JP2002114839A - Method for synthesizing unsaturated polyester resin using recycled polyethylene terephthalate - Google Patents
Method for synthesizing unsaturated polyester resin using recycled polyethylene terephthalateInfo
- Publication number
- JP2002114839A JP2002114839A JP2000306218A JP2000306218A JP2002114839A JP 2002114839 A JP2002114839 A JP 2002114839A JP 2000306218 A JP2000306218 A JP 2000306218A JP 2000306218 A JP2000306218 A JP 2000306218A JP 2002114839 A JP2002114839 A JP 2002114839A
- Authority
- JP
- Japan
- Prior art keywords
- pet
- polyester resin
- glycol
- polyethylene terephthalate
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は、リサイクルされた
ポリエチレン−テレフタレート(以下、R−PETと略称す
る)を原料に用いた不飽和ポリエステル樹脂(以下、ポ
リエステル樹脂と略称する)の製造方法に関するもので
ある。The present invention relates to a method for producing an unsaturated polyester resin (hereinafter abbreviated as a polyester resin) using recycled polyethylene terephthalate (hereinafter abbreviated as R-PET) as a raw material. It is.
【0002】[0002]
【従来の技術】R−PETを用いてポリエステル樹脂を得る
方法は公知であり、一般にはグリコールとR−PETを同
時に仕込み、グリコールの沸点でR−PETをグリコール分
解し、低分子量の生成物とした後、所望量のα−β不飽
和多塩基酸(又はその酸無水物)を加えて重縮合を行う
方法が採れれている。2. Description of the Related Art A method for obtaining a polyester resin using R-PET is known. Generally, glycol and R-PET are simultaneously charged, and R-PET is glycol-decomposed at the boiling point of glycol to obtain a low-molecular-weight product. Then, a desired amount of an α-β unsaturated polybasic acid (or an acid anhydride thereof) is added to carry out polycondensation.
【0003】然し、この方法の欠点は、グリコールの沸
点以上に温度を高めることができないため、解重合に時
間を要することである。[0003] However, a disadvantage of this method is that depolymerization takes time because the temperature cannot be raised above the boiling point of glycol.
【0004】反応時間が長引けば、結果としてR−PETの
低コストを生かすことができなくなる。If the reaction time is prolonged, the low cost of R-PET cannot be utilized as a result.
【0005】解重合の時間を短縮するために、R−PETを
熔融させておき、その中にグリコールを滴下する方法も
提案されている(特開平8−151438、特開2000−777
0)。[0005] In order to shorten the time for depolymerization, a method has been proposed in which R-PET is melted and glycol is dropped therein (JP-A-8-151438, JP-A-2000-777).
0).
【0006】[0006]
【発明が解決しようとする課題】特に特開2000−7770に
開示されているように、R−PET中に予め錫の有機化合物
を必要量加えておくと、熔融状態でのPETの分解が非常
に速やかとなり、時間短縮に有効であることが判明し
た。In particular, as disclosed in Japanese Patent Application Laid-Open No. 2000-7770, when an organic compound of tin is added in advance to an R-PET, decomposition of the PET in a molten state becomes extremely difficult. It turned out to be quick and effective in reducing time.
【0007】残された問題点は、反応容器に仕込んだR
−PETの熔融に時間を要することである。即ち、R−PET
はフレーク状かペレット状で市販されているが、その嵩
高さのため重量の割に容積が大で、含まれる空気の量が
多く、これが断熱的な働きをしてR−PETの熔融を妨げる
ことである。The remaining problem is that the R
-It takes time to melt PET. That is, R-PET
Is commercially available in the form of flakes or pellets, but because of its bulkiness, it has a large volume for its weight and contains a large amount of air, which acts as an adiabatic material and hinders the melting of R-PET. That is.
【0008】[0008]
【課題を解決するための手段】本発明者らは、この欠点
を解消してR−PETを原料とするポリエステル樹脂を極力
短時間内に合成する方法について検討を重ねた結果、ニ
ーダー或はエクストルダーといった熔融混練可能な装置
を用い、熔融したR−PETを直ちに反応容器中に仕込み
(この時、反応容器はPETの熔融温度以上に加温してお
くことが望ましい)、グリコールを加えて分解反応を行
わせることによって、R−PETの熔融に要する時間を著し
く短縮することができることを見出した。The present inventors have studied a method of synthesizing a polyester resin using R-PET as a raw material within a short time as a result of solving the above drawbacks. Using a device capable of melt-kneading, such as a rudder, immediately put the molten R-PET into a reaction vessel (at this time, it is desirable that the reaction vessel is heated to a temperature higher than the melting temperature of PET), and add glycol to decompose. By conducting the reaction, it has been found that the time required for melting R-PET can be significantly reduced.
【0009】[0009]
【発明の実施の形態】即ち、フレーク状R−PETを反応容
器に仕込み、加熱熔融させるのに120分を要した場合、
所望の吐出量を有するコニーダーでR−PETを混練熔融さ
せ、反応容器内にそのまま仕込むケースでは10〜20分程
度の時間を必要とするのみで、大幅な時間短縮を実現す
ることができる。BEST MODE FOR CARRYING OUT THE INVENTION That is, when it took 120 minutes to charge flake-shaped R-PET into a reaction vessel and heat and melt it,
In a case where R-PET is kneaded and melted by a co-kneader having a desired discharge amount and charged in a reaction vessel as it is, only a time of about 10 to 20 minutes is required, and a drastic time reduction can be realized.
【0010】本発明に使用されるR−PETは、主としてP
ETボトルよりのリサイクル品で、フレーク状乃至ペレッ
ト状を呈している。The R-PET used in the present invention is mainly composed of P
It is a recycled product from ET bottles and is in the form of flakes or pellets.
【0011】またR−PETは混練機を加熱されながら通
過する際に含有水分は蒸発して系外に排出されるので、
乾燥する必要はない。When R-PET passes through the kneader while being heated, the water content evaporates and is discharged out of the system.
No need to dry.
【0012】却って、0.5〜10重量(%)程度の水分を
含んでいる場合には、R−PETが混練機を加熱されなが
ら通過する際に、その水分がR−PETの分解に寄与するの
で、水分の存在は望ましいことである。On the contrary, when the water contains about 0.5 to 10% by weight (%) of water, the water contributes to the decomposition of R-PET when the R-PET passes through the kneader while being heated. The presence of moisture is desirable.
【0013】R−PETの熔融混練で熔融状態で吐出させる
ための混練機は、通常の一軸乃至二軸のエクストルーダ
ー、コニーダーが良く、その種類を特定する必要はな
い。A kneader for discharging in a molten state by melt kneading of R-PET is usually a single-shaft or two-shaft extruder or a co-kneader, and it is not necessary to specify the type.
【0014】本発明は、R−PETを熔融し反応容器に仕込
んだ後、所望のグリコールを加え、R−PETを分解するこ
と並びに分解後αーβ不飽和多塩基酸又はその酸無水物
の一種又は二種以上を加えて重縮合を行わせることによ
りポリエステル樹脂とすることである。According to the present invention, after R-PET is melted and charged into a reaction vessel, a desired glycol is added to decompose R-PET, and after decomposition, α-β unsaturated polybasic acid or an acid anhydride thereof is produced. A polyester resin is obtained by performing polycondensation by adding one or more kinds.
【0015】このために用いられるグリコールは、例え
ば次の種類が挙げられる、エチレングリコール、ジエチ
レングリコール、プロピレングリコール、ジプロピレン
グリコール、ネオペンチルグリコール、2−メチルプロ
パンジオール1,3、1,3ブタンジオール、1,4ブタ
ンジオール、3−メチルペンタンジオール1,5、1,2
ブタンジオール、水素化ビスフェノールA、ビスフェノ
ールAエチレンオキシド付加物、ビスフェノールAプロピ
レンキシド付加物、勿論相互の併用もでき、また3官能
以上の多価アルコールを必要に応じて併用することも可
能である。The glycols used for this purpose include, for example, the following types: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 2-methylpropanediol 1,3,1,3 butanediol, 1,4 butanediol, 3-methylpentanediol 1,5,1,2
Butanediol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, of course, can be used in combination with each other, and a trifunctional or higher functional polyhydric alcohol can be used in combination, if necessary.
【0016】グリコール分解の際は分解反応を促進する
ために錫の有機化合物(例えばジブチル錫ジオキシド、
オクチル酸錫)、或はチタンの有機化合物(テトライソ
ポロポキシチタンの例)を、R−PETの仕込量100重量部
に対して0.01重量部以上1重量部以下、より望ましくは
0.05重量部以上0.5重量部以下、を併用させることが好
ましい。At the time of glycol decomposition, an organic compound of tin (for example, dibutyltin dioxide,
Tin octylate) or an organic compound of titanium (example of tetraisopoloxytitanium) in an amount of 0.01 to 1 part by weight, more preferably 100 parts by weight of R-PET, more preferably
It is preferable to use 0.05 to 0.5 parts by weight in combination.
【0017】熔融R−PETにこれらの分解触媒を加える
と、PETのグリコール分解が著しく促進される。When these decomposition catalysts are added to molten R-PET, the glycol decomposition of PET is remarkably promoted.
【0018】ポリエステル樹脂化するためのα−β不飽
和多塩基酸(又はその酸無水物)は、一般に無水マレイ
ン酸、フマル酸が用いられており、本発明には十分であ
る。As the α-β unsaturated polybasic acid (or an acid anhydride thereof) for converting into a polyester resin, maleic anhydride or fumaric acid is generally used, which is sufficient for the present invention.
【0019】他の飽和或は不飽和の多塩基酸(又はその
酸無水物)の併用は自由である。The use of other saturated or unsaturated polybasic acids (or their anhydrides) is free.
【0020】α−β不飽和酸又はその酸無水物の一種又
は二種以上を加え重縮合を完了した後は、所望のモノマ
ーに溶解してポリエステル樹脂が得られる。After the addition of one or two or more α-β unsaturated acids or acid anhydrides to complete the polycondensation, the polyester is dissolved in a desired monomer to obtain a polyester resin.
【0021】モノマーは一般にはスチレンであるが、そ
の他にはメタクリル酸メチル、ジアリルフタレート、な
ども用途によっては使用することができる。The monomer is generally styrene, but in addition, methyl methacrylate, diallyl phthalate and the like can be used depending on the application.
【0022】R−PET、グリコール、不飽和酸の使用割合
は、用途によって変更するが、ほぼR−PET10〜80モル
(%)、グリコール20〜90モル(%)、不飽和酸10〜80
モル(%)である。The proportions of R-PET, glycol and unsaturated acid vary depending on the application, but are generally about 10 to 80 mol (%) of R-PET, 20 to 90 mol (%) of glycol, and 10 to 80 mol of unsaturated acid.
Mole (%).
【0023】PETのモル数は下式の構造を1モルとして
計算する。The number of moles of PET is calculated based on the following structure as 1 mole.
【化1】 Embedded image
【0024】本発明により得られたポリエステル樹脂は
各種用途に有用であるが、実用化に応じて各種の添加
剤、例えば熱可塑性のポリマー乃至オリゴマー、着色
剤、離型剤、安定剤等を使用することができることは勿
論である。The polyester resin obtained by the present invention is useful for various applications, but various additives such as thermoplastic polymers or oligomers, coloring agents, release agents, stabilizers and the like are used according to practical use. Of course you can.
【0025】[0025]
【実施例】次に本発明の理解を助けるために、以下に実
施例を示す。 実施例1 熔融混練のためのエクストルーダーは、栗本鉄工(株)
S−1ニーダーを用いた。攪拌機、還溜コンデンサー、滴
下ロート、ガス導入管付温度計を付した1Lセパラブル
フラスコを、マントルヒーター内で270℃に余熱しなが
ら、上記エクストルーダーを用いて含水率2.1重量
(%)のフレーク状PETを熔融させ、約15分でフラスコ
内に400g(2.00モル)供給した。EXAMPLES Next, examples will be shown below to facilitate understanding of the present invention. Example 1 An extruder for melting and kneading was manufactured by Kurimoto Tekko Co., Ltd.
An S-1 kneader was used. A 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer equipped with a gas inlet tube is preheated to 270 ° C in a mantle heater, and flakes having a water content of 2.1% by weight are obtained using the extruder. The PET was melted, and 400 g (2.00 mol) was supplied into the flask in about 15 minutes.
【0026】ジブチル錫ジオキシド0.8gを加え、15分2
70℃で攪拌した後、プロピレングリコール170gを10分
掛けて滴下した。0.8 g of dibutyltin dioxide was added, and 15 minutes
After stirring at 70 ° C., 170 g of propylene glycol was added dropwise over 10 minutes.
【0027】この間温度は210℃付近まで低下したが、R
−PETの固化析出は見られなかった。During this time, the temperature dropped to around 210 ° C.
-No solidification precipitation of PET was observed.
【0028】210〜220℃で3時間グリコール分解を行う
と、数平均分子量はほぼ600 位まで低下したので、温度
を180℃に下げ、無水マレイン酸196gを加えた。When the glycol was decomposed at 210-220 ° C. for 3 hours, the number average molecular weight was reduced to about 600. Therefore, the temperature was lowered to 180 ° C., and 196 g of maleic anhydride was added.
【0029】温度200〜205℃、窒素気流中で3時間重縮
合を行った後、ほぼ30Trrの減圧下更に1時間反応を行っ
た。After performing polycondensation in a nitrogen stream at a temperature of 200 to 205 ° C. for 3 hours, the reaction was further carried out under a reduced pressure of approximately 30 Trr for 1 hour.
【0030】酸価21.9の段階で温度を180℃に下げ、ハ
イドロキノン0.24g加え、更に温度160℃でスチレン510
gを2つに分け、第1回目としてほぼ300gを加え溶解し
た。生成ポリエステル樹脂を2Lポリエチレン容器に移
し、残りのスチレンを加え、振盪して均一溶液とした。At an acid value of 21.9, the temperature was lowered to 180 ° C., and 0.24 g of hydroquinone was added.
g was divided into two, and approximately 300 g was added and dissolved as the first time. The resulting polyester resin was transferred to a 2 L polyethylene container, the remaining styrene was added, and the mixture was shaken to obtain a uniform solution.
【0031】最終的に得られたポリエステル樹脂(A)
は、僅かに濁りを帯びた淡黄褐色で、ハーゼン色数30
0、粘度9.1ポイズであった。The finally obtained polyester resin (A)
Is a slightly turbid, light yellow-brown color with a Hazen color number of 30
0, viscosity 9.1 poise.
【0032】比較例 エクストルーダーを用いずにフラスコ内に直接フレーク
状PETを実施例1と同量仕込んだ場合、マントルヒーター
の加熱温度270℃では、R−PETの完全熔融にほぼ110分を
要した。COMPARATIVE EXAMPLE In a case where the same amount of flake PET as in Example 1 was directly charged into the flask without using an extruder, it took about 110 minutes for R-PET to completely melt at a heating temperature of a mantle heater of 270 ° C. did.
【0033】その後の操作は実施例1と同様であった。
得られたポリエステル(B)は僅かに濁りを帯びた黄褐色
で、ハーゼン色数450、粘度7.9ポイズであった。The subsequent operation was the same as in Example 1.
The obtained polyester (B) was slightly turbid yellow-brown, had a Hazen color number of 450 and a viscosity of 7.9 poise.
【0034】実施例2 実施例1と同様の装置に、含水率1.2重量(%)のPETボ
トルよりリサイクルされたフレーク状R−PETを、同様の
エクストルーダーにより約10分掛けて予想されたフラス
コに290g仕込んだ。Example 2 In the same apparatus as in Example 1, flaky R-PET recycled from a PET bottle having a water content of 1.2 wt. 290g.
【0035】次いでテトライソプロポキシチタン0.4gを
加え、265〜267℃で20分攪拌した後、ネオペンチルグリ
コール115gを3回に分けほぼ10分間に投入した。グリコ
ール投入による熔融PETの凝固は起こらなかった。Next, 0.4 g of tetraisopropoxytitanium was added, and the mixture was stirred at 265 to 267 ° C. for 20 minutes, and then 115 g of neopentyl glycol was added in three portions for almost 10 minutes. No solidification of the molten PET by glycol injection occurred.
【0036】エクストルーダー中をR−PETが通過して熔
融する時間はほぼ3分であったが、この間分子量は数平
均で当初23000であったものが10900に低下した。The time required for the R-PET to pass through the extruder and melt was approximately 3 minutes. During this time, the molecular weight was initially 23,000 in number average, but dropped to 10900.
【0037】220〜230℃で3時間グリコール分解を行っ
た後の数平均分子量は700に低下し、完全に透明であっ
た。The number average molecular weight after glycol decomposition at 220 to 230 ° C. for 3 hours was reduced to 700, and it was completely transparent.
【0038】温度を180℃に下げ、無水マレイン酸98gを
加え、窒素気流下200〜205℃で3時間重縮合を行った
後、20〜25Torrの減圧下40分縮合を進めた。The temperature was lowered to 180 ° C., 98 g of maleic anhydride was added, polycondensation was carried out at 200 to 205 ° C. for 3 hours in a nitrogen stream, and then condensation was carried out for 40 minutes under a reduced pressure of 20 to 25 Torr.
【0039】酸価19.9の段階で加熱、減圧を中止し、温
度180℃でハイドロキノン0.15g投入して空気気流に切
替え、更に160℃でスチレン325gを加え、溶解してポリ
エステル樹脂(C)が得られた。At an acid value of 19.9, heating and depressurization were stopped, 0.15 g of hydroquinone was introduced at a temperature of 180 ° C., the air flow was switched, and 325 g of styrene was added at 160 ° C. and dissolved to obtain a polyester resin (C). Was done.
【0040】成分は濁りを帯びた淡褐色でハーゼン色数
250、粘度14.4ポイズであった。The components are turbid, light brown and have a Hazen color number.
250, viscosity 14.4 poise.
【0041】[0041]
【発明の効果】以上要するに、この発明によれば極めて
短時間の内にR−PETを反応容器内に熔融混合することが
できるため、ポリエステル樹脂の合成時間を短縮するこ
とができる。In summary, according to the present invention, R-PET can be melt-mixed in a reaction vessel within a very short time, so that the polyester resin synthesis time can be shortened.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 玉田 亮三 兵庫県尼崎市大浜町2丁目26番地 株式会 社クボタ武庫川製造所内 (72)発明者 井口 康宏 兵庫県尼崎市大浜町2丁目26番地 株式会 社クボタ武庫川製造所内 Fターム(参考) 4J029 AA07 AB04 AD06 BA02 BA03 BA04 BA07 BA08 BA09 BA10 BD10 BF09 BF10 GA11 GA13 GA14 HB02 HB06 JE162 JE182 JF321 JF371 KA02 KB11 KB21 KG01 KG02 KG03 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryozo Tamada 2-26-26 Ohama-cho, Amagasaki-shi, Hyogo Pref. F-term in Kubota Mukogawa Works (reference) 4J029 AA07 AB04 AD06 BA02 BA03 BA04 BA07 BA08 BA09 BA10 BD10 BF09 BF10 GA11 GA13 GA14 HB02 HB06 JE162 JE182 JF321 JF371 KA02 KB11 KB21 KG01 KG02 KG03
Claims (1)
トを、その融点以上の温度で混練機にて熔融混練した上
で反応容器に仕込み、必要量のグリコールを加えてポリ
エチレン−テレフタレートを分解し、更にα− β不飽
和多塩基酸又はその酸無水物の一種又は二種以上を加え
て重縮合を行うことを特徴とするリサイクルされたポリ
エチレン−テレフタレートを用いた不飽和ポリエステル
樹脂の合成方法。1. The recovered polyethylene-terephthalate is melt-kneaded at a temperature not lower than its melting point in a kneader and then charged into a reaction vessel. A required amount of glycol is added to decompose the polyethylene-terephthalate. A method for synthesizing an unsaturated polyester resin using recycled polyethylene-terephthalate, wherein polycondensation is performed by adding one or more kinds of β-unsaturated polybasic acids or acid anhydrides thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2000306218A JP3488880B2 (en) | 2000-10-05 | 2000-10-05 | Method for synthesizing unsaturated polyester resin using recycled polyethylene-terephthalate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000306218A JP3488880B2 (en) | 2000-10-05 | 2000-10-05 | Method for synthesizing unsaturated polyester resin using recycled polyethylene-terephthalate |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002114839A true JP2002114839A (en) | 2002-04-16 |
JP3488880B2 JP3488880B2 (en) | 2004-01-19 |
Family
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7897651B2 (en) * | 2005-12-09 | 2011-03-01 | Kazutoshi Ikenaga | Method for depolymerizing polyester and unsaturated polyester, and method for recovering polyester monomer using the depolymerization |
-
2000
- 2000-10-05 JP JP2000306218A patent/JP3488880B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7897651B2 (en) * | 2005-12-09 | 2011-03-01 | Kazutoshi Ikenaga | Method for depolymerizing polyester and unsaturated polyester, and method for recovering polyester monomer using the depolymerization |
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