JPH0248021B2 - - Google Patents
Info
- Publication number
- JPH0248021B2 JPH0248021B2 JP58006649A JP664983A JPH0248021B2 JP H0248021 B2 JPH0248021 B2 JP H0248021B2 JP 58006649 A JP58006649 A JP 58006649A JP 664983 A JP664983 A JP 664983A JP H0248021 B2 JPH0248021 B2 JP H0248021B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyamide
- carboxyl groups
- parts
- aliphatic dicarboxylic
- 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 - Lifetime
Links
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- 229920002614 Polyether block amide Polymers 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000000539 dimer Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- -1 polyoxyethylene Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FBBZRYBHLMZXRU-UHFFFAOYSA-N 3-(3,3-diaminopropoxy)propane-1,1-diamine Chemical compound NC(N)CCOCCC(N)N FBBZRYBHLMZXRU-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- BWBRNVIOVBTSJT-UHFFFAOYSA-N diamino oxalate Chemical compound NOC(=O)C(=O)ON BWBRNVIOVBTSJT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Description
本発明は新規なブロツクポリエーテルアミドの
製法に関する。
ブロツクポリエーテルアミドの製法としては、
両末端にカルボキシル基を有するポリアミドと両
末端にアミノ基を有するポリエーテルとを溶融状
態で重合させる方法（特公昭45−7559号）が公知
である。この方法によれば、両末端にカルボキシ
ル基を有するポリアミドは、炭素原子数12までの
脂肪族ジカルボン酸の存在下でポリアミド形成性
モノマーを重合させることにより得る。ついで、
これを両末端にアミノ基を有するポリオキシエチ
レンと重合させることにより、吸湿性、帯電防止
性の優れた繊維形成能のあるブロツクポリエーテ
ルアミドを得ている。このブロツクポリエーテル
アミドは；耐水性、耐熱性、低温衝撃性などの点
で、充分に満足できるものではない。
本発明は公知方法における欠点のないブロツク
ポリエーテルアミドの製法を提供する。
本発明によれば、
(A) ポリアミド形成性モノマーと炭素数14〜48の
脂肪族ジカルボン酸との重縮合によつて得られ
る両末端にカルボキシル基を有するポリアミ
ド、及び
(B) 式 H2N−R1−Ｏ（−R2O）−oR1−NH2
（式中、R1及びR2は、それぞれ、炭素数３以
上のアルキレン基であり、ｎは２〜60である。）
で表わされる末端アミノポリオキシアルキレン
を重縮合させることを特徴とするブロツクポリ
エーテルアミドの製法が提供される。
ポリアミド形成性モノマーとしては、ω−ラク
タム、ω−アミノカルボン酸及びジアミンとジカ
ルボン酸との塩が例示される。ω−ラクタムの具
体例としては、カプロラクタム、エナントラクタ
ム、デカラクタム、ウンデカラクタム及びドデカ
ラクタムが挙げられる。ω−アミノカルボン酸の
具体例としては、６−アミノカプロン酸、10−ア
ミノデカン酸、11−アミノウンデカン酸及び12−
アミノドデカン酸が挙げられる。ジアミンとシカ
ルボン酸との塩の具体例としては、エチレンジア
ミン、トリメチレンジアミン、テトラメチレンジ
アミン、ヘキサメチレンジアミン、ウンデカメチ
レンジアミン、ドデカメチレンジアミン、２，
２，４−／２，４，４−トリメチルヘキサメチレ
ンジアミン、１，３−／１，４−ビス（アミノメ
チル）シクロヘキサン、ビス（４，4′−アミノシ
クロヘキシル）メタン、ｍ−／ｐ−キシリレンジ
アミノのようなジアミンと、シユウ酸、コハク
酸、グルタル酸、アジピン酸、ピメリン酸、スベ
リン酸、アゼライン酸、セバシン酸、ドデカン二
酸、１，４−シクロヘキサンジカルボン酸、テレ
フタル酸、イソフタル酸のようなジカルボン酸と
の塩が挙げられる。
本発明において使用されるジカルボン酸の具体
例を下に示す。
本発明において好ましく使用されるジカルボン
酸は、炭素数８〜24の一塩基性脂肪酸、例えばオ
レイン酸、リノール酸、リノレン酸等をカツプリ
ングすることによつて得られる二量化脂肪族ジカ
ルボン酸（ダイマー酸）である。ダイマー酸の中
でも、生成ブロツクポリエーテルアミドの着色を
抑制する観点から、不飽和度の低いものが特に好
ましく使用される。
本発明における両末端にカルボキシル基を有す
るポリアミド(A)は、前記のポリアミド形成性モノ
マーと炭素数14〜48の脂肪族ジカルボン酸との重
縮合によつて得られる。末端カルボキシル基のう
ち一方は炭素数14〜48の脂肪族ジカルボン酸に由
来する。上記の成分を用いた重縮合は公知の方法
で行われる。例えば、ラクタムを適量の水および
脂肪族ジカルボン酸の共存下に加熱重縮合させる
方法、ω−アミノカルボン酸を適量の脂肪族ジカ
ルボン酸の共存下に加熱重縮合させる方法、前記
ジアミンとジカルボン酸とからなる塩を適量の水
および脂肪族ジカルボン酸の共存下に加熱重縮合
させる方法である。加熱重縮合は、一般に、150
〜350℃の温度で行われる。ラクタムを用いる際
には、適量の水および脂肪族ジカルボン酸と共に
加圧容器中、約１〜30Kg／cm2の加圧下に150〜280
℃に加熱し、次いで放圧、さらに場合によつては
減圧して加熱重縮合を完結させる。ω−アミノカ
ルボン酸を用いる場合には、適量の脂肪族ジカル
ボン酸と共に、常圧下に、180〜280℃に加熱して
重縮合させる。
脂肪族ジカルボン酸の量は、平均分子量が300
〜15000、好ましくは600〜8000の両末端にカルボ
キシル基を有するポリアミドを得るように適宜選
択される。
末端アミノポリオキシアルキレン(B)は、分子鎖
内に炭素数３以上の直鎖又は分岐のオキシアルキ
レン繰返し単位を有し、かつ分子鎖の両末端にア
ミノ基を有するものであり、例えば、プロピレン
オキサイド、テトラヒドロフランの単独又は共重
合で得られるポリマーの末端にアミノ基を導入す
ることによつて合成することができる。前記式に
おけるｎの好ましい値は４〜40である。尚、末端
アミノポリオキシアルキレン(B)は、その主鎖中に
オキシエチレン繰返し単位を高くとも50モル％有
するポリマーを包含する。具体例としては、ポリ
オキシプロピレンアミン、ビス（３−アミノプロ
ピル）ポリテトラヒドロフランが挙げられる。
本発明においては、成分(A)と成分(B)とを重縮合
させることによりブロツクポリエーテルアミドを
製造する。
成分(A)及び成分(B)は、成分(A)のカルボキシル基
と成分(B)のアミノ基とがほぼ当量になる割合で、
反応に供される。成分(A)及び成分(B)の重縮合は公
知の方法で行われる。例えば、150〜350℃、好ま
しくは200〜350℃の温度で溶融重縮合される。
最終製品の特性を改良するために、重縮合の途
中又は後で、酸化防止剤、光や熱に対する安定
剤、難燃剤、及び顔料のような添加剤を添加する
ことができる。
本発明で得られるブロツクポリエーテルアミド
は、熱可塑的に加工可能であり、特に耐水性、耐
熱性、可撓性、低温耐衝撃性、ゴム弾性に優れた
成形品を与える。かかる成形品としては、射出成
形品、ならびに管、ホース、異形材、シート、モ
ノフイラメント、繊維のような押出製品が挙げら
れる。又、本発明によるブロツクポリエーテルア
ミドは、被覆材料としても使用され得る。さら
に、本発明によるブロツクポリエーテルアミドは
ポリアミド樹脂と相溶性が良く、ポリアミド樹脂
とブレンドして用いた際にその耐衝撃性や柔軟
性、弾性を大幅に改善することができる。
以下実施例によつて本発明を説明する。なお、
実施例中、「部」は「重量部」を意味する。相対
溶液粘度（ηr）は、メタクレゾール中25℃、
0.5wt／vol％で測定した。融点（Tn）及びガラ
ス転移点（Tg）はDSCにより測定した。重合物
は熱プレスによりフイルムとし、絶乾フイルムの
引張物性を24℃、相対湿度65％で測定した。又、
熱安定性は示差熱天秤で測定した。
実施例 １
ω−アミノドデカン酸及びダイマー酸（エメリ
ー社製、エンボール1010）を240℃、窒素雰囲気
下で４時間重縮合して、平均分子量1792の両末端
にカルボキシル基を有するプレポリマーを得た。
このプレポリマー67.58部及びビス（３−アミノ
プロピル）ポリテトラヒドロフラン（BASF社
製、o≒750）28.24部を撹拌装置付反応容器に
仕込んだ。これを240℃、窒素雰囲気下で３時間
加熱したのち、１時間かけて270℃とし、さらに
３時間加熱し、重縮合を完結させた。淡黄色の柔
軟な靭性ある重合物を得た。重合物をメタノール
で８時間ソツクスレー抽出したところ抽出率は
4.4％であつた。抽出後の重合物のηrは1.75でTn
は156℃であつた。
比較例 １
実施例１のビス（３−アミノプロピル）ポリテ
トラヒドロフランに代えてポリエチレンオキサイ
ドジアミノプロピルエーテルを使用した。得られ
た重合物は水に著しく膨潤した。
実施例 ２
実施例１と同様にして得た平均分子量2670の両
末端にカルボキシル基を有するプレポリマー
87.73部及びポリオキシプロピレンアミン（ジエ
フアーソンケミカル社製、ジエフアーミンＤ−
400）12.27部を240℃、窒素雰囲気下で６時間縮
合した。無色の柔軟で靭性ある重合物が得られ、
抽出率は4.6％であつた。
比較例 ２
実施例２のダイマー酸をドデカン二酸にかえて
得た平均分子量1605の両末端にカルボキシル基を
有するプレポリマー75.32部及びポリオキシプロ
ピレンアミン（ジエフアーソンケミカル社製、ジ
エフアーミルＤ−400）18.79部を実施例２と同様
な方法で重合した。得られた重合物の抽出率は
2.2％であつた。
実施例 ３
実施例１と同様にして得た平均分子量2404の両
末端にカルボキシル基を有するプレポリマー
72.41部及びビス（３−アミノプロピル）ポリテ
トラヒドロフラン（BASF社製、o≒750）
22.59部を実施例１と同様に重合した。淡黄色の
靭性ある重合物が得られ、抽出率は2.7％であつ
た。
比較例 ３
実施例３のダイマー酸をドデカン二酸にかえて
得た平均分子量1605の両末端にカルボキシル基を
有するプレポリマー64.71部及びビス（３ーアミ
ノプロピル）ポリテトラヒドロフラン（BASF社
製、o≒750）30.23部を実施例３と同様な方法
で重合した。得られた重合物の抽出率は2.8％で
あつた。
実施例２、３及び比較例２、３の結果を第１表
に示す。
The present invention relates to a novel process for producing block polyetheramides. The manufacturing method for block polyether amide is as follows:
A method of polymerizing a polyamide having carboxyl groups at both ends and a polyether having amino groups at both ends in a molten state (Japanese Patent Publication No. 45-7559) is known. According to this method, a polyamide having carboxyl groups at both ends is obtained by polymerizing a polyamide-forming monomer in the presence of an aliphatic dicarboxylic acid having up to 12 carbon atoms. Then,
By polymerizing this with polyoxyethylene having amino groups at both ends, a block polyether amide with excellent hygroscopicity and antistatic properties and fiber-forming ability is obtained. This block polyether amide is not fully satisfactory in terms of water resistance, heat resistance, low temperature impact resistance, etc. The present invention provides a process for preparing block polyetheramides that does not have the disadvantages of known processes. According to the present invention, (A) a polyamide having carboxyl groups at both ends obtained by polycondensation of a polyamide-forming monomer and an aliphatic dicarboxylic acid having 14 to 48 carbon atoms, and (B) a polyamide having the formula H 2 N -R 1 -O(-R 2 O) - o R 1 -NH 2 (In the formula, R 1 and R 2 are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60.)
A method for producing a block polyether amide is provided, which is characterized by polycondensing a terminal aminopolyoxyalkylene represented by the following formula. Examples of polyamide-forming monomers include ω-lactams, ω-aminocarboxylic acids, and salts of diamines and dicarboxylic acids. Specific examples of ω-lactams include caprolactam, enantlactam, decalactam, undecalactam, and dodecalactam. Specific examples of ω-aminocarboxylic acids include 6-aminocaproic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminoundecanoic acid.
Aminododecanoic acid is mentioned. Specific examples of salts of diamine and dicarboxylic acid include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,
2,4-/2,4,4-trimethylhexamethylene diamine, 1,3-/1,4-bis(aminomethyl)cyclohexane, bis(4,4'-aminocyclohexyl)methane, m-/p-xylene diamines such as diamino, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Examples include salts with such dicarboxylic acids. Specific examples of dicarboxylic acids used in the present invention are shown below. Dicarboxylic acids preferably used in the present invention are dimerized aliphatic dicarboxylic acids (dimer acids) obtained by coupling monobasic fatty acids with 8 to 24 carbon atoms, such as oleic acid, linoleic acid, linolenic acid, etc. ). Among dimer acids, those with a low degree of unsaturation are particularly preferably used from the viewpoint of suppressing coloration of the produced block polyetheramide. The polyamide (A) having carboxyl groups at both ends in the present invention is obtained by polycondensation of the polyamide-forming monomer and an aliphatic dicarboxylic acid having 14 to 48 carbon atoms. One of the terminal carboxyl groups is derived from an aliphatic dicarboxylic acid having 14 to 48 carbon atoms. Polycondensation using the above components is carried out by known methods. For example, a method of heating and polycondensing a lactam in the presence of an appropriate amount of water and an aliphatic dicarboxylic acid, a method of heating and polycondensing an ω-aminocarboxylic acid in the presence of an appropriate amount of an aliphatic dicarboxylic acid, and a method of heating and polycondensing a lactam in the presence of an appropriate amount of water and an aliphatic dicarboxylic acid; This method involves heating and polycondensing a salt consisting of the following in the coexistence of an appropriate amount of water and an aliphatic dicarboxylic acid. Heating polycondensation is generally performed at 150
It is carried out at a temperature of ~350 °C. When using a lactam, it is mixed with an appropriate amount of water and an aliphatic dicarboxylic acid in a pressurized container under a pressure of about 1 to 30 kg/ cm2 .
The mixture is heated to .degree. C., and then the pressure is released and, if necessary, the pressure is reduced to complete the heating polycondensation. When ω-aminocarboxylic acid is used, it is polycondensed by heating to 180 to 280°C under normal pressure together with an appropriate amount of aliphatic dicarboxylic acid. The amount of aliphatic dicarboxylic acid has an average molecular weight of 300
It is appropriately selected to obtain a polyamide having carboxyl groups at both ends of 15,000 to 15,000, preferably 600 to 8,000. Terminal amino polyoxyalkylene (B) has linear or branched oxyalkylene repeating units having 3 or more carbon atoms in the molecular chain and has amino groups at both ends of the molecular chain, such as propylene. It can be synthesized by introducing an amino group at the end of a polymer obtained by single or copolymerization of oxide or tetrahydrofuran. A preferable value of n in the above formula is 4 to 40. Note that the terminal aminopolyoxyalkylene (B) includes a polymer having at most 50 mol% of oxyethylene repeating units in its main chain. Specific examples include polyoxypropylene amine and bis(3-aminopropyl) polytetrahydrofuran. In the present invention, a block polyether amide is produced by polycondensing component (A) and component (B). Component (A) and component (B) are in a ratio such that the carboxyl group of component (A) and the amino group of component (B) are approximately equivalent,
Subjected to reaction. Polycondensation of component (A) and component (B) is carried out by a known method. For example, melt polycondensation is carried out at a temperature of 150 to 350°C, preferably 200 to 350°C. Additives such as antioxidants, light and heat stabilizers, flame retardants, and pigments can be added during or after polycondensation to improve the properties of the final product. The block polyetheramide obtained in the present invention can be thermoplastically processed, and provides molded articles particularly excellent in water resistance, heat resistance, flexibility, low-temperature impact resistance, and rubber elasticity. Such molded articles include injection molded articles and extruded products such as tubes, hoses, profiles, sheets, monofilaments, fibers. The block polyetheramides according to the invention can also be used as coating materials. Furthermore, the block polyetheramide according to the present invention has good compatibility with polyamide resins, and when used in blends with polyamide resins, its impact resistance, flexibility, and elasticity can be significantly improved. The present invention will be explained below with reference to Examples. In addition,
In the Examples, "part" means "part by weight". Relative solution viscosity (ηr) at 25°C in metacresol;
Measured at 0.5wt/vol%. Melting point (T n ) and glass transition point (T g ) were measured by DSC. The polymer was heat-pressed into a film, and the tensile properties of the bone-dry film were measured at 24°C and 65% relative humidity. or,
Thermal stability was measured using a differential thermal balance. Example 1 ω-Aminododecanoic acid and dimer acid (manufactured by Emery Co., Ltd., Emball 1010) were polycondensed at 240°C in a nitrogen atmosphere for 4 hours to obtain a prepolymer having an average molecular weight of 1792 and carboxyl groups at both ends. .
67.58 parts of this prepolymer and 28.24 parts of bis(3-aminopropyl)polytetrahydrofuran (manufactured by BASF, o≈750 ) were charged into a reaction vessel equipped with a stirring device. This was heated at 240°C under a nitrogen atmosphere for 3 hours, then heated to 270°C over 1 hour, and further heated for 3 hours to complete polycondensation. A pale yellow, flexible and tough polymer was obtained. When the polymer was Soxhlet extracted with methanol for 8 hours, the extraction rate was
It was 4.4%. The ηr of the polymer after extraction is 1.75 and T n
The temperature was 156℃. Comparative Example 1 Polyethylene oxide diaminopropyl ether was used in place of bis(3-aminopropyl)polytetrahydrofuran in Example 1. The obtained polymer swelled significantly in water. Example 2 Prepolymer having carboxyl groups at both ends and having an average molecular weight of 2670 obtained in the same manner as Example 1
87.73 parts and polyoxypropylene amine (manufactured by DiFerson Chemical Co., Ltd., DiFArmine D-
12.27 parts of 400) were condensed at 240°C under a nitrogen atmosphere for 6 hours. A colorless, flexible and tough polymer is obtained,
The extraction rate was 4.6%. Comparative Example 2 75.32 parts of a prepolymer having an average molecular weight of 1605 and carboxyl groups at both ends obtained by replacing the dimer acid of Example 2 with dodecanedioic acid, and polyoxypropylene amine (manufactured by DiFerson Chemical Co., Ltd., DiFarmil D-400) ) 18.79 parts were polymerized in the same manner as in Example 2. The extraction rate of the obtained polymer is
It was 2.2%. Example 3 Prepolymer having carboxyl groups at both ends and having an average molecular weight of 2404 obtained in the same manner as in Example 1
72.41 parts and bis(3-aminopropyl)polytetrahydrofuran (manufactured by BASF, o ≒750)
22.59 parts were polymerized in the same manner as in Example 1. A pale yellow, tough polymer was obtained, with an extraction rate of 2.7%. Comparative Example 3 64.71 parts of a prepolymer having an average molecular weight of 1605 and carboxyl groups at both ends obtained by replacing the dimer acid in Example 3 with dodecanedioic acid, and bis(3-aminopropyl) polytetrahydrofuran (manufactured by BASF, o ≈750) 30.23 parts were polymerized in the same manner as in Example 3. The extraction rate of the obtained polymer was 2.8%. The results of Examples 2 and 3 and Comparative Examples 2 and 3 are shown in Table 1.
【表】
実施例 ４
実施例１と同様にして得た平均分子量6090の両
末端にカルボキシル基を有するプレポリマー
70.87部及びポリオキシプロピレンアミン（ジエ
フアーソンケミカル社製、ジエフアーミンＤ−
2000）23.27部を実施例２と同様に重合した。淡
黄色の靭性ある重合物が得られた。抽出率は5.5
％で抽出後のηrは1.41、Tnは177℃であつた。
実施例 ５
実施例１で使用したダイマー酸を未水添物（ヘ
ンケル日本(株)製、バーサダイム288）にかえて実
施例２と同様な方法で実施した。
実施例 ６
実施例２で使用したダイマー酸を未水添物（ヘ
ンケル日本(株)製、バーサダイム288）にかえて実
施例２と同様な方法で実施した。
実施例 ７
カプロラクタムとダイマー酸（エメリー社製、
エンポール1010）と水（カプロラクタムに対し４
％）を260℃封圧下（９Kg／cm2）で４時間重縮合
して得た平均分子量1907の両末端にカルボキシル
基を有するプレポリマー71.76部及びポリオキシ
プロピレンアミン（ジエフアーソンケミカル社
製、ジエフアーミンＤ−400）28.24部を実施例２
と同様な方法で重合し、無色の靭性ある重合物を
得た。
実施例 ８
実施例７で使用した両末端にカルボキシル基を
有するプレポリマー71.76部及びビス（３−アミ
ノプロピル）ポリテトラヒドロフラン（BASF社
製、o≒750）28.24部を実施例２と同様な方法
で重合し、靭性ある重合物を得た。
実施例５〜８で得られた重合物の特性を第２表
に示す。[Table] Example 4 Prepolymer having carboxyl groups at both ends and having an average molecular weight of 6090 obtained in the same manner as Example 1
70.87 parts and polyoxypropylene amine (manufactured by DiFerson Chemical Co., Ltd., DiFArmine D-
2000) 23.27 parts were polymerized in the same manner as in Example 2. A pale yellow, tough polymer was obtained. Extraction rate is 5.5
%, ηr after extraction was 1.41, and T n was 177°C. Example 5 The same method as in Example 2 was carried out except that the dimer acid used in Example 1 was replaced with an unhydrogenated product (Versadime 288, manufactured by Henkel Japan Co., Ltd.). Example 6 The same method as in Example 2 was carried out except that the dimer acid used in Example 2 was replaced with an unhydrogenated product (Versadime 288, manufactured by Henkel Japan Co., Ltd.). Example 7 Caprolactam and dimer acid (manufactured by Emery Co., Ltd.)
Empol 1010) and water (4 for caprolactam)
%) under confining pressure (9 Kg/cm 2 ) for 4 hours at 260°C and 71.76 parts of a prepolymer having an average molecular weight of 1907 and having carboxyl groups at both ends, and polyoxypropylene amine (manufactured by DiFerson Chemical Co., Ltd.). Example 2
Polymerization was carried out in the same manner as above to obtain a colorless and tough polymer. Example 8 71.76 parts of the prepolymer having carboxyl groups at both ends used in Example 7 and 28.24 parts of bis(3-aminopropyl) polytetrahydrofuran (manufactured by BASF, o≈750 ) were mixed in the same manner as in Example 2. Polymerization was conducted to obtain a tough polymer. The properties of the polymers obtained in Examples 5 to 8 are shown in Table 2.
Claims (1)
48の脂肪族ジカルボン酸との重縮合によつて得
られる両末端にカルボキシル基を有するポリア
ミド、及び (B) 式 H2N−R1−Ｏ（−R2O）−oR1−NH2 （式中、R1及びR2は、それぞれ、炭素数３以
上のアルキレン基であり、ｎは２〜60である。）
で表わされる末端アミノポリオキシアルキレン
を重縮合させることを特徴とするブロツクポリ
エーテルアミドの製法。[Scope of Claims] 1 (A) a polyamide-forming monomer and a carbon number of 14 or more;
A polyamide having carboxyl groups at both ends obtained by polycondensation with aliphatic dicarboxylic acid of 48, and (B) formula H 2 N−R 1 −O(−R 2 O)− o R 1 −NH 2 (In the formula, R 1 and R 2 are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60.)
A method for producing a block polyether amide, which comprises polycondensing a terminal aminopolyoxyalkylene represented by the formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP664983A JPS59133224A (en) | 1983-01-20 | 1983-01-20 | Production of block polyether-amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP664983A JPS59133224A (en) | 1983-01-20 | 1983-01-20 | Production of block polyether-amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59133224A JPS59133224A (en) | 1984-07-31 |
| JPH0248021B2 true JPH0248021B2 (en) | 1990-10-23 |
Family
ID=11644220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP664983A Granted JPS59133224A (en) | 1983-01-20 | 1983-01-20 | Production of block polyether-amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59133224A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286341A (en) * | 2002-01-28 | 2003-10-10 | Ube Ind Ltd | Polyamide elastomer |
| JP2004351678A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Corrugated tube |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61293223A (en) * | 1985-06-20 | 1986-12-24 | Tokyo Inst Of Technol | Polyether-polyamide multiblock copolymer and its production |
| US5097070A (en) * | 1989-11-03 | 1992-03-17 | Texaco Chemical Company | High molecular weight trifunctional polyoxyethylene amines |
| AU4699796A (en) * | 1995-02-17 | 1996-09-04 | W.R. Grace & Co.-Conn. | Thermoplastic block copolymer with inherent anti-fog properties |
| US7994076B2 (en) | 2007-12-07 | 2011-08-09 | Toyo Boseki Kabushiki Kaisha | Fabric for airbag |
| JP5435328B2 (en) * | 2007-12-07 | 2014-03-05 | 東洋紡株式会社 | Airbag fabric |
| US8541321B2 (en) | 2008-05-15 | 2013-09-24 | Toyo Boseki Kabushiki Kaisha | Copolymerized polyether polyamide resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55133424A (en) * | 1979-02-26 | 1980-10-17 | Inventa Ag | Polyetherpolyamide*its manufacture and flexible injection molded product containing said polyetherpolyamide |
-
1983
- 1983-01-20 JP JP664983A patent/JPS59133224A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55133424A (en) * | 1979-02-26 | 1980-10-17 | Inventa Ag | Polyetherpolyamide*its manufacture and flexible injection molded product containing said polyetherpolyamide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286341A (en) * | 2002-01-28 | 2003-10-10 | Ube Ind Ltd | Polyamide elastomer |
| JP2004351678A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Corrugated tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59133224A (en) | 1984-07-31 |
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