CN104059224A - Polyamide resin, preparation method thereof and polyamide resin composition - Google Patents
Polyamide resin, preparation method thereof and polyamide resin composition Download PDFInfo
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- CN104059224A CN104059224A CN201310091525.6A CN201310091525A CN104059224A CN 104059224 A CN104059224 A CN 104059224A CN 201310091525 A CN201310091525 A CN 201310091525A CN 104059224 A CN104059224 A CN 104059224A
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Abstract
The invention provides polyamide resin containing a diamine unit and a diacid unit as well as a preparation method. The relative viscosity of a concentrated sulfuric acid solution with concentration of 0.01g/ml of polyamide resin is 1.80-6.00 at 25 DEG C, and contains ionic liquid with relative weight accounting 100-20000ppm for that of polyamide resin. The melting point of polyamide resin is more than 250 DEG C and has good fusion delay stability and the like, and the polyamide resin can be formed to resin moulding product, fiber or membrane used for automobile parts and mechanical parts through any moulding methods such as injection moulding.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of full-bodied polyamide resin that contains ionic liquid and there is good melting delay stability.
Background technology
Crystallinity polymeric amide taking nylon 6, nylon 66 etc. as representative, due to the easiness of its excellent characteristic and melt-shaping, 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, follow the development of surface mounting technology (SMT), need to there is good melting for the polymeric amide of this technical field and be detained stability, comprising reflow soldering thermotolerance.In this case, still need exploitation to there is good heat resistance high quality polymeric amide.The polymerization of polymeric amide or add and be detained stability in order to improve molten polyamide man-hour, the means that Phosphorus compound is added in polymkeric substance as catalyzer or heat-resistant agent have been known general methods.
In addition, the oxalic acid being disclosed is polymeric amide and to compare water-intake rate low for other polyamide resin of identical amide group concentration, expects to change and become problem and in the unworkable field of polymeric amide, apply flexibly at present in the physical property causing due to water suction.The open report that current oxalic acid is polymeric amide is a lot, for example, at reference S.W.Shalaby., J.Polym.Sci., 11, in 1 (1973), 1,6-hexanediamine is polyamide 62 as the oxalic acid of two amine units, and its fusing point (approximately 320 DEG C) is higher, there will be obvious decomposition when melt-processed.For the disclosed polyoxamide of space portion (WO2011/136263) PA62/2-M52 resin, the relative viscosity wherein with the polyoxamide resin of more than 280 DEG C fusing point is not all improved (relative viscosity is lower than 2.05), and the viscosity of polymkeric substance there will be obvious decline when melt-processed.For the disclosed polyoxamide of space portion (JP2011236387) PA52 resin, although viscosity is improved, its poor melting is detained stability and will be caused the viscosity of polyoxamide resin in melt-processed process to occur declining by a relatively large margin.Be that polymeric amide needs further to be developed so there is the oxalic acid of good melting delay stability.
Ionic liquid has been subjected to widely and has paid close attention to as the solvent of environment-friendly type, it has good designability---can combine by the kind that regulates zwitterion, conventionally no color or smell, steam forces down, not volatile, the problem of environmental pollution of having eliminated organic substance volatilization and cause, is referred to as " green can design solvent ".Ionic liquid is applied to the research of polyamide resin extensively to be carried out, and main application is as polymerization solvent or depolymerizes and use solvent.For example, in reference ISRN Polymer ScienceVolume2012.page7 " Ionic Liquid-Catalyzed Preparation of AromaticPolyamides Containing PhthalazinoneMoiety " literary composition, mention using ionic liquid as solvent polymeric all aromatic nylon.In patent WO2011004138A1, disclose the method for preparing nylon 66 using ionic liquid as solvent, and the fusing point of gained nylon 66 is all lower than known nylon 66 fusing points.Reference Organic Letters,, vol.9 in 2007, mention in " AnEfficient Method To Depolymerize Polyamide Plastics:A New Use of IonicLiquids " literary composition of No.13, page2533-2535 and make nylon 6 be depolymerized to the example of caprolactam monomer as solvent with ionic liquid.In addition, ionic liquid is added in polymkeric substance as tenderizer.For example, Degussa discloses a kind of polymer composition in patent CN1681878 " polymer composition being formed by polymkeric substance and ionic liquid ", it contains at least one at least part of crystallization and has the compound of softening properties and wherein contain the ionic liquid as 0.1 % by weight to 30 % by weight of tenderizer without the polymkeric substance of ionic group and at least one.So far, prepare high-polymerization degree taking ionic liquid as catalyzer and there is also openly not the reporting of polyamide resin that stability is detained in good melting.
Summary of the invention
We found through experiments, and can prepare high-polymerization degree and have the polyamide resin that stability is detained in good melting taking ionic liquid as catalyzer.In the present invention, improve the polymerization degree of gained polymeric amide using ionic liquid as catalyzer, and gained polyamide resin has good delay stability.
The invention provides a kind of polyamide resin that contains two amine units and two acid units, the relative viscosity that the 0.01g/ml concentration concentrated sulfuric acid solution of this polyamide resin is tested at 25 DEG C is 1.80-6.00, the ionic liquid that to contain with respect to the weight of polyamide resin be 100-20000ppm.
Two above-mentioned acid units are not particularly limited.The starting monomer that can enumerate two acid units is preferably oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1, 11-undecyl diacid, 1, 12-dodecyl diacid, 1, 13-tridecyl diacid, 1, 14-tetradecyl diacid, 1, 15-pentadecyl diacid, 1, 16-hexadecyl diacid, 1, 18-octadecyl diacid, or 1, aliphatic diacid or its corresponding various ester compounds such as 19-nonadecyl diacid, or 1, 4-/1, ring-type diacid or its corresponding various ester compounds such as 3-cyclohexane diacid, or terephthalic acid, or one or more in the aromatic diacid such as m-phthalic acid or its corresponding various ester compounds.The oxalic acid unit that two above-mentioned acid units contain, its content is preferably 50～100 % by mole with respect to the total amount of two acid units.Starting monomer as oxalic acid unit is not particularly limited, and can be enumerated as one or more in oxalate diester, oxalic acid, oxalic acid acyl chlorides or oxalic acid acyl chlorides ester etc.Be preferably oxalate diester.The present invention is not particularly limited for oxalate diester.The oxalate diester that can enumerate is further preferable over one or more in dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or oxalic acid di tert butyl carbonate.
The starting monomer of two above-mentioned amine units is preferably 1,3-propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-undecane diamines, 1,12-dodecane diamines, 1,13-tridecane diamines, 1,14-tetradecane diamines, 1,15-pentadecane diamines, 1,16-n-Hexadecane diamines, 1,17-heptadecane diamines, 1,18-octadecamethylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 2-methyl isophthalic acid, one or more in 8-octamethylenediamine, cyclohexane diamine or benzene dimethylamine.When the carbonatoms of two amine units is lower than 3 time, the viscosity that likely occurs polyamide resin is difficult to improve and the too high unmanageable tendency of fusing point of polyamide resin; When the carbonatoms of two amine units is higher than 10 time, likely there is the fusing point tendency that causes thermotolerance to reduce on the low side of polyamide resin.From the viewpoint of the crystallinity of polyamide resin, preferably two amine units of straight chain.In addition, dystectic from the viewpoint of polyamide resin, the starting monomer of two amine units further preferably 1,4-butanediamine, 1, in 5-pentamethylene diamine or 1,6-hexanediamine one or more, its content is preferably 10～100 % by mole with respect to the starting monomer total amount of diamines, more preferably 50～100 % by mole, be further preferably 80～100 % by mole, more more preferably 90～100 % by mole.The starting monomer of two amine units most preferably is 1,5-pentamethylene diamine.
Consider the thermotolerance of polyamide resin and the possibility of melt-processed, the content (with respect to amide group mole number in 1g polymeric amide) of the amide group of polyamide resin of the present invention is preferably 7.5mmol/g～14.5mmol/g, more preferably 10.5mmol/g～14.0mmol/g.If amide group content is lower than 7.5mmol/g, the too low thermotolerance that may cause of the fusing point of polymeric amide declines, if amide group content higher than 14.5mmol/g, too high may causing of the fusing point of polymeric amide cannot be carried out melt-processed.
The relative viscosity η r of the polyamide resin being obtained by the present invention is taking 96% concentrated sulfuric acid solution as solvent, and the polyamide resin sulphuric acid soln that concentration is 0.01g/ml is determined in 1.80～6.00 scope at 25 DEG C, more preferably 2.10～5.00.Further be preferably 2.40～4.00.η r was lower than 1.80 o'clock, and molding may become fragile, and had the too low tendency possibility of shock strength.On the other hand, η r was higher than 6.00 o'clock, and melt viscosity may uprise, shaping processability variation.
Above-mentioned ionic liquid is not particularly limited, and ionic liquid can be selected from N, imidazoles, N that N ' alkyl replaces, one or more in the salt of pyridine, quaternary ammonium alkyl or Wan Ji quaternary phosphine that N ' alkyl replaces.The substituted alkyl of described ionic liquid is that carbonatoms is preferably the aliphatics of 1-20 or the alkyl of aromatic direct-connected or side chain.Can enumerate as chlorination 1,3-methylimidazole, 1,3-methylimidazole Dimethyl phosphate, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl bromination imidazoles, 1-ethyl-3-methyl iodate imidazoles, 1-ethyl-3-methylimidazole methane sulfonates, 1-ethyl-3-methylimidazole trifluoro-methanyl sulfonate, 1-ethyl-3-methylimidazole hydrosulfate, 1-ethyl-3-methylimidazole ethyl sulfonate, 1-ethyl-3-methylimidazole dicyan amine salt, 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole tetrachloro ferrate, 1-methyl-3-propyl group iodate imidazoles, 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl bromination imidazoles, 1-butyl-3-methyl iodate imidazoles, 1-butyl-3-Methylimidazole trifluoro-methanyl sulfonate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methyl hexafluorophosphate imidazoles, 1-butyl-3-Methylimidazole tetrachloro ferrate, 1-hexyl-3-methyl imidazolitm chloride, 1-hexyl-3-Methylimidazole bromide, 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-methyl-3-n-octyl imidazolium bromide, 1-butyl-2,3-dimethyl chlorination imidazoles, 1-ethyl pyridinium chloride, 1-ethylpyridine bromide, 1-butyl pyridinium chloride, 1-butyl pyridinium bromide, 1-butyl-pyridinium hexafluorophosphate, 1-butyl-3-picoline bromide, 1-ethyl-3-picoline esilate, 1-butyl-4-picoline bromine salt, 1-butyl-4-picoline hexafluorophosphate, tetrabutylammonium chloride, Tetrabutyl amonium bromide, the just pungent ammonium of methyl three closes two (trifluoromethane sulphonyl) imines, four butyl phosphonium bromides, two (trimethyl fluoride sulfonyl) imines of tributyl (2-methoxy ethyl) phosphorus, or two (trimethyl fluoride sulfonyl) imines of triethyl sulfonium one or more.More preferably chlorination 1, 3-methylimidazole, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl bromination imidazoles, 1-ethyl-3-methyl iodate imidazoles, 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl bromination imidazoles, 1-butyl-3-methyl iodate imidazoles, 1-hexyl-3-methyl imidazolitm chloride, 1-hexyl-3-Methylimidazole bromide, 1-methyl-3-n-octyl imidazolium bromide, 1-butyl-2, 3-dimethyl chlorination imidazoles, 1-ethyl pyridinium chloride, 1-ethylpyridine bromide, 1-butyl pyridinium chloride, 1-butyl pyridinium bromide, 1-butyl-3-picoline bromide, or one or more in 1-butyl-4-picoline bromine salt.
In high temperature process process or in hot environment use, all can there is thermooxidative degradation in polyamide resin, its reason is as " polymer degradation and stability " (vol.49,1995) record in 127～133 pages: the methylene radical adjacent with nitrogen in amide group electron detachment easily occurs and form free radical because this free radical can with imido grpup on lone-pair electron and the π key of carbonyl form stable resonance structure.Also easily there is similar thermooxidative degradation in the amide group containing in the Component units of polyamide resin of the present invention.For example, easily there is the electron detachment of the methylene radical that nitrogen in amide group is adjacent for polyamide resins such as polyamide 66s, produce thermooxidative degradation; In Component units for polyamide resin, contain oxamide unit, adjacent two pairs of amide group on oxamide unit can form more stable resonance structure than general single amide group, the electron detachment that is more prone to occur the methylene radical that nitrogen in amide group is adjacent, produces thermooxidative degradation.The present invention has found that ionic liquid can suppress the thermooxidative degradation of polymeric amide effectively, especially larger to the effect of dystectic polyamide resin (polyamide resin of fusing point more than 280 DEG C) thermooxidative degradation.
The content of above-mentioned polyamide resin intermediate ion liquid is 100～20000ppm with respect to polyamide resin weight, preferably 100～18000ppm, more preferably 100～15000ppm, more more preferably 100～10000ppm.If the content of ionic liquid is lower than 100ppm, the viscosity of polymkeric substance may be difficult to improve and its melting delay stability may be poor, cause it to process: if the content of ionic liquid is higher than 20000ppm, in polymkeric substance, may easily produce gel object, jello cannot melt-processed, to remain in products formed and become focal point of stress, and will cause products formed that the possibility of stress cracking easily occurs in practical application.
Adopt TA DSC-Q100 analytical instrument, accurately take about 5mg sample, under nitrogen atmosphere, above-mentioned polyamide resin is warmed up to than the temperature of the endotherm(ic)peak being occurred (T0) and exceeds the temperature of 30 DEG C with 20 DEG C/min of heat-up rates, at this temperature, keep 2 minutes, then drop to 30 DEG C with the cooling rate of 20 DEG C/min, at 30 DEG C, keep 2 minutes.Next, be warmed up to the temperature T m of the endotherm(ic)peak observing while exceeding 30 DEG C than T0 as the fusing point of above-mentioned polyamide resin taking the heat-up rate of 20 DEG C/min, its fusing point is preferably more than 250 DEG C, further preferably more than 255 DEG C, more further preferably more than 265 DEG C, finally preferably more than 275 DEG C.If fusing point is less than 250 DEG C, the too low thermotolerance that may cause of fusing point declines.
Stability feature is detained in the melting of the polyamide resin being obtained by the present invention: the sulphuric acid soln relative viscosity be detained 30 minutes at the temperature of high 20 DEG C than fusing point time is made as Y, and when the sulphuric acid soln relative viscosity before delay is made as X, Y/X is preferably 0.75～1.40.Further preferably 0.80～1.30, further preferably 0.85～1.20.If Y/X is lower than 0.75, the resin in melt-processed process may have obvious decomposition, has a strong impact on its mechanical property.If Y/X is higher than 1.40, the resin in melt-processed process may have obvious viscosity to increase, and will increase machine-shaping difficulty.
The present invention also provides the preparation method of above-mentioned polyamide resin, and it comprises the following steps:
Step (a) is by diamine source and solution is carried out in di-carboxylic acid source or melt polymerization obtains low molecular weight prepolymer;
Step (b): the low molecular weight prepolymer that step (a) is obtained carries out melt polymerization or solid state polymerization obtains polyamide resin;
Wherein: the ionic liquid adding in step (a) or in step (b) is as catalyzer.
In preparation method of the present invention, identical with the content of two amine units above for the content in diamine source.Identical with the content of two acid units above for the content in di-carboxylic acid source.
Within the scope of the preparation method of above-mentioned polyamide resin, can enumerate lower noodle producing method:
Prepolymer preparation (oxalic acid is polymeric amide):
The starting monomer of polyamide resin is the above-mentioned starting monomer of two amine units and the starting monomer of two acid units (two acid units comprise 50%～100% oxalic acid unit and form).First in the general reactor with prolong, add organic solvent, then add the starting monomer of two amine units, and replace with nitrogen, and then the starting monomer that adds two acid units is by its blend.Then start the temperature that stirring heating is warmed up to solvent refluxing and react 3～5 hours, then filter and carry out 3～5 times cleaning with methyl alcohol or ethanol, the prepolymer obtaining is dried.As organic solvent, be not particularly limited, can use toluene, dimethylbenzene, trichlorobenzene, phenol or trifluoroethanol etc., can be preferably toluene.
Prepolymer preparation (non-oxalic acid is polymeric amide):
The starting monomer of polyamide resin is the above-mentioned starting monomer of two amine units and the starting monomer of two acid units.In reaction tube, add the starting monomer of two amine units, starting monomer and the water of two acid units.And then test tube is put into autoclave, and after being warming up to certain temperature and still internal pressure and acquiring a certain degree, maintain under this pressure and react 2-5 hour, then cooling.Taking out prepolymer is dried.
The melt polymerization of prepolymer:
Prepolymer and above-mentioned ionic liquid (the addition weight ratio of ionic liquid is 100～20000ppm with respect to polyamide resin weight) fully mix by required proportioning, then add in reactor, and replace with rare gas element.This reactor is placed in well heater, then starts to be heated to the above temperature of fusing point of prepolymer, polymerase 10 .5～5 hour of reducing pressure, and final pressure is 5000～20Pa, or under inert gas flow, carries out polymerization under atmospheric pressure 0.5～5 hour.
The solid state polymerization of prepolymer:
Prepolymer and above-mentioned ionic liquid (the addition weight ratio of ionic liquid is 100～20000ppm with respect to polyamide resin weight) fully mix by required proportioning, then add in reactor, and replace with rare gas element.Then below fusing point, carry out the decompression solid state polymerization of 0.5～30 hour at it, final pressure is 300～20Pa, or under inert gas flow, carries out the normal pressure solid state polymerization of 0.5～30 hour.
In adding in thermal polycondensation of above-mentioned polyamide resin, owing at high temperature carrying out polyreaction, thereby straight chain aliphatie diamine based on short carbon chain volatilizees in polymerization system, or make the reasons such as lower boiling product volatilization by deamination reaction, along with the carrying out of polymerization, in polymerization system, total amino amount may reduce with respect to total carboxylic acid's base or oxalic acid ester group (oxalic acid is polymeric amide) content, therefore, in the stage that adds raw material, excessively add in advance the straight chain aliphatie diamine of the short carbon chain of specified quantitative and control the amino amount in polymerization system, polyamide resin for synthetic high molecular is preferred.When the mole number of the starting monomer of the short carbon chain straight chain aliphatie diamine unit using as raw material is made as to a, when the mole number of the starting monomer of two acid units is made as to b, preferably raw material ratio of components being adjusted to a/b is 1.003～1.10, a/b more preferably 1.008～1.08, is further preferably 1.01～1.05.If a/b is less than 1.003, the total amino amount in polymeric system is relative few with the amount of total carboxylic acid's base or oxalic acid ester group (oxalic acid is polymeric amide), is difficult to obtain the polymkeric substance of high molecular.If a/b is greater than 1.10, in polymerization system, total amino amount is relative too much with the amount of total total carboxylic acid's base or oxalic acid ester group (oxalic acid is polymeric amide), is difficult to obtain the polymkeric substance of high molecular.
In preparation method of the present invention, described ionic liquid is selected from N, imidazoles, N that N ' alkyl replaces, one or more in the salt of pyridine, quaternary ammonium alkyl or Wan Ji quaternary phosphine that N ' alkyl replaces.Particular content is identical with the description of ionic liquid above.
In polyamide resin of the present invention, can also add as required various packing materials, thereby, the present invention also provides a kind of Amilan polyamide resin composition, coordinates the Amilan polyamide resin composition of 0.1～200 weight portion packing material with respect to above-mentioned polyamide resin 100 weight portions.Concrete packing material is as follows.
Inorganic filling material is as graphite, barium sulfate, calcium carbonate, weisspiessglanz, titanium oxide, aluminum oxide, nickel, aluminium, iron, steel, talcum, wilkinite, polynite, mica titanium dioxide, silicon-dioxide, aluminium sesquioxide or silicate etc.For some layered silicates, can adopt organic ammonium salt that interlayer ion is carried out to the silicate that organises after cationic exchange.For the appearance excellence of polyamide resin, the median size of inorganic filler is preferably 0.001～10 μ m.If median size is less than 0.001 μ m, the melt processable of gained Amilan polyamide resin composition can significantly reduce, and in addition, if particle diameter is greater than 10 μ m, products formed appearance has the tendency of variation.Its addition is preferably 0.1～200 weight portion with respect to polyamide resin 100 weight portions.
The fibrous packing material of organic system and the fibrous packing material of inorganic system.Fiber-filled material as organic system can be enumerated fully aromatic polyamide fiber, the cellulosic fibres etc. such as aromatic polyamide fibers.Fibrous packing material as inorganic system can list glass fibre, carbon fiber or boron fibre etc.In addition, also have steel fiber, aluminum borate, gypsum, calcium carbonate, sepiolite, firmly return in the mineral compound whisker such as calcium stone or your lime stone or needle-like crystal etc. one or more.In addition, can use the macrofiber of length 5～50mm, also can use length is the staple fibre of 0.05～5mm, and its addition is preferably 0.1～200 weight part with respect to polyamide resin 100 weight parts.
In polyamide resin preparation of the present invention, can also add as required various additives, for example, in weather resisting agent, releasing agent or lubricant, pigment, dyestuff, softening agent, static inhibitor, fire retardant or other polymkeric substance one or more.Specifically, weather resisting agent is Resorcinol system, salicylate system, benzotriazole system, benzophenone series or hindered amine system etc.; Releasing agent or lubricant are fatty alcohol, aliphatic amide, aliphatics bisamide, allophanamide or polyethylene wax etc.; Pigment is Cadmium Sulfide, phthalocyanine or carbon black etc.; Dyestuff is nigrosine or nigrosine etc.; Softening agent is P-hydroxybenzoic acid monooctyl ester or N-butylbenzenesulfonamide etc.; Static inhibitor is that alkyl sulphate type negatively charged ion is that static inhibitor, quaternary ammonium salt cationic are that static inhibitor, the such nonionic of polyoxyethylene sorbitan monostearate are that static inhibitor or trimethyl-glycine are both sexes static inhibitor etc.; Fire retardant is the composition of the oxyhydroxide such as trimeric cyanamide, magnesium hydroxide or aluminium hydroxide, ammonium polyphosphate, bromo polyethylene, bromo polyphenylene sulfide, brominated polycarbonates, brominated epoxy resin or bromo-derivative fire retardant and antimonous oxide etc.; Other polymkeric substance are polymeric amide, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystalline polymers, ABS resin, SAN resin or polystyrene etc.
In addition, in order to improve the impact property of polyamide resin, the present invention also provides a kind of Amilan polyamide resin composition, coordinates the Amilan polyamide resin composition of the packing material of 5～100 weight portion shock-resistance with respect to above-mentioned polyamide resin 100 weight portions.For example: by alkenes compounds and conjugated diolefin one or more and come equal (being total to) polymers.
Above-mentioned equal (being total to) polymers can be enumerated as the multipolymer of ethene copolymer, conjugated diolefin homopolymer and conjugated diene/aromatic ethylene compound.Ethene copolymer is two membered copolymers or the multi-component copolymer of ethene and other cell cubes.Other cell cubes can be enumerated as more than 3 alpha-olefin, non-conjugated diene hydrocarbon, vinyl acetate between to for plastic, vinyl alcohol, the α of carbon, beta-unsaturated carboxylic acid and inductor thereof.Its addition is preferably 5～200 weight portions with respect to polyamide resin 100 weight portions.If more than addition is greater than 5 weight parts, the impact of polyamide resin is improved significantly; If addition is less than 200 kinds of amounts part, be conducive to the shaping processing of polyamide resin.
Polyamide resin of the present invention can by injection molding, extrusion moulding, blow molding, vacuum forming, melt-spinning or film moulding etc. arbitrarily forming method be shaped to required shape, can be for the synthetic resin such as trolley part, mechanical part, fiber or film etc.Concrete purposes: automobile engine cooling water based part, the particularly pump part such as the radiator water box part such as top and bottom of radiator tank, cooling fluid reserve tank, water pipe, water pump shell, water pump impeller, valve etc., and the parts that contact with water coolant in motor car engine.Electrical and electronic parts is small-sized switch, the shell of switch, lamp socket, junctor, the housing of junctor, connector shell, IC socket class, bobbin, bobbin cover, rly., relay1 box, capacitor protector, the internal part of electric motor, small size motor shell, gear cam, the equilibrium theory, pad, isolator, fastening piece, button, wire clamp, caster, safety helmet, electronic table trigger insulating element, fuse unit, the shell of terminal, wheel cover, suction tracheae, bearing retainer, electric wire optical cable coating layer, or the electrical and electronic parts that is representative such as fiber-optic cable oversheath, automobile associated components, computer associated components, machinery associated components or other various uses.
Embodiment
Illustrate by the following examples the present invention, but the present invention is not subject to any restriction of these embodiment.Various characteristics in embodiment and comparative example, all measures by the following method.
(1) sulfuric acid relative viscosity:
Taking 96% sulfuric acid as solvent, the polyamide resin lipoprotein solution that compound concentration is 0.01g/ml is measured relative viscosity at 25 DEG C
(2) stability is detained in melting
Under nitrogen atmosphere, being heated to the sample that keeps at the temperature of above 20 DEG C of fusing point after 30 minutes is dissolved in and in 96% sulfuric acid, tests its relative viscosity (Y) with the concentration of 0.01g/ml, sulfuric acid relative viscosity before being detained is made as to (X), obtains the conservation rate (Y/X) of sulfuric acid relative viscosity.
(3) thermal property:
Adopt TA DSC-Q100 analytical instrument, accurately take about 5mg sample, test condition is as follows: under nitrogen atmosphere, gained polyamide resin is warmed up to than the temperature of the endotherm(ic)peak being occurred (T0) and exceeds the temperature of 30 DEG C with 20 DEG C/min of heat-up rates, at this temperature, keep 2 minutes, then drop to 30 DEG C with the cooling rate of 20 DEG C/min, at 30 DEG C, keep 2 minutes.Next, be warmed up to the temperature T m of the endotherm(ic)peak observing while exceeding 30 DEG C than T0 with the heat-up rate of 20 DEG C/min.
Be called for short explanation:
1,5-pentamethylene diamine: purity is 98%, purchased from TCI company.
1,6-hexanediamine: purity is 98%, purchased from TCI company.
Dibutyl oxalate: analytical pure, purchased from Sigma-Aldrich company.
1,6-hexanodioic acid: analytical pure, purchased from Aladdin company.
1-ethyl-3-methyl iodate imidazoles: analytical pure, purchased from TCI company.
1-ethyl-3-methyl bromination imidazoles: analytical pure, purchased from TCI company.
1-butyl-3-methyl imidazolitm chloride: analytical pure, purchased from TCI company.
Embodiment 1
In 1000ml three-necked flask, add 500ml toluene, then to 32.033g (0.3135mol) 1 in toluene solvant, 5-pentamethylene diamine, starts after nitrogen purging to stir, and in this system, adds 60.675g(0.3000mol again) dibutyl oxalate.Then be warming up to 130 DEG C, continue back flow reaction 5 hours with this condition, filter, washing, the dry relative viscosity that obtains are 1.27 prepolymer.
Gained 2.000g prepolymer and 0.952mg1-ethyl-3-methyl iodate imidazoles are fully mixed, then be fed in the glass test tube that diameter is 19mm, then repeatedly replace 5 times with nitrogen, then under nitrogen gas stream, be placed in the metal bath of 325 DEG C, be decompressed to below 100Pa with 20 minutes, then make its reaction 40 minutes.Polymer property is in table 1.
Comparative example 1
Repeat embodiment 1, different is not add 1-ethyl-3-methyl iodate imidazoles.Polymer property is in table 1.
Comparative example 2
The preparation of prepolymer is same as the preparation of prepolymer in embodiment 1, and the prepolymer of 2.000g adds in the glass test tube that diameter is 19mm, and replaces with nitrogen.Then carry out below the decompression solid state polymerization of 5 hours at 280 DEG C, final pressure is 60Pa.Polymer property is in table 1.
Embodiment 2
PA66 prepares 1
In the glass test tube that is 19mm at diameter, add 5.984g (0.0515mol) 1,6-hexanediamine, 7.307g (0.050mol) 1,6-hexanodioic acid and 13.291g deionized water.Then this test tube is placed in autoclave, with nitrogen purging, then starts to heat up, pressure starts to raise.In the time that temperature rises to 220 DEG C, pressure rises to 1.78MPa, and 1.78MPa pressure remains unchanged, and continues to react stopped reaction after 2 hours, and temperature is now 241 DEG C.Prepolymer in cooling rear taking-up autoclave.The dry relative viscosity that obtains is 1.20 prepolymer.
Gained 2.000g prepolymer and 0.952mg1-ethyl-3-methyl iodate imidazoles are fully mixed, then be fed in the glass test tube that diameter is 19mm, then repeatedly replace 5 times with nitrogen, then under nitrogen gas stream, be placed in the metal bath of 282 DEG C, be decompressed to below 100Pa with 20 minutes, then make 40 points of its reactions.Polymer property is in table 1.
Comparative example 3
Repeat embodiment 2, different is not add 1-ethyl-3-methyl iodate imidazoles.Polymer property is in table 1.
Embodiment 3
Repeat embodiment 1, the amount that different is adds 1-ethyl-3-methyl iodate imidazoles is 0.48mg, and polymer property is in table 2.
Embodiment 4
Repeat embodiment 1, the amount that different is adds 1-ethyl-3-methyl bromination imidazoles is 38.21mg, and polymer property is in table 2.
Comparative example 4
Repeat embodiment 1, the amount of different is 1-ethyl-3-methyl iodate imidazoles is 45.20mg, and polymer property is in table 2.
Comparative example 5
Repeat embodiment 1, the amount of different is 1-ethyl-3-methyl iodate imidazoles is 0.24mg, and polymer property is in table 2.
Comparative example 6
PA66 prepares 2
In there-necked flask, add 40.000g1-butyl-3-methyl imidazolitm chloride and 16.170g nylon salt, and logical nitrogen gas stirring 15 minutes.Be warming up to 180 DEG C, and react 6 hours under nitrogen gas stream, then in 20 minutes, be decompressed to 10KPa and dewater, and maintain 1 hour under pressure.Then resulting polymers is cooled to room temperature and adds 400ML water to reflux, then suction filtration.Reusable heat water is dry under vacuum after cleaning.Polymer property is in table 3.
Comparative example 7
Repeat the polymkeric substance that embodiment 1 makes, then its polymkeric substance refluxes and within 5 hours, removes ionic liquid in boiling water, and the characteristic of the polymkeric substance of removal ionic liquid is in table 3.
Table 1
In table 1, for PA52, PA66, the relative viscosity of adding the polymkeric substance after 1-ethyl-3-methyl iodate imidazoles is much improved.In addition, relatively can find out that from embodiment 1 and comparative example 2 1-ethyl-3-methyl iodate imidazoles is detained stability to the melting of PA52 and has special effect.
Table 2
In table 2, add 1-ethyl-3-methyl iodate imidazoles excessive or very few after polymkeric substance, add the excessive polymer gel of 1-ethyl-3-methyl iodate imidazoles to be not suitable for machine-shaping, add the very few polymkeric substance relative viscosity of 1-ethyl-3-methyl iodate imidazoles too low.
Table 3
In table 3, use nylon 66 fusing points, the viscosity that obtain all very low using ionic liquid as solvent, and after original nylon 52 intermediate ion liquid are removed, the melting of polymkeric substance is detained stability and is obviously reduced.
Claims (12)
1. a polyamide resin that contains two amine units and two acid units, it is characterized in that: the relative viscosity that the 0.01g/ml concentration concentrated sulfuric acid solution of this polyamide resin is tested at 25 DEG C is 1.80-6.00 the ionic liquid that to contain with respect to the weight of polyamide resin be 100-20000ppm.
2. polyamide resin according to claim 1, is characterized in that: the fusing point of described polyamide resin is more than 250 DEG C.
3. polyamide resin according to claim 1, is characterized in that: ionic liquid is selected from N, imidazoles, N that N ' alkyl replaces, one or more in the salt of pyridine, quaternary ammonium alkyl or Wan Ji quaternary phosphine that N ' alkyl replaces.
4. polyamide resin according to claim 1, is characterized in that: 50～100 % by mole of two acid units is oxalic acid unit.
5. polyamide resin according to claim 1, is characterized in that: 10～100 % by mole of two amine units is 1,5-pentamethylene diamine unit.
6. polyamide resin according to claim 1, it is characterized in that: sulphuric acid soln relative viscosity when described polyamide resin is detained 30 minutes at the temperature of high 20 DEG C than fusing point is made as Y, when sulphuric acid soln relative viscosity before delay is made as X, Y/X is 0.75～1.40.
7. a method of preparing the polyamide resin described in any one in claim 1-6, is characterized in that: comprise the following steps:
Step (a): by diamine source with solution is carried out in di-carboxylic acid source or melt polymerization obtains low molecular weight prepolymer;
Step (b): the low molecular weight prepolymer that step (a) is obtained carries out melt polymerization or solid state polymerization obtains polyamide resin;
Wherein: the ionic liquid adding in step (a) or in step (b) is as catalyzer.
8. preparation method according to claim 7, is characterized in that: ionic liquid is selected from N, imidazoles, N that N ' alkyl replaces, one or more in the salt of pyridine, quaternary ammonium alkyl or Wan Ji quaternary phosphine that N ' alkyl replaces.
9. preparation method according to claim 7, is characterized in that: 50～100 % by mole of described di-carboxylic acid source is oxalic acid source.
10. preparation method according to claim 7, is characterized in that: 10～100 % by mole of described diamine source is 1,5-pentamethylene diamine source.
11. Amilan polyamide resin compositions, is characterized in that: the Amilan polyamide resin composition that coordinates 0.1～200 weight portion packing material with respect to the polyamide resin 100 weight portions described in any one in claim 1～6.
12. Amilan polyamide resin compositions, is characterized in that: the Amilan polyamide resin composition that coordinates the packing material of 5～100 weight portion shock-resistance with respect to the polyamide resin 100 weight portions described in any one in claim 1～6.
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| CN107250273A (en) * | 2015-03-03 | 2017-10-13 | 尤尼吉可株式会社 | Amilan polyamide resin composition |
| WO2017205130A1 (en) * | 2016-05-25 | 2017-11-30 | Corning Optical Communications LLC | Flame retardant additive for a low smoke, zero halogen compound |
| CN111554973A (en) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | Full-solid polymer electrolyte based on dendritic polyamide-6 nanofiber membrane and preparation method thereof |
| CN112280031A (en) * | 2020-10-30 | 2021-01-29 | 郭勇 | High-temperature-resistant semi-aromatic polymer and preparation method thereof |
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| CN102503890A (en) * | 2011-11-28 | 2012-06-20 | 江南大学 | Method for recovering epsilon-caprolactam by catalytically hydrolyzing waste nylon 6 with acid ionic liquid |
| CN102651981A (en) * | 2009-12-10 | 2012-08-29 | 巴斯夫欧洲公司 | Antistatic thermoplastic compositions |
| CN102869701A (en) * | 2010-04-30 | 2013-01-09 | 宇部兴产株式会社 | Polyamide resin |
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| CN102471588A (en) * | 2009-07-31 | 2012-05-23 | 三洋化成工业株式会社 | Antistatic resin composition |
| CN102651981A (en) * | 2009-12-10 | 2012-08-29 | 巴斯夫欧洲公司 | Antistatic thermoplastic compositions |
| CN102869701A (en) * | 2010-04-30 | 2013-01-09 | 宇部兴产株式会社 | Polyamide resin |
| CN102503890A (en) * | 2011-11-28 | 2012-06-20 | 江南大学 | Method for recovering epsilon-caprolactam by catalytically hydrolyzing waste nylon 6 with acid ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107250273A (en) * | 2015-03-03 | 2017-10-13 | 尤尼吉可株式会社 | Amilan polyamide resin composition |
| WO2017205130A1 (en) * | 2016-05-25 | 2017-11-30 | Corning Optical Communications LLC | Flame retardant additive for a low smoke, zero halogen compound |
| US10759922B2 (en) | 2016-05-25 | 2020-09-01 | Corning Optical Communications LLC | Flame retardant additive for a low smoke, zero halogen compound |
| US10975226B2 (en) | 2016-05-25 | 2021-04-13 | Corning Optical Communications LLC | Flame retardant additive for a low smoke, zero halogen compound |
| CN111554973A (en) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | Full-solid polymer electrolyte based on dendritic polyamide-6 nanofiber membrane and preparation method thereof |
| CN112280031A (en) * | 2020-10-30 | 2021-01-29 | 郭勇 | High-temperature-resistant semi-aromatic polymer and preparation method thereof |
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