CN103539937B - The application of a kind of polyamide, its synthetic method and this polyamide - Google Patents
The application of a kind of polyamide, its synthetic method and this polyamide Download PDFInfo
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- CN103539937B CN103539937B CN201210227190.1A CN201210227190A CN103539937B CN 103539937 B CN103539937 B CN 103539937B CN 201210227190 A CN201210227190 A CN 201210227190A CN 103539937 B CN103539937 B CN 103539937B
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Abstract
The invention discloses the application of a kind of polyamide, its synthetic method and this polyamide. Synthetic method of the present invention comprises 1) reinforced: terephthalic acid monomers, hexamethylene diamine monomer, nylon salt and other reaction promoters are joined in reactor in proportion; 2) inflation: be filled with protection gas in reactor, the pressure in reactor is added to 0.2-1.0MPa, contain CO in wherein said protection gas2，CO2The volume content that accounts for described protection gas is 50-100%; 3) pre-polymerization: heating reactor, makes the mixture in reactor carry out prepolymerization reaction. The polyamide making by synthetic method of the present invention, is not easy flavescence, and color characteristics is good. Polyamide disclosed by the invention is mainly used in material, automobile component, office appliance or the house articles for use for manufacture of Electrical and Electronic equipment.
Description
Technical field
The present invention relates to the synthetic field of polyamide, particularly answering of a kind of polyamide, its synthetic method and this polyamideWith.
Background technology
Polyamide, because having good combination property, comprises mechanical property, heat resistance, mar proof, chemical proofingAnd self lubricity, and coefficient of friction is low, has certain anti-flammability, is easy to processing etc., it is extensively suitable for glass fibre and itsIts filler filling enhancing modified, improves performance and expands range of application. Semiaromatic polyamide composition was due to its heat resistance in recent yearsCan and mechanical property more excellent and by focus development.
At present, prepare polyamide comparatively usual way be, first by the monomer of semiaromatic binary acid and diaminesWith water mix after under inert gas state, carry out prepolymerization, then the prepolymer obtaining is carried out solid-phase tack producing reaction orThe reaction of melting tackify. Because fusing point and the decomposition temperature of polyamide are comparatively approaching, under the hot conditions when synthetic, be very easy toFlavescence, the polyamide after flavescence has certain limitation in application, therefore the anti-yellowing change of polyamide research become one importantProblem.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of synthetic method of polyamide.
Further, be also necessary to provide a kind of polyamide.
Further, be also necessary to provide a kind of application of polyamide.
A synthetic method for polyamide, is characterized in that, comprises the following steps,
Reinforced: terephthalic acid monomers, hexamethylene diamine monomer, nylon salt and other reaction promoters are joined to reaction in proportionIn still;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas2，CO2Account for the body of described protection gasLong-pending content is 50-100%;
Pre-polymerization: heating reactor, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, prepolymerization reaction completes after discharging, after described prepolymer product is dried, carries out solid-phase tack producing, obtains polyamidesAmine.
Wherein, in described aeration step, the pressure in reactor is added to 0.2-0.3MPa, 0.3-0.6MPa or 0.6-1.0MPa。
Wherein, CO2The volume ratio that accounts for described protection gas is 50-60% or 60-100%.
Wherein, described protection gas also comprises nitrogen and/or argon gas, also can comprise the inert gas that other is conventional.
Wherein, before described aeration step, also comprise steps A: reactor is vacuumized, be then filled with protection gas to normal pressure,Described steps A repeats at least twice. Preferably in triplicate, the benefit of this step is for oxygen residual in emptying reactorGas.
Wherein, it is preferred that described nylon salt accounts for the ratio of described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amount10-50mol%.
Wherein, it is more excellent that described nylon salt accounts for the ratio of described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amountChoosing is 20-40mol%.
Wherein, described nylon salt comprises hexamethylene diamine adipate (nylon salt), hexamethylene diamine sebacate, hexamethylene diamine 12At least one in diacid salt, hexamethylene diamine 13 diacid salt, hexamethylene diamine 14 diacid salt and hexamethylene diamine 16 diacid salt.
Wherein, described prepolymerization reaction is under agitation to heat reactor, and heating reactor is to 210-220 DEG C, 220-250 DEG COr 250-260 DEG C, carry out prepolymerization reaction 1-3 hour.
A kind of polyamide is that raw material prepares through processing with the prepared product of above-mentioned method.
Wherein, described polyamide is injection molded into after colour table, the GanzWhiteness value recording more than 70, its method of testing referenceASTME313-2010, described colour table is after infrared reflow soldering, and the GanzWhiteness value recording is more than 34.
An application for polyamide, described polyamide is applied to the manufacture material of Electrical and Electronic equipment, automobile component,Office appliance or at home articles for use.
The synthetic method of polyamide of the present invention, is partly or entirely used CO in the pre-polymerization stage2As prepolymerization reactionThe protection gas in stage. Due to CO2With respect to N2Larger density, molecular weight and the dissolubility in water, can better get rid ofIn reactor and be dissolved in the O in water2Thereby, reduce the same O of amido link2The chance of contact, and then effectively prevent the face of prepolymerLook flavescence. The color of good prepolymer is the guarantee of good polymer color equally, has effectively prevented the flavescence of polyamide,The whiteness value of the prepared polyamide of the present invention is higher than not using CO2The product obtaining as the synthetic method of protection gas.
Detailed description of the invention
The invention discloses a kind of synthetic method of polyamide, better with the polyamide color characteristics that this kind of method is synthetic,Not obviously flavescence.
A synthetic method for polyamide, is characterized in that, comprises the following steps,
Reinforced: terephthalic acid monomers, hexamethylene diamine monomer, nylon salt and other reaction promoters are joined to reaction in proportionIn still;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas2，CO2Account for the body of described protection gasLong-pending content is 50-100%;
Pre-polymerization: heating reactor, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, prepolymerization reaction completes after discharging, after described prepolymer product is dried, carries out solid-phase tack producing, obtains polyamidesAmine.
Wherein, in described aeration step, the pressure in reactor is added to 0.2-0.3MPa, 0.3-0.6MPa or 0.6-1.0MPa。
Wherein, CO2The volume ratio that accounts for described protection gas is 50-60% or 60-100%.
Wherein, described protection gas also comprises nitrogen and/or argon gas, also can comprise the inert gas that other is conventional.
Wherein, before described aeration step, also comprise steps A: reactor is vacuumized, be then filled with protection gas to normal pressure,Described steps A repeats at least twice. Preferably in triplicate, the benefit of this step is for oxygen residual in emptying reactorGas.
Wherein, it is preferred that described nylon salt accounts for the ratio of described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amount10-50mol%.
Wherein, it is more excellent that described nylon salt accounts for the ratio of described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amountChoosing is 20-40mol%.
Wherein, described nylon salt comprises hexamethylene diamine adipate (nylon salt), hexamethylene diamine sebacate, hexamethylene diamine 12At least one in diacid salt, hexamethylene diamine 13 diacid salt, hexamethylene diamine 14 diacid salt and hexamethylene diamine 16 diacid salt.
Wherein, described prepolymerization reaction is under agitation to heat reactor, and heating reactor is to 210-220 DEG C, 220-250 DEG COr 250-260 DEG C, carry out prepolymerization reaction 1-3 hour.
A kind of polyamide is that raw material prepares through processing with the prepared product of above-mentioned method.
Wherein, described polyamide is injection molded into after colour table, the GanzWhiteness value recording more than 70, its method of testing referenceASTME313-2010, described colour table is after infrared reflow soldering, and the GanzWhiteness value recording is more than 34.
An application for polyamide, described polyamide is applied to the manufacture material of Electrical and Electronic equipment, automobile component,Office appliance or at home articles for use.
Test respectively the relative viscosity of gained prepolymer product and polyamide, its method of testing is with reference to man of the People's Republic of China (PRC)Standard GB12006.1-89, polyamide viscosity number assay method.
Concrete method of testing for measuring the polyamide that concentration is 0.25g/dl in 98% the concentrated sulfuric acid of 25 ± 0.01 DEG CRelative viscosity ηr. Adopt the NCY-2 automatic viscometer that Shanghai Si Erda scientific instrument Co., Ltd produces to measure.
The fusing point of test gained prepolymer product and polyamide, its method of testing is with reference to ASTMD3418-2003, StandardTestMethodforTransitionTemperaturesofPolymersByDifferentialScanningCalorimetry。
Concrete grammar is the fusing point that adopts PerkinElmerDimondDSC analyzer test sample. Nitrogen atmosphere, streamSpeed is 40mL/min. When test, be first warming up to 340 DEG C with 10 DEG C/min, keep 2min at 340 DEG C, then cooling with 10 DEG C/minTo 50 DEG C, then be warming up to 340 DEG C with 10 DEG C/min, endotherm peak temperature is now made as to fusing point Tm。
Whiteness value (the W of test gained prepolymer productpre) and Gan Ci (GANZ) whiteness value of polyamide, its method of testing ginsengAccording to ASTME313-2010, StandardPracticeforCalculatingYellownessandWhitenessIndicesfromInstrumentallyMeasuredColorCoordinates。
The whiteness value of prepolymer product is the whiteness of measuring powder after directly prepolyer granule being pulverized. Polyamide whiteThe measurement of degree value is that polyamide is injection molded into after colour table, uses the precious LIBEROX-ritecolor-Eye7000A colour examining of reasonInstrument carries out color measurement. Record its GanzWhiteness value WI1 and represent, this colour table, after infrared reflow soldering, is surveyed againMeasure its GanzWhiteness value WI2 and represent, WI1 and WI2 the results are shown in table.
Below in conjunction with specific embodiments the present invention is further detailed, it should be noted that, following enforcementReaction temperature in example and reaction time are examples of protection domain of the presently claimed invention, and other is protected in the present inventionScope in reaction temperature be applicable to too the present invention, will not enumerate at this.
What the nylon salt adding in following embodiment was chosen is nylon 66-salt, adopts the Buddhist nun of cited other of the present inventionDragon salt is applicable to the present invention too, is not enumerating at this.
What the reaction promoter adding in following embodiment was chosen at this is sodium hypophosphite, and with its preferred content, adoptsThe reaction promoter of cited other of the present invention and other interpolation scope are also applicable to the present invention, are not enumerating at this.
Embodiment 1
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.2MPa. Under agitation 2In individual hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature liter of reactantHigh to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterKeep constant pressure, react rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described in advancePoly-product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 2
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite,,After vacuumizing, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.3MPa. Under agitationIn 2 hours, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature of reactantBe elevated to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterAnd maintenance constant pressure has reacted rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described inPrepolymer product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 3
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.6MPa. Under agitation 2In individual hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature liter of reactantHigh to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterKeep constant pressure, react rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described in advancePoly-product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 4
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 1MPa. Under agitation 2In hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature of reactant raiseTo 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, protects by removing formed waterHold constant pressure, reacted rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described pre-polymerizationProduct solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Comparative example 1
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fills N2Pressure to reactor is 0.3MPa. In under agitation 2 hours, be warmed up to 220 DEG C, reactant mixture is existed220 DEG C are stirred 1 hour, then under agitation make the temperature of reactant be elevated to 230 DEG C. Reaction at the constant temperature of 230 DEG C andUnder the constant voltage of 2.2MPa, proceed 2 hours, keep constant pressure by removing formed water, reacted rear discharging,Prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, and described prepolymer product is under 250 DEG C, 50kPa vacuum conditionSolid-phase tack producing 10 hours, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 5
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill CO2Three times, finally by CO2Pressure rises to 0.3MPa. In under agitation 2 hours, be warmed up to 220 DEG C, will react mixingThing stirs 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C. Reaction at the constant temperature of 230 DEG C andUnder the constant voltage of 2.2MPa, proceed 2 hours, keep constant pressure by removing formed water, reacted rear discharging,Prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, and described prepolymer product is under 250 DEG C, 50Pa vacuum conditionSolid-phase tack producing 10 hours, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 6
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill CO2Three times, finally fill CO2After pressure rises to 0.2MPa, then be filled with wherein high-purity N2Rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make reactionThe temperature of thing is elevated to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removingThe water forming and keep constant pressure, react rear discharging, and prepolymer vacuum drying 24 hours at 80 DEG C, obtains pre-polymerization productThing, described prepolymer product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 7
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill CO2Three times, finally fill CO2After pressure rises to 0.18MPa, then be filled with wherein high-purity N2Rise to pressure0.3MPa. In under agitation 2 hours, be warmed up to 220 DEG C, reactant mixture stirred 1 hour at 220 DEG C, then under agitationMake the temperature of reactant be elevated to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, passes throughRemove formed water and keep constant pressure. Reacted rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtainsPrepolymer product, prepolymer product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 8
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill CO2Three times, finally fill CO2After pressure rises to 0.15MPa, then be filled with wherein high-purity N2Rise to pressure0.3MPa. In under agitation 2 hours, be warmed up to 220 DEG C, reactant mixture stirred 1 hour at 220 DEG C, then under agitationMake the temperature of reactant be elevated to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, passes throughRemove formed water and keep constant pressure. Reacted rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtainsPrepolymer product, prepolymer product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 9
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill CO2Three times, finally fill CO2After pressure rises to 0.1MPa, then be filled with wherein high-purity N2Rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make reactionThe temperature of thing is elevated to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removingForm water and keep constant pressure. Reacted rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains pre-polymerization and producesThing, prepolymer product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Comparative example 2
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 17.5mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outVacuum, fill N2Three times, last high-purity N2Rise to 0.3MPa to pressure. In under agitation 2 hours, be warmed up to 220 DEG C, will react mixedCompound stirs 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C. React the constant temperature at 230 DEG CWith under the constant voltage of 2.2MPa, proceed 2 hours, keep constant pressure by removing formed water. After having reacted, go outMaterial, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, and prepolymer product is solid under 250 DEG C, 50Pa vacuum conditionPhase tackify 10 hours, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 10
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 10.2mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.3MPa. Under agitation 2In individual hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature liter of reactantHigh to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterKeep constant pressure, react rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described in advancePoly-product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 11
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 27.2mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.3MPa. Under agitation 2In individual hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature liter of reactantHigh to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterKeep constant pressure, react rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described in advancePoly-product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
Embodiment 12
In the autoclave pressure of being furnished with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth, add 20mol1 of terephthalic acid (TPA), 20.8mol, 6-hexamethylene diamine, 40.8mol nylon salt, 134.5g benzoic acid, 10.15g sodium hypophosphite, take outAfter vacuum, fill CO2To normal pressure, after repeating to vacuumize, fill CO2Process three times, finally by CO2Pressure rises to 0.3MPa. Under agitation 2In individual hour, be warmed up to 220 DEG C, reactant mixture is stirred 1 hour at 220 DEG C, then under agitation make the temperature liter of reactantHigh to 230 DEG C. Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, by removing formed waterKeep constant pressure, react rear discharging, prepolymer vacuum drying 24 hours at 80 DEG C, obtains prepolymer product, described in advancePoly-product solid-phase tack producing 10 hours under 250 DEG C, 50Pa vacuum condition, obtains polyamide.
According to above-mentioned method of testing, prepolymer product and polyamide are detected, it the results are shown in table.
The test result of table 1 embodiment 1-4 and comparative example 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Terephthalic acid (TPA)/mol | 20 | 20 | 20 | 20 | 20 |
| 1,6-hexamethylene diamine/mol | 20.8 | 20.8 | 20.8 | 20.8 | 20.8 |
| Nylon salt/mol | 17.5 | 17.5 | 17.5 | 17.5 | 17.5 |
| CO2Pressure/MPa | 0.2 | 0.3 | 0.6 | 1 | 0 |
| N2Pressure/MPa | 0 | 0 | 0 | 0 | 0.3 |
| Prepolymer whiteness value Wpre | 85.6 | 86.2 | 87.3 | 87.4 | 80.8 |
| Melting point polymer Tm/℃ | 304 | 305 | 305 | 305 | 304 |
| Polymer relative viscosity | 2.235 | 2.241 | 2.233 | 2.240 | 2.238 |
| Polymer WI1 | 70.3 | 70.9 | 71.2 | 71.1 | 60.1 |
| Polymer WI2 | 44.0 | 44.3 | 44.8 | 45.1 | 28.2 |
The test result of table 2 embodiment 5-9 and comparative example 2
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 2 | |
| Terephthalic acid (TPA)/mol | 20 | 20 | 20 | 20 | 20 | 20 |
| 1,6-hexamethylene diamine/mol | 20.8 | 20.8 | 20.8 | 20.8 | 20.8 | 20.8 |
| Nylon salt/mol | 17.5 | 17.5 | 17.5 | 17.5 | 17.5 | 17.5 |
| CO2Volume content | 100 | 66.7% | 60% | 50% | 33.3% | 0 |
| Pressure/the MPa of protection gas | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Prepolymer whiteness value Wpre | 86.0 | 85.4 | 84.8 | 84.1 | 82.6 | 80.9 |
| Melting point polymer Tm/℃ | 304 | 304 | 305 | 304 | 305 | 305 |
| Polymer relative viscosity | 2.239 | 2.235 | 2.241 | 2.240 | 2.236 | 2.238 |
| Polymer WI1 | 71.2 | 70.3 | 69.5 | 68.2 | 66.5 | 60.3 |
| Polymer WI2 | 45.1 | 44.2 | 43.1 | 41.8 | 40.9 | 32.1 |
The test result of table 3 embodiment 2,10-12
| Embodiment 10 | Embodiment 2 | Embodiment 11 | Embodiment 12 | |
| Terephthalic acid (TPA)/mol | 20 | 20 | 20 | 20 |
| 1,6-hexamethylene diamine/mol | 20.8 | 20.8 | 20.8 | 20.8 |
| Nylon salt/mol | 10.2 | 17.5 | 27.2 | 40.8 |
| Pressure/the MPa of protection gas | 0.3 | 0.3 | 0.3 | 0.3 |
| Prepolymer whiteness value Wpre | 86.6 | 86 | 84.9 | 83.5 |
| Melting point polymer Tm/℃ | 328 | 304 | 285 | 267 |
| Polymer relative viscosity | 2.259 | 2.238 | 2.239 | 2.243 |
| Polymer WI1 | 68.6 | 70.5 | 68.6 | 68.1 7 --> |
| Polymer WI2 | 37.3 | 38.2 | 35.3 | 34.6 |
Testing result comparison from table 1 to table 3 can be found at the pre-polymerization stage of polyamide CO2While making protection gas,To prepolymer product and the whiteness value of polyamide have raising clearly, and along with containing CO2The force value of protection gas larger,The whiteness value of prepolymer product and polyamide is just larger, in the time that protection gas also comprises other gas, and CO2Volume content is larger, pre-polymerizationThe whiteness value of product and polyamide is just larger.
Polyamide of the present invention is applied to the manufacture material of Electrical and Electronic equipment, automobile component, office appliance orArticles for use at home.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, everyly utilize thisThe equivalent transformation that bright description is done, or be directly or indirectly used in other relevant technical fields, be all in like manner included inIn scope of patent protection of the present invention.
Claims (9)
1. a method that improves polyamide whiteness, is characterized in that, in building-up process, adopts and contains CO2Protection gas, synthesizedJourney comprises the following steps:
Reinforced: terephthalic acid monomers, hexamethylene diamine monomer, nylon salt and other reaction promoters are joined to reactor in proportionIn;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas2，CO2The volume that accounts for described protection gas containsAmount be 50 ?60% or 60 ?100%;
Pre-polymerization: heating reactor, makes the mixture in reactor carry out prepolymerization reaction;
Prepolymerization reaction completes after discharging, after described prepolymer product is dried, carries out solid-phase tack producing, obtains polyamide.
2. method according to claim 1, is characterized in that:
In described aeration step, by the pressure in reactor add to 0.2 ?0.3MPa, 0.3 ?0.6MPa or 0.6 ?1.0MPa.
3. method according to claim 1, is characterized in that:
Described protection gas also comprises nitrogen and/or argon gas.
4. method according to claim 1, is characterized in that:
Before described aeration step, also comprise steps A: reactor is vacuumized, be then filled with protection gas to normal pressure, described steps ARepeat at least twice.
5. method according to claim 1, is characterized in that:
The ratio that described nylon salt accounts for described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amount be 10 ?50mol%.
6. method according to claim 1, is characterized in that:
The ratio that described nylon salt accounts for described terephthalic acid monomers, hexamethylene diamine monomer and nylon salt total amount be 20 ?40mol%.
7. method according to claim 1, is characterized in that:
Described nylon salt comprises hexamethylene diamine adipate, hexamethylene diamine sebacate, hexamethylene diamine 12 diacid salt, hexamethylene diamine 13At least one in hydrochlorate, hexamethylene diamine 14 diacid salt and hexamethylene diamine 16 diacid salt.
8. method according to claim 1, is characterized in that:
Described prepolymerization reaction is under agitation to heat reactor, heating reactor to 210 ?220 DEG C, 220 ?250 DEG C or 250 ?260DEG C, carry out prepolymerization reaction 1 ?3 hours.
9. method according to claim 1, is characterized in that:
The polyamide obtaining is injection molded into after colour table, and the GanzWhiteness value recording is more than 70, and its method of testing is with reference to ASTME313 ?2010, described colour table is after infrared reflow soldering, the GanzWhiteness value recording is more than 34.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202961A (en) * | 1977-10-28 | 1980-05-13 | Ciba-Geigy Corporation | Transparent polyamide from aromatic dicarboxylic acid and disubstituted decane diamine |
| CN87104650A (en) * | 1986-07-08 | 1988-01-20 | 罗纳·布朗克化学公司 | With hexamethylene diamine, hexanodioic acid also selects for use at least a other short-chain dicarboxylic acid and dimeracid to prepare the method for copolyamide |
| CN101372531A (en) * | 2008-10-17 | 2009-02-25 | 华南理工大学 | Transparent co-polyamide and preparation thereof |
| CN101768266A (en) * | 2009-12-25 | 2010-07-07 | 郑州大学 | Method for preparing semi-aromatic nylon |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1084324A (en) * | 1965-06-23 | |||
| JPS4999698A (en) * | 1973-01-29 | 1974-09-20 | ||
| JPH07228695A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Production of new polyamide |
| JP3499066B2 (en) * | 1995-10-06 | 2004-02-23 | ローランドディー．ジー．株式会社 | Engraving machine and engraving method using the same |
| DE19745099B4 (en) * | 1997-10-11 | 2014-11-06 | Lurgi Zimmer Gmbh | Use of an additive having chain regulating and stabilizing properties in the production of polycaprolactam |
| JP4010853B2 (en) * | 2002-04-09 | 2007-11-21 | 帝人株式会社 | Aromatic polyamide whisker and method for producing the same |
| CN101215375B (en) * | 2008-01-11 | 2010-11-10 | 郑州大学 | Long carbon chain condensed ring semi-fragrant nylon and synthesis technique thereof |
| CN102153741B (en) * | 2010-02-11 | 2013-11-06 | 上海杰事杰新材料(集团)股份有限公司 | Homopolymer and copolymer of long-carbon-chain semi-aromatic high-temperature-resistant polyamide and synthesis method thereof |
-
2012
- 2012-07-03 CN CN201210227190.1A patent/CN103539937B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202961A (en) * | 1977-10-28 | 1980-05-13 | Ciba-Geigy Corporation | Transparent polyamide from aromatic dicarboxylic acid and disubstituted decane diamine |
| CN87104650A (en) * | 1986-07-08 | 1988-01-20 | 罗纳·布朗克化学公司 | With hexamethylene diamine, hexanodioic acid also selects for use at least a other short-chain dicarboxylic acid and dimeracid to prepare the method for copolyamide |
| CN101372531A (en) * | 2008-10-17 | 2009-02-25 | 华南理工大学 | Transparent co-polyamide and preparation thereof |
| CN101768266A (en) * | 2009-12-25 | 2010-07-07 | 郑州大学 | Method for preparing semi-aromatic nylon |
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