CN103421185A - Aliphatic polyamide resin and use thereof - Google Patents
Aliphatic polyamide resin and use thereof Download PDFInfo
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- CN103421185A CN103421185A CN2012101806887A CN201210180688A CN103421185A CN 103421185 A CN103421185 A CN 103421185A CN 2012101806887 A CN2012101806887 A CN 2012101806887A CN 201210180688 A CN201210180688 A CN 201210180688A CN 103421185 A CN103421185 A CN 103421185A
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Abstract
The invention relates to an aliphatic polyamide resin and a use thereof. The aliphatic polyamide resin has a high melting point and good crystallinity, and contains 1, a 1,5-pentamethylene diamine unit, 2, a C4-C18 straight-chain aliphatic diamine unit in addition to the 1,5-pentamethylene diamine unit and 3, an oxalic acid unit, wherein the amount of the 1,5-pentamethylene diamine unit is 30-95mol% of the total amount of the 1,5-pentamethylene diamine unit and the C4-C18 straight-chain aliphatic diamine unit. The aliphatic polyamide resin comprises the aliphatic polyamide having a high melting point, good crystallinity, low water absorption and good processability. The aliphatic polyamide resin can be used for fibers, films or resin molded products such as automobile parts and mechanical parts.
Description
Technical field
The present invention relates to a kind of polyamide resin, be specifically related to a kind of have good thermotolerance, melting delay stability and crystalline fatty polyamide resin.
Background technology
Take the crystallinity polymeric amide that nylon 6, nylon 66 etc. are representative, easiness due to its excellent characteristic and melt-shaping, be widely used as dress material use, industry goods, materials and equipments fiber or general engineering plastics, but, on the other hand, also pointed out that the physical property that causes due to water suction changes, the problem such as deteriorated in the alcohol of acid, high temperature, hot water, improve the requirement of seeking dimensional stability, polymeric amide that resistance to chemical reagents is more excellent.In the electrical and electronic parts field, follow the development of surface mounting technology (SMT), for the high thermotolerance of polymeric amide needs of this technical field, comprising the reflow soldering thermotolerance.In this case, still need exploitation not only to there is good heat resistance, and there is good dimensional stability, the high quality polymeric amide of good mechanical properties and good chemical resistance.
On the other hand, known use oxalic acid is called as polyoxamide as the polyamide resin of dicarboxylic acid composition, with other polyamide resin of identical amide group concentration, to compare water-intake rate low, expectation changes and becomes problem in the physical property caused due to water suction, and in the unworkable field of polymeric amide, is applied flexibly at present.
For example, at reference S.W.Shalaby., J.Polym.Sci., 11, in 1 (1973), 1, the 6-hexanediamine is as the polyoxamide of two amine components, and its fusing point (approximately 320 ℃) is than heat decomposition temperature (in nitrogen, 1% weight reduces approximately 310 ℃ of temperature) height, so melt processing temperature is too high will cause melting to be detained the stability variation.Disclosed oxalic acid for space section is polymeric amide (WO2008/072754) PA92/2-methyl-82 resin, there is low water absorbable, solvent resistance and good processed-type, but its fusing point is 240 ℃ of left and right, and for requiring dystectic purposes, its thermotolerance is bad.Disclosed oxalic acid for space section is urethane (WO2011/136263) PA62/2-M52 resin, and its weak crystallinity is obvious weakness.
Summary of the invention
The defect simultaneously had for good heat resistance, good crystallinity and the low water absorbable that solves fatty polyamide in prior art, the invention provides a kind of fatty polyamide with high-melting-point, good melting anelasticity, good crystallinity and low water absorbable, and this fatty polyamide has excellent machining property.
The invention provides a kind of polyamide resin, this polyamide resin contains:
(1) 1,5-pentamethylene diamine unit,
The straight chain aliphatie diamine unit that beyond (2) 1,5-pentamethylene diamine unit, carbonatoms is 4～18,
(3) oxalic acid unit;
30～95mol% of the total amount that wherein, (1) 1,5-pentamethylene diamine unit content is (1) and (2) unit.
Above-mentioned (1) unit content, consider the reasons such as the thermal property of polymkeric substance and mechanical property, and (1) unit content is (1) and (2)) 30～95mol% of the total amount of unit.Lower than 30mol%, will cause that the polyamide resin fusing point is too low or too high when (1) unit content.If the polymeric amide fusing point is too low, directly reduced thermotolerance; If the polymeric amide fusing point is too high, will cause that too high its processing characteristics that causes of polyamide resin fusing point descends.During higher than 95mol%, will cause that too high its processing characteristics that causes of polyamide resin fusing point descends when (1) unit content, degree of crystallinity significantly increases and causes its impact property obviously to descend.
Described (2) 1, the straight chain aliphatie diamine unit that beyond 5-pentamethylene diamine unit, carbonatoms is 4～18 is preferably 1,4-butanediamine unit, 1,6-hexanediamine unit, 1,7-heptamethylene diamine unit, 1,8-octamethylenediamine unit, 1,9-nonamethylene diamine unit, 1,11-undecane two amine units, 1,12-dodecane two amine units, 1,13-tridecane two amine units, 1, the 14-tetradecane two amine units, 1,15-pentadecane two amine units, 1,16-n-Hexadecane two amine units, 1, one or more in 17-heptadecane two amine units or 1,18-octadecamethylene diamine unit.When (2) unit, composition is selected from carbonatoms lower than 4, will cause its viscosity to be difficult to improve, and too high being difficult to of its fusing point processes.When (2) unit composition is selected from carbonatoms, higher than 18, will cause the too low thermotolerance that causes of its fusing point bad, when (2) unit composition is selected from other, with side group or cyclic group, will reduce the regularity of polymer molecular chain, and cause crystallinity to descend.
The oxalic acid source of using in the mill as (3) the oxalic acid unit in polymeric amide of the present invention, can preferably use oxalate diester, the present invention is not particularly limited for oxalate diester, these oxalate diesters need only and amino reactivity, and the oxalate diester that can enumerate is 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 molecular weight of the polyamide resin obtained by the present invention is not particularly limited, and take 96% concentrated sulfuric acid solution as solvent, the polyamide resin that working concentration is 0.01g/ml, and the relative viscosity η r measured under 25 ℃ is preferably in 1.6～6.0 scope.More preferably 2.0～4.5.Be particularly preferably 2.4～4.0.η r was lower than 1.6 o'clock, and molding may become fragile, and physical property reduces.On the other hand, η r was higher than 6.0 o'clock, and melt viscosity may uprise, the shaping processability variation.
The thermal property of the polyamide resin obtained by the present invention is with differential scanning heat meter under inert gas atmosphere, drop to 30 ℃ with the cooling rates of 20 ℃/minute from molten state, the endotherm peak temperature Tm then occurred in the temperature-rise period with the determination of heating rate of 20 ℃/minute is preferably 260 ℃ to 300 ℃.More preferably 270 ℃ to 300 ℃ of endotherm peak temperature Tm, more preferably 280 ℃ to 300 ℃.The temperature T m of endotherm(ic)peak is during lower than 260 ℃, and the thermotolerance of polymkeric substance may reduce, and can't obtain practical application at the applied at elevated temperature environment.On the other hand, during high 300 ℃ of the temperature of endotherm(ic)peak, corresponding processing temperature is higher, and it may cause polymkeric substance, in the course of processing, decomposed can occur, and will reduce its mechanical property.
The polymeric amide crystallization velocity obtained by the present invention: described polyamide resin is counted by differential scanning heat under inert gas atmosphere, cool to from molten state the exothermic peak temperature Tc occurred 30 ℃ of processes with the cooling rates of 20 ℃/minute, then the endotherm peak temperature Tm to occur in the heat-up rate temperature-rise period of 20 ℃/minute, preferably 20 ℃～45 ℃ of the temperature difference (Tm-Tc) scopes between exothermic peak temperature Tc and endotherm peak temperature Tm.Further preferably 25 ℃～40 ℃, if Tm-Tc lower than 20 ℃, Tc is high, may easily form crystal grain excessive, causes its mechanical property variation that becomes fragile.If Tm-Tc is higher than 45 ℃, crystallization velocity may descend.
The crystallinity of the polyamide resin that the present invention obtains: described polyamide resin is counted by differential scanning heat under inert gas atmosphere, cool to 30 ℃ with the cooling rates of 20 ℃/minute from molten state, in situation about then heating up with the heat-up rate of 20 ℃/minute, more than the heat of the endotherm(ic)peak of appearance is preferably 50J/g.Further preferred 55J/g, more preferably 60J/g.If be less than 50J/g, its unisexuality modulus, intensity all may descend.
The melting anelasticity feature of the polymeric amide obtained by the present invention is: the sulphuric acid soln relative viscosity while at the temperature of high 20 ℃ than fusing point, being detained 30 minutes is made as Y, when the sulfuric acid relative viscosity before being detained is made as X, Y/X is preferably 0.85～1.40, further preferably 0.85～1.30, more preferably 0.90～1.20.If Y/X is lower than 0.85, the resin in the 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 the melt-processed process may have obvious viscosity to increase, and will increase the machine-shaping difficulty.
Polyamide resin in the present invention has following characteristics: 25 ℃ of saturated water absorptions are preferably below 4.0%.Further preferably below 0.35%.
The present invention is not particularly limited for the preparation method of above-mentioned polyamide resin, can use above-mentioned 1,5-pentamethylene diamine, 1, straight chain aliphatie diamine, oxalic acid that beyond the 5-pentamethylene diamine, carbonatoms is 4～18.30～95mol% of the total amount that wherein, (1) 1,5-pentamethylene diamine content is (1) and (2).Above-mentioned raw materials is added in the general reactor with prolong, use 1,5-pentamethylene diamine, 1, the straight chain aliphatie diamine that beyond the 5-pentamethylene diamine, carbonatoms is 4～18 and oxalic acid all soluble solvent mix it, and are replaced with nitrogen.Then starting the temperature that stirring heating is warmed up to solvent refluxing is reacted.As the equal soluble solvent of diamines and oxalic acid, be not particularly limited, can use toluene, dimethylbenzene, trichlorobenzene, phenol or trifluoroethanol etc., can be preferably toluene.The prepolymer obtained carries out drying.This prepolymer slowly is warming up to the above temperature of fusing point at reactor under normal pressure, all after melting, start the polymerization of reducing pressure, final pressure is 1000～20Pa, or this prepolymer being carried out at its 20 ℃～70 ℃ temperature below fusing point to the decompression solid state polymerization of 0.5～30 hour, final pressure is 300～20Pa.
Add thermal polycondensation at polyamide resin, owing at high temperature carrying out polyreaction, thereby the straight chain aliphatie diamine based on short carbon chain is from volatilization in polymerization system or make the reason such as lower boiling product volatilization by deamination reaction, carrying out along with polymerization, in polymerization system, total amino amount may reduce with respect to total barkite content, therefore, in the stage that adds raw material, excessively adding in advance the straight chain aliphatie diamine of the short carbon chain of specified quantitative and control the amino amount in polymerization system, is preferred for the polyamide resin that synthesizes high molecular.When the mole number of the short carbon chain straight chain aliphatie diamine that will use as raw material is made as a, when the mole number of oxalate diester is made as to b, preferably the raw material ratio of components being adjusted to a/b is 1.003～1.10, more preferably the raw material ratio of components being adjusted to it is 1.008～1.08 than a/b, more preferably 1.01～1.05.If a/b is less than 1.003, the total amino amount in polymeric system is relative few with total barkite, 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 barkite, is difficult to obtain the polymkeric substance of high molecular.
Can also add as required various additives in polyamide resin preparation of the present invention, for example one or more in antioxidant, thermo-stabilizer, weather resisting agent, releasing agent or lubricant, pigment, dyestuff, softening agent, static inhibitor, fire retardant, inorganic filler or other polymkeric substance.Specifically, antioxidant and thermostability are hindered phenol system, quinhydrones system, phosphorous acid ester system or their replacement body, copper halide or iodine compound etc.; 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 the 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.; The composition that fire retardant is 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.; The well known materials of inorganic filler for generally using as resin extender, for example: graphite, barium sulfate, sal epsom, calcium carbonate, magnesiumcarbonate, weisspiessglanz, titanium oxide, aluminum oxide, zinc oxide, ferric oxide, zinc sulphide, zinc, nickel, aluminium, copper, iron, steel, glass fibre, carbon fiber, potassium titanate crystal whisker, aluminium borate whisker, silicon carbide fiber, ceramic fiber, fibrous magnesium silicate, wollastonite, silico-aluminate also have the inorganic nucleators such as talcum, wilkinite, polynite, mica titanium dioxide, silicon-dioxide, aluminium sesquioxide, magnesiumcarbonate, silicate in addition.For some layered silicates, can adopt organic ammonium salt that interlayer ion is carried out to the organic montmorillonoid 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 polyamide resin can significantly reduce, and in addition, if particle diameter is greater than 10 μ m, the products formed appearance has the tendency of variation.Other polymkeric substance are that polymeric amide, polyethylene, polyphenyl are rare, polyester, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystalline polymers, ABS resin, SAN resin or polystyrene etc.
Polyamide resin of the present invention, or the composition that contains 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 resins such as trolley part, mechanical part, fiber or film etc.Concrete purposes: automobile engine cooling water based part, the parts that contact with water coolant in particularly pump parts such as the radiator water box parts such as the top of radiator tank and bottom, cooling fluid reserve tank, water pipe, water pump shell, water pump impeller, valve etc., and 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, the 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, the suction tracheae, bearing retainer, electric wire optical cable coating layer, or fiber-optic cable oversheath etc. is the electrical and electronic parts of representative, the automobile associated components, the 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 measure by the following method.
(1) sulfuric acid relative viscosity:
Measure the relative viscosity that concentration is the 0.01g/ml polymeric amide in 96% vitriol oil of 25 ℃.
(2) thermal property:
Adopt TA DSC-Q100 analytical instrument, get about 5mg sample, test condition is as follows: under nitrogen atmosphere, the gained polyamide resin is warmed up to than the temperature of high 30 ℃ of fusing point, at the temperature of high 30 ℃ than fusing point, keep 2 minutes, the temperature T c of the exothermic peak observed while then with the cooling rate of 20 ℃/minute, dropping to 30 ℃ keeps 2 minutes under 30 ℃.Temperature T m and the heat Δ Hm of the endotherm(ic)peak observed while next, being warmed up to than the temperature of high 30 ℃ of fusing point with the heat-up rate of 20 ℃/minute.
(3) be detained stability
Under nitrogen atmosphere, be heated at the temperature of above 20 ℃ of fusing point the sample that keeps after 30 minutes and be dissolved in test its relative viscosity (Y) in 96% sulfuric acid 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 viscosity.
(4) 25 ℃ of saturated rate of moisture absorption:
By polymkeric substance hot pressing film forming at the temperature of high 20 ℃ than fusing point, and promptly cooling in frozen water, and thickness of sample is 0.2mm (50mm*50mm).Sample is immersed in the water of 25 ℃ to constant weight, and weighing.Then sample is dried to constant weight at 120 ℃.Calculate the weight ratio (%) of dry front and back.
Be called for short explanation:
DA4:1,4-butanediamine DA5:1,5-pentamethylene diamine, M-DA5:2-methyl isophthalic acid, 5 pentamethylene diamines, DA6:1,6-hexanediamine, DA9:1,9-nonamethylene diamine, M-DA8:2-methyl isophthalic acid, 8 octamethylenediamines, DA10:1,10-decamethylene diamine, DA14:1,14-tetradecyl diamines, DA18:1,18-octadecyl diamines, DA20:1,20-eicosyl diamines, DBO: dibutyl oxalate, DEO: oxalic acid diethyl ester, AA: hexanodioic acid, DC10:1,10-sebacic acid.
DA4: purity is 98%, purchased from Sigma-Aldrich company.
DA5: purity is 98%, purchased from TCI company.
M-DA5: purity is 98%, purchased from TCI company.
DA6: purity is 98%, purchased from Sigma-Aldrich company.
DA9: purity is 98%, purchased from Sigma-Aldrich company.
M-DA8: purity is 98%, purchased from Sigma-Aldrich company.
DA10: purity is 98%, purchased from Wuxi company of Xingda.
DA14: purity is 98%, purchased from Sigma-Aldrich company.
DA18: purity is 98%, purchased from Sigma-Aldrich company.
DA20: purity is 98%, purchased from Sigma-Aldrich company.
DBO: purity is 99%, purchased from Sigma-Aldrich company.
DEO: purity is 99%, purchased from Sigma-Aldrich company.
AA: analytical pure, purchased from Aladdin company.
DC10: analytical pure, purchased from Aladdin company.
Embodiment 1
Add 20.80g (0.204mol) 1 in the 500ml three-necked flask, the 5-pentamethylene diamine, 1.25g (0.0107mol) 1, the 6-hexanediamine, 150ml toluene, stir and be warming up to 50 ℃ after nitrogen purging.After all dissolving, diamines adds 42.53g (0.2105mol) dibutyl oxalate.Then under agitation be warming up to 130 ℃, with this condition, continue back flow reaction 5 hours, filter, washing, drying obtain the prepolymer that relative viscosity is 1.3.
The about 5g of gained prepolymer is fed in the glass reaction test tube that diameter is 22mm, by under the decompression remained in reaction tubes below 50Pa, then repeatedly carry out the normal pressure that is operated to of 5 these importing nitrogen, then under nitrogen gas stream, be placed in the metal bath of 280 ℃, be decompressed to below 60Pa with 20 minutes, then make its reaction 5 hours.
Embodiment 2
Repeat embodiment 1, different is that (1) DA5 unit is 80: 20 with the mol ratio of (2) DA6 unit, the results are shown in table one.
Embodiment 3
The preparation method of prepolymer repeats embodiment 1, and different is that (1) DA5 unit is 65: 35 with the mol ratio of (2) DA6 unit,
The gained prepolymer is fed in the glass reaction test tube that diameter with stirring is 50mm, by under the decompression remained in reaction tubes below 50Pa, then repeatedly carry out the normal pressure that is operated to of 5 these importing nitrogen, then be warming up to heating and melting in 295 ℃ of oil baths under nitrogen gas stream, after melting, with 1 hour, be decompressed to below 60Pa fully, then make its reaction 2 hours.Then import nitrogen to normal pressure, take out from oil bath, under nitrogen gas stream, be cooled to room temperature, obtain as tough and tensile polyamide polymer.
Various physical property to the gained polyamide resin are estimated, and acquired results as shown in Table 1.
Embodiment 4
Repeat embodiment 3, different is that (1) DA5 unit is 50: 50 with the mol ratio of (2) DA6 unit, the results are shown in table one
Embodiment 5
Repeat embodiment 1, different is that (1) DA5 unit is 30: 70 with the mol ratio of (2) DA6 unit, the results are shown in table one.
Embodiment 6
Repeat embodiment 3, different is that (1) DA5 unit is 81.6: 20 with the mol ratio of (2) DA10 unit, the results are shown in table one.
Embodiment 7
Repeat embodiment 3, different is that (1) DA10 unit is 81.6: 20 with the mol ratio of (2) DA14 unit, the results are shown in table one.
Embodiment 8
Repeat embodiment 3, different is that (1) DA5 unit is to the results are shown in table one at 81.6: 20 with the mol ratio of (2) DA18 unit.
Embodiment 9
Repeat embodiment 1, different is that (1) DA5 unit is 80: 20 with the mol ratio of (2) DA6 unit, and (3) unit is DEO, the results are shown in table one.
Comparative example 1
Repeat embodiment 1, different is that (1) unit is DA5, the results are shown in table two.
Comparative example 2
Repeat embodiment 1, different is that (1) DA5 unit is 15: 85 with the mol ratio of (2) DA6 unit: the results are shown in table two.
Comparative example 3
Repeat embodiment 1, different is that (1) DA4 unit is 80: 20 with the mol ratio of (2) DA6 unit, the results are shown in table two.
Comparative example 4
Repeat embodiment 3, different is that (1) DA5 unit is 81.6: 20 with the mol ratio of (2) DA20 unit, the results are shown in table two.
Comparative example 5
Repeat embodiment 3, different is that (1) DA5 unit is 80: 20 with the mol ratio of (2) DA6 unit,, the diprotic acid unit is hexanodioic acid, the results are shown in table two.
Comparative example 6
Repeat embodiment 3, different is that (1) DA5 unit is sebacic acid with diprotic acid unit, (2) DA6 unit, the results are shown in table two.
Comparative example 7
Repeat embodiment 1, that different is (1) cells D A5, and (2) unit is M-DA5, the results are shown in table two.
Comparative example 8
Repeat embodiment 1, that different is (1) cells D A6, and (2) unit is M-DA5, the results are shown in table two.
Comparative example 9
Repeat embodiment 3, that different is (1) cells D A9, and (2) unit is M-DA8, the results are shown in table two.
Claims (11)
1. a polyamide resin, it is characterized in that: this polyamide resin contains:
(1) 1,5-pentamethylene diamine unit,
The straight chain aliphatie diamine unit that beyond (2) 1,5-pentamethylene diamine unit, carbonatoms is 4～18,
(3) oxalic acid unit;
30～95mol% of the total amount that wherein, (1) 1,5-pentamethylene diamine unit content is (1) and (2) unit.
2. polyamide resin according to claim 1, it is characterized in that: described (2) 1, the straight chain aliphatie diamine unit that beyond 5-pentamethylene diamine unit, carbonatoms is 4～18 is selected from 1, 4-butanediamine unit, 1, 6-hexanediamine unit, 1, 7-heptamethylene diamine unit, 1, 8-octamethylenediamine unit, 1, 9-nonamethylene diamine unit, 1, 11-undecane two amine units, 1, 12-dodecane two amine units, 1, 13-tridecane two amine units, 1, the 14-tetradecane two amine units, 1, 15-pentadecane two amine units, 1, 16-n-Hexadecane two amine units, 1, 17-heptadecane two amine units, or 1, one or more in 18-octadecamethylene diamine unit.
3. polyamide resin according to claim 1, it is characterized in that: described (3) oxalic acid unit comes from oxalate diester, is selected from 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.
4. polyamide resin according to claim 1, it is characterized in that: take 96% sulfuric acid as solvent, the relative viscosity that the polyamide resin lipoprotein solution that working concentration is 0.01g/ml is measured under 25 ℃ is 1.6～6.0.
5. polyamide resin according to claim 1, it is characterized in that: described polyamide resin is counted by differential scanning heat under inert gas atmosphere, drop to 30 ℃ with the cooling rates of 20 ℃/minute from molten state, the endotherm peak temperature Tm occurred of then take in the temperature-rise period of determination of heating rate of 20 ℃/minute is 260 ℃ to 300 ℃.
6. polyamide resin according to claim 1, it is characterized in that: described polyamide resin is counted by differential scanning heat under inert gas atmosphere, cool to from molten state the exothermic peak temperature Tc occurred 30 ℃ of processes with the cooling rates of 20 ℃/minute, then the endotherm peak temperature Tm to occur in the heat-up rate temperature-rise period of 20 ℃/minute, the temperature difference (Tm-Tc) scope between exothermic peak temperature Tc and endotherm peak temperature Tm is 20 ℃～45 ℃.
7. polyamide resin according to claim 1, it is characterized in that: described polyamide resin is counted by differential scanning heat under inert gas atmosphere, cool to 30 ℃ with the cooling rates of 20 ℃/minute from molten state, in situation about then heating up with the heat-up rate of 20 ℃/minute, the heat Δ Hm of the endotherm(ic)peak of appearance is more than 50J/g.
8. polyamide resin according to claim 1 is characterized in that: the sulphuric acid soln relative viscosity while at the temperature of high 20 ℃ than fusing point, being detained 30 minutes is made as Y, and when the sulfuric acid relative viscosity before being detained is made as X, Y/X is 0.85～1.40.
9. according to claim 1 a described polyamide resin, it is characterized in that: 25 ℃ of saturated water absorptions of described polyamide resin are below 4.0%.
10. the application of the described polyamide resin of any one in preparing molding in a claim 1～9.
11., according to claim 11 a described polyamide resin molding product, it is characterized in that: a kind of in trolley part, mechanical part, fiber or film.
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| CN106008963A (en) * | 2016-06-29 | 2016-10-12 | 东华大学 | Polyoxamide powder and preparation method thereof |
| CN106220845A (en) * | 2016-07-26 | 2016-12-14 | 广东新会美达锦纶股份有限公司 | A kind of polyoxamide powder and preparation method thereof |
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