JPS58154723A - Copolyamide resin - Google Patents
Copolyamide resinInfo
- Publication number
- JPS58154723A JPS58154723A JP3691082A JP3691082A JPS58154723A JP S58154723 A JPS58154723 A JP S58154723A JP 3691082 A JP3691082 A JP 3691082A JP 3691082 A JP3691082 A JP 3691082A JP S58154723 A JPS58154723 A JP S58154723A
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- group
- polymer
- polyolefin
- 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.)
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Links
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- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
本発嘴は新規な低吸水率共重合ポリアミド樹脂に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel low water absorption copolyamide resin.
周知の如く、ポリアミド樹脂は繊維はじめ広・範な用途
に周込もれてい為が、ア建ド艙合を有する構造によ〕本
質的に吸水率が^く、成鳳晶の寸法安定性が劣り九〉、
電気的特性などの物性が湿度によ如大龜〈変化するなど
の欠点がある。例えば、ポリアミド樹脂はそのインピー
メンスOIL直依存性と紬晶性鳥分子であ為九めに明確
な融点を有し、温度ヒユーズとして用い得る%性を刹用
して、電気毛布、電気カーペットるが、かかる用途にお
いてはポリアミド樹脂のインピーダンスが温III!に
よって影響されないことが必要である。従ってポリアミ
ド樹脂のうち、比較的吸湿性の小さいナイロン11.ナ
イロン12がかかる用途に用いられhが、それでも゛な
お、m度の影響を受けるという点において充分満足でき
る性能は得られていない。As is well known, polyamide resin is widely used in a wide range of applications including fibers, but due to its structure with adhesion, it inherently has a high water absorption rate and has excellent dimensional stability. is inferior to 9〉,
It has the disadvantage that physical properties such as electrical characteristics change significantly depending on humidity. For example, polyamide resin has a very clear melting point due to its direct dependence on impedance oil and crystalline bird molecules, and can be used as a temperature fuse, making it possible to make electric blankets and electric carpets. , in such applications, the impedance of polyamide resin is 3! It is necessary to be unaffected by Therefore, among polyamide resins, nylon 11. Although nylon 12 is used in such applications, h is still affected by m degrees, and therefore has not achieved sufficiently satisfactory performance.
本発@om的は、ボリアイド樹脂の■有の欠点である吸
水性を改善し、なおボリアミド樹脂に%有の横槍的性質
、威櫃加工性、柔軟性を有する改嵐されえ新規共重合ポ
リアミド樹脂を提供することにある。This product is a new copolymerized polyamide that improves the water absorption, which is a drawback of bolyamide resin, and has the horizontal properties, machinability, and flexibility that bolyamide resin has. Our goal is to provide resin.
即ち、本発明は、下記の一般式(1)又は(2)で表わ
される繰返し単位を一種以上有す為ポリアミド高分子成
分99〜5重量部と両末端がカルボン酸基、アミノ基又
は水酸基である平複分子量500〜10,000 K)
11す1し747處分1〜?1重量部を共重合してなゐ
新規共重合ポリアミド樹脂
−Ml(OllR)nGo −(1)
(式中、nはs〜11の整数)
−MHXMI100YOO−(1)
(式中、X ハOmI!、、 (mは4〜11011I
i歇)、イソホロン基、フェニレン基又は7クロヘキシ
レン基を表わし、x #i0/lj(1は4〜10の整
数)、フェニレン基又はシクロヘキシレン基を表わす)
K関する。That is, the present invention has 99 to 5 parts by weight of a polyamide polymer component having at least one type of repeating unit represented by the following general formula (1) or (2), and both terminals are a carboxylic acid group, an amino group, or a hydroxyl group. (average molecular weight 500-10,000 K)
11th 1st 747th place 1~? 1 part by weight of a novel copolymerized polyamide resin -Ml(OllR)nGo -(1) (wherein, n is an integer of s to 11) -MHXMI100YOO-(1) (wherein, !,, (m is 4~11011I
i) represents an isophorone group, a phenylene group or a 7-chlorohexylene group;
Regarding K.
本発明の共重合ポリアミドを構成する上記〇−一般式1
)又は(2)で表わ畜れ為繰返し単位を一種以上有する
ボリアオド高分子成分を構成する単量体としては、例え
ば(1)弐に対応するものとしては、カプロラクタム、
ラウリルラクタム、11アンノウンデカン酸、12ア建
ノドデカン酸などがあプ、(2)に対応するtのとして
は、ヘキtメテレ/アジパ建ド、へ午すメテレンtパV
(ド、ヘキ!メチレンドデカ建ド等の外、テレフタル酸
、シクロヘキサンジカルボン酸等の麿を有する二塩基酸
のジアミン塩、フェニレンジアミン、シクロヘキサンジ
アミン、イソホロンジアミン等のジアミンの二塩基酸塩
等があげられるO
又、本発明の共重合ポリアミドを構成するポリオレフィ
ン成分である、両末端がカルボン酸基、アミノ基又は水
酸基であるポリオレフィンは、例えば一種以上のオレフ
ィン毫ツマ−からラジカル重合によって得られ為が、両
車端にカルボン酸基、又はア建)基、又は水酸基の官能
基を導入すゐ九めに、關鍮剤、溶剤の他、温度、圧力等
の重合条件が適幽に遍ばれ為。The above 〇-General formula 1 constituting the copolymerized polyamide of the present invention
) or (2), monomers constituting the boriaod polymer component having one or more types of repeating units include, for example, those corresponding to (1) 2 include caprolactam,
Examples include lauryl lactam, 11-unundecanoic acid, 12-annododecanoic acid, etc., and examples of t corresponding to (2) include hextmetele/adipate, hexmetelet, etc.
(Hehe! In addition to methylene dodeca-densate, etc., diamine salts of dibasic acids with a radical such as terephthalic acid and cyclohexane dicarboxylic acid, dibasic acid salts of diamines such as phenylene diamine, cyclohexane diamine, and isophorone diamine, etc.) Furthermore, the polyolefin having carboxylic acid groups, amino groups or hydroxyl groups at both ends, which is the polyolefin component constituting the copolyamide of the present invention, can be obtained, for example, by radical polymerization from one or more olefin polymers. In order to introduce a functional group such as a carboxylic acid group, an alkyl group, or a hydroxyl group at both ends of the car, the polymerization conditions such as temperature and pressure, as well as the polymerization agent and solvent, must be carefully controlled. .
虞は本発明の上記ポリオレフィン成分は、二つ以上の二
重結合を有する毫ツマ−を、車端にカルボン酸基、アミ
ノ基、又は水酸基から選ばれ九官能基を導入して線状に
重合し九俵、これに水嵩添加することによりても得られ
為・例えば、ポリブタジェンをリビング重合し、エポ今
シ化合物で重合停止す為ことによりて車端に水酸基を導
入し、[Kこれ七本−すれば、両車端が水酸基であるポ
リオレフィンが得られる0水添1れるポリブタジェンは
、1.!−締舎、1.4− )ランス締金、1,4−シ
ス結合等いかなる結合を含んでいてもよい。僅し水5o
sa畜からは1.2−縮合の割合が多いことが望1Lへ
ポリオレフィンの両末端以外、即ち主鎖O途中には全く
上記の官能基が無く、両末端には100−官能基が導入
されているものを得ることが連層であるが、特にラジカ
ル重合時、連鎖移動によシ主鎖の途中に着千の官能基が
導入さi;ることは避けられず、又、轡にリビング重合
停止時K、10口憾両末端に官能基を導入することも困
難である。従って、本li@の共重合ボリアミド製造の
九めOポリオレフィン成分としては一分子#IIAり上
記の官能基が1.トI、O儒導入されているポリオレア
インを用いることが出来、−分子轟妙の官能基数が1.
5〜2.2のポリオレフィンがjl!に好適に用いられ
得る。The above-mentioned polyolefin component of the present invention may be linearly polymerized by introducing a nine-functional group selected from a carboxylic acid group, an amino group, or a hydroxyl group at the end of the polymer having two or more double bonds. This can also be obtained by adding a large amount of water to this. For example, by living polymerizing polybutadiene and stopping the polymerization with an epoxy compound, a hydroxyl group may be introduced at the end of the car, and [K this seven bales can be obtained.] - Then, a polyolefin having hydroxyl groups at both ends is obtained.Polybutadiene subjected to 0 hydrogenation and 1 is obtained by 1. ! - Clamping, 1.4-) Lance clamping, 1,4-cis bonding, etc. may be included. a little water 5o
It is desired that the ratio of 1.2-condensation is high from SA to 1L.There is no above-mentioned functional group at all other than both ends of the polyolefin, that is, in the middle of the main chain O, and 100-functional groups are introduced at both ends. However, especially during radical polymerization, it is unavoidable that thousands of functional groups are introduced in the middle of the main chain due to chain transfer. It is also difficult to introduce functional groups to both K and 10 terminals when polymerization is terminated. Therefore, as the ninth O polyolefin component for producing the copolymerized polyamide of this li@, one molecule of #IIA contains the above functional groups. It is possible to use a polyolein in which 1 and 2 are introduced, and the number of functional groups in the molecule is 1.
5-2.2 polyolefin is jl! It can be suitably used for.
又、二り以上の二重結合を有するモノ!−〇重合体を完
全に水添す為ことは技術的KijlJIであ)、従りて
本li@の共重合ボリア電ド側造の丸めのポリオレフィ
ン成分としては70憾以上の水添率O水添重合体が好適
に用いられ、90−以上の水添率の水添重合体が更に好
適に用いられる。水添率100憾でない水添重合体は構
造上厳密には狭義のポリオレアインには會★れないかも
知れないが、重置@にいうポリオレフィン成分Kld、
100嚢未満の水添率の重合体をも粗金する。Also, things that have two or more double bonds! -〇In order to completely hydrogenate the polymer, it is a technical requirement), therefore, as the rounded polyolefin component of the copolymerized boria electrode side structure of this li@, the hydrogenation rate O water with a hydrogenation rate of 70 or more is required. Added polymers are preferably used, and hydrogenated polymers with a hydrogenation rate of 90 or more are more preferably used. Hydrogenated polymers with a hydrogenation rate of less than 100 may not be technically polyolein in the narrow sense due to their structure, but the polyolefin component Kld referred to in superposition@,
Polymers with a hydrogenation rate of less than 100 cells are also refined.
肯、重置−のポリオレフィン成分に験でその分子量がl
o(1未満であると吸水性を低下1せ為効果が少なく、
又10,000よ)大暑いと物性的に好壇しいものが得
−いので、平場分子量がwoo〜t o、o o oで
あ為ことが望ましい口重発明の共重合ボリア建ド樹脂に
おける岡威分の共重合比率にりいてはボリアミド高分子
成分が99重量部を越えると4)蝋質がポ91しフィン
成分を會オないボリア建ドとは埋同じとなり、又ポリオ
レフィン成分が91重量部を越えると、ポリオレアイン
とほぼ同勢の性質となる丸め、何れも好ましくない。共
重合比率は好重しくはボリア々ド高分子成分vs−go
重量都に対し、ポリオレフィン成分@〜7o重量蕩であ
る。Experiments have shown that the molecular weight of the polyolefin component is 1.
o (If it is less than 1, the water absorbency will decrease by 1 and the effect will be small,
10,000) In the case of very hot weather, it is difficult to obtain good physical properties, so it is desirable that the average molecular weight is between woo to o, o o o. Regarding the copolymerization ratio of Takei Oka, if the polyamide polymer component exceeds 99 parts by weight, 4) the waxy content will be 91 parts by weight, which is the same as the boria-based resin without a fin component, and the polyolefin component will be 91 parts by weight. If the weight part is exceeded, the properties are almost the same as those of polyolein, which is undesirable. The copolymerization ratio is preferably the boriad polymer component vs.
The weight of the polyolefin component is ~7 o.
本慟嘴の共重合ボリアミド樹脂を得為丸めの重合方法は
、使用されるポリオレアインの有す合は、全知のボリア
建ドを得る丸めの方法と本質的に同様の方法によりて重
合畜れる。最も審鳥には、共重合体を構成するポリオし
フィン成分を會11いボリア々ド嶌分子成分をそcIl
IL量体から重合する場合に用いられるものと同じ重と
を共重合させて本発明の共重合ボリアオドを得ることが
出来る。The copolymerized polyamide resin of the present invention is polymerized by a method essentially similar to the rounding method used to obtain the polyoleain, depending on the polyoleain used. In most cases, the polyester fin component constituting the copolymer is combined with the polyamide molecule component.
The copolymerized boriaodide of the present invention can be obtained by copolymerizing the same polymer as that used in polymerizing the IL polymer.
爾、ζOII共重合体の分子量を調整す4九めにポリオ
レアイン成分の4ル歇を考慮して、ジアミン又はジカル
ボン酸を添加することができる〇
ジアミンとしては、例えばヘキサメチレンシアイン、ド
デカメチレンジアミンのようなアルキレンシア(ン、例
えばシフ曹ヘキ!ンジア電/のような脂穢族シアずン、
例えばツェエレンジアインのような芳香族ジアンン、あ
るいはイッホロンジアンン等が用いられ得る。Finally, in order to adjust the molecular weight of the ζOII copolymer, a diamine or a dicarboxylic acid can be added, taking into consideration the 4 rules of the polyolein component. As the diamine, for example, hexamethylene cyanide, dodecamethylene diamine, etc. Alkylenesia (n, for example, Schiff Cao Heki! Njia Den/, such as Alkylenesia (n),
For example, an aromatic diane such as zeelendiain, ichorondiane, or the like can be used.
ジカルボン酸としてはアジピン酸、セバシン酸、ドデカ
/二酸のような脂肪族ジカルボン酸、脂−族カルボン酸
、フタル酸のような芳香族ジカルボン酸が用いられ得為
。As the dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodeca/diacid, aliphatic carboxylic acids, and aromatic dicarboxylic acids such as phthalic acid can be used.
一方、使用され為ポリオレアインの有する盲詭基が水酸
基であみ場合の重置−〇共重合ボリア建ド樹脂を得り丸
めの共重合方法は纏重合、l又は−婁重合のいずれでも
良い。この鳩舎、共重合体の分子量を調整する九めにポ
リオレフィン成分の毫ル歇を考慮して、ジカルボン酸を
添加することがで自る。ジカルボン酸としてはアジピン
酸、セバシン酸、ドデカンニ酸のような脂肪族ジカルボ
ン酸、脂肪族ジルボン酸、フタル酸のような芳香族ジカ
ルボンsIがM−もれ得るO
かかる両末端に水酸基を有すゐポリオレフィンを用いて
本li@に係る共重合ボリアイド樹脂を合成するには、
ジカルボン酸とアミ)酸又はジカルボン酸とシア(ンの
縮合反応によ珈、あるいはジカルボン酸の存在下のツク
JA01@II重合により、末端にカルボン−基を有す
るボリアミドオリゴ!−を形成させ、このオリゴマーの
末端カルボン酸基と、両末端に水酸基を有するポリオレ
フィンとのエステル形成反応によpプロッタ共重合体を
形成させる。ポリオレフィンジオールはボリア建ドオリ
ゴマ−の合成の後添加してもよく、又ポリアンド合成の
轟初から共存させてお亀、ア建ド結合形成反応とエステ
ル結合形成反応が並行して起こるようにすることも可能
である。いずれにしてもアミド結合の形成反応とエステ
ル結合の形成反応ではこれら可逆反応の平衡電歇に葺が
ある丸め、アミド結合形成が先行して起こり、エステル
結合形成反応によ)プロッタ共重合体を完成させるえめ
には、高温減圧下の脱離水除去工@が必須であ為。On the other hand, when the blind group of the polyoleain used is a hydroxyl group, the copolymerization method for obtaining a superposition-〇 copolymerized boria-dened resin may be either bulk polymerization, l- or -mu-polymerization. In order to adjust the molecular weight of the copolymer, a dicarboxylic acid can be added, taking into account the pattern of the polyolefin component. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dodecanoic acid, and aromatic dicarboxylic acids such as aliphatic dilboxylic acid and phthalic acid. To synthesize the copolymer polyamide resin according to this li@ using polyolefin,
By condensation reaction of dicarboxylic acid and amino acid or dicarboxylic acid and cyanide, or by polymerization in the presence of dicarboxylic acid, polyamide oligo!- having a carboxyl group at the terminal is formed, A p-plotter copolymer is formed by an ester formation reaction between the terminal carboxylic acid group of this oligomer and a polyolefin having hydroxyl groups at both ends.The polyolefin diol may be added after the synthesis of the boria-based oligomer, or It is also possible to coexist from the beginning of polyand synthesis so that the reaction for forming an amide bond and the reaction for forming an ester bond occur in parallel. In the formation reaction, the equilibrium of these reversible reactions is rounded, the amide bond formation occurs first, and the plotter copolymer is completed (by the ester bond formation reaction) by removing the desorbed water under reduced pressure at high temperature. @ is required.
又、ポリオレフィンジオールとジカルボン酸との縮合反
応を先ず行なって、末端にカルボン鐵基を有するポリエ
ステルオリゴマーを合成し、このオリゴマーの存在下に
ア建ノ酸又はジカルボン酸とジアミンの重縮合反応、あ
るいはラクタムのM項重合を行なって、エステル交換反
応を伴う一合反応によ如ブロック共重合体とする方法、
あるいは上述のポリエステルオリゴマーとボリア、イド
オリゴ!−の反応によ)エステル交換反応を伴り九縮合
反応によ勤ブ■ツク共重合体とする方法も町−である。Alternatively, a condensation reaction between a polyolefin diol and a dicarboxylic acid is first performed to synthesize a polyester oligomer having a carboxyl iron group at the terminal, and in the presence of this oligomer, a polycondensation reaction between an adenanoic acid or a dicarboxylic acid and a diamine, or A method of conducting M-term polymerization of a lactam to obtain a block copolymer through a monomerization reaction accompanied by a transesterification reaction,
Or the above-mentioned polyester oligomers, boria, and idooligos! A method of producing a block copolymer by a nine-condensation reaction accompanied by a transesterification reaction (by a reaction of -) is also popular.
本発明の共重合ボリアイド樹脂の製造にはチタン系触媒
が良好な結果を与え為o*にテトラブチルチタネート、
テトラメチルチタネートのとと1テトラアルキルチタネ
ート、シェラ酸チタンカリのとと自シエク酸チタン金属
塩等が好ましい0又その他の触媒としてはジブチルスズ
オキサイド、ジブチルスズラウレートのとを自スズ化合
物、酢**のごと自船化合物が挙けられる。In the production of the copolymerized polyamide resin of the present invention, a titanium-based catalyst gives good results, so tetrabutyl titanate,
Tetramethyl titanate, 1tetraalkyl titanate, potassium titanium schellaate, and titanium metal salt of autocycate are preferred.Other catalysts include dibutyltin oxide, dibutyltin laurate, autotin compound, and vinegar**. This includes own ship compounds.
又少量の共重合IIMではシ/IIへキをンジメタノー
ル、1,6−ヘキサンジオールなgo飽。In addition, in a small amount of copolymerized IIM, dimethanol and 1,6-hexanediol can be used.
ジオール成分及びトリメシン酸、グリ−リン、ペンタエ
リスリトールなどの多盲能化舎物が含有されていてもよ
い。A diol component and a multi-blind agent such as trimesic acid, glycol, and pentaerythritol may be contained.
本発明の共重合ボリアイド樹脂は、ボリアイド高分子成
分とポリオレアイン成分からなるブロックポリマーであ
るが、本発明の共重合ボリアイド樹脂の分子量は数平均
分子量として約1.000乃盃ioo、oooolll
llである。The copolymerized polyamide resin of the present invention is a block polymer consisting of a polyamide polymer component and a polyolein component, and the molecular weight of the copolymerized polyamide resin of the present invention is about 1.000 as a number average molecular weight.
It is ll.
本発明の共重合ボリアイド樹脂には重合時もしくは重合
後成形前に酸化賭止剛、熱分解安定剤、耐光剤などの安
定剤を、又耐加水分解改嵐剤、着色剤、難燃剤、補強材
、充填剤、各種成形助剤、可臘剤、などの添加剤を任意
に配合して用いてもよい。The copolymerized polyamide resin of the present invention is coated with stabilizers such as oxidation stabilizers, thermal decomposition stabilizers, and light stabilizers during polymerization or after polymerization and before molding, as well as hydrolytic storm reforming agents, colorants, flame retardants, and reinforcing agents. Additives such as materials, fillers, various molding aids, and lubricating agents may be optionally mixed and used.
本発明の共重合ボリアイドは低吸水率であ)、水分圧よ
る寸法、物性の変化が少なく、且つ熱安定性が良好であ
る丸め、射出・押出等による成形品に好適に用いられ為
。又、この共重合体は吸水率の低い熱接着剤、S*接着
剤、コーティング剤としても用いられ得るo[K、この
共重合体中のポリオレアイン成分の量が墨O重重量風上
のものは柔軟であ)、且つ耐衝撃性に優れる丸め、柔軟
性t*求されるエラストマーとしての用途KIIkて又
は傭隼改棗剤として有11に用いられ得る■
頁に本穐@O共重合ボリアイドは吸水愉が小さい丸めに
、電気特性、4I#ICインピーダンスの温度依専性が
小さく、又ボリアイドブ回ツタ部分の明瞭な融点による
熱ヒユーズとして0411性もある九めに、インピーダ
ンスの温II!依帯性及び熱ヒユーズ性を利用する電気
毛布、電気カーペット篭の感熱素子としての用途には4
11に有利に用いられ得る。The copolymerized polyamide of the present invention has a low water absorption rate), has little change in dimensions and physical properties due to water pressure, and has good thermal stability, so it is suitable for use in molded products by rounding, injection, extrusion, etc. This copolymer can also be used as a thermal adhesive with a low water absorption rate, an S* adhesive, and a coating agent. It is flexible) and can be used for various applications as an elastomer requiring rounding and flexibility with excellent impact resistance. Ninth, the impedance temperature II! 4 for use as a heat-sensitive element in electric blankets and electric carpet baskets that utilize dependence and thermal fusing properties.
11 can be advantageously used.
又、本発明の共重合ボリアイド樹脂は、ナイロン−11
、12、612等のボリアミド樹脂にブレンドして用い
ることt′c龜る。その配合量は、上記ボリアイド樹脂
9!、!〜50重量郁に対し、本発明共重合ボリア々ド
樹脂0.01〜70重量部であゐ。Moreover, the copolymerized polyamide resin of the present invention is made of nylon-11
, 12, 612, and the like. The blending amount is the above-mentioned Bolioid resin 9! ,! 0.01 to 70 parts by weight of the copolymerized polyamide resin of the present invention per 50 parts by weight.
次に本発明を実施例にりいてlK@す為。Next, the present invention will be explained in examples.
実施例−1
―−ア電ノドデカン酸墨!、6f%a、#−ドデカンジ
カルボンー94.541を攪拌器付−セパラブルフラス
コ中で窒素気流下vc19(1’C14時閣縮合反応さ
せ、仁の反応温金物へ数平均分子量(Mn)14?Oの
車端に水酸基を有する水嵩化ポリブタジェン2 ?、4
tとジブチルすずオキナイド0.OI fを添加し、
頁K 1?O℃で窒素気流下7時間反応せしめえ。得ら
れ九低纏合lL屓応物のうち14tをステンレススチー
ル製叩イクロボンベへ移し、1■III!0減圧下に2
10℃で1時間、2!10℃で2時間、270℃で8時
間反応ぜしめえ。得られたポリマーは末端基分析によ為
数平均分子量が?、100であり1強靭なシートに威渥
することかで龜九〇
得られたポリ!−を粗砕しトルエン<ヨpyツクスレー
抽出を1・時間性なり九が・ トルエンに可溶な車端に
水酸基を有すゐ水素化ポリブタジェンは機跡li直しか
抽出畜れず、プロッタ共纏舎がほぼ完全KIIJζりて
いることを示し魁得られ九ポリ!−を鳳−タレゾールi
11.0.5WtIsO機度、25℃でマr@jを測定
し九ところ1.22であった。Example-1 --Adenododecanoic acid ink! , 6f%a, #-dodecane dicarbonate 94.541 was subjected to a condensation reaction under a nitrogen atmosphere in a separable flask with a stirrer, and the number average molecular weight (Mn) was 14. ?Water-volumized polybutadiene with hydroxyl group at the end of ?O 2 ?, 4
t and dibutyltin oxide 0. Add OI f;
Page K 1? React for 7 hours at 0° C. under nitrogen flow. 14 tons of the obtained 90% combined product was transferred to a stainless steel bomb cylinder, and 1■III! 0 under reduced pressure 2
React at 10°C for 1 hour, 2!10°C for 2 hours, and at 270°C for 8 hours. What is the number average molecular weight of the obtained polymer according to end group analysis? , 100 and 1 Poly got 90 by being proud of the strong sheet! - Crushed toluene < Yopyutxley extraction for 1 time and 9 hours - Hydrogenated polybutadiene, which has a hydroxyl group at the end that is soluble in toluene, can only be extracted directly from the plotter. It shows that it is almost completely KIIJζ, and it is 9 points! -Otori-Tarezor i
11. Mar@j was measured at 25°C in a 0.5WtIsO machine and found to be 1.22.
得られ九ポリ!−の元素分析値は0784重量−1n
t z、i重量参、1M、−重量一で、場瞼値のそれヤ
れ077,1重量嚢、II 12.I重量嚢、M墨、7
重量11sK夷験llAl1範−内で一款し九・工lス
ベタトルにはナイロン−11に轡徴的@721S。Obtained nine poly! - elemental analysis value is 0784 weight -1n
t z, i weight reference, 1M, - weight 1, that of the eyelid value 077, 1 weight bag, II 12. I weight bag, M ink, 7
The weight is 11sK, and the weight is within the range of 11Al1, and the weight is 9.5mm, and the nylon-11 is suitable for @721S.
15sS 、 1!40 、1100 m−14Dll
収と水嵩化ポリブタジェンに特徴的1k 2942ts
−”の吸収と両者を結ぶエステル結合KJ因する17易
6m−1の1lllLが見られ九。15sS, 1!40, 1100 m-14Dll
Characteristic 1k 2942ts for yield and water bulking polybutadiene
-'' absorption and the ester bond KJ that connects the two, 1llllL of 17y6m-1 can be seen.9.
実施例−2
m−7ζノドデカン酸41.I P%#−一ドデカ/ジ
カルボン酸14 ?及び両車端及び鎖中に一分子轟す二
個以上の水酸基を結合している、水酸基価4 m ([
011If/ t )、100℃におけ為帖lj 14
polesのポリエチレンオリゴマー14.7−、ジ
ブチルすずオキナイドo、o i tをメプルヘリカル
リボン攪拌―付自20−−オートタレープに仕込み、電
圧で窒素気流下K 1?l)℃4時間纏舎反応を行1に
い、Iに01口110減圧下に1時間かけて210 ’
C壜で昇温し、IK!暗間かけて270℃に昇温後、そ
の温直にS時間保持し反応せしめた。得られたポリ!−
はm−クレゾール中、o、swt嘔のIl&直、2M℃
で1reJを一定したところ1.2墨であり九。Example-2 m-7ζ nododecanoic acid 41. IP%#-mono-dodeca/dicarboxylic acid 14? and a hydroxyl value of 4 m ([
011If/t), at 100℃ 14
Pole's polyethylene oligomer 14.7- and dibutyltin oquinide O, O it were charged into a maple helical ribbon stirring-attachment 20- autotarepe and heated under a nitrogen stream at a voltage of K1? l) Hold the reaction for 4 hours at ℃.
Raise the temperature with C bottle and IK! After raising the temperature to 270° C. in the dark, the mixture was kept at that temperature for S hours to react. Poly obtained! −
is in m-cresol, o, swt, Il & direct, 2M°C.
When I fixed 1reJ, it was 1.2 ink, which was 9.
得られ九ポリ!−の元素分析値は0 74.4重量嗟、
H1!、墨重量暢、1149重量憾重量層論値のそれぞ
れ074.1重量悌、1112.4重量饅、M S、0
重量憾に夷験誤葺I!■内で一歇し、九。IRスペクト
ルにはナイロン−11に特徴的な72s。Obtained nine poly! The elemental analysis value of - is 0 74.4 wt.
H1! , black weight, 1149 weight, weight layer theory value, respectively 074.1 weight, 1112.4 weight, MS, 0
I'm afraid I'm wrong! ■Take a break inside, then go to 9. The IR spectrum shows 72s, which is characteristic of nylon-11.
1sSs 、 1440 、32@O5−10il[と
ホ9 ! f V 7及びナイロン−12のメチレン鎖
に由来する2?10―−1の吸収と両者を結ぶエステル
結合の1750s−”の吸NILが見られ丸。1sSs, 1440, 32@O5-10il [and Ho9! f V 7 and the 2?10--1 absorption derived from the methylene chain of nylon-12 and the 1750s-'' absorption NIL of the ester bond connecting the two are observed.
得られ九ポリ!−を粗砕しトルエンによpソックスV−
抽出を10時間行なり九が、トルエンに可溶なポリエチ
レンオリゴマーは機跡@直しか抽出畜れず、ブロック共
縮合がほぼ児童に起こっていることを示しえ。Obtained nine poly! - is coarsely crushed and mixed with toluene p-sock V-
After 10 hours of extraction, only traces of the polyethylene oligomer soluble in toluene could be extracted, indicating that block cocondensation was almost entirely occurring.
又、D 80 (Diff@r@ntlal loan
ning Oalorim−・ter )によって一定
しえ融点は177℃であり九。Also, D 80 (Diff@r@ntlal loan
The melting point is 177°C, which is 9.
40℃水中に1遍間浸漬し九と自01水率は0.78憾
でありた0
実施例−1
一−ア建ノドデカン@ 41.@t % g、s−ドデ
カンジカルボン酸1.6を及び両末端及び鎖中に一分子
in二個以上の水酸基を結合してい為、水酸基価47
(KOH19/ t )、墨O℃にシは為粘度?30
poiteのポリブテン−1オリゴマー16.4f%ジ
ブチルすずオキナイドo、o s tをダブルヘリカル
リボン攪拌器付自100 dオートタレープに仕込み、
常圧で窒素気流下にt?(1’C4時間線合反応を行な
い、更K O,t mN@O減圧下に1時間かけて!1
0 ’C壜で昇温し、更に2時Mかけて270′CK昇
温後、そO温度に2時間保持し反応ぜしめ九。得られ九
ポリマーは臆−クレゾール中0.5vt憾の濃度、スI
Cでマr・lを測定し九ところ1.40f6′)九。When immersed in water at 40°C for one hour, the water ratio was 0.78. @t % g, s-dodecanedicarboxylic acid 1.6 and two or more hydroxyl groups in one molecule in both ends and in the chain, so the hydroxyl value is 47
(KOH19/t), viscosity at O℃? 30
Poite's polybutene-1 oligomer 16.4f% dibutyltin oquinide was charged into a 100 d autotalepe equipped with a double helical ribbon stirrer.
Under nitrogen flow at normal pressure? (Carry out the linear combination reaction for 1'C for 4 hours, and then reduce the pressure of K O,t mN@O for 1 hour!1
The temperature was raised to 0'C in a bottle, and then the temperature was raised to 270'C over 2 hours, and the reaction was then maintained at that temperature for 2 hours to complete the reaction. The nine polymers obtained were prepared at a concentration of 0.5vt in cresol.
Measure r.l at C and get 1.40f6')9.
得られ九ポリマーの元素分析値は074.4重量憾、[
11,4重量憾、M4.?重量嚢で、憑論値のそれぞれ
074.2重量憾、1112.4重量憾、15.0重量
暢に夷験誤葺範■内で一款しえ。I鳳スペクトルにはナ
イロン−1!に41黴的1に7!I。The elemental analysis value of the obtained nine polymers was 074.4 weight, [
11.4 weight, M4. ? In terms of weight, the values are 074.2 weight, 1112.4 weight, and 15.0 weight, which are all within the normal range. Nylon-1 for the I-Otori spectrum! 41 molds 1 to 7! I.
11!!Is * 1440 s暴!・Os−”0吸収
とポリブテン−1に%徴的& !?41#−1Lt)吸
収と両者を紬ぶエステル結合に起因す為17 S 6
cm−1の徴収が見られ魁得られ九ポリマーを粗砕し、
トルエンによ〉ソツタスV−抽出を10時間行なったが
、トルエンに可溶なポリブテン−1オリゴマーは機跡@
j[Lか抽出されず、ブロック共縮合が壇ぼ完全に起こ
りていることを示しえ。11! ! Is * 1440 s violent!・Os-"0 absorption and polybutene-1% characteristic &!?41#-1Lt) absorption and due to the ester bond that connects both 17 S 6
cm-1 was observed, and the nine polymers obtained were coarsely crushed,
Sotutus V-extraction with toluene was performed for 10 hours, but no trace of polybutene-1 oligomer soluble in toluene was found.
Show that j[L is not extracted and the block cocondensation has completely occurred.
なお、DIOKよって一定し九融点は172℃であった
、。The melting point of DIOK was 172°C, which was constant.
40℃水中に1遍間浸漬し九ときの吸水率は0.5・憾
であった0
実施例−4
12アミノドデカン酸76.40t、ヘキtメチレンジ
アミン1.s 7 F 4両末端カルボン酸水素添加ポ
リブタジェン(1,!ビニル結合60−以上のポリブタ
ジェンを9614水添、末端カルボン酸基漁lLO,9
115tn*q/l ) H,?2−を暴no−三角フ
ラスコに入れ、三角フツス=中K11m1を流しながら
これを宜io’CKmlllkしえ。12ア(ノドデカ
ン酸の溶融と共に縮合が始壇)、水分が泡となって出て
くる。zio℃で番時間−熱し丸後冷却して三角フラス
コを割如、重合物合本り出した。淡黄色半透明で衝撃に
強い重合体が得られ九〇この重合体はナイロン12威分
/水添ポリブタジェン−へキtメチレンシアtノ縮合体
成分の比率が707BOに椙幽する。After being immersed in water at 40°C for one hour, the water absorption rate was 0.5. s 7 F 4 Hydrogenated polybutadiene with carboxylic acid at both ends (1,! 9614 hydrogenation of polybutadiene with 60 or more vinyl bonds, hydrogenated with terminal carboxylic acid groups lLO, 9
115tn*q/l) H,? Put 2- into an Erlenmeyer flask, and pour it in while pouring 11ml of Erlenmeyer. 12A (condensation begins with the melting of nododecanoic acid), water comes out in the form of bubbles. The mixture was heated at 30° C. for several hours, then cooled, and the polymer was taken out from the Erlenmeyer flask. A light yellow, translucent, impact-resistant polymer was obtained, and the ratio of nylon 12/hydrogenated polybutadiene/hetyl methylene cyano condensate component was as high as 707 BO.
この重合体をメタクレゾールK11ljlしてり、1憾
S液とし、オストワルド帖直針によjl!ICK1にけ
ゐ椙対粘ttat定すると1.4i″eあり魁この重合
体をプレス成形により平板として40℃水中に10日間
浸漬後、デュポン式水分針により吸水率を一定すると1
.21憾でありえ。This polymer was made into metacresol K11 ljl, made into 1 S liquid, and jl! ICK1 has 1.4i''e when determining the viscosity versus viscosity.This polymer is press-molded into a flat plate and immersed in 40℃ water for 10 days.If the water absorption rate is fixed using a DuPont water needle, then it is 1.
.. 21 I regret it.
又、I)IOKよって一定し九融点は17!℃であり九
。Also, I) IOK is constant and the melting point is 17! ℃ and nine.
この重合体の元素分析値tIII−IK示す。Elemental analysis values tIII-IK of this polymer are shown.
表−1
この重合体の赤外吸収スペクトルには、ナイ四ン12ホ
啼ポリマーO徴ll1LK加え、740all e2
?40ar1に弱い吸収があゐ。Table 1 The infrared absorption spectrum of this polymer includes 740all e2
? There is weak absorption in 40ar1.
夷膣例−易
12ア電ノドデカン駿4?、11 t 、へ中ナメテレ
ンジア々ン04 ? v、実施例−4で用い九水添ポリ
ブタジェンij!rtloosg三角フラスコに仕込み
、実施例−4と同様にして重合を行ない、冷却後重合物
を取)出しえo*黄色亭透明で硬くて耐衝撃性のある重
合体が得られ丸。Yoshivagina example - 12 aden nododekan Shun 4? , 11 t, Hechuname Terenji Aan 04? v, nona-hydrogenated polybutadiene ij used in Example-4! A transparent, hard, and impact-resistant polymer was obtained after cooling.
この重合体はナイロン1!威分/水添ボリプタジエ/−
へ1?サメチレンジア建ン縮合体成分の比率が90/1
0KII幽す為。This polymer is nylon 1! Iwun/Hydrogenated voluptasie/-
To 1? The ratio of the same ethylene diene condensate component is 90/1
To hide 0KII.
この重合体を実施例−4と同様和して@定した結果、相
対帖[1,70%吸水率1.4!参、融点176℃でめ
った。This polymer was summed and determined in the same manner as in Example-4, and the relative value was 1.70% water absorption 1.4! It was melted at a melting point of 176°C.
この重合体の元素分析値をjl−2に示す。The elemental analysis values of this polymer are shown in jl-2.
表−2
夷−例−6
12アンノドデカン酸64.51 t 、ヘキtメチレ
ンシアiン2.41f 、実施例−4で用い九水添ボリ
プタジエ748.20 tをboo−セパラブルフラス
コに仕込み電嵩を流し、攪拌しながら220℃で2時間
加熱し友。淡黄色で#1とんど透明の柔軟な重合体が得
られ九。この重合体はナイロン12成分/水添ポリブタ
ジェン−へ命tメチレンシアイン縮合体成分の比率がI
O/I OK@幽する。Table 2 - Example 6 64.51 t of 12-annododecanoic acid, 2.41 f of hext methylene cyanide, and 748.20 t of nonahydrogenated polybutadiene used in Example 4 were charged into a boo-separable flask and the electric capacity was increased. Pour the water under the sink and heat at 220℃ for 2 hours while stirring. A pale yellow, #1 almost transparent flexible polymer was obtained. This polymer has a ratio of nylon 12 component/hydrogenated polybutadiene component to methylene cyanide condensate component.
O/I OK@ghost.
この重合体を実施例−4と同機にしてIII定し九結果
、相対帖[1,io、吸水率1.07、融点167℃で
あり九。This polymer was tested in the same machine as in Example 4, and the results were 9.
この重合体O元素分析値を表−IK示す。The O elemental analysis values of this polymer are shown in Table IK.
表−5
この重合体の赤外吸収スペクトルには、ナイロン12ホ
毫ポリマーの吸収に加えて、76rm *28!Oa
s” 、 2?400s” K弱い吸収がある0実施例
−7
12アイノドデカ/酸52.7a t 、ヘキすメチレ
ンシアイア5,661%実施例−4で用い九水添ポリブ
タジェン!7,48 tを50011jセノくラブルフ
ラスコに仕込み、実施例−6と同様に重合を行なった。Table 5 The infrared absorption spectrum of this polymer includes, in addition to the absorption of the nylon 12 polymer, 76rm *28! Oa
s'', 2?400s'' K weak absorption Example-7 12-inododeca/acid 52.7 at, hex-methylene siaa 5,661% Nona-hydrogenated polybutadiene used in Example-4! 7.48 t was charged into a 50011J size rubble flask, and polymerization was carried out in the same manner as in Example-6.
淡黄色で極めて柔軟な重合体が得られ丸。A pale yellow, extremely flexible polymer was obtained with a round shape.
仁の重合体はナイロン12成分/水添ポリブタジェン−
へキサメチン/シアイン縮合体成分の比率が30/70
に相幽する。The polymer is nylon 12 components/hydrogenated polybutadiene.
The ratio of hexamethine/cyaine condensate components is 30/70
to be with you.
この重合体を実施例−4と同11KL、て一定した結果
、相対帖[1,18%吸水率0.?i、融点15り℃’
であった。As a result of using this polymer at the same 11 KL as in Example 4, the relative volume [1.18% water absorption rate 0. ? i, melting point 15℃'
Met.
この重合体の元素分析値を表−4に示す。Table 4 shows the elemental analysis values of this polymer.
表−4
この重合体の赤外吸収スペクトルには、ナイロン12ホ
モポリマーの吸収に加えて、760s−1,2140s
%2?40s K弱い吸収がある。Table 4 The infrared absorption spectrum of this polymer includes, in addition to the absorption of nylon 12 homopolymer, 760s-1, 2140s
%2?40s There is weak absorption of K.
=1
実施例−8
12ア建ノドデカン酸74.40 t 、 4ア電ツカ
プロン酸5.・O#、へ命tメチレンシア建ン1j11
−1実施例−4で用いた水添ポリブタジェン24.10
1を500 aJセパツプルフラスコに仕込み窒素を流
し攪拌しながら240℃で墨時間加熱し九。淡黄色半透
明の重合体が得られた〇この重合体は、ナイロン12威
分/ナイロン6成分/水−ボリブタジエンーヘキすメチ
レンシアミン縮合体成分の比率が707S721sK相
当する。= 1 Example-8 74.40 t of 12-aryan nododecanoic acid, 5.・O#, to life t methylene chloride 1j11
-1 Hydrogenated polybutadiene used in Example-4 24.10
1 was placed in a 500 aJ separate flask and heated at 240° C. for a period of time with stirring under nitrogen flow. A light yellow, translucent polymer was obtained. This polymer had a ratio of nylon 12 components/nylon 6 components/water-volibutadiene-hexylmethylenecyamine condensate component of 707S721sK.
この重合体の物性を実施例−4と同様にして一定し九繍
果、相対粘度1.40、吸水率1.s7僑、融点168
℃であり九〇
この重合体の元素分析値を表−5K示す。The physical properties of this polymer were kept constant as in Example 4, with a relative viscosity of 1.40 and a water absorption rate of 1.40. s7 overseas, melting point 168
℃ and 90. The elemental analysis values of this polymer are shown in Table 5K.
表−5
実施例−9
11ア建ノウンデカン酸74.89 F 、へ+1メチ
レンジアミン1.S 7 f 、実施例−4で用い九水
添ポリブタジェン211.92 t t500 dセパ
ラブルフラスコに仕込み、実施例−8と同様に重合を行
なり九。淡黄色半透明で衝撃に強い重合体が得られ丸。Table-5 Example-9 11-denoundecanoic acid 74.89 F, +1 methylene diamine 1. S 7 f and 211.92 t t 500 d of the nona-hydrogenated polybutadiene used in Example 4 were charged into a separable flask, and polymerization was carried out in the same manner as in Example 8. A pale yellow, translucent, impact-resistant polymer is obtained.
この重合体は、ナイロン11成分/水添ポリブタジェン
−へキサメチレンシアきン縮合体成分の比率が7o/s
oK411mする。This polymer has a ratio of nylon 11 component/hydrogenated polybutadiene-hexamethylene cyakine condensate component of 7 o/s
oK411m.
この重合体を実施例−4と同様にして一定した結果、相
対粘度1.46、吸水率1.41嚢、融点186℃で6
つ九〇。This polymer was stabilized in the same manner as in Example 4, and as a result, the relative viscosity was 1.46, the water absorption rate was 1.41 bags, and the melting point was 186°C.
One ninety.
この重合体の元素分析値を表−6に示す。Table 6 shows the elemental analysis values of this polymer.
表 −に
の重合体の赤外吸収スペクトルには、ナイロン11ホモ
ポリマーの吸収に加えて、760m−”、2960 m
−” K @ イ吸収カアイ。The infrared absorption spectra of the polymers shown in Table 1 include absorptions of 760 m-'', 2960 m-'' and 2960 m-'' in addition to the absorption of nylon 11 homopolymer.
−” K @ i absorption kaai.
なお同様にして一定し九ナイロン11ホ毫ポリマーの融
点は192℃であ〕、吸水率は1.9参であり九。Similarly, the melting point of nylon 11 film polymer is 192°C], and the water absorption rate is 1.9 cm.
実施例−10
40!オートクレーブに、ラウリルラクタム14に@、
実施例−4に用い九水添ポリプIジエン578 t 、
ヘキナメチレンジア電ンs1.4F。Example-10 40! In the autoclave, in lauryl lactam 14 @,
Nine hydrogenated polyp I diene used in Example-4 578t,
Hekinamethylene diane s1.4F.
水700Fを仕込み、窒素置換を行なってから、5時間
かけて、罐内温度を270℃に昇温した。After charging 700F of water and purging with nitrogen, the temperature inside the can was raised to 270C over 5 hours.
この間−内圧力が2Of#/s”となるように圧を放出
調整した。270℃、204/a”の条件でS時間反応
を続は友後、4時間かけて徐々に放圧し、圧力を0とす
ると共に徐々に温度を250℃に降下させえ。放圧終了
と同時に1内に窒素を流し2時間後にオートクレーブ底
部よ染型合体を押し出しペレット化し九。During this time, the pressure was released and adjusted so that the internal pressure was 2Of#/s. 0 and gradually lower the temperature to 250°C. At the same time as the pressure release was completed, nitrogen was flowed into the autoclave 1 and after 2 hours, the dyed mixture at the bottom of the autoclave was extruded and pelletized.
この重合体は、ナイロン12/水添ポリブタジェン−へ
キサメチレンジアミン縮合体成分の比率が70/墨OK
椙幽する。This polymer has a ratio of nylon 12/hydrogenated polybutadiene-hexamethylene diamine condensate component of 70/black OK
Sugiyuu.
この重合体の相対粘fは1.1s7であつ九。The relative viscosity f of this polymer is 1.1s7.
相対粘度1.90のナイロン12ホモポリマーと、この
共重合体を重量比率7 Q/S O,及び50/!1o
ilL合し、5osaφ押出機に−cm練押出し、ペレ
ット化し、ブレンド品を得え。この共重合体2種類のブ
レンド品及び椙対帖J[1,90のナイロン12ホモポ
リマーをノツチ付シャルピー衝撃試験片に成形し、25
℃及びO′cKjIkけるシャルピー衝撃強度を一定し
た。結果を表−アに示す。A nylon 12 homopolymer with a relative viscosity of 1.90 and this copolymer were mixed in a weight ratio of 7 Q/S O, and 50/! 1o
il and L were combined, extruded into a -cm extruder using a 5osaφ extruder, and pelletized to obtain a blended product. A blend of these two types of copolymers and a nylon 12 homopolymer of Sugi Taicho J [1,90] were molded into a Charpy impact test piece with a notch.
The Charpy impact strength at °C and O'cKjIk was kept constant. The results are shown in Table A.
表−7よ)この共重合体が耐衝ll11kK優れる曵け
てなく、この共重合体をブレンドすることによってナイ
ロン12ホ毫ポリマーの衝撃強度が向上することがわか
る。It can be seen from Table 7 that this copolymer has an excellent impact resistance of 11 kK, and that blending this copolymer improves the impact strength of the nylon 12 film polymer.
参考例−1
実施例−1oritljjiシートを40℃O水中に一
遍間保持し丸後の水分は0.802重量−でありえ。Reference Example-1 Example-1 An oritljji sheet is held in 40°C water for a period of time, and the water content after the rounding can be 0.802 weight.
このシートのインピーダンスを70℃真空乾燥す日間後
のドライな状態及び40℃水中保持−透間後の状1に於
て測定し九とζろ、それぞれ1001m、so℃におい
てi、o x t o’ρ−及びえ4x10’#sf”
あ如、その差はわずか0) X 10’t−測定し九と
ζろ、融解範11153〜176℃、ビーク温[170
℃、融解熱7.I QILj / fの明瞭な紬a性^
分子の融解挙動を示し友。この様にインピーダンスが1
直の影響を受けK<<、又明瞭な融点によって熱しユー
ズとしても用い得るので、仁O共重合ポリエステルアi
ド樹腫は電気毛布や電気カーペットの感熱素子として好
適に用い得る。The impedance of this sheet was measured in the dry state after vacuum drying at 70°C and in the state 1 after being held in water at 40°C. 'ρ-and 4x10'#sf”
Well, the difference is only 0)
°C, heat of fusion 7. I QILj / f's clear ponga nature ^
A friend that shows the melting behavior of molecules. In this way, the impedance is 1
Since it can be used for heating and use due to its clear melting point, it
Dodenoma can be suitably used as a heat-sensitive element for electric blankets and electric carpets.
参考例−1
数平均分子量24,000のナイロン12のシートを4
0℃の水中に一遍間保持し丸後の水分は1.6重量憾で
あつ九〇このシートのインピーダンスを70℃S日関O
X空乾燥後と水中40℃−透間保持後に測定し九とζろ
110OH、Is 0℃において、s、o x 1o’
Qexs及び1.I X 10’ρ−であり、その差は
1.? X 10 g−にも遣しえ。Reference example-1 4 sheets of nylon 12 with a number average molecular weight of 24,000
The impedance of this sheet was 70°C when it was kept in water at 0°C for a period of time and the water content after the round was 1.6%.
X Measured after drying in the air and after holding in water at 40°C.
Qexs and 1. I X 10'ρ-, and the difference is 1. ? Also send it to X 10 g-.
このシートにりいてもD80を測定し九とζろ、融解範
囲164〜1魯4℃、ピーク温度178℃、融解熱は9
.20&j / t″e#)りた。Even on this sheet, D80 was measured and the melting range was 164-14℃, the peak temperature was 178℃, and the heat of fusion was 9
.. 20&j/t″e#).
12 )L バ−12 )L bar
Claims (1)
位を一種以上有す為ボリアミド高分子成分99〜S重量
部と両末端がカルボン酸基、アミノ基又は水酸基である
平均分子量SOW〜10.000のポリオレフイノ成分
1〜91重量部を共重合してなる新規共重合ポリアミド
樹脂 一旧lc町)n00− (1) (式中、nFis 〜11の整数) −mtxmiaoyoo −(2) (式中、XはOl、H,、(mは4〜110111k)
。 イソホロ7基、フエニレン基又はシフ−へ中シレン基を
表わし、!はOj町j(jは4〜104D整歇)、フエ
墨しン基又はV/ロヘ中シレン基な表わす) 2 ボリアミド鳥分子成分とポリオレアイン成分との比
率がボリア建ド高分子成分?5−10重量鶴に対しポリ
オレフイノ成分!S〜70重量部である特許請求の@−
嬉1項紀執の共重合ポリアミド樹脂。[Claims] 1. Since it has one or more repeating units represented by the following general formula (1) or (2), the polyamide polymer component has 99 to S weight parts and both terminals are carboxylic acid groups or amino groups. or a new copolymerized polyamide resin obtained by copolymerizing 1 to 91 parts by weight of a polyolefin component having an average molecular weight SOW of 10.000, which is a hydroxyl group) n00- (1) (in the formula, nFis is an integer of 11) -mtxmiaoyoo -(2) (wherein, X is Ol, H, (m is 4 to 110111k)
. Represents an isophoro7 group, a phenylene group, or a Schiff-silene group, and! (represents Oj town j (j is 4 to 104D regular), Hue ink group or V/Lohe middle silene group) 2 Is the ratio of the polyamide bird molecular component and polyolein component to the boria-based polymer component? Polyolefin ingredient for 5-10 weight cranes! S ~ 70 parts by weight @- of the patent claim
A copolymerized polyamide resin with a special reputation.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3691082A JPS58154723A (en) | 1982-03-09 | 1982-03-09 | Copolyamide resin |
PCT/JP1982/000068 WO1982003219A1 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
US06/651,633 US4555566A (en) | 1981-03-16 | 1982-03-16 | Copolymer polyamide resin containing polyolefin moiety |
DE8282900827T DE3278735D1 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
EP82900827A EP0073838B2 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
US06/888,095 US5025070A (en) | 1981-03-16 | 1986-07-17 | Copolymer polyamide resin from hydrogenated polyolefin condensate |
US07/475,184 US5093421A (en) | 1981-03-16 | 1990-02-02 | Copolymer polyamide resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3691082A JPS58154723A (en) | 1982-03-09 | 1982-03-09 | Copolyamide resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58154723A true JPS58154723A (en) | 1983-09-14 |
JPH0210176B2 JPH0210176B2 (en) | 1990-03-07 |
Family
ID=12482925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3691082A Granted JPS58154723A (en) | 1981-03-16 | 1982-03-09 | Copolyamide resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58154723A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60158217A (en) * | 1984-01-27 | 1985-08-19 | Ube Ind Ltd | Production of block polyester-amide |
JPS6341531A (en) * | 1986-08-08 | 1988-02-22 | Mitsubishi Chem Ind Ltd | Production of polyamide |
JPH04507427A (en) * | 1989-07-31 | 1992-12-24 | アライド―シグナル・インコーポレーテッド | Copolymer of dodecane terephthalamide |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54132796A (en) * | 1978-04-05 | 1979-10-16 | Daicel Ltd | High molecular temperature sensing body |
JPS55128202A (en) * | 1979-03-28 | 1980-10-03 | Daicel Ltd | High molecular heat sensitive material |
JPS562366A (en) * | 1979-06-15 | 1981-01-12 | Huels Chemische Werke Ag | Molten adhesive for article which contacts with internal combustion engine fuel |
-
1982
- 1982-03-09 JP JP3691082A patent/JPS58154723A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54132796A (en) * | 1978-04-05 | 1979-10-16 | Daicel Ltd | High molecular temperature sensing body |
JPS55128202A (en) * | 1979-03-28 | 1980-10-03 | Daicel Ltd | High molecular heat sensitive material |
JPS562366A (en) * | 1979-06-15 | 1981-01-12 | Huels Chemische Werke Ag | Molten adhesive for article which contacts with internal combustion engine fuel |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60158217A (en) * | 1984-01-27 | 1985-08-19 | Ube Ind Ltd | Production of block polyester-amide |
JPS6341531A (en) * | 1986-08-08 | 1988-02-22 | Mitsubishi Chem Ind Ltd | Production of polyamide |
JPH0323571B2 (en) * | 1986-08-08 | 1991-03-29 | Mitsubishi Chem Ind | |
JPH04507427A (en) * | 1989-07-31 | 1992-12-24 | アライド―シグナル・インコーポレーテッド | Copolymer of dodecane terephthalamide |
Also Published As
Publication number | Publication date |
---|---|
JPH0210176B2 (en) | 1990-03-07 |
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