JPH04218529A - Polyamide having high glass transition temperature - Google Patents
Polyamide having high glass transition temperatureInfo
- Publication number
- JPH04218529A JPH04218529A JP26952390A JP26952390A JPH04218529A JP H04218529 A JPH04218529 A JP H04218529A JP 26952390 A JP26952390 A JP 26952390A JP 26952390 A JP26952390 A JP 26952390A JP H04218529 A JPH04218529 A JP H04218529A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- glass transition
- transition temperature
- lactam
- aromatic group
- 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.)
- Granted
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 21
- 229920002647 polyamide Polymers 0.000 title claims abstract description 21
- 230000009477 glass transition Effects 0.000 title claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- 150000002009 diols Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003955 ε-lactams Chemical class 0.000 abstract 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000000835 fiber Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AGEILULECXEYHO-UHFFFAOYSA-N 1,6-bis(7-oxoazepan-2-yl)hexane-1,6-dione Chemical compound C1CCCC(=O)NC1C(=O)CCCCC(=O)C1CCCCC(=O)N1 AGEILULECXEYHO-UHFFFAOYSA-N 0.000 description 1
- JSQGOXTYKZBABW-UHFFFAOYSA-N 3-(3-hydroxyanilino)phenol Chemical compound OC1=CC=CC(NC=2C=C(O)C=CC=2)=C1 JSQGOXTYKZBABW-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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、ラクタム類のアルカリ重合法を利用して製造
するガラス転移温度の高いポリアミドに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyamide with a high glass transition temperature produced using an alkaline polymerization method of lactams.
（従来の技術及びその問題点）
ω−ラクタムをアルカリ触媒および助触媒の作用で重合
させる方法、いわゆるアルカリ重合法は公知である。こ
の方法で得られるポリアミドは、引張強さ、曲げ強さ、
弾性率などの機械的強度や耐溶剤性などが優れており、
機械部品や工業資材として使用されている。しかし、こ
の方法で得たポリアミドのガラス転移温度はそれほど高
くなく、高温時での使用に問題があり、ガラス転移温度
の高いポリアミドが求められていた。(Prior Art and its Problems) A method of polymerizing ω-lactam by the action of an alkaline catalyst and a cocatalyst, a so-called alkaline polymerization method, is known. The polyamide obtained by this method has high tensile strength, bending strength,
It has excellent mechanical strength such as elastic modulus and solvent resistance,
It is used as machine parts and industrial materials. However, the glass transition temperature of the polyamide obtained by this method is not so high, and there is a problem in using it at high temperatures, so a polyamide with a high glass transition temperature has been sought.
ω−ラクタムのアルカリ重合法で製造するポリアミドの
改良方法には数多くの提案があり、ジアミンやジオール
を使用し、改良する方法も公知である。There are many proposals for improving polyamides produced by alkaline polymerization of ω-lactams, and methods for improving polyamides using diamines and diols are also known.
たとえば、英国特許第１０６７１５３号明細書、英国特
許第１０９９２６５号明細書および特公昭４３−２０４
７５号公報には、分子末端または側鎖に水酸基を有する
ポリオールとジイソシアネートとの反応生成物で、末端
または側鎖にイソシアネート基を有するポリウレタンを
助触媒として用い、ε−カプロラクタムのアルカリ重合
を行なうことが提案されている。しかし、これらの方法
で得られるポリアミドは衝撃特性の改良や吸水性の向上
には効果があるが、ガラス転移温度の向上には効果がな
い。For example, British Patent No. 1067153, British Patent No. 1099265, and Japanese Patent Publication No. 43-204
No. 75 discloses that ε-caprolactam is subjected to alkaline polymerization using a polyurethane, which is a reaction product of a polyol having a hydroxyl group at the molecular end or side chain and a diisocyanate, and has an isocyanate group at the end or side chain as a cocatalyst. is proposed. However, although polyamides obtained by these methods are effective in improving impact properties and water absorption, they are not effective in improving glass transition temperature.
また、ω−ラクタムのアルカリ重合法を利用し、ガラス
転移温度の高いポリアミドを製造する従来技術は見当た
らない。Further, there is no conventional technology that utilizes an alkaline polymerization method of ω-lactam to produce a polyamide with a high glass transition temperature.
（問題点を解決する為の技術的手段）
本発明の目的は、ω−ラクタムのアルカリ重合を利用し
てガラス転移温度の高いポリアミドを得ることにある。(Technical means for solving the problems) An object of the present invention is to obtain a polyamide with a high glass transition temperature by utilizing alkaline polymerization of ω-lactam.
本発明の目的は、ω−ラクタムを
（１）アルカリ触媒
（２）多官能助触媒および
（３）芳香族基を有するジアミンまたは／およびジオー
ルの存在下で重合させることにより達成される。The object of the present invention is achieved by polymerizing ω-lactams in the presence of (1) an alkali catalyst, (2) a polyfunctional cocatalyst and (3) a diamine or/and diol having an aromatic group.
本発明によれば、ガラス転移温度が高く、高温でも弾性
率の高いポリアミドを得ることができる。According to the present invention, a polyamide having a high glass transition temperature and a high elastic modulus even at high temperatures can be obtained.
本発明で使用されるω−ラクタムの具体例としては、γ
−ブチロラクタム、δ−バレロラクタム、ε−カプロラ
クタム、ω−エナントラクタム、ω−カプリルラクタム
、ω−ウンデカノラクタム、ω−ラウリンラクタムが挙
げられる。これらのω−ラクタムは単独で使用してもよ
く、２種以上を併用してもよい。Specific examples of ω-lactams used in the present invention include γ
-butyrolactam, δ-valerolactam, ε-caprolactam, ω-enantholactam, ω-capryllactam, ω-undecanolactam, and ω-laurinlactam. These ω-lactams may be used alone or in combination of two or more.
アルカリ触媒としては、公知のω−ラクタムのアルカリ
重合法において使用されるアルカリ触媒をすべて用いる
ことができる。その具体例としては、アルカリ金属、ア
ルカリ土類金属、これらの水素化物、酸化物、水酸化物
、炭酸塩、アルキル化物、アルコキシド、グリニャール
化合物、ソジウムナフタレン、さらには上記金属または
金属化合物とω−ラクタムとの反応生成物、たとえば、
ω−ラクタムのナトリウム塩、カリウム塩などが挙げら
れる。As the alkali catalyst, all alkali catalysts used in known alkaline polymerization methods of ω-lactams can be used. Specific examples thereof include alkali metals, alkaline earth metals, their hydrides, oxides, hydroxides, carbonates, alkylated products, alkoxides, Grignard compounds, sodium naphthalene, and the above metals or metal compounds. - reaction products with lactams, e.g.
Examples include sodium salts and potassium salts of ω-lactams.
アルカリ触媒の使用量は、ω−ラクタムに対して、０．
０５〜１０モル％、特に０．２〜５モル％であることが
好ましい。The amount of the alkali catalyst used is 0.
It is preferably from 0.05 to 10 mol%, particularly from 0.2 to 5 mol%.
多官能助触媒としてはω−ラクタムのアルカリ重合で使
用できる多官能助触媒はすべて使用可能である。その具
体例としては、トルエンジイソシアネート、４，４′−
ジフェニルメタンジイソシアネート、ヘキサメチレンジ
イソシアネート、ポリメチレンポリフェニルポリイソシ
アネート、カルボジイミドで変性されたジイソシアネー
トなどのポリイソシアネート、ヘキサメチレン−１，６
−ビスカルバミドカプロラクタム、Ｎ，Ｎ′−ジフェニ
ル−Ｐ−フェニレンビスカプロラクタムなどのカルバミ
ドラクタム、テレフタロイルクロリド、アジピン酸クロ
リド、セバシン酸クロリドなどの酸クロリド、アジポイ
ルビスカプロラクタム、テレフタロイルビスカプロラク
タムなどのポリアシルラクタムが挙げられる。これらの
中でも、ジイソシアネートおよびカルバミドラクタムが
好ましく使用できる。As the polyfunctional cocatalyst, any polyfunctional cocatalyst that can be used in alkaline polymerization of ω-lactam can be used. Specific examples include toluene diisocyanate, 4,4'-
Polyisocyanates such as diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, diisocyanate modified with carbodiimide, hexamethylene-1,6
- Carbamide lactams such as biscarbamide caprolactam, N,N'-diphenyl-P-phenylene biscaprolactam, acid chlorides such as terephthaloyl chloride, adipic acid chloride, sebacic acid chloride, adipoyl biscaprolactam, terephthaloyl biscaprolactam, etc. Examples include polyacyllactams. Among these, diisocyanates and carbamide lactams can be preferably used.
芳香族基を有するジアミンの具体例としては１，４−ビ
ス（４−アミノフェノキシ）ベンゼン、１，３−ビス（
４−アミノフェノキシ）ベンゼン、４，４′−ジアミノ
ジフェニルスルホン、２，２′−ビス〔４−（４′−ア
ミノフェノキシ）フェニル〕プロパン、ｐ−フェニレン
ジアミン、４，４′−ジアミノビフェニル、４，４′−
ジアミノジフェニルケトン、４，４′−ジアミノジフェ
ニルエーテル、４，４′−ジアミノジフェニルメタン、
２，４−ジアミノトルエンなどがある。Specific examples of diamines having an aromatic group include 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(
4-aminophenoxy)benzene, 4,4'-diaminodiphenylsulfone, 2,2'-bis[4-(4'-aminophenoxy)phenyl]propane, p-phenylenediamine, 4,4'-diaminobiphenyl, 4 ,4'-
Diaminodiphenyl ketone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
Examples include 2,4-diaminotoluene.
また、芳香族基を有するジオールの具体例としてはビス
フェノールＡ、ビスフェノールＳ、ヒドロキノン、４，
４′−ビフェノール、３，３′−ジヒドロキシジフェニ
ルアミン、４，４′−ジヒドロキシジフェニルサルファ
イド、４，４′−ジヒドロキシジフェニルメタン、１，
５−ジヒドロキシナフタリン、４，４′−ジヒドロキシ
ベンジル、４，４′−ジヒドロキシベンゾフェノンなど
が挙げられる。Further, specific examples of diols having an aromatic group include bisphenol A, bisphenol S, hydroquinone, 4,
4'-biphenol, 3,3'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 1,
Examples include 5-dihydroxynaphthalene, 4,4'-dihydroxybenzyl, and 4,4'-dihydroxybenzophenone.
芳香族基を有するジアミンまたはジオールの使用量は、
ω−ラクタムに対して１〜３０重量％、好ましくは３〜
２０重量％である。使用量が上記下限より少ないと得ら
れるポリアミドのガラス転移温度は上昇せず、使用量が
上限より多い場合は重合反応が不均一となり、良好なポ
リアミドを得ることが難しく、ポリアミド本来の物性が
大きく低下するため好ましくない。The amount of diamine or diol having an aromatic group is
1 to 30% by weight, preferably 3 to 30% by weight based on ω-lactam
It is 20% by weight. If the amount used is less than the above lower limit, the glass transition temperature of the resulting polyamide will not rise, and if the amount used is more than the upper limit, the polymerization reaction will be non-uniform, making it difficult to obtain a good polyamide, and the original physical properties of the polyamide will be significantly affected. This is not preferable because it lowers the temperature.
多官能助触媒の使用量は多官能助触媒の官能基数ａと（
３）の化合物のアミノ基または水酸基数をとが１＜ａ／
ｂ≦２．２になる割合で使用される。多官能助触媒の使
用量がこの下限より少ないと、反応速度が遅くなり、得
られたポリアミドの重合率は低くなり好ましくない。ま
た、この上限より多くても効果は変わらない。The amount of the polyfunctional co-catalyst to be used is determined by the number of functional groups a of the multi-functional co-catalyst and (
3) The number of amino groups or hydroxyl groups in the compound is 1<a/
It is used at a ratio that satisfies b≦2.2. If the amount of the polyfunctional cocatalyst used is less than this lower limit, the reaction rate will be slow and the polymerization rate of the obtained polyamide will be low, which is not preferable. Furthermore, even if the amount is greater than this upper limit, the effect remains the same.
本発明におけるω−ラクタムのアルカリ重合は、公知の
方法に従って行なうことができる。重合温度は、重合す
べきω−ラクタムの融点以上２８０℃以下の温度であれ
ば良いが、生成するポリアミドの融点未満の温度である
ことが好ましい。重合時間は、通常、３時間以下である
。重合に際しては、ω−ラクタム、アルカリ触媒、多官
能助触媒および芳香族基を有するジアミンまたは／およ
びジオールを直接混合しても良いし、ω−ラクタム、ア
ルカリ触媒に多官能助触媒と芳香族基を有するジアミン
または／およびジオールとの反応生成物を混合しても良
い。The alkaline polymerization of ω-lactam in the present invention can be carried out according to known methods. The polymerization temperature may be at least the melting point of the ω-lactam to be polymerized and at most 280° C., but is preferably at a temperature below the melting point of the polyamide to be produced. Polymerization time is usually 3 hours or less. During polymerization, the ω-lactam, an alkali catalyst, a polyfunctional cocatalyst, and a diamine or/and diol having an aromatic group may be directly mixed together, or the ω-lactam, an alkali catalyst, a polyfunctional cocatalyst, and an aromatic group may be mixed together. The reaction product with the diamine and/or diol having the above may be mixed.
多官能助触媒と芳香族基を有するジアミンまたは／およ
びジオールとの反応は、反応溶媒の存在下または不存在
下に、多官能助触媒と芳香族基を有するジアミンまたは
／およびジオールを混合することにより、行うことがで
きる。The reaction between the polyfunctional cocatalyst and the diamine or/and diol having an aromatic group can be carried out by mixing the polyfunctional cocatalyst and the diamine or/and diol having an aromatic group in the presence or absence of a reaction solvent. This can be done by
反応溶媒としては、例えば、ベンゼン、トルエン、キシ
レン、溶融ω−ラクタムが挙げられる。Examples of the reaction solvent include benzene, toluene, xylene, and molten ω-lactam.
工業的には、反応生成物から特に分離する必要のない溶
融ω−ラクタムを反応溶媒として使用することが好まし
い。反応温度は、通常１０〜２００℃であり、好ましく
は８０〜１５０℃である。また、溶融ω−ラクタムを反
応溶媒として使用する場合の反応温度は、その融点以上
の温度である。Industrially, it is preferable to use a molten ω-lactam, which does not need to be particularly separated from the reaction product, as the reaction solvent. The reaction temperature is usually 10 to 200°C, preferably 80 to 150°C. Further, the reaction temperature when using a molten ω-lactam as a reaction solvent is a temperature equal to or higher than its melting point.
本発明において、実質的に重合反応を阻害しない可塑剤
、充填剤、繊維、発泡剤、染顔料、さらには酸化防止剤
などの安定剤の存在下に、ω−ラクタムを重合させるこ
ともできる。好ましい可塑剤としてはＮ−アルキルピロ
リドン、ジアルキルイミダゾリジノンが挙げられ、その
使用量はω−ラクタムに対して通常２〜２５重量％であ
る。充填剤の具体例としては、炭酸カルシウム、ワラス
トナイト、カオリン、黒鉛、石こう、長石、雲母、アス
ベスト、カーボンブラック、二硫化モリブデンが挙げら
れる。繊維の具体例としては、ミルドガラス、繊維状マ
ゲネシウム化合物、チタン酸カリウム繊維、鉱物繊維、
グラファイト繊維、ボロン繊維、スチール繊維が挙げら
れる。充填剤および／または繊維の使用量は、ω−ラク
タムに対して通常２〜５０重量％である。発泡剤の具体
例としては、ベンゼン、トルエン、キシレンが挙げられ
、その使用量はω−ラクタムに対して通常１〜１５重量
％である。In the present invention, the ω-lactam can also be polymerized in the presence of stabilizers such as plasticizers, fillers, fibers, blowing agents, dyes and pigments, and even antioxidants, which do not substantially inhibit the polymerization reaction. Preferred plasticizers include N-alkylpyrrolidone and dialkylimidazolidinone, and the amount used is usually 2 to 25% by weight based on the ω-lactam. Specific examples of fillers include calcium carbonate, wollastonite, kaolin, graphite, gypsum, feldspar, mica, asbestos, carbon black, and molybdenum disulfide. Specific examples of fibers include milled glass, fibrous magnesium compounds, potassium titanate fibers, mineral fibers,
Examples include graphite fiber, boron fiber, and steel fiber. The amount of fillers and/or fibers used is usually 2 to 50% by weight, based on the ω-lactam. Specific examples of blowing agents include benzene, toluene, and xylene, and the amount used is usually 1 to 15% by weight based on the ω-lactam.
本発明は、キャスティング法または反応射出成形法によ
って、ω−ラクタムから直接に丸棒、板、パイプあるい
は自動車部品、家電部品、スポーツ部品などの成形品を
製造する方法として有効である。さらに、本発明によっ
て得られたポリアミドをチップにし、これを用いて射出
成形法、押出成形法などによって各種成形品、シート、
繊維などに成形することも可能である。The present invention is effective as a method for producing molded products such as round bars, plates, pipes, automobile parts, home appliance parts, sports parts, etc. directly from ω-lactam by a casting method or a reaction injection molding method. Furthermore, the polyamide obtained according to the present invention is made into chips, which are used to produce various molded products, sheets, etc. by injection molding, extrusion molding, etc.
It is also possible to form it into fibers or the like.
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
実施例、比較例に記載したガラス転移温度および貯蔵弾
性率はレオメトリツクス社製の粘弾性アナライザーＲＭ
Ｓを用い、ＴＥＮＳＹＯＮ ＣＯＭＰＲＥＳＳＩＯＮ法
により、周波数１１Ｈｚで、−１５０〜２００℃の温度
範囲で測定したデータより求めた。ガラス転移温度はｔ
ａｎδのピーク温度で示した。測定は幅５ｍｍ、長さ２
２ｍｍ、厚み０．５ｍｍのテストピースを使用し、４８
時間減圧乾燥した後、行った。The glass transition temperature and storage modulus described in Examples and Comparative Examples were determined using the Rheometrics Analyzer RM manufactured by Rheometrics.
It was determined from data measured using S at a frequency of 11 Hz and a temperature range of -150 to 200°C by the TENSYON COMPRESSION method. The glass transition temperature is t
It is shown as the peak temperature of andδ. Measurements are width 5mm, length 2
Using a test piece of 2 mm and 0.5 mm thickness, 48
After drying under reduced pressure for an hour, it was carried out.
実施例１
（Ａ）成分として１００℃に加熱された実質的に無水の
ε−カプロラクタム１００ｇにナトリウムメチラート（
純度９５％）０．５％を添加し、副生するメタノールを
減圧下に留去して、アルカリ触媒液を調整した。Example 1 As component (A), sodium methylate (
0.5% (purity 95%) was added, and by-produced methanol was distilled off under reduced pressure to prepare an alkaline catalyst solution.
（Ｂ）成分として１００℃に加熱された実質的に無水の
ε−カプロラクタム８０．８ｇに、カルボジイミド基で
変性させた４，４′−ジフェニルメタンジイソシアネー
ト（日本ポリウレタン（株）製の商品名ミリオネートＭ
ＴＬ、以下ミリオネートＭＴＬと称する）を９．２ｇお
よび２，２ビス〔４−（４′−アミノフェノキシ）フェ
ニル〕プロパン１０ｇを加え、均一に混合し１２０℃で
３０分間反応させた。As component (B), 4,4'-diphenylmethane diisocyanate (trade name: Millionate M, manufactured by Nippon Polyurethane Co., Ltd.) is prepared by adding 80.8 g of substantially anhydrous ε-caprolactam heated to 100°C and modifying it with a carbodiimide group.
TL (hereinafter referred to as Millionate MTL) and 10 g of 2,2bis[4-(4'-aminophenoxy)phenyl]propane were added, mixed uniformly, and reacted at 120°C for 30 minutes.
次にＡ、Ｂ成分を４０ｇづつ取出し混合撹拌を行って、
ただちに、１６０℃に加熱した縦３００ｍｍ、横３００
ｍｍ、厚さ１ｍｍのサイズの金型に入れ、１時間保持し
た。得られた試験片を使ってガラス転移温度および８０
℃の貯蔵弾性率を測定した。Next, take out 40g of components A and B and mix and stir.
Immediately heat a 300 mm long and 300 mm wide sheet to 160°C.
It was placed in a mold with a size of 1 mm and a thickness of 1 mm, and held for 1 hour. Using the obtained test piece, the glass transition temperature and 80
The storage modulus in °C was measured.
結果を表１に示した。The results are shown in Table 1.
比較例１
（Ｂ）成分として１００℃に加熱された実質的に無水の
ε−カプロラクタム１００ｇにミリオネートＭＴＬを２
．５７ｇを加えて調整した他は実施例１に従って試験片
を作製し、ガラス転移温度、８０℃の貯蔵弾性率を測定
した。結果を表１に示した。Comparative Example 1 As component (B), 2 millionate MTL was added to 100 g of substantially anhydrous ε-caprolactam heated to 100°C.
．． A test piece was prepared according to Example 1, except that 57 g was added, and the glass transition temperature and storage modulus at 80°C were measured. The results are shown in Table 1.
比較例２
（Ｂ）成分として１００℃に加熱された実質的に無水の
ε−カプロラクタム８０．８ｇにミリオネートＭＴＬ９
．２ｇおよび分子量約４００のポリエチレングリコール
１０ｇを加えて調整した他は実施例１に従って試験片を
作製し、ガラス転移温度、８０℃の貯蔵弾性率を測定し
た。結果を表１に示した。Comparative Example 2 Millionate MTL9 was added to 80.8 g of substantially anhydrous ε-caprolactam heated to 100°C as component (B).
．． A test piece was prepared according to Example 1, except that 2 g of polyethylene glycol and 10 g of polyethylene glycol having a molecular weight of about 400 were added, and the glass transition temperature and storage modulus at 80° C. were measured. The results are shown in Table 1.
実施例２
１２０℃に加熱された実質的に無水のε−カプロラクタ
ム７３．３ｇにミリオネートＭＴＬを１６．７ｇおよび
ビスフェノールＡを１０ｇ加えて均一に混合してＢ成分
を調整した他は実施例１と同様の方法で試験片を作製し
、ガラス転移温度、８０℃の貯蔵弾性率を測定した。結
果を表１に示した。Example 2 Same as Example 1 except that 16.7 g of Millionate MTL and 10 g of bisphenol A were added to 73.3 g of substantially anhydrous ε-caprolactam heated to 120°C and mixed uniformly to adjust the B component. A test piece was prepared in the same manner, and the glass transition temperature and storage modulus at 80°C were measured. The results are shown in Table 1.
（発明の効果）
本発明では、公知のω−ラクタムのアニオン重合の際に
芳香族基を有するジアミンおよび／またはジオールを添
加することにより、ガラス転移温度の高いポリアミドを
得ることが出来る。(Effects of the Invention) In the present invention, a polyamide with a high glass transition temperature can be obtained by adding a diamine and/or diol having an aromatic group during the anionic polymerization of a known ω-lactam.
Claims (3)
ジオールの存在下で重合させることを特徴とするガラス
転移温度の高いポリアミド。3. A polyamide with a high glass transition temperature, characterized in that it is polymerized in the presence of a diamine and/or diol having an aromatic group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26952390A JP2906629B2 (en) | 1990-10-09 | 1990-10-09 | Manufacturing method of polyamide with high glass transition temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26952390A JP2906629B2 (en) | 1990-10-09 | 1990-10-09 | Manufacturing method of polyamide with high glass transition temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04218529A true JPH04218529A (en) | 1992-08-10 |
| JP2906629B2 JP2906629B2 (en) | 1999-06-21 |
Family
ID=17473579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26952390A Expired - Lifetime JP2906629B2 (en) | 1990-10-09 | 1990-10-09 | Manufacturing method of polyamide with high glass transition temperature |
Country Status (1)
| Country | Link |
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| JP (1) | JP2906629B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014515425A (en) * | 2011-05-30 | 2014-06-30 | ライン・ケミー・ライノー・ゲーエムベーハー | Novel compositions for the production of cast polyamide |
-
1990
- 1990-10-09 JP JP26952390A patent/JP2906629B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014515425A (en) * | 2011-05-30 | 2014-06-30 | ライン・ケミー・ライノー・ゲーエムベーハー | Novel compositions for the production of cast polyamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2906629B2 (en) | 1999-06-21 |
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