JPS62252426A - Production of nylon 6 - Google Patents
Production of nylon 6Info
- Publication number
- JPS62252426A JPS62252426A JP9578186A JP9578186A JPS62252426A JP S62252426 A JPS62252426 A JP S62252426A JP 9578186 A JP9578186 A JP 9578186A JP 9578186 A JP9578186 A JP 9578186A JP S62252426 A JPS62252426 A JP S62252426A
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- type
- cooling
- silicate
- cooling rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000004677 Nylon Substances 0.000 abstract description 6
- 229920001778 nylon Polymers 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 4
- DNHDZMQRJHRYFX-UHFFFAOYSA-N 12-aminododecanoic acid;hydrochloride Chemical compound Cl.NCCCCCCCCCCCC(O)=O DNHDZMQRJHRYFX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229960002684 aminocaproic acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 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、a型あるいはr型所望の結晶構造を有するナ
イロン6を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing nylon 6 having a desired a-type or r-type crystal structure.
ナイロン6は、バランスの取れた特性の為に代表的なエ
ンジニアリング・グラスチックとしての地位を有してお
り、特に自動車産業での需要は今後も拡大すると期待さ
れる。Nylon 6 has a position as a representative engineering glass due to its well-balanced properties, and demand is expected to continue to grow, especially in the automobile industry.
ナイロン6は、結晶性ポリマーであり、この為引張り強
度や剛性では優れた特性を示すが、一方この為、衝撃強
度が自動車外板等に開用するには十分な値を有していな
い。特に大型部品に適する迅速なア〃カリ触媒重合法で
製造されるナイロン6は、他の加水分解重公法等で製造
されるナイロン6より、#撃強度が低いとされている(
M、I、コ−ハン編、“ナイロン・プラスチックス”(
NyIon Plastics ) 、 P 457
、イン!−サイエyス(Interscience )
、 1973 )。Nylon 6 is a crystalline polymer and therefore exhibits excellent properties in terms of tensile strength and rigidity, but on the other hand, it does not have a sufficient impact strength for use in automobile exterior panels and the like. Nylon 6, which is produced using a rapid alkali-catalyzed polymerization method that is especially suitable for large parts, is said to have a lower impact strength than nylon 6 produced using other hydrolytic polymerization methods.
“Nylon Plastics,” edited by M. I. Cohan (ed.
NyIon Plastics), P 457
,in! -Interscience
, 1973).
ナイロン6の画筆強度の改善は、ナイロン工業分野での
中心的課題の1つであり、エラストマーとのブレンドや
共直会による改善が試みられている(例えば特公昭61
−5809号、特公昭54−40120号)。しかしな
がら、これらの方法は必然的にナイロン6の非結晶化あ
るいは低結晶化をもたらしてしまう。Improving the brush strength of nylon 6 is one of the central issues in the nylon industry, and attempts have been made to improve it by blending it with elastomers or collaborating with it (for example,
-5809, Special Publication No. 54-40120). However, these methods inevitably result in amorphous or low crystallization of nylon 6.
ナイロン6の結晶構造には、平面ジグザグのa型とらせ
ん構造のγ型とが知られており、a型ナイロン6は、高
融点と高密度を有し、r型ナイロン6は低融点と低密度
であり、a型結晶と非晶質の中間的性質を有する。The crystal structures of nylon 6 are known as the a-type with a planar zigzag structure and the γ-type with a spiral structure.A-type nylon 6 has a high melting point and high density, and R-type nylon 6 has a low melting point and It has a density that is intermediate between a-type crystal and amorphous.
従って、同じナイロン6でもより一1性の必要な部材に
はa型が、より衝撃強度の必要な部材にはγ晶用される
ことにより、ナイロン6の有用性は更に高まる。そのた
めにa型あるいはγ型を作り分けて、ナイロン6を製造
することが要望されている。Therefore, the usefulness of nylon 6 is further increased by using the a-type nylon 6 for members that require more uniformity and the γ crystal for members requiring more impact strength. For this reason, it is desired to manufacture nylon 6 separately into a-type or γ-type.
しかし、従来の方法により得られるナイロン6はもっば
ら安定型とされるα型のみであり、γ型のものはa型を
ヨウ素処理等の特殊な処理によっテ作うれている(I、
、E、アレクサンダー、“高分子のX線回折”、化学同
人、1973)。However, nylon 6 obtained by conventional methods is only the α type, which is considered to be the most stable type, and the γ type is made from the a type by special treatments such as iodine treatment (I,
, E. Alexander, “X-ray diffraction of polymers”, Kagaku Dojin, 1973).
そこで9本発明者らは、上記の問題を解決すべく、鋭意
検討した結果9本発明を成すに至ったものである。In order to solve the above problems, the inventors of the present invention have conducted intensive studies and have completed the present invention.
本発明はmamあるい°はγ型のいずれか所望の結晶構
造のナイロン6を簡便に製造する方法を提供しようとす
るものである。The present invention aims to provide a method for easily producing nylon 6 having a desired crystal structure of either mam or gamma type.
本発明は、ケイd塩の存在下においてナイロン6の化ツ
マ−をその溶融温度以とで置台する重合工程と、冷却速
度を制御して、該ナイロン6を溶融温度以上から160
℃以下まで冷却する冷却工程とから成ることを特徴とす
るナイロン6の製造方法である。The present invention involves a polymerization process in which a polymer of nylon 6 is placed on a table at a temperature below its melting temperature in the presence of a silica salt, and a cooling rate is controlled to convert the nylon 6 from above its melting temperature to 160%.
This is a method for producing nylon 6 characterized by comprising a cooling step of cooling to below .degree.
以下9本発明の構成をより詳細に説明する。Hereinafter, the configuration of the present invention will be explained in more detail.
本発明において9重合工程でのケイ酸塩の存在及び冷却
工程での冷却速度の制御によりa型またはγ型のいずれ
か所望の結晶構造のナイロン6を製造することができる
と考えられる。In the present invention, it is believed that by controlling the presence of silicate in the polymerization step and the cooling rate in the cooling step, it is possible to produce nylon 6 having a desired crystal structure of either the a-type or the γ-type.
ケイ酸塩としては、モンモリロナイト、バーミキュライ
ト、へロイサイト等が挙げられ、これらのうちの1種ま
たは211以上を(資)用する。Examples of the silicate include montmorillonite, vermiculite, heloysite, etc., and one or more of these may be used.
なお、ケイ酸塩をナイロン6のモノマーに均一に分散さ
せるために予め有機物で膨潤させておくことが好ましい
。該有機物は置台金阻害しない限り炭化水素、アミン、
カルボン酸、アルコール。In addition, in order to uniformly disperse the silicate in the nylon 6 monomer, it is preferable to swell it with an organic substance in advance. The organic matter may contain hydrocarbons, amines,
Carboxylic acid, alcohol.
ハロゲン化物等いずれでもよいが、ケイ酸塩と陽イオン
交換反応によって強固な化学結合を形成するオニウムイ
オンを分子中に有する化合物が望ましい。該有機物を具
体的に列挙するとトリメチルアミン、トリエチルアミン
、ヘキシルアミン、シクロヘキシルアミン、ドデシルア
ミン、エチレンジアミン、ヘキサメチレンジアミン、ヘ
キサメチレンテトラミン、ポリアリルアミン、ピリジン
。Any compound such as a halide may be used, but a compound having an onium ion in its molecule that forms a strong chemical bond with a silicate through a cation exchange reaction is desirable. Specific examples of the organic substances include trimethylamine, triethylamine, hexylamine, cyclohexylamine, dodecylamine, ethylenediamine, hexamethylenediamine, hexamethylenetetramine, polyallylamine, and pyridine.
アニリン、ベンジルアミン、ビス(アミノメチlv)ベ
ンゼン、アミノフェノール、アラニン、4−アミノ酪酸
、6−アミノカプロン酸、12−アミノドデカン酸、1
6−アミツヘキサデカン酸等の強酸塩が挙げられるが、
これらに限定されるものではない。なお、ここで甘う強
酸としては、塩酸。Aniline, benzylamine, bis(aminomethylv)benzene, aminophenol, alanine, 4-aminobutyric acid, 6-aminocaproic acid, 12-aminododecanoic acid, 1
Examples include strong acid salts such as 6-amitsuhexadecanoic acid,
It is not limited to these. The strong acid used here is hydrochloric acid.
臭化水素酸、硫酸、リン酸等が挙げられる。しかして、
上記有機物は1種または2種以上で使用する。Examples include hydrobromic acid, sulfuric acid, phosphoric acid, and the like. However,
The above organic substances may be used alone or in combination of two or more.
上記ケイ酸塩の添加量(重合工程における存在量)は、
ナイロン6の七ツマー100重量部に対して1001〜
100重量部の範囲内が望ましい。The amount of the silicate added (the amount present in the polymerization process) is
1001 to 100 parts by weight of nylon 6
It is preferably within the range of 100 parts by weight.
該添加量が1001重量部未満では、a型とγ型の混合
物が生成しやすい。また100重量部を越える場合には
0反応混合物が高粘度となり2反応速度が低下するおそ
れがある。更に好ましくは1lL01〜50重量部の範
囲内がよい。If the amount added is less than 1001 parts by weight, a mixture of a-type and γ-type is likely to be produced. If the amount exceeds 100 parts by weight, the viscosity of the reaction mixture may become high and the reaction rate may decrease. More preferably, it is within the range of 1 lL01 to 50 parts by weight.
ナイロン60重合方法としては、既存の方法。The nylon 60 polymerization method is an existing method.
例えばカブロックタムの加水分解重合法、カプロラクタ
ムのアルカリ触媒重合法、6−アミノカプロン酸の脱水
重合法等いかなる方法でもよい。For example, any method such as hydrolysis polymerization of cabrolactam, alkali-catalyzed polymerization of caprolactam, dehydration polymerization of 6-aminocaproic acid, etc. may be used.
また重合温度は、ナイロン6の溶融温度以上の温度とす
る。一般的にその溶融温度は220℃程度である。これ
は、ナイロン6の溶融温度未満では重合反応中に結晶析
出が起こり1本発明での冷却速度の制御による結晶析出
が行えないからである。Further, the polymerization temperature is set to be higher than the melting temperature of nylon 6. Generally, its melting temperature is about 220°C. This is because if the temperature is lower than the melting temperature of nylon 6, crystal precipitation occurs during the polymerization reaction, and crystal precipitation cannot be achieved by controlling the cooling rate in the present invention.
また、ナイロン6のモノマーとしては、カブロラダム、
6−アミノカプロン酸等がat=けラレ、 コれらのう
ちの1種または2a1以上で(資)用する。In addition, as monomers for nylon 6, cabroladum,
6-Aminocaproic acid, etc. are used in one of these or 2a1 or more.
なお1重合工程において、実質的に重合反応を阻害しな
い添加物1例えばガラス繊維、lIi料、酸化防止剤等
を存在させておいてもよい。In addition, in one polymerization step, additives 1 that do not substantially inhibit the polymerization reaction, such as glass fibers, IIi additives, antioxidants, etc., may be present.
冷却工程において、前記重合したナイロン6を溶融温度
以上から160℃以下までに冷却する。In the cooling step, the polymerized nylon 6 is cooled from above its melting temperature to below 160°C.
この際に冷却速度を制御することによって、α型あるい
はγ型のいずれかの結晶構造を有するナイロン6を作り
分ける。なお、160℃に達する前に冷却速度の制御を
停めると所望の結晶構造のナイロン6が得られない。At this time, by controlling the cooling rate, nylon 6 having either an α-type or a γ-type crystal structure is produced. Note that if the control of the cooling rate is stopped before the temperature reaches 160°C, nylon 6 with the desired crystal structure cannot be obtained.
上記冷却速度の制御は、α型のナイロン6を製造する場
合には4゛C/分以下の冷却速度とし、またr型のナイ
ロン6を製造する場合には10℃/分以上の冷却速度と
することにより行なう。The cooling rate is controlled at a cooling rate of 4°C/min or less when producing α-type nylon 6, and at a cooling rate of 10°C/min or more when producing r-type nylon 6. Do by doing.
すなわち、4℃/分以下の緩やかな冷却の場合には90
%以上がα型のナイロン6が形成される。In other words, in the case of slow cooling of 4°C/min or less, 90
% or more of α-type nylon 6 is formed.
なお、この場合の冷却速度の下限としてはα1℃/分と
するのが望ましい、[lL1゛C/分より遅い場合には
冷却に24時間以上かかり経済的メリットが少ない。こ
の冷却方法としては、ナイロン6を重合した反応器を重
会後、オイルバス中に浸漬し。In this case, it is desirable that the lower limit of the cooling rate be α1°C/min; if it is slower than 1L1°C/min, cooling will take more than 24 hours and there will be little economic benefit. In this cooling method, the reactor in which nylon 6 was polymerized was immersed in an oil bath after polymerization.
オイルの自然放熱に任せる方法等がある。ま友。There are methods such as leaving it to the natural heat dissipation of the oil. Mayu.
冷却プロセスを正確にプログラムして徐冷してもよい。The cooling process may be precisely programmed for slow cooling.
また、10℃/分以上の急臘な冷却の場合には90%以
上がγ型のナイロン6が形成される。なお、この場合の
冷却速度の上限としては、900℃/分とするのが実用
的で望ましい。この冷却方法としては、ナイロン6を型
片した反応器を重会後、オイルパス等の加熱装置から出
して、GA)室温で空冷する。(B)反応器の外部から
氷水で冷却する(q反応器の外部から液体窒素で冷却す
る。あるいは0溶融状態にあるナイロン6を水中に注入
する方法等がある。また、冷却プロセスを正確にプログ
ラムして急冷してもよい。Further, in the case of rapid cooling at 10° C./min or more, 90% or more of γ-type nylon 6 is formed. Note that it is practical and desirable that the upper limit of the cooling rate in this case is 900° C./min. As for this cooling method, after piling up the reactor molded with nylon 6, it is taken out from a heating device such as an oil path and air cooled at room temperature. (B) Cooling with ice water from the outside of the reactor (q Cooling with liquid nitrogen from the outside of the reactor. Alternatively, there are methods such as injecting nylon 6 in a zero molten state into water. You can program it to cool down quickly.
本発明により得られるナイロン6はケイ酸塩の添加量等
によりナイロン6とケイ酸塩との複合物として得られる
ことがある。この複合物は1本発明者らが先に提案した
(特願昭60−217396号)ように分子レベルでナ
イロン6とケイ酸塩トが複合し9機械的強度及び耐熱性
に優れたものであり、有効に利用し得るものである。ま
た、複合物よりケイ酸塩のみを除去するには9m−クレ
ゾール、ギ酸1m−クレゾーA//クロロホルム等の溶
剤によってナイロン6を溶解させることにより容易に行
なうことができる。Nylon 6 obtained by the present invention may be obtained as a composite of nylon 6 and silicate depending on the amount of silicate added. As previously proposed by the present inventors (Japanese Patent Application No. 60-217396), this composite is a composite of nylon 6 and silicate at the molecular level and has excellent mechanical strength and heat resistance. Yes, it can be used effectively. Further, only silicate can be easily removed from the composite by dissolving nylon 6 with a solvent such as 9m-cresol or 1m-cresol formic acid/chloroform.
本発明によれば、amあるいはγ型のいずれか所望の結
晶構造を有するナイロン6を簡便に製造することができ
る。この本発明の効果が得られ、 るメカニズムは明
確ではないが2本発明の重合工程におけるケイ酸塩の存
在及び冷却工程における冷却速度の制御によるものと考
えられる。According to the present invention, nylon 6 having a desired am or γ crystal structure can be easily produced. Although the mechanism by which this effect of the present invention is obtained is not clear, it is thought to be due to the presence of silicate in the polymerization step of the present invention and the control of the cooling rate in the cooling step.
以下1本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例1゜
100fのモンモリロナイト(クニミネ工業−試製、商
品名[クニビアFJ)を101の水に分散し、これに5
1.2 ’lの12−アミノドデカン酸と24m1の濃
塩酸を加え、5分間攪拌した後。Example 1 100f of montmorillonite (Kunimine Kogyo - trial production, trade name [Kunibia FJ) was dispersed in 101% of water, and 5% of the water was dispersed.
After adding 1.2'l of 12-aminododecanoic acid and 24ml of concentrated hydrochloric acid and stirring for 5 minutes.
−過し九。更に、これを十分洗浄した後、真空乾燥した
。これにより12−アミノドデカン酸の塩酸塩で膨潤し
たモンモリロナイト(12−Mと略記する。)を調製し
た。- Past nine. Furthermore, this was thoroughly washed and then vacuum dried. In this way, montmorillonite (abbreviated as 12-M) swollen with 12-aminododecanoic acid hydrochloride was prepared.
次に攪拌機付きの反応器に10ofのカブロックタムと
α2fの上記12−Mを入れ、オイルバス中で100℃
で攪拌すると粘性の高い均一分散液が得られた。これに
2.42の水素化すl−IJウムを加え、続いてオイル
パス中で250℃に昇温した後、1.37FのN−アセ
チルカブロックタムを加え、加熱を30分間続けた。そ
の後1反応器をオイルパスから出し、氷水にて外部より
冷却した。Next, put 10of of cabrotam and the above 12-M of α2f into a reactor equipped with a stirrer, and heat the mixture to 100°C in an oil bath.
A highly viscous homogeneous dispersion was obtained. To this was added 2.42 liters of sulfur hydride, and the temperature was then raised to 250° C. in an oil path, then 1.37 F of N-acetyl carbloctam was added, and heating was continued for 30 minutes. Thereafter, one reactor was taken out of the oil path and cooled externally with ice water.
たX線回折法で面間隔dを測定したところ、4.2人に
r型と帰属されるピークがあるが、a型とされる4、4
A及び五8ムのピークは全く見られず。When the interplanar spacing d was measured using X-ray diffraction method, 4.2 peaks were assigned to r-type, but 4 and 4 peaks were assigned to a-type.
A and 58m peaks were not observed at all.
実質的にr型であった。It was essentially r-type.
実施例2
実施例1と同様にして重合工程を行ない、す 5イロン
6を重合し、加熱を停止した後も反応器をオイルパス中
で徐冷した。この徐冷は、100℃まで2.8〜[15
℃/分の冷却速度とした。Example 2 A polymerization step was carried out in the same manner as in Example 1 to polymerize Su5Iron6, and even after the heating was stopped, the reactor was slowly cooled in an oil path. This slow cooling is carried out from 2.8 to [15
The cooling rate was set at °C/min.
得られたナイロン6について、実施例1と同様にして面
間隔dを測定したところ、4.4ムと五81のピークは
得られ九が、42人のピークは見られず、実質的にam
でめった。When the interplanar spacing d of the obtained nylon 6 was measured in the same manner as in Example 1, peaks of 4.4 mm and 581 were obtained, and 9, but no peak of 42 was observed, and substantially
I failed.
比較例1゜
プログツム温度コントローラーを接続したマントルヒー
タを用いて反応器を加熱した以外は。Comparative Example 1° except that the reactor was heated using a mantle heater connected to a program temperature controller.
芙施例1と同様にして重合工程を行なった。次に5℃/
分の冷却速度で100℃まで冷却した。The polymerization step was carried out in the same manner as in Example 1. Next 5℃/
It was cooled to 100° C. at a cooling rate of 100 min.
得られたナイロン6について、実施例1と同様にして面
間隔dft測定したところ、 4.4 A 、 4.2
X及び五8λのピークが等強度で観測された。各々の結
晶型のピーク面積の比より算出して、このナイロン6に
はα型とr型とが60:40で混在していることが明ら
かになった。The surface spacing dft of the obtained nylon 6 was measured in the same manner as in Example 1, and the results were 4.4 A and 4.2.
The peaks of X and 58λ were observed with equal intensity. Calculation from the ratio of the peak areas of each crystal type revealed that this nylon 6 contained a mixture of α type and r type at a ratio of 60:40.
比較例2
実施例1における12−Mは用いないで、他は実施例1
と同様にしてナイロン60重合工程。Comparative Example 2 12-M in Example 1 was not used, and the rest were as in Example 1.
Polymerize nylon 60 in the same manner as above.
冷却工程を行ない、その面間隔dの測定を行なった。A cooling process was performed, and the interplanar spacing d was measured.
その結果、44又と5−8差のピークは得られず。As a result, a peak with a difference of 5-8 from 44 was not obtained.
42差のピークは得られ、ナイロン6は実質的にa型で
あった。A peak with a difference of 42 was obtained, indicating that the nylon 6 was essentially a-type.
なお、上記実施例1,2及び比較例1.2の測定結果を
表に示す。The measurement results of Examples 1 and 2 and Comparative Example 1.2 are shown in the table.
表より明らかなごとく9本実施例により、α型またはr
型のいずれか所望の結晶構造を有するナイロン6を製造
できることが分る。As is clear from the table, α-type or r-type
It is found that nylon 6 can be produced with any desired crystal structure.
表 待針出願人 株式会社 豊田中央研究所table pin applicant Toyota Central Research Institute Co., Ltd.
Claims (3)
をその溶融温度以上で重合する重合工程と、冷却速度を
制御して、該ナイロン6を溶融温度以上から160℃以
下まで冷却する冷却工程とから成ることを特徴とするナ
イロン6の製造方法。(1) A polymerization step in which nylon 6 monomer is polymerized at a temperature above its melting temperature in the presence of a silicate, and a cooling step in which the nylon 6 is cooled from above the melting temperature to below 160°C by controlling the cooling rate. A method for producing nylon 6, characterized by comprising:
160℃以下まで4℃/分以下の冷却速度で冷却するこ
とによりα型の結晶構造を有するナイロン6を製造する
特許請求の範囲第(1)項記載のナイロン6の製造方法
。(2) In the cooling step, nylon 6 having an α-type crystal structure is produced by cooling nylon 6 from the melting temperature or higher to 160°C or lower at a cooling rate of 4°C/min or less. 1) The method for producing nylon 6 as described in section 1).
160℃以下まで10℃/分以上の冷却速度で冷却する
ことによりγ型の結晶構造を有するナイロン6を製造す
る特許請求の範囲第(1)項記載のナイロン6の製造方
法。(3) In the cooling step, nylon 6 having a γ-type crystal structure is produced by cooling nylon 6 from the melting temperature or higher to 160°C or lower at a cooling rate of 10°C/min or more. 1) The method for producing nylon 6 as described in section 1).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9578186A JPS62252426A (en) | 1986-04-24 | 1986-04-24 | Production of nylon 6 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9578186A JPS62252426A (en) | 1986-04-24 | 1986-04-24 | Production of nylon 6 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62252426A true JPS62252426A (en) | 1987-11-04 |
Family
ID=14147015
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9578186A Pending JPS62252426A (en) | 1986-04-24 | 1986-04-24 | Production of nylon 6 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62252426A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001329167A (en) * | 2000-05-24 | 2001-11-27 | Toray Ind Inc | Polyamide resin composition |
US6780522B1 (en) * | 1998-10-16 | 2004-08-24 | Wolff Walsrode Ag | Transparent high strength polyamide film |
JP2013253215A (en) * | 2012-05-11 | 2013-12-19 | Toyobo Co Ltd | Long-fiber reinforced polyamide resin molded product |
-
1986
- 1986-04-24 JP JP9578186A patent/JPS62252426A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6780522B1 (en) * | 1998-10-16 | 2004-08-24 | Wolff Walsrode Ag | Transparent high strength polyamide film |
JP2001329167A (en) * | 2000-05-24 | 2001-11-27 | Toray Ind Inc | Polyamide resin composition |
JP4543500B2 (en) * | 2000-05-24 | 2010-09-15 | 東レ株式会社 | Manufacturing method of polyamide resin molded body |
JP2013253215A (en) * | 2012-05-11 | 2013-12-19 | Toyobo Co Ltd | Long-fiber reinforced polyamide resin molded product |
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