JPH02251532A - Polymerization of high molecular weight polyhexamethylene terephthalamide - Google Patents
Polymerization of high molecular weight polyhexamethylene terephthalamideInfo
- Publication number
- JPH02251532A JPH02251532A JP7040489A JP7040489A JPH02251532A JP H02251532 A JPH02251532 A JP H02251532A JP 7040489 A JP7040489 A JP 7040489A JP 7040489 A JP7040489 A JP 7040489A JP H02251532 A JPH02251532 A JP H02251532A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- polyhexamethylene terephthalamide
- prepolymer
- molecular weight
- temperature
- 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
- -1 polyhexamethylene terephthalamide Polymers 0.000 title claims abstract description 21
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 title abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- CSVBIURHUGXNCS-UHFFFAOYSA-N 6-azaniumylhexylazanium;terephthalate Chemical compound NCCCCCCN.OC(=O)C1=CC=C(C(O)=O)C=C1 CSVBIURHUGXNCS-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高分子量ポリヘキサメチレンテレフタルアミド
(ナイン6Tとも呼ばれる)の重合法に関する。更に詳
しくは、ゲル生成を極力防止した高重合度のポリヘキサ
メチレンテレフタルアミドの重合法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for polymerizing high molecular weight polyhexamethylene terephthalamide (also referred to as Nine 6T). More specifically, the present invention relates to a method for polymerizing polyhexamethylene terephthalamide with a high degree of polymerization that minimizes gel formation.
本発明によって得られるポリヘキサメチレンテレフタル
アミドを主成分とするポリマーは、ポリマー鎖中にベン
ゼン核を有する高融点ナイロンであり、このポリマーか
ら耐熱性、耐薬品性が優れ、物理的にも種々の優れた特
性を有する繊維、フィルムなどを得ることが期待できる
。The polymer mainly composed of polyhexamethylene terephthalamide obtained by the present invention is a high melting point nylon having a benzene nucleus in the polymer chain.This polymer has excellent heat resistance and chemical resistance, and has various physical properties. It is expected that fibers, films, etc. with excellent properties can be obtained.
ナイロン6Tは高融点で分解温度が融点に近いために、
ナイロン6.6やナイロン6のようなポリアミドに一般
に用いられている溶融重合は使用できず、ヘキサメチレ
ンジアミンとテレフタル酸ジクロリドとの界面重合、或
いはへキサメチレンジアミンとテレフタル酸との塩から
造られるナイロン6T塩の固相重合により合成される。Nylon 6T has a high melting point and its decomposition temperature is close to the melting point, so
Melt polymerization, which is commonly used for polyamides such as nylon 6.6 and nylon 6, cannot be used; instead, it is made from interfacial polymerization of hexamethylene diamine and terephthalic acid dichloride, or from a salt of hexamethylene diamine and terephthalic acid. Synthesized by solid phase polymerization of nylon 6T salt.
界面重合による合成は、テレフタル酸クロリドの反応性
が高く取扱いが難しかしい上、又非常に高価なために工
業的に製造することは困難である。Synthesis by interfacial polymerization is difficult to handle due to the high reactivity of terephthalic acid chloride, and is also very expensive, making it difficult to produce it industrially.
後者の固相重合も数多く研究されている0例えば、特開
昭62−20527号公報ではナイロン6T塩を150
°C以上で融点以下の温度で減圧下又は不活性ガス下で
固相重合する方法が開示されている。The latter solid phase polymerization has also been extensively studied. For example, in Japanese Patent Application Laid-Open No. 62-20527, nylon 6T salt was
A method is disclosed in which solid phase polymerization is carried out at a temperature above .degree. C. and below the melting point under reduced pressure or under an inert gas.
しかしながら、この方法では常圧又は減圧下でナイロン
6T塩が重合開始する温度よりも分解してヘキサメチレ
ンジアミンが逃散し始める温度の方が低いために、高重
合度のポリマーを製造することができない。又、特公昭
41−11634号公報、usp3、365.428で
は、ナイロン6T塩を260〜300°C125〜50
kg/cdの加圧下で初期重合させた後に、常圧にもど
し不活性ガス下、260〜300℃で固相重合する方法
が開示されている。又、この初期重合の段階で少し過剰
のへキサメチレンジアミンを添加することも合せて開示
されている。しかし、この方法では固有粘度2.Oa/
g以上の高重合度のポリマーを得ようとして長時間固相
重合すると、濃硫酸に溶けないゲル状物が多量に生成す
るという問題を有していた。However, this method cannot produce a polymer with a high degree of polymerization because the temperature at which nylon 6T salt starts to polymerize under normal pressure or reduced pressure is lower than the temperature at which it decomposes and hexamethylene diamine begins to escape. . Furthermore, in Japanese Patent Publication No. 41-11634, USP 3, 365.428, nylon 6T salt is heated at 260-300°C 125-50°C.
A method is disclosed in which initial polymerization is carried out under pressure of kg/cd, and then the pressure is returned to normal pressure and solid phase polymerization is carried out at 260 to 300° C. under an inert gas. It is also disclosed that a slight excess of hexamethylene diamine is added at this initial polymerization stage. However, with this method, the intrinsic viscosity is 2. Oa/
When solid phase polymerization is carried out for a long period of time in an attempt to obtain a polymer with a high degree of polymerization of more than 100 g, there is a problem in that a large amount of gel-like material that is insoluble in concentrated sulfuric acid is produced.
本発明の目的は、上記のようなゲルの生成を極力防ぐこ
とができ、かつ高重合度のポリヘキサメチレンテレフタ
ルアミドを得るための重合法を提供することにある。An object of the present invention is to provide a polymerization method for obtaining polyhexamethylene terephthalamide with a high degree of polymerization, which can prevent the formation of gel as described above as much as possible.
(課題を解決するための手段]
すなわち本発明は、固有粘度が0.ld1/g以上であ
るポリヘキサメチレンテレフタルアミドを主成分とする
プレポリマーを、0.05〜5重量%の次亜リン酸の金
属塩の存在下で、150 ’C以上融点未満の温度で、
減圧又は不活性ガス気流下で重合することを特徴とする
高分子量ポリヘキサメチレンテレフタルアミドの重合法
である。(Means for Solving the Problems) That is, the present invention uses a prepolymer mainly composed of polyhexamethylene terephthalamide having an intrinsic viscosity of 0.ld1/g or more, and a prepolymer containing 0.05 to 5% by weight of hypophosphorus. in the presence of a metal salt of an acid at a temperature of 150' C or more and below the melting point,
This is a method for polymerizing high molecular weight polyhexamethylene terephthalamide, which is characterized by polymerizing under reduced pressure or an inert gas stream.
本発明で用いるプレポリマーは、ポリヘキサメチレンテ
レフタルアミド骨格を繰り返し単位中に70%以上、好
ましくは80%以上有するアミド系ポリマーである。こ
のようなプレポリマーは、ジカルボン酸化合物とジアミ
ン化合物とを固相重合、フェノール系溶剤を用いた溶液
重合などの常法によって得ることができる。その際、テ
レフタル酸とへキサメチレンジアミン以外の共重合成分
として、ジカルボン酸化合物としては、例えば炭素数4
〜12の直鎖脂肪族ジカルボン酸、シクロヘキサンジカ
ルボン酸、イソフタル酸、オルトフタル酸、ナフタレン
ジカルボン酸、ジフェニルジカルボン酸などが挙げられ
る。又、ジアミン化合物としては、例えば炭素数2〜1
2の直鎖脂肪族ジアミン、シクロヘキサンジアミン、フ
ェニレンジアミン、ジアミノメチルシクロヘキサンキシ
リレンジアミンなどが挙げられる。The prepolymer used in the present invention is an amide polymer having 70% or more, preferably 80% or more of polyhexamethylene terephthalamide skeletons in repeating units. Such a prepolymer can be obtained by a conventional method such as solid phase polymerization of a dicarboxylic acid compound and a diamine compound or solution polymerization using a phenolic solvent. At that time, as a copolymerization component other than terephthalic acid and hexamethylene diamine, a dicarboxylic acid compound having a carbon number of 4, for example,
-12 straight chain aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, and the like. In addition, as a diamine compound, for example, a carbon number of 2 to 1
2, straight chain aliphatic diamine, cyclohexane diamine, phenylene diamine, diaminomethylcyclohexane xylylene diamine, and the like.
このようにして得られるプレポリマーは実質的に未反応
モノマーが残存しないことが重要であり、その固有粘度
は0.1 d17g以上、好ましくは0.2 d17g
以上であることが必要である。ここでいう固有粘度は0
.4 a/gの濃度で濃硫酸溶液にて温度35°Cで測
定した値である。未反応上ツマ−が残存していると、本
発明の重合段階でモノマーの逃散が起こり、モルバラン
スを崩し、高分子量化が困難となる。この問題を解決す
るために、固有粘度が0、1 a/g以上のプレポリマ
ー用をいるのであり、そうすることによって、逃散によ
るモルバランス崩れは防ぐことができる。It is important that the prepolymer thus obtained has substantially no unreacted monomer remaining, and its intrinsic viscosity is 0.1 d17g or more, preferably 0.2 d17g.
It is necessary that it is above. The intrinsic viscosity here is 0
.. The value was measured in a concentrated sulfuric acid solution at a concentration of 4 a/g at a temperature of 35°C. If unreacted sulfur remains, the monomer escapes during the polymerization step of the present invention, disrupting the molar balance and making it difficult to obtain a high molecular weight. In order to solve this problem, a prepolymer having an intrinsic viscosity of 0.1 a/g or more is needed, and by doing so, it is possible to prevent molar balance collapse due to escape.
本発明では重合に先立って次亜リン酸の金属塩をプレポ
リマーに付与するが、これは後に行なう重合において重
合度の向上、ゲル状物の抑制という点て著しく効果があ
る0本発明において、次亜リン酸の金属塩は重合反応の
前及び途中のいかなる段階で、−段もしくは多段階に加
えることができる。プレポリマー合成前に予め添加する
こともできるが、プレポリマーの合成中或いは精製の際
変質したり逸散するので重合前に加えるのが好ましい。In the present invention, a metal salt of hypophosphorous acid is added to the prepolymer prior to polymerization, which is extremely effective in improving the degree of polymerization and suppressing gel-like substances in the subsequent polymerization. The metal salt of hypophosphorous acid can be added in one stage or in multiple stages at any stage before or during the polymerization reaction. Although it can be added in advance before prepolymer synthesis, it is preferable to add it before polymerization because it may deteriorate or escape during prepolymer synthesis or purification.
次亜リン酸の金属塩としては、ナトリウム塩、カルシウ
ム塩などが好ましく用いられる。又、その付与量として
はプレポリマーに対して0.05〜5重量%、好ましく
は0.1〜2重量%である。0.05重量以下では重合
度を上げるという効果がなく、5重量%以下では重合反
応を疎外する。付与方法は特に規定するものではなく、
例えば水、アルコールなどの溶液の形態で付与すること
ができる。As the metal salt of hypophosphorous acid, sodium salt, calcium salt, etc. are preferably used. Further, the amount applied is 0.05 to 5% by weight, preferably 0.1 to 2% by weight based on the prepolymer. If it is less than 0.05% by weight, there is no effect of increasing the degree of polymerization, and if it is less than 5% by weight, the polymerization reaction will be hindered. The granting method is not particularly stipulated;
For example, it can be applied in the form of a solution such as water or alcohol.
その際、付与量を抑えるという点で、プレポリマーの粒
径は小さい方が良く、粒径としては好ましくはIIII
l以下、さらに好ましくは0.1M以下である。In this case, in terms of suppressing the amount applied, it is better to have a smaller particle size of the prepolymer, and the particle size is preferably III
1 or less, more preferably 0.1M or less.
本発明においては次亜リン酸塩を付与したプレポリマー
を溶融することなく重合を行なう。具体的にはこのプレ
ポリマーを威圧又は不活性ガスの流通できる容器に仕込
み、150°C以上に加熱して生成及び残存する水その
他を系外に留出させて高分子量化させる。その際、重合
系への酸素の混入はポリマーの着色、部分架橋によるゲ
ル化などの原因となるので充分に考慮することが必要で
ある。この反応の温度条件としては150°C以上、好
ましくは180°Cで融点未満、さらに好ましくは、2
40°C以上300°C未満である0反応温度が150
°C未満では反応が進行せず好ましくなく、又上述温度
以上では分解、着色などが起こり好ましくない。In the present invention, polymerization is carried out without melting the prepolymer to which hypophosphite has been added. Specifically, this prepolymer is charged into a container through which an inert gas can be circulated under pressure, and heated to 150° C. or higher to distill generated and remaining water and other substances out of the system, thereby increasing the molecular weight. At this time, sufficient consideration must be given to the incorporation of oxygen into the polymerization system, as this may cause coloration of the polymer, gelation due to partial crosslinking, etc. The temperature conditions for this reaction are 150°C or higher, preferably 180°C below the melting point, more preferably 2
0 reaction temperature is 40°C or more and less than 300°C 150
If the temperature is lower than .degree. C., the reaction will not proceed, which is not preferable, and if the temperature is above the above-mentioned temperature, decomposition, coloring, etc. may occur, which is not preferable.
反応時間は温度、次亜リン酸塩の付与量、装置などによ
って異なるので一義的には定め難いが、一般に1〜10
0時間、好ましくは30〜40時間である。減圧を用い
る場合1000Pa以下、好ましくは300Pa以下で
ある。The reaction time varies depending on the temperature, the amount of hypophosphite applied, the equipment, etc., so it is difficult to define it unambiguously, but it is generally 1 to 10 minutes.
0 hours, preferably 30 to 40 hours. When using reduced pressure, the pressure is 1000 Pa or less, preferably 300 Pa or less.
なお、本発明を実施するにあたって、必要に応じて酸化
防止剤、光安定剤、熱安定剤などの添加物を加えたりす
ることも可能である。In carrying out the present invention, additives such as antioxidants, light stabilizers, and heat stabilizers may be added as necessary.
以下、本発明を実施例により、具体的に説明する。なお
、実施例中の固有粘度は、0.4g/aの濃度で濃硫酸
溶液にて温度35゛Cで測定したものである。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples. The intrinsic viscosity in the Examples was measured at a temperature of 35°C using a concentrated sulfuric acid solution at a concentration of 0.4 g/a.
実施例1
撹拌機及び圧力ゲージを取付けたステンレス製のオート
クレーブにヘキサメチレンジアンモニウムテレフタレー
ト塩7gと窒素バブリングしたバラクレゾール28gを
仕込み、窒素置換を行ない、1時間かけて内湯を200
℃まで昇温し、その温度で2時間保持した。その際、内
圧は1kg/ajGであった。その後、1時間かけて内
温を225°Cまで昇温し、その温度で20時間保持し
た。その際、内圧は徐々に上がり、最終的には4.4k
g/c+IIGとなった。その後、120 ’Cまで冷
却し、パージを行ない、加圧系で、260 ’Cで3時
間、さらに280°Cで4時間反応させた。その際の各
温度での最終圧力は260°Cで3.5kg/cnG
、280°Cで4.8 kg/dGであった0反応終了
後、冷却してメタノールを用いて析出、洗浄し、真空乾
燥した。Example 1 A stainless steel autoclave equipped with a stirrer and a pressure gauge was charged with 7 g of hexamethylene diammonium terephthalate salt and 28 g of nitrogen bubbled baracresol, replaced with nitrogen, and heated to 200 g over the course of 1 hour.
The temperature was raised to .degree. C. and maintained at that temperature for 2 hours. At that time, the internal pressure was 1 kg/ajG. Thereafter, the internal temperature was raised to 225°C over 1 hour and maintained at that temperature for 20 hours. At that time, the internal pressure gradually rose and finally reached 4.4k.
It became g/c+IIG. Thereafter, the mixture was cooled to 120'C, purged, and reacted in a pressurized system at 260'C for 3 hours and then at 280°C for 4 hours. The final pressure at each temperature is 3.5 kg/cnG at 260°C.
, 4.8 kg/dG at 280° C. After completion of the reaction, the product was cooled, precipitated using methanol, washed, and dried in vacuum.
得られたプレポリマーは白色であり、その固有粘度は0
.32d1/gであった。このプレポリマーを粉砕して
60メツシユのふるいにかけ、プレポリマー粒子を得た
。The obtained prepolymer is white and its intrinsic viscosity is 0.
.. It was 32d1/g. This prepolymer was crushed and passed through a 60 mesh sieve to obtain prepolymer particles.
得られたプレポリマー粒子5gを100−のメスフラス
コにとり、予め、次亜リン酸ソーダを0.2重量%の濃
度で溶解した水12.5 gメタノール10gを加え、
窒素雰囲気下、65°Cで3時間撹拌した。その後、エ
バポレーターで濃縮して真空乾燥した。5 g of the obtained prepolymer particles were placed in a 100-meter volumetric flask, and 12.5 g of water and 10 g of methanol in which sodium hypophosphite had been dissolved at a concentration of 0.2% by weight were added.
The mixture was stirred at 65°C for 3 hours under a nitrogen atmosphere. Thereafter, it was concentrated using an evaporator and dried under vacuum.
このプレポリマーを粉砕して、撹拌機付の固相重合装置
を用いて、窒素気流下、295°Cで5時間、固相重合
したものの固有粘度は1.9 a/gであり、35時間
固相重合したものの固有粘度は2.8a/gであった。This prepolymer was pulverized and subjected to solid phase polymerization at 295°C for 5 hours under a nitrogen stream using a solid phase polymerization apparatus equipped with a stirrer, and the intrinsic viscosity of the product was 1.9 a/g, and it was polymerized for 35 hours. The intrinsic viscosity of the solid-phase polymerized product was 2.8 a/g.
これらのポリマーは白色であり、又、濃硫酸に不溶なゲ
ル状物も含まれていなかった。These polymers were white in color and did not contain gel-like substances that were insoluble in concentrated sulfuric acid.
比較例
実施例1と同様の操作をして、固有粘度0.34d1/
gのプレポリマーを得た。このプレポリマーを次亜リン
酸ソーダの付与をすることなく、窒素気流下、295°
Cで5時間、固相重合した。得られたポリマーの固有粘
度は1.4 a/gであった。35時間固相重合したも
のには濃硫酸に不溶なゲル状物が認められ、その固有粘
度は1.9a/gであった。Comparative Example By performing the same operation as in Example 1, the intrinsic viscosity was 0.34 d1/
g of prepolymer was obtained. This prepolymer was heated at 295° under a nitrogen stream without adding sodium hypophosphite.
Solid phase polymerization was carried out at C for 5 hours. The intrinsic viscosity of the obtained polymer was 1.4 a/g. A gel-like substance insoluble in concentrated sulfuric acid was observed in the product subjected to solid phase polymerization for 35 hours, and its intrinsic viscosity was 1.9 a/g.
本発明はゲル状物の生成を極力防ぎかつ高分子量のポリ
ヘキサメチレンテレフタルアミドを得るために、極めて
有力な重合方法である。The present invention is an extremely effective polymerization method for obtaining high molecular weight polyhexamethylene terephthalamide while preventing the formation of gel-like substances as much as possible.
又、このポリマーを用いることにより耐熱性、耐薬品性
に優れ、物理的にも種々の優れた特性を有する繊維、フ
ィルムなどの成形品を得ることができる。Moreover, by using this polymer, molded products such as fibers and films that have excellent heat resistance and chemical resistance, and various excellent physical properties can be obtained.
近年、超高分子量ポリエチレンで開発されたゲル延伸法
を種々のポリマーに応用する試みがなされている。この
技術を応用するためには高分子量のポリマーが必要であ
り、将来このような技術を応用する際にも有用であり期
待できる。In recent years, attempts have been made to apply the gel stretching method developed for ultra-high molecular weight polyethylene to various polymers. In order to apply this technology, a polymer with a high molecular weight is required, and it is expected that it will be useful when applying such technology in the future.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
ンテレフタルアミドを主成分とするプレポリマーを、0
.05〜5重量%の次亜リン酸の金属塩の存在下で、1
50℃以上融点未満の温度で、減圧又は不活性ガス気流
下で重合することを特徴とする高分子量ポリヘキサメチ
レンテレフタルアミドの重合法A prepolymer mainly composed of polyhexamethylene terephthalamide with an intrinsic viscosity of 0.1 dl/g or more,
.. In the presence of 05-5% by weight of metal salts of hypophosphorous acid, 1
A method for polymerizing high molecular weight polyhexamethylene terephthalamide, which is characterized by polymerizing at a temperature of 50°C or higher and lower than the melting point under reduced pressure or an inert gas stream.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7040489A JPH02251532A (en) | 1989-03-24 | 1989-03-24 | Polymerization of high molecular weight polyhexamethylene terephthalamide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7040489A JPH02251532A (en) | 1989-03-24 | 1989-03-24 | Polymerization of high molecular weight polyhexamethylene terephthalamide |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02251532A true JPH02251532A (en) | 1990-10-09 |
Family
ID=13430492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7040489A Pending JPH02251532A (en) | 1989-03-24 | 1989-03-24 | Polymerization of high molecular weight polyhexamethylene terephthalamide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02251532A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6391983B1 (en) | 1997-02-14 | 2002-05-21 | Sola International Holdings, Ltd. | Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer |
US6658474B2 (en) | 1998-11-26 | 2003-12-02 | Samsung Electronics Co., Ltd. | Home network system and method of allocating node identification |
JP2012136670A (en) * | 2010-12-28 | 2012-07-19 | Unitika Ltd | Method of manufacturing polyamide |
-
1989
- 1989-03-24 JP JP7040489A patent/JPH02251532A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6391983B1 (en) | 1997-02-14 | 2002-05-21 | Sola International Holdings, Ltd. | Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer |
US6658474B2 (en) | 1998-11-26 | 2003-12-02 | Samsung Electronics Co., Ltd. | Home network system and method of allocating node identification |
JP2012136670A (en) * | 2010-12-28 | 2012-07-19 | Unitika Ltd | Method of manufacturing polyamide |
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