JPS629611B2 - - Google Patents
Info
- Publication number
- JPS629611B2 JPS629611B2 JP10587877A JP10587877A JPS629611B2 JP S629611 B2 JPS629611 B2 JP S629611B2 JP 10587877 A JP10587877 A JP 10587877A JP 10587877 A JP10587877 A JP 10587877A JP S629611 B2 JPS629611 B2 JP S629611B2
- Authority
- JP
- Japan
- Prior art keywords
- acid chloride
- terephthalic acid
- liquid
- continuous
- self
- 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.)
- Expired
Links
- 239000007788 liquid Substances 0.000 claims description 66
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 30
- -1 N-substituted amide Chemical class 0.000 claims description 27
- 125000003277 amino group Chemical group 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000004140 cleaning Methods 0.000 claims description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 69
- 239000000243 solution Substances 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 239000000178 monomer Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000457 gamma-lactone group Chemical group 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Landscapes
- Polyamides (AREA)
Description
【発明の詳細な説明】
本発明は、ポリパラフエニレンテレフタルアミ
ドの新規な、かつ工業的規模で実施しうる連続製
造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new continuous process for the production of polyparaphenylene terephthalamide which can be carried out on an industrial scale.
ポリパラフエニレンテレフタルアミドはアミド
基が芳香族環のパラ位に結合したくり返しからな
り、その成形品が耐熱性、高強力等の優れた機械
的性質を持つポリマーとして非常に有用であり、
各方面への幅広い用途が期待されている。 Polyparaphenylene terephthalamide is composed of repeating amide groups bonded to the para-position of an aromatic ring, and its molded products are extremely useful as polymers with excellent mechanical properties such as heat resistance and high strength.
It is expected to have a wide range of applications in various fields.
ポリパラフエニレンテレフタルアミドの製造
は、一般的に高重合度のポリマーを得るために、
Ｎ−置換アミド型溶媒中でテレフタル酸クロライ
ドとパラフエニレンジアミンとを低温重縮合する
ことで行なわれる。 The production of polyparaphenylene terephthalamide generally involves the following steps to obtain a polymer with a high degree of polymerization:
This is carried out by low-temperature polycondensation of terephthalic acid chloride and paraphenylenediamine in an N-substituted amide type solvent.
この低温重縮合においては、重合開始より重合
終了までの間に液相、固相、粉体状と三段階の相
変化を示す上に、液相から固相への相変化が極め
て早く、重合開始より急激に粘度が上がり２〜３
分で固化してしまう。またこの重合系の特徴でも
あるが、固相をさらに撹拌して微粉末にすること
によつてさらに重合が進み、実用的水準の重合度
のポリマーとなるのである。 In this low-temperature polycondensation, there are three phase changes from the start of polymerization to the end of polymerization: liquid, solid, and powder. The viscosity increases rapidly from the start, 2-3
It will solidify in minutes. Another feature of this polymerization system is that by further stirring the solid phase to form a fine powder, the polymerization progresses further, resulting in a polymer with a practical level of polymerization.
このような急激な相変化を示し、且つ各々の相
又は状態に適した有効な撹拌効果を付与すること
を要求される重合系においては、回分式重合に比
べて、各々の相に要求される機能に対応した装置
を組合せることのできる連続重合の方がはるかに
有利かつ合理的である。また、回分式重合に比べ
連続重合の方が生産されるポリマーの重合度分布
の小さな良質のポリマーが得られることが期待さ
れるだけでなく回分式の場合より大幅に省力化で
きる可能性が大であることなどから、ポリパラフ
エニレンテレフタルアミドの連続製造法の開発が
熱望されてきた。 In a polymerization system that shows such a rapid phase change and is required to provide an effective stirring effect suitable for each phase or state, compared to batch polymerization, the amount of water required for each phase is Continuous polymerization is much more advantageous and rational because it allows for combination of equipment corresponding to different functions. In addition, continuous polymerization is not only expected to yield higher quality polymers with a narrower polymerization degree distribution than batch polymerization, but also has the potential to significantly save labor compared to batch polymerization. Therefore, there has been a great deal of enthusiasm for the development of a continuous production method for polyparaphenylene terephthalamide.
ところが、ポリパラフエニレンテレフタルアミ
ドに連続重合させようとしたとき、テレフタル酸
クロライドとパラフエニレンジアミンとは相当厳
密にモル比管理をして供給しないと望ましい重合
度のポリマーを安定して得ることが困難であるに
もかかわらず、これらの両モノマーの連続供給精
度は現在市販されている連続供給機、例えば定量
ポンプや定量連続粉体フイーダー等ではやや不足
気味であることと、従来の連続重合装置におい
て、長時間運転すると、混合及び初期重合させる
工程にスケールが付着生成することの２つの問題
点があつた。 However, when trying to continuously polymerize polyparaphenylene terephthalamide, it is difficult to stably obtain a polymer with a desired degree of polymerization unless the molar ratio of terephthalic acid chloride and paraphenylenediamine is controlled very strictly. Although it is difficult to continuously supply these monomers, the accuracy of continuous feeding of these monomers is somewhat insufficient with currently commercially available continuous feeders, such as metering pumps and metering continuous powder feeders, and conventional continuous polymerization When the apparatus is operated for a long period of time, there are two problems: scale is formed during the mixing and initial polymerization steps.
このような問題点をかかえているポリパラフエ
ニレンテレフタルアミドの連続重合法において、
本発明者らは先に特願昭50−65254号（特開昭51
−142100号）にてプレポリマー、即ち、
を作り、これとテレフタル酸クロライドを連続的
に反応させることにより連続定量精度の問題は基
本的に解決されることを示した。一方、米国特許
第3849074号及び同、第3850888号によると、重合
開始時の両モノマー液の混合を、両モノマー液を
噴射ノズルより「等質量速度」で噴出し、衝突せ
しめることによつて行い、スケールの生成を空中
プランジヤーで掃除する構造の混合機及びこの混
合機を利用したポリパラフエニレンテレフタルア
ミドの連続製造法が提案されている。ところが、
この装置及び方法では、スケールの生成がたえま
なく起こり、従つて掃除用のプランジヤーをほと
んど常時作動させる必要があつて操作が繁雑であ
り、その他「等質量速度」にするため両モノマー
の供給に関する制御が難しいなどの欠点を有して
いる。 In the continuous polymerization method of polyparaphenylene terephthalamide, which has such problems,
The present inventors previously filed Japanese Patent Application No. 50-65254.
-142100), prepolymers, i.e. It was shown that the problem of continuous quantitative accuracy can be basically solved by making and continuously reacting this with terephthalyl chloride. On the other hand, according to U.S. Pat. No. 3,849,074 and U.S. Pat. No. 3,850,888, both monomer liquids are mixed at the start of polymerization by jetting both monomer liquids at "equal mass velocity" from a jet nozzle and causing them to collide. , a mixer with a structure in which scale formation is cleaned with an aerial plunger, and a method for continuous production of polyparaphenylene terephthalamide using this mixer have been proposed. However,
In this apparatus and method, scale formation occurs constantly, the cleaning plunger must be operated almost constantly, the operation is complicated, and the supply of both monomers is complicated to achieve an "equal mass rate." It has drawbacks such as difficulty in control.
本発明者らはこのような事情に鑑み、初期撹拌
工程において、スケールの生成がなくかつ初期混
合が必要十分におこなわれるポリパラフエニレン
テレフタルアミドの連続重合システムの開発に努
めるうちに、意外にも特別の初期撹拌装置を設け
ずに、セルフクリーニング型連続混合機のセルフ
クリーニング面にモノマー液を特別な方法で供給
する方法によつてこの問題が基本的に解決するこ
と、特にモノマー液の供給線速度を一定値以上に
したとき高重合度のポリマーが得られることを見
出し、先に特許出願した。一方、モノマー液の供
給線速度を或る値以下にしたとき、得られるポリ
マーの重合度は小さくなつたり、むらができたり
するものの、モノマー液を特別なセルフクリーニ
ング面に供給した場合には、重合度はやや小さい
が依然実用的水準にあり、しかもこのようにして
得られるポリマーは意外にも極めて耐硫酸性に優
れていることを発見し、さらに検討を重ねて本発
明として完成させたものである。 In view of these circumstances, the present inventors made an effort to develop a continuous polymerization system for polyparaphenylene terephthalamide in which there is no scale formation in the initial stirring step and sufficient initial mixing is performed. However, this problem can basically be solved by a special method of supplying the monomer liquid to the self-cleaning surface of the self-cleaning continuous mixer without installing a special initial stirring device, especially when supplying the monomer liquid. They discovered that a polymer with a high degree of polymerization could be obtained by increasing the linear velocity above a certain value, and filed a patent application earlier. On the other hand, when the linear velocity of the monomer liquid is lowered below a certain value, the degree of polymerization of the resulting polymer decreases or becomes uneven; however, when the monomer liquid is supplied to a special self-cleaning surface, Although the degree of polymerization is somewhat low, it is still at a practical level, and it was discovered that the polymer obtained in this way has surprisingly excellent sulfuric acid resistance, and after further investigation, the present invention was completed. It is.
即ち本発明は、式
（式中、ｎは系内の全分子の数平均値で、０≦ｎ
≦３を示す）で表わされるモノマー又はオリゴマ
ーとＮ−置換アミド型溶剤よりなるアミノ基含有
液と液状テレフタル酸クロライドとを、芳香族ア
ミノ基と芳香族カルボン酸クロライド基とのモル
比が一定値になるように、セルフクリーニング型
２軸連続混合機の２つの回転軸中心に挟まれた区
域のセルフクリーニング面に前記両液を平均線速
度100cm／sec以下で連続的に直接供給し、セルフ
クリーニング型連続２軸混合機にて粉体になるま
で、混練し連続重合させるのである。このよう
に、混合及び初期重合専用の工程を特別に設け
ず、重合機中にこれらの工程を含ませることによ
つて、装置が大幅に簡素化し、操作も簡単になり
運転の管理がやりやすくなる。また、両液（アミ
ノ基含有液と液状テレフタル酸クロライド）を直
接セルフクリーニング面に供給するための従来の
連続重合機では避けられなかつたスケールの付着
生成を完全に防ぐことができる。 That is, the present invention is based on the formula (In the formula, n is the number average value of all molecules in the system, 0≦n
≦3) and an amino group-containing liquid consisting of an N-substituted amide type solvent and liquid terephthalic acid chloride, the molar ratio of the aromatic amino group to the aromatic carboxylic acid chloride group is a constant value. Both liquids are continuously and directly supplied to the self-cleaning surface in the area sandwiched between the two rotating shafts of the self-cleaning two-shaft continuous mixer at an average linear velocity of 100 cm/sec or less to achieve self-cleaning. The mixture is kneaded and continuously polymerized in a continuous twin-screw mixer until it becomes a powder. In this way, by including these processes in the polymerization machine instead of providing special processes for mixing and initial polymerization, the equipment can be greatly simplified, and operation can be simplified and operations can be easily managed. Become. Furthermore, it is possible to completely prevent the formation of scale adhesion, which was unavoidable in conventional continuous polymerization machines in which both liquids (amino group-containing liquid and liquid terephthalic acid chloride) are directly supplied to the self-cleaning surface.
本発明の特徴は、上述のように両液を直接重合
機のセルフクリーニング面に供給することによつ
てスケールの付着生成をふせぐことにあるのであ
るが、両液の供給線速度が大きい場合、重合度の
大きいポリマーが得られやすいという利点があ
る。一方、両液の供給線速度を小さくした場合重
合度が少し低かつたり、重合度に経時的にむらが
あつたりすることが多いが、意外なことに得られ
るポリマーの耐硫酸性、つまり硫酸溶液中におけ
る安定性が非常に良い。この原因は詳細には判つ
ていないが、多分、未反応モノマーや低分子両オ
リゴマーの含有量が極めて少ないことが、一つの
原因になつているのであろう。 As mentioned above, the feature of the present invention is to prevent the formation of scale adhesion by directly supplying both liquids to the self-cleaning surface of the polymerization machine. However, when the linear velocity of supply of both liquids is high, It has the advantage that it is easy to obtain a polymer with a high degree of polymerization. On the other hand, when the linear velocity of both liquids is reduced, the degree of polymerization tends to be a little low or the degree of polymerization becomes uneven over time, but surprisingly, the sulfuric acid resistance of the resulting polymer Very good stability in solution. Although the cause of this is not known in detail, one of the causes is probably that the content of unreacted monomers and low molecular weight oligomers is extremely low.
換言すれば、供給線速度の大きい場合、両液の
謂ゆるミクロ混合が優れているのに対し、供給線
速度が小さい場合、謂ゆるマクロ混合に優れてい
るのではないかと推定される。なお、実用的レベ
ル重合度のポリマーを重合度の経時的なむらを少
なくして得るには、両液の供給方法に特別な工夫
を加える必要がある。即ち、セルフクリーニング
型２軸連続混合機の２つの回転軸中心に挟まれた
区域のセルフクリーニング面に供給されるべきで
ある。前記両液の具体的な供給線速度として100
cm／sec以下に選ばれるべきであり、好ましくは
80cm／sec以下である。 In other words, it is presumed that when the supply linear velocity is high, so-called micro-mixing of both liquids is excellent, whereas when the supply linear velocity is low, so-called macro-mixing is excellent. Note that in order to obtain a polymer with a practical level of polymerization degree while reducing unevenness in the degree of polymerization over time, it is necessary to add special measures to the method of supplying both liquids. That is, it should be supplied to the self-cleaning surface of the self-cleaning two-shaft continuous mixer in the area sandwiched between the two rotating shafts. 100 as the specific linear velocity of supply of both liquids.
cm/sec or less, preferably
It is 80cm/sec or less.
また、両液の供給量は重合機の重合物の吐出可
能量よりも大きくならないようにする必要があ
る。吐出可能量よりも供給量が多いと重合供給中
のセルフクリーニング面にも重合物がたまつてく
るため、モノマー又はオリゴマーの混合むらがで
きたり、両液の供給ラインに大きな圧力がかかつ
たり、両液の導入口が詰まつたりすることが起こ
るからである。 Further, it is necessary to ensure that the amount of both liquids supplied does not exceed the amount that the polymerization machine can discharge. If the amount supplied is larger than the amount that can be discharged, the polymer will accumulate on the self-cleaning surface during polymerization and supply, resulting in uneven mixing of monomers or oligomers, or large pressure will be applied to the supply lines for both liquids. This is because the inlets for both liquids may become clogged.
重合機への供給線速度とは、重合機入口におけ
る単位時間当りの導入液量（体積／時間で表わさ
れる）を導入口の断面積で除した商で表わされる
量である。 The linear velocity of supply to the polymerization machine is the amount expressed by the quotient of the amount of liquid introduced per unit time (expressed in volume/time) at the inlet of the polymerization machine divided by the cross-sectional area of the introduction port.
次に、本発明の方法によるポリパラフエニレン
テレフタルアミドの連続重合を操作の順に従つて
説明する。 Next, the continuous polymerization of polyparaphenylene terephthalamide according to the method of the present invention will be explained in the order of operations.
本発明の方法で連続重合する場合、まずアミノ
基含有液と液状テレフタル酸クロライドを各々別
固に調製する必要がある。 When carrying out continuous polymerization using the method of the present invention, it is first necessary to separately prepare the amino group-containing liquid and the liquid terephthalic acid chloride.
本発明にいうアミノ基含有液とは、
（式中、ｎは系内全分子の数平均値を意味し、０
≦ｎ≦３）とＮ−置換アミド型溶剤とより成る溶
液組成物のことである。ここで、ｎ＝０の、即ち
パラフエニレンジアミン溶液の場合は、Ｎ−置換
アミド型溶剤にパラフエニレンジアミンを溶解し
て調製することができる。また０≦ｎ≦３のいわ
ゆるオリゴマー溶液の場合は、Ｎ−置換アミド型
溶剤にパラフエニレンジアミン及びパラフフエニ
レンジアミン１モルに対してｎ／（ｎ＋１）モル
のテレフタル酸クロライドを溶解して調製するこ
とができる。 The amino group-containing liquid according to the present invention is (In the formula, n means the number average value of all molecules in the system, and 0
≦n≦3) and an N-substituted amide type solvent. Here, in the case of n=0, that is, a paraphenylenediamine solution, it can be prepared by dissolving paraphenylenediamine in an N-substituted amide type solvent. In the case of a so-called oligomer solution where 0≦n≦3, paraphenylenediamine and n/(n+1) mol of terephthalic acid chloride per 1 mol of paraphenylenediamine are dissolved in an N-substituted amide type solvent. It can be prepared.
ここで、パラフエニレンジアミン溶液を使用す
る場合とオリゴマー溶液を使用する場合の特徴を
比較すると、前者の場合、溶液の調製は簡単であ
るが、パラフエニレンジアミンとテレフタル酸ク
ロライドのモル比の管理がややしづらい、後者は
この逆である。両者とも基本的には本発明の方法
に採用でき、連続重合に関する細部の条件等より
決定すればよい。 Here, when comparing the characteristics of using a paraphenylene diamine solution and using an oligomer solution, in the former case, the solution preparation is easy, but the molar ratio of paraphenylene diamine and terephthalic acid chloride is The latter is the opposite, as it is a little more difficult to manage. Both can basically be employed in the method of the present invention, and may be determined based on detailed conditions regarding continuous polymerization.
オリゴマー溶液を使用するとき、オリゴマー
におけるオリゴマー溶液内の全分子の数平均値と
して０≦ｎ≦３である。ｎは上限が存在する理由
は、ｎがあまり大きくなるとオリゴマー溶液の粘
度が大きくなつて連続定量供給機がその能力を十
分に発揮しなくなる恐れがあること、また、オリ
ゴマー溶液が沈澱したりゲル化したりすることが
あるからである。 When using an oligomer solution, the oligomer The number average value of all molecules in the oligomer solution is 0≦n≦3. The reason why there is an upper limit for n is that if n becomes too large, the viscosity of the oligomer solution will increase and the continuous metering feeder may not be able to fully demonstrate its capacity, and the oligomer solution may precipitate or gel. This is because there are times when
アミノ基含有液の溶剤として用いられるＮ−置
換アミド型溶剤としては、ヘキサメチルフオスフ
オルアミド、Ｎ−メチル−２−ピロリドン、Ｎ・
Ｎ−ジメチルアセトアミド、Ｎ−アセチルピロリ
ジンなどが挙げられる。また、これらの単独又は
混合溶剤に塩化カルシウムや塩化リチウムなどの
無機塩を添加した系やγ−ブチロラクトン、γ−
バレロラクトンなどのγ−ラクトン類やクロロホ
ルムなどの溶剤を添加した系なども用いられてよ
い。無機塩を添加した系を用いる時は、無機塩が
完溶していることが好ましいが、微細なスラリー
で分散していても使用不可能ではない。 N-substituted amide type solvents used as solvents for amino group-containing liquids include hexamethylphosphoramide, N-methyl-2-pyrrolidone, N.
Examples include N-dimethylacetamide and N-acetylpyrrolidine. In addition, systems in which inorganic salts such as calcium chloride and lithium chloride are added to these solvents alone or in combination, γ-butyrolactone, γ-
A system to which a γ-lactone such as valerolactone or a solvent such as chloroform is added may also be used. When using a system containing an inorganic salt, it is preferable that the inorganic salt is completely dissolved, but it is not impossible to use the system even if the inorganic salt is dispersed in a fine slurry.
これらの中で特に好ましく用いられる溶剤系
は、モノマーやオリゴマーの溶解性、副反応の少
ないなどの点から、ヘキサメチルフオスフオルア
ミドとＮ−メチル−２−ピロリドン又はγ−ラク
トン類との混合物、Ｎ−メチル−２−ピロリドン
に塩化カルシウム又は塩化リチウムを添加して溶
解、分散した系、Ｎ・Ｎ−ジメチルアセトアミド
に塩化カルシウム又は塩化リチウムを添加して溶
解、分散した系、Ｎ−アセチルピロリジンに塩化
カルシウム又は塩化リチウムを添加して溶解、分
散した系である。 Among these, a particularly preferred solvent system is a mixture of hexamethylphosphoramide and N-methyl-2-pyrrolidone or γ-lactones, from the viewpoint of solubility of monomers and oligomers, low side reactions, etc. , a system in which calcium chloride or lithium chloride is added to N-methyl-2-pyrrolidone and dissolved and dispersed, a system in which calcium chloride or lithium chloride is added to N-dimethylacetamide and dissolved and dispersed, N-acetylpyrrolidine This is a system in which calcium chloride or lithium chloride is added to and dissolved and dispersed.
アミノ基含有液はその安定性などの点より−10
〜60℃で用いるのが好ましい。 Amino group-containing liquids have −10
Preferably it is used at ~60°C.
一方、液状テレフタル酸クロライドとしては、
テレフタル酸クロライドの溶融液、テレフタル酸
クロライドをＮ−メチル−２−ピロリドンに溶解
した溶液、テレフタル酸クロライドをγ−ラクト
ン類、例えばγ−ブチロラクトンなどに溶解した
溶液などが用いられる。テレフタル酸クロライド
は、元来相当に化学的活性の大きい化合物である
ためその安定性が問題になり易く、固体状態が最
も安定性に優れているので、これらの面からこれ
を粉末状態で重合機に供給するのが最も望ましい
が、粉体をはじめ固体状態での連続定量供給は、
現在の工業水準では液体状態のそれに比べ相当に
劣るため、モノマーのモル比を厳しく管理するこ
とを要求される本発明の連続重合には適さない。 On the other hand, as liquid terephthalic acid chloride,
A melt of terephthalic acid chloride, a solution of terephthalic acid chloride dissolved in N-methyl-2-pyrrolidone, a solution of terephthalic acid chloride dissolved in γ-lactones such as γ-butyrolactone, etc. are used. Since terephthalic acid chloride is originally a compound with considerable chemical activity, its stability tends to be a problem, and since it is most stable in a solid state, from these points of view it is difficult to use it in a polymerization machine in a powder state. However, continuous quantitative supply of powder or other solid state is most desirable.
At the current industrial level, it is considerably inferior to that in a liquid state, and therefore is not suitable for the continuous polymerization of the present invention, which requires strict control of the molar ratio of monomers.
テレフタル酸クロライドを溶融した場合、その
安定性などより85〜110℃で用いるのがよい。一
方、テレフタル酸クロライドを他の溶剤に溶かし
た溶液を使用する場合は、−10〜40℃で用いるの
が好ましい。また、このような溶液中のテレフタ
ル酸クロライドの安定性は、溶融液を使用した場
合に比べてやや劣るという欠点を持つが、金属材
料に対する腐食性が小さいこと、アミノ基含有液
との供給量の比を１により近くすることが可能に
なり両液の混合がうまく行なわれるなどの利点を
もつている。 When terephthalic acid chloride is melted, it is preferable to use it at a temperature of 85 to 110°C due to its stability. On the other hand, when using a solution of terephthalic acid chloride dissolved in another solvent, it is preferably used at -10 to 40°C. In addition, the stability of terephthalic acid chloride in such a solution has the drawback that it is slightly inferior to that in the case of using a molten liquid, but it has a disadvantage that it is less corrosive to metal materials, and the supply amount with the amino group-containing liquid is lower. This has the advantage that it is possible to bring the ratio closer to 1, and the two liquids can be mixed well.
このようにして調製されたアミノ基含有液と液
状テレフタル酸クロライドとは、各々連続定量供
給機を経て、芳香族アミノ基と芳香族カルボン酸
クロライド基とのモル比が一定値になるようにセ
ルフクリーニング型２軸連続混合機に連続的に直
接導入される必要がある。ここにいう連続定量供
給機とは、連続的に液を精度よく定量しつつ、２
軸連続混合機に供給しうる機器又はシステムのこ
とであり、汎用の工業用定量輸送機、例えば、プ
ランジヤー式、ダイヤフラム式などの定量ポン
プ、スクリユーフイーダー、定量ヘツド圧供給シ
ステムなどを利用することが出来る。なお、定量
ポンプを使用する場合、ポンプの脈流を防止又は
減少させる意味から、脈流吸収器を使用したり、
いわゆる無脈動型のものを用いるのは好ましい実
施態様の１つである。 The amino group-containing liquid and the liquid terephthalic acid chloride prepared in this way are each passed through a continuous metering feeder and then self-adjusted so that the molar ratio of the aromatic amino group to the aromatic carboxylic acid chloride group becomes a constant value. It must be continuously introduced directly into a cleaning type twin-screw continuous mixer. The continuous metering feeder referred to here refers to the continuous quantitative feeding machine that continuously measures the liquid with high accuracy and
Refers to equipment or systems that can be supplied to a continuous axial mixer, and utilize general-purpose industrial metering conveyance equipment, such as plunger-type, diaphragm-type metering pumps, screw feeders, metering head pressure supply systems, etc. I can do it. When using a metering pump, a pulsating flow absorber should be used to prevent or reduce the pulsating flow of the pump.
One of the preferred embodiments is to use a so-called pulsation-free type.
芳香族アミノ基と芳香族カルボン酸クロライド
基とのモル比を一定にするのは、生産されるポリ
マーの重合度を一定のものにするための要請であ
り、この比がほぼ１であるとき最も高い重合度の
ポリマーが得られる。 Keeping the molar ratio of the aromatic amino group and the aromatic carboxylic acid chloride group constant is a requirement to keep the degree of polymerization of the produced polymer constant, and when this ratio is approximately 1, it is most effective. A polymer with a high degree of polymerization is obtained.
上記のような連続定量供給機によつて供給され
たアミノ基含有液及び液状テレフタル酸クロライ
ドは、これをセルフクリーニング型２軸連続混合
機の２つの回転軸中心に挟まれた区域内のセルフ
クリーニング面に、先にも述べたように、両液を
100cm／sec以下の供給線速度で連続的に直接供給
して重合を開始し、連続混合機即ち重合機中で粉
体状になるまで混練して重合度を高める必要があ
る。 The amino group-containing liquid and liquid terephthalic acid chloride supplied by the continuous metering feeder as described above are self-cleaned in the area sandwiched between the two rotating shafts of the self-cleaning two-shaft continuous mixer. As mentioned earlier, apply both liquids on the
It is necessary to start polymerization by continuously and directly feeding at a linear feed speed of 100 cm/sec or less, and to increase the degree of polymerization by kneading in a continuous mixer, that is, a polymerization machine, until it becomes a powder.
アミノ基含有液及び液状テレフタル酸クロライ
ド含有液の重合機への導入は、混合効果を一層向
上させる目的で、各々の液を２ケ所以上の導入口
より導くことは自由に行なわれてよく、導入口の
配置も特別に制限はない。 When introducing the amino group-containing liquid and the liquid terephthalic acid chloride-containing liquid into the polymerization machine, each liquid may be introduced freely through two or more inlets for the purpose of further improving the mixing effect. There are no particular restrictions on the placement of the mouth.
セルフクリーニング型２軸連続混合機とは米国
3195865号、同じく3198491号、同じく3618902号
などに記されたいわゆる「全表面更新型連続２軸
ニーダー」のことである。「全表面更新型連続２
軸ニーダー」は凸レンズ型又はおむすび型などの
突出部をもつた「パドル」が並行な２軸にとりつ
けられ、一方の軸のパドルの突出部でシリンダー
及び他方の軸の相対するパドルの表面をかきとり
ながら両軸とも同一方向に回転する構造のもの
で、反応物を混練する必要な剪断力はパドル間及
びパドルとシリンダー間で発生させ、一方反応物
の輸送力はいわゆるスクリユーユニツトの導入、
傾斜したパドルの採用、隣接するパドル間の位相
の選択などで発生させることができ、回転方向と
これらの組み合せで送り出し力と捩り力とを自由
に生み出すことが出来る。 What is a self-cleaning twin-shaft continuous mixer?
It refers to the so-called "full surface renewal type continuous two-shaft kneader" described in No. 3195865, No. 3198491, No. 3618902, etc. “Full surface renewal type continuous 2
A "shaft kneader" has "paddles" with protrusions such as a convex lens type or a rice ball shape attached to two parallel shafts, and the protrusion of the paddle on one shaft scrapes the surface of the cylinder and the opposing paddle on the other shaft. However, both shafts rotate in the same direction, and the shearing force necessary to knead the reactants is generated between the paddles and between the paddle and the cylinder, while the transport force of the reactants is generated by the introduction of a so-called screw unit.
This can be generated by using inclined paddles, selecting the phase between adjacent paddles, etc., and it is possible to freely generate feed-out force and torsional force by changing the rotation direction and their combination.
「全表面更新型連続２軸ニーダー」において、
捩り力を生じさせる機構を重合機内に一部採用す
ることによつて、重合機内で反応物の一部をリサ
イクルさせることができ、これによつて高重合度
のポリマー及び重合度分布の小さいポリマーを得
ることが出来る。 In the "full surface renewal type continuous two-axis kneader",
By partially incorporating a mechanism that generates torsional force into the polymerization machine, it is possible to recycle a part of the reactants within the polymerization machine, thereby making it possible to produce polymers with a high degree of polymerization and polymers with a small degree of polymerization distribution. can be obtained.
重合機中での混練時間は、およそ５〜20分の間
に選ばれる。また、混練の強さの程度としては、
剪断速度で表わされて、ほぼ100sec-1以上が１つ
の目安となる。 The kneading time in the polymerizer is chosen between approximately 5 and 20 minutes. In addition, the strength of kneading is as follows:
Expressed in terms of shear rate, one guideline is approximately 100 sec -1 or more.
重合機として、同じものを直列に２機以上組み
合せて構成することも適宜行なわれてよい。 As the polymerization machine, two or more of the same machines may be combined in series as appropriate.
重合機中の滞在時間は、先にも述べたように通
常５〜20分の間に選ばれるが、これの調整は、例
えば、反応物のリサイクル機構の採用、混練ハネ
の回転速度、重合機出口の開度、反応物の供給
量、重合機の段数などで行うことが出来る。 As mentioned above, the residence time in the polymerization machine is usually selected between 5 and 20 minutes, but this can be adjusted by, for example, adopting a reactant recycling mechanism, the rotation speed of the kneading blades, and the polymerization machine. This can be controlled by adjusting the opening degree of the outlet, the amount of reactants supplied, the number of stages of the polymerization machine, etc.
重合機中の反応物の温度が80℃以上になると高
重合度のポリマーを得る上で障害となる副反応が
しばしば起こるので約80℃以下にするのが好まし
い。この条件を満たすために、水、その他冷媒を
用い慣用の手段で重合機を冷却するのもよい。 If the temperature of the reactants in the polymerization machine exceeds 80°C, side reactions often occur that impede obtaining a polymer with a high degree of polymerization, so it is preferably kept at about 80°C or below. In order to satisfy this condition, the polymerization machine may be cooled by conventional means using water or other refrigerants.
本発明の連続重合は、通常モノマー濃度0.2〜
1.0mol／で行なわれる。 In the continuous polymerization of the present invention, the monomer concentration is usually 0.2 to
It is carried out at 1.0 mol/.
本発明の連続重合の任意の工程に、ゴミ等の不
溶性の不純分を取り除く目的で、過用フイルタ
ー等を取り付けることは自由に行なわれてよい。 An excess filter or the like may be freely attached to any step of the continuous polymerization of the present invention for the purpose of removing insoluble impurities such as dust.
今までポリパラフエニレンテレフタルアミドに
ついてのみ述べて来たが、これ以外の芳香族ポリ
アミドの連続重合にも本発明の方法はポリパラフ
エニレンテレフタルアミドと同様の相変化をする
ものに関しては適用可能である。 Until now, only polyparaphenylene terephthalamide has been described, but the method of the present invention can also be applied to the continuous polymerization of other aromatic polyamides that undergo phase changes similar to polyparaphenylene terephthalamide. It is.
さて、このようにして製造された粉体状の重合
物は、そのまま、又は更に粉砕をうけつつ、或い
は一旦チツプ状に成形された後、水やアルカリ水
溶液、アセトン、メタノール、クロロホルム等で
洗浄され、次いで乾燥を受けてポリマーとして単
離される。重合物をチツプに成形するのは、洗浄
及び乾燥を工業的規模で実施する上で好ましい方
法であるが、本発明の連続重合法を採用すれば、
重合機の出口に成形用ブレーカーを取り付けるだ
けで比較的簡単にチツプ状に成形できる利点があ
る。 Now, the powdered polymer produced in this way can be used as it is, while being further pulverized, or once formed into chips, and then washed with water, aqueous alkaline solution, acetone, methanol, chloroform, etc. , then dried and isolated as a polymer. Forming a polymer into chips is a preferred method for carrying out washing and drying on an industrial scale, but if the continuous polymerization method of the present invention is adopted,
It has the advantage that it can be formed into chips relatively easily by simply attaching a forming breaker to the outlet of the polymerization machine.
得られたポリマーは、これを硫酸や前記のＮ−
置換アミド型溶剤等に再溶解して、調整したドー
プから、湿式や乾式又はいわゆる乾式ジエツト湿
式などの成形方法で、繊維やフイルム、フイブリ
ツドなどに成形することができる。 The obtained polymer is treated with sulfuric acid or the above-mentioned N-
The dope prepared by redissolving it in a substituted amide type solvent or the like can be molded into fibers, films, fibrids, etc. by a wet molding method, a dry molding method, or a so-called dry jet wet molding method.
これらの成形品は、産業用、衣料用を問わず幅
広く利用され、例えばタイヤ、ベルト等のゴムの
補強剤、樹脂の補強剤等の分野や耐熱服、耐熱フ
イルム、耐熱紙、中空糸等として用いられ、その
高強力、高ヤング率、耐熱性、難燃性などの特徴
が十二分に発揮される。 These molded products are widely used in both industrial and clothing applications, such as rubber reinforcing agents for tires and belts, reinforcing agents for resins, heat-resistant clothing, heat-resistant films, heat-resistant paper, hollow fibers, etc. Its characteristics such as high strength, high Young's modulus, heat resistance, and flame retardancy are fully demonstrated.
以下に本発明を具体的に説明するために実施例
を示すが、実施例中に示す重合度の目安としての
対数粘度（ηinh）は98.5重量％の濃硫酸に濃度
Ｃ＝0.5ｇ／dlでポリマーを溶かした溶液を、30
℃にて常法により測定したものである。 Examples are shown below to specifically explain the present invention, and the logarithmic viscosity (ηinh) as a guideline for the degree of polymerization shown in the examples is obtained by adding 98.5% by weight of concentrated sulfuric acid to a concentration of C=0.5g/dl. Add the polymer solution to 30
Measured using a conventional method at ℃.
ηinh＝ｌｎηｒｅｌ／Ｃ
また、耐硫酸性は、対数粘度測定溶液をさらに
60℃で４時間静置したあとの対数粘度を元の対数
粘度で除した値（百分率）で示す。 ηinh=lnηrel/C In addition, for sulfuric acid resistance, the logarithmic viscosity measurement solution is
It is expressed as a value (percentage) obtained by dividing the logarithmic viscosity after standing at 60°C for 4 hours by the original logarithmic viscosity.
実施例 １
内容積80のステンレス性の撹拌槽に、Ｎ−メ
チル−２−ピロリドン60.00Kg精秤して入れ、次
に撹拌下に粉末状の無水塩化カルシウムを40.00
Kg精秤して添加し、室温下に溶解した。１時間
後、粉末状のパラフエニレンジアミン3.888Kg精
秤して添加し約１時間撹拌をつづけた。次に撹拌
下にテレフタル酸クロライドを粉末状で2.436Kg
精秤して添加し、アミノ基含有液、すなわち、ｎ
＝１のオリゴマー溶液を調製した。Example 1 60.00 kg of N-methyl-2-pyrrolidone was accurately weighed and placed in a stainless steel stirring tank with an internal volume of 80 kg, and then 40.00 kg of powdered anhydrous calcium chloride was added while stirring.
Kg was accurately weighed, added, and dissolved at room temperature. After 1 hour, 3.888 kg of powdered paraphenylenediamine was accurately weighed and added, and stirring was continued for about 1 hour. Next, add 2.436 kg of terephthalic acid chloride in powder form while stirring.
Accurately weigh and add the amino group-containing liquid, i.e., n
An oligomer solution of =1 was prepared.
一方、ジヤケツトに0.5Kg／cm2Ｇの水蒸気を通
すことのできる内容積約15のステンレス製タン
クに、約８Kgのテレフタル酸クロライドの塊を入
れて、水蒸気をジヤケツトに通し融解した。 On the other hand, about 8 kg of terephthalic acid chloride was placed in a stainless steel tank with an internal volume of about 15 kg through which water vapor of 0.5 kg/cm 2 G could pass through the jacket, and the water vapor was passed through the jacket to melt it.
次に本実施例に用いた連続重合装置について説
明する。 Next, the continuous polymerization apparatus used in this example will be explained.
「定量連続供給機」としては、２機ともダイヤ
フラム式の定量ポンプを用いた。また、重合機と
して栗本鉄工所製「クリモトコンテイニユアスニ
ーダー＃５型機」を用いた。このコンテイニユア
スニーダーは先述の凸レンズ型のパドルをもつた
いわゆる「全表面更新型連続２軸ニーダー」の１
種で、入口部に近いところに送り込み用スクリユ
ーがある他は、残りの大半のパドルを内容物をリ
サイクルさせうる配列とした。 Both diaphragm-type metering pumps were used as the "continuous metering feeders." In addition, "Kurimoto Container Kneader #5" manufactured by Kurimoto Iron Works was used as a polymerization machine. This continuous kneader is one of the so-called "full surface renewal type continuous two-axis kneaders" that have a convex lens-type paddle mentioned above.
Besides the screw for feeding near the inlet, most of the rest of the paddles were arranged to allow the contents to be recycled.
連続重合装置の運転開始は次のようにして行な
つた。すなわち、まずアミノ基含有液を定量ポン
プでコンテイニユアスニーダーに送液し、次いで
テレフタル酸クロライド溶融液を定量ポンプでコ
ンテイニユアスニーダーに注入した。なお、テレ
フタル酸クロライド溶融液を送る配管は全てジヤ
ケツト付として、ジヤケツトには90℃に温調され
た熱媒を送り、かつ配管はテフロンコーテイング
したものを用いた。テレフタル酸クロライド溶融
液とアミノ基含有液を、各々の定量ポンプの最大
吐出量で15分間注入したあと、前者を51.5ml／
minに後者を1100ml／minになるように各々の定
量ポンプをセツトした。なお、コンテイニユアス
ニーダーのセルフクリーニング面への平均線速度
は、テレフタル酸クロライド溶融液側を約80cm／
sec、アミノ基含有液側を約50cm／secにした。ま
た、供給口はコンテイニユアスニーダーの中心、
即ち、２軸の中間中央の上方に、軸方向に約５cm
の間隔で設置した。 The operation of the continuous polymerization apparatus was started as follows. That is, first, the amino group-containing liquid was sent to the continuous kneader using a metering pump, and then the terephthalic acid chloride melt was injected into the continuous kneader using the metering pump. Note that all the piping for conveying the terephthalic acid chloride melt was equipped with a jacket, a heating medium whose temperature was controlled at 90°C was conveyed to the jacket, and the piping was coated with Teflon. After injecting the terephthalyl chloride melt and the amino group-containing solution for 15 minutes at the maximum discharge rate of each metering pump,
Each metering pump was set so that the latter was 1100 ml/min. The average linear velocity of the continuous kneader towards the self-cleaning surface is approximately 80cm/
sec, and the amino group-containing liquid side was set to approximately 50 cm/sec. In addition, the supply port is located at the center of the container kneader.
That is, approximately 5 cm in the axial direction above the middle center of the two axes.
installed at intervals of
上述のように運転した結果、最初は液状のもの
が流出してきたが、すこしずつ粘度が増しはじ
め、一旦何も出なくなつた。それから数分後こん
どは流動性のないゲル状物が吐出されはじめ、次
第に粉末状のものに変わつてゆき、しかもはじめ
は湿つた感じであつたのが乾いたパン屑状に変つ
てゆき、この状態で安定した。なお、重合物はコ
ンテイニユアスニーダー中で約10分程度混練され
る間、コンテイニユアスニーダーに設けられたジ
ヤケツトに水道水を流し冷却したことにより、吐
出物の温度は35〜40℃であつた。 As a result of operating as described above, at first some liquid came out, but the viscosity gradually started to increase and once nothing came out. After a few minutes, a gel-like substance with no fluidity began to be discharged, and gradually it turned into a powder-like substance, and what started out as a wet feeling turned into a dry crumb-like substance. Stable condition. While the polymer was kneaded in the continuous kneader for about 10 minutes, the temperature of the discharged product was kept at 35 to 40°C by cooling it by running tap water through a jacket provided in the continuous kneader. Ta.
連続重合装置は約１時間何のトラブルもなく運
転できた。乾いたパン屑状の吐出物を約10分毎に
サンプリングし、家庭用ミキサー中で粉砕しつつ
水洗して乾燥して得られたポリマーのηinhは順
に5.06、5.25、5.21、5.34、5.16、5.28であつた。
また、耐硫酸性は平均91％であつた。 The continuous polymerization apparatus could be operated for about 1 hour without any trouble. Dry crumb-like discharge was sampled every 10 minutes, crushed in a household mixer, washed with water, and dried. The resulting polymers had ηinh values of 5.06, 5.25, 5.21, 5.34, 5.16, and 5.28. It was hot.
In addition, the average sulfuric acid resistance was 91%.
実施例 ２
ヘキサメチルフオスフオルアミド60.00Kgを精
秤して実施例１と同じ撹拌槽に入れ、撹拌下に粉
末状のパラフエニレンジアミン6.480Kgを精秤し
て添加し、約１時間撹拌した後、撹拌槽に設けら
れたジヤケツトに冷媒を通して10℃に冷却し、ア
ミノ基含有液を調製した。Example 2 60.00 kg of hexamethylphosphoramide was accurately weighed and placed in the same stirring tank as in Example 1, and while stirring, 6.480 kg of powdered paraphenylenediamine was accurately weighed and added, and stirred for about 1 hour. After that, a refrigerant was passed through a jacket provided in a stirring tank and cooled to 10°C to prepare an amino group-containing liquid.
一方、内容積50のステンレス製の撹拌槽に、
Ｎ−メチル−２−ピロリドン30.00Kgを精秤して
入れ、この撹拌槽に設けられたジヤケツトに冷却
水を通して10℃に冷却した後、撹拌下に粉末状の
テレフタル酸クロライド12.180Kgを精秤して添加
し約30分撹拌して、テレフタル酸クロライド溶液
を調製した。 On the other hand, in a stainless steel stirring tank with an internal volume of 50,
30.00 kg of N-methyl-2-pyrrolidone was accurately weighed and put into it, and cooled to 10°C by passing cooling water through a jacket provided in the stirring tank. After stirring, 12.180 kg of powdered terephthalic acid chloride was accurately weighed. and stirred for about 30 minutes to prepare a terephthalic acid chloride solution.
コンテイニユアスニーダーへ送液する配管は、
配管に設けられているジヤケツトに冷媒を通し、
送液中も両液とも10℃に保つようにした。また定
量ポンプの設定は、アミノ基含有液を1400ml／
min、テレフタル酸クロライド溶液を700ml／min
にし、コンテイニユアスニーダーのセルフクリー
ニング面への平均線速度が両液とも約60cm／sec
にし、アミノ基含有液の供給口を一方の回転軸の
上方に、テレフタル酸クロライド溶液の供給口を
他方の回転軸の上方に設けた。 The piping that sends liquid to the container kneader is
Pass the refrigerant through the jacket installed in the piping,
Both liquids were kept at 10°C during liquid feeding. In addition, the metering pump setting is to pump 1400ml/amino group-containing liquid.
min, 700ml/min of terephthalic acid chloride solution
The average linear velocity of both liquids to the self-cleaning surface of the continuous kneader is approximately 60 cm/sec.
The supply port for the amino group-containing liquid was provided above one rotating shaft, and the supply port for the terephthalic acid chloride solution was provided above the other rotating shaft.
なお、コンテイニユアスニーダーのパドル配
列、ポンプ等の装置は実施例１と同じものを用い
た。 Note that the paddle arrangement of the container kneader, pumps, and other devices were the same as in Example 1.
上のようにして運転した結果、実施例１とほぼ
同じ状況であつた。なお、10分毎にサンプルング
した水洗乾燥後のポリマーのηinhは、5.45、
5.42、5.37、5.50であり、耐硫酸性は平均93％で
あつた。 As a result of the operation as described above, the situation was almost the same as in Example 1. The ηinh of the polymer after washing and drying sampled every 10 minutes was 5.45,
5.42, 5.37, and 5.50, and the average sulfuric acid resistance was 93%.
比較例 １
実施例２と同じ溶媒系を用い、装置としてはコ
ンテイニユアスニーダーの上に米国特許3849074
号及び同第3850888号に記載されているような、
両モノマー液を噴射ノズルより「等質量速度」で
噴出し、衝突させることにより混合し、スケール
の生成を中空のプランジヤーで掃除する構造の混
合機を取り付け、アミノ基含有液及びテレフタル
酸クロライド溶液を実施例１と同じようにして導
くようにし、また、定量ポンプの設定は、アミノ
基含有液を1000ml／min、テレフタル酸クロライ
ド溶液を500ml／minにし、噴出ノズルよりの線
速度が各々254cm／sec、245cm／secになるように
運転した。Comparative Example 1 The same solvent system as in Example 2 was used, and the apparatus was a container kneader using US Pat. No. 3,849,074.
No. 3850888,
Both monomer solutions are ejected from an injection nozzle at an "equal mass velocity" and mixed by collision, and a mixer is installed that cleans scale formation with a hollow plunger, and the amino group-containing solution and terephthalic acid chloride solution are mixed. The metering pump was set to 1000 ml/min for the amino group-containing solution and 500 ml/min for the terephthalic acid chloride solution, and the linear velocity from the jet nozzle was 254 cm/sec. , 245cm/sec.
上のようにして運転した結果、スケールの付着
のためモノマー液配管内の圧がたびたび上昇し、
中空状のプランジヤーをそのたびに動かす必要が
あつた。また、運転開始から40分程たつた時、テ
レフタル酸クロライド溶液側の噴射ノズルが詰ま
り（テレフタル酸クロライド溶液側の配管内圧が
上昇）運転を中止した。なお、コンテイニユアス
ニーダーより出てきた重合物を10分おきにサンプ
リングし、水洗乾燥した後、測定したポリマーη
inhは4.83、5.08、4.94であり、耐硫酸性は平均75
％であつた。 As a result of operating as above, the pressure inside the monomer liquid piping frequently increases due to scale adhesion.
It was necessary to move the hollow plunger each time. Also, about 40 minutes after the start of operation, the injection nozzle on the terephthalic acid chloride solution side became clogged (the internal pressure of the pipe on the terephthalic acid chloride solution side increased), and the operation was stopped. In addition, the polymer η that came out of the container kneader was sampled every 10 minutes, washed with water, and then dried.
inh is 4.83, 5.08, 4.94, and the average sulfuric acid resistance is 75
It was %.
比較例 ２
平均線速度を両液とも約750cm／secにした以外
は実施例２と全く同じ条件で連続重合させた。得
られたポリマーのηinhは6.35、6.32、6.40、6.39
と大きかつたが耐硫酸性は平均67％と、本発明の
方法で重合したポリマーより低かつた。Comparative Example 2 Continuous polymerization was carried out under exactly the same conditions as in Example 2, except that the average linear velocity of both solutions was about 750 cm/sec. The obtained polymer ηinh is 6.35, 6.32, 6.40, 6.39
However, the average sulfuric acid resistance was 67%, which was lower than that of the polymer polymerized by the method of the present invention.
比較例 ３
平均線速度を両液ともに130cm／secにした以外
は実施例２と同じ条件で連続重合させた。得られ
ポリマーのηinhは5.83、5.78、5.91、5.85で、耐
硫酸性は平均77％であつた。Comparative Example 3 Continuous polymerization was carried out under the same conditions as in Example 2, except that the average linear velocity was 130 cm/sec for both solutions. The obtained polymers had a ηinh of 5.83, 5.78, 5.91, and 5.85, and an average sulfuric acid resistance of 77%.
Claims (1)
≦３を示す）で表わされるモノマー又はオリゴマ
ーとＮ−置換アミド型溶剤から成るアミノ基含有
液と、液状テレフタル酸クロライドとを、芳香族
アミノ基と芳香族カルボン酸クロライド基とのモ
ル比が実質的に一定値になるように、セルフクリ
ーニング型２軸連続混合機の２つの回転軸中心に
挟まれた区域のセルフクリーニング面に前記両液
を平均線速度100cm／sec以下で連続的に直接供給
し、該セルフクリーニング型２軸連続混合機にて
粉体状になるまで混練することを特徴とするポリ
パラフエニレンテレフタルアミドの連続製造方
法。 ２ Ｎ−置換アミド型溶剤がＮ−メチル−２−ピ
ロリドン、Ｎ・Ｎ−ジメチルアセトアミド又はＮ
−アセチルピロリジンに、塩化カルシウム又は塩
化リチウムを添加したものである特許請求の範囲
第１項記載のポリパラフエニレンテレフタルアミ
ドの連続製造方法。 ３ アミノ基含有液を−10〜60℃で混合機に供給
し混合することを特徴とする特許請求の範囲の第
１項記載のポリパラフエニレンテレフタルアミド
の連続製造方法。 ４ 液状テレフタル酸クロライドがテレフタル酸
クロライドを溶融したもので、85〜110℃で混合
機に供給することを特徴とする特許請求の範囲第
１項記載のポリパラフエニレンテレフタルアミド
の連続製造方法。 ５ 液状テレフタル酸クロライドがテレフタル酸
クロライドをＮ−メチル−２−ピロリドン又はγ
−ラクトン類に溶解したもので、−10〜40℃で混
合機に供給することを特徴とする特許請求の範囲
第１項記載のポリパラフエニレンテレフタルアミ
ドの連続製造方法。 ６ アミノ基含有液と液状テレフタル酸クロライ
ドの両液を平均線速度80cm／sec以下でセルフク
リーニング型２軸連続混合機の２つの回転軸中心
に挟まれた区域のセルフクリーニング面に供給混
合することを特徴とする特許請求の範囲第１項記
載のポリパラフエニレンテレフタルアミドの連続
製造方法。 ７ セルフクリーニング型２軸連続混合機の重合
物吐出可能量がアミノ基含有液と液状テレフタル
酸クロライドの両液の供給量の合計よりも少なく
ないことを特徴とする特許請求の範囲第１項記載
のポリパラフエニレンテレフタルアミドの連続製
造方法。[Claims] 1 formula (In the formula, n is the number average value of all molecules in the system, 0≦n
≦3) and an amino group-containing liquid consisting of an N-substituted amide type solvent and liquid terephthalic acid chloride, the molar ratio of aromatic amino groups to aromatic carboxylic acid chloride groups is substantially Continuously and directly supply both liquids at an average linear velocity of 100 cm/sec or less to the self-cleaning surface of the self-cleaning type two-shaft continuous mixer in the area sandwiched between the two rotating shaft centers so that the temperature remains constant. A method for continuously producing polyparaphenylene terephthalamide, characterized in that the mixture is kneaded in the self-cleaning biaxial continuous mixer until it becomes a powder. 2 N-substituted amide type solvent is N-methyl-2-pyrrolidone, N・N-dimethylacetamide or N
- The method for continuously producing polyparaphenylene terephthalamide according to claim 1, wherein calcium chloride or lithium chloride is added to acetylpyrrolidine. 3. The method for continuously producing polyparaphenylene terephthalamide according to claim 1, characterized in that the amino group-containing liquid is supplied to a mixer at -10 to 60°C and mixed. 4. The continuous production method for polyparaphenylene terephthalamide according to claim 1, wherein the liquid terephthalic acid chloride is a molten terephthalic acid chloride and is supplied to a mixer at 85 to 110°C. 5 Liquid terephthalic acid chloride converts terephthalic acid chloride into N-methyl-2-pyrrolidone or γ
- A method for continuous production of polyparaphenylene terephthalamide according to claim 1, characterized in that the polyparaphenylene terephthalamide is dissolved in lactones and fed to a mixer at -10 to 40°C. 6 Supply and mix both the amino group-containing liquid and the liquid terephthalic acid chloride liquid at an average linear velocity of 80 cm/sec or less to the self-cleaning surface of the self-cleaning two-shaft continuous mixer in the area sandwiched between the two rotating shaft centers. A method for continuously producing polyparaphenylene terephthalamide according to claim 1, characterized in that: 7. Claim 1, characterized in that the amount of polymer that can be discharged from the self-cleaning biaxial continuous mixer is not less than the total amount of supplied amounts of both the amino group-containing liquid and the liquid terephthalic acid chloride. A method for continuous production of polyparaphenylene terephthalamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10587877A JPS5439494A (en) | 1977-09-05 | 1977-09-05 | Continuous preparation of poly-para-phenylene terephthalamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10587877A JPS5439494A (en) | 1977-09-05 | 1977-09-05 | Continuous preparation of poly-para-phenylene terephthalamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5439494A JPS5439494A (en) | 1979-03-26 |
| JPS629611B2 true JPS629611B2 (en) | 1987-03-02 |
Family
ID=14419180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10587877A Granted JPS5439494A (en) | 1977-09-05 | 1977-09-05 | Continuous preparation of poly-para-phenylene terephthalamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5439494A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017214743A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Process for preparing poly(terephthaloyl-p-phenylene diamine) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4309528A (en) * | 1980-01-16 | 1982-01-05 | Standard Oil Company (Indiana) | Injection moldable amide-imide copolymers |
| JP6272866B2 (en) * | 2012-09-03 | 2018-01-31 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing polyamide by polycondensation |
| CN108623803B (en) * | 2018-06-22 | 2020-08-04 | 清华大学 | High-concentration continuous stable polymerization method and system for poly (p-phenylene terephthalamide) |
-
1977
- 1977-09-05 JP JP10587877A patent/JPS5439494A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017214743A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Process for preparing poly(terephthaloyl-p-phenylene diamine) |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5439494A (en) | 1979-03-26 |
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