JPS6140692B2 - - Google Patents
Info
- Publication number
- JPS6140692B2 JPS6140692B2 JP85879A JP85879A JPS6140692B2 JP S6140692 B2 JPS6140692 B2 JP S6140692B2 JP 85879 A JP85879 A JP 85879A JP 85879 A JP85879 A JP 85879A JP S6140692 B2 JPS6140692 B2 JP S6140692B2
- Authority
- JP
- Japan
- Prior art keywords
- caprolactam
- dialkylamino
- polymerization
- catalyst
- present
- 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
- 150000003950 cyclic amides Chemical class 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 description 20
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- CFZGIDYCUWFUJR-UHFFFAOYSA-N 3-(dimethylamino)azepan-2-one Chemical compound CN(C)C1CCCCNC1=O CFZGIDYCUWFUJR-UHFFFAOYSA-N 0.000 description 6
- -1 α-methylpropylamino-ε-caprolactam Chemical compound 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- KRDJNXNRTUJHRK-UHFFFAOYSA-N 1,3-dimethyl-1,3-bis(phenylcarbamoyl)urea Chemical compound C=1C=CC=CC=1NC(=O)N(C)C(=O)N(C)C(=O)NC1=CC=CC=C1 KRDJNXNRTUJHRK-UHFFFAOYSA-N 0.000 description 1
- MFUPLJQNEXUUDW-UHFFFAOYSA-N 2-phenylisoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 MFUPLJQNEXUUDW-UHFFFAOYSA-N 0.000 description 1
- SZTYQQPJAPWXLU-UHFFFAOYSA-N 3-(dibutylamino)azepan-2-one Chemical compound CCCCN(CCCC)C1CCCCNC1=O SZTYQQPJAPWXLU-UHFFFAOYSA-N 0.000 description 1
- HHCVJOUNOYDDJX-UHFFFAOYSA-N 3-(diethylamino)azepan-2-one Chemical compound CCN(CC)C1CCCCNC1=O HHCVJOUNOYDDJX-UHFFFAOYSA-N 0.000 description 1
- GUWNZHDVJNHBMU-UHFFFAOYSA-N 3-(dipropylamino)azepan-2-one Chemical compound CCCN(CCC)C1CCCCNC1=O GUWNZHDVJNHBMU-UHFFFAOYSA-N 0.000 description 1
- IGEFUZDZFLHZRZ-UHFFFAOYSA-N 3-(propan-2-ylamino)azepan-2-one Chemical compound CC(C)NC1CCCCNC1=O IGEFUZDZFLHZRZ-UHFFFAOYSA-N 0.000 description 1
- ANZBBKOAUKBPKG-UHFFFAOYSA-N 3-morpholin-4-ylazepan-2-one Chemical compound O=C1NCCCCC1N1CCOCC1 ANZBBKOAUKBPKG-UHFFFAOYSA-N 0.000 description 1
- WZIAZKYQVWGAHM-UHFFFAOYSA-N 3-piperidin-1-ylazepan-2-one Chemical compound O=C1NCCCCC1N1CCCCC1 WZIAZKYQVWGAHM-UHFFFAOYSA-N 0.000 description 1
- QXHLFEWVURXKCP-UHFFFAOYSA-N 3-pyrrolidin-1-ylazepan-2-one Chemical compound O=C1NCCCCC1N1CCCC1 QXHLFEWVURXKCP-UHFFFAOYSA-N 0.000 description 1
- AHCDZZIXAMDCBJ-UHFFFAOYSA-N CCC[Na] Chemical compound CCC[Na] AHCDZZIXAMDCBJ-UHFFFAOYSA-N 0.000 description 1
- ZCUFTCUMEDALHC-UHFFFAOYSA-N CC[K] Chemical compound CC[K] ZCUFTCUMEDALHC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PKMBLJNMKINMSK-UHFFFAOYSA-N magnesium;azanide Chemical compound [NH2-].[NH2-].[Mg+2] PKMBLJNMKINMSK-UHFFFAOYSA-N 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZNQFZPCFVNOXJQ-UHFFFAOYSA-N n-acetyl-n-methylacetamide Chemical compound CC(=O)N(C)C(C)=O ZNQFZPCFVNOXJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 description 1
- UJTRRNALUYKHQE-UHFFFAOYSA-N sodium;diphenylmethylbenzene Chemical compound [Na+].C1=CC=CC=C1[C-](C=1C=CC=CC=1)C1=CC=CC=C1 UJTRRNALUYKHQE-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Description
本発明は塩基性ポリアミドの製造方法に関する
ものである。
通常、α―ジアルキルアミノ―ε―カプロラク
タムの単独重合あるいはα―ジアルキルアミノ―
ε―カプロラクタムと環状アミド類との共重合体
を工業的に製造する方法は溶融重合方法が考えら
れるが、α―ジアルキルアミノ―ε―カプロラク
タムの組成比率が多くなつてくると高分子量の重
合体を得ることは困難となつてくる。
α―ジアルキルアミノ―ε―カプロラクタムを
単独あるいはα―ジアルキルアミノ―ε―カプロ
ラクタムと環状アミド類を１種以上を任意の割合
で重合できれば該重合体は鎖状高分子の側鎖に３
級窒素を有する塩基性ポリアミドが得られること
が期待される。そのため鋭意検討研究した結果、
本発明に到達したものである。すなわち本発明の
目的は該塩基性ポリアミドを得るため、α―ジア
ルキルアミノ―ε―カプロラクタムを単独あるい
はα―ジアルキルアミノ―ε―カプロラクタムと
環状アミド類を１種または２種以上とを重合ある
いは共重合するに際し、塩基性触媒を用いて重合
する方法を提供するものである。
すなわち、本発明はα―ジアルキルアミノ―ε
―カプロラクタムを単独あるいはα―ジアルキル
アミノ―ε―カプロラクタムと一般式
（式中ｎは３から11の数を示す）で示される環
状アミド類の１種または２種以上とを塩基性触媒
の存在下で重合することを特徴とする塩基性ポリ
アミドの製造方法にある。
本発明で使用するα―ジアルキルアミノ―ε―
カプロラクタムは一般式
（式中ＲとR′は低級アルキル基または環状ア
ミンの残基を示す）
で示されるα―ジアルキルアミノ―ε―カプロラ
クタムの具体例は例えばα―ジメルアミノ―ε―
カプロラクタム、α―ジエチルアミノ―ε―カプ
ロラクタム、α―ジプロピルアミノ―ε―カプロ
ラクタム、α―ジブチルアミノ―ε―カプロラク
タム、α―メチルエチルアミノ―ε―カプロラク
タム、α―メチルプロピルアミノ―ε―カプロラ
クタム、α―メチルブチルアミノ―ε―カプロラ
クタム、α―エチルプロピルアミノ―ε―カプロ
ラクタム、α―エチルブチルアミノ―ε―カプロ
ラクタム、α―プロピルブチルアミノ―ε―カプ
ロラクタム、α―ピロリジノ―ε―カプロラクタ
ム、α―ピペリジノ―ε―カプロラクタム、α―
モルホリノ―ε―カプロラクタムなどである。
また本発明で使用する環状アミド類としては例
えば２―ピロリドン、２―ピペリドン、ε―カプ
ロラクタム、ω―ラウロラクタムなどが挙げられ
る。
α―ジアルキルアミノ―ε―カプロラクタムと
環状アミド類とを共重合する場合に両者の共重合
組成比は任意に選択することができるが、本発明
の製造方法が顕著に効果を発揮するのはα―ジア
ルキルアミノ―ε―カプロラクタムの含有率が10
モル以上である。10モル％以下の場合は通常の溶
融重合で重合可能な場合もある。
本発明に用いられる塩基性触媒は次のようなも
のがあげられる。すなわち、リチウム、ナトリウ
ム、カリウム、マグネシウム、カルシウム、スト
ロンチウムなどのようなアルカリおよびアルカリ
土類金属またはその水素化物、硼水素化物、酸化
物、水酸化物、炭酸塩ならびに有機金属化合物た
とえばブチルリチウム、エチルカリウム、プロピ
ルナトリウム、フエニルナトリウム、トリフエニ
ルメチルナトリウム、ジフエニルマグネシウム、
ジエチル亜鉛、トリエチルアルミウム、トリイソ
プロピルアルミニウム、ジイソブチルアルミニウ
ム水素化物、ナトリウムアミド、マグネシウムア
ミド、マグネシウムアニリド、さらにはグリニヤ
ール試薬たとえばエチルマグネシウムクロライ
ド、メチルマグネシウムブロマイド、フエニルマ
グネシウムブロマイドなどがあげられる。特に好
ましくは金属リチウム、金属ナトリウム、金属カ
リウム、トリエチルアルミニウム、ジエチル亜鉛
などが挙げられる。
また必要に応じて助触媒を用いることも何ら制
限するものでないが、その場合助触媒としは、Ｎ
―アセチル―ε―カプロラクタム、Ｎ―フエニル
フタールイミド、Ｎ，N′―ビス（フエニルカル
バミル）―Ｎ，N′―ジメチル尿素、Ｎ，Ｎ―ジ
アセチルメチルアミンなどが一般に用いられる。
触媒、助触媒の添加量は単量体１モル当り1/20モ
ルから1/500モルが好ましい。触媒、助触媒の添
加量が1/20モル以上になると重合体の重合度は著
しく低下するともに着色も増大してくる。また1/
５００モル以下の場合は重合速度が著しく低下する
か、全く重合しなくなる。
重合反応は不活性ガス気流下もしくは減圧下の
もとで行なわれる。重合温度は150℃から250℃が
好ましい。重合温度が150℃以下の場合は重合速
度は顕著に遅くなり実用的でない。また250℃以
上の場合は、α―ジアルキルアミノ―ε―カプロ
ラクタムの熱分解が促進され、かえつて重合度は
低下する方向にある。重合時間は数分から数時間
である。重合の開始前、重合の途中あるいは重合
の未期に顔料、耐候剤、耐熱剤、抗酸化剤等のい
わゆる添加剤を添加することは何んら差支えな
い。
かくしてα―ジアルキルアミノ―ε―カプロラ
クタムの単独あるいはα―ジアルキルアミノ―ε
―カプロラクタムと環状アミド類とを重合あるい
は共重合した塩基性ポリアミドが得られる。本発
明の塩基性ポリアミドはメタノール、エタノー
ル、クロロホルム等の有機溶剤、水、酸性水溶液
などに可溶性であるため、サイジング剤、紙力補
強剤、接着剤、コーテイング剤、印写材料用樹脂
等に有用な重合体として用いられる。
次に本発明の実施例を示す。
実施例 １
水分量0.02％以下に乾燥したα―ジメチルアミ
ノ―ε―カプロラクタム15.6gを窒素ガス気流
中、100℃で溶融する。これに金属ナトリウムを
0.023gとＮ―アセチル―ε―カプラクタムを
0.155gを添加して溶解する。重合温度180℃、重
合時間0.5時間、１時間、６時間でそれぞれ重合
せしめα―ジメチルアミノ―ε―カプロラクタム
の透明な淡黄色の重合体Ａ，Ｂ，Ｃをそれぞれ得
た。重合体Ｂに分析値は次のとおりであつた。
元素分析 （C8H16N2O）oとして
理論値 Ｃ：61.50％ Ｈ：10.30％
Ｎ：17.93％
実測値 Ｃ：60.9％ Ｈ：10.83％
Ｎ：17.80％
軟化点 108〜119℃
98％硫酸中重合体1g／100濃度の25℃におけ
る相対粘度（以下ηrと略す）：3.06
30℃、70％RH中での吸湿率：20.2％
赤外線吸収スペクトル（IR）主ピーク：
3300、2950、1660、1560、1460、1260、
1040CM-1
核磁気共鳴ススペクトル（NMR）主ピーク：
1.5、2.2、2.7、3.2、7.0、7.2ppm
重合体Ａ，Ｂのηrはそれぞれ2.95および3.18で
あつた。重合体Ａ，Ｃについての軟化点、元素分
析、IR、NMRの測定結果は重合体Ｂの場合と同
様であつた。
実施例 ２
水分量0.02％以下に乾燥したα―ジメチルアミ
ノ―ε―カプロラクタム15.6gを窒素ガス気流
中、100℃で溶融する。これに金属ナトリウムを
0.023gとＮ―アセチル―ε―カプロラクタムを
0.155gとを添加して溶解する。また別にε―カプ
ロラクタム11.3gを窒素ガス気流中、100℃で溶融
する。これに金属ナトリウムを0.023gとＮ―アセ
チル―ε―カプロラクタムを0.155gとを添加して
溶解する。次いに両者を混合したのち重合温度
180℃、重合時間60分間重合することによつてα
―ジメチルアミノ―ε―カプロラクタムとε―カ
プロラクタムの１：１モルの透明な淡黄色の共重
合体が得られた。
元素分析
理論値 Ｃ：62.42％ Ｈ：10.10％
Ｎ：15.60％
実測値 Ｃ：62.23％ Ｈ：10.37％
Ｎ：15.55％
軟化点 75〜86℃
ηr ：2.91
IR主ピーク：3300、2950、1660、1560、
1460、1260、1040CM-1
実施例 ３
実施例２と同様の重合条件で、α―ジメチルア
ミノ―ε―カプロラクタムとε―カプロクタムの
混合比が20：80、40：60、58：42、79：21（モ
ル：モル）について共重合した。得られた共重合
体はいずれも透明な淡黄色のものであつた。この
共重合体のηrと軟化点および共重合体をフエノ
ール80部とエチルアルコール20部の混合溶媒にと
かし、１／10規定塩酸で中和滴定して共重合体単
位重量当り中和に要した塩酸量を塩基性度として
求めた。結果をIBおよび元素分析の測定結果と
ともり表１に示した。
The present invention relates to a method for producing basic polyamide. Usually, homopolymerization of α-dialkylamino-ε-caprolactam or α-dialkylamino-
Melt polymerization is a possible method for industrially producing copolymers of ε-caprolactam and cyclic amides, but as the composition ratio of α-dialkylamino-ε-caprolactam increases, high molecular weight polymers are produced. It becomes difficult to obtain. If α-dialkylamino-ε-caprolactam alone or α-dialkylamino-ε-caprolactam and one or more cyclic amides can be polymerized in any ratio, the polymer will have 3 ions in the side chain of the chain polymer.
It is expected that a basic polyamide having a class nitrogen will be obtained. Therefore, as a result of intensive research,
This has led to the present invention. That is, the purpose of the present invention is to polymerize or copolymerize α-dialkylamino-ε-caprolactam alone or α-dialkylamino-ε-caprolactam and one or more cyclic amides in order to obtain the basic polyamide. In this case, the present invention provides a method of polymerizing using a basic catalyst. That is, the present invention provides α-dialkylamino-ε
-Caprolactam alone or α-dialkylamino-ε-caprolactam and general formula (In the formula, n represents a number from 3 to 11) A method for producing a basic polyamide, which comprises polymerizing one or more cyclic amides in the presence of a basic catalyst. . α-dialkylamino-ε- used in the present invention
Caprolactam is a general formula (In the formula, R and R' represent a lower alkyl group or a cyclic amine residue.) Specific examples of α-dialkylamino-ε-caprolactam include α-dimelamino-ε-
Caprolactam, α-diethylamino-ε-caprolactam, α-dipropylamino-ε-caprolactam, α-dibutylamino-ε-caprolactam, α-methylethylamino-ε-caprolactam, α-methylpropylamino-ε-caprolactam, α -Methylbutylamino-ε-caprolactam, α-ethylpropylamino-ε-caprolactam, α-ethylbutylamino-ε-caprolactam, α-propylbutylamino-ε-caprolactam, α-pyrrolidino-ε-caprolactam, α-piperidino -ε- Caprolactam, α-
Morpholino-ε-caprolactam and the like. Examples of the cyclic amides used in the present invention include 2-pyrrolidone, 2-piperidone, ε-caprolactam, and ω-laurolactam. When copolymerizing α-dialkylamino-ε-caprolactam and cyclic amides, the copolymerization composition ratio of the two can be arbitrarily selected, but the production method of the present invention is particularly effective in α- -Dialkylamino-ε-caprolactam content is 10
More than a mole. If the amount is 10 mol% or less, it may be possible to polymerize by ordinary melt polymerization. The basic catalysts used in the present invention include the following. i.e. alkali and alkaline earth metals such as lithium, sodium, potassium, magnesium, calcium, strontium etc. or their hydrides, borohydrides, oxides, hydroxides, carbonates and organometallic compounds such as butyllithium, ethyl Potassium, propyl sodium, phenyl sodium, triphenyl methyl sodium, diphenyl magnesium,
Examples include diethylzinc, triethylaluminum, triisopropylaluminium, diisobutylaluminum hydride, sodium amide, magnesiumamide, magnesium anilide, and Grignard reagents such as ethylmagnesium chloride, methylmagnesium bromide, phenylmagnesium bromide, and the like. Particularly preferred are metallic lithium, metallic sodium, metallic potassium, triethylaluminum, diethylzinc, and the like. Furthermore, there is no restriction on the use of a co-catalyst as necessary; however, in that case, the co-catalyst may be N
-Acetyl-ε-caprolactam, N-phenylphthalimide, N,N'-bis(phenylcarbamyl)-N,N'-dimethylurea, N,N-diacetylmethylamine, etc. are generally used.
The amount of the catalyst and co-catalyst added is preferably 1/20 to 1/500 mole per mole of monomer. When the amount of the catalyst or co-catalyst added is 1/20 mole or more, the degree of polymerization of the polymer decreases markedly and coloring increases. Also 1/
If the amount is less than 500 mol, the polymerization rate will drop significantly or polymerization will not occur at all. The polymerization reaction is carried out under an inert gas stream or under reduced pressure. The polymerization temperature is preferably 150°C to 250°C. If the polymerization temperature is 150° C. or lower, the polymerization rate will be significantly slow, making it impractical. Furthermore, if the temperature is 250°C or higher, the thermal decomposition of α-dialkylamino-ε-caprolactam is promoted, and the degree of polymerization tends to decrease. Polymerization time is from several minutes to several hours. There is no problem in adding so-called additives such as pigments, weathering agents, heat resistant agents, antioxidants, etc. before the start of polymerization, during polymerization, or before polymerization. Thus α-dialkylamino-ε-caprolactam alone or α-dialkylamino-ε-caprolactam
- A basic polyamide is obtained by polymerizing or copolymerizing caprolactam and a cyclic amide. Since the basic polyamide of the present invention is soluble in organic solvents such as methanol, ethanol, and chloroform, water, and acidic aqueous solutions, it is useful for sizing agents, paper strength reinforcing agents, adhesives, coating agents, resins for printing materials, etc. It is used as a polymer. Next, examples of the present invention will be shown. Example 1 15.6 g of α-dimethylamino-ε-caprolactam dried to a moisture content of 0.02% or less is melted at 100°C in a nitrogen gas stream. Add metallic sodium to this
0.023g and N-acetyl-ε-calactam
Add 0.155g and dissolve. Polymerization was carried out at a polymerization temperature of 180° C. and a polymerization time of 0.5 hours, 1 hour, and 6 hours, respectively, to obtain transparent pale yellow polymers A, B, and C of α-dimethylamino-ε-caprolactam, respectively. The analytical values for Polymer B were as follows. Elemental analysis (C 8 H 16 N 2 O) as o Theoretical value C: 61.50% H: 10.30% N: 17.93% Actual value C: 60.9% H: 10.83% N: 17.80% Softening point 108-119℃ 98% sulfuric acid Relative viscosity at 25℃ of medium polymer 1g/100 concentration (hereinafter abbreviated as η r ): 3.06 Moisture absorption rate at 30℃ and 70%RH: 20.2% Infrared absorption spectrum (IR) main peaks: 3300, 2950, 1660 , 1560, 1460, 1260,
1040CM -1 nuclear magnetic resonance spectrum (NMR) main peak:
1.5, 2.2, 2.7, 3.2, 7.0, 7.2 ppm The η r of Polymers A and B were 2.95 and 3.18, respectively. The softening point, elemental analysis, IR, and NMR measurement results for Polymers A and C were similar to those for Polymer B. Example 2 15.6 g of α-dimethylamino-ε-caprolactam dried to a moisture content of 0.02% or less is melted at 100°C in a nitrogen gas stream. Add metallic sodium to this
0.023g and N-acetyl-ε-caprolactam
Add and dissolve 0.155g. Separately, 11.3 g of ε-caprolactam is melted at 100°C in a nitrogen gas stream. To this, 0.023 g of metallic sodium and 0.155 g of N-acetyl-ε-caprolactam are added and dissolved. Next, after mixing both, the polymerization temperature is
α by polymerizing at 180℃ for 60 minutes.
A transparent pale yellow copolymer of -dimethylamino-ε-caprolactam and ε-caprolactam in a 1:1 molar ratio was obtained. Elemental analysis Theoretical value C: 62.42% H: 10.10% N: 15.60% Actual value C: 62.23% H: 10.37% N: 15.55% Softening point 75-86℃ η r : 2.91 IR main peak: 3300, 2950, 1660, 1560,
1460, 1260, 1040CM -1 Example 3 Under the same polymerization conditions as in Example 2, the mixing ratio of α-dimethylamino-ε-caprolactam and ε-caprolactam was 20:80, 40:60, 58:42, 79: 21 (mol: mol) was copolymerized. All of the obtained copolymers were transparent and light yellow in color. The η r and softening point of this copolymer and the copolymer were dissolved in a mixed solvent of 80 parts of phenol and 20 parts of ethyl alcohol, and the amount required for neutralization per unit weight of the copolymer was determined by neutralization titration with 1/10 N hydrochloric acid. The amount of hydrochloric acid added was determined as basicity. The results are shown in Table 1 along with the measurement results of IB and elemental analysis.
【表】
実施例 ４
水分量0.02％以下に乾燥したα―ジメチルアミ
ノ―ε―カプロラクタム15.6gを窒素ガス気流
中、100℃で溶融する。これに金属ナトリウムを
0.023gとＮ―アセチル―ε―カプロラクタムを
0.155gとを添加して溶解する。また別にω―ラウ
ロラクム19.7gを窒素ガス気流中165℃で溶融す
る。これに金属ナトリウムを0.023gとＮ―アセチ
ル―ε―カプロラクタムを0.155gとを添加して溶
解する。次いで両者が混合したのち重合温度230
℃、重合時間120分間加熱重合するこによつて、
α―ジメチルアミノ―ε―カプロラクタムとω―
ラウロラクタムの１：１モルの透明な淡黄色の共
重合体が得られた。
元素分析
理論値 Ｃ：67.94％ H11.12％
Ｎ：11.89％
実測値 Ｃ：67.51％ Ｈ：11.39％
Ｎ：67.46％
軟化点 62―75℃
ηr 2.71[Table] Example 4 15.6 g of α-dimethylamino-ε-caprolactam dried to a moisture content of 0.02% or less is melted at 100°C in a nitrogen gas stream. Add metallic sodium to this
0.023g and N-acetyl-ε-caprolactam
Add and dissolve 0.155g. Separately, 19.7 g of ω-laurolacum was melted at 165°C in a nitrogen gas stream. To this, 0.023 g of metallic sodium and 0.155 g of N-acetyl-ε-caprolactam are added and dissolved. Then, after mixing the two, the polymerization temperature was set to 230
By heating and polymerizing at ℃ for 120 minutes,
α-dimethylamino-ε-caprolactam and ω-
A clear pale yellow copolymer of 1:1 molar laurolactam was obtained. Elemental analysis Theoretical value C: 67.94% H11.12% N: 11.89% Actual value C: 67.51% H: 11.39% N: 67.46% Softening point 62-75℃ η r 2.71
Claims (1)
を単独あるいは、α―ジアルキルアミノ―ε―カ
プロラクタムと一般式 （式中ｎは３から11の数を示す）で示される 環状アミド類は一種または二種以上とを塩基性
触媒の存在下で重合することを特徴とする塩基性
ポリアミドの製造方法。[Scope of Claims] 1 α-dialkylamino-ε-caprolactam alone or together with α-dialkylamino-ε-caprolactam of the general formula (In the formula, n represents a number from 3 to 11) A method for producing a basic polyamide, which comprises polymerizing one or more cyclic amides in the presence of a basic catalyst.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP85879A JPS5592736A (en) | 1979-01-05 | 1979-01-05 | Preparation of basic polyamide |
| US06/108,941 US4297477A (en) | 1979-01-05 | 1979-12-31 | Polyamide having --NH--(CH2)4 --CH(NRR')--CO--units |
| DE8080100010T DE3062647D1 (en) | 1979-01-05 | 1980-01-03 | Polyamides and a process for their preparation from a substituted epsilon-caprolactam |
| EP80100010A EP0013553B1 (en) | 1979-01-05 | 1980-01-03 | Polyamides and a process for their preparation from a substituted epsilon-caprolactam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP85879A JPS5592736A (en) | 1979-01-05 | 1979-01-05 | Preparation of basic polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5592736A JPS5592736A (en) | 1980-07-14 |
| JPS6140692B2 true JPS6140692B2 (en) | 1986-09-10 |
Family
ID=11485346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP85879A Granted JPS5592736A (en) | 1979-01-05 | 1979-01-05 | Preparation of basic polyamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5592736A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310494U (en) * | 1986-07-07 | 1988-01-23 | ||
| JPH01119135U (en) * | 1988-02-03 | 1989-08-11 | ||
| JPH0514991U (en) * | 1991-08-03 | 1993-02-26 | オンキヨー株式会社 | Ring light emitting device |
-
1979
- 1979-01-05 JP JP85879A patent/JPS5592736A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310494U (en) * | 1986-07-07 | 1988-01-23 | ||
| JPH01119135U (en) * | 1988-02-03 | 1989-08-11 | ||
| JPH0514991U (en) * | 1991-08-03 | 1993-02-26 | オンキヨー株式会社 | Ring light emitting device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5592736A (en) | 1980-07-14 |
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