CN107915839A

CN107915839A - A kind of polyamide and preparation method thereof

Info

Publication number: CN107915839A
Application number: CN201610887981.5A
Authority: CN
Inventors: 左璞晶; 宋婷婷; 陈斌; 加藤公哉; 大久保拓郎
Original assignee: Toray Advanced Materials Research Laboratories China Co Ltd
Current assignee: Toray Advanced Materials Research Laboratories China Co Ltd
Priority date: 2016-10-11
Filing date: 2016-10-11
Publication date: 2018-04-17
Also published as: JP2019530766A; WO2018068705A1; CN109715705B; CN109715705A

Abstract

A kind of the present invention is intended to provide chain fatty polyamide resin with excellent molding processibility, hot property and mechanical performance and preparation method thereof.Its technical characteristics is as follows：A kind of chain fatty polyamide resin containing polyether diamine block, the structure of the polyether diamine block shown in formula I,A, b and c are respective identical or different positive number in above-mentioned Formulas I, R₁、R₂And R₃For the alkyl of each identical or different hydrogen or carbon number 1~10；0.5~15wt% that the number-average molecular weight of the polyether diamine block is 500~1500 and content of the polyether diamine block in chain fatty polyamide resin is chain fatty polyamide total resin weight；The chain fatty polyamide resin is that solvent is configured to chain fatty polyamide resin solution of the concentration as 0.01g/ml using 96wt% sulfuric acid, and the relative viscosity η r measured at 25 DEG C are 1.1~4.0.

Description

A kind of polyamide and preparation method thereof

Technical field

The invention belongs to polymeric material field, more particularly to a kind of chain fatty adoption acyl containing polyether diamine block Polyimide resin and preparation method thereof.

Background technology

Polyamide is due to characteristics such as excellent mechanical performance, heat resistances, being widely used in fiber, various The various products formeds such as container, film, electronic unit, auto parts and components and mechanical part.

In recent years, the demand such as products formed miniaturization, complex-shapedization, thin-walled property, lightweight is growing, therefore, has It is particularly important that research and development of excellent molding processibility and the material of mechanical performance also become.On the other hand, relatively low processing and forming Temperature and shorter molding cycle are also beneficial to energy-saving and emission-reduction.In general, with the increase of polyamide molecular weight, polyamides The mechanical performance of polyimide resin is consequently increased.But also bring along such as melt viscosity increase, shaping while molecular weight increase to add The counter productives such as work reduction.

In order to improve polyamide fluidity of molten, polyamide is branched be a kind of common method (in State patent CN200880109110.4, CN200780011031.5, CN96199350.2, CN200980143835.X).It is but branched Structure can reduce the crystal property and mechanical performance of polyamide.

Japan Patent JPA1986163935 discloses a kind of polyamide with improved mechanical performance and molding processibility Resin, the polyamide end are the alkyl with 6~22 carbon atoms, its relative viscosity is 2.5~6.But this method The polyamide melt viscosity of gained is still higher, for products formed miniaturization growing in recent years, complicates, thin-walled property With light-weighted requirement, the problem of molding processibility is insufficient, still has.On the other hand, Chinese patent CN200780013670.5 A kind of copolymer for including alternate polyamide block PA and polyether block PE is disclosed, which has improved light And mechanical performance.Another Chinese patent CN200610082682.0 discloses a kind of thermoplastic elastomer (TPE), the thermoplastic elastomehc Property body can carry out reaction coupling by the Polvamide prepolymer with C-terminal base and isocyanate-terminated polyether prepolymer Obtain.But the melt viscosity of the polyether amide block copolymer described in above-mentioned patent is still higher, its molding processibility deficiency Problem still has.Also there are the more corresponding polyamide homopolymer decline of fusing point is larger, melt crystallization temperature is relatively low, injection at the same time The problems such as curing rate is slow during shaping, molding cycle is long.

Chinese patent CN201510744922.8 discloses a kind of height comprising polyamide thermoplastic and amido end capped polyether Thermoplastic polyamide resin composition is flowed, but most of amido end capped polyether is not change with polyamide in the composition Learn the state that bond is closed to exist, although polyamide can be reduced to a certain extent with amido end capped polyether existing for above-mentioned state The melt viscosity of resin combination, but effect unobvious.On the other hand, also there are products formed table for above-mentioned Amilan polyamide resin composition The shortcomings that face amido end capped polyether easily separates out.

It is terminal-modified that international monopoly WO2015/182693 discloses a kind of low melting viscosity with particular end based structures Polyamide.Although the end that polyether structure is imported into polyamide greatly reduces the melt viscosity of polyamide, Since monoamine base polyethers acts on the end-blocking of polyamide reactive terminal, the raising degree of polymerization is caused to take a long time, so as to cause Production efficiency is low.

International monopoly WO2012/111636 discloses a kind of semiaromatic polyamide composition elasticity containing polyether diamine block Body.The semiaromatic polyamide composition bullet with good heat resistance, crystallinity and flexibility has been obtained by introducing polyether diamine block Property body, but compared with corresponding semiaromatic polyamide composition homopolymer, the problem of being remarkably decreased there are mechanical performances such as stretch moduluses.

The content of the invention

The present invention provides a kind of chain fatty adoption acyl with excellent molding processibility, hot property and mechanical performance Polyimide resin and preparation method thereof.By being imported in chain fatty polyamide strand there is the flexible of specified molecular weight to gather While ether diamine block achievees the purpose that to reduce melt viscosity, raising moulding processability, compared with corresponding homopolymer, contain The hot property for having the chain fatty polyamide resin of polyether diamine block is kept, at the same the deterioration of mechanical performance also by Control is in minimum level.On the other hand, required polymerization time is also reduced in the polyamide preparation method.

The present invention is made of herein below：

1st, a kind of chain fatty polyamide resin containing polyether diamine block, the structure of the polyether diamine block is such as Shown in Formulas I,

A, b and c are respective identical or different positive number in above-mentioned Formulas I, R₁、R₂And R₃For each identical or different hydrogen Or the alkyl of carbon number 1~10；The number-average molecular weight of the polyether diamine block exists for 500~1500 and polyether diamine block Content in chain fatty polyamide resin is 0.5~15wt% of chain fatty polyamide gross weight；The chain fat It is molten as the chain fatty polyamide resin of 0.01g/ml that fat polyamide resin using 96wt% sulfuric acid is that solvent is configured to concentration Liquid, the relative viscosity η r measured at 25 DEG C are 1.1~4.0.

2nd, the chain fatty polyamide resin according to above-mentioned 1,3.6≤a+c≤6.0 in the Formulas I, and, 9.0≤ B≤12.5, R₁、R₂And R₃It is at the same time methyl.

3rd, the chain fatty polyamide resin according to above-mentioned 1, the chain fatty polyamide resin, which removes, to be contained The block of other structures is free of beyond polyether diamine block.

4th, the chain fatty polyamide resin according to above-mentioned 1, the chain fatty polyamide resin have base The terminal groups shown in Formula II in 0.005~0.1mmol/g of chain fatty polyamide total resin weight

—Y—(R₄—O)_m—R₅Formula II；

In above-mentioned Formula II-Y- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (= O)-NH- or-CH (OH)-CH₂-, m be 2~100 integer, R₄The alkylidene for being 2~10 for carbon number, R₅It is former for carbon Subnumber is 1~30 alkyl.

5th, the chain fatty polyamide resin according to above-mentioned 1, the chain fatty polyamide resin have base The terminal groups shown in formula III in 0.005~0.1mmol/g of chain fatty polyamide total resin weight

- Z-R₆Formula III；

In above-mentioned formula III-Z- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH₂-, R₆The alkyl or aryl for being 1~30 for carbon number substitutes alkyl, aryl or alkane Base substituted aryl.

6th, the chain fatty polyamide resin according to any one in above-mentioned 1~5, is surveyed using gel permeation chromatography The scope of the weight average molecular weight Mw of the chain fatty polyamide resin obtained is 10000~400000.

7th, the chain fatty polyamide resin according to any one in above-mentioned 1~5, the chain fatty adoption Amide resin fusing point is more than 215 DEG C.

8th, a kind of preparation method of chain fatty polyamide resin, using amino carboxylic acid, lactams or binary acid/binary Addition is poly- as shown in formula IV during one or more in amine prepare chain fatty polyamide resin for monomer polymerization Ether diamine,

D, e and f are respective identical or different positive number in above-mentioned formula IV, R₇、R₈And R₉For each identical or different hydrogen Or the alkyl of carbon number 1~10；The molecular weight of the polyether diamine is 500~1500 and the additive amount of polyether diamine is described 0.5~15wt% of amino carboxylic acid, lactams or binary acid/diamine monomer gross weight.

9th, the chain fatty polyamide process for preparing resins according to above-mentioned 8, d, e, f take following number in the formula IV Value：During d+f=3.6, e=9.0；During d+f=6.0, e=12.5；R₇、R₈And R₉It is at the same time methyl.

10th, the chain fatty polyamide process for preparing resins according to above-mentioned 8, also added change shown as a formula V Compound

U—(R₁₀—O)_n—R₁₁Formula V；

In above-mentioned Formula V n be 2~100 integer, R₁₀The alkylidene for being 2~10 for carbon number, R₁₁It is 1 for carbon number ~30 alkyl, U NH₂-, HO-, HO-C (=O)-, O=C=N-R₁₂- NH-C (=O)-O-, O=C=N- R₁₃- NH-C (=O)-NH- orHere R₁₂Or R₁₃For each identical or different carbon number be 1~ 20 alkylidene.

11st, the chain fatty polyamide process for preparing resins according to above-mentioned 8, also added the change as shown in Formula IV Compound

W-R₁₄Formula IV；

R in above-mentioned Formula IV₁₄The alkyl or aryl for being 1~30 for carbon number substitutes alkyl, aryl or alkyl substituting aromatic base, W- is NH₂-, HO-, HO-C (=O)-, O=C=N-R₁₅- NH-C (=O)-O-, O=C=N-R₁₆- NH-C (=O)-NH- orHere R₁₅Or R₁₆The alkylene for being 1~20 for each identical or different carbon number Base.

Foregoing invention content is described in detail below：

A kind of chain fatty polyamide resin containing polyether diamine block, the structure such as formula of the polyether diamine block Shown in I,

A, b and c are respective identical or different positive number in above-mentioned Formulas I, R₁、R₂And R₃For each identical or different hydrogen Or the alkyl of carbon number 1~10；The number-average molecular weight of the polyether diamine block exists for 500~1500 and polyether diamine block Content in chain fatty polyamide resin is 0.5~15wt% of chain fatty polyamide total resin weight；The chain Shape aliphatic polyamide resin is that solvent is configured to chain fatty polyamide tree of the concentration as 0.01g/ml using 96wt% sulfuric acid Lipoprotein solution, the relative viscosity η r measured at 25 DEG C are 1.1~4.0.

The chain fatty polyamide resin of the present invention has poly- as shown in above-mentioned Formulas I at least in a part of strand Ether diamine block.Chain fatty polyamide resin described here is preferably aromatic composition content in the poly- of below 20wt% Amide resin, further preferred aromatic composition content below 10wt% and without branched structure polyamide.

For structure shown in Formulas I due to containing ehter bond, its motility is stronger, while also stronger with amido link compatibility.Pass through The flexible polyether diamines block is introduced in chain fatty polyamide strand, improves the flexibility of polyamide molecule, therefore The transport properties of molecules of polyamide greatly increases, so as to reduce melt viscosity, improves moulding processability.

A, b and c are preferably respective positive number in the range of identical or different 1~30 in above-mentioned Formulas I, in a, b and c value Any one more than 30 when, melt viscosity reducing effect is deteriorated, while polyether diamine block structure heat resistance also becomes poor；And a, B, when and any one of c values are less than 1, the crystallinity infringement to polyamide is larger.Reduce and imitate in view of melt viscosity Fruit and the crystallinity of gained polyamide, a, b and c meet that following conditions are more preferable：3.6≤a+c≤6.0 and 9.0≤b≤ 12.5.Further preferred a+c=3.6 and b=9.0, or a+c=6.0 and b=12.5；Still more preferably a+c=6.0 and b =12.5.

R in above-mentioned Formulas I₁、R₂And R₃For the alkyl of each identical or different hydrogen or carbon number 1~10.In view of poly- The reduction of stability and Interchain interaction and molecule the interchain complexing of ether diamine block structure, R₁、R₂And R₃For The alkyl of carbon number 1~10 is preferably.Work as R₁、R₂And R₃For alkyl when, R₁、R₂And R₃Middle carbon number is fewer, itself and polyamides The compatibility of amine essential building blocks is also higher, the more difficult formation condensed state of polyether diamine block, preferably R₁、R₂And R₃For The alkyl of carbon number 1~5, further preferred R₁、R₂And R₃For the alkyl of carbon number 1~2, most preferably R₁、R₂And R₃Together When be methyl.

The number-average molecular weight of polyether diamine block shown in above-mentioned Formulas I is 500-1500, i.e. the number of polyether diamine block is divided equally Son amount is more than 500 and less than 1500.When number-average molecular weight is less than 500, crystallinity, the mechanical performance of corresponding polyamide can become Difference.In view of the holding of polyamide crystallinity and mechanical performance, the number-average molecular weight of further preferred polyether diamine block More than 550, still more preferably the number-average molecular weight of polyether diamine block is more than 850.On the other hand, the number of polyether diamine block When average molecular weight is more than 1500, the effect that melt viscosity reduces is poor, so that the improvement of shaping processability is limited.Further preferably The number-average molecular weight of polyether diamine block is less than 1200, and the number-average molecular weight of still more preferably polyether diamine block is less than 1100。

Polyether diamine block in the chain fatty polyamide resin of the present invention shown in Formulas I is in chain fatty polyamide Content is 0.5wt%~15wt% (using the weight of chain fatty polyamide resin as 100wt%, similarly hereinafter) in resin, is passed through It is more than 0.5wt% to make the mass content of polyether diamine block shown in Formulas I, and can reach reduces melt viscosity, improves processing and forming The purpose of property.Content preferred 1wt% more than of the polyether diamine block in the chain fatty polyamide resin, further It is preferred that more than 1.5wt%, still more preferably more than 2wt%；On the other hand, by making the quality of polyether diamine block shown in Formulas I Content is below 15wt%, and the crystallinity and mechanical performance that can make chain fatty polyamide resin are preferably kept, Preferably below 11wt%, more preferably below 6wt%, are still more preferably below 4.5wt%.Herein, it is above-mentioned Polyether diamine block shown in Formulas I passes through 1H-NMR (cores relative to the content (wt%) of the chain fatty polyamide resin Magnetic hydrogen compose) test obtain.

The chain fatty polyamide resin of the present invention is 0.01g/ using the 96wt% concentrated sulfuric acids as solvent, being configured to concentration During the solution of ml, the relative viscosity η r measured at 25 DEG C are 1.1-4.0.When η r are less than 1.1, the mechanical property of composition compared with Difference.It is preferred that η r are higher than 1.2, further preferably higher than 1.4.On the other hand, when η r are higher than 4, molecular weight is excessive, thus melt viscosity Excessive to cause shaping processability excessively poor, preferably η r are less than 3.When containing mass content more than 1% in Amilan polyamide resin composition During filler described below, viscosimetric analysis is carried out after filler should be removed to the state to mass content less than 1%.

The chain fatty polyamide resin of the present invention can contain the embedding of other structures in addition to containing polyether diamine block Section, such as polyolefin block, polyester block.But consider melt viscosity reducing effect and crystalline holding, preferably described chain Shape aliphatic polyamide resin is free of the block of other structures in addition to containing polyether diamine block.Other structures referred herein Block refers to the other polymers block in addition to polyether diamine block that number of repeat unit is more than 8.

The terminal groups of chain fatty polyamide resin of the present invention do not specially require, can be amino or carboxyl so Reactive terminal groups, or other non-reacted terminal groups.In order to further reduce the chain fatty of the present invention The melt viscosity of polyamide resin, as terminal groups of the non-reacted terminal groups preferably as shown in Formula II

—Y—(R₄—O)_m—R₅Formula II；

In above-mentioned Formula II-Y- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (= O)-NH- or-CH (OH)-CH₂-, m be 2~100 integer, R₄The alkylidene for being 2~10 for carbon number, R₅It is former for carbon Subnumber is 1~30 alkyl.In view of the compatibility with polyamide essential building blocks ,-Y- is preferred in above-mentioned Formula II For-NH- ,-O- or-C (=O)-.When m in above-mentioned Formula II is less than 2, melt viscosity reduces and the effect of crystallinity holding Fruit is poor, so that the improvement of molding processibility is limited.It is preferred that m is more than 4, further preferred m is more than 8, and most preferably m is more than 10.Separately On the one hand, when m is more than 100, the end based structures heat resistance is poor.It is preferred that m is less than 70, further preferred m is less than 35, most preferably M is less than 25.In above-mentioned Formula II, R₄For the alkylidene of carbon number 2~10, it is contemplated that with polyamide essential building blocks The alkylidene of compatibility, preferably carbon number 2~6, the alkylidene of further preferred carbon number 2~4.Meanwhile R₅It is former for carbon The alkyl of subnumber 1~30.R₅Middle carbon number is fewer, it is also higher with the compatibility of polyamide essential building blocks, Therefore R₅It is preferred that carbon number is 1~20 alkyl, further preferred carbon number is 1~10 alkyl, still more preferably Carbon number is 1~5 alkyl, is most preferably methyl.

The chain fatty polyamide resin of the present invention at least contains Formula II institute in the end of a part of polyamide molecule chain The terminal groups shown, above-mentioned end base content in chain fatty polyamide resin described in 1g is 0.005mmol~0.1mmol, By by the terminal groups shown in Formula II in chain fatty polyamide resin described in 1g content control 0.005mmol with On, polyamide molecular weight when melting delay can be made to increase slower, so that improving melting is detained stability, on the other hand It can also make the melt viscosity of polyamide further be reduced, so that molding processibility is improved, preferably 0.01mmol More than, further preferred more than 0.02mmol, still more preferably more than 0.03mmol；On the other hand, by by shown in Formula II Content control of the terminal groups in chain fatty polyamide resin described in 1g in below 0.1mmol, chain fat can be made The molecular weight of fat polyamide resin is easier to make for, be preferably below 0.08mmol, further preferred 0.07mmol with Under, still more preferably below 0.06mmol.Herein, the terminal groups shown in above-mentioned Formula II are relative to the polyamide Content (mmol/g) is obtained by 1H-NMR (nucleus magnetic hydrogen spectrum) tests.Melting is detained stability by the way that the polyamide is existed Under blanket of nitrogen, at Tm+40 DEG C of fusing point melting be detained 1 it is small when after its weight average molecular weight (Mw) measured by GPC, and calculate its phase Mw increment rates before being detained for melting, are represented with percentage.Above-mentioned Mw increment rates are further excellent for less than 60% preferably Select less than 40%, still more preferably less than 20%.

As the non-reacted terminal groups of the chain fatty polyamide resin of the present invention, another kind is preferably such as formula III Shown terminal groups

- Z-R₆Formula III；

In above-mentioned formula III-Z- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH₂-, R₆The alkyl or aryl for being 1~30 for carbon number substitutes alkyl, aryl or alkane Base substituted aryl.In view of the compatibility with polyamide essential building blocks, in above-mentioned formula III-Z- be preferably- NH- ,-O- or-C (=O)-, R₆Preferably carbon number is 1~20 alkyl or phenyl.

The chain fatty polyamide resin of the present invention preferably at least contains formula in the end of a part of polyamide molecule chain Terminal groups shown in III, above-mentioned end base in chain fatty polyamide resin described in 1g content for 0.005mmol~ 0.1mmol, by the way that content control of the terminal groups shown in formula III in chain fatty polyamide resin described in 1g is existed More than 0.005mmol, can rise polyamide molecular weight when melting delay slower, stablize so as to improve melting and be detained Property, preferably more than 0.01mmol, further preferred more than 0.02mmol, still more preferably more than 0.03mmol；On the other hand, By controlling content of the terminal groups shown in formula III in chain fatty polyamide resin described in 1g in below 0.1mmol, It can be easier to make for the molecular weight to chain fatty polyamide resin, be preferably below 0.08mmol.Herein, Terminal groups shown in above-mentioned formula III are surveyed relative to the content (mmol/g) of the polyamide by 1H-NMR (nucleus magnetic hydrogen spectrum) Examination obtains.

The present invention is to the weight average molecular weight (Mw) of chain fatty polyamide resin preferably more than 10,000.When Mw reaches When more than 10,000, mechanical performance can be further enhanced.Mw further preferred 20, more than 000, still more preferably More than 30,000.In addition, Mw preferably less than 400,000.When Mw is less than 400,000, melt viscosity is relatively low, and shaping processability is preferable. Mw further preferred less than 300,000, still more preferably less than 250,000.Weight average molecular weight (Mw) can pass through gel permeation chromatography (GPC) measure.

It is contemplated that heat-resist chain fatty polyamide resin is obtained, therefore chain fatty polyamide resin Fusing point (Tm) preferably more than 215 DEG C.In general the fusing point of copolyamide resin and melt crystallization temperature can decline, But the present invention passes through the above-mentioned restriction to the structure of polyether diamine block, number-average molecular weight and content so that imports polyether diamine The fusing point of chain fatty polyamide resin after block and the reduction control of crystallization temperature are in minimum scope.With corresponding chain The fusing point of shape fatty polyamide homopolymer is compared, under the fusing point of the chain fatty polyamide resin containing polyether diamine block Drop is no more than 5 DEG C, and preferably fusing point, which declines, is no more than 3 DEG C.Meanwhile with the fused junction of corresponding chain fatty polyamide homopolymer Brilliant temperature is compared, and the melt crystallization temperature of the chain fatty polyamide resin containing polyether diamine block, which declines, is no more than 5 DEG C, Preferred molten crystallization temperature, which declines, is no more than 3 DEG C.The fusing point and melt crystallization temperature of polyamide described here are by showing Difference scanning calorimeter (DSC) measure obtains：By polyamide resin accurate weighing 5-7mg, in a nitrogen atmosphere with 20 DEG C/ The heating rate of min is higher by 30 DEG C of temperature from the temperature T0 that 20 DEG C start to warm up to the endothermic peak than occurring, in this temperature Lower constant temperature 2min, is then cooled to after 20 DEG C with the rate of temperature fall of 20 DEG C/min and is warming up to again with the heating rate of 20 DEG C/min Than the temperature that T0 is higher by 30 DEG C, fusing point (Tm) is defined as with the temperature of the endothermic peak occurred in second of temperature-rise period.

The main composition of the chain fatty polyamide resin of the present invention can be enumerated but be not limited only to following instance：Gather in oneself Acid amides (nylon 6), polyhexamethylene adipamide (nylon66 fiber), nylon 46 (nylon 46), poly hexamethylene adipamide pentanediamine (nylon 56), polytetramethylene sebacamide (nylon 410), poly- decanedioyl pentanediamine (nylon 510), polyhexamethylene sebacamide (nylon 610), Poly- dodecanoamide (nylon 612) and the copolymer of above-mentioned polymer.Certain heat resistance, toughness or surface in order to obtain The characteristics such as performance, can also select the blend of terminal-modified polyamide of more than two kinds.Fusing point described here is by showing Difference scanning calorimeter (DSC) measure obtains：By polyamide accurate weighing 5-7mg, in a nitrogen atmosphere with 20 DEG C/min's Heating rate is higher by 30 DEG C of temperature from the temperature T0 that 20 DEG C start to warm up to the endothermic peak than occurring, at this temperature constant temperature 2min, is then cooled to after 20 DEG C with the rate of temperature fall of 20 DEG C/min and is warming up to again with the heating rate of 20 DEG C/min than T0 high Go out 30 DEG C of temperature, fusing point (Tm) is defined as with the temperature of the endothermic peak occurred in second of temperature-rise period.

Further preferred polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon66 fiber), poly hexamethylene adipamide pentanediamine (Buddhist nun Dragon 56), polytetramethylene sebacamide (nylon 410), poly- decanedioyl pentanediamine (nylon 510), polyhexamethylene sebacamide (nylon Or polycaprolactam/polyhexamethylene adipamide copolymer (nylon 6/66) 610).

There is the chain fatty polyamide resin of above-mentioned relative viscosity scope in order to obtain, after can using in the present invention The manufacture method of the chain fatty polyamide resin containing polyether diamine block described in face, i.e., by amino acid, lactams or Dicarboxylic acids/diamine is as the polyether diamine shown in raw material monomer and formula IV with preferable total amino amount described below [NH₂] and the ratio between total carboxyl amount [COOH] [NH₂]/[COOH] matched.When raw material is lactams, the amino amount [NH₂] or carboxyl amount [COOH] for lactams hydrolysis after amino amount [NH₂] or carboxyl amount [COOH].

There is the chain fatty polyamide resin of above-mentioned Mw scopes in order to obtain in the present invention, can use described below The chain fatty polyamide resin containing polyether diamine block manufacture method, amino acid, interior acyl that will be as raw material Polyether diamine shown in amine, dicarboxylic acids and diamine and formula IV is with preferable total amino amount [NH described below₂] and total carboxylic The ratio between base unit weight [COOH] [NH₂]/[COOH] matched.When raw material is lactams, the amino amount [NH₂] or carboxyl amount [COOH] is the amino amount [NH after lactams hydrolysis₂] or carboxyl amount [COOH].

The melt viscosity ratio as shown in following formula VII is also defined in the present invention：

Melt viscosity ratio (%)=(melt viscosity of the chain fatty polyamide resin containing polyether diamine block)/ (there is identical molecular weight with the chain fatty polyamide resin containing polyether diamine block but do not contain polyether diamine block The melt viscosity of chain fatty polyamide resin) } × 100 (%) (Formula VII).

Chain fatty polyamide resin wherein containing polyether diamine block refers to chain fatty of the present invention There is the chain fatty polyamide resin of polyether diamine block shown in Formulas I in polyamide resin.The present invention such as Formula VII institute The melt viscosity of definition than preferably less than 80%, it is further preferred by less than 50%, still more preferably less than 40%.It is referred to herein Melt viscosity be by introduced in the strand of chain fatty polyamide resin the method for polyether diamine block reduce it is molten The index of melt-viscosity effect.When melt viscosity is compared within the above range, moulding processability can be improved.

In Formula VII, there is identical molecular weight but not with the chain fatty polyamide resin containing polyether diamine block Chain fatty polyamide resin containing polyether diamine block refers to Mw in the chain fatty race containing polyether diamine block The chain fatty polyamide tree for not containing polyether diamine block in less than more than 95% 105% scope of polyamide Mw Fat.In order to more accurately evaluate visbreaking effect, this do not contain the Mw of the chain fatty polyamide resin of polyether diamine block with Chain fatty polyamide resin M w containing polyether diamine block is closer better, that is, does not contain the chain of polyether diamine block The preferred scope of the Mw of aliphatic polyamide resin is the chain fatty polyamide resin M w's containing polyether diamine block 100%.In addition, melt viscosity can be tested to obtain using rotational rheometer.

In the present invention, than the means taken, can include for example makes the melt viscosity in above range in order to obtain The methods of polyether diamine shown in above-mentioned Formulas I is in above-mentioned preferred scope.

In the following, the preparation method of the chain fatty polyamide resin of the present invention is described in detail.The chain of the present invention Shape aliphatic polyamide resin can include but be not limited only to following preparation method：As chain fatty polyamide resin The method that the raw material of main composition is copolymerized under the conditions of existing for the polyether diamine as described in following formula IVs.The method of copolymerization can To include following methods：Using as the raw material of the main composition of chain fatty polyamide resin such as amino carboxylic acid, lactams or Addition is such as formula during one or more in binary acid/diamine prepare chain fatty polyamide resin for monomer polymerization Polyether diamine shown in IV,

D, e and f are respective positive number in the range of identical or different 1~30 in above-mentioned formula IV, times in d, e and f value One more than 30 when, melt viscosity reducing effect may be poor, while polyether diamine block structure heat resistance is also poor；And d, e, , may be larger to the infringement of the crystallinity of polyamide and any one of f values are when being less than 1.D, e and f meets that following conditions are It is good：3.6≤d+f≤6.0 and 9.0≤e≤12.5.Further preferred d+f=3.6 and e=9.0, or d+f=6.0 and e= 12.5；Still more preferably d+f=6.0 and e=12.5.

R in above-mentioned Formulas I₇、R₈And R₉For the alkyl of each identical or different hydrogen or carbon number 1~10；In view of poly- The stability of ether diamine block structure, R₇、R₈And R₉For carbon number 1~10 alkyl preferably.Work as R₇、R₈And R₉For alkyl When, R₇、R₈And R₉Middle carbon number is fewer, it is also higher with the compatibility of polyamide essential building blocks, preferably R₇、 R₈And R₉For the alkyl of carbon number 1~5, further preferred R₇、R₈And R₉For the alkyl of carbon number 1~2, most preferably R₇、 R₈And R₉It is at the same time methyl.

The preferred 500-1500 of the number-average molecular weight of polyether diamine shown in above-mentioned formula IV, when number-average molecular weight is less than 500, to poly- The crystalline obstruction of amide resin is larger.In view of the crystalline holding of polyamide, the number of preferred, polyethers diamines is divided equally Son amount is more than 550, and the number-average molecular weight of further preferred polyether diamine is more than 580.On the other hand, number-average molecular weight is more than 1500 When, the melt viscosity of product reduces not sufficiently effective.The number-average molecular weight of preferred, polyethers diamines is less than 1200, further preferably gathers The number-average molecular weight of ether diamine is less than 1100.

The additive amount of polyether diamine in the preparation method of the chain fatty polyamide resin of the present invention shown in formula IV is excellent The 0.5-15wt% of the amino carboxylic acid, lactams or binary acid/diamine monomer gross weight is elected as (with amino carboxylic acid, interior acyl Amine or binary acid/diamine monomer gross weight are 100wt%, similarly hereinafter), it is contemplated that the melt viscosity and molding processibility of product, The additive amount of the polyether diamine be preferably the amino carboxylic acid, lactams or binary acid/diamine monomer gross weight 1wt% with On, further preferred more than 1.5wt%, still more preferably more than 2wt%；On the other hand, it is contemplated that the crystallinity of product, formula The additive amount of polyether diamine shown in IV is preferably the amino carboxylic acid, lactams or binary acid/diamine monomer gross weight Below 12wt%, more preferably below 11wt%, be still more preferably below 5.5wt%, be most preferably 4.5wt% with Under.

Polyether diamine shown in above-mentioned formula IV can specifically be enumerated but be not limited only to following polyether diamine： RE-900、RT-1000、One in ED-900 (commercial product from Huntsman) Kind is a variety of, and the two or more such as above-mentioned polyether diamines enumerated can be selected to be used in mixed way.

Polyether diamine shown in above-mentioned formula IV both can be before polymerization starts and amino carboxylic acid, lactams or binary acid/bis- One or more in first amine are added at the same time, can also be in the random time addition in the polymerization process after polymerization starts.

By one or more raw material monomers in amino carboxylic acid, lactams or binary acid/diamine shown in formula IV When the method for progress combined polymerization prepares chain fatty polyamide resin under the conditions of polyether diamine is existing, it can use described The method that temperature more than chain fatty polyamide melting point resin carries out melt polymerization, can also use in the chain fatty The method that solid phase is carried out below the fusing point of polyamide resin.

By one or more raw material monomers in amino carboxylic acid, lactams or binary acid/diamine shown in formula IV When the method for progress combined polymerization prepares chain fatty polyamide resin under the conditions of polyether diamine is existing, it may be necessary to add Polymerization accelerant.As the preferred phosphoric acid of polymerization accelerant, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, polyphosphoric acids or above-mentioned phosphoric acid The inorganic phosphorous compounds such as alkali metal salt, alkali salt, further preferred sodium phosphite or sodium hypophosphite etc..Polymerization accelerant Usage amount preferably 0.001~1 parts by weight (with except described in (A) have the compound of structure shown in formula (II) beyond prepare gather The weight of the raw material of amide resin is 100 parts by weight).By controlling the additive amount of polymerization accelerant in above-mentioned 0.001~1 weight In the range of measuring part, the mechanical performance and molding processibility that can make gained polyamide are preferably balanced.

In order to make the relative viscosity η r of chain fatty polyamide resin or weight average molecular weight Mw reach above-mentioned in the present invention Preferred scope, it is necessary to using as the polyether diamine shown in the amino carboxylic acid of raw material, lactams, binary acid and diamine and formula IV with Preferable total amino amount [NH described below₂] and the ratio between total carboxyl amount [COOH] [NH₂]/[COOH] control 0.95~1.05 In the range of preferably, [NH₂]/[COOH] preferred scope be 0.98~1.02, more preferably 0.99~1.01.Work as raw material For lactams when, the amino amount [NH₂] or carboxyl amount [COOH] for lactams hydrolysis after amino amount [NH₂] or carboxyl amount [COOH]。

By one or more raw material monomers in amino carboxylic acid, lactams or binary acid/diamine shown in formula IV When the method for progress combined polymerization prepares chain fatty polyamide resin under the conditions of polyether diamine is existing, it can also add such as formula Compound shown in V：

U—(R₁₀—O)_n—R₁₁Formula V；

In view of the compatibility with polyamide essential building blocks, U- is preferably NH in above-mentioned Formula V₂-, HO-, Or HO-C (=O)-.When n in above-mentioned Formula V is less than 2, the effect that melt viscosity reduces and crystallinity is kept is poor, from into The improvement of type processability is limited.It is preferred that n is more than 4, further preferred n is more than 8, and most preferably n is more than 10.On the other hand, n is more than When 100, the end based structures heat resistance is poor.It is preferred that n is less than 70, further preferred n is less than 35, and most preferably n is less than 25.It is above-mentioned In Formula V, R₁₀For the alkylidene of carbon number 2~10, it is contemplated that the compatibility with polyamide essential building blocks, preferably carbon The alkylidene of atomicity 2~6, the alkylidene of further preferred carbon number 2~4.Meanwhile R₁₁For the alkane of carbon number 1~30 Base.R₁₁Middle carbon number is fewer, it is also higher with the compatibility of polyamide essential building blocks, therefore R₁₁It is preferred that carbon Atomicity is 1~20 alkyl, and further preferred carbon number is 1~10 alkyl, still more preferably carbon number for 1~ 5 alkyl, is most preferably methyl.

By one or more raw material monomers in amino carboxylic acid, lactams or binary acid/diamine shown in formula IV When the method for progress combined polymerization prepares chain fatty polyamide resin under the conditions of polyether diamine is existing, it can also add such as formula Compound shown in VI：

W-R₁₄Formula IV；

In view of the compatibility with polyamide essential building blocks, W- is preferably NH in above-mentioned Formula IV₂-, HO-, Or HO-C (=O)-, R₁₄Preferably carbon number is the alkyl or phenyl of 1-20.

Chain fatty polyamide refers to not containing the straight-chain fatty polyamide of alicyclic structure in the present invention, except this Outside there is no special limitation to the species of chain fatty polyamide resin, can be using diacid and diamines as raw material monomer system Standby chain fatty polyamide resin or the chain fatty adoption prepared using amino acid or lactams as raw material monomer Amide resin.Following instance but not only can be enumerated as the raw material monomer for forming chain fatty polyamide resin backbone structure It is limited to following instance：The amino acid such as 6-aminocaprolc acid, 11- aminoundecanoic acids, 12-aminolauric acid or Aminomethylbenzoic Acid； The lactams such as epsilon-caprolactams or omega-lauric lactam；Ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, Octamethylenediamine, nonamethylene diamine, decamethylene diamine, hendecane diamines, dodecamethylene diamine, tridecane diamine, tetradecane diamines, pentadecane diamines, Hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane diamines, eicosane diamines, 2- methyl isophthalic acids, 5- pentanediamines or 2- The aliphatic diamine such as methyl isophthalic acid, 8- octamethylenediamines；Oxalic acid, butanedioic acid, adipic acid, suberic acid, azelaic acid, decanedioic acid or dodecane The aliphatic dicarboxylic acids such as diacid.The corresponding alkyl diester of dicarboxylic acids and diacid chloride, which can be similarly used as, forms chain fatty adoption The raw material monomer of amide backbone structure is enumerated.Chain fatty polyamide resin in the present invention can be by all described above Chain fatty polyamide homopolymer or chain fatty polyamide copolymer prepared by raw material monomer.The chain Aliphatic polyamide resin can be a kind of polyamide, can also be made of two or more polyamides.The present invention is right The concrete structure of chain fatty polyamide resin is not particularly limited, but considers heat resistance and crystallinity, preferably chain fat More than the 80mol% of fat polyamide backbone repeat unit is made of the construction unit of the above-mentioned raw material monomer origin enumerated, into One step is preferably more than 90mol%, is most preferably 100mol%.

In the chain fatty polyamide resin of the present invention, it can add in the range of beneficial effects of the present invention are not damaged Filled, other kinds of polymer and various additives are compounded.

Filler in above-mentioned chain fatty polyamide resin can use the filler of general resin, and filler adds Add intensity, rigidity, heat resistance and the dimensional stability for the products formed that can make to be obtained by above-mentioned chain fatty polyamide resin It is further enhanced.Filler can be enumerated but be not limited only to following instance：Glass fibre, carbon fiber, titanium potassium acid crystals must, aoxidize Zinc whisker, aluminium borate whisker, aromatic polyamide fibre, alumina fibre, silicon carbide fibre, asbestos fibre, gypsum fiber or The inorganic or organic filler of the threadiness such as metallic fiber；Wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, leaf wax Stone, bentonite, montmorillonite, asbestos, silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, carbonic acid Calcium, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, glass microballoon, ceramic fine bead, The Non-fibrous inorganic filler such as boron nitride, carborundum or silica；Above-mentioned filler can also choose two or more cooperations and add Add.Above-mentioned filler can be hollow, in addition, above-mentioned filler also can be through isocyanic acid based compound, organic silane compound, organic The coupling agent treatments such as titanate based compound, organoborane compounds or epoxide.Above-mentioned montmorillonite can also be lamella Between ion pass through organic ammonium salt carry out cation exchange after organic montmorillonite.Preferred the inorganic of threadiness of above-mentioned filler is filled out Material, further preferred glass fibre or carbon fiber.

Other kinds of polymer can be enumerated but be not limited only to example below in above-mentioned chain fatty polyamide resin： The polyolefin such as polyethylene or polypropylene；The modified polyolefins such as the copolymer that alkene and/or conjugated diene hydrocarbon compound polymerize The elastomers such as hydrocarbon, polyamide-based elastomer or polyester-based elastomer；Polyester, makrolon, polyphenylene oxide, polyphenylene sulfide, liquid crystal gather Compound, polysulfones, polyether sulfone, ABS resin, SAN resins or polystyrene.Above-mentioned polymer can also select two or more cooperation to add Add.In order to improve the impact resistance of the obtained products formed of chain fatty polyamide resin, preferred alkenes and/or conjugated diene The elastomers such as the improved polyalkenes such as the copolymer that hydrocarbon compound polymerize, polyamide-based elastomer or polyester-based elastomer.On Stating elastomer can also select two or more to be used cooperatively.

Above-mentioned polymer (or copolymer) can enumerate but be not limited only to following instance：Vinyl copolymer, conjugated diene Hydrocarbon system polymer or conjugated diene-aromatic vinyl copolymer etc..

Vinyl copolymer refers to ethene and the copolymer of other monomers.Can be enumerated with the other monomers of ethylene copolymer but It is not limited only to following instance：Alpha-olefin, non-conjugated diene hydrocarbon, vinyl acetate, vinyl alcohol, the α of carbon number more than 3, β-insatiable hunger With acid or derivatives thereof.Above-mentioned monomer can also select two or more to be copolymerized with ethene.The alpha-olefin of carbon number more than 3 It can enumerate but be not limited only to following instance：Propylene, 1- butylene, 1- amylenes or 3- Methyl-1-pentenes, preferably propylene or 1- fourths Alkene.Non-conjugated diene hydrocarbon can be enumerated but be not limited only to following instance：5- methylene -2- norbornene, 5- ethylidene -2- drop ice Piece alkene, 5- vinyl -2- norbornene, 5- acrylic -2- norbornene, 5- isopropenyl -2- norbornene, 5- cyclobutenyls - 2- norbornene, 5- (2- methyl-2-butenes base) -2- norbornene, 5- (2- ethyl -2- cyclobutenyls) -2- norbornene or 5- The norbornene compounds such as methyl -5- vinyl norbornenes；Dicyclopentadiene, methyl tetrahydroquinone, tetrahydroindene, 1,5- rings pungent two Alkene, Isosorbide-5-Nitrae-hexadiene, 6- methyl isophthalic acids, preferably 5- heptadiene or 11- oleatridecadienes etc., 5- methylene -2- norbornene, 5- Ethylidene -2- norbornene, dicyclopentadiene or 1,4- hexadienes.Alpha, beta-unsaturated acid can be enumerated but is not limited only to following Example：Acrylic acid, methacrylic acid, ethylacrylic acid, 2- butenoic acids, maleic acid, fumaric acid, itaconic acid, citraconic acid or butylene Diacid etc..The derivative of alpha, beta-unsaturated carboxylic acid can be enumerated but be not limited to following instance：The alkane of above-mentioned alpha, beta-unsaturated carboxylic acid Base ester, aryl ester, glyceride, acid anhydrides or acid imide etc..

Conjugated diene based polymer refers to the polymer obtained by least one conjugate diene polymerization.It is described here Conjugated diene can enumerate but be not limited only to following instance：1,3-butadiene, isoprene (2- methyl isophthalic acids, 3- fourths two Alkene), 2,3- dimethyl -1,3-butadiene or 1,3-pentadiene etc..Above-mentioned conjugated diene can also select two or more progress Copolymerization.In addition, the unsaturated bond of the polymer can be by hydrogenating the reduction carried out partially or completely.

Conjugated diene-aromatic vinyl copolymer refers to the copolymer of conjugated diene and aromatic vinyl, can be with It is block copolymer or random copolymer.The adducible example of conjugated diene prepares conjugated diene with above-mentioned The raw material of based polymer is identical, preferably 1,3-butadiene and isoprene.Aromatic vinyl can enumerate following instance：Benzene second Alkene, o-methyl styrene, m-methyl styrene, p-methylstyrene, 1,3- dimethyl styrenes or vinyl naphthalene etc., preferably Styrene.In addition, the unsaturated bond beyond the double bond in addition to aromatic rings of conjugated diene-aromatic vinyl copolymer also may be used To pass through hydrogenated fractions or complete reduction.

Anti-impact agent can specifically be enumerated：Ethylene/propene copolymer, Ethylene/1-butene copolymer, ethene/1- hervene copolymers Thing, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propene/5- ethylidene -2- norbornene copolymers, be not hydrogenated with or add Hydrogen styrene/isoprene/styrene triblock copolymer, be not hydrogenated with or be hydrogenated with styrene/butadiene/styrene three block and be total to Some or all of carboxylic acid group and sodium, lithium, potassium, zinc or calcium in polymers, ethylene/methacrylic acid or copolymer The salt of formation, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, the copolymerization of ethylene/methacrylic acid methyl esters Thing, ethylene/ethyl acrylate-g- copolymer-maleic anhydrides (" g " represents grafting herein, similarly hereinafter), ethylene/methyl acrylate-g- Copolymer-maleic anhydride, ethylene/ethyl acrylate-g- maleimide copolymers, ethylene/ethyl acrylate-g-N- phenyl horses Come the partly-hydrolysed thing of imide copolymer or the copolymer, ethylene/methacrylic acid glycidyl ester copolymer, second Alkene/vinylacetate/glycidyl methacrylate copolymer, ethylene/methacrylic acid methyl esters/Glycidyl methacrylate are sweet Grease copolymer, ethylene/acrylic acid glycidyl ester copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymerization Thing, ethene/glycidyl ether copolymers, ethylene/propene-g- copolymer-maleic anhydrides, ethylene/propene-g- maleic anhydrides Thing, ethylene/butylene -1-g- copolymer-maleic anhydrides, ethylene/propene/Isosorbide-5-Nitrae-hexadiene-g- copolymer-maleic anhydrides, ethylene/propylene Alkene/dicyclopentadiene-g- copolymer-maleic anhydrides, ethylene/propene/2,5- norbornadiene-g- copolymer-maleic anhydrides, second Alkene/propylene-g-N- phenyl maleimide copolymers, ethylene/butylene -1-g-N- phenyl maleimide copolymers, hydrogenation (benzene Ethene/Butadiene/Styrene-g- maleic anhydrides) copolymer, hydrogenation (styrene/isoprene/styrene-g- maleic anhydrides) Copolymer, ethylene/propene-g- glycidyl methacrylate copolymers, ethylene/butylene -1-g- Glycidyl methacrylates are sweet Grease copolymer, ethylene/propene/Isosorbide-5-Nitrae-hexadiene-g- glycidyl methacrylate copolymers, ethylene/propene/bicyclic penta Diene-g- glycidyl methacrylate copolymers, hydrogenation (styrene/butadiene/styrene-g- Glycidyl methacrylates Glyceride) copolymer, 12/ PolyTHF copolymer of nylon, 12/ polypropylene glycol copolymers of nylon, poly terephthalic acid fourth two Ester/PolyTHF copolymer or polybutylene terephthalate/polypropylene glycol copolymers etc..Above-mentioned copolymer optimal ethylene/ Part or all of carboxylic acid group and salt, the second of sodium, lithium, potassium, zinc or calcium formation in methacrylic acid copolymer and copolymer Alkene/propylene-g- copolymer-maleic anhydrides, ethylene/butylene -1-g- copolymer-maleic anhydrides.

Additive can specifically be enumerated：Antioxidant or heat stabilizer (steric hindrance phenol system, hydroquinone system, phosphorous acid system or Their substitution product, copper halide, iodine compound etc.), weather resisting agent (resorcinol system, salicylic acid system, enumerate BTA system, hexichol Base ketone system or steric hindrance amine system etc.), releasing agent and lubricant (fatty alcohol, aliphatic amide, aliphatic diamides or two ureas or Tissuemat E etc.), pigment (calcium sulfide, phthalocyanine or carbon black etc.), dyestuff (nigrosine etc.), (P-hydroxybenzoic acid is just pungent for plasticiser Ester or N-butylbenzenesulfonamide), antistatic additive (alkyl sulphate type anionic system antistatic additive, 4 grades of ammonium salt type cationic systems The nonionic system such as antistatic additive, polyoxyethylene sorbitan monostearate antistatic additive or the both sexes of trimethylglycine system resist Electrostatic agent), fire retardant (hydroxide such as melamine cyanurate, magnesium hydroxide, aluminium hydroxide, polyvinyl ammonium, bromination The bromide fire retardants such as polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin or above-mentioned bromide fire retardant and three Aoxidize the composition of two antimony).Above-mentioned additive can also select two or more compounding.

The present invention chain fatty polyamide resin can by injection molding, extrusion molding, blow molding, vacuum into Required shape is made in the random molding methods such as type, melt spinning or film shaping.By the chain fatty adoption acyl of the present invention The products formed that polyimide resin and composition containing the chain fatty polyamide resin obtain can be applied to following instance：Electricity The fibers such as the synthetic resins such as device/electronic product components, automobile component, mechanical part, clothing/industry, packaging/electromagnetic recording etc. Film.

Embodiment

With reference to embodiment, the invention will be further described, but this does not illustrate that present invention is limited only to these implementations Example.

For being described as follows for the test involved in embodiment and comparative example：

(1) measure of relative viscosity η r：Obtained polyamide sample is dissolved in each embodiment and comparative example In the concentrated sulfuric acid of 96wt%, the solution that polyamide resin lipid concentration is 0.01g/ml is configured to, is surveyed at 25 DEG C with Ubbelohde viscometer Measure relative viscosity.

(2) polyether diamine block concentration shown in Formulas I：It is obtained in each embodiment and comparative example to have shown in above-mentioned Formulas I The polyamide of polyether diamine block, is dissolved in the deuterated concentrated sulfuric acid with the concentration of 50mg/ml, is 256 times in scanning times Under the conditions of using Japan Electronics JEOL ECX 400P carry out 1H-NMR nuclear-magnetism tests.To in above-mentioned Formulas I in 1H-NMR spectrograms The ethylidene (- CH adjacent with oxygen on polyether diamine block₂- O-) on the corresponding peak of hydrogen and the polyamides as main composition After the corresponding peak of hydrogen on amine backbone repeat unit is belonged to, peak area and each knot as obtained by being integrated to each peak Polyether diamine block concentration in polyamide is calculated in number of hydrogen atoms contained by structure.

(3) terminal groups content shown in Formula II：It is obtained in each embodiment and comparative example that there is end shown in above-mentioned Formula II The polyamide of base, is dissolved in the deuterated concentrated sulfuric acid with the concentration of 50mg/ml, is used under conditions of being 256 times in scanning times Japan Electronics JEOL ECX 400P carry out 1H-NMR nuclear-magnetism tests.To R5 in terminal groups shown in above-mentioned Formula II in 1H-NMR spectrograms On the corresponding peak of hydrogen and after being belonged to as the corresponding peak of hydrogen on the polyamide skeleton repetitive unit of main composition, lead to Cross the peak area obtained by being integrated to each peak and polyamide Chinese style is calculated in the number of hydrogen atoms contained by each structure Terminal groups content shown in II.

(4) terminal groups content shown in formula III：It is obtained in each embodiment and comparative example that there are terminal groups shown in formula III Polyamide, be dissolved in the concentration of 50mg/ml in the deuterated concentrated sulfuric acid, scanning times be 256 times under conditions of use day This electronics JEOL ECX 400P carry out 1H-NMR nuclear-magnetism tests.To R6 in terminal groups shown in above-mentioned formula III in 1H-NMR spectrograms On the corresponding peak of hydrogen and after being belonged to as the corresponding peak of hydrogen on the polyamide skeleton repetitive unit of main composition, lead to Cross the peak area obtained by being integrated to each peak and polyamide Chinese style is calculated in the number of hydrogen atoms contained by each structure Terminal groups content shown in III.

(5) hot property

Using the differential scanning calorimeter (DSC Q100) of TA companies, obtained polyamide in each embodiment and comparative example Resin 5~7mg of accurate weighing, is started to warm up to than occurring with the heating rate of 20 DEG C/min from 20 DEG C in a nitrogen atmosphere The temperature T0 of endothermic peak is higher by 30 DEG C of temperature, and constant temperature 2min at this temperature, is then dropped with the rate of temperature fall of 20 DEG C/min To 20 DEG C, melt crystallization temperature Tc and fusion-crystallization enthalpy △ Hc are determined temperature by this temperature lowering curve：Tc is heat release in temperature-fall period The corresponding temperature of peak point at peak, △ Hc are the peak area of exothermic peak in temperature-fall period.Again with 20 DEG C/min after above-mentioned cooling Heating rate be warming up to 30 DEG C of temperature be higher by than T0, fusing point T_mWith melting enthalpy △ H_mDetermined by this secondary temperature elevation curve：T_m For the corresponding temperature of peak point of endothermic peak during secondary temperature elevation, △ H_mFor the peak area of endothermic peak during secondary temperature elevation.

(6) molecular weight

The polyamide 2.5mg obtained in each embodiment and comparative example is taken to be dissolved in sodium trifluoroacetates of the 4ml containing 0.005N Hexafluoroisopropanol in after, with measuring number-average molecular weight Mn and weight average molecular weight Mw, measurement strip after the filtering of 0.45 μm of filter Part is as follows

Pump：E-Alliance GPC system (Waters systems)

Detector：Composition distribution Waters 2414 (Waters systems)

Chromatographic column：Shodex HFIP-806M (2)+HFIP-LG

Solvent：Hexafluoroisopropanol (sodium trifluoroacetate of addition 0.005N)

Flow velocity：1ml/min

Sample injection rate：0.1ml

Temperature：30℃

Molecular weight calibration：Polymethyl methacrylate.

(7) melt viscosity

It is small that the polyamide obtained in each embodiment and comparative example is placed in vacuum drying chamber at 80 DEG C dry 12 When more than after, formed a film with film laminator hot pressing and be cut into the disk of diameter 25mm after (thickness 0.7mm), use rotational rheometer (Antonpaar systems, 25 parallel-plate of MCR302, φ) is using the following method measure melt viscosity：Under nitrogen atmosphere, by above-mentioned sample Product 260 DEG C melt 5 minutes, parallel plate spacing 0.5mm, vibration mode measure, 0.5~6.88Hz of frequency, measure 50 points (0.5 minute), amplitude 1%.Complex viscosity measured value when using frequency as 1.02Hz is as melt viscosity.

(8) stretch modulus

According to ASTM D638 standard testings, batten size is the TypeIV in ASTM D638, using Shimadzu AG--IS 1KN tests stretch modulus, 23 DEG C, humidity 50%RH, draw speed 10mm/min of test temperature, fixture spacing 60mm.Stretching die The result of amount takes the average value of 5 batten test results.The injecting condition of batten is as follows：

Injection moulding machine：ST10S2V (NISSEI systems)

Injection temperature：250 DEG C (embodiment 1~16, comparative examples 1~9,12~17)

220 DEG C (comparative examples 10,11)

Mold temperature：80 DEG C (embodiment 1~16, comparative examples 1~9,12~17)

90 DEG C (comparative examples 10,11)

(9) products formed humid heat treatment

The shaping batten tested for above-mentioned stretch modulus is placed in the constant temperature that temperature is 60 DEG C, relative humidity is 95%RH When processing 1000 is small in constant humidity cabinet.

(10) Mw increment rates after melting is detained

Weigh the polyamide obtained in each embodiments of 2g and comparative example to be placed in experiment tube, by system nitrogen displacement Afterwards under nitrogen flowing with metal bath by polyamide in experiment tube be heated rapidly to 260 DEG C and it is static 1 it is small when melt it is stagnant Stay, Mw tests to obtain by GPC after gained melting is detained.

The raw material used in embodiment and comparative example is as follows：

Hexamethylene diamine：TCI

Decanedioic acid：Hebei Kai De biomaterials Co., Ltd

Adipic acid：Alfa

M-xylene diamine：TCI

Caprolactam：BASF

Polyether diamine：JEFFAMINE ED-600 (Mn=600), the JEFFAMINE ED-900 (Mn=of Huntsman 900), JEFFAMINE EDR-148 (Mn=148), JEFFAMINE ED-2003 (Mn=2000), JEFFAMINE XTJ-542 (Mn=1000), ELASTAMINE RE-900 (Mn=900), ELASTAMINE RT-1000 (Mn=1000)

Polyethylene glycol：Alfa (Mn=1000)

Stearic acid：TCI

Benzoic acid：TCI.

Embodiment 1

By 210.4g hexamethylene diamines, 375.0g decanedioic acid, 25.9g JEFFAMINE ED-600 (Mn=600), 160g go from Sub- water is added in reaction kettle, by reaction kettle it is closed after with nitrogen displacement three times.The heter temperature of reaction kettle is set as 180 DEG C After begin to warm up, 2 it is small when after heter temperature is set as 270 DEG C.After reacting kettle inner pressure reaches 1.75MPa, by putting Pressure in kettle is maintained into 1.75MPa until temperature in the kettle is increased to 250 while air valve releases vapor in reaction kettle ℃.After temperature in the kettle reaches 250 DEG C, heater setpoint temperatures are reduced to 260 DEG C, and when 1 is small it is interior by pressure in kettle from 1.75MPa is gradually decreased to normal pressure (temperature in the kettle is 260 DEG C when reaching normal pressure).Nitrogen stream is passed through into kettle after being down to normal pressure, and The melt polymerization (263 DEG C of maximum temperature reached) of 10 minutes is carried out under nitrogen flowing, obtains the nylon containing polyether diamine block 610.The relative viscosity for the nylon 610 that the above method obtains is used as 1.73, melt viscosity 16Pas.The above method is obtained After the nylon 610 pelletizing arrived, apparatus,Soxhlet's is put into, passes through nucleus magnetic hydrogen spectrum after unreacted polyether diamine is removed with methanol The content that (1H-NMR) test obtains polyether diamine block is 5.1wt%.Other physical property are as shown in table 1.

Embodiment 2 and 3, comparative example 1-3

The logical nitrogen time is as shown in Table 1 more after reaching normal pressure according to pressure in the change shown in table 1 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 1.

Table 1

Embodiment 1-3 is compared with comparative example 1, it can be seen that the melting of the nylon 610 containing 5.1wt% polyether diamine blocks Viscosity is only the 8-9% of the melt viscosity of the nylon 610 homopolymer without polyether diamine block with identical weight average molecular weight, In addition crystallinity and mechanicalness indifference.In addition, it can see by comparative example 2, when the number-average molecular weight of polyether diamine block During less than 500, crystallization temperature, fusing point and the mechanical performance of polyamide are decreased obviously, and polyether diamine is embedding in comparative example 3 The number-average molecular weight of section is more than 1500, its melt viscosity declines unobvious.

Embodiment 4-6, comparative example 4 and 5

The logical nitrogen time is as shown in Table 2 more after reaching normal pressure according to pressure in the change shown in table 2 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 2.

Table 2

Compared with the comparative example 4 of relatively low polyether diamine block concentration (0.1wt%), the melting of embodiment 2 and embodiment 4-6 Viscosity, which declines, to be become apparent from.Compared with the comparative example 5 of higher polyether diamine block concentration (20wt%), embodiment 2 and embodiment 4-6 Maintain the crystallinity and mechanical performance equal with comparative example 1.

Comparative example 6-8

Lead to the nitrogen time as shown in table 3 more after reaching normal pressure according to pressure in the change shown in table 3 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 3.

Table 3

Pass through comparing embodiment 2 and comparative example 6-8, compared with the polyether block containing other structures, the melting of embodiment 2 Viscosity reduction effect is more preferable.

Embodiment 7-10

Lead to the nitrogen time as shown in table 4 more after reaching normal pressure according to pressure in the change shown in table 4 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 4.

Table 4

By embodiment 7-10 compared with embodiment 2 it can be seen that, Mw after its melting is detained during containing non-reacted terminal groups Increment rate is relatively low, and it is preferable that stability is detained in melting.

Embodiment 11

By 500g caprolactams, 4.1g adipic acids, 25g JEFFAMINE ED-900 (Mn=900), 160g deionized waters Add reaction kettle in, by reaction kettle it is closed after with nitrogen displacement three times.Opened after the heter temperature of reaction kettle is set as 290 DEG C Begin to heat.After reacting kettle inner pressure reaches 1MPa, by kettle while releasing by vapor in vent valve goalkeeper's reaction kettle Pressure maintains 1MPa until temperature in the kettle is increased to 250 DEG C.After temperature in the kettle reaches 250 DEG C, by heater setpoint temperatures It is reduced to 260 DEG C, and interior when 1 is small pressure in kettle be gradually decreased to normal pressure from 1MPa (temperature in the kettle is 260 when reaching normal pressure ℃).Nitrogen stream is passed through into kettle after being down to normal pressure, and carries out the melt polymerization (maximum temperature reached of 10 minutes under nitrogen flowing 263 DEG C), obtain the nylon 6 containing polyether diamine block.After obtained 6 pelletizing of nylon, apparatus,Soxhlet's is put into, uses methanol It is 1.77 that relative viscosity is tested after unreacted caprolactam and polyether diamine are removed, melt viscosity 18Pas.Pass through core The content that magnetic hydrogen spectrum (1H-NMR) test obtains polyether diamine block is 5.6wt%.Other physical property are as shown in table 5.

Embodiment 12 and 13, comparative example 9

Lead to the nitrogen time as shown in table 5 more after reaching normal pressure according to pressure in the change shown in table 5 and kettle except raw material Outside changing, other operations are as embodiment 11.The properties of gained nylon 6 are as shown in table 5.

Comparative example 10

269.7g m-xylene diamines, 404.5g decanedioic acid, 18g JEFFAMINE ED-900 (Mn=900), 160g are gone Ionized water add reaction kettle in, by reaction kettle it is closed after with nitrogen displacement three times.The heter temperature of reaction kettle is set as 180 Begun to warm up after DEG C, 2 it is small when after heter temperature is set as 240 DEG C.After reacting kettle inner pressure reaches 1.5MPa, by putting Pressure in kettle is maintained into 1.5MPa until temperature in the kettle is increased to 220 while air valve releases vapor in reaction kettle ℃.After temperature in the kettle reaches 220 DEG C, heater setpoint temperatures are reduced to 230 DEG C, and when 1 is small it is interior by pressure in kettle from 1.5MPa is gradually decreased to normal pressure (temperature in the kettle is 230 DEG C when reaching normal pressure).Normal pressure is down to obtain containing polyether diamine block Nylon MXD10.The relative viscosity for the nylon MXD10 that the above method obtains is used as 1.81, melt viscosity 150Pas.Will be upper After the nylon MXD10 pelletizings that the method for stating obtains, apparatus,Soxhlet's is put into, is passed through after unreacted polyether diamine is removed with methanol The content that nucleus magnetic hydrogen spectrum (1H-NMR) test obtains polyether diamine block is 5.1wt%.Other physical property are as shown in table 5.

Comparative example 11

In addition to raw material is according to the change shown in table 5, other operations are as comparative example 10.Gained nylon MXD10's is each Item performance is as shown in table 5.

Table 5

Compared with the nylon 6 homopolymer in comparative example 9, melt viscosity significantly reduces embodiment 11-13.By comparing Example 10 and comparative example 11, the semi-aromatic nylon MXD10 containing polyether diamine block, with corresponding semi-aromatic nylon homopolymer Compare, melt viscosity reducing effect is poor in comparative example 10, while mechanical performance declines substantially.

Embodiment 14

Lead to the nitrogen time as shown in table 6 more after reaching normal pressure according to pressure in the change shown in table 6 and kettle except raw material Outside changing, other operations are as embodiment 11.The properties of gained nylon 6 are as shown in table 6.

Embodiment 15

Lead to the nitrogen time as shown in table 6 more after reaching normal pressure according to pressure in the change shown in table 6 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 6.

Comparative example 12

It is uniformly mixed after 3kg nylon 6,30g JEFFAMINE ED-600 (Mn=600) are dried.By above-mentioned mixing Thing is sent into double screw extruder (TEX30 α, Nippon Steel Works), and melting mixing obtains nylon 6 composition at 250 DEG C.After measured The fusing point of above-mentioned nylon 6 composition is 219 DEG C, and weight average molecular weight Mw is 46300, melt viscosity 45Pas, and stretch modulus is 2.2GPa.The nylon 6 composition that the above method is obtained is put into apparatus,Soxhlet's, is removed unreacted polyether diamine with methanol Its relative viscosity is tested afterwards the content of polyether diamine block is obtained for 2.47, by nucleus magnetic hydrogen spectrum (1H-NMR) test be 0.1wt%, other physical property are as shown in table 6.

Comparative example 13

In addition to raw material is according to the change shown in table 6, other operations are as comparative example 12.Gained nylon 6 composition Properties are as shown in table 6.

Table 6

Dropped in comparative example 12 and comparative example 13 by the melt viscosity of the obtained Amilan polyamide resin composition of melting mixing Poorly efficient fruit is poorer than embodiment 14 and embodiment 15, while products formed observes precipitate, and 14 He of embodiment after moisture absorption is handled Precipitate precipitation is not observed in embodiment 15.By unreacted polyethers two in the Amilan polyamide resin composition in comparative example 12 Amine carries out nucleus magnetic hydrogen spectrum (1H-NMR) test and obtains and the polyether diamine of polyamide generation chemical bonds after being removed with methanol Content is only 0.1wt%, illustrates that most polyether diamines are not have the shape of chemical bonds with polyamide in comparative example 12 State exists.

Embodiment 16,17, comparative example 14-17

Lead to the nitrogen time as shown in table 7 more after reaching normal pressure according to pressure in the change shown in table 7 and kettle except raw material Outside changing, other operations are as embodiment 1.The properties of gained nylon 610 are as shown in table 7.

Table 7

Polyether block structure is combined with the end of polyamide in obtained product in comparative example 14-16, although it is molten Melt-viscosity reducing effect is also very significantly, but the polymerization time needed for it is longer.

Claims

A kind of 1. chain fatty polyamide resin containing polyether diamine block, it is characterised in that：The polyether diamine block Structure shown in formula I,

A, b and c are respective identical or different positive number in above-mentioned Formulas I, R₁、R₂And R₃For each identical or different hydrogen or carbon The alkyl of atomicity 1~10；The number-average molecular weight of the polyether diamine block is 500~1500 and polyether diamine block is in chain Content in aliphatic polyamide resin is 0.5~15wt% of chain fatty polyamide total resin weight；The chain fat It is molten as the chain fatty polyamide resin of 0.01g/ml that fat polyamide resin using 96wt% sulfuric acid is that solvent is configured to concentration Liquid, the relative viscosity η r measured at 25 DEG C are 1.1~4.0.
2. chain fatty polyamide resin according to claim 1, it is characterised in that：3.6≤a+c in the Formulas I≤ 6.0, and, 9.0≤b≤12.5, R₁、R₂And R₃It is at the same time methyl.
3. chain fatty polyamide resin according to claim 1, it is characterised in that：The chain fatty polyamide Resin is free of the block of other structures in addition to containing polyether diamine block.
4. chain fatty polyamide resin according to claim 1, it is characterised in that：The chain fatty polyamide Resin has the terminal groups shown in the Formula II based on 0.005~0.1mmol/g of chain fatty polyamide total resin weight

—Y—(R₄—O)_m—R₅Formula II；

In above-mentioned Formula II-Y- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)- NH- or-CH (OH)-CH₂-, m be 2~100 integer, R₄The alkylidene for being 2~10 for carbon number, R₅For carbon number For 1~30 alkyl.
5. chain fatty polyamide resin according to claim 1, it is characterised in that：The chain fatty polyamide Resin has the terminal groups shown in the formula III based on 0.005~0.1mmol/g of chain fatty polyamide total resin weight

- Z-R₆Formula III；

In above-mentioned formula III-Z- for-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (= O)-NH- or-CH (OH)-CH₂-, R₆The alkyl or aryl for being 1~30 for carbon number substitutes alkyl, aryl or alkyl to take For aryl.
6. the chain fatty polyamide resin according to any one in Claims 1 to 5, it is characterised in that：Using solidifying The scope of the weight average molecular weight Mw for the chain fatty polyamide resin that glue penetration chromatography measures is 10000~400000.
7. the chain fatty polyamide resin according to any one in Claims 1 to 5, it is characterised in that：Described Chain fatty polyamide melting point resin is more than 215 DEG C.
A kind of 8. preparation method of chain fatty polyamide resin, it is characterised in that：Using amino carboxylic acid, lactams or binary Addition is such as formula IV institute during one or more in acid/diamine prepare chain fatty polyamide resin for monomer polymerization The polyether diamine shown,

D, e and f are respective identical or different positive number in above-mentioned formula IV, R₇、R₈And R₉For each identical or different hydrogen or carbon The alkyl of atomicity 1~10；The molecular weight of the polyether diamine is 500~1500 and the additive amount of polyether diamine is the amino 0.5~15wt% of carboxylic acid, lactams or binary acid/diamine monomer gross weight.
9. chain fatty polyamide process for preparing resins according to claim 8, it is characterised in that：D in the formula IV, E, f takes values below：During d+f=3.6, e=9.0；During d+f=6.0, e=12.5；R₇、R₈And R₉It is at the same time methyl.
10. chain fatty polyamide process for preparing resins according to claim 8, it is characterised in that：Also added as Compound shown in Formula V

U—(R₁₀—O)_n—R₁₁Formula V；

In above-mentioned Formula V n be 2~100 integer, R₁₀The alkylidene for being 2~10 for carbon number, R₁₁It is 1~30 for carbon number Alkyl, U NH₂-, HO-, HO-C (=O)-, O=C=N-R₁₂- NH-C (=O)-O-, O=C=N-R₁₃- NH-C (=O)-NH- orHere R₁₂Or R₁₃It is 1~20 for each identical or different carbon number Alkylidene.
11. chain fatty polyamide process for preparing resins according to claim 8, it is characterised in that：Also added as Compound shown in Formula IV

W-R₁₄Formula IV；

R in above-mentioned Formula IV₁₄The alkyl or aryl for being 1~30 for carbon number substitutes alkyl, aryl or alkyl substituting aromatic base, W- For NH₂-, HO-, HO-C (=O)-, O=C=N-R₁₅- NH-C (=O)-O-, O=C=N-R₁₆- NH-C (= O)-NH- orHere R₁₅Or R₁₆The alkylidene for being 1~20 for each identical or different carbon number.