JPS62256829A - Production of polyamide molding - Google Patents
Production of polyamide moldingInfo
- Publication number
- JPS62256829A JPS62256829A JP9835286A JP9835286A JPS62256829A JP S62256829 A JPS62256829 A JP S62256829A JP 9835286 A JP9835286 A JP 9835286A JP 9835286 A JP9835286 A JP 9835286A JP S62256829 A JPS62256829 A JP S62256829A
- Authority
- JP
- Japan
- Prior art keywords
- lactams
- acid amide
- lactam
- mold
- polymerization
- 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 7
- 229920002647 polyamide Polymers 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000465 moulding Methods 0.000 title abstract description 7
- 150000003951 lactams Chemical class 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 11
- 239000000194 fatty acid Substances 0.000 abstract description 11
- 229930195729 fatty acid Natural products 0.000 abstract description 11
- 150000004665 fatty acids Chemical class 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 239000004604 Blowing Agent Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract 2
- 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 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006082 mold release agent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 sodium lactam Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PECBPCUKEFYARY-ZPHPHTNESA-N n-[(z)-octadec-9-enyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC PECBPCUKEFYARY-ZPHPHTNESA-N 0.000 description 3
- CPUBMKFFRRFXIP-YPAXQUSRSA-N (9z,33z)-dotetraconta-9,33-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O CPUBMKFFRRFXIP-YPAXQUSRSA-N 0.000 description 2
- VGDRLZFDIUUMDP-UHFFFAOYSA-N 1-butyl-1-octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCN(C(N)=O)CCCC VGDRLZFDIUUMDP-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- GCAONVVVMAVFDE-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC GCAONVVVMAVFDE-CLFAGFIQSA-N 0.000 description 1
- VZGOTNLOZGRSJA-ZZEZOPTASA-N (z)-n-octadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC VZGOTNLOZGRSJA-ZZEZOPTASA-N 0.000 description 1
- XDSXQYLETRMUPE-UHFFFAOYSA-N 1,1-dioctadecylurea Chemical compound CCCCCCCCCCCCCCCCCCN(C(N)=O)CCCCCCCCCCCCCCCCCC XDSXQYLETRMUPE-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
- DJQAMASGWPHRSZ-UHFFFAOYSA-N 1-butyl-3-octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)NCCCC DJQAMASGWPHRSZ-UHFFFAOYSA-N 0.000 description 1
- JGXNGCUACVIHHA-UHFFFAOYSA-N 1-octadecyl-1-phenylurea Chemical compound CCCCCCCCCCCCCCCCCCN(C(N)=O)C1=CC=CC=C1 JGXNGCUACVIHHA-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000095 alkaline earth hydride Inorganic materials 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
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 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
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000000524 functional group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 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
- 150000002561 ketenes Chemical class 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 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
- 239000011259 mixed solution 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
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 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
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (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、離
型性の良好なポリアミド成形品を製造する方法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing polyamide molded articles with good mold releasability using an alkaline polymerization method of lactams.
(従来の技術及びその問題点)
ラクタム類をアルカリ触媒及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を利用して、ラクタム
類の重合及び成形を同時に行うことは公知である。(Prior Art and its Problems) It is known to simultaneously polymerize and mold lactams using a method of polymerizing lactams under the action of an alkali catalyst and a cocatalyst, a so-called alkaline polymerization method.
上記方法においては、金型表面と成形品表面の一部とが
付着するため、成形品の取り出しに時間がかかり、成形
サイクルが長くなるとか、成形品表面の平滑性が損なわ
れるとかの欠点がある。In the above method, the mold surface and a part of the molded product surface adhere to each other, so it takes time to take out the molded product, the molding cycle becomes longer, and the smoothness of the molded product surface is impaired. be.
従来、金型からの成形品の離型性を改善する方法として
、金型表面にシリコーンのような外部離型剤を塗布する
方法が知られている。しかし、この方法は、成形のたび
に外部離型剤を塗布する必要があり、さらに離型剤を均
一に塗布することが困難であるという問題がある。BACKGROUND ART Conventionally, as a method for improving the releasability of a molded article from a mold, a method of applying an external mold release agent such as silicone to the surface of the mold is known. However, this method has the problem that it is necessary to apply an external mold release agent every time molding is performed, and that it is difficult to uniformly apply the mold release agent.
特公昭47−51479号公報には、ラクタム類のアル
カリ重合を行うに際し、ラクタム類にアルキルナフタレ
ン又はメチルフェニルポリノロキサンを添加することに
より、成形品の離型性を改良する方法が開示されている
。ぼた、特公昭48−17560号公報には、ラクタム
類のアルカリ重合時に、ラクタム類にホスホン酸の金属
塩又はポリオキシアルキレングリコールの芳香族エーテ
ルを添加することによって、成形品の離型性を向上する
方法が記載されている。Japanese Patent Publication No. 47-51479 discloses a method for improving the mold releasability of a molded article by adding alkylnaphthalene or methylphenyl polyoloxane to lactams during alkaline polymerization of lactams. There is. Bota, Japanese Patent Publication No. 48-17560, discloses that during alkaline polymerization of lactams, a metal salt of phosphonic acid or an aromatic ether of polyoxyalkylene glycol is added to the lactams to improve the mold releasability of the molded product. Describes how to improve it.
これらの方法は原料のラクタム類に内部離型剤を添加す
るだけでよいため、外部離型剤を金型に塗布する方法に
比べて作業性は改善される。しかし、内部離型剤として
使用される上記の化合物はラクタム類の重合速度が低下
することやラクタム類との相溶性が悪く、均一に分散さ
せることが難しい等の欠点がちシ、また。成形品の金型
からの取シ出しは容易になるものの、成形品が金型表面
から離型するまでの時間は、内部離型剤を使用しないと
きに比較して、それほど短縮されない。These methods require only the addition of an internal mold release agent to the raw material lactam, so workability is improved compared to methods in which an external mold release agent is applied to the mold. However, the above-mentioned compounds used as internal mold release agents have drawbacks such as a decrease in the polymerization rate of lactams, poor compatibility with lactams, and difficulty in uniformly dispersing them. Although the molded product can be easily removed from the mold, the time it takes for the molded product to be released from the mold surface is not so shortened compared to when no internal mold release agent is used.
(問題点を解決するだめの技術的手段)本発明の目的は
、ラクタム類のアルカリ重合において特定の内部離型剤
を使用することによシ。(Technical means for solving the problem) The object of the present invention is to solve the problem by using a specific internal mold release agent in the alkaline polymerization of lactams.
ラクタム類の重合速度を低下させることなく、ラクタム
類に容易に分散し、成形品が金型から離型するまでの時
間が短くなシ、かつ成形品の取シ出し作業が容易な方法
を提供することにある。Provides a method that easily disperses into lactams without reducing the polymerization rate of lactams, shortens the time it takes for a molded product to be released from a mold, and facilitates removal of the molded product. It's about doing.
上記目的は、ラクタム類をアルカリ触媒及び助触媒の作
用で重合成形させる方法において。The above object is a method for polymerizing lactams by the action of an alkali catalyst and a cocatalyst.
式RCONH(CH)nNI(COR(1)。Formula RCONH(CH)nNI(COR(1).
ROOMHR’ (If)及び
RNHCONHR’ (III)
(式中、R,R’は炭素数7〜30の飽和又は不飽和脂
肪族基であり、nは5〜1Cの整数である)で示される
脂肪酸アマイドの1種類以上を、ラクタム類に対して0
,05〜2重量%添加することによって達成される。Fatty acids represented by ROOMHR' (If) and RNHCONHR' (III) (wherein R, R' are saturated or unsaturated aliphatic groups having 7 to 30 carbon atoms, and n is an integer of 5 to 1C) One or more types of amides, zero for lactams
, 05 to 2% by weight.
一般に、アマイド基(−CONH−)を有する化合物は
、ラクタム類のアルカリ重合速度を低下させることが知
られているが1本発明で使用する脂肪族アマイドは重合
反応に悪影響を及ぼさない特殊な化合物と考えられる。Generally, it is known that compounds having an amide group (-CONH-) reduce the alkaline polymerization rate of lactams, but the aliphatic amide used in the present invention is a special compound that does not have a negative effect on the polymerization reaction. it is conceivable that.
本発明で使用されるラクタム類の具体例としては、r−
ブチロラクタム、δ−バレロラクタム。Specific examples of lactams used in the present invention include r-
Butyrolactam, δ-valerolactam.
ε−カグロラクタム、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及びω−ラウリ
ンラクタムが挙げられる。これらのラクタム類は単独で
使用してもよく、2種以上を併用してもよい。Examples include ε-caglolactam, ω-enantholactam, ω-capryllactam, ω-undecanolactam and ω-laurinlactam. These lactams may be used alone or in combination of two or more.
アルカリ触媒としては、公知のラクタム類のアルカリ重
合法において使用される化合物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。As the alkali catalyst, all compounds used in known alkaline polymerization methods of lactams can be used. Specific examples include alkali metals, alkaline earth metals, and hydrides thereof.
酸化物、水酸化物、炭酸塩、アルキル化物又はアルコキ
シド、グリニヤール化合物、ソジウムナフタレン、さら
に上記金属又は金属化合物とラクタム類との反応生成物
1例えば、ナトリウムラクタム、カリウムラクタム、ラ
クタムマグネシウムブロマイドが挙げられる。アルカリ
触媒の使用量は。Oxides, hydroxides, carbonates, alkylated products or alkoxides, Grignard compounds, sodium naphthalene, and reaction products of the above metals or metal compounds with lactams 1 Examples include sodium lactam, potassium lactam, and lactam magnesium bromide. It will be done. What is the amount of alkaline catalyst used?
ラクタム類に対して0,05〜10モルチ、特に0.2
〜5モル係であることが好ましい。0.05 to 10 molar relative to lactams, especially 0.2
It is preferable that it is 5 molar ratio.
助触媒についても、公知のラクタム類のアルカリ重合法
において使用される化合物をすべて用いることができる
。その具体例としては、N−アシルラクタム、有機イン
シアネート、酸塩化物、酸無水物、エステル、尿素誘導
体、カルボジイミド及びケテンが挙げられる。さらに1
分子末端に水酸基、チオール基、アミノ基あるいはカル
ボキシル基を2個以上有するポリマーと、アジポイルビ
スカプロラクタム、セバコイルビスカプロラクタム、ヘ
キサメチレン−1,6−ビスカプロラクタム。As for the co-catalyst, all compounds used in known alkaline polymerization methods for lactams can be used. Specific examples include N-acyllactams, organic incyanates, acid chlorides, acid anhydrides, esters, urea derivatives, carbodiimides and ketenes. 1 more
Polymers having two or more hydroxyl groups, thiol groups, amino groups or carboxyl groups at the molecular terminals, adipoyl biscaprolactam, sebacoyl biscaprolactam, hexamethylene-1,6-biscaprolactam.
あるいはジイソシアネートとを、前記ポリマーの官能基
に対して当量以上反応させて得られる反応生成物も助触
媒として使用することができる。これらの反応生成物を
助触媒として使用することにより、得られるポリアミド
の耐衝撃性を大きく改善することができる。助触媒の使
用量は、ラクタム類に対して0.03〜10モル襲であ
ることが好ましい。Alternatively, a reaction product obtained by reacting diisocyanate in an amount equivalent to or more than the functional group of the polymer can also be used as a cocatalyst. By using these reaction products as co-catalysts, the impact resistance of the resulting polyamide can be greatly improved. The amount of co-catalyst used is preferably 0.03 to 10 mol per lactam.
式(1)、(I[)及び<m>で示される脂肪酸アマイ
ドは、飽和又は不飽和脂肪酸のアマイドで1式(I)の
具体例としては、ヘキサメチレンビスオレイン酸アミド
、ヘキサメチレンビスステアリン酸アミド等1式(■)
では、N−オレイルオレイン酸アミド、N−ステアリル
オレイン酸アミド、N−オレイルパルミチン酸アミド、
N−オレイルパルミチン酸アミド、N−オレイルステア
リン酸アミド、N−ステアリルエルカ酸アミド。The fatty acid amide represented by formula (1), (I[) and <m> is an amide of saturated or unsaturated fatty acid, and specific examples of formula (I) include hexamethylenebisoleic acid amide, hexamethylenebisstearin 1 type of acid amide etc. (■)
So, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl palmitic acid amide,
N-oleyl palmitic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide.
N−ステアリルステアリン酸アミド等が1式(III)
ではN−ブチル−N−ステアリル尿素、N−プビルーN
−スf7’)ル尿素、N−アリルーN−ステアリル尿素
、N−フェニル−N−ステアリル尿素。N-stearyl stearic acid amide etc. is 1 formula (III)
So, N-butyl-N-stearylurea, N-pubi-N
-suf7') lurea, N-aryl-N-stearylurea, N-phenyl-N-stearylurea.
N−ステアリル−N−ステアリル尿素等がある。Examples include N-stearyl-N-stearylurea.
これらの中でも、ヘキサメチレンビスオリイン酸アミド
、N−オレイルステアリン酸アミド及びN−ブチル−N
−ステアリル尿素が好ましい。これらの脂肪酸アマイド
は単独で使用してもよく。Among these, hexamethylene bis oleic acid amide, N-oleyl stearic acid amide and N-butyl-N
-Stearyl urea is preferred. These fatty acid amides may be used alone.
2種以上を併用してもよい。Two or more types may be used in combination.
脂肪酸アマイドの使用量は、ラクタム類に対して0.0
1〜2重量である。使用量が下限よシ小さいと成形品の
離型性を改良する効果が乏しく、使用量が上限よシ多い
とラクタム類の重合反応速度が低下する。The amount of fatty acid amide used is 0.0 compared to lactams.
1-2 weight. If the amount used is less than the lower limit, the effect of improving the mold releasability of the molded article will be poor, and if the amount used is more than the upper limit, the polymerization reaction rate of the lactam will decrease.
脂肪酸アマイドは通常ラクタム類のアルカリ重合に先立
って、ラクタム類に添加される。Fatty acid amides are usually added to lactams prior to alkaline polymerization of the lactams.
本発明におけるラクタム類のアルカリ重合は。Alkaline polymerization of lactams in the present invention.
それ自体公知の方法に従って行うことができ6゜重合温
度は重合すべきラクタム類の融点以上であり、かつ生成
ポリアミドの融点未満の温度でちる。It can be carried out according to methods known per se, and the polymerization temperature is set at 6° above the melting point of the lactam to be polymerized and below the melting point of the polyamide produced.
重合時間は通常1時間以下である。Polymerization time is usually 1 hour or less.
本発明において、実質的に重合反応を阻害しない可塑剤
、充填材、繊維1発泡剤、染料、顔料。In the present invention, plasticizers, fillers, fiber blowing agents, dyes, and pigments that do not substantially inhibit the polymerization reaction.
酸化防止剤などの存在下にラクタム類を重合させること
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などが挙げられ、
その使用量はラクタム類に対して通常2〜25重量係で
ある。充填材の具体列としては、炭酸カルシウム、ワラ
ストナイト、カオリン、黒鉛1石コウ8長石、雲母、ア
スベスト。Lactams can also be polymerized in the presence of antioxidants and the like. Preferred plasticizers include N-alkylpyrrolidone, dialkylimidazolidinone, etc.
The amount used is usually 2 to 25 parts by weight based on the lactam. Specific examples of fillers include calcium carbonate, wollastonite, kaolin, graphite, 1 stone, 8 feldspar, mica, and asbestos.
カーボンブラック、二硫化モリブデンなどが挙げられる
。繊維の具体例としては、ミルドグラス。Examples include carbon black and molybdenum disulfide. A specific example of fiber is milled glass.
繊維状マグネシウム化合物、チタン酸カリウム叡維、鉱
物繊維、グラファイト繊維、ボロン繊維。Fibrous magnesium compound, potassium titanate fiber, mineral fiber, graphite fiber, boron fiber.
スチール繊維などが挙げられる。充填材及び/又は繊維
の使用量は、ラクタム類に対して通常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、
キシレンなどが挙げラレ、ソの使用量はラクタム類に対
して通常1〜15重量係である。本発明はキャスティン
グ法又は反応射出成形法によってラクタム類から直接に
丸棒、板。Examples include steel fiber. The amount of fillers and/or fibers used is usually 2 to 50% by weight, based on the lactams. Specific examples of blowing agents include benzene, toluene,
Examples include xylene, and the amount used is usually 1 to 15 parts by weight relative to the lactams. The present invention produces round rods and plates directly from lactams by casting method or reaction injection molding method.
パイプあるいは自動車部品などの成形品を製造する方法
として好適である。This method is suitable as a method for manufacturing molded products such as pipes or automobile parts.
(発明の効果)
本発明は、実施例、比較例に示す通シ、特定の脂肪酸ア
マイドを添加してε−カプロラクタムを重合成形すると
、これらを添加しない比較例1に比べて離型開始時間は
約130秒、離型完了時間は約190秒短縮される。こ
れによシ成形サイクルが短縮され、生産性が向上と共に
品笈が安定した成形品が得られるきわめて優れた製法で
ある。(Effects of the Invention) As shown in Examples and Comparative Examples, the present invention shows that when ε-caprolactam is polymerized by adding a specific fatty acid amide, the mold release start time is shorter than in Comparative Example 1 in which these are not added. The mold release completion time is reduced by about 130 seconds, and the mold release completion time is reduced by about 190 seconds. This is an extremely excellent manufacturing method that shortens the molding cycle, improves productivity, and produces molded products with stable quality.
(実施例) 以下に実施例を示す。(Example) Examples are shown below.
重合速度、離型開始時間及び離型完了時間は。What are the polymerization rate, mold release start time, and mold release completion time?
それぞれ、100°Cで混合したモノマー液をただちに
160°Cのオイルバス内に保持されているガラス製試
験管中に入れてラクタム類を重合させた際の、七ツマー
液の混合開始からモノマー液が非流動化するまでの時間
、モノマー液の混合開始から生成したポリマーの一部が
試験管の管壁から離型を始めるまでの時間、及びモノマ
ー液の混合開始から生成ポリマーが完全に試験管の管壁
から離型するまでの時間を意味する。In each case, when the monomer solution mixed at 100°C was immediately put into a glass test tube kept in a 160°C oil bath to polymerize lactams, the monomer solution was The time from the start of mixing of the monomer liquid until a part of the produced polymer begins to release from the tube wall of the test tube, and the time from the start of mixing of the monomer liquid until the produced polymer completely leaves the test tube. means the time it takes for the mold to be released from the pipe wall.
又、脂肪酸アマイドのラクタム類への溶解性ば。Also, the solubility of fatty acid amide in lactams.
100°Cに昇温したカプロラクタム液に脂肪酸アマイ
ドを添加し、5重量係以上溶解するものを01〜5重量
係溶解するものをΔ、1重量多以下のものを×とした。A fatty acid amide was added to a caprolactam solution heated to 100°C, and those that dissolved by weight of 5 or more were rated as Δ, those that dissolved by weight of 01 to 5 were rated as Δ, and those that dissolved by 1 or less by weight were marked as ×.
実施例1
100°Cに加熱された実質的に無水のε−カプロラク
タム1007にナトリウムメチラート(純度95%)0
5yを添加し1副生ずるメタノールを減圧下に留去して
、アルカリ触媒液(A成分)を調製した。Example 1 Sodium methylate (95% purity) 0 to substantially anhydrous ε-caprolactam 1007 heated to 100°C
5y was added and methanol produced as a by-product was distilled off under reduced pressure to prepare an alkaline catalyst solution (component A).
100°Cに加熱された実質的に無水のε−カプロラク
タム100りに、ヘキサメチレンジイソシアネート0.
2 f及びN−ブチル−シーステアリル尿素19を加え
、窒素ガス雰囲気下で均一に攪拌して、B成分を調整し
た。To 100 parts of substantially anhydrous ε-caprolactam heated to 100°C, 0.0 parts of hexamethylene diisocyanate is added.
2f and N-butyl-cystearylurea 19 were added and stirred uniformly under a nitrogen gas atmosphere to prepare component B.
A成分及びB成分を混合攪拌し、混合物をただちに、1
60’Cのオイルパス中に保持しである試験管(内容積
250 cc 、径3c、、高さ36cm)に入れ、窒
素ガス雰囲気下で重合させ1重合速度。Mix and stir component A and component B, and immediately add 1
A test tube (inner volume: 250 cc, diameter: 3 cm, height: 36 cm) was placed in an oil path at 60'C, and polymerization was carried out under a nitrogen gas atmosphere at a polymerization rate of 1.
離型開始時間及び離型完了時間を測定した。The mold release start time and mold release completion time were measured.
又、N−ブチル−シーステアリル尿素のカプロラクタム
への溶解性も測定した。結果を第1表に示す。The solubility of N-butyl-cystearylurea in caprolactam was also measured. The results are shown in Table 1.
比較例1
N−ブチル−シーステアリル尿素を添加しなかった以外
は実施例1と同様の方法を繰り返した。Comparative Example 1 The same method as Example 1 was repeated, except that N-butyl-cystearylurea was not added.
結果を第1表に示す。The results are shown in Table 1.
比較例2
N−ブチル−N′−ステアリル尿素に代えてポリエチレ
ングリコールモノオレイルエーテル12を使用した以外
は実施例1と同様の方法を繰シ返した。結果を第1表に
示す。Comparative Example 2 The same method as in Example 1 was repeated except that polyethylene glycol monooleyl ether 12 was used in place of N-butyl-N'-stearylurea. The results are shown in Table 1.
比較例3
N−ブチル−シーステアリル尿素に代えてα−メチルナ
フタリン12を使用した以外は実施例1と同様の方法を
繰シ返した。結果を第1表に示す。Comparative Example 3 The same method as in Example 1 was repeated except that α-methylnaphthalene 12 was used in place of N-butyl-cystearylurea. The results are shown in Table 1.
比較例4
N−ブチル−シーステアリル尿素に代えてステアリン酸
アマイド17を使用した以外は実施例1と同様の方法を
繰シ返した。結果を第1表に示す。Comparative Example 4 The same method as in Example 1 was repeated except that stearamide 17 was used in place of N-butyl-cystearylurea. The results are shown in Table 1.
比較例5
N−ブチル−シーステアリル尿素に代えてm−キシリレ
ンピスステアリン酸アミド12を使用した以外は実施例
1と同様の方法を繰り返した。結果を第1表に示す。Comparative Example 5 The same method as Example 1 was repeated except that m-xylylene pistearamide 12 was used in place of N-butyl-cystearylurea. The results are shown in Table 1.
実施例2
110°Cに加熱された実質的に無水のε−カプロラク
タム200yにナトリウムメチラート0.5 、り
を添加し、副生ずるメタノールを減圧下に留去して、ア
ルカリ触媒液を調製した。Example 2 0.5 ml of sodium methylate was added to 200y of substantially anhydrous ε-caprolactam heated to 110°C, and by-produced methanol was distilled off under reduced pressure to prepare an alkaline catalyst liquid. .
上記アルカリ触媒液に第2表に記載の脂肪酸アマイドの
所定量を添加゛して均一に混合した後、攪拌下にヘキサ
メチレン−1,6−ピスカルパミドカプロラクタム0,
7fを添加した。この混合液を実施例1と同様の操作で
重合させ1重合速度、離型開始時間及び離型完了時間を
測定した。又、溶解性も調べた。結果を第2表に示す。After adding a predetermined amount of fatty acid amide listed in Table 2 to the above alkaline catalyst solution and mixing uniformly, hexamethylene-1,6-piscarpamide caprolactam 0,
7f was added. This mixed solution was polymerized in the same manner as in Example 1, and the polymerization rate, mold release start time, and mold release completion time were measured. The solubility was also investigated. The results are shown in Table 2.
実施例5
ナイロンRIM成形装置のA成分槽に実質的に無水のε
−力プロラクタム4Kg及びナトリウムカプロラクタム
100tを入れ、温度を100°Cに保持した。Example 5 Substantially anhydrous ε in the A component tank of a nylon RIM molding device
- 4 kg of prolactam and 100 t of sodium caprolactam were added, and the temperature was maintained at 100°C.
B成分槽には、実質的に無水のε−力プロラクタムZ4
に9.キシリレンジインシアネート2232、シェフア
ミンD −2000、(三片テキサコケミカル■製)1
.6に9.ガラスカットファイバー(富士ファイバーグ
ラス■製、 FESS−005−0413)1.6 K
SI及びN−オレイルステアリン酸アミド12グを添加
し、100°Cで均一に混合した。The B component tank contains substantially anhydrous ε-force prolactam Z4.
9. Xylylene diincyanate 2232, Chefamine D-2000, (manufactured by Mikata Texaco Chemical) 1
.. 6 to 9. Glass cut fiber (manufactured by Fuji Fiber Glass ■, FESS-005-0413) 1.6 K
12 g of SI and N-oleyl stearamide were added and mixed uniformly at 100°C.
A成分及びB成分を1:1の容量比でミキシングヘッド
に供給して衝突混合させ、ついでミキシングヘッドから
140°Cに加熱されている内容積285ccの箱状金
型に射出した。射出から1分後に金型を開くことが出来
、平滑性の良い表面の成形品を容易に取り外すことが出
来た。Component A and component B were supplied to a mixing head at a volume ratio of 1:1 and mixed by collision, and then injected from the mixing head into a box-shaped mold having an internal volume of 285 cc and heated to 140°C. The mold could be opened one minute after injection, and the molded product with a smooth surface could be easily removed.
比較例6
N−オレイルアテアリン酸アミドを使用しなかった以外
は実施例5と同様の方法を繰り返した。Comparative Example 6 The same method as Example 5 was repeated, except that N-oleyl atearamide was not used.
射出から6分後に金型を開いたが、成形品の大部分が金
型に付着していたため、成形品を直ちに金型から取り外
すことができなかった。The mold was opened 6 minutes after injection, but the molded product could not be immediately removed from the mold because most of the molded product was attached to the mold.
第1表 〉Table 1 〉
Claims (1)
させる方法において、 式RCONH(CH)_nNHCOR RCONHR′及び RNHCONHR′ (式中、R、R′は炭素数7〜30の飽和又は不飽和脂
肪族基であり、nは5〜10の整数である。)で示され
る脂肪酸アマイドの1種類以上を、ラクタム類に対して
0.05〜2重量%添加することを特徴とするポリアミ
ド成形品の製法。[Claims] A method for polymerizing lactams by the action of an alkali catalyst and a cocatalyst, comprising the formulas RCONH(CH)_nNHCOR RCONHR' and RNHCONHR' (wherein, R and R' are saturated carbon atoms having 7 to 30 carbon atoms). or an unsaturated aliphatic group, and n is an integer of 5 to 10. Manufacturing method for polyamide molded products.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61098352A JPH0689132B2 (en) | 1986-04-30 | 1986-04-30 | Manufacturing method of polyamide moldings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61098352A JPH0689132B2 (en) | 1986-04-30 | 1986-04-30 | Manufacturing method of polyamide moldings |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62256829A true JPS62256829A (en) | 1987-11-09 |
JPH0689132B2 JPH0689132B2 (en) | 1994-11-09 |
Family
ID=14217498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61098352A Expired - Lifetime JPH0689132B2 (en) | 1986-04-30 | 1986-04-30 | Manufacturing method of polyamide moldings |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0689132B2 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5531803A (en) * | 1978-08-25 | 1980-03-06 | Ube Ind Ltd | Polyamide composition |
-
1986
- 1986-04-30 JP JP61098352A patent/JPH0689132B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5531803A (en) * | 1978-08-25 | 1980-03-06 | Ube Ind Ltd | Polyamide composition |
Also Published As
Publication number | Publication date |
---|---|
JPH0689132B2 (en) | 1994-11-09 |
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