JPH03290432A - Polyhexamethylene adipamide low in branching and production thereof - Google Patents
Polyhexamethylene adipamide low in branching and production thereofInfo
- Publication number
- JPH03290432A JPH03290432A JP9233690A JP9233690A JPH03290432A JP H03290432 A JPH03290432 A JP H03290432A JP 9233690 A JP9233690 A JP 9233690A JP 9233690 A JP9233690 A JP 9233690A JP H03290432 A JPH03290432 A JP H03290432A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- prepolymer
- polyhexamethylene adipamide
- autoclave
- branching
- 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
- 229920002302 Nylon 6,6 Polymers 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 7
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 10
- 239000011541 reaction mixture Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RNQBCZCPNUHWLV-UHFFFAOYSA-N 1,8-dioxacyclotetradecane-2,7-dione Chemical compound O=C1CCCCC(=O)OCCCCCCO1 RNQBCZCPNUHWLV-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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〕
この発明は、分岐の少ないポリへキサメチレンアジパミ
ド及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to polyhexamethylene adipamide with little branching and a method for producing the same.
つまり、分岐の原因であるビスヘキサメチレントリアミ
ン（ＢＨＴ）の量が少ないポリヘキサメチレンアジパミ
ド及びその製造方法に関するものである。In other words, the present invention relates to polyhexamethylene adipamide with a small amount of bishexamethylene triamine (BHT), which is a cause of branching, and a method for producing the same.
従来、ポリアミドの製造方法としては、例えばＵＳＰ
３．５６２．２０６に記載されているように、５０％の
ＡＨ塩の水溶液を用いて、これを濃縮し、溶融重合して
プレポリマーを得て、これを同相重合する方法が取られ
てきた。しかし、このような方法では、ポリマーの分岐
の原因となるＢＨＴ （ビスヘキサメチレントリアミン
）が生威し、ポリマー中に分岐を持った、つまり直鎖状
ではないポリマーを生成することが判ってきた。そして
、これは、紡糸時の粘度斑の要因となると考えられ、Ｂ
ＨＴを減らすことが均一な紡糸性を得、紡糸収率を向上
させる上で必要であると考えられる。Conventionally, as a method for manufacturing polyamide, for example, USP
As described in 3.562.206, a method has been adopted in which a 50% aqueous solution of AH salt is used, concentrated, melt polymerized to obtain a prepolymer, and this is in-phase polymerized. . However, it has been found that with this method, BHT (bishexamethylene triamine), which causes branching in the polymer, is allowed to grow, producing a polymer with branches, that is, a non-linear polymer. . This is thought to be a cause of viscosity unevenness during spinning, and B
It is believed that reducing HT is necessary to obtain uniform spinnability and improve spinning yield.
従って、本発明の解決しようとする課題は、ボリフ−中
に分岐の少ないポリヘキサメチレンアジパミドを提供す
ることであり、またその製造方法を提供することにある
。Therefore, the problem to be solved by the present invention is to provide polyhexamethylene adipamide with less branching in the boron, and also to provide a method for producing the same.
この発明に係わるポリヘキサメチレンアジパミドは、前
述の課題を解決するものであって、ポリマー中のビスヘ
キサメチレントリアミン（ＢＨＴ）がポリマー１ｇ当た
り０．４ｍｇ以下であることを特徴とする分岐の少ない
ポリヘキサメチレンアジパミドである。The polyhexamethylene adipamide according to the present invention solves the above-mentioned problems, and is a branched polyhexamethylene adipamide characterized in that the amount of bis-hexamethylene triamine (BHT) in the polymer is 0.4 mg or less per 1 g of the polymer. less polyhexamethylene adipamide.
また本発明の分岐の少ないポリヘキサメチレンアジパミ
ドの製造方法は、ポリヘキサメチレンアジパミドを重合
するに当たり、ヘキサメチレンジアンモニウムアジペー
ト（ＡＨ塩）を密閉加圧容器を用いて加熱反応させた後
、冷却してこれをプレポリマーとし、このプレポリマー
を固相状態で更に加熱重合することを特徴とする。In addition, the method for producing polyhexamethylene adipamide with less branching of the present invention involves heating and reacting hexamethylene diammonium adipate (AH salt) using a closed pressurized container when polymerizing polyhexamethylene adipamide. Thereafter, it is characterized in that it is cooled to form a prepolymer, and this prepolymer is further heat-polymerized in a solid phase state.
本発明でいうポリヘキサメチレンアジパミド（ナイロン
６６）は、他のポリマーを１５％以下含んでも良い。更
に、必要に応じて、熱安定剤、酸化防止剤、光安定剤、
顔料、艶消し剤、触媒を含んでも良い。The polyhexamethylene adipamide (nylon 66) referred to in the present invention may contain 15% or less of other polymers. Furthermore, heat stabilizers, antioxidants, light stabilizers,
It may also contain pigments, matting agents, and catalysts.
また、本発明でいうポリヘキサメチレンアジパミド〈ナ
イロン６６〉は、ポリマーの分岐の原因であるビスヘキ
サメチレントリアミン（ＢＨＴ）の含有量がポリマー１
ｇ当たり０．４ｍｇ以下、好ましくは０．４ｍｇ〜０．
０１■である。In addition, the polyhexamethylene adipamide (nylon 66) referred to in the present invention has a content of bishexamethylene triamine (BHT), which is a cause of polymer branching, in the polymer 1.
0.4 mg or less per g, preferably 0.4 mg to 0.
It is 01■.
ＢＨＴの含有量が０．４ｍｇ以上では、紡糸収率を向上
させる効果が少ない。好ましくは、０．３■以下である
。また、ＢＩＴの含有量は少なければ少ない程よいが、
０．０１■以下のポリマーを得ることは、難しい。When the content of BHT is 0.4 mg or more, the effect of improving the spinning yield is small. Preferably, it is 0.3 or less. Also, the lower the BIT content, the better.
It is difficult to obtain a polymer of 0.01 .mu.m or less.
また、本発明でいうポリヘキサメチレンアジパミド（ナ
イロン６６）の数平均分子量は、１万〜５０万である。Moreover, the number average molecular weight of polyhexamethylene adipamide (nylon 66) as used in the present invention is 10,000 to 500,000.
このようなナイロン６６の製造方法の一態様を以下に開
示する。One aspect of the method for manufacturing such nylon 66 will be disclosed below.
まず、当モルのへキサメチレンジアミンとアジピン酸か
らなるＡＨ塩を密閉反応容器に入れ、１５０℃〜３００
℃の温度で１〜２４時間程時間開状態で重合し、その後
、室温まで冷却してプレポリマーを得る。First, an equimolar amount of AH salt consisting of hexamethylene diamine and adipic acid was placed in a sealed reaction container, and the temperature was increased from 150°C to 300°C.
Polymerization is carried out in an open state at a temperature of 1 to 24 hours at a temperature of 0.degree. C., and then cooled to room temperature to obtain a prepolymer.
例えば、２９０℃で反応する場合は、１時間反応すれば
良く、また、２４０℃の場合は、１．５時間反応すれば
プレポリマーを得ることができる。For example, when reacting at 290°C, it is sufficient to react for 1 hour, and when reacting at 240°C, a prepolymer can be obtained by reacting for 1.5 hours.
ここで用いるＡＨ塩は、当モルになるようにヘキサメチ
レンジアミンとアジピン酸とを、水あるはメタノール中
で混合して反応させることにより得られる。このＡＨ塩
を再結晶化した後、乾燥し、固体のＡＨ塩を得ることが
できる。The AH salt used here can be obtained by mixing hexamethylene diamine and adipic acid in equimolar amounts in water or methanol and reacting them. After recrystallizing this AH salt, it is dried to obtain a solid AH salt.
この固体のＡＨ塩を密閉容器に入れ密閉状態で重合する
。なお、重合中には圧力を抜かないようにするが、これ
は、ヘキサメチレンジアミンの飛散を防ぐためである。This solid AH salt is placed in a closed container and polymerized in a closed state. Note that the pressure is not released during the polymerization in order to prevent hexamethylene diamine from scattering.
また、重合が終了したらすぐに冷却する。これは、プレ
ポリマーの熱劣化を防ぐためである。In addition, immediately after the polymerization is completed, it is cooled. This is to prevent thermal deterioration of the prepolymer.
プレポリマーの分子量は、１０００〜４０００程度が好
ましい。好ましくは、２０００〜３０００である。１０
００以下では、後の固相重合でＨＭＤが飛散し末端基濃
度のバランスが崩れ高分子量のポリマーが得られなくな
る。また、４０００以上にするには、重合により生じた
水を除かなくてはならない。したがって、密閉状態で重
合する場合には、これ以上にすることは難しい。The molecular weight of the prepolymer is preferably about 1000 to 4000. Preferably it is 2000-3000. 10
If it is less than 00, HMD will be scattered during the subsequent solid phase polymerization, the balance of end group concentration will be lost, and a high molecular weight polymer will not be obtained. In addition, in order to increase the molecular weight to 4000 or more, it is necessary to remove water produced by polymerization. Therefore, when polymerizing in a closed state, it is difficult to increase the amount more than this.
得られたプレポリマーを適当な大きさに粉砕した後、不
活性ガス流通下、あるいは、減圧下で１６０℃〜２３０
℃の温度で３〜１００時間加熱し、固相重合する。After pulverizing the obtained prepolymer to an appropriate size, it was heated at 160°C to 230°C under an inert gas flow or under reduced pressure.
Solid state polymerization is carried out by heating for 3 to 100 hours at a temperature of .degree.
固相重合するのは、高重合化するときのＢＨＴの増加を
押さえるためである。The purpose of solid phase polymerization is to suppress the increase in BHT during high polymerization.
本発明で使用した測定方法を以下に示す。The measurement method used in the present invention is shown below.
◎硫酸相対粘度の測定
９５ｗｔ％の濃硫酸に１ ｇ／ａになるようにポリマー
を溶解し、２５℃でオストワルド粘度管を用いて測定し
た。◎Measurement of sulfuric acid relative viscosity A polymer was dissolved in 95 wt% concentrated sulfuric acid to a concentration of 1 g/a, and measured at 25°C using an Ostwald viscosity tube.
◎アミノ末端基濃度の測定
５ｇのポリマーを９Ｑｗｔ％のフェノール溶液に５０℃
で溶解した後、室温に戻し１ ／１０ Ｎ塩酸で滴定し
て求めた。◎Measurement of amino end group concentration 5g of polymer was added to 9Qwt% phenol solution at 50°C.
After dissolving in water, the solution was returned to room temperature and titrated with 1/10 N hydrochloric acid.
◎カルボキシル末端基の測定
５ｇのポリマーをベンジルアルコールに１８０℃で溶解
し、１８０℃でフェノールフタレインを指示薬として１
／１０水酸化ナトリウムで滴定して求めた。◎Measurement of carboxyl end groups 5g of polymer was dissolved in benzyl alcohol at 180°C, and phenolphthalein was used as an indicator at 180°C.
/10 Determined by titration with sodium hydroxide.
◎ＢＨＴの測定
４０ｍｇのポリマーを１０−のガラスアンプルに入れ、
４７％臭化水素を０．４ ｍｌ’加え、窒素で充分に置
換した後封管する。これを１５０℃で４時間加熱し、ポ
リマーを加水分解する。冷却後ガラスアンプルを開封し
、遠心エバポレーターを用イテ、６０℃４時間蒸発乾固
し、さらに８０℃２時間オイルポンプで減圧しながら乾
燥する。これに、内部標準としてｐ−ｔｅｒｐｈｅｎｙ
ｌ ／ｐｙｒ ｉｄ ｉｎを２０ ｍｇ ／ ５０ ｍ
ｌ！加え、さらにＮ、０ｂｉｓ （ｔｒｉｍｅｔｈｙｌ
ｓｉｌｙｌ） ａｃｅｔａｍｉｄｅを０．５ｍｊ！加え
、９０℃で０．５時間加熱し、ＴＭＳ誘導体化する。◎Measurement of BHT Put 40 mg of polymer into a 10-glass ampoule.
Add 0.4 ml' of 47% hydrogen bromide, and after thoroughly purging with nitrogen, seal the tube. This is heated at 150° C. for 4 hours to hydrolyze the polymer. After cooling, the glass ampoule was opened and evaporated to dryness at 60°C for 4 hours using a centrifugal evaporator, and then dried under reduced pressure using an oil pump for 2 hours at 80°C. In addition, p-terpheny was added as an internal standard.
l/pyrid in 20 mg/50 m
l! In addition, N, 0bis (trimethyl
silyl) 0.5 mj of acetamide! In addition, the mixture was heated at 90° C. for 0.5 hour to effect TMS derivatization.
さらに、ｎ−ｍｅｔｙ ｌｂ ｉｓｔ ｒ ｉｆ １ｕ
ｏｒｏａｃｅｔａｒｎ ｉｄｅを０．５−加え９０℃０
．５時間加熱し、ＴＦＡ誘導体化する。Furthermore, n-mety lb ist r if 1u
Add 0.5- oroaceturn ide and 90℃0
．． Heat for 5 hours to derivatize TFA.
これをガスクロマトグラフィーで測定した。あらかじめ
作成した検量線を用いてＢＨＴのピーク強度からその量
を求めた。This was measured by gas chromatography. The amount of BHT was determined from the peak intensity of BHT using a calibration curve prepared in advance.
以下実施例により本発明を詳述する。 The present invention will be explained in detail with reference to Examples below.
実施例１゜
当モルのへキサメチレンジアミンとアジピン酸からなる
ＡＨ塩〈ヘキサメチレンアジペート〉８０ｇをガラス管
に入れ、これを２００−のオートクレーブに入れて密閉
した。次に、オートクレーブ内の空気を窒素で５回置換
した。このオートクレーブを２９０℃に加熱したオイル
バスにつけて、１時間加熱した。この間圧力は上昇した
が、オートクレーブは密閉したままで圧力の調整はしな
かった。Example 1 80 g of an AH salt (hexamethylene adipate) consisting of equivalent moles of hexamethylene diamine and adipic acid was placed in a glass tube, and the tube was placed in a 200-cm autoclave and sealed. Next, the air in the autoclave was replaced with nitrogen five times. This autoclave was placed in an oil bath heated to 290°C and heated for 1 hour. During this time, the pressure increased, but the autoclave remained closed and the pressure was not adjusted.
１時間加熱した後、オートクレーブを水中に浸漬して急
冷した。オートクレーブが室温になってから、中のポリ
マーを取り出した。After heating for 1 hour, the autoclave was immersed in water for rapid cooling. After the autoclave reached room temperature, the polymer inside was taken out.
ポリマーは、白色の固体であった。この９５ｗｔ％硫酸
相対粘度は、１．３であった。また、末端基の定量を行
ったところアミノ末端基３９５ｍｇｅｑ／ｋｇ。The polymer was a white solid. The relative viscosity of this 95 wt% sulfuric acid was 1.3. Furthermore, when the terminal group was quantified, the amino terminal group was 395 mgeq/kg.
カルボキシル末端基は３９４ｍｇｅｑ／ｋｇであった。Carboxyl end groups were 394 mgeq/kg.
このプレポリマーを粉砕して、１〜０．５ ｍｍの大き
さにした。This prepolymer was ground to a size of 1 to 0.5 mm.
このプレポリマー５０ｇを反応容器に入れ、窒素で充分
に置換した後、反応容器を回転しながら窒素を５００ｄ
／分の流量で流して、２２０℃で１５時間加熱した。50g of this prepolymer was placed in a reaction vessel, and the atmosphere was sufficiently replaced with nitrogen.Then, while rotating the reaction vessel, nitrogen was removed for 500d.
The mixture was heated at 220°C for 15 hours at a flow rate of 1/min.
こうしてポリマーを得た。このポリマーの硫酸相対粘度
を測定したところ、３．６であった。A polymer was thus obtained. The relative viscosity of this polymer in sulfuric acid was measured and found to be 3.6.
また、ＢＨＴの量を測定したところ、０．２７ｍｇ／ｇ
であった。In addition, when the amount of BHT was measured, it was found to be 0.27 mg/g.
Met.
比較例１゜
当モルのへキサメチレンジアミンとアジピン酸からなる
ＡＨ塩（ヘキサメチレンアジペート〉水溶液１６０ｇを
ガラス管に入れ、これを２００−のオートクレーブに入
れて密閉した。次に、オートクレーブ内の空気を窒素で
５回置換した。このオートクレーブを２９０℃に加熱し
たオイルバスにつけて、１時間加熱した。この間圧力が
上昇したので、オートクレーブのノズルを調整し、１７
．５ｋｇ／ｃ＋＋ｆに合わせた。１時間重合後、圧力を
常圧に戻し、その後オートクレーブを水中に浸漬して急
冷した。Comparative Example 1 160 g of an aqueous solution of AH salt (hexamethylene adipate) consisting of equivalent moles of hexamethylene diamine and adipic acid was placed in a glass tube, and this was placed in a 200-cm autoclave and sealed.Next, the air inside the autoclave was was replaced with nitrogen five times.The autoclave was placed in an oil bath heated to 290°C and heated for 1 hour.During this time, the pressure rose, so the autoclave nozzle was adjusted and
．． Adjusted to 5kg/c++f. After polymerization for 1 hour, the pressure was returned to normal pressure, and then the autoclave was immersed in water for rapid cooling.
オートクレーブが室温になってから、中のポリマーを取
り出した。After the autoclave reached room temperature, the polymer inside was taken out.
ポリマーは、白色の固体であった。この９５ｗｔ％硫酸
相対粘度は、２．２であった。また、末端基の定量を行
ったところアミノ末端基８５ｍｇｅｑ／ｋｇ、カルボキ
シル末端基は１１２ ｍｇｅＱ ／ ｋｇであった。The polymer was a white solid. The relative viscosity of this 95 wt% sulfuric acid was 2.2. Furthermore, when the terminal groups were quantified, the amino terminal groups were 85 mgeQ/kg, and the carboxyl terminal groups were 112 mgeQ/kg.
このプレポリマーを粉砕して、１〜０．５ ｍｍの大き
さにした。This prepolymer was ground to a size of 1 to 0.5 mm.
このプレポリマー５０ｇを反応容器に入れ、窒素で充分
に置換した後、反応容器を回転しながら窒素を５００ｒ
ｒＬＩ！／分の流量で流して、２２０℃で１５時間加熱
した。50g of this prepolymer was placed in a reaction vessel, and after the atmosphere was sufficiently replaced with nitrogen, nitrogen was introduced at 500 rpm while rotating the reaction vessel.
rLI! The mixture was heated at 220°C for 15 hours at a flow rate of 1/min.
こうしてポリマーを得た。このポリマーの硫酸相対粘度
を測定したところ、３．７であった。A polymer was thus obtained. The relative viscosity of this polymer in sulfuric acid was measured and found to be 3.7.
また、ＢＨＴの量を測定したところ、０．８０ｍｇ／ｇ
であった。In addition, when the amount of BHT was measured, it was found to be 0.80 mg/g.
Met.
実施例２゜
当モルのへキサメチレンジアミンとアジピン酸からなる
ＡＨ塩（ヘキサメチレンアジペート）１０ｇをガラス管
に入れ、これを２００１ｎｌのオートクレーブに入れて
密閉した。次に、オートクレーブ内の空気を窒素で５回
置換した。このオートクレーブを１８０℃に加熱したオ
イルバスにつけて、２０時間加熱した。この間圧力は上
昇したが、オートクレーブは密閉したままで圧力の調整
はしなかった。Example 2 10 g of an AH salt (hexamethylene adipate) consisting of equimolar amounts of hexamethylene diamine and adipic acid was placed in a glass tube, which was then placed in a 2001 nl autoclave and sealed. Next, the air in the autoclave was replaced with nitrogen five times. This autoclave was placed in an oil bath heated to 180°C and heated for 20 hours. During this time, the pressure increased, but the autoclave remained closed and the pressure was not adjusted.
２０時間加熱した後、オートクレーブを水中に浸漬して
急冷した。オートクレーブが室温になってから、中のポ
リマーを取り出した。After heating for 20 hours, the autoclave was immersed in water for rapid cooling. After the autoclave reached room temperature, the polymer inside was taken out.
ポリマーは、白色の固体であった。この９５ｗｔ％硫酸
相対粘度は、１．５であった。また、末端基の定量を行
ったところアミノ末端基３８１■ｅｑ／ｋｇ。The polymer was a white solid. The relative viscosity of this 95 wt% sulfuric acid was 1.5. Further, when the terminal group was quantified, the amino terminal group was 381 eq/kg.
カルボキシル末端基は３８７■ｅｃｌ／ｋｇであった。The carboxyl end group was 387 ecl/kg.
このプレポリマーを粉砕して、１−０．５ｍの大きさに
した。This prepolymer was ground to a size of 1-0.5 m.
このプレポリマー９ｇを反応容器に入れ、窒素で充分に
置換した後、反応容器を回転しながら窒素を５００ｍＮ
／分の流量で流して、２００℃で７時間加熱した。9 g of this prepolymer was placed in a reaction vessel, and the atmosphere was sufficiently replaced with nitrogen, and then 500 mN of nitrogen was added while rotating the reaction vessel.
The mixture was heated at 200° C. for 7 hours at a flow rate of 1/min.
こうしてポリマーを得た。このポリマーの硫酸相対粘度
を測定したところ、２．６であった。A polymer was thus obtained. The relative viscosity of this polymer in sulfuric acid was measured and found to be 2.6.
また、ＢＨＴの量を測定したところ、０．０８■／ｇで
あった。Further, when the amount of BHT was measured, it was 0.08 .mu./g.
実施例３゜
当モルのへキサメチレンジアミンとアジピン酸からなる
固体のＡＨ塩５０ｇをガラス管に入れ、これを２００ｍ
Ｉ！のオートクレーブに入れて密閉した。Example 3 50 g of a solid AH salt consisting of equimolar amounts of hexamethylene diamine and adipic acid was placed in a glass tube, and the tube was heated for 200 m
I! It was placed in an autoclave and sealed.
次に、オートクレーブ内の空気を窒素で５回置換した。Next, the air in the autoclave was replaced with nitrogen five times.
このオートクレーブを２９０℃に加熱したオイルバスに
つけて、１時間加熱した。この間圧力が上昇したので、
オートクレーブのノズルを調整し、１７．５ｋｇ／ｃｍ
！に合わせた。１時間重合後、圧力を１ｋｇ／ｃｎｆ分
の速さで常圧に戻し、その後オートクレーブを水中に浸
漬して冷却した。オートクレーブが室温になってから、
中のポリマーを取り出した。This autoclave was placed in an oil bath heated to 290°C and heated for 1 hour. During this time, the pressure increased, so
Adjust the autoclave nozzle to 17.5kg/cm.
! tailored to. After polymerization for 1 hour, the pressure was returned to normal pressure at a rate of 1 kg/cnf, and then the autoclave was immersed in water for cooling. After the autoclave reaches room temperature,
The polymer inside was taken out.
ポリマーは、白色の固体であった。この９５ｗｔ％硫酸
相対粘度は、２．４であった。また、末端基の定量を行
ったところアミノ末端基７５■ｅｑ／ｋｇ、カルボキシ
ル末端基は１１８■ｅｑ／ｋｇであった。The polymer was a white solid. The relative viscosity of this 95 wt% sulfuric acid was 2.4. Further, when the terminal groups were quantified, the amino terminal group was 75 ■eq/kg, and the carboxyl terminal group was 118 ■eq/kg.
このプレポリマーを粉砕して、１〜０．５ ｍｍの大き
さにした。This prepolymer was ground to a size of 1 to 0.5 mm.
このプレポリマー４０ｇを反応容器に入れ、窒素で充分
に置換した後、反応容器を回転しながら窒素を５００ｍ
ｊ！／分の流量で流して、２００℃で６時間加熱した。40g of this prepolymer was placed in a reaction vessel, and the atmosphere was sufficiently replaced with nitrogen.Then, while rotating the reaction vessel, 500ml of nitrogen was added.
j! The mixture was heated at 200° C. for 6 hours at a flow rate of 200° C./min.
こうしてポリマーを得た。このポリマーの硫酸相対粘度
を測定したところ、３．１であった。A polymer was thus obtained. The relative viscosity of this polymer in sulfuric acid was measured and found to be 3.1.
また、ＢＨＴの量を測定したところ、０．４０■／ｇで
あった。Further, the amount of BHT was measured and found to be 0.40 .mu./g.
実施例４゜
実施例１〜３、比較例１で得られたポリマーおよびＢＨ
Ｔを添加したポリマーをキャビログラフＩＢ（東洋精機
製作新製）を用いて試験した。測定温度３００℃で試験
した結果を表１に示した。なお、値は、剪断粘度５００
ｐｏｉｓｅの時の値を採用した。Example 4゜Polymer and BH obtained in Examples 1 to 3 and Comparative Example 1
The T-added polymer was tested using Cavilograph IB (manufactured by Toyo Seiki Seisakusho). Table 1 shows the results of testing at a measurement temperature of 300°C. Note that the value is a shear viscosity of 500
The value at the time of poise was adopted.
この表から、ＢＨＴが０．４ｍｇ／ｇ以下になると、紡
糸性の目安となるダイスウェル比、つまり紡孔径（Ｄｏ
）と吐出したポリマーの径（Ｄ）の比が、０．８■／ｇ
以上の物に比べて、極めて小さくなっていることが判る
。From this table, when BHT is 0.4 mg/g or less, the die swell ratio, which is a guideline for spinnability, or the spinning pore diameter (Do
) and the diameter (D) of the discharged polymer is 0.8 / g
It can be seen that it is extremely small compared to the ones above.
そして、ＢＨＴＯ量が０．４ｍｇ／ｇ以下ではＢＨＴの
影響が急激に小さくなっている。Furthermore, when the amount of BHTO is 0.4 mg/g or less, the influence of BHT decreases rapidly.
このダイスウェル比が大きくなるということは弾性の影
響が出ていることを示しており、これは、紡糸性にとっ
て悪影響を与える。An increase in the die swell ratio indicates the influence of elasticity, which has an adverse effect on spinnability.
実際、紡糸収率にＢＨＴＩが影響していることが確かめ
られた。In fact, it was confirmed that BHTI influenced the spinning yield.
以上の様に、ＢＨＴの少ないポリへキサメチレンアジパ
ミド、つまり分岐の少ないポリヘキサメチレンアジパミ
ドは、ＢＨＴが０．４ｍｇ／ｇ以下ではＤ／Ｄ、の値も
小さくなり、ひいては極めて優れた紡糸性を示す。As mentioned above, polyhexamethylene adipamide with low BHT, that is, polyhexamethylene adipamide with low branching, has a small D/D value when BHT is 0.4 mg/g or less, and is extremely superior. It exhibits excellent spinnability.
Claims (1)
Ｔ）がポリマー１ｇ当たり０．４ｍｇ以下であることを
特徴とする分岐の少ないポリヘキサメチレンアジパミド
。 ２、ポリヘキサメチレンアジパミドを重合するに当たり
、ヘキサメチレンジアンモニウムアジペート（ＡＨ塩）
を密閉加圧容器を用いて加熱反応させた後、冷却してこ
れをプレポリマーとし、このプレポリマーを固相状態で
更に加熱重合することを特徴とする分岐の少ないポリヘ
キサメチレンアジパミドの製造方法。[Claims] 1. Bishexamethylenetriamine (BH
Polyhexamethylene adipamide with little branching, characterized in that T) is 0.4 mg or less per 1 g of polymer. 2. When polymerizing polyhexamethylene adipamide, hexamethylene diammonium adipate (AH salt)
of polyhexamethylene adipamide with little branching, which is characterized by heating and reacting using a sealed pressurized container, cooling it to form a prepolymer, and further heating and polymerizing this prepolymer in a solid phase state. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9233690A JPH03290432A (en) | 1990-04-09 | 1990-04-09 | Polyhexamethylene adipamide low in branching and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9233690A JPH03290432A (en) | 1990-04-09 | 1990-04-09 | Polyhexamethylene adipamide low in branching and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03290432A true JPH03290432A (en) | 1991-12-20 |
Family
ID=14051555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9233690A Pending JPH03290432A (en) | 1990-04-09 | 1990-04-09 | Polyhexamethylene adipamide low in branching and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03290432A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239908A (en) * | 2007-03-29 | 2008-10-09 | Mitsui Chemicals Inc | Method of producing polyamide |
| WO2008126802A1 (en) | 2007-04-06 | 2008-10-23 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent element |
-
1990
- 1990-04-09 JP JP9233690A patent/JPH03290432A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239908A (en) * | 2007-03-29 | 2008-10-09 | Mitsui Chemicals Inc | Method of producing polyamide |
| WO2008126802A1 (en) | 2007-04-06 | 2008-10-23 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent element |
| US8586199B2 (en) | 2007-04-06 | 2013-11-19 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
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