JP4432175B2 - Method for decomposing polyimide and method for producing polyimide using decomposition and recovery product as raw material - Google Patents

Method for decomposing polyimide and method for producing polyimide using decomposition and recovery product as raw material Download PDF

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JP4432175B2
JP4432175B2 JP34994299A JP34994299A JP4432175B2 JP 4432175 B2 JP4432175 B2 JP 4432175B2 JP 34994299 A JP34994299 A JP 34994299A JP 34994299 A JP34994299 A JP 34994299A JP 4432175 B2 JP4432175 B2 JP 4432175B2
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polyimide
molecular weight
low molecular
decomposition
raw material
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JP2001163973A (en
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賢治 鵜原
英樹 森山
弘司 横山
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Du Pont Toray Co Ltd
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    • 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
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    • Y02W30/62—Plastics recycling; Rubber recycling

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Description

【０００１】
【発明の属する技術分野】
本発明は、ポリイミドを分解する方法、およびその回収した低分子量物質をリサイクルして、それを原料の一部として用いたポリイミドの製造方法に関する。
【０００２】
【従来の技術】
ポリイミドは、耐熱性かつ難燃性であるため、使用済みまたは使用されない場合は分解せず埋め立てるか焼却されていた。しかし近年の地球環境問題への関心の高まりから、原料への回収を目的に、酸またはアルカリ水溶液で加水分解することが試みられている。
【０００３】
しかしながら、上記の従来方法では、埋め立て用地の確保、焼却炉が必要であり付近の住民への配慮が必要である。また酸およびアルカリでの加水分解では中和工程が必要であり、薬品を使用するためその原料に対して不純物となり原料へ使用できることが困難であった。
【０００４】
【発明が解決しようとする課題】
本発明は、上述した従来技術における問題点の解決を課題として検討した結果達成されたものであり、ポリイミドを分解する方法、特にその分解物を回収し、リサイクル原料として用いる方法及びそれを原料として用いることを目的とするものである。
【０００５】
【課題を解決するための手段】
上記の目的を達成するための本発明は、下記式(I)で表される反復単位のポリイミドまたはその前駆体であるポリアミド酸を水と共存させて２５０℃以上３５０℃以下、１０ＭPa以上１００ＭPa以下の条件で反応させ、低分子量物質に分解させるポリイミドの分解方法であり、
【０００６】
【化４】

Figure 0004432175
[式(I)中、Ａｒ1は下記式(II)で示される４価の芳香族基であり、
【０００７】
【化５】
Figure 0004432175
（式(II)中Ｘは−ＣＯ−、−Ｏ−、−ＳＯ2−、−ＣＨ2−、−Ｃ（ＣＨ3）2−、−Ｃ（ＣＦ3）2−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）
Ａｒ２は下記式(III)で示される２価の芳香族基である。
【０００８】
【化６】
Figure 0004432175
（式(III)中Ｙは直結、−ＣＯ−、−Ｏ−、−ＳＯ2−、−ＣＨ2−、−Ｃ（ＣＨ3）2−、−Ｃ（ＣＦ3）2−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）]
また、このようにして得た低分子量物質を回収し、その回収低分子量原料を原料の一部として用いて合成したポリイミドである。
【０００９】
ポリイミドを構成する酸成分としてはピロメリット酸またはビフェニルテトラカルボン酸が、ジアミンとしてはオキシジアニリンまたはパラフェニレンジアミンが好ましい。また、ポリイミドがその前駆体であるポリアミド酸と共存した状態でも、有機溶剤を含んでいても良い。
【００１０】
有機溶剤を含んだ場合は予め有機溶剤を抽出し除く前処理を行って分解を行うこともできる。
【００１１】
ポリイミドを分解する際に共存させる「水」とは液体、気体または高温高圧条件下に存在する超臨界水のいずれをも含むものである。
【００１３】
この好ましい条件で得られた分解生成物を回収し原料の一部として用いることもできる。この場合、全原料の内１〜１０重量％を回収された原料を用いることが好ましい。
【００１４】
【発明の実施の形態】
以下、本発明の構成について詳述する。
【００１５】
本発明に用いられるポリイミドは、下記式(I)で表される反復単位のポリイミドである。
【００１６】
【化７】
Figure 0004432175
[式(I)中、Ａｒ1は下記式(II)で示される４価の芳香族基であり、
【００１７】
【化８】
Figure 0004432175
（式(II)中Ｘは−ＣＯ−、−Ｏ−、−ＳＯ2−、−ＣＨ2−、−Ｃ（ＣＨ3）2−、−Ｃ（ＣＦ3）2−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）
Ａｒ２は下記式(III)で示される２価の芳香族基である。
【００１８】
【化９】
Figure 0004432175
（式(III)中Ｙは直結、−ＣＯ−、−Ｏ−、−ＳＯ2−、−ＣＨ2−、−Ｃ（ＣＨ3）2−、−Ｃ（ＣＦ3）2−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）]
しかし、このポリイミドはポリイミドカルボン酸エステル、ポリイミドアミドエステルなどが含まれても良い。またそれらのブレンド、２成分重合体でも多成分共重合体でも良い。共重合の場合、ブロックポリマーか又はランダムポリマーかのいずれかでも良い。
【００１９】
本発明に用いられるポリアミド酸はポリイミドの重合前（前駆体）のポリマーでも、重合後一部を加水分解した物でも良い。
【００２０】
ポリイミドまたはポリアミド酸に用いられる原料は、イミド環を生成するものであれば良い。好ましい原料として、酸無水物としてピロメリット酸二無水物、ビフェニルテトラカルボン酸酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、およびトリメリット酸無水物などがある。アミンとして、オキシジアニリン、フェニレンジアミン、メチレンジアニリンなどがある。
【００２１】
分解回収される低分子量物質としては、上記原料およびさらに分解が進んだテレフタル酸、アニリン、さらには二酸化炭素、窒素などがあるが、リサイクルの面から上記ポリイミドの原料が好ましい。従って、分解条件もこれらの原料でとどまる条件が好ましい。
【００２２】
ポリイミドまたはポリアミド酸の分解は、分解を促進させる媒体と共に高温高圧雰囲気下で行われる。分解を促進させる媒体としては、水またはアルコールである。アルコールとしてはメタノール、エタノールが好ましい。水の形態としては液体、気体または超臨界水である。超臨界水とは温度が３７４℃以上、または圧力が２２ＭＰa以上の状態の水を言う。超臨界水は酸素を溶残させる能力が強いので、亜臨界領域が好ましい。
【００２３】
原料を回収する場合は、媒体内の溶存酸素は少なくすることが好ましい。更に酸化を防止するため水素を溶存させることも好ましい。また酸原料の回収率を高めるため二酸化炭素も併用できる。
【００２４】
媒体に対するポリイミドまたはポリアミド酸の比率は５０重量％以下が好ましい。好ましくは１０重量％以下である。下限は反応の効率から１重量％以上である。
【００２５】
ポリイミドまたはポリアミド酸は粉砕してスラリー状で媒体と混合され連続的に配管を通して反応容器内へ送り込むこともできる。
【００２６】
分解反応の条件としては、２５０℃〜３５０℃、１０ＭPa〜１００ＭPaである。
【００２７】
またこの方法で酸とジアミンを回収した場合、その原料を一部原料として使用することも好ましい。
【００２８】
反応器の材質としては、ニッケル合金、クロム合金、チタンコートが使用される。
【００２９】
分解の手順としては、ポリイミド、水、窒素をオートクレーブに充填し、電気炉で加熱する。設定温度で所定時間（例えば約１時間）保持し、その後室温まで冷却する。次にオートクレーブを解放し、水溶液を取り出し、濾紙で固形分とを分離する。
【００３０】
【実施例】
以下、実施例により、本発明を具体的に説明するが、本発明は、これら実施例に限定されるものではない。なお各フィルム特性値は、下記の方法で測定したものである。
【００３１】
また、下記の実施例中で、略号ＤＭＡＣはジメチルアセトアミドを、ＰＭＤＡはピロメリット酸二無水物を、ＰＤＡはｐ−フェニレンジアミンを、また、ＯＤＡはオキシジアニリンを、ＢＰＤＡはビフェニルテトラカルボン二酸無水物を表す略記である。
（１）分解率
（分解後の固形分の重さ／分解前の試料量）×１００
（２）原料回収率
水溶液をガスクロで分析し、予め判っている原料の検量線より、原料回収率を求めた。
［実施例１］
ＰＭＤＡとＯＤＡの原料を用いポリイミドフィルムＡを作成した。
【００３２】
材質チタン合金のオートクレーブ（容積５００ｃｃ）中にポリイミドフィルムＡと純水を入れた。窒素で約１時間バブリング後、所定圧力まで窒素ガスで昇圧した。その後オートクレーブを電気炉で３００℃に昇温した。圧力は３０MPaであった。この状態で３０分保持後、１時間かけて冷却を行った。その後圧力弁を解放し大気圧にした。
【００３３】
内容物を濾過し内容物を取り出しＤＭＡＣに溶解させた。固形分を取り除くため濾過し濾液を凍結乾燥した。固形分１重量％をクロロホルム／メタノール混合溶媒に溶かしガスクロ（ＧＣ）でＰＭＤＡおよびＯＤＡの量を定量した。安息香酸、テレフタル酸、アニリンなどはＧＣ−ＭＳ、ＮＭＲ、ＩＲで帰属し定量化した。結果を表１、２に示す。
［実施例１〜３、比較例１〜１０］
実施例１に準じて行った。結果を表１、２に示す。
【００３４】
【表１】
Figure 0004432175
【００３５】
【表２】
Figure 0004432175
【００３６】
【発明の効果】
本発明の方法によれば、ポリイミドが容易に分解し、その分解した低分子量物質を回収し、また、ポリイミドを合成することが可能であり、リサイクル事業として利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for decomposing polyimide and a method for producing polyimide by recycling the recovered low molecular weight substance and using it as a part of the raw material.
[0002]
[Prior art]
Since polyimide is heat resistant and flame retardant, it has been landfilled or incinerated without being decomposed when used or not used. However, due to the recent increase in interest in global environmental problems, attempts have been made to hydrolyze with an acid or alkaline aqueous solution for the purpose of recovery to raw materials.
[0003]
However, the above-described conventional methods require landfill sites and incinerators, which require consideration for nearby residents. Further, the hydrolysis with acid and alkali requires a neutralization step, and since chemicals are used, it becomes difficult for the raw materials to become impurities and to be used for the raw materials.
[0004]
[Problems to be solved by the invention]
The present invention has been achieved as a result of studying the solution of the above-described problems in the prior art as a problem, and is a method for decomposing polyimide, particularly a method for recovering the decomposition product and using it as a recycle material, and using it as a material. It is intended to be used.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a repeating unit polyimide represented by the following formula (I) or a polyamic acid that is a precursor thereof in coexistence with water at 250 ° C. or higher and 350 ° C. or lower and 10 MPa or higher and 100 MPa or lower. It is a decomposition method of polyimide that is reacted under the conditions of
[0006]
[Formula 4]
Figure 0004432175
[In the formula (I), Ar1 is a tetravalent aromatic group represented by the following formula (II):
[0007]
[Chemical formula 5]
Figure 0004432175
(In the formula (II), X is selected from —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO—. (It is a divalent organic group, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)
Ar2 is a divalent aromatic group represented by the following formula (III).
[0008]
[Chemical 6]
Figure 0004432175
(In Formula (III), Y is a direct bond, —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO— A divalent organic group selected, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)]
Moreover, it is the polyimide which collect | recovered the low molecular weight substance obtained in this way, and synthesize | combined using the recovered low molecular weight raw material as a part of raw material.
[0009]
Pyromellitic acid or biphenyltetracarboxylic acid is preferred as the acid component constituting the polyimide, and oxydianiline or paraphenylenediamine is preferred as the diamine. Moreover, even if the polyimide coexists with its precursor polyamic acid, it may contain an organic solvent.
[0010]
When an organic solvent is included, the decomposition can be performed by pre-treating and removing the organic solvent in advance.
[0011]
The “water” that coexists when the polyimide is decomposed includes any liquid, gas, or supercritical water existing under high temperature and high pressure conditions.
[0013]
The decomposition product obtained under these preferable conditions can be recovered and used as a part of the raw material. In this case, it is preferable to use a raw material in which 1 to 10% by weight of the total raw material is recovered.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0015]
The polyimide used in the present invention is a polyimide having a repeating unit represented by the following formula (I).
[0016]
[Chemical 7]
Figure 0004432175
[In the formula (I), Ar1 is a tetravalent aromatic group represented by the following formula (II):
[0017]
[Chemical 8]
Figure 0004432175
(In the formula (II), X is selected from —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO—. (It is a divalent organic group, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)
Ar2 is a divalent aromatic group represented by the following formula (III).
[0018]
[Chemical 9]
Figure 0004432175
(In Formula (III), Y is a direct bond, —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO— A divalent organic group selected, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)]
However, this polyimide may contain polyimide carboxylic acid ester, polyimide amide ester, and the like. Further, a blend thereof, a two-component polymer or a multi-component copolymer may be used. In the case of copolymerization, it may be either a block polymer or a random polymer.
[0019]
The polyamic acid used in the present invention may be a polymer before polymerization (precursor) of polyimide, or a product obtained by partially hydrolyzing after polymerization.
[0020]
The raw material used for polyimide or polyamic acid may be any material that generates an imide ring. Preferred raw materials include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, and trimellitic anhydride as acid anhydrides. Examples of amines include oxydianiline, phenylenediamine, and methylenedianiline.
[0021]
Examples of the low molecular weight substance to be decomposed and recovered include the above raw materials and terephthalic acid, aniline, carbon dioxide, nitrogen, etc., which are further decomposed, but the above polyimide raw materials are preferable from the viewpoint of recycling. Accordingly, it is preferable that the decomposition conditions remain with these raw materials.
[0022]
The decomposition of the polyimide or polyamic acid is performed in a high-temperature and high-pressure atmosphere together with a medium that promotes the decomposition. The medium for promoting the decomposition is water or alcohol. As the alcohol, methanol and ethanol are preferable. The form of water is liquid, gas or supercritical water. Supercritical water refers to water having a temperature of 374 ° C. or higher or a pressure of 22 MPa or higher. Since supercritical water has a strong ability to dissolve oxygen, the subcritical region is preferable.
[0023]
When recovering the raw material, it is preferable to reduce the dissolved oxygen in the medium. It is also preferable to dissolve hydrogen in order to prevent oxidation. Carbon dioxide can also be used in combination to increase the recovery rate of the acid raw material.
[0024]
The ratio of polyimide or polyamic acid to the medium is preferably 50% by weight or less. Preferably it is 10 weight% or less. The lower limit is 1% by weight or more from the efficiency of the reaction.
[0025]
Polyimide or polyamic acid can be pulverized and mixed with a medium in a slurry state and continuously fed into a reaction vessel through a pipe.
[0026]
The conditions for the decomposition reaction are 250 ° C. to 350 ° C. and 10 MPa to 100 MPa.
[0027]
Moreover, when an acid and diamine are collect | recovered by this method, it is also preferable to use the raw material partially as a raw material.
[0028]
As a material for the reactor, a nickel alloy, a chromium alloy, or a titanium coat is used.
[0029]
As a decomposition procedure, polyimide, water, and nitrogen are filled in an autoclave and heated in an electric furnace. Hold at the set temperature for a predetermined time (for example, about 1 hour), and then cool to room temperature. Next, the autoclave is released, the aqueous solution is taken out, and the solid content is separated with a filter paper.
[0030]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Each film characteristic value is measured by the following method.
[0031]
In the following examples, the abbreviation DMAC is dimethylacetamide, PMDA is pyromellitic dianhydride, PDA is p-phenylenediamine, ODA is oxydianiline, and BPDA is biphenyltetracarboxylic diacid. Abbreviation for anhydride.
(1) Decomposition rate (weight of solid after decomposition / sample amount before decomposition) × 100
(2) Raw material recovery rate The aqueous solution was analyzed by gas chromatography, and the raw material recovery rate was determined from a known calibration curve of the raw material.
[Example 1]
A polyimide film A was prepared using PMDA and ODA raw materials.
[0032]
A polyimide film A and pure water were placed in a titanium alloy autoclave (volume: 500 cc). After bubbling with nitrogen for about 1 hour, the pressure was increased with nitrogen gas to a predetermined pressure. Thereafter, the autoclave was heated to 300 ° C. in an electric furnace. The pressure was 30 MPa. After maintaining in this state for 30 minutes, cooling was performed over 1 hour. The pressure valve was then released to atmospheric pressure.
[0033]
The contents were filtered and the contents were taken out and dissolved in DMAC. Filtered to remove solids and the filtrate was lyophilized. A solid content of 1% by weight was dissolved in a chloroform / methanol mixed solvent, and the amount of PMDA and ODA was determined by gas chromatography (GC). Benzoic acid, terephthalic acid, aniline, and the like were assigned and quantified by GC-MS, NMR, and IR. The results are shown in Tables 1 and 2.
[Examples 1 to 3 and Comparative Examples 1 to 10 ]
It carried out according to Example 1. The results are shown in Tables 1 and 2.
[0034]
[Table 1]
Figure 0004432175
[0035]
[Table 2]
Figure 0004432175
[0036]
【The invention's effect】
According to the method of the present invention, polyimide can be easily decomposed, the decomposed low molecular weight substance can be recovered, and polyimide can be synthesized, which can be used as a recycling business.

Claims (5)

下記式(I)で表される反復単位のポリイミドまたはその前駆体であるポリアミド酸を水またはアルコールと共存させて２５０℃以上３５０℃以下、１０ＭPa以上１００ＭPa以下の条件で反応させ、低分子量物質に分解させることを特徴とするポリイミドの分解方法。
Figure 0004432175
 [式(I)中、Ａｒ1は下記式(II)で示される４価の芳香族基であり、
Figure 0004432175
 （式(II)中Ｘは−ＣＯ−、−Ｏ−、−ＳＯ２−、−ＣＨ２−、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＦ３）２−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）
Ａｒ２は下記式(III)で示される２価の芳香族基である。
Figure 0004432175
 （式(III)中Ｙは直結、−ＣＯ−、−Ｏ−、−ＳＯ２−、−ＣＨ２−、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＦ３）２−、−ＣＯＯＺＯＣＯ−から選ばれる２価の有機基であり、Ｚはカルボン酸エステル結合能のあるジオールを置換することができる２価の有機基である。）]The polyimide of the repeating unit represented by the following formula (I) or the polyamic acid which is a precursor thereof is coexisted with water or alcohol and reacted under conditions of 250 ° C. or higher and 350 ° C. or lower, 10 MPa or higher and 100 MPa or lower to form a low molecular weight substance. A method for decomposing polyimide, comprising decomposing.
Figure 0004432175
 [In the formula (I), Ar1 is a tetravalent aromatic group represented by the following formula (II):
Figure 0004432175
 (In the formula (II), X is selected from —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO—. (It is a divalent organic group, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)
Ar2 is a divalent aromatic group represented by the following formula (III).
Figure 0004432175
 (In Formula (III), Y is a direct bond, —CO—, —O—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —COOZOCO— A divalent organic group selected, and Z is a divalent organic group capable of substituting a diol having a carboxylate bond ability.)] 水が液体、気体または超臨界水であることを特徴とする請求項１に記載の分解方法。  The decomposition method according to claim 1, wherein the water is liquid, gas, or supercritical water. 低分子量物質がカルボン酸およびアミンを含むことを特徴とする請求項１に記載の分解方法。  The decomposition method according to claim 1, wherein the low molecular weight substance contains a carboxylic acid and an amine. 低分子量物質がテトラカルボン酸およびジアミンを含むことを特徴とする請求項１に記載の分解方法。  The decomposition method according to claim 1, wherein the low molecular weight substance contains tetracarboxylic acid and diamine. 請求項１〜４いずれかに記載の低分子量物質を回収し、その回収低分子量物質を原料の一部として用いて合成することを特徴とするポリイミドの製造方法。A method for producing a polyimide , comprising recovering the low molecular weight substance according to any one of claims 1 to 4 and synthesizing the recovered low molecular weight substance as a part of a raw material.
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