JPS59217724A - Method for storing solution of catalyst for production of polyester - Google Patents
Method for storing solution of catalyst for production of polyesterInfo
- Publication number
- JPS59217724A JPS59217724A JP58093118A JP9311883A JPS59217724A JP S59217724 A JPS59217724 A JP S59217724A JP 58093118 A JP58093118 A JP 58093118A JP 9311883 A JP9311883 A JP 9311883A JP S59217724 A JPS59217724 A JP S59217724A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- solution
- catalyst
- glycol
- phosphoric acid
- 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
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は２色調、透明性及び熱安定性の優れたポリエス
テルを製造することのできるアンチモン化合物とリン化
合物とを含有した触媒溶液の貯留法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for storing a catalyst solution containing an antimony compound and a phosphorus compound that can produce a polyester having two colors, excellent transparency, and thermal stability.
ポリエステル、とりわけポリエチレンテレフタレートは
繊維又はフィルムとして非密に有用な重合体であり、そ
の製造法に関してはすでに多くの方法が知られている。Polyesters, particularly polyethylene terephthalate, are polymers that are useful in non-dense fibers or films, and many methods are already known for their production.
ポリエステルの製造には。For the production of polyester.
重縮合触媒を使用する必要があるが、アンチモン化合物
、特に三酸化アンチモンが優れた触媒活性を有するうえ
、安価であるという理由から最も広く用いられており、
同時に重縮合時に熱安定化剤としてリン化合物を併用す
る方法が広く用いられている。Although it is necessary to use a polycondensation catalyst, antimony compounds, especially antimony trioxide, are the most widely used because they have excellent catalytic activity and are inexpensive.
At the same time, a method in which a phosphorus compound is used as a thermal stabilizer during polycondensation is widely used.
しかるに９重縮合触媒としてアンチモン化合物を用い、
熱安定化剤としてリン化合物を併用した場合、前記リン
化合物とアンチモン化合物とが複雑に反応したりして不
溶性の微粒子を形成し、その結果、生成ポリエステルの
色調を悪くすることが知られている。However, using an antimony compound as a 9-polycondensation catalyst,
It is known that when a phosphorus compound is used in combination as a heat stabilizer, the phosphorus compound and antimony compound react in a complicated manner to form insoluble fine particles, resulting in poor color tone of the polyester produced. .
また、熱安定化剤として一般に用いられているリン酸の
アルキルエステルのようなリン化合物は重縮合反応時に
系外に飛散しやすく、多量に添加しなければならないと
いった問題があった。In addition, phosphorus compounds such as alkyl esters of phosphoric acid, which are commonly used as thermal stabilizers, tend to scatter out of the system during the polycondensation reaction and have to be added in large amounts.
この点について１本発明者らは種々検討の結果リン化合
物としてリン酸を用いれば１重縮合反応時にほとんど飛
散しないことを見出したが、単にリン酸をアンチモン化
合物と併用したのでは、リン酸のアルキルエステルなど
を用いた場合よりも透明性が一層悪化するという欠点が
あった。Regarding this point, the present inventors have conducted various studies and found that if phosphoric acid is used as the phosphorus compound, there will be almost no scattering during the single polycondensation reaction, but if phosphoric acid is simply used in combination with an antimony compound, There was a drawback that the transparency was worse than when using an alkyl ester or the like.
本発明者らはリン酸とアンチモン化合物とを併用してポ
リエステルを製造する際の前記欠点を解消するため種々
検討を行った結果、リン酸を予めグリコールの還流下で
処理し、処理液にアンチモン化合物を添加して得られた
触媒溶液を反応系に添加して重縮合することにより一挙
にこの問題が解決できることを見い出し、先に提案した
。The present inventors have conducted various studies in order to eliminate the above-mentioned drawbacks when producing polyester using a combination of phosphoric acid and an antimony compound, and as a result, they have found that phosphoric acid is treated in advance under refluxing glycol, and antimony is added to the treatment liquid. We found that this problem could be solved all at once by adding a catalyst solution obtained by adding the compound to the reaction system and polycondensing it, and proposed it earlier.
しかしながら、このようにしてｆｌ！ｉｔ！！！した触
媒溶液は、調製後、短時間の間に使用する場合には良好
な結果を示すが、常温下で長時間貯留しておくと、リン
酸のグリコール処理液とアンチモン化合物の間になんら
かの反応が起こり、系に不溶性の微粒子が生成したり、
触媒活性が失われるというトラブルが生しることが判明
した。However, in this way fl! It! ! ! This catalyst solution shows good results when used within a short period of time after preparation, but if it is stored for a long time at room temperature, some kind of reaction may occur between the glycol-treated phosphoric acid solution and the antimony compound. occurs, producing insoluble particles in the system,
It has been found that this causes a problem of loss of catalytic activity.
本発明は、かかる事情に鑑み、さらに鋭意研究を重ねた
結果、前記触媒溶液を保温貯留することにより不溶性の
粒子も生成せず、触媒の失活も起こらない事実を見い出
し１本発明を完成するに至った。In view of the above circumstances, the present invention has been made through intensive research, and the present invention has been completed by discovering the fact that insoluble particles are not generated and the catalyst is not deactivated by thermally storing the catalyst solution.1. reached.
すなわち９本発明は、リン酸のグリコール溶液をグリコ
ールを還流させながら加熱処理し、処理液にアンチモン
化合物を添加することによって調製したポリエステル製
造用触媒溶液を貯留するに際し、５０〜２００℃の温度
に保持することを特徴とするものである。That is, the present invention heat-treats a glycol solution of phosphoric acid while refluxing the glycol, and when storing a catalyst solution for polyester production prepared by adding an antimony compound to the treated solution, the solution is heated to a temperature of 50 to 200°C. It is characterized by holding.
本発明に使用されるアンチモン化合物としては。Antimony compounds used in the present invention include:
三酸化アンチモン、塩化アンチモン、＃酸アンチモン等
従来公知のアンチモン化合物があげられるが、すでに述
べたように二酸化アンチモンが好適である。Conventionally known antimony compounds such as antimony trioxide, antimony chloride, and antimony acid may be used, but as already mentioned, antimony dioxide is preferred.
本発明において、熱安定化剤としてはリン酸が用いられ
るが、すでに述べたように重縮合中に反応系外へ飛散し
ないので、従来のリン化合物よりも添加量が少なくてす
むというメリットがある。In the present invention, phosphoric acid is used as a thermal stabilizer, but as mentioned above, it does not scatter out of the reaction system during polycondensation, so it has the advantage that the amount added can be smaller than that of conventional phosphorus compounds. .
本発明において、触媒溶液の調製に用いられるグリコー
ルとしては、製造すべきポリエステルを構成するグリコ
ール成分と同じものが好ましく。In the present invention, the glycol used for preparing the catalyst solution is preferably the same as the glycol component constituting the polyester to be produced.
特にエチレングリコールが望ましい。また、グリコール
による還流処理は１０分間以上、好ましくは３０分間以
上行うのが好ましい。還流時間が１０分間未満の場合に
は、処理液にアンチモン化合物を添加した時点で処理液
自体が白濁し、好ましくない。Ethylene glycol is particularly desirable. Further, the reflux treatment with glycol is preferably carried out for 10 minutes or more, preferably 30 minutes or more. If the reflux time is less than 10 minutes, the treatment liquid itself becomes cloudy at the time the antimony compound is added to the treatment liquid, which is not preferable.
本発明において、リン酸をグリコール溶液として還流処
理する際の・リン酸の濃度としては特に制限はないが１
通常０．１〜１０モル％の範囲が好適である。リン酸濃
度が０．１モル％未満の場合には十分な色調改善効果を
得ようとするとどうしてもグリコールの量が多くなり９
反応系への添加時に問題が生じる。一方、リン酸濃度が
１０モル％よりも高くなると還流時間を必要以上に長く
する必要があり、触媒溶液の調製コストが高くつくとい
う欠点がある。In the present invention, when refluxing phosphoric acid as a glycol solution, the concentration of phosphoric acid is not particularly limited;
Usually, a range of 0.1 to 10 mol% is suitable. If the phosphoric acid concentration is less than 0.1 mol%, the amount of glycol will inevitably increase in order to obtain a sufficient color tone improvement effect9.
Problems arise during addition to the reaction system. On the other hand, if the phosphoric acid concentration is higher than 10 mol %, the reflux time needs to be longer than necessary, which has the drawback of increasing the cost of preparing the catalyst solution.
本発明において、リン酸のグリコール溶液の処理液にア
ンチモン化合物を添加する方法としては。In the present invention, the method of adding an antimony compound to a treatment solution of a glycol solution of phosphoric acid is as follows.
アンチモン化合＃４ｉ独を直接添加する方法でもよいが
、前記グリコールに分散あるいは熔解させたものを添加
する方法が望ましい。Although it is possible to directly add antimony compound #4i, it is preferable to add the antimony compound #4i after being dispersed or dissolved in the glycol.
５一
本発明は、このようにして調製した触媒溶液を５０〜２
００℃に保温して貯留することを特徴とするものであり
、特に好ましい貯留温度は１２０〜１８０℃である。こ
の温度が５０℃よりも低いと十分な効果が現れず、２０
０℃よりも高くなると好ましくない反応が生ずるように
なる。51 The present invention uses the catalyst solution prepared in this manner at 50 to 2
It is characterized by being stored at a temperature of 00°C, and a particularly preferable storage temperature is 120 to 180°C. If this temperature is lower than 50℃, sufficient effect will not be obtained, and 20℃
When the temperature is higher than 0°C, undesirable reactions begin to occur.
なお、アンチモン化合物、コバルト化合物及びリン化合
物を含んだグリコール溶液を７０〜１２０℃の温度で保
温貯留する方法が特開昭５６−５３６２６号公報に提案
されており、それなりの効果はあるがアンチモン化合物
特有のくすみは容易に解消されず、とりわけリン化合物
としてリン酸を用いた場合にはその傾向が強かった。し
かるに９本発明のようにリン酸を予め特定条件でグリコ
ール処理したのぢ、アンチモン化合物を添加した触媒溶
液を高温で保持することにより、前記問題点が解消され
るのである。Note that a method of thermally storing a glycol solution containing an antimony compound, a cobalt compound, and a phosphorus compound at a temperature of 70 to 120°C has been proposed in JP-A-56-53626, and although it has some effects, it The characteristic dullness was not easily eliminated, and this tendency was particularly strong when phosphoric acid was used as the phosphorus compound. However, when phosphoric acid is treated with glycol under specific conditions as in the present invention, the above-mentioned problems can be solved by maintaining the catalyst solution containing the antimony compound at a high temperature.
触媒溶液を反応系に添加する時期はエステル交換反応又
はエステル化反応がほぼ終了した時点。The catalyst solution is added to the reaction system when the transesterification reaction or esterification reaction is almost completed.
すなわち反応率が９０％以上になった時点である。That is, this is the point when the reaction rate reaches 90% or more.
＝６−
また２反応系への添加量は、ポリエステルを構成する全
酸成分に対してアンチモン化合物がＯ’、００１〜０．
１モル％で、しかもリン酸が０．００５〜０．１モル％
になる量が好ましい。アンチモン化合物の添加量が０．
００１モル％未満の場合には重縮合が円滑に進行しない
し、またリン酸の添加量が０．００５モル％未満の場合
には満足のいく色調改善効果が得られない。=6- Also, the amount of the antimony compound added to the two reaction systems is O', 001 to 0.
1 mol%, and 0.005 to 0.1 mol% of phosphoric acid
It is preferable that the amount is as follows. The amount of antimony compound added is 0.
If the amount of phosphoric acid added is less than 0.001 mol%, polycondensation will not proceed smoothly, and if the amount of phosphoric acid added is less than 0.005 mol%, a satisfactory color tone improvement effect will not be obtained.
また、このような触媒溶液を使用して製造されるポリエ
ステルとしては、ポリエチレンテレフタレートホモポリ
エステルの他に第３成分としてイソフタル酸、５−すｉ
・リウムスルホイソフタル酸。In addition, polyester produced using such a catalyst solution contains isophthalic acid and 5-silicon as a third component in addition to polyethylene terephthalate homopolyester.
・Rium sulfoisophthalic acid.
ナフタリン−２，６−ジカルボン酸、アジピン酸。Naphthalene-2,6-dicarboxylic acid, adipic acid.
セバシン酸等の二塩基ＦＩＺ、、 ｐ−オキシ安息香
酸。Dibasic FIZ such as sebacic acid, p-oxybenzoic acid.
ｐ−オキシエトキシ安息香酸等のオキシ酸、トリメチレ
ングリコール、１．４−ブタンジオール等のポリメチレ
ングリコール、ジエチレングリコール。Oxyacids such as p-oxyethoxybenzoic acid, polymethylene glycols such as trimethylene glycol, 1,4-butanediol, and diethylene glycol.
トリエチレングリコール等のポリエチレングリコール、
プロピレングリコール、シクロヘキサン−１，４−ジメ
タツール、ペンタエリスリトール等のポリオール及びこ
れらのエステル形成性誘導体を共重合したポリエステル
があげられる。Polyethylene glycols such as triethylene glycol,
Examples include polyesters obtained by copolymerizing polyols such as propylene glycol, cyclohexane-1,4-dimetatool, and pentaerythritol, and ester-forming derivatives thereof.
また、ポリエステルの製造に際しては１種々の添加剤８
例えば艷消剤としての二酸化チタン、易滑剤としての二
酸化ケイ素や着色を目的とした各種着色用顔料等を添加
することができる。In addition, when manufacturing polyester, 1 various additives 8
For example, titanium dioxide as a dissipating agent, silicon dioxide as a lubricant, various coloring pigments, etc. can be added.
次に、実施例をあげて本発明をさらに具体的に説明する
が２本発明はこれによって限定されるものではない。Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
なお１例中ポリエステルの極限粘度〔η〕は。In addition, in one example, the intrinsic viscosity [η] of polyester is as follows.
フェノールと四塩化エタンの等重量混合溶媒を用いて、
２０℃で測定して溶液粘度から求めたものである。ま
た、ポリエステルの色調は溶融状態での透明性を目視に
より観察するとともにチップ化物を１５０℃で１時間結
晶化処理したのち２色差計を用いてり、ａ、ｂ値を求め
た。Using a mixed solvent of equal weights of phenol and tetrachloroethane,
It was determined from the solution viscosity measured at 20°C. The color tone of the polyester was determined by visually observing its transparency in the molten state, and by crystallizing the chipped product at 150° C. for 1 hour, and then using a two-color difference meter to determine the a and b values.
Ｌ値は明度（値が大きいほど明るい）、ａ値は赤−縁糸
の色相（＋は赤味、−は緑味）、ｂ値は黄−青光の色相
（＋は黄味、−は青味）を表す。The L value is the lightness (the larger the value, the brighter), the a value is the red-edge hue (+ is reddish, - is greenish), and the b value is the yellow-blue hue (+ is yellowish, - is bluish).
ポリマーの色調としては、Ｌ値は大きいほど、ａ値はＯ
に近いほど、ｂ値はマイナス側で極端に大きくならない
限り小さいほど好ましい。As for the color tone of the polymer, the larger the L value, the better the a value is O.
It is preferable that the b value be as small as possible, unless it becomes extremely large on the negative side.
実施例
（イ）触媒溶液の調製
リン酸の１モル％エチレングリコール溶液を２００℃の
温度で１時間還流させた処理液に別途調製した三酸化ア
ンチモンの１モル％エチレングリコール溶液を添加混合
して調製した。Example (a) Preparation of catalyst solution A separately prepared 1 mol% ethylene glycol solution of antimony trioxide was added to a treatment solution in which a 1 mol% ethylene glycol solution of phosphoric acid was refluxed at a temperature of 200°C for 1 hour. Prepared.
（ロ）触媒溶液の貯留
上記（イ）で調製した触媒溶液を１表１に示した温度で
常温下、それぞれ３日間及び７日間保温貯留を行った。(b) Storage of catalyst solution The catalyst solution prepared in (a) above was stored at room temperature for 3 days and 7 days, respectively, at the temperatures shown in Table 1.
（ハ）ポリエステルの製造
ビス（β−ヒドロキシエチル）テレフタレート及びその
オリゴマーの存在するエステル化反応器にテレフタル酸
とエチレングリコールのモル比１ ： １．６のスラリ
ーラミｌ続的に供給し、２６０℃、常圧下で滞留時間６
時間にてエステル化反応を行い１反応率９−
９５％のエステル化生成物を連続的に得た。(c) Production of polyester A slurry laminate of terephthalic acid and ethylene glycol in a molar ratio of 1:1.6 was continuously fed to an esterification reactor in which bis(β-hydroxyethyl) terephthalate and its oligomer were present, and heated at 260°C. Residence time 6 under normal pressure
The esterification reaction was carried out over a period of time to continuously obtain esterified products with a reaction rate of 9-95%.
このエステル化生成物をガラス製重合反応器に移し、酸
成分１モルに対し、三酸化アンチモンが２×１０１モル
、リン酸が５×１０−４モルになるよう上記（ロ）で貯
留した触媒溶液を添加し、２８５℃で減圧を開始し。This esterification product was transferred to a glass polymerization reactor, and the catalyst stored in (b) above was adjusted so that antimony trioxide was 2 x 101 mol and phosphoric acid was 5 x 10-4 mol per 1 mol of the acid component. Add solution and start vacuum at 285°C.
最終減圧度１トルで２時間重縮合した。Polycondensation was carried out for 2 hours at a final vacuum of 1 torr.
得られたポリエステル特性値を表１に示す。Table 1 shows the obtained polyester characteristic values.
なお１重縮合時の熔融ポリエステルの色調は、いずれも
透明で、くすみは全くみられなかった。The color tone of the molten polyester upon single polycondensation was transparent in all cases, and no dullness was observed at all.
表１
１０−
比較例１
実施例の（イ）と同様の方法でリン酸とアンチモン化合
物とから触媒溶液を調製し、常温、常圧にて３日間貯留
し、これを用いて実施例の（ハ）と同様にしてポリエス
テルの製造を行った。Table 1 10- Comparative Example 1 A catalyst solution was prepared from phosphoric acid and an antimony compound in the same manner as in Example (a), stored at room temperature and normal pressure for 3 days, and used to prepare Example (A). Polyester was produced in the same manner as in c).
得られたポリエステルの〔η〕は０．６８であった。[η] of the obtained polyester was 0.68.
また、触媒溶液中には調製後、貯留１日日にすでに不溶
性の微粒子が析出しており８重縮合時の溶融ポリエステ
ルはくすんだ色調であり、チップ化物の色調はＬ値６３
．７． ａ値１．３ 、 ｂ値２．４であった。In addition, insoluble fine particles were already precipitated in the catalyst solution on the first day of storage after preparation, and the molten polyester at the time of 8-poly condensation had a dull color, and the color tone of the chipped product had an L value of 63.
．． 7. The a value was 1.3 and the b value was 2.4.
比較例２
別々に調製したリン酸の１モル％エチレングリコール溶
液と三酸化アンチモンの１モル％エチレングリコール溶
液とを常温で混合後、１５０℃に加熱保温して３日間貯
留した触媒溶液を実施例の（ハ）と同じ要領で反応系に
添加してポリエステルを製造した。Comparative Example 2 A catalyst solution was obtained by mixing a separately prepared 1 mol% ethylene glycol solution of phosphoric acid and a 1 mol% ethylene glycol solution of antimony trioxide at room temperature, then heating and keeping the mixture at 150°C and storing it for 3 days. Polyester was produced by adding it to the reaction system in the same manner as in (c).
重縮合時における溶融ポリエステルの色ｉｌｌはくすん
でおり、チップ化物の色調はＬ値５４．３． ａ値１．
３．ｂ値２．９とよくなかった。The color of the molten polyester during polycondensation is dull, and the color tone of the chipped material has an L value of 54.3. a value 1.
3. The b value was 2.9, which was not good.
特許出願人 日本エステル株式会社 代理人 児 玉 雄 三Patent applicant: Nihon Ester Co., Ltd. Agent Yuzo Kodama
Claims (1)
ながら加熱処理し、処理液にアンチモン化合物を添加す
ることによって調製したポリエステル製造用触媒溶液を
貯留するに際し。 ５０〜２００℃の温度に保持することを特徴とするポリ
エステル製造用触媒溶液の貯留法。 （２）グリコールがエチレングリコールである特許請求
の範囲第１項記載の方法。[Claims] (When storing a catalyst solution for polyester production prepared by heating a glycol solution of 11-phosphoric acid while refluxing the glycol and adding an antimony compound to the treated solution. A method for storing a catalyst solution for polyester production, the method comprising maintaining the catalyst solution at a certain temperature. (2) The method according to claim 1, wherein the glycol is ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093118A JPS59217724A (en) | 1983-05-26 | 1983-05-26 | Method for storing solution of catalyst for production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093118A JPS59217724A (en) | 1983-05-26 | 1983-05-26 | Method for storing solution of catalyst for production of polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59217724A true JPS59217724A (en) | 1984-12-07 |
| JPH0318651B2 JPH0318651B2 (en) | 1991-03-13 |
Family
ID=14073600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58093118A Granted JPS59217724A (en) | 1983-05-26 | 1983-05-26 | Method for storing solution of catalyst for production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59217724A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04114032A (en) * | 1990-09-04 | 1992-04-15 | Fuji Photo Film Co Ltd | Preparation of catalyst by dissolution thereof |
| WO2001014452A1 (en) * | 1999-08-24 | 2001-03-01 | Eastman Chemical Company | Preparation of polyesters employing antimony catalysts and acidic phosphorus compounds |
| US6384180B1 (en) | 1999-08-24 | 2002-05-07 | Eastman Chemical Company | Method for making polyesters employing acidic phosphorus-containing compounds |
-
1983
- 1983-05-26 JP JP58093118A patent/JPS59217724A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04114032A (en) * | 1990-09-04 | 1992-04-15 | Fuji Photo Film Co Ltd | Preparation of catalyst by dissolution thereof |
| WO2001014452A1 (en) * | 1999-08-24 | 2001-03-01 | Eastman Chemical Company | Preparation of polyesters employing antimony catalysts and acidic phosphorus compounds |
| US6384180B1 (en) | 1999-08-24 | 2002-05-07 | Eastman Chemical Company | Method for making polyesters employing acidic phosphorus-containing compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0318651B2 (en) | 1991-03-13 |
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