JPH11158259A - Process for solid state polymerization of polyester - Google Patents
Process for solid state polymerization of polyesterInfo
- Publication number
- JPH11158259A JPH11158259A JP33041397A JP33041397A JPH11158259A JP H11158259 A JPH11158259 A JP H11158259A JP 33041397 A JP33041397 A JP 33041397A JP 33041397 A JP33041397 A JP 33041397A JP H11158259 A JPH11158259 A JP H11158259A
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- JP
- Japan
- Prior art keywords
- chips
- polymerization
- polyester
- chip
- solid
- 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.)
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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエステルチッ
プの固相重合方法に関するものである。更に詳しくは、
固相重合時のチップ融着がなく、生産性の良好な固相重
合方法に関するものである。TECHNICAL FIELD The present invention relates to a method for solid-state polymerization of polyester chips. More specifically,
The present invention relates to a solid-state polymerization method that does not cause chip fusion during solid-state polymerization and has good productivity.
【０００２】[0002]
【従来の技術】ポリエステルの固相重合は、通常回分式
または連続式の装置で減圧または不活性ガス流通下にお
いて、高温でおこなわれることが知られている。この内
竪型の装置の場合には、攪拌によって発生するチップの
削れ粉を、装置の下方から上方へ不活性ガスの気流にの
せて除去できるというメリットを有し、多くの公知例
（特開昭６３−１９１８２３、特開平４−２１４７３
３、特開 平５−３４５３２０）があり、実用化されて
いる。2. Description of the Related Art It is known that solid phase polymerization of polyester is usually carried out in a batch or continuous apparatus at a high temperature under reduced pressure or under a flow of an inert gas. In the case of this inner vertical type apparatus, there is an advantage that chip shavings generated by agitation can be removed by applying an inert gas stream from below to above the apparatus, and many known examples (Japanese Patent Application Laid-Open 63-191823, JP-A-4-21473
3, JP-A-5-345320), which has been put to practical use.
【０００３】しかしながら竪型の固相重合装置の場合に
は、チップの自重による融着が起こるという固有の問題
を有している。特に近年共重合ポリエステルが多用化さ
れているが、共重合ポリエステルは融点が低いため一層
融着しやすく、生産性低下に大きく影響している。However, in the case of a vertical solid-state polymerization apparatus, there is an inherent problem that the chips are fused by their own weight. Particularly, in recent years, copolyesters have been widely used, but the copolyester has a low melting point, so that it is more easily fused, which greatly affects the reduction in productivity.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、特に
前述した従来公知の竪型固相重合方法の欠点を排除し、
融点の低いポリエステルチップであっても、融着させず
に固相重合することにより、生産性の高いチップを提供
することである。SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks of the known vertical solid-state polymerization method.
An object of the present invention is to provide a highly productive chip by solid-phase polymerization without melting even a polyester chip having a low melting point.
【０００５】[0005]
【課題を解決するための手段】前記課題は、ポリエステ
ルチップを固相重合する際、固相重合装置内のチップ充
填体積を、静置時の１．０３〜１．１８倍とすることを
特徴とするポリエステルの固相重合方法によって達成で
きる。An object of the present invention is to provide a solid-phase polymerization of a polyester chip, wherein the chip filling volume in the solid-state polymerization apparatus is set to be 1.03 to 1.18 times the stationary state. Can be achieved by a solid-phase polymerization method for polyester.
【０００６】[0006]
【発明の実施の形態】本発明のポリエステルチップは、
芳香族ジカルボン酸成分とグリコール成分から成るポリ
エステル、及び該ポリエステルを主として構成する芳香
族ジカルボン酸成分、あるいはグリコール成分以外のジ
カルボン酸成分及び／またはグリコール成分を２５重量
％以下共重合したポリエステルを言う。芳香族ジカルボ
ン酸成分及び／またはグリコール成分からなるポリエス
テルとしては、従来公知の、例えばポリエチレンテレフ
タレート、ポリブチレンテレフタレート、ポリエチレン
ナフタレート等を挙げることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyester chip of the present invention
A polyester composed of an aromatic dicarboxylic acid component and a glycol component, and an aromatic dicarboxylic acid component mainly constituting the polyester, or a polyester obtained by copolymerizing a dicarboxylic acid component and / or a glycol component other than the glycol component in an amount of 25% by weight or less. Examples of the polyester comprising an aromatic dicarboxylic acid component and / or a glycol component include conventionally known, for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
【０００７】前記したポリエステルに共重合するジカル
ボン酸成分及び／またはグリコール成分としては、例え
ばテレフタル酸、イソフタル酸、ナフタレンジカルボン
酸等の芳香族ジカルボン酸、アジピン酸、セバシン酸、
ダイマー酸、マレイン酸等の脂肪族ジカルボン酸等を挙
げることができる。Examples of the dicarboxylic acid component and / or glycol component copolymerized with the polyester include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, adipic acid, sebacic acid, and the like.
Examples thereof include aliphatic dicarboxylic acids such as dimer acid and maleic acid.
【０００８】グリコール成分としては、例えばエチレン
グリコール、プロパンジオール、ブタンジオール、ヘキ
サンジオール等の脂肪族グリコール、ビスフェノール
Ａ、ビスフェノールＳ等の芳香族グリコール、シクロヘ
キサンジメタノール等の脂環族グリコール等を挙げるこ
とができる。Examples of the glycol component include aliphatic glycols such as ethylene glycol, propanediol, butanediol and hexanediol, aromatic glycols such as bisphenol A and bisphenol S, and alicyclic glycols such as cyclohexanedimethanol. Can be.
【０００９】次に本発明で好適に用いることのできる竪
型固相重合装置について、図１で詳細に説明する。本装
置は竪型円筒と下部が逆円錐形状の組み合わせからなる
固相重合塔１に、原料ポリエステルチップ投入口２、お
よび不活性ガス供給口６排気口３、固相重合終了チップ
の排出口７が設けられている。装置内部の攪拌部は水平
方向の翼５を複数本有する攪拌軸４で構成されている。
固相重合に際しては、まず不活性ガスを連続的に供給
し、更に攪拌軸４を回転させこの状態で、チップ投入口
２より原料ポリエステルチップを定量投入する。投入終
了後不活性ガス供給口６から供給される不活性ガスの温
度を、徐々に所定の温度まで上げていき、所定の温度に
到達後、ポリエステルチップが所定の重合度に到達する
まで最終温度で加熱を続ける。所定の重合度に到達後、
直ちに供給する不活性ガスを冷却風に切り替え、ポリエ
ステルチップを規定の温度まで冷却する。固相重合後の
ポリエステルチップはチップ排出口７より全量排出す
る。不活性ガスは入手のしやすさ、コストの点で窒素ガ
スが好ましい。Next, a vertical solid-state polymerization apparatus that can be suitably used in the present invention will be described in detail with reference to FIG. In this apparatus, a raw material polyester chip inlet 2, an inert gas supply port 6, an exhaust port 3, and a solid state polymerization finished chip outlet 7 are provided in a solid-state polymerization tower 1 having a combination of a vertical cylinder and a lower part having an inverted conical shape. Is provided. The stirring section inside the apparatus is constituted by a stirring shaft 4 having a plurality of horizontal blades 5.
At the time of solid-phase polymerization, first, an inert gas is continuously supplied, and the stirring shaft 4 is further rotated. In this state, a fixed amount of raw material polyester chips is introduced from the chip inlet 2. After completion of the charging, the temperature of the inert gas supplied from the inert gas supply port 6 is gradually increased to a predetermined temperature, and after reaching the predetermined temperature, the final temperature is maintained until the polyester chip reaches a predetermined degree of polymerization. Continue heating with. After reaching the specified degree of polymerization,
The supplied inert gas is immediately switched to cooling air, and the polyester chip is cooled to a specified temperature. After the solid-phase polymerization, all the polyester chips are discharged from the chip outlet 7. The inert gas is preferably a nitrogen gas from the viewpoint of availability and cost.
【００１０】次に本発明の固相重合装置内部におけるチ
ップの充填体積は、固相重合塔１の下部におけるチップ
の自重による融着を防ぐため、浮かせた状態にすること
で結晶化時の融着を防ぐことができる。具体的には不活
性ガスを流通した状態で、所定量のポリエステルチップ
をチップ投入口２より投入した後、不活性ガスの供給流
量を制御してチップを浮かせた状態にする。その際、チ
ップの充填体積は静置時の１．０３〜１．１３倍がよ
い。好ましくは１．０５〜１．１５倍、更に好ましくは
１．０７〜１．１８倍がよい。１．０３倍未満であると
固相重合塔下部でチップの自重による融着が発生する。
一方、１．１８倍を越えるとチップの飛散が激しくなり
生産量が低下するので好ましくない。Next, the filling volume of the chips in the solid-state polymerization apparatus of the present invention is set to a floating state in order to prevent the chips from being fused by their own weight in the lower part of the solid-state polymerization tower 1, so that the melting during crystallization is performed. Wear can be prevented. Specifically, after a predetermined amount of polyester chips are charged through the chip inlet 2 with the inert gas flowing, the supply flow rate of the inert gas is controlled so that the chips are floated. At this time, the filling volume of the chip is preferably 1.03 to 1.13 times that at the time of standing. Preferably it is 1.05 to 1.15 times, more preferably 1.07 to 1.18 times. If the ratio is less than 1.03 times, fusion of the chips due to their own weight occurs at the bottom of the solid-state polymerization tower.
On the other hand, when the ratio exceeds 1.18 times, the scattering of chips becomes severe and the production amount is reduced, which is not preferable.
【００１１】チップを均一に浮かせるためには、不活性
ガスの供給方向、供給速度を均一にすることが望まし
く、例えばチップサイズよりも小さな穴を多数設けたプ
レート等を介して供給することがよい。In order to make the chips float uniformly, it is desirable to make the supply direction and the supply speed of the inert gas uniform, and for example, it is preferable to supply the inert gas through a plate having many holes smaller than the chip size. .
【００１２】次に、不活性ガスの塔内流速は、０．４〜
１．０ｍ／ｓの範囲とすることが好ましい。この際チッ
プの飛散をおさえるために、チップ飛散防止板を取り付
けることは構わない。またその形状については特に問わ
ないがたとえばチップサイズよりも小さな目の金網を不
活性ガス排気口に設置する等の方法がある。Next, the flow rate of the inert gas in the tower is from 0.4 to 0.4.
It is preferable to be in the range of 1.0 m / s. At this time, a chip scattering prevention plate may be attached in order to suppress chip scattering. There is no particular limitation on the shape, but there is a method of, for example, installing a wire mesh smaller than the chip size in the inert gas exhaust port.
【００１３】ポリエステルチップの加熱昇温速度も融着
防止に効果的である。本発明においては、Ｔｇ−５℃〜
Ｔｇ＋１５℃の範囲を０．３℃／分以下の速度で加熱昇
温することで目的を一層達成できる。好ましくは０．２
℃／分以下である。０．３℃／分以上を越えると、特に
共重合ポリエステルチップの場合は融着が発生しやす
い。The heating and heating rate of the polyester chip is also effective in preventing fusion. In the present invention, Tg−5 ° C.
The object can be further achieved by heating and raising the temperature in the range of Tg + 15 ° C. at a rate of 0.3 ° C./min or less. Preferably 0.2
° C / min or less. If it exceeds 0.3 ° C./min or more, fusion tends to occur particularly in the case of a copolyester chip.
【００１４】[0014]
【実施例】以下実施例を挙げて本発明をさらに具体的に
説明する。なお、実施例中で用いた物性は次の方法によ
り求めた。The present invention will be described more specifically with reference to the following examples. The physical properties used in the examples were determined by the following methods.
【００１５】（１）ガラス転移温度（Ｔｇ） 示差走査熱量計（パーキン・エルマー社製ＤＳＣ−２
型）により、１０℃／分の昇温速度で測定した。(1) Glass transition temperature (Tg) Differential scanning calorimeter (DSC-2 manufactured by Perkin Elmer)
(Type) at a heating rate of 10 ° C./min.
【００１６】（２）固有粘度 ポリエステルチップをオルソクロロフェノールに溶解
し、２５℃において測定した。(2) Intrinsic viscosity A polyester chip was dissolved in orthochlorophenol and measured at 25 ° C.
【００１７】（３）竪型固相重合装置内部でのチップ充
填体積 不活性ガスを流していない状態でのチップ粒面に対し
て、不活性ガスを流した際のチップ粒面から体積を計算
する。(3) Chip filling volume inside the vertical solid-state polymerization apparatus The volume is calculated from the chip particle surface when the inert gas is flown, with respect to the chip particle surface when the inert gas is not flowing. I do.
【００１８】（４）チップの融着 固相重合終了後、乾燥装置から排出する途中に格子（目
開き６ｍｍ）を設置し、それに捕捉された２連以上のチ
ップ個数で融着程度を判断する。(4) Chip fusion After the solid-phase polymerization is completed, a grid (aperture: 6 mm) is set in the middle of discharging from the drying device, and the degree of fusion is determined based on the number of two or more chips captured by the lattice. .
【００１９】実施例１ テレフタル酸９５モル％、イソフタル酸５モル％、固有
粘度０．６、Ｔｇ７５℃の共重合ポリエステルチップ１
００重量部を、窒素ガス雰囲気下で図１のような竪型固
相重合装置に投入した。投入終了後に窒素流量を０．４
ｍ／ｓに調節し、ポリエステルチップの充填体積が、静
置時の１．０３倍になるようにした。次にヒーターで窒
素ガスを加熱しポリエステルチップ温度が７０〜９０℃
の範囲を０．３℃／分の速度で昇温した。その後２１０
℃まで４時間かけて昇温しそのままの温度を保ち固相重
合をおこなった。所定の重合度に到達した後、冷却しチ
ップを払い出した。格子上に融着チップは２コ捕捉され
た。Example 1 Copolyester chip 1 having 95 mol% of terephthalic acid, 5 mol% of isophthalic acid, an intrinsic viscosity of 0.6 and a Tg of 75 ° C.
In a nitrogen gas atmosphere, 00 parts by weight was charged into a vertical solid-state polymerization apparatus as shown in FIG. After the end of charging, set the nitrogen flow rate to 0.4
m / s so that the filling volume of the polyester chip was 1.03 times that at the time of standing. Next, the nitrogen gas is heated by a heater, and the polyester chip temperature is 70 to 90 ° C.
Was raised at a rate of 0.3 ° C./min. Then 210
The temperature was raised to 4 ° C. over 4 hours, and the solid-state polymerization was performed while maintaining the temperature. After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. Two fused chips were captured on the grid.
【００２０】実施例２ 窒素流量を０．８ｍ／ｓ、チップの充填体積倍率を１．
１５倍、７０〜９０℃の範囲を０．２℃／分の速度で昇
温する以外は実施例１と同様に固相重合をおこなった。
格子上に融着チップは捕捉されなかった。Example 2 The nitrogen flow rate was 0.8 m / s, and the chip filling volume ratio was 1.
Solid phase polymerization was carried out in the same manner as in Example 1 except that the temperature was increased 15 times, in the range of 70 to 90 ° C at a rate of 0.2 ° C / min.
No fused tip was captured on the grid.
【００２１】実施例３ 窒素流量を１．０ｍ／ｓ、チップの充填体積倍率を１．
１８倍、７０〜９０℃の範囲を０．３℃／分の速度で昇
温する以外は実施例１と同様に固相重合をおこなった。
格子上に融着チップは捕捉されなかった。Example 3 The flow rate of nitrogen was 1.0 m / s, and the filling volume ratio of the chip was 1.
Solid-state polymerization was carried out in the same manner as in Example 1 except that the temperature was increased by 18 times from 70 to 90 ° C at a rate of 0.3 ° C / min.
No fused tip was captured on the grid.
【００２２】実施例４ テレフタル酸７５モル％、イソフタル酸２５モル％、固
有粘度０．６、Ｔｇ７０℃の共重合ポリエステルチップ
１００重量部を、窒素ガス雰囲気下の竪型固相重合装置
に投入した。投入終了後に窒素流量を０．４ｍ／ｓに調
節し、ポリエステルチップの充填体積が、静置時の１．
０３倍になるようにした。次に、ヒーターで窒素ガスを
加熱し、ポリエステルチップ温度が６５〜８５℃の範囲
を０．３℃／分の速度で昇温した。その後１８０℃まで
４時間をかけて昇温し、そのままの温度を保ち固相重合
をおこなった。所定の重合度に到達した後、冷却しチッ
プを払い出した。格子上には４コの融着チップが捕捉さ
れた。Example 4 100 parts by weight of a copolyester chip having 75 mol% of terephthalic acid, 25 mol% of isophthalic acid, an intrinsic viscosity of 0.6 and a Tg of 70 ° C. were put into a vertical solid-state polymerization apparatus under a nitrogen gas atmosphere. . After completion of the charging, the nitrogen flow rate was adjusted to 0.4 m / s, and the filling volume of the polyester chip was 1.
03 times. Next, the nitrogen gas was heated by a heater, and the temperature of the polyester chip was raised in the range of 65 to 85 ° C at a rate of 0.3 ° C / min. Thereafter, the temperature was raised to 180 ° C. over 4 hours, and the temperature was kept as it was to carry out solid phase polymerization. After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. Four fused chips were captured on the grid.
【００２３】実施例５ 窒素流量を０．８ｍ／ｓ、チップの充填体積倍率を１．
１５、チップの昇温速度を０．２℃／分とする以外は実
施例４と同様に固相重合をおこなった。格子上に捕捉さ
れ融着チップは２コであった。Example 5 The nitrogen flow rate was 0.8 m / s, and the chip filling volume ratio was 1.
15. Solid-state polymerization was carried out in the same manner as in Example 4 except that the temperature rising rate of the chip was set at 0.2 ° C./min. There were two fused chips captured on the grid.
【００２４】実施例６ 窒素流量を１．０ｍ／ｓ、チップの充填体積を１．１８
とする以外は、実施例４と同様に固相重合をおこなっ
た。格子上に融着チップは捕捉され なかった。Example 6 The nitrogen flow rate was 1.0 m / s and the chip filling volume was 1.18.
Solid state polymerization was carried out in the same manner as in Example 4 except that No fused tip was captured on the grid.
【００２５】比較例１ 実施例１において窒素流量を０．３ｍ／ｓ、ポリエステ
ルチップの充填体積が、静置時の１．０２倍になるよう
にした以外は同じ方法で固相重合をおこなった。所定の
重合度に到達した後、冷却しチップを払い出した。格子
上には融着チップが８コ捕捉された。Comparative Example 1 Solid-state polymerization was carried out in the same manner as in Example 1 except that the nitrogen flow rate was 0.3 m / s, and the filling volume of the polyester chips was 1.02 times that at the time of standing. . After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. Eight fusion chips were captured on the grid.
【００２６】比較例２ 実施例１において窒素流量を０．２ｍ／ｓ、ポリエステ
ルチップ充填体積が、静置時の１．０１倍になるように
し、７０〜９０℃の範囲の昇温速度を０．４℃／分とす
る以外は同じ方法で固相重合をおこなった。所定の重合
度に到達した後、冷却しチップを払い出した。格子上に
は融着チップが１２コ捕捉されていた。Comparative Example 2 In Example 1, the nitrogen flow rate was set to 0.2 m / s, the filling volume of the polyester chip was set to be 1.01 times that at the time of standing, and the heating rate in the range of 70 to 90 ° C. was set to 0. Solid phase polymerization was carried out in the same manner except that the temperature was changed to 4 ° C./min. After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. Twelve fused chips were captured on the lattice.
【００２７】比較例３ 実施例４において窒素流量を０．３ｍ／ｓ、ポリエステ
ルチップ充填体積が、静置時の１．０２倍、６５〜８５
℃の範囲の昇温速度を０．３℃／分とする以外は同じ方
法で固相重合をおこなった。所定の重合度に到達した
後、冷却しチップを払い出した。格子上には融着チップ
が３０コ捕捉された。Comparative Example 3 In Example 4, the nitrogen flow rate was 0.3 m / s, and the filling volume of the polyester chip was 1.02 times that of standing, 65 to 85 times.
Solid-state polymerization was carried out by the same method except that the rate of temperature rise in the range of ° C was 0.3 ° C / min. After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. 30 fusion chips were captured on the grid.
【００２８】比較例４ 実施例４において窒素流量を０．２ｍ／ｓ、ポリエステ
ルチップの充填体積が、静置時の１．０１倍、６５〜８
５℃の範囲の昇温速度を０．４℃／分とする以外は同じ
方法で固相重合をおこなった。所定の重合度に到達した
後、冷却しチップを払い出した。格子上には融着チップ
が４０コ捕捉された。Comparative Example 4 In Example 4, the nitrogen flow rate was 0.2 m / s, and the filling volume of the polyester chip was 1.01 times that of standing, 65 to 8 times.
Solid-state polymerization was carried out in the same manner except that the rate of temperature rise in the range of 5 ° C was 0.4 ° C / min. After reaching a predetermined degree of polymerization, the mixture was cooled and chips were discharged. Forty fusion chips were captured on the grid.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】本発明の固相重合方法は、竪型固相重合
装置内でチップの融着がなく、生産性を向上できる。特
に、融着しやすい共重合ポリエステルの場合有効であ
る。According to the solid phase polymerization method of the present invention, there is no fusion of chips in a vertical solid phase polymerization apparatus, and the productivity can be improved. In particular, it is effective in the case of a copolymer polyester which is easily fused.
【図１】本発明で好ましく用いることのできる、竪型固
相重合装置FIG. 1 is a vertical solid-state polymerization apparatus that can be preferably used in the present invention.
１：固相重合塔 ２：チップ投入口 ３：窒素ガス排気口 ４：攪拌軸 ５：攪拌翼 ６：窒素ガス供給口 ７：チップ排出口 1: solid-state polymerization tower 2: chip inlet 3: nitrogen gas outlet 4: stirring shaft 5: stirring blade 6: nitrogen gas inlet 7: chip outlet
Claims (2)
相重合装置内のチップ充填体積を、静置時の１．０３〜
１．１８倍とすることを特徴とするポリエステルの固相
重合方法。When a polyester chip is subjected to solid-state polymerization, a chip filling volume in a solid-state polymerization apparatus is set to 1.03 to 1.03 in a stationary state.
1. A solid-phase polymerization method for polyester, characterized in that the ratio is 1.18 times.
リエステルチップを予めＴｇ−５℃〜Ｔｇ＋１５℃の範
囲を０．３℃／分以下の速度で、昇温することを特徴と
する請求項１記載のポリエステルの固相重合方法。2. The method according to claim 1, wherein, when the polyester chip is subjected to solid-phase polymerization, the temperature of the polyester chip is previously raised in the range of Tg-5 ° C. to Tg + 15 ° C. at a rate of 0.3 ° C./min or less. A method for solid-state polymerization of the polyester as described above.
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| Application Number | Priority Date | Filing Date | Title |
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| JP33041397A JP3680523B2 (en) | 1997-12-01 | 1997-12-01 | Method for solid-phase polymerization of polyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33041397A JP3680523B2 (en) | 1997-12-01 | 1997-12-01 | Method for solid-phase polymerization of polyester |
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| JP3680523B2 JP3680523B2 (en) | 2005-08-10 |
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Cited By (3)
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|---|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005506918A (en) * | 2001-10-29 | 2005-03-10 | フェリンガー、マルクス | Method and apparatus for increasing the intrinsic viscosity of polyester |
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| JP2007177228A (en) * | 2005-12-02 | 2007-07-12 | Toray Ind Inc | Method for producing polyester composition |
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