JPS5823824A - Preparation of aromatic polyester - Google Patents
Preparation of aromatic polyesterInfo
- Publication number
- JPS5823824A JPS5823824A JP12286181A JP12286181A JPS5823824A JP S5823824 A JPS5823824 A JP S5823824A JP 12286181 A JP12286181 A JP 12286181A JP 12286181 A JP12286181 A JP 12286181A JP S5823824 A JPS5823824 A JP S5823824A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- aromatic
- aromatic polyester
- temperature
- polymer
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は芳香族ポリエステルの製造方法に関するもので
ある。全芳香族ポリエステルは構造にもとすく優れた性
質を有するが、特に耐熱性の点ではあらゆる樹脂の中で
ぬきんでている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic polyester. Fully aromatic polyester has excellent structural properties, but it stands out among all resins in terms of heat resistance.
なかでもテレ7りμ酸やイソフタル酸とバラヒドロキシ
安息香酸あるいはその誘導体と4.41−ジヒドロキシ
ジフェニルあるいはその誘導体から製造される全芳香族
ポリエステルは射出成形可能でかつ各種物性、即ち機械
的性質、電気的性質、熱安定性等に優れている上、高い
耐熱性、耐薬品性、耐油性、耐放射線性、寸法安定性な
ど数々の優れた性能をもちあわせており、機械部品、電
気・電子部品、自動車部品など種々の分野で用いられて
いる。Among these, wholly aromatic polyesters produced from tere-7-μ acid, isophthalic acid, parahydroxybenzoic acid or its derivatives, and 4,41-dihydroxydiphenyl or its derivatives can be injection molded and have various physical properties, such as mechanical properties, In addition to having excellent electrical properties and thermal stability, it also has many excellent properties such as high heat resistance, chemical resistance, oil resistance, radiation resistance, and dimensional stability, making it suitable for mechanical parts, electrical and electronic It is used in various fields such as parts and automobile parts.
く成形性が悪いという欠点がある。また高い成形加工温
度を必要とするため、成形時のポリマ−〇熱劣化、着色
などの問題があり、これらの点からも成形性の改曽が望
まれていた。It has the disadvantage of poor moldability. In addition, since high molding temperatures are required, there are problems such as thermal deterioration and coloring of the polymer during molding, and from these points of view as well, improvements in moldability have been desired.
このような間層を解決するための従来から知られている
方法としてより流動性のよい(成形性のよい)樹脂とブ
レンドするという方法がある。たとえばポリエチレンフ
タレートやポリカーボネートなどとブレンドし成形する
という方法である。しかしながら先に述べたテレフタル
酸やイソフタμ酸、パラヒドロキシ安息香酸、4.4′
−ジヒドワキシジフェニルなどから得られる全芳香族ポ
リエステμとポリエチレンテレフタレートやポリカーボ
ネートとの混合、造粒、成形を行なう際、全芳香族ポリ
エステルの均一化する温度領域で各工程を行なうと、こ
の温度では熱安定性に劣るポリエチレンテレフタレート
やlリカーボネートは熱分解をおこしやすく、またこれ
らの樹脂が安定して均一化しうる温度領域で処理すると
全芳香族ポリエステルの流動に不十分な温度のため組成
物の系全体が均一分散体とはならない。系全体を均一化
するために混合、造粒、成形などの各工程における樹脂
の滞留時間を長くすることも可能ではあるが均一分散に
はほど遠く、またその状態にするために多大の時間を要
することになり、現実的ではない。A conventionally known method for solving this interlayer problem is to blend it with a resin that has better fluidity (good moldability). For example, it is blended with polyethylene phthalate, polycarbonate, etc. and molded. However, the aforementioned terephthalic acid, isophthalic acid, parahydroxybenzoic acid, 4.4'
- When mixing, granulating, and molding fully aromatic polyester μ obtained from dihydroxydiphenyl etc. with polyethylene terephthalate or polycarbonate, if each step is performed in the temperature range where fully aromatic polyester is uniform, the temperature However, polyethylene terephthalate and l-licarbonate, which have poor thermal stability, are easily thermally decomposed, and if these resins are treated in a temperature range where they can be stabilized and homogenized, the temperature is insufficient for the flow of fully aromatic polyester, so the composition The entire system is not a homogeneous dispersion. Although it is possible to lengthen the residence time of the resin in each process such as mixing, granulation, and molding in order to homogenize the entire system, it is far from uniformly dispersed, and it takes a lot of time to achieve that state. That's not realistic.
別法として全芳香族ポリエステルの成形温度を低下させ
る目的で、全芳香族ポリエステルの分子量の低いものを
用いて、上に述べたように、成形性の優れた樹脂ととも
に混合、造粒、成形を行なうξとも可能ではあるが、全
芳香族ポリエステルのもつ種々の優れた性能を低下させ
てしまうことになる。Alternatively, in order to lower the molding temperature of wholly aromatic polyester, a wholly aromatic polyester with a low molecular weight is mixed, granulated, and molded with a resin having excellent moldability, as described above. Although it is possible to do ξ, the various excellent properties of wholly aromatic polyesters will be degraded.
また溶液によるブレンド方法も考えられるが、全芳香族
ぼりエステルの場合、分解をともなわずに均一に溶解し
うる溶媒は現在のところ見い出されておらず、きわめて
困難といえよう。A blending method using a solution is also considered, but in the case of wholly aromatic esters, no solvent has been found so far that can uniformly dissolve them without decomposition, and this would be extremely difficult.
分散性が十分でないと、樹脂や成形品が溶媒や試薬番こ
さらされた特番こ一部劣化したり成形時のショットごと
のバラツキが見られたり、成形品の強度が不均一であっ
たりする。If dispersibility is insufficient, parts of the resin or molded product exposed to solvent or reagents may deteriorate, variations may occur from shot to shot during molding, or the strength of the molded product may be uneven. .
以上述べたように通常のブレンド方法からは、1与こ述
べた全芳香族ポリエステルの成形性を改良することは困
難といえる。As mentioned above, it can be said that it is difficult to improve the moldability of the above-mentioned wholly aromatic polyester using the usual blending method.
本発明者らは、このような現状に鑑み、通常のブレンド
法において見られるような物性の低下や、分散が悪いた
め生じる不都合なしに、全芳香族ポリエステルの成形性
を改良すべく鋭意検討した結果、全芳香族ポリエステル
の製造特番C1重合反応系に芳香族ポリスルホンをある
特定の割合で存在せしめ、かつ重合を実質的に溶媒を存
在させない塊状重合法で行なうことにより、全芳香族ポ
リエステルのもつ優れた性能を低下させることなく、全
芳香族ポリエステルの成形性を改良できることを見い出
した。In view of the current situation, the present inventors have conducted extensive studies to improve the moldability of wholly aromatic polyester without the deterioration of physical properties or inconveniences caused by poor dispersion that occur in conventional blending methods. As a result, by making aromatic polysulfone exist in a certain proportion in the polymerization reaction system and carrying out the polymerization using a bulk polymerization method in which substantially no solvent is present, the properties of fully aromatic polyester can be improved. It has been found that the moldability of wholly aromatic polyester can be improved without reducing its excellent performance.
芳香族ポリスルホンは全芳香族ポリエステルの重合特番
こ存在せしめる必要がある。単に芳香族ポリスルホンを
全芳香族ポリエステルにブレンドしただけでは、成形性
の改良は困難であった。この原因は均一分散性が悪いこ
とによると考えられる。ブレンドの場合は成形品表面番
こ不均一な模様がみられた。Aromatic polysulfone must be present in the polymerization process of fully aromatic polyester. It was difficult to improve moldability by simply blending aromatic polysulfone with wholly aromatic polyester. This is thought to be due to poor uniform dispersibility. In the case of the blend, an uneven pattern was observed on the surface of the molded product.
また重合は、実質的に溶媒を存在させない塊状重合法で
行なう必要がある。Further, the polymerization must be carried out by a bulk polymerization method in which substantially no solvent is present.
芳香族ポリエステルの製造法としては、生成したホ0リ
マーを溶解せしめる有機溶媒を重合溶媒とする溶液重合
法、生成したポリマーが重合に用いた溶媒から沈澱して
くる懸濁重合法、溶媒を用いない塊状重合法などが知ら
れている。Aromatic polyesters can be produced using a solution polymerization method in which an organic solvent is used as a polymerization solvent to dissolve the produced holimer, a suspension polymerization method in which the produced polymer is precipitated from the solvent used for polymerization, and a suspension polymerization method in which a solvent is used. Bulk polymerization methods are known.
テレフタル酸やイソフタμ酸とバラヒドロキシ安mit
酸と4.4′−ジヒドロキシジフェニμなどから製造さ
れる全芳香族ポリエステルの場合はこれを溶かし得る溶
媒が現在までのところ見い出されていないため、溶液重
合法は採用し難い、懸濁重合法としては水添ターフェニ
ルやジフェニルエーテル、ジフェニル混合物のような高
沸点溶媒が用いられるが、これらの溶媒の除去、回収、
lリマーの洗浄など工程が複雑となる上、単位バッチ当
たりのポリマー生産量が少ないという経済的不利を有し
ている。塊状重合法は経済的番こは最も優れた重合法で
あるが、芳香族lリエステルの製造にはあまり適用され
ていない、その理由は、ポリエチレンテレフタレートの
ような脂肪族ポリエステルと比較して芳香族ポリエステ
ルは融点が高く、溶融状態を維持するには高温を必要と
するため、ポリマーの着色劣化が著しく商品としての価
値が減じられるからである。この着色劣化の問題が解決
されれば、プリマー品質ならびに経済性を満足すること
のできるプロセスとして工業的意義は甚大なものがある
。Terephthalic acid, isophthalic acid and parahydroxyamino acid
In the case of fully aromatic polyesters produced from acids and 4,4'-dihydroxydiphenyl μ, etc., no solvent has been found to date that can dissolve them, so solution polymerization is difficult to employ, and suspension polymerization is difficult. Legally, high boiling point solvents such as hydrogenated terphenyl, diphenyl ether, and diphenyl mixtures are used, but these solvents can be removed, recovered,
It is economically disadvantageous in that the steps such as cleaning the remer are complicated and the amount of polymer produced per unit batch is small. Bulk polymerization is the most economical polymerization method, but it has not been widely applied to the production of aromatic polyesters.The reason is that aromatic polyesters are This is because polyester has a high melting point and requires high temperatures to maintain its molten state, resulting in significant color deterioration of the polymer, which reduces its commercial value. If this problem of color deterioration can be solved, it will have great industrial significance as a process that can satisfy primer quality and economical efficiency.
本発明者らは上記全芳香族ポリエステルの製造時、重合
反応系に芳香族ポリスμホンを存在せしめかつ重合を実
質的に溶媒を存在させない塊状重合法で行なうと、着色
劣化の少ない芳香族ポリエステルが得られるとともに、
芳香族ポリスμホンを存在させることなく重合して得ら
れる全芳香族ポリエステルやあるいは芳香族ポリスμホ
ンを存在させるにしても、他の方法(例えば懸濁重合)
で得られた芳香族ポリエステfvIこ比べ成形性が良く
、また物性的にも優れていることを見い出し本発明に到
った。The present inventors discovered that when producing the above-mentioned fully aromatic polyester, an aromatic polyester with less deterioration in coloring was obtained by making an aromatic polyphonic acid exist in the polymerization reaction system and carrying out the polymerization by a bulk polymerization method in which substantially no solvent was present. is obtained, and
A fully aromatic polyester obtained by polymerization without the presence of an aromatic poly-μphone, or even if an aromatic poly-μ-phone is present, other methods (for example, suspension polymerization) can be used.
It has been found that the aromatic polyester fvI obtained in the above has better moldability and superior physical properties, and has led to the present invention.
即ち本発明は一般式人
(上式中、XはC0〜C4のアルキル基1、−o−、−
5o2、−s−または−co−であり、m 、 nは0
または1である。d:eの比は1:1から10:Iの範
囲にあり、C:Iの比は9:10から 10二〇の間に
ある。That is, the present invention relates to the general formula (in the above formula, X is a C0 to C4 alkyl group 1, -o-, -
5o2, -s- or -co-, m and n are 0
or 1. The d:e ratio ranges from 1:1 to 10:I and the C:I ratio ranges from 9:10 to 1020.
また上式中の芳香環の置換基は互いにパラまたはメタの
位置にある。)
であられされる全芳香族ポリエステ〃の製造特番こ重合
反応系に芳香族ポリスルホンを最終生成ポリマーの5〜
40重量%となるような割合で存在せしめかつ重合を実
質釣書ζ溶媒を存在させない塊状重合法で行なうことを
特徴とする芳香族ポリエステルの製造方法に関するもの
である。Furthermore, the substituents on the aromatic ring in the above formula are in para or meta positions with respect to each other. ) A special number for the production of fully aromatic polyester prepared by adding aromatic polysulfone to the polymerization reaction system.
The present invention relates to a method for producing an aromatic polyester, characterized in that the aromatic polyester is present in a proportion of 40% by weight, and the polymerization is carried out by a bulk polymerization method in which substantially no solvent is present.
芳香族ポリスルホンを存在せしめて得られた芳香族ポリ
エステ、4’lこおいては、芳香族ポリスルホンを存在
させないで重合した場合に比べて成形性が改良されてい
る上、単に芳香族ポリスルホンをブレンドしたものに比
べても成形品の表面、内部は均一であり良好な分散状態
となっている。またブレンド品でみられるような種々9
物性の低下、特に熱安定性や機械的強度の低下が少ない
という結果が得られた。The aromatic polyester obtained in the presence of aromatic polysulfone, 4'l, has improved moldability compared to polymerization in the absence of aromatic polysulfone, and it is also possible to simply blend aromatic polysulfone. Compared to the molded product, the surface and interior of the molded product are uniform and well-dispersed. In addition, there are various 9 types that can be found in blended products.
The results showed that there was little decrease in physical properties, especially in thermal stability and mechanical strength.
また芳香族ポリスμホンを存在せしめて重合することに
より、塊状重合法を用いても着色劣化の少ない芳香族ポ
リエステμが得られ、かつ成形性が改良されたことによ
り、経済性およびポリマー品質とも満足できる芳香族ポ
リエステルの製造法が見い出された。塊状重合時におけ
る着色劣化の低減は、芳香族ポリスルホンによる溶融粘
度の低下によると考えられる。In addition, by polymerizing in the presence of aromatic polyester μphones, aromatic polyester μ with less color deterioration can be obtained even when bulk polymerization is used, and moldability is improved, resulting in improved economic efficiency and polymer quality. A satisfactory process for producing aromatic polyesters has been found. The reduction in color deterioration during bulk polymerization is thought to be due to the reduction in melt viscosity due to the aromatic polysulfone.
本発明に用いられる全芳香族ポリエステルの成分として
は例えばバラヒドロキシ安息香酸、メタヒドロキシ安息
香酸、テレフタル酸、イソフタル酸、ハイドロキノン、
レゾyシン、4゜4′−ジヒドロキシジフェニル、4
、4’−ジヒドロキシジフェニルメタン/7.4.4°
−ジヒドロキシジフェニルスルホン、4,4−ジヒドロ
キシジフェニ〃スμフィト、 4 、4’−ジヒドロキ
シベンゾフェノン、 4 、4’−ジヒドロキシジフェ
ニルメタンなどやこれらの誘導体を用いることができる
。Components of the wholly aromatic polyester used in the present invention include, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, terephthalic acid, isophthalic acid, hydroquinone,
Reso-ycin, 4゜4'-dihydroxydiphenyl, 4
, 4'-dihydroxydiphenylmethane/7.4.4°
-dihydroxydiphenylsulfone, 4,4-dihydroxydiphenyl phyto, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, and derivatives thereof can be used.
これらの組み合わせのうちバラヒドロキシ安息香酸ある
いはそのエステル、テレフタル酸あるいはそのエステル
、4 、4’−ジヒドロキレジフェニルあるいはそのエ
ステルの組み合せが特に好ましい。Among these combinations, combinations of parahydroxybenzoic acid or its ester, terephthalic acid or its ester, and 4,4'-dihydroxyldiphenyl or its ester are particularly preferred.
全芳香族ポリエステルの重合時に用いられる芳香族ポリ
スμホンは一般に
(式中、Yは酸素または硫黄または4.4’−ビスフェ
ノールのような芳香族ジオールの残基である。)
なる構造単位をもっている。−例として−QI−o +
5o2−なる繰返し単位をもつインペリアルケ°ミカル
インダストリーズ社の「ビクなる繰返し単位をもっU、
C,C1社の「Udel J などがあげられる。Aromatic polyphones used in the polymerization of fully aromatic polyesters generally have the following structural units: . -As an example-QI-o +
Imperial Chemical Industries Co., Ltd. has a repeating unit of 5o2-.
Examples include ``Udel J'' by companies C and C1.
全芳香族ポリエステルの重合時に用いられる芳香族ポリ
スルホンの量は最終生成ポリマーの5〜40重量−であ
る必要がある。この範囲以下ではその効果は養十分でな
く、またこの範囲以上では、得られる芳香族ポリエステ
ルの熱的、機械的物性が十分でない。The amount of aromatic polysulfone used during the polymerization of the fully aromatic polyester should be between 5 and 40% by weight of the final product polymer. Below this range, the effect will not be sufficient, and above this range, the resulting aromatic polyester will not have sufficient thermal and mechanical properties.
重合方法としては塊状重合方法が用いられる。As the polymerization method, a bulk polymerization method is used.
塊状重合法は一般に知られているいかなる方法を用いて
もよい。Any generally known bulk polymerization method may be used.
一例をあげればまず一般式Aであられされる全芳香族ポ
リエステルを構成しうるための化合物と芳香族ポリスル
ホンをはじめ化同時化反応槽に仕込む方法がある。その
後加温して重合反応を行なわせるわけであるが、重合反
応は約200〜400℃、好ましくは250〜350
tで常圧ないしは減圧系、不活性気体雰囲気中で行なわ
れる。また残渣が重合体の物性に悪影着を与えないか、
または簡単な処理により活性をなくしつる触媒を用いて
重合を進めることも可能である。For example, there is a method in which a compound for forming a wholly aromatic polyester represented by the general formula A and an aromatic polysulfone are charged into a chemical reaction tank. Thereafter, the polymerization reaction is carried out by heating, and the polymerization reaction is carried out at a temperature of approximately 200 to 400°C, preferably 250 to 350°C.
The reaction is carried out at normal pressure or reduced pressure in an inert gas atmosphere. Also, check whether the residue will adversely affect the physical properties of the polymer.
Alternatively, it is also possible to proceed with polymerization using a catalyst whose activity can be eliminated by simple treatment.
より好ましい塊状重合法は重合温度下で重合によって生
成する重合体に常にその重合体が固化しないような剪断
力を加え重合を進行させ、重合体を固化させることなく
固体の多分散系の状態で実質的にすべてが固相になるま
で重合を行なう方法であり、用いうる最高温度は使用す
るモノマー、オリゴマー、あるいはポリマーの沸点や分
解点番こよって一部左右されるが、この温度限界は、最
初比較的低温で縮合を行ない、縮合が進行するにつれて
温度を上昇させる。A more preferable bulk polymerization method is to proceed with the polymerization by constantly applying a shearing force to the polymer produced by polymerization at the polymerization temperature so that the polymer does not solidify, and to maintain the polymer in a solid polydisperse state without solidifying the polymer. This is a method in which polymerization is carried out until substantially all of the polymer becomes a solid phase, and the maximum temperature that can be used depends in part on the boiling point and decomposition point of the monomer, oligomer, or polymer used, but this temperature limit is as follows: The condensation is initially carried out at a relatively low temperature and the temperature is increased as the condensation progresses.
最初180〜250℃の温度で、次いで上昇させ250
〜380℃の温度で、好まL/ < j、t 300〜
360℃で常圧ないしは減圧系で重合を行なう。固体多
分散体になってしまえばその融着温度および分解温度を
考慮しながら昇温することも可能で、300〜400℃
、好ましくは310〜370 ”C1ただし、分解温度
以下および融着温度以下であれば、高ければ高いほど反
応速度ははやくなる。Initially at a temperature of 180-250℃, then increased to 250℃
At a temperature of ~380°C, preferred L/<j, t 300~
Polymerization is carried out at 360° C. under normal pressure or reduced pressure. Once it becomes a solid polydisperse, it is possible to raise the temperature while taking into consideration the fusion temperature and decomposition temperature, and it is possible to raise the temperature to 300-400℃.
, preferably 310 to 370''C1 However, as long as the temperature is below the decomposition temperature and below the fusion temperature, the higher the temperature, the faster the reaction rate.
又別の方法として第1の反応槽に一般式Aであられされ
る全芳香族ポリエステルを構成しつるための化合物と芳
香族ポリスルホンを同時に仕込み、重縮合によりプレポ
リマーを生成させ、第2の反応槽番こ移し高分子量化す
る方法も用いられる。第1の反応槽において生成させた
プレポリマーを溶融状態で取り出し、粉砕して均一化し
たのち、第2の反応槽において高分子量化してもよくま
た該プレポリマーを押出機によりベレット化して第2の
反応槽で高分子量化してもよい。Alternatively, a compound for forming a wholly aromatic polyester represented by the general formula A and an aromatic polysulfone are simultaneously charged into the first reaction tank, a prepolymer is produced by polycondensation, and the second reaction is carried out. A method of increasing the molecular weight by transferring to a tank is also used. The prepolymer produced in the first reaction tank may be taken out in a molten state, pulverized and homogenized, and then made to have a high molecular weight in the second reaction tank. The molecular weight may be increased in a reaction tank.
あるいは、さらに別の方法として、芳香族ポリスルホン
をはじめから仕込むのではなく、弐Aであられされる全
芳香族ポリエステルの重合反応時に逐次添加していく方
法もある。もしこの方法を第1.第2の反応槽を用いる
2段重合で行なうときは、第1の反応槽で重合させると
きに逐次追加する方がより好ましい。Alternatively, as yet another method, instead of charging the aromatic polysulfone from the beginning, there is a method in which the aromatic polysulfone is added sequentially during the polymerization reaction of the wholly aromatic polyester prepared by A. If this method is the first. When carrying out two-stage polymerization using the second reaction tank, it is more preferable to add the components sequentially during the polymerization in the first reaction tank.
このようにして得られた芳香族ポリエステルは着色が少
なく、成形性に優れかつ耐熱性、機械的性質などの優れ
たポリマーである。The aromatic polyester thus obtained is a polymer with little coloration, excellent moldability, and excellent heat resistance and mechanical properties.
本発明によって得られた芳香族ポリエステルには安定剤
、着色剤、充填剤などプラスチックに加えられる通常の
添加剤を重合体の特性を損なわない範囲で加えることが
できる。充填剤としては例えばシリカ、粉末石英もしく
は砂、ヒユームドシリカ、炭化珪素、酸化アルミニウム
、ガラス繊維、酸化錫、酸化鉄、酸化亜鉛、炭素、グラ
ファイトその他顔料として二酸化チタンならび6ζ他の
無機材料および耐熱性の有機顔料を用いることができる
。The aromatic polyester obtained according to the present invention can contain additives commonly added to plastics, such as stabilizers, colorants, fillers, etc., to the extent that they do not impair the properties of the polymer. Fillers include, for example, silica, powdered quartz or sand, fumed silica, silicon carbide, aluminum oxide, glass fibers, tin oxide, iron oxide, zinc oxide, carbon, graphite, and as pigments titanium dioxide and other inorganic materials and heat-resistant materials. Organic pigments can be used.
本発明によって得られた重合物はプレス成形、射出成形
、押出成形などの方法により成形物、フィルム、シート
などの形で機械部品、電気、電子部品、自動車部品や各
種容器、包装材料などエンジニャリングプラスチックと
して高い性能を要求される分野で広範聞書ζ用いられる
。The polymer obtained by the present invention can be used in the form of molded products, films, sheets, etc. by methods such as press molding, injection molding, and extrusion molding, such as mechanical parts, electrical and electronic parts, automobile parts, various containers, and packaging materials. It is widely used in fields where high performance is required as a ring plastic.
以下書ζ実施例および比較例で本発明を説明するが、こ
れは例示的なものであり、ξれに限定されるものではな
い。The present invention will be explained below with reference to Examples and Comparative Examples, but these are illustrative and are not limited thereto.
実施例1
いかり型攪拌翼を有し、かつ重合槽の槽壁と攪拌翼との
クリアランスの小さな重合槽にバラアセトキシ安息香酸
756 F (5,48モ/L/)、テレフタル酸45
3 p (2,73モル)、4.4’−ジヒドロキシジ
フェニ/l/ 508 F (2,73モル)、ポリエ
ーテルスルホン(インペリアルケミカルインダストリー
ズ社製 ピクトレックス100 F) 1691 (
最終生成ポリマーの10重量−に相当する)及び無水酢
酸1337 F(13,1モ/L/)を投入した。Example 1 In a polymerization tank having an anchor-type stirring blade and with a small clearance between the tank wall and the stirring blade, 756 F (5,48 mo/L/) of acetoxybenzoic acid and 45% terephthalic acid were placed.
3 p (2,73 mol), 4,4'-dihydroxydipheny/l/508 F (2,73 mol), polyether sulfone (Pictrex 100 F manufactured by Imperial Chemical Industries) 1691 (
(equivalent to 10% by weight of the final product polymer) and acetic anhydride 1337 F (13.1 mo/L/) were charged.
窒素ガス雰囲気下で攪拌しながら1時間で150℃まで
加温し、この温度で3時間還流を行なった。その後昇温
させながら反応の結果化じる酢酸を留去し、高剪断下で
330℃まで昇温させた。さらに強力な攪拌で2時間重
合を続け、その後徐々に冷却し200℃まで強力攪拌を
続けた後槽外へ重合物をとりだした。The mixture was heated to 150° C. in 1 hour while stirring under a nitrogen gas atmosphere, and refluxed at this temperature for 3 hours. Thereafter, the acetic acid produced as a result of the reaction was distilled off while the temperature was raised, and the temperature was raised to 330°C under high shear. Polymerization was further continued for 2 hours with strong stirring, and then gradually cooled down to 200° C., and strong stirring was continued, after which the polymerized product was taken out of the tank.
回収量は1570 f (理論量の93.1 % >で
あった。ξれを粉砕したのちアルミ製のロータリーオー
ブンに移し、窒素気流下、系全体を回転し粉末を十分に
攪拌しながら320℃まで6時間かかって徐々に昇温し
320℃で3時間処理した後、冷却し200℃で粉末を
とり出した。The recovered amount was 1570 f (>93.1% of the theoretical amount). After pulverizing the ξ, it was transferred to an aluminum rotary oven and heated at 320°C under a nitrogen stream while rotating the entire system and thoroughly stirring the powder. The temperature was gradually increased over 6 hours until the temperature reached 320°C for 3 hours, and then the powder was cooled and taken out at 200°C.
得られた粉末は1540 Fであった。このポリマーを
田辺プラスチック機械製単軸押出機V!5−30−28
(スクリュー径30■、L/D〜28)を用いて、シ
リンダ一温度320℃、スクリュー回転数5Qrpmで
造粒した後住友重機械製射出成形機ネオマy ) N4
7/2B により射出成形した。種々の金型を用いて
バー70−流動長を測定したりダンベル型試験片、アイ
ゾツト衝撃強度試験片を成形し、それぞれの物性値を測
定した。The resulting powder had a temperature of 1540F. This polymer is processed using Tanabe Plastic Machinery's single-screw extruder V! 5-30-28
(Screw diameter 30cm, L/D ~ 28), after granulation at a cylinder temperature of 320°C and screw rotation speed of 5Qrpm, an injection molding machine manufactured by Sumitomo Heavy Industries (Neomy) N4
7/2B was injection molded. Using various molds, the flow length of the bar 70 was measured, and dumbbell-shaped test pieces and Izot impact strength test pieces were molded, and the physical properties of each were measured.
結果を表1に示す。以下に述べる比較例1〜3に比べて
成形温度範囲が広くかつ比較的低温で成形できることが
わかる。また成形品の外観もなめらかで物性値の成形温
度依存性も小さい。The results are shown in Table 1. It can be seen that the molding temperature range is wider than in Comparative Examples 1 to 3 described below, and molding can be performed at a relatively low temperature. In addition, the appearance of the molded product is smooth, and the dependence of physical properties on molding temperature is small.
比較例1
実施例1において、ポリエーテルスルホンを全く用いず
に行なった以外は実施例1と同様番こして重合及び後処
理を行ない、全芳香族lリエステ/L/1412炉(理
論値の93.0チ)を得た。このものを実施例1と同様
番こ造粒、射出成形した。結果を表I IC示す。実施
例1に比べると成形温度範囲が狭く、またより高温を必
要とする。成形品には配向がみられ、物性値は全体に高
いか成形温度依存性は実施例1より大きい。Comparative Example 1 Polymerization and post-treatment were carried out in the same manner as in Example 1, except that no polyether sulfone was used at all. .0chi) was obtained. This product was granulated and injection molded in the same manner as in Example 1. The results are shown in Table IIC. Compared to Example 1, the molding temperature range is narrower and a higher temperature is required. Orientation was observed in the molded product, and the physical property values were generally high or the molding temperature dependence was greater than in Example 1.
比較例2
比較例1で得られた全芳香族ポリエステル900Fに実
施例1で用いたポリエーテルスルホン100 Fをスー
パーミキサーを用いて混合攪拌した。得られたポリマー
を実施例1と同様にして造粒、射出成形した。結果を表
1魯ζ示す。比較例1に比べるとやや成形温度範囲は広
いが、実施例1よりは狭くまた成形品は不均一で高温成
形では一部焼けがみられる。Comparative Example 2 The fully aromatic polyester 900F obtained in Comparative Example 1 was mixed with the polyether sulfone 100F used in Example 1 using a super mixer. The obtained polymer was granulated and injection molded in the same manner as in Example 1. The results are shown in Table 1. Although the molding temperature range is slightly wider than that of Comparative Example 1, it is narrower than that of Example 1, and the molded product is non-uniform, with some burns observed during high-temperature molding.
また物性値は全体に低い。In addition, the physical property values are generally low.
比較例3
バラアセトキシ安息香酸900 F (5,0モA/)
、テレフタル酸415 f (2,5モル)、4,4′
−ジヒロドキシジフェニルージアセチ〃化物675F(
2,5モ/L/)、ポリエーテルスルホン(インペリア
ルケミカルインダストリーズ社製 ピクトレックス10
0P) 154 F (最終生成ポリマーの10重量
優に相当する)及び高沸点溶媒としてサントサーム66
(三菱モンサント化成社製) 14oo Fを反応器
中に入れ、窒素ガス雰囲気中でこれらの混合物をたえず
攪拌しながら1時間で180℃まで加温し、さらに10
時間かかって320℃まで上昇させた。Comparative Example 3 Baracetoxybenzoic acid 900 F (5.0 moA/)
, terephthalic acid 415 f (2,5 mol), 4,4'
-dihydroxydiphenyl diacetide 675F (
2,5 mo/L/), polyether sulfone (Pictrex 10 manufactured by Imperial Chemical Industries)
0P) 154 F (corresponding to well over 10% by weight of the final product polymer) and Santotherm 66 as a high boiling solvent.
(manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) 14oo F was placed in a reactor, and the mixture was heated to 180°C in 1 hour with constant stirring in a nitrogen gas atmosphere.
It took a while to raise the temperature to 320°C.
攪拌をなお320℃で16時間続け、ついで340℃で
3時間加熱することによりスラリーが形成された。反応
混合物を放冷して、さらにサントサーム66を1000
g加え、70℃とした。アセトンを1920 9加え
スラリーを一過し粉末を7七トンによりソックスレー抽
出してサントサーム88を除去した。この粉末を110
℃で5時間減圧乾燥しはリマー1340F(理論量の8
6.8 % )を得た。 この粉末をアIvミ製のp−
タリーオーブンに移し窒素気流下、系全体を回転し粉末
を十分攪拌しながら200℃で10時間保った後、30
0℃まで6時間かかって徐々に昇温し、この温度で2時
間保った後、200℃まで冷却し粉末をとりだした。こ
のグリマーを実施例1と同様に造粒、射出成形した。結
果を表1に示す。成形温度範囲は比較例2とほぼ同じで
、実施例1より狭い。また成形品は不均一で高温で成形
すると焼けが見られる。また物性値も実施例1に比べる
と低い。Stirring was continued for another 16 hours at 320°C, followed by heating at 340°C for 3 hours to form a slurry. The reaction mixture was allowed to cool, and 1000% of Santotherm 66 was added.
g was added and the temperature was set at 70°C. Acetone was added at 1,920 liters, the slurry was passed through, and the powder was Soxhlet-extracted with 7,7 tons to remove Santotherm 88. 110% of this powder
Dry under reduced pressure at ℃ for 5 hours.
6.8%). This powder was added to the p-
Transferred to a tally oven and kept at 200°C for 10 hours while rotating the entire system under nitrogen flow and thoroughly stirring the powder, and then
The temperature was gradually raised to 0°C over 6 hours, maintained at this temperature for 2 hours, and then cooled to 200°C and the powder was taken out. This glimmer was granulated and injection molded in the same manner as in Example 1. The results are shown in Table 1. The molding temperature range is almost the same as Comparative Example 2 and narrower than Example 1. Also, the molded product is uneven and burns can be seen when molded at high temperatures. Moreover, the physical property values are also lower than those of Example 1.
実施例2
実施例1と同様の方法で、実施例1で用いたポリエーテ
ルスルホンが最終生成ポリマーペレットを得た。種々の
金型を用いてダンベル型試験片、アイゾツト衝撃強度試
験片、ウニ〃ド強度試験片及び熱変形温度測定用試験片
を射出成形し、それぞれの物性値を測定した。結果を表
2に示す。比較のためにポリエーテルスルホンが0.5
0 %の場合も示した。Example 2 In the same manner as in Example 1, polyether sulfone used in Example 1 was used to obtain final product polymer pellets. Dumbbell-shaped test pieces, Izot impact strength test pieces, sea urchin strength test pieces, and heat distortion temperature measurement test pieces were injection molded using various molds, and the physical properties of each were measured. The results are shown in Table 2. For comparison, polyether sulfone is 0.5
The case of 0% is also shown.
ポリエーテルスルホンにより成形品の外観が改良される
と共に、種々の物性、特にウェルド部の強度が大幅に改
良されている仁とがわかる。また物性値の成形温度依存
性も小さくなっている。ポリエーテルスルホンが最終生
成がリマーの50Wt*となれば、外観は良好であるが
、物性値が全体に低くなる。It can be seen that polyether sulfone improves the appearance of the molded product and also significantly improves various physical properties, especially the strength of the weld area. Furthermore, the dependence of physical properties on molding temperature is also reduced. If the final product of polyether sulfone is 50 Wt* of Rimer, the appearance will be good, but the physical properties will be lower overall.
実施例3
実施例1と同様の装置にパラヒドロキシ安息香酸112
2 f (8,13モル)、テレフタμ酸450 f
(2,71モル)、4.4′−ジヒドロキシジフェニル
504 f (2,71モ/L/)ポリスμホン(U、
C,C0社製 P−1700) 458.79 (最終
生成ポリマーの20重量優に相当する。)、無水酢酸1
659 fを投入した。実施例1と同様にして以後の操
作を行ないポリマー2112 F(理論値の92.1
% )を得た。このポリマーを実施例1と同様に造粒、
射出成形し、物性値を測定した。結果を表3に示す。Example 3 Parahydroxybenzoic acid 112 was added to the same apparatus as in Example 1.
2 f (8,13 mol), terephthalic acid 450 f
(2,71 mol), 4,4'-dihydroxydiphenyl 504 f (2,71 mol/L/) polyμphone (U,
P-1700 manufactured by C, C0) 458.79 (corresponds to over 20% by weight of the final polymer), 1 acetic anhydride
I invested 659 f. The subsequent operations were carried out in the same manner as in Example 1 to obtain polymer 2112F (theoretical value of 92.1
%) was obtained. This polymer was granulated in the same manner as in Example 1,
It was injection molded and its physical properties were measured. The results are shown in Table 3.
実施例4
実施例1と同様の装置にバラヒドロキシ安息香酸751
(5,48%/L/)、ftz7タAz酸453F (
2,73モ/!/)、4.4’−ジヒドレキシジフx、
二1v4101 (2,20’E: /’ )、ハイ
ドロキノン59.4 t (0,54モ/L/)、ポリ
エーテルスルホン(インペリアμヶ電力μインダストリ
ーズ社製 ピクトレックス 200P ) 369F
(最終生成ポリマーの20重量%に相当する。)、無−
氷酢酸1337 F (13,1モ/I/)を投入した
。Example 4 Rose hydroxybenzoic acid 751 was added to the same apparatus as in Example 1.
(5,48%/L/), ftz7taaz acid 453F (
2,73 mo/! /), 4.4'-dihydrexidif x,
21v4101 (2,20'E: /'), hydroquinone 59.4 t (0,54 mo/L/), polyether sulfone (Pictrex 200P manufactured by Imperia μ Industries) 369F
(corresponding to 20% by weight of the final produced polymer), no-
Glacial acetic acid 1337 F (13,1 mo/I/) was charged.
実施例1と同様にして以後の操作を行ないポリマーを得
た。The subsequent operations were carried out in the same manner as in Example 1 to obtain a polymer.
仁の一すマー6001 Kガラス繊維400 Fを混ぜ
、はぼ淘−に分散させたのち造粒、射出成形した。結果
を表4に示す。Jin's Issumer 6001K glass fiber 400F was mixed and dispersed in Habo-shu, followed by granulation and injection molding. The results are shown in Table 4.
Claims (1)
lo、 −*−8−または−CO−であり、m 、 m
は0または1である。dHeの比は1:1から10:1
の範囲にあり、e:tの比は9:10から10:9の聞
書とある。 また上式中の芳香環の置換基は互いにパラまたはメタの
位置にある。) であられされる全芳香族ポリエステルの製造時に1重合
反応系に芳嘗族ポリスμホンを最終生成lリマ−の6〜
40重量−となるような割合で存在曽しめかつ重合を実
質的に溶媒を存在させない塊状重合法で行なうことを特
徴とする芳香族ポリエステルの製造方法。[Claims] General formula: (In the above formula, X is a C-C4 alkyl μ group, -0-, m1
lo, -*-8- or -CO-, m, m
is 0 or 1. The ratio of dHe is 1:1 to 10:1
The e:t ratio is said to be in the range of 9:10 to 10:9. Furthermore, the substituents on the aromatic ring in the above formula are in para or meta positions with respect to each other. ) During the production of a fully aromatic polyester, an aromatic polyphonic acid is added to the polymerization reaction system to form a final product.
A method for producing an aromatic polyester, characterized in that the aromatic polyester is present in a proportion of 40% by weight, and the polymerization is carried out by a bulk polymerization method substantially in the absence of a solvent.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12286181A JPS5823824A (en) | 1981-08-04 | 1981-08-04 | Preparation of aromatic polyester |
US06/356,241 US4414365A (en) | 1981-03-16 | 1982-03-08 | Process for producing an aromatic polyester composition |
EP82102011A EP0060531B2 (en) | 1981-03-16 | 1982-03-12 | A process for producing an aromatic polyester composition |
DE8282102011T DE3268220D1 (en) | 1981-03-16 | 1982-03-12 | A process for producing an aromatic polyester composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12286181A JPS5823824A (en) | 1981-08-04 | 1981-08-04 | Preparation of aromatic polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5823824A true JPS5823824A (en) | 1983-02-12 |
JPH0139450B2 JPH0139450B2 (en) | 1989-08-21 |
Family
ID=14846444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12286181A Granted JPS5823824A (en) | 1981-03-16 | 1981-08-04 | Preparation of aromatic polyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5823824A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4748394A (en) * | 1985-06-18 | 1988-05-31 | Mitsubishi Denki Kabushiki Kaisha | Control apparatus for escalator |
-
1981
- 1981-08-04 JP JP12286181A patent/JPS5823824A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4748394A (en) * | 1985-06-18 | 1988-05-31 | Mitsubishi Denki Kabushiki Kaisha | Control apparatus for escalator |
Also Published As
Publication number | Publication date |
---|---|
JPH0139450B2 (en) | 1989-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0060531B2 (en) | A process for producing an aromatic polyester composition | |
DE3000610C2 (en) | Process for the production of aromatic polyesters | |
US4313870A (en) | Process for producing polycondensates | |
EP0019242B1 (en) | A process for producing oxybenzoyl copolyesters | |
US3884876A (en) | Partially crosslinked linear aromatic polyesters | |
JPH1081739A (en) | Polyester resin and its production | |
US3479318A (en) | Mouldable polyester compositions containing finely divided pyrophyllite | |
KR100722949B1 (en) | High Heat-resistance Wholly Aromatic Polyester Composition and Manufacturing Method thereof | |
CN111393823B (en) | Gn-PET/PC alloy with excellent mechanical property and preparation method thereof | |
JPH024608B2 (en) | ||
EP0357079B1 (en) | Process for producing aromatic polyesters | |
JPS5823824A (en) | Preparation of aromatic polyester | |
US4560740A (en) | Method for producing aromatic polyesters | |
JPH0696668B2 (en) | Resin composition | |
JPS6221808B2 (en) | ||
JPH024610B2 (en) | ||
JP2838119B2 (en) | Manufacturing method of aromatic polyester | |
US3849362A (en) | Incorporation of fillers in insoluble,infusible oxybenzoyl polymers | |
JPH0139451B2 (en) | ||
JPH01292057A (en) | Polymer composition | |
JPS6221809B2 (en) | ||
JPH02189360A (en) | Polymer composition and article obtained therefrom | |
JPS62240353A (en) | Molding resin composition | |
US20230026150A1 (en) | Polyether ketone ketone and a process for preparation thereof | |
US4268431A (en) | Colorant-thickener dispersions for unsaturated polyester resin compositions |