CN104059224B - A kind of polyamide and preparation method thereof and Amilan polyamide resin composition - Google Patents

Abstract

The present invention provides a kind of polyamide containing diamine unit and two acid units and preparation method thereof, the relative viscosity that the 0.01g/ml concentration concentrated sulfuric acid solution of the polyamide is tested at 25 DEG C is 1.80 6.00, the ionic liquid that the weight containing relative to polyamide is 100 20000ppm.Its fusing point is more than 250 DEG C and is detained the characteristics such as stability with good melting, and can be shaped to can be used for the synthetic resins such as automobile component, mechanical part, fiber or film etc. by the arbitrary forming method such as injection moulding.

Description

A kind of polyamide and preparation method thereof and Amilan polyamide resin composition

Technical field

The invention belongs to polymeric material field, and in particular to a kind of containing ionic liquid and with good melting It is detained the highly viscous polyamide of stability.

Background technology

It is easy due to its excellent characteristic and melt-shaping with the crystallinity polyamide for representative such as nylon 6, nylon66 fiber Property, it is widely used as dress material use, industry goods, materials and equipments fiber or general engineering plastics.In addition, in electrical and electronic parts field In, with surface mounting technology（SMT）Development, needed for the polyamide in the technical field with good melting delay Stability, including reflow soldering heat resistance.In this case, it is still necessary to which exploitation has the high-quality polyamides of good heat resistance Amine.It is detained stability when the polymerization or processing of polyamide in order to improve molten polyamide, phosphorus species are used as catalyst or resistance to The means that thermit powder is added in polymer have been known general methods.

In addition, the oxalic acid system polyamide being disclosed water absorption rate compared with other polyamides of identical amide groups concentration It is low, expect that physical property change turns into caused by due to water suction and lived in problem and the unworkable field of current polyamide With.The open report of current oxalic acid system polyamide is a lot, such as in bibliography S.W.Shalaby., J.Polym.Sci., 11, In 1 (1973), 1,6- hexamethylene diamine is used as the oxalic acid system polyamide 62 of diamine unit, its fusing point（About 320 DEG C）Higher, melt-processed When obvious decomposition occurs.For polyoxamide disclosed in space portion（WO2011/136263）PA62/2-M52 resins, wherein having The relative viscosity for having the polyoxamide resin of 280 DEG C of melt point above is not all improved（Relative viscosity is less than 2.05）, and Obvious decline occurs in the viscosity of polymer during melt-processed.For polyoxamide disclosed in space portion（JP2011236387） PA52 resins, although viscosity is improved, but its poor melting is detained during stability will cause melt-processed Declining by a relatively large margin occurs in the viscosity of polyoxamide resin.So having with the oxalic acid system polyamide that stability is detained in good melting Treat further exploitation.

Ionic liquid has been subjected to extensive concern as the solvent of environment-friendly type, and it has good designability --- and can To be combined by the species for adjusting zwitterion, usual no color or smell, steam is forced down, not volatile, eliminates organic matter Problem of environmental pollution caused by matter volatilization, is referred to as " green can design solvent ".Ionic liquid is applied to polyamide Research carried out extensively, main application is as solvent for polymerization or depolymerizes and use solvent.Such as bibliography ISRN Polymer ScienceVolume2012.page7《Ionic Liquid-Catalyzed Preparation of AromaticPolyamides Containing PhthalazinoneMoiety》Mentioned ionic liquid in one text as molten Agent polymerize all aromatic nylon.Disclosed in patent WO2011004138A1 using ionic liquid as solvent and prepare nylon66 fiber Method, and the fusing point of gained nylon66 fiber is below known nylon66 fiber fusing point.Bibliography Organic Letters, 2007, Vol.9, No.13, page2533-2535's《AnEfficient Method To Depolymerize Polyamide Plastics:A New Use of IonicLiquids》Mentioned in one text with ionic liquid being depolymerized to nylon 6 as solvent The example of caprolactam monomer.In addition, ionic liquid is added in polymer as softening agent.For example, Degussa exists Patent CN1681878《The polymer composition formed by polymer and ionic liquid》In disclose a kind of combination of polymers Thing, it contains at least one at least part crystallization and the polymer without ionic group and at least one chemical combination with softening properties Thing and the ionic liquid for wherein containing the 0.1 weight % to 30 weight % as softening agent.So far, using ionic liquid as Catalyst preparation high polymerization degree was simultaneously reported with not the disclosing also for polyamide that stability is detained in good melting.

The content of the invention

We experimentally found that, high polymerization degree can be prepared by catalyst of ionic liquid and with good melting It is detained the polyamide of stability.The degree of polymerization of gained polyamide is improved in the present invention using ionic liquid as catalyst, and And gained polyamide has good delay stability.

The present invention provides a kind of polyamide containing diamine unit and two acid units, the 0.01g/ of the polyamide The relative viscosity that ml concentration concentrated sulfuric acid solution is tested at 25 DEG C is 1.80-6.00, the weight containing relative to polyamide For 100-20000ppm ionic liquid.

Two above-mentioned acid units are not particularly limited.The starting monomer that two acid units can be enumerated is preferably oxalic acid, the third two Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, 1,11- undecyls diacid, 1,12- ten Dialkyl group diacid, 1,13- tridecyls diacid, 1,14- myristyls diacid, 1,15- pentadecyls diacid, 1,16- hexadecanes The aliphatic diacids such as base diacid, 1,18- octadecyls diacid or 1,19- nonadecyl diacid or its corresponding various esters The ring-type diacid such as compound or Isosorbide-5-Nitrae -/1,3- cyclohexane diacids or its corresponding various ester type compounds or terephthalic acid (TPA) or One or more in the aromatic diacids such as phthalic acid or its corresponding various ester type compound.Two above-mentioned acid units contain Oxalic acid unit, its content is preferably 50~100 moles of % relative to the total amount of two acid units.It is used as the raw material list of oxalic acid unit Body is not particularly limited, and can be enumerated as the one or more in oxalate diester, oxalic acid, oxalic acid acyl chlorides or oxalic acid acyl chlorides ester etc.. Preferably oxalate diester.The present invention is not particularly limited for oxalate diester.The oxalate diester that can enumerate further preferably in Dimethyl oxalate, diethy-aceto oxalate, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or grass One or more in sour di tert butyl carbonate.

The starting monomer of above-mentioned diamine unit be preferably 1,3- propane diamine, Putriscine, 1,5- pentanediamines, 1,6- oneself Diamines, 1,7- heptamethylene diamines, 1,8- octamethylenediamines, 1,9- nonamethylene diamines, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecanes Diamines, 1,13- tridecane diamines, 1,14- tetradecanes diamines, 1,15- pentadecanes diamines, 1,16- hexadecanes diamines, 1,17- ten Seven alkane diamines, 1,18- octadecamethylene diamines, 2- methyl isophthalic acids, 5- pentanediamines, 2- methyl isophthalic acids, 8- octamethylenediamines, cyclohexane diamine or benzene two One or more in methylamine.When the carbon number of diamine unit is less than 3, it is possible to which the viscosity for polyamide occur is difficult Raising and the too high unmanageable tendency of fusing point of polyamide；When the carbon number of diamine unit is higher than 10, having can The relatively low tendency for causing heat resistance to reduce of fusing point of polyamide can occur.From the aspect of the crystallinity of polyamide, It is preferred that the diamine unit of straight chain.In addition, from polyamide it is dystectic from the aspect of, the starting monomer of diamine unit enters one Walk one or more in preferred Putriscine, 1,5- pentanediamines or 1,6- hexamethylene diamine, raw material list of its content relative to diamines Body total amount is preferably 10~100 moles of %, more preferably 50~100 moles %, is still more preferably 80~100 moles of %, More it is more preferably 90~100 moles of %.The starting monomer of diamine unit is most preferably 1,5- pentanediamines.

The possibility of heat resistance and melt-processed in view of polyamide, the amide groups of polyamide of the invention Content（Relative to amide groups molal quantity in 1g polyamide）Preferably 7.5mmol/g~14.5mmol/g, more preferably 10.5mmol/g~14.0mmol/g.If amide groups content is less than 7.5mmol/g, the fusing point of polyamide is too low may cause it is resistance to Hot to decline, if amide groups content is higher than 14.5mmol/g, the fusing point of polyamide is too high may to be led to not melt to add Work.

The relative viscosity η r of the polyamide obtained by the present invention are that, using 96% concentrated sulfuric acid solution as solvent, concentration is 0.01g/ml polyamide sulfuric acid solution, is determined in the range of 1.80~6.00 at 25 DEG C, more preferably 2.10~5.00.Still more preferably it is 2.40~4.00.When η r are less than 1.80, formed products may become fragile, and there is impact strength Too low tendency may.On the other hand, when η r are higher than 6.00, melt viscosity may be uprised, and shaping processability is deteriorated.

Above-mentioned ionic liquid is not particularly limited, and ionic liquid can be selected from N, the alkyl-substituted imidazoles of N ', N, N ' One or more in the salt of alkyl-substituted pyridine, quaternary ammonium alkyl or Wan Ji quaternary phosphines.The substitution alkyl of the ionic liquid is Carbon number is preferably 1-20 aliphatic or aromatic direct-connected or side chain alkyl.Can enumerate as：Chlorination 1,3- Methylimidazole, 1,3- methylimidazoles Dimethyl phosphate, 1- ethyl -3- methylimidazolium chlorides, 1- ethyl -3- methyl Limidazolium, 1- ethyl -3- methylpyridinium iodides imidazoles, 1- ethyl-3-methylimidazoles methane sulfonates, 1- ethyl -3- first Base imidazolium trifluoromethane sulfonate, 1- ethyl-3-methylimidazoles disulfate, 1- ethyl-3-methylimidazole ethylsulfonic acids Salt, 1- ethyl-3-methylimidazole dicyan amine salt, 1- ethyl-3-methylimidazoles tetrafluoroborate, 1- ethyl-3-methylimidazoles Hexafluorophosphate, 1- ethyl-3-methylimidazole tetrachloros ferrate, 1- methyl -3- propyl group iodate imidazoles, 1- butyl -3- Methylimidazolium chloride, 1- butyl -3- methy limidazoliums, 1- butyl -3- methylpyridinium iodides imidazoles, 1- butyl -3- methyl Imidazolium trifluoromethane sulfonate, 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- butyl -3- methyl hexafluorophosphates imidazoles, 1- butyl -3- methylimidazole tetrachloros ferrate, 1- hexyl -3- methylimidazolium chlorides, 1- hexyl -3- methylimidazole bromines Compound, 1- hexyl -3- methyl imidazolium tetrafluoroborates, 1- methyl -3- n-octyls imidazolium bromide, 1- butyl -2,3- two Methylimidazolium chloride, 1- ethyl pyridinium chlorides, 1- ethyl pyridinium bromides, 1- butyl pyridinium chloride, 1- butyl bromination pyrroles Pyridine, 1- butyl-pyridiniums hexafluorophosphate, 1- butyl -3- picolines bromide, 1- ethyl -3- picolines esilate, 1- butyl -4- picolines bromide, 1- butyl -4- picolines hexafluorophosphate, tetrabutylammonium chloride, TBAB, The just pungent ammonium of methyl three closes the double (trifluoros of double (fluoroform sulphonyl) imines, Si butyl phosphonium bromide, tributyl (2- methoxy ethyls) phosphorus Sulfonyloxy methyl) imines or double (trimethyl fluoride sulfonyl) imines of triethyl group sulfonium it is one or more.More preferably chlorination 1,3- bis- Methylimidazole, 1- ethyl -3- methylimidazolium chlorides, 1- ethyl -3- methy limidazoliums, 1- ethyl -3- methylpyridinium iodide miaows Azoles, 1- butyl -3- methylimidazolium chlorides, 1- butyl -3- methy limidazoliums, 1- butyl -3- methylpyridinium iodides imidazoles, 1- hexyl -3- methylimidazolium chlorides, 1- hexyl -3- methyl imidazolium bromides, 1- methyl -3- n-octyl imidazoles brominations Thing, 1- butyl -2,3- dimethylammonium chlorides imidazoles, 1- ethyl pyridinium chlorides, 1- ethyl pyridinium bromides, 1- butyl chlorination pyrroles One kind or many in pyridine, 1- butyl pyridinium bromide, 1- butyl -3- picolines bromide or 1- butyl -4- picoline bromides Kind.

Thermal oxidative degradation can all occur in high temperature working processes or in hot environment use for polyamide, and its reason is such as 《polymer degradation and stability》(vol.49,1995) described in page 127~133：With in amide groups Electron detachment formation free radical easily occurs for the adjacent methylene of nitrogen, because this free radical can be with the lone pair electrons on imido grpup Stable resonant structure is formed with the pi bond of carbonyl.The amide groups contained in the Component units of the polyamide of the present invention also holds Easily occurs similar thermal oxidative degradation.For example, the nitrogen easily occurred for polyamides such as polyamide 66s in amide groups is adjacent Methylene electron detachment, produce thermal oxidative degradation；For containing oxalyl amine unit, grass in the Component units of polyamide Adjacent two pairs of amide groups on amide units can form more stable resonant structure than general single amide groups, be more prone to Occur the electron detachment of the adjacent methylene of nitrogen in amide groups, produce thermal oxidative degradation.Can present invention finds ionic liquid Effectively to suppress the thermal oxidative degradation of polyamide, especially to dystectic polyamide（Polyamides of the fusing point more than 280 DEG C Polyimide resin）The effect of thermal oxidative degradation is bigger.

The content of above-mentioned polyamide intermediate ion liquid is 100~20000ppm relative to polyamide weight, excellent Select 100~18000ppm, more more preferably more preferably 100~15000ppm, 100~10000ppm.If The content of ionic liquid is less than 100ppm, the viscosity of polymer may be difficult improve and its melting be detained stability may be compared with Difference, causes it not process：If the content of ionic liquid, which is higher than in 20000ppm, polymer, may easily produce jello Body, jello can not melt-processed, will remain in products formed into stress concentration point, products formed will be caused in practical application Easily occurs the possibility of stress fracture.

Using TA DSC-Q100 analytical instrument, about 5mg samples are accurately weighed, in a nitrogen atmosphere, by above-mentioned polyamide The temperature (T0) that resin is warming up to the endothermic peak than occurring with 20 DEG C/min of programming rates is higher by 30 DEG C of temperature, warm herein Degree is lower to be kept for 2 minutes, is then dropped to 30 DEG C with 20 DEG C/min of cooling rate, is kept for 2 minutes at 30 DEG C.Next, with 20 DEG C/min programming rate to be warming up to the temperature Tm of the endothermic peak observed when being higher by 30 DEG C than T0 be above-mentioned polyamide Fusing point, its fusing point is preferably more than 250 DEG C, further preferred more than 255 DEG C, more further preferred more than 265 DEG C, final excellent Select more than 275 DEG C.If fusing point is less than 250 DEG C, fusing point is too low to cause heat resistance to decline.

Stability is detained in the melting of the polyamide obtained by the present invention：At a temperature of than fusing point high 20 DEG C Sulfuric acid solution relative viscosity when being detained 30 minutes is set to Y, and when the sulfuric acid solution relative viscosity before delay is set to X, Y/X is preferably 0.75~1.40.Further preferred 0.80~1.30, still more preferably 0.85~1.20.If Y/X is less than 0.75, in melting Resin in process may have obvious decomposition, have a strong impact on its mechanical performance.If Y/X is higher than 1.40, add in melting Resin during work may have obvious viscosity increase, it will increase machine-shaping difficulty.

The present invention also provides the preparation method of above-mentioned polyamide, and it comprises the following steps：

Diamine source and dicarboxylic acids source are carried out step (a) into solution or melt polymerization obtains low molecular weight prepolymer；

Step (b)：The low molecular weight prepolymer obtained to step (a) carries out melt polymerization or solid phase obtains polyamide Resin；

Wherein：In step（a）Or in step（b）The ionic liquid of middle addition is used as catalyst.

In the preparation method of the present invention, the content for diamine source is identical with the content of above diamine unit.For The content in dicarboxylic acids source is identical with the content of above two acid units.

Lower noodle producing method can be enumerated in the range of the preparation method of above-mentioned polyamide：

It is prepared by prepolymer（Oxalic acid system polyamide）：

The starting monomer of polyamide is the starting monomer of above-mentioned diamine unit and the starting monomer of two acid units（Two Acid unit is formed comprising 50%~100% oxalic acid unit）.Organic solvent first is added in the typically reactor with condenser pipe, Then add the starting monomer of diamine unit, and enter line replacement with nitrogen, then add again the starting monomers of two acid units by its Blending.Then start agitating and heating be warming up to solvent refluxing temperature carry out reaction 3~5 hours, then filtered and use first Alcohol or ethanol carry out 3~5 times and cleaned, and obtained prepolymer is dried.As organic solvent, it is not particularly limited, can be with Can be preferably toluene using toluene, dimethylbenzene, trichloro-benzenes, phenol or trifluoroethanol etc..

Prepolymer is prepared (non-oxalic acid system polyamide)：

The starting monomer of polyamide is the starting monomer of above-mentioned diamine unit and the starting monomer of two acid units. Starting monomer, the starting monomer and water of two acid units of diamine unit are added in reaction tube.Then test tube is put into high pressure again In kettle, it is warming up to after pressure reaches to a certain degree in certain temperature and kettle, maintains to react 2-5 hour at this pressure, so After cool down.Prepolymer is taken out to be dried.

The melt polymerization of prepolymer：

Prepolymer and above-mentioned ionic liquid（The addition weight ratio of ionic liquid is relative to polyamide weight 100~20000ppm）It is sufficiently mixed, is then added in reactor, and enter line replacement with inert gas by required proportioning.This is anti- Answer device to be placed into heater, then begin to warm up the fusing point temperatures above for being warming up to prepolymer, carry out decompression polymerase 10 .5~5 Hour, final pressure is 5000~20Pa, or progress polymerization under atmospheric pressure 0.5~5 hour under inert gas flow.

The solid phase of prepolymer：

Prepolymer and above-mentioned ionic liquid（The addition weight ratio of ionic liquid is relative to polyamide weight 100~20000ppm）It is sufficiently mixed, is then added in reactor, and enter line replacement with inert gas by required proportioning.Then The depressurized solid phase carried out below its fusing point 0.5~30 hour polymerize, and final pressure is 300~20Pa, or in indifferent gas The normal pressure solid phase of progress 0.5~30 hour under body air-flow.

In the heating polycondensation of above-mentioned polyamide, due to carrying out polymerisation at high temperature, thus based on short carbon chain Straight-chain aliphatic diamines volatilized out of polymerization system or by the deamination reaction reason such as make lower boiling product volatilize, with The progress of polymerization, total amino amount is relative to total carboxylic acid's base or oxalic acid ester group in polymerization system（Oxalic acid system polyamide）Content may It can reduce, therefore, add the stage of raw material, excessively the straight-chain aliphatic diamines of the short carbon chain of addition specified quantitative is controlled in advance Amino amount in polymerization system processed, is preferred for synthesizing the polyamide of HMW.When will make as raw material The molal quantity of the starting monomer of short carbon chain straight-chain aliphatic diamine unit is set to a, by rubbing for the starting monomer of two acid units When your number is set to b, preferably by raw material ratio of components be adjusted to a/b for 1.003~1.10, a/b be more preferably 1.008~ 1.08, it is still more preferably 1.01~1.05.If a/b is less than total amino amount and total carboxylic in 1.003, polymeric system Acidic group or oxalic acid ester group（Oxalic acid system polyamide）Amount it is relatively few, it is difficult to obtain the polymer of HMW.If a/b is more than 1.10, then total amino amount and total total carboxylic acid's base or oxalic acid ester group in polymerization system（Oxalic acid system polyamide）Amount it is relatively excessive, it is difficult To obtain the polymer of HMW.

In the preparation method of the present invention, the ionic liquid is selected from N, the alkyl-substituted imidazoles of N ', N, the substitution of N ' alkyl Pyridine, the one or more in the salt of quaternary ammonium alkyl or Wan Ji quaternary phosphines.Particular content is identical with the description of ionic liquid above.

Various packing materials can also be added as needed in the polyamide of the present invention, thus, the present invention is also provided A kind of Amilan polyamide resin composition, coordinates 0.1~200 weight portion filling material relative to the above-mentioned weight portion of polyamide 100 The Amilan polyamide resin composition of material.Specific packing material is as follows.

Inorganic filling material is such as：Graphite, barium sulfate, calcium carbonate, antimony oxide, titanium oxide, aluminum oxide, nickel, aluminium, iron, steel, cunning Stone, bentonite, montmorillonite, mica titanium dioxide, silica, alundum (Al2O3) or silicate etc..For some laminar silicic acids Salt, can carry out interlayer ion the silicate that organises after cation exchange using organic ammonium salt.For polyamide Appearance is excellent, and the average grain diameter of inorganic filler is preferably 0.001~10 μm.If average grain diameter is less than 0.001 μm, The melt processable of gained Amilan polyamide resin composition can be significantly reduced, if in addition, particle diameter is more than 10 μm, surface of the molded article Outward appearance has the tendency of variation.Its addition is preferably 0.1~200 weight portion relative to the weight portion of polyamide 100.

The fibrous filler material of organic system and the fibrous filler material of inorganic system.Material is filled as the fiber of organic system Material can enumerate the fully aromatic polyamide fibers such as aromatic polyamide fibers, cellulose fibre etc..Filled out as the threadiness of inorganic system Glass fibre, carbon fiber or boron fibre etc. can be included by filling material.In addition, also metallic fiber, aluminium borate, gypsum, carbonic acid Calcium, sepiolite, it is hard return it is one or more in the inorganic compound such as calcium stone or your lime stone whisker or acicular crystal etc..Furthermore, it is possible to Using 5~50mm of length long fibre, the chopped fiber that length is 0.05~5mm can also be used, its addition is preferably relative In 0.1~200 parts by weight of the parts by weight of polyamide 100.

The polyamide of the present invention can also be added as needed on various additives, such as weather resisting agent, the demoulding in preparing One or more in agent or lubricant, pigment, dyestuff, plasticizer, antistatic additive, fire retardant or other polymers.Specifically, Weather resisting agent is resorcinol system, salicylate system, enumerate BTA system, benzophenone series or amine system of being obstructed etc.；Releasing agent or lubrication Agent is aliphatic alcohol, aliphatic amide, aliphatic bisamide, allophanamide or Tissuemat E etc.；Pigment is cadmium sulfide, phthalocyanine or carbon black Deng；Dyestuff is nigrosine or nigrosine etc.；Plasticizer is P-hydroxybenzoic acid monooctyl ester or N-butylbenzenesulfonamide etc.；It is anti-quiet Electric agent is alkyl sulphate type anion system antistatic additive, quaternary ammonium salt cationic system antistatic additive, polyoxyethylene sorbitan Nonionic system antistatic additive as sugar alcohol monostearate or glycine betaine system both sexes antistatic additive etc.；Fire retardant is melamine The hydroxide such as amine, magnesium hydroxide or aluminium hydroxide, ammonium polyphosphate, bromo polyethylene, bromo polyphenylene sulfide, the poly- carbonic acid of bromo Composition of ester, brominated epoxy resin or bromo-derivative fire retardant and antimony oxide etc.；Other polymers are polyamide, poly- second Alkene, polypropylene, polyester, makrolon, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, ABS resin, SAN resins or polystyrene Deng.

In addition, the impact property in order to improve polyamide, the present invention also provides a kind of Amilan polyamide resin composition, phase Coordinate the polyamide group of the packing material of 5~100 weight portion impact resistances for the above-mentioned weight portion of polyamide 100 Compound.For example：In alkenes compounds and conjugated diolefin it is one or more and Lai equal (common) polymers.

Above-mentioned equal (common) polymers can be enumerated as ethene copolymer, conjugated diolefin homopolymer and conjugated diene The copolymer of hydrocarbon/aromatic ethylene compound.Ethene copolymer is two membered copolymers or polynary of ethene and other cell cubes Copolymerization.Other cell cubes can be enumerated as the alpha-olefin of carbon more than 3, non-conjugated diene hydrocarbon, vinyl acetate, vinyl alcohol, α, Beta-unsaturated carboxylic acid and its inductor.Its addition is preferably 5~200 weight portions relative to the weight portion of polyamide 100. If addition is more than more than 5 parts by weight, the impact to polyamide improves significantly；If addition is less than 200 Amount part is planted, is conducive to the forming of polyamide.

The polyamide of the present invention can be spun by injection moulding, extrusion molding, blow molding, vacuum forming, melting The arbitrary forming method such as silk or film shaping can be used for the resins such as automobile component, mechanical part come the shape needed for being shaped to Products formed, fiber or film etc..Specific purposes：The top of automobile engine cooling water based part, particularly radiator tank and Pump parts such as the radiator water box part such as bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc., and vapour The part contacted in car engine with cooling water.Electrical and electronic parts be small-sized switch, switch shell, lamp socket, connector, Housing, connector shell, IC sockets class, bobbin, bobbin cover, relay, electrical relaybox, capacitor protector, the motor of connector Internal part, small size motor shell, gear cam, the equilibrium theory, pad, insulator, fastener, buckle, wire clamp, Caster, peace Full cap, electronic table starter insulating element, fuse box, the shell of terminal, wheel cover, suction tracheae, bearing retainer, electric wire optical cable Clad or fibre optics cable oversheath etc. are the electrical and electronic parts, automobile associated components, computer dependent part of representative Part, mechanical associated components or other various uses.

Embodiment

The present invention is illustrated by the following examples, but the present invention is not by any restriction of these embodiments.Implement Various characteristics in example and comparative example, are determined by the following procedure.

(1) relative sulfuric acid viscosity：

Using 96% sulfuric acid as solvent, compound concentration is 0.01g/ml polyamide resin lipoprotein solution, determines and glues relatively at 25 DEG C Degree

（2）Stability is detained in melting

In a nitrogen atmosphere, the sample after more than fusing point being kept for 30 minutes at a temperature of 20 DEG C is heated to 0.01g/ml's Concentration, which is dissolved in 96% sulfuric acid, tests its relative viscosity（Y）, the relative sulfuric acid viscosity before delay is set to（X）, obtain sulfuric acid phase To the conservation rate of viscosity（Y/X）.

（3）Thermal property：

Using TA DSC-Q100 analytical instrument, about 5mg samples are accurately weighed, test condition is as follows：In a nitrogen atmosphere, The temperature (T0) that gained polyamide is warming up into the endothermic peak than occurring with 20 DEG C/min of programming rates is higher by 30 DEG C Temperature, is kept for 2 minutes, then drops to 30 DEG C with 20 DEG C/min of cooling rate at this temperature, is kept for 2 minutes at 30 DEG C. Next, the temperature Tm of the endothermic peak observed when being warming up to 20 DEG C/min of programming rate and be higher by 30 DEG C than T0.

Abbreviation explanation：

1,5- pentanediamine：Purity is 98%, purchased from TCI companies.

1,6- hexamethylene diamine：Purity is 98%, purchased from TCI companies.

Dibutyl oxalate：Analysis is pure, purchased from Sigma-Aldrich companies.

1,6- adipic acid:Analysis is pure, purchased from Aladdin company.

1- ethyl -3- methylpyridinium iodide imidazoles：Analysis is pure, purchased from TCI companies.

1- ethyl -3- methy limidazoliums：Analysis is pure, purchased from TCI companies.

1- butyl -3- methylimidazolium chlorides：Analysis is pure, purchased from TCI companies.

Embodiment 1

500ml toluene, then the 32.033g (0.3135mol) 1,5- into toluene solvant are added in 1000ml three-neck flasks Start stirring after pentanediamine, nitrogen purging, and add 60.675g into this system again（0.3000mol）Dibutyl oxalate.Then 130 DEG C are warming up to, back flow reaction 5 hours are continued with the condition, filtering washs, is dried to obtain the pre-polymerization that relative viscosity is 1.27 Thing.

Gained 2.000g prepolymers and 0.952mg1- ethyl -3- methylpyridinium iodide imidazoles are sufficiently mixed, are then fed to In a diameter of 19mm teat glass, then carried out replacing 5 times repeatedly with nitrogen, 325 DEG C are then placed under nitrogen flowing In metal bath, below 100Pa was decompressed to 20 minutes, then it is reacted 40 minutes.Polymer property is in table 1.

Comparative example 1

Embodiment 1 is repeated, the difference is that without addition 1- ethyl -3- methylpyridinium iodide imidazoles.Polymer property is in table 1 In.

Comparative example 2

The preparation of prepolymer is same as prepolymer in embodiment 1 and prepared, and 2.000g prepolymer is added to a diameter of In 19mm teat glass, and enter line replacement with nitrogen.Then the depressurized solid phase carried out below 280 DEG C 5 hours polymerize, finally Pressure be 60Pa.Polymer property is in table 1.

Embodiment 2

PA66 prepares 1

5.984g (0.0515mol) 1,6- hexamethylene diamines, 7.307g are added in a diameter of 19mm teat glass (0.050mol) 1,6- adipic acids and 13.291g deionized waters.Then this test tube is placed into autoclave, purged with nitrogen, Then start to warm up, pressure starts rise.Pressure rises to 1.78MPa when temperature rises to 220 DEG C, and 1.78MPa pressure is maintained not Become, continue to stop reaction after reacting 2 hours, temperature now is 241 DEG C.The prepolymer in autoclave is taken out after cooling.Dry Obtain the prepolymer that relative viscosity is 1.20.

Gained 2.000g prepolymers and 0.952mg1- ethyl -3- methylpyridinium iodide imidazoles are sufficiently mixed, are then fed to In a diameter of 19mm teat glass, then carried out replacing 5 times repeatedly with nitrogen, 282 DEG C are then placed under nitrogen flowing In metal bath, below 100Pa was decompressed to 20 minutes, then it is reacted 40 points.Polymer property is in table 1.

Comparative example 3

Embodiment 2 is repeated, the difference is that without addition 1- ethyl -3- methylpyridinium iodide imidazoles.Polymer property is in table 1 In.

Embodiment 3

Embodiment 1 is repeated, the difference is that the amount of addition 1- ethyl -3- methylpyridinium iodide imidazoles is 0.48mg, polymer is special Property is in table 2.

Embodiment 4

Embodiment 1 is repeated, the difference is that the amount of addition 1- ethyl -3- methy limidazoliums is 38.21mg, polymer is special Property is in table 2.

Comparative example 4

Embodiment 1 is repeated, the difference is that the amount of 1- ethyl -3- methylpyridinium iodide imidazoles is 45.20mg, polymer property exists In table 2.

Comparative example 5

Embodiment 1 is repeated, the difference is that the amount of 1- ethyl -3- methylpyridinium iodide imidazoles is 0.24mg, polymer property exists In table 2.

Comparative example 6

PA66 prepares 2

40.000g1- butyl -3- methylimidazolium chlorides and 16.170g nylon salts are added in three-necked flask, and is led to Nitrogen gas stirring 15 minutes.180 DEG C are warming up to, and is reacted 6 hours under nitrogen flowing, then 10KPa is decompressed in 20 minutes and enters Row water removal, and maintain 1 hour under stress.Then resulting polymers are cooled to room temperature and add the backflow of 400ML water, then taken out Filter.Reusable heat water is dried under vacuum after cleaning.Polymer property is in table 3.

Comparative example 7

The polymer that embodiment 1 is made is repeated, then its polymer flows back 5 hours in boiling water and removes ionic liquid, removes The characteristic of the polymer of ionic liquid is in table 3.

Table 1

In table 1, for PA52, for PA66, polymer after addition 1- ethyl -3- methylpyridinium iodide imidazoles glues relatively Degree is much improved.In addition, comparing from embodiment 1 and comparative example 2 it can be seen that 1- ethyl -3- methylpyridinium iodide imidazoles pair Stability is detained in PA52 melting has special effect.

Table 2

In table 2, for the polymer after addition 1- ethyl -3- methylpyridinium iodide imidazoles is excessive or very few, 1- second is added The excessive polymer gel of base -3- methylpyridinium iodides imidazoles is not suitable for machine-shaping, adds 1- ethyl -3- methylpyridinium iodide imidazoles Very few Polymer relative viscosity is too low.

Table 3

In table 3, use obtained nylon66 fiber fusing point, viscosity all very low as solvent ionic liquid, and will be original After the intermediate ion liquid of nylon 52 is removed, stability is detained in the melting of polymer substantially to be reduced.

Claims (11)

1. a kind of polyamide containing diamine unit and two acid units, it is characterised in that：The 50~100 of two acid unit Mole % is oxalic acid unit, and the relative viscosity that the 0.01g/ml concentration concentrated sulfuric acid solution of the polyamide is tested at 25 DEG C is 1.80-6.00, the ionic liquid that the weight containing relative to polyamide is 100-20000ppm.

2. polyamide according to claim 1, it is characterised in that：The fusing point of the polyamide be 250 DEG C with On.

3. polyamide according to claim 1, it is characterised in that：Ionic liquid is selected from N, the alkyl-substituted miaows of N ' One or more in azoles, N, the salt of the alkyl-substituted pyridines of N ', quaternary ammonium alkyl or Wan Ji quaternary phosphines.

4. polyamide according to claim 1, it is characterised in that：10~100 moles of % of diamine unit are 1,5- Pentanediamine unit.

5. polyamide according to claim 1, it is characterised in that：The polyamide is at 20 DEG C higher than fusing point At a temperature of be detained 30 minutes when sulfuric acid solution relative viscosity be set to Y, when the sulfuric acid solution relative viscosity before delay is set to X, Y/X For 0.75~1.40.

6. a kind of method for preparing the polyamide any one of claim 1-5, it is characterised in that：Including following step Suddenly：

Step (a)：Diamine source and dicarboxylic acids source are subjected to solution or melt polymerization obtains low molecular weight prepolymer；

Step (b)：The low molecular weight prepolymer obtained to step (a) carries out melt polymerization or solid phase obtains polyamide resin Fat；

Wherein：In step (a) or in step (b), the ionic liquid of addition is used as catalyst.

7. preparation method according to claim 6, it is characterised in that：Ionic liquid is selected from N, the alkyl-substituted miaows of N ' One or more in azoles, N, the salt of the alkyl-substituted pyridines of N ', quaternary ammonium alkyl or Wan Ji quaternary phosphines.

8. preparation method according to claim 6, it is characterised in that：50~100 moles of % in the dicarboxylic acids source are Oxalic acid source.

9. preparation method according to claim 6, it is characterised in that：10~100 moles of % in the diamine source are 1, 5- pentanediamines source.

10. Amilan polyamide resin composition, it is characterised in that：Relative to polyamide according to any one of claims 1 to 5 100 weight portions coordinate the Amilan polyamide resin composition of 0.1~200 weight portion packing material.

11. Amilan polyamide resin composition, it is characterised in that：Relative to polyamide according to any one of claims 1 to 5 100 weight portions coordinate the Amilan polyamide resin composition of the packing material of 5~100 weight portion impact resistances.