行った。その結果、加熱により気化する成分として、ＡＭＳとＭＭＡが主成分として検出された。以下、ＰＹ－ＧＣ／ＭＳ分析の条件を下記表１～３に示す。
[Example 2]
The copolymer of AMS and MMA obtained in Example 1 was subjected to pyrolysis gas chromatography mass spectrometry (PY-GC/MS) under the following conditions. As a result, AMS and MMA were detected as the main components that vaporize upon heating. The conditions for PY-GC/MS analysis are shown in Tables 1 to 3 below.
［実施例３］
実施例１で得られたＡＭＳとＭＭＡの共重合ポリマーを、Ｎ２環境下、昇温速度１０℃／分で４００℃まで温度上昇させ、気化した成分を室温に冷却して液体成分が得た。この液体成分を実施例１と同様にしてポリマー合成した結果、実施例１と同様のＡＭＳとＭＭＡの共重合ポリマーが得られ、反復利用が可能であることが確認できた。
[Example 3]
The copolymer of AMS and MMA obtained in Example 1 was heated to 400°C at a heating rate of 10°C/min in an N2 environment, and the vaporized component was cooled to room temperature to obtain a liquid component. . As a result of polymer synthesis using this liquid component in the same manner as in Example 1, a copolymer of AMS and MMA similar to that in Example 1 was obtained, and it was confirmed that repeated use was possible.
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