JPS63112619A - Solid state polymerization of polyester - Google Patents
Solid state polymerization of polyesterInfo
- Publication number
- JPS63112619A JPS63112619A JP25950386A JP25950386A JPS63112619A JP S63112619 A JPS63112619 A JP S63112619A JP 25950386 A JP25950386 A JP 25950386A JP 25950386 A JP25950386 A JP 25950386A JP S63112619 A JPS63112619 A JP S63112619A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- polymerization
- solid phase
- phase polymerization
- dew point
- 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.)
- Pending
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 57
- 229920000728 polyester Polymers 0.000 title claims abstract description 24
- 239000007787 solid Substances 0.000 title abstract 3
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 12
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 6
- -1 polybutylene terephthalate Polymers 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はポリエステルのチップを不活性気体中で固相重
合する方法に関し、特に重合速度が速く、均一な高重合
度のポリエステルを得ることができる固相重合方法に関
するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method of solid-phase polymerizing polyester chips in an inert gas, and particularly to a method that achieves a fast polymerization rate and can obtain a uniform polyester with a high degree of polymerization. The present invention relates to a solid phase polymerization method that can be used.
〈従来の技術〉
ポリエステルの固相重合とは溶融重合で得られたポリエ
ステル粒子を不活性気体中で更に重合することであり従
来から広く知られている０例えば、ポリブチレンテレフ
タレートの粒子を無攪はん下で予備乾燥し２次いで窒素
気流下、高温で連続的に固相重合する方法が特公昭５９
−５２８９５号公報に記載されている。<Prior art> Solid phase polymerization of polyester is a process in which polyester particles obtained by melt polymerization are further polymerized in an inert gas. A method of preliminary drying under solder and then continuous solid phase polymerization at high temperature under a nitrogen stream was published in 1983.
It is described in JP-A-52895.
また１粒子の内部と表層部の重合度を均質化するため、
固相重合雰囲気中に１．４−ブタンジオールを混入する
方法が特公昭５８−５１０１７号公報に示されている。In addition, in order to homogenize the degree of polymerization between the inside and surface layer of one particle,
A method of mixing 1,4-butanediol into the solid phase polymerization atmosphere is disclosed in Japanese Patent Publication No. 58-51017.
〈発明が解決しようとする問題〉
従来のポリエステルの面相重合は、たとえば特公昭５９
−５２８９５号公報に記載されているようにポリエステ
ルの粒子を固相重合槽へ連続供給し、約２００℃の窒素
を流通して約１０〜２０時間重合するが、このようにし
て得られるベレットは確かに重合するものの重合度にば
らつ者を生じ安定した高重合度のポリエステルが得られ
ない欠点があった。ベレットの重合度が不均一になると
、たとえばこれを成形する際、溶融粘度が一定せず成形
品の形状１機械強度に悪影響を及ぼす。<Problem to be solved by the invention> Conventional surface phase polymerization of polyester was developed, for example, in
As described in Japanese Patent No. 52895, polyester particles are continuously fed into a solid phase polymerization tank and polymerized for about 10 to 20 hours by passing nitrogen at about 200°C, but the pellets obtained in this way are Although it does polymerize, it has the disadvantage that the degree of polymerization varies, making it impossible to obtain a polyester with a stable high degree of polymerization. If the degree of polymerization of the pellet becomes non-uniform, for example, when the pellet is molded, the melt viscosity will not be constant, which will adversely affect the shape 1 mechanical strength of the molded product.
この重合度のばらつきは従来、固相重合槽中雰囲気温度
、気体流量等に起因するものと考えられ。Conventionally, this variation in the degree of polymerization is thought to be caused by the atmospheric temperature, gas flow rate, etc. in the solid phase polymerization tank.
種々検討がなされたが、満足できる結果は得られてなか
った０本発明はかかる従来技術の欠点を解消するため、
検討した結果得られたものである。Various studies have been carried out, but no satisfactory results have been obtained.The present invention aims to eliminate the drawbacks of the prior art.
This was obtained as a result of consideration.
したがって９本発明の目的は重合速度が速く。Therefore, the object of the present invention is to increase the polymerization rate.
かつ均質な重合度を有するポリエステルを得るための固
相重合方法を提供することにある。Another object of the present invention is to provide a solid phase polymerization method for obtaining a polyester having a homogeneous degree of polymerization.
〈問題点を解決するための手段〉
上記目的を達成するため１本発明は次の手段をとるもの
である。<Means for Solving the Problems> In order to achieve the above object, the present invention takes the following measures.
即ち１本発明のポリエステルの固相重合方法はポリエス
テルを固相重合槽中で固相重合する際固相重合槽中へ循
環する不活性気体の露点を一４０℃より低い温度に制御
することを特徴とするものである。That is, 1. The solid phase polymerization method for polyester of the present invention includes controlling the dew point of the inert gas circulating into the solid phase polymerization tank to a temperature lower than -40°C when polyester is solid phase polymerized in the solid phase polymerization tank. This is a characteristic feature.
以下１本発明に使用できるポリエステルとしては芳香族
ジカルボン酸またはそのエステルと炭素原子数２〜４の
ジオールから得られ名ポリエステルがあげられるが、中
でも射出成形用途に有用なポリブチレンテレフタレート
が好ましい。Examples of polyesters that can be used in the present invention include polyesters obtained from aromatic dicarboxylic acids or esters thereof and diols having 2 to 4 carbon atoms, and among them polybutylene terephthalate, which is useful for injection molding applications, is preferred.
また、これらのポリエステルには１例えば脂肪族ジカル
ボン酸等の他の成分を共重合させることができる。Further, other components such as aliphatic dicarboxylic acids can be copolymerized with these polyesters.
固相重合槽に供給されるポリエステルはベレット状が好
ましく、吐出直後のものでもよいが、予備乾燥を行なっ
たものでもよい。The polyester supplied to the solid phase polymerization tank is preferably pellet-shaped, and may be immediately after being discharged, or may be pre-dried.
不活性気体としては窒素、二酸化炭素があるが工業的に
は窒素が好ましい。Examples of the inert gas include nitrogen and carbon dioxide, but nitrogen is preferred industrially.
本発明において最も特徴的なことは不活性気体の露点、
即ち、不活性気体中の水分率を制御することにある。The most characteristic feature of the present invention is the dew point of the inert gas,
That is, the objective is to control the moisture content in the inert gas.
不活性気体は通常２固相重合槽の下部から上部にむかっ
て流され、槽上部から系外にでた不活性気体は再び槽下
部から循環挿入される。このとき、不活性気体の露点を
常に一４０℃より低い温度にｌｌ！御する必要がある。The inert gas is normally flowed from the bottom to the top of the two solid-phase polymerization tanks, and the inert gas that has exited the system from the top of the tank is recirculated and inserted from the bottom of the tank. At this time, the dew point of the inert gas should always be lower than -40°C! need to be controlled.
露点が一４０℃以上になると重合速度が急激に遅くなり
固相重合槽から排出される製品の重合度が急激に低下す
る。When the dew point exceeds 140° C., the polymerization rate decreases rapidly and the degree of polymerization of the product discharged from the solid phase polymerization tank decreases rapidly.
好ましい露点範囲は−５０〜−７５℃である。The preferred dew point range is -50 to -75°C.
不活性気体の露点を一４０℃より低い温度に維持して循
環させる方法としては、循環窒素をクーラーで冷却し、
吸湿剤により脱湿する方法、あるいは循環窒素に高純度
の窒素を補愼し循環窒素の水分を保つ方法がある。As a method of circulating the inert gas while maintaining its dew point at a temperature lower than -40°C, the circulating nitrogen is cooled with a cooler.
There is a method of dehumidifying using a moisture absorbent, or a method of supplementing the circulating nitrogen with high-purity nitrogen to maintain the moisture content of the circulating nitrogen.
固相重合中の雰囲気温度はポリエステルの種類により異
なるが、一般的には１７０℃以上、融点−１Ｏ℃であり
９例えばポリブチレンテレフタレートを重合する場合は
１９０〜２１５℃であり。The atmospheric temperature during solid phase polymerization varies depending on the type of polyester, but is generally 170° C. or higher, with a melting point of -10° C.9 For example, in the case of polymerizing polybutylene terephthalate, it is 190 to 215° C.
好ましくは１９５〜２０５℃以下である。 また１本発
明の効果を十分に発揮するため雰囲気温度は±０．３℃
にコントロールすることが好ましい。Preferably it is 195 to 205°C or less. In addition, in order to fully exhibit the effects of the present invention, the ambient temperature is ±0.3℃.
It is preferable to control the
ポリマーが固相重合槽に滞留する時間は５ＨｒＳ〜２５
Ｈｒｓが適当であり好ましくは７Ｈｒ ｓ〜２０Ｈｒｓ
である。The time the polymer stays in the solid phase polymerization tank is 5HrS~25
Hrs is appropriate, preferably 7Hrs to 20Hrs
It is.
く作用〉
本発明の最大の特徴はポリエステルの固相重合における
重合度のばらつきが不活性気体中の露点、即ち、水分率
にあることを見出した点にあり。Effects> The greatest feature of the present invention lies in the discovery that the variation in the degree of polymerization in solid phase polymerization of polyester is due to the dew point in an inert gas, that is, the moisture content.
この露点を一４０℃より低い温度１範囲にコントロール
することにより、均一な重合度を有するポリエステルが
連続的に得られるのである。By controlling this dew point to a temperature range lower than -40°C, polyester having a uniform degree of polymerization can be continuously obtained.
重合速度が水分率に影響を受けることは一般的によく知
られたことであるが、露点が一４０℃以上では理由は明
確ではないが重合速度が急激に遅くなる。It is generally well known that the polymerization rate is affected by the moisture content, but when the dew point is 140°C or higher, the polymerization rate decreases rapidly for reasons that are not clear.
〈実施例〉
本発明の固相重合に使用する装置の概略を第１図にしめ
す、これは大略予備乾燥槽２および固相重合槽６．クー
ラー１２．脱湿塔１３．ヒーター１４より構成されてい
る。 実施に際して、まず未乾燥ＰＢＴ粒子は輸送供給
装置１により予備乾燥槽２に供給される。予備乾燥槽２
には下部送入口から１３０℃に加熱された気体３を送入
し、供給されたＰＢＴを水分含有率が０．０ＩＷＴ％以
下となるまで予備乾燥する。乾燥されたＰＢＴ粒子は次
いで排出バルブ４および中間貯槽５を経て固相重合槽６
へ連続的に供給される。固相重合槽６に充填されたＰＢ
Ｔ粒子は槽下部に設けられた送入口から供給される１９
０〜２１０℃に加熱された気体７により固相重合された
後１ｍ出バルブ８をへて取出貯槽９に排出される。中間
貯槽５は粒面針１０および粒面コントロールユニット１
１ををし、固相重合時間を一定に保つ設備である。予備
乾燥工程および固相重合工程で使用する気体はう
本発明な場合前者に空気、後者に窒素を用いる。<Example> The outline of the apparatus used for the solid phase polymerization of the present invention is shown in FIG. Cooler 12. Dehumidification tower 13. It is composed of a heater 14. In implementation, first, undried PBT particles are supplied to a pre-drying tank 2 by a transport supply device 1. Pre-drying tank 2
Gas 3 heated to 130° C. is introduced from the lower inlet, and the supplied PBT is preliminarily dried until the moisture content becomes 0.0 IWT% or less. The dried PBT particles then pass through a discharge valve 4 and an intermediate storage tank 5 to a solid phase polymerization tank 6.
Continuously supplied to PB filled in solid phase polymerization tank 6
T particles are supplied from the inlet provided at the bottom of the tank19
After being subjected to solid phase polymerization with gas 7 heated to 0 to 210°C, it is discharged into a takeout storage tank 9 through a 1 m outlet valve 8. The intermediate storage tank 5 has a grain surface needle 10 and a grain surface control unit 1.
1 and keep the solid phase polymerization time constant. In the present invention, the gases used in the preliminary drying step and the solid phase polymerization step are air for the former and nitrogen for the latter.
７′より排気した窒素はクーラー１２で冷却し説湿塔１
３で水分を除去する。窒素は露点計１５で露点を測定し
制御する 露点が高い場合は脱湿剤の交換を行う、さら
に窒素はヒーター１４で加熱され固相重合槽６に供給さ
れ循環使用される。Nitrogen exhausted from 7' is cooled by cooler 12 and sent to humidity tower 1.
Remove moisture in step 3. The nitrogen is controlled by measuring the dew point with a dew point meter 15. If the dew point is high, the dehumidifier is replaced. Furthermore, the nitrogen is heated with a heater 14 and supplied to the solid phase polymerization tank 6 for circulation.
本実験においては重合度をＪＩＳ Ｋ７２１０号に基
ずくメルトフローレ一ト （Ｍ、Ｆ、Ｒ）であられした
。In this experiment, the degree of polymerization was determined using melt flow rate (M, F, R) based on JIS K7210.
Ｍ、 Ｆ、 Ｒ，が２０．０ＣＧ／１０ＭｒＮ）のＰＢ
Ｔ粒子を予備乾燥槽へ供給し１５０℃の加熱空気で２１
（ｒｓ乾燥した後排出バルブにより固相重合槽へ供給し
１表１に示す条件で１８Ｈｒｓ固相重合を行った９表よ
り１９５℃、２００℃、２０５℃ともに、露点が一４０
°Ｃ以上に窒素中の水分率が上昇することにより現品の
重合度が低下していることが分かる。従って、循環窒素
の水分率を制御することにより比較的安定した重合度を
もつ製品を得ることができる。PB with M, F, R, 20.0CG/10MrN)
The T particles were supplied to a pre-drying tank and heated with air at 150°C for 21 hours.
(After rs drying, it was supplied to the solid phase polymerization tank through the discharge valve and solid phase polymerization was carried out for 18 hours under the conditions shown in Table 1. From Table 9, the dew point was 140℃ at 195℃, 200℃, and 205℃.
It can be seen that the degree of polymerization of the actual product decreases as the moisture content in nitrogen increases above °C. Therefore, by controlling the moisture content of circulating nitrogen, a product with a relatively stable degree of polymerization can be obtained.
表１ （２５０℃、１０１００Ｏ測疋した。Table 1 (Measured at 250°C and 10,100O.
〈発明の効果〉
本発明は固相重合中の不活性気体の４点を一定に制御す
るものであるため１次の効果を発揮する（１）固相重合
速度が常に一定となり、得られるポリエステルの重合度
が均一になる。<Effects of the Invention> Since the present invention controls four points of inert gas during solid phase polymerization, it exhibits the following effects: (1) The solid phase polymerization rate is always constant, and the resulting polyester The degree of polymerization becomes uniform.
（２）その結果、溶融粘度が均一となり、優れた成形品
が得られる。(2) As a result, the melt viscosity becomes uniform and an excellent molded article can be obtained.
（３）露点の制御のみであるため、工業的に容易に実施
することができる。(3) Since only the dew point is controlled, it can be easily implemented industrially.
第１図は本発明の一実施ｔ！様で使用する装置の概略図
である。
６一−−固相重合櫂
１３−一一説湿塔FIG. 1 shows one implementation of the present invention! FIG. 61--Solid phase polymerization paddle 13-11 wet tower
Claims (1)
合槽中へ循環する不活性気体の露点を−４０℃より低い
温度に制御することを特徴とするポリエステルの固相重
合方法。A method for solid-phase polymerization of polyester, which comprises controlling the dew point of an inert gas circulating into the solid-phase polymerization tank to a temperature lower than -40° C. when polyester is solid-phase polymerized in a solid-phase polymerization tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25950386A JPS63112619A (en) | 1986-10-30 | 1986-10-30 | Solid state polymerization of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25950386A JPS63112619A (en) | 1986-10-30 | 1986-10-30 | Solid state polymerization of polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63112619A true JPS63112619A (en) | 1988-05-17 |
Family
ID=17335002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25950386A Pending JPS63112619A (en) | 1986-10-30 | 1986-10-30 | Solid state polymerization of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63112619A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0534603A2 (en) * | 1991-08-23 | 1993-03-31 | Kabushiki Kaisha Shinkasho | Continuous polyester filaments suitable for making carpets |
| JP2009221872A (en) * | 2008-03-13 | 2009-10-01 | Toshiba Carrier Corp | Hermetic compressor and refrigerating cycle device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58134118A (en) * | 1982-02-02 | 1983-08-10 | ザ・グツドイア−・タイヤ・アンド・ラバ−・コンパニ− | Manufacture of high molecular polyester |
-
1986
- 1986-10-30 JP JP25950386A patent/JPS63112619A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58134118A (en) * | 1982-02-02 | 1983-08-10 | ザ・グツドイア−・タイヤ・アンド・ラバ−・コンパニ− | Manufacture of high molecular polyester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0534603A2 (en) * | 1991-08-23 | 1993-03-31 | Kabushiki Kaisha Shinkasho | Continuous polyester filaments suitable for making carpets |
| JP2009221872A (en) * | 2008-03-13 | 2009-10-01 | Toshiba Carrier Corp | Hermetic compressor and refrigerating cycle device |
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