CN103539937A - Polyamide, and synthesis method and application thereof - Google Patents
Polyamide, and synthesis method and application thereof Download PDFInfo
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- CN103539937A CN103539937A CN201210227190.1A CN201210227190A CN103539937A CN 103539937 A CN103539937 A CN 103539937A CN 201210227190 A CN201210227190 A CN 201210227190A CN 103539937 A CN103539937 A CN 103539937A
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Abstract
The invention discloses a polyamide, and a synthesis method and application thereof. The synthesis method comprises the following steps: 1) feeding: proportionally adding terephthalic acid monomer, hexamethylendiamine monomer, nylon salt and other reaction assistants into a reaction kettle; 2) gas charging: charging shielding gas into the reaction kettle until the pressure in the reaction kettle is 0.2-1.0 MPa, wherein the shielding gas contains 50-100 vol% of CO2; and 3) prepolymerization: heating the reaction kettle to perform prepolymerization reaction on the mixture in the reaction kettle. The polyamide prepared by the synthesis method has the advantages of low yellowing tendency and favorable color property. The polyamide disclosed by the invention is mainly applicable to a manufacturing material of electric and electronic equipment, automobile part, office supply or home supply.
Description
Technical field
The present invention relates to polymeric amide synthetic field, the particularly application of a kind of polymeric amide, its synthetic method and this polymeric amide.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance, be easy to processing etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improves performance and broadened application scope.In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
At present, prepare polymeric amide comparatively usual method be, first will the monomer of semiaromatic diprotic acid and diamines and water under rare gas element state, carry out prepolymerization after mixing, then the prepolymer obtaining is carried out to solid-phase tack producing reaction or the reaction of melting tackify.Because fusing point and the decomposition temperature of polymeric amide are comparatively approaching, under the hot conditions when synthetic, be very easy to flavescence, the polymeric amide after flavescence has certain limitation in application, so the anti-yellowing change research of polymeric amide becomes an important problem.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of synthetic method of polymeric amide.
Further, be also necessary to provide a kind of polymeric amide.
Further, be also necessary to provide a kind of application of polymeric amide.
A synthetic method for polymeric amide, is characterized in that, comprises the following steps,
Reinforced: terephthalic acid monomers, hexanediamine monomer, nylon salt and other reaction promoters are joined in reactor in proportion;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas
2, CO
2the volume content that accounts for described protection gas is 50-100%;
Pre-polymerization: reacting by heating still, 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 polymeric amide.
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, CO
2the 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 rare gas element 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 reactor.
Wherein, the ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is 10-50mol% preferably.
Wherein, the ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is more preferably 20-40mol%.
Wherein, described nylon salt comprises at least one in hexanediamine adipate (nylon salt), hexanediamine sebacate, hexanediamine 12 diacid salt, hexanediamine 13 diacid salt, hexanediamine 14 diacid salt and hexanediamine 16 diacid salt.
Wherein, described prepolymerization reaction is reacting by heating still under agitation, and reacting by heating still, to 210-220 ℃, 220-250 ℃ or 250-260 ℃, carries out prepolymerization reaction 1-3 hour.
, with the prepared product of above-mentioned method, be that raw material prepares through processing.
Wherein, described polymeric amide is injection molded into after colour table, and the GanzWhiteness value recording is more than 70, and its testing method is with reference to ASTM E313-2010, and described colour table is after infrared reflow soldering, and the GanzWhiteness value recording is more than 34.
An application for polymeric amide, described polymeric amide is applied to the manufacture material of Electrical and Electronic equipment, trolley part, office appliance or at home articles for use.
The synthetic method of polymeric amide of the present invention, is partly or entirely used CO in the pre-polymerization stage
2protection gas as the prepolymerization reaction stage.Due to CO
2with respect to N
2larger density, molecular weight and the solvability in water, can better get rid of in reactor and be dissolved in the O in water
2thereby, reduce the same O of amido linkage
2the chance of contact, and then effectively prevent its colour changed into yellow of prepolymer.The color of good prepolymer is the guarantee of good polymer color equally, has effectively prevented the flavescence of polymeric amide, and the whiteness value of the prepared polymeric amide of the present invention is higher than not using CO
2the resulting product of synthetic method as protection gas.
Embodiment
The invention discloses a kind of synthetic method of polymeric amide, better with the polymeric amide color characteristics that this kind of method is synthetic, obviously flavescence.
A synthetic method for polymeric amide, is characterized in that, comprises the following steps,
Reinforced: terephthalic acid monomers, hexanediamine monomer, nylon salt and other reaction promoters are joined in reactor in proportion;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas
2, CO
2the volume content that accounts for described protection gas is 50-100%;
Pre-polymerization: reacting by heating still, 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 polymeric amide.
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, CO
2the 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 rare gas element 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 reactor.
Wherein, the ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is 10-50mol% preferably.
Wherein, the ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is more preferably 20-40mol%.
Wherein, described nylon salt comprises at least one in hexanediamine adipate (nylon salt), hexanediamine sebacate, hexanediamine 12 diacid salt, hexanediamine 13 diacid salt, hexanediamine 14 diacid salt and hexanediamine 16 diacid salt.
Wherein, described prepolymerization reaction is reacting by heating still under agitation, and reacting by heating still, to 210-220 ℃, 220-250 ℃ or 250-260 ℃, carries out prepolymerization reaction 1-3 hour.
, with the prepared product of above-mentioned method, be that raw material prepares through processing.
Wherein, described polymeric amide is injection molded into after colour table, and the GanzWhiteness value recording is more than 70, and its testing method is with reference to ASTM E313-2010, and described colour table is after infrared reflow soldering, and the GanzWhiteness value recording is more than 34.
An application for polymeric amide, described polymeric amide is applied to the manufacture material of Electrical and Electronic equipment, trolley part, office appliance or at home articles for use.
Test respectively the relative viscosity of gained prepolymer product and polymeric amide, its testing method is with reference to the standard GB12006.1-89 of man of the People's Republic of China (PRC), polymeric amide viscosity number measuring method.
Concrete testing method for measuring the relative viscosity that concentration is the polymeric amide of 0.25g/dl in 98% the vitriol oil of 25 ± 0.01 ℃
η r.Adopt the NCY-2 automatic viscometer that Shanghai Si Erda scientific instrument company limited produces to measure.
The fusing point of test gained prepolymer product and polymeric amide, its testing method is with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry.
Concrete grammar is the fusing point that adopts Perkin Elmer Dimond dsc analysis instrument specimen.Nitrogen atmosphere, flow velocity is 40mL/min.During test, first with 10 ℃/min, be warming up to 340 ℃, at 340 ℃, keep 2min, then with 10 ℃/min, be cooled to 50 ℃, then be warming up to 340 ℃ with 10 ℃/min, endotherm peak temperature is now made as to fusing point
t m.
Whiteness value (the W of test gained prepolymer product
pre) and Gan Ci (GANZ) whiteness value of polymeric amide, its testing method is with reference to ASTM E313-2010, Standard Practice for Calculating Yellowness and Whiteness Indices from Instrumentally Measured Color Coordinates.
The whiteness value of prepolymer product is after directly prepolyer granule being pulverized, to measure the whiteness of powder.The whiteness value measurement of polyamide resin is that polyamide resin is injection molded into after colour table, uses the precious LIBERO X-rite color-Eye 7000A color measurement instrument of reason to carry out color measurement.Record its GanzWhiteness value and represent with WI1, this colour table, after infrared reflow soldering, is again measured to its GanzWhiteness value and represented with WI2, 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; temperature of reaction in following embodiment and reaction times are examples of protection domain of the presently claimed invention; temperature of reaction in other scope of protecting in the present invention is applicable to the present invention too, at this, will not enumerate.
What the nylon salt adding in following embodiment was chosen is nylon 66-salt, and the nylon salt of other that employing the present invention is cited is applicable to the present invention too, at this, is not enumerating.
What the reaction promoter adding in following embodiment was chosen at this is sodium hypophosphite, and with its preferred content, adopts the reaction promoter of cited other of the present invention and other interpolation scope to be also applicable to the present invention, at this, is not enumerating.
Embodiment 1
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.2MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 2
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite,, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 3
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.6MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 4
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 1MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Comparative example 1
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill N
2pressure to reactor is 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50kPa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 5
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill CO
2three times, finally by CO
2pressure rises to 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 6
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2after pressure rises to 0.2MPa, then be filled with wherein high-purity N
2rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 7
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2after pressure rises to 0.18MPa, then be filled with wherein high-purity N
2rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keeps constant pressure.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtains prepolymer product, and prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 8
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2after pressure rises to 0.15MPa, then be filled with wherein high-purity N
2rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keeps constant pressure.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtains prepolymer product, and prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 9
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2after pressure rises to 0.1MPa, then be filled with wherein high-purity N
2rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keeps constant pressure.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtains prepolymer product, and prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Comparative example 2
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 17.5mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, vacuumize, fill N
2three times, last high-purity N
2rise to 0.3MPa to pressure.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keeps constant pressure.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtains prepolymer product, and prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 10
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 10.2mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 11
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 27.2mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide are detected, it the results are shown in table.
Embodiment 12
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 20mol terephthalic acid, 20.8mol, 6-hexanediamine, 40.8mol nylon salt, 134.5g phenylformic acid, 10.15g sodium hypophosphite, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.In under agitation 2 hours, be warmed up to 220 ℃, reaction mixture is stirred 1 hour at 220 ℃, then under agitation make the temperature of reactant be elevated to 230 ℃.Reaction is proceeded 2 hours under the constant voltage of the constant temperature of 230 ℃ and 2.2MPa, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 ℃, obtain prepolymer product, described prepolymer product solid-phase tack producing 10 hours under 250 ℃, 50Pa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer product and polymeric amide 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/mol | 20 | 20 | 20 | 20 | 20 |
| 1,6-hexanediamine/mol | 20.8 | 20.8 | 20.8 | 20.8 | 20.8 |
| Nylon salt/mol | 17.5 | 17.5 | 17.5 | 17.5 | 17.5 |
| CO 2Pressure/MPa | 0.2 | 0.3 | 0.6 | 1 | 0 |
| N 2Pressure/MPa | 0 | 0 | 0 | 0 | 0.3 |
| Prepolymer whiteness value W pre | 85.6 | 86.2 | 87.3 | 87.4 | 80.8 |
| Melting point polymer T m/℃ | 304 | 305 | 305 | 305 | 304 |
| Polymkeric substance relative viscosity | 2.235 | 2.241 | 2.233 | 2.240 | 2.238 |
| Polymkeric substance WI1 | 70.3 | 70.9 | 71.2 | 71.1 | 60.1 |
| Polymkeric substance 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/mol | 20 | 20 | 20 | 20 | 20 | 20 |
| 1,6-hexanediamine/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 |
| CO 2Volume 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 W pre | 86.0 | 85.4 | 84.8 | 84.1 | 82.6 | 80.9 |
| Melting point polymer T m/℃ | 304 | 304 | 305 | 304 | 305 | 305 |
| Polymkeric substance relative viscosity | 2.239 | 2.235 | 2.241 | 2.240 | 2.236 | 2.238 |
| Polymkeric substance WI1 | 71.2 | 70.3 | 69.5 | 68.2 | 66.5 | 60.3 |
| Polymkeric substance 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/mol | 20 | 20 | 20 | 20 |
| 1,6-hexanediamine/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 W pre | 86.6 | 86 | 84.9 | 83.5 |
| Melting point polymer T m/℃ | 328 | 304 | 285 | 267 |
| Polymkeric substance relative viscosity | 2.259 | 2.238 | 2.239 | 2.243 |
| Polymkeric substance WI1 | 68.6 | 70.5 | 68.6 | 68.1 |
| Polymkeric substance WI2 | 37.3 | 38.2 | 35.3 | 34.6 |
Detected result comparison from table 1 to table 3 can be found at the pre-polymerization stage of polymeric amide CO
2while making protection gas, the prepolymer product obtaining and the whiteness value of polymeric amide have raising clearly, and along with containing CO
2the force value of protection gas larger, the whiteness value of prepolymer product and polymeric amide is just larger, when protection gas also comprises other gas, CO
2volume content is larger, and the whiteness value of prepolymer product and polymeric amide is just larger.
Polymeric amide of the present invention is applied to the manufacture material of Electrical and Electronic equipment, trolley part, office appliance or at home articles for use.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent transformation that utilizes description of the present invention to do, or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (12)
1. a synthetic method for polymeric amide, is characterized in that, comprises the following steps:
Reinforced: terephthalic acid monomers, hexanediamine monomer, nylon salt and other reaction promoters are joined in reactor in proportion;
Inflation: be filled with protection gas in reactor, contain CO in wherein said protection gas
2, CO
2the volume content that accounts for described protection gas is 50-60% or 60-100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction.
2. the synthetic method of polymeric amide according to claim 1, is characterized in that:
Prepolymerization reaction completes after discharging, after described prepolymer product is dried, carries out solid-phase tack producing, obtains polymeric amide.
3. the synthetic method of polymeric amide according to claim 1, is characterized in that:
In described aeration step, the pressure in reactor is added to 0.2-0.3MPa, 0.3-0.6MPa or 0.6-1.0MPa.
4. the synthetic method of polymeric amide according to claim 1, is characterized in that:
Described protection gas also comprises nitrogen and/or argon gas.
5. the synthetic method of polymeric amide 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 A repeats at least twice.
6. the synthetic method of polymeric amide according to claim 1, is characterized in that:
The ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is 10-50mol%.
7. the synthetic method of polymeric amide according to claim 1, is characterized in that:
The ratio that described nylon salt accounts for described terephthalic acid monomers, hexanediamine monomer and nylon salt total amount is 20-40mol%.
8. the synthetic method of polymeric amide according to claim 1, is characterized in that:
Described nylon salt comprises at least one in hexanediamine adipate, hexanediamine sebacate, hexanediamine 12 diacid salt, hexanediamine 13 diacid salt, hexanediamine 14 diacid salt and hexanediamine 16 diacid salt.
9. the synthetic method of polymeric amide according to claim 1, is characterized in that:
Described prepolymerization reaction is reacting by heating still under agitation, and reacting by heating still, to 210-220 ℃, 220-250 ℃ or 250-260 ℃, carries out prepolymerization reaction 1-3 hour.
10. a polymeric amide, is characterized in that:
With the arbitrary described prepared product of method of claim 1-9, be that raw material prepares through processing.
11. polymeric amide according to claim 10, is characterized in that:
Described polymeric amide is injection molded into after colour table, and the GanzWhiteness value recording is more than 70, and its testing method is with reference to ASTM E313-2010, and described colour table is after infrared reflow soldering, and the GanzWhiteness value recording is more than 34.
The application of 12. 1 kinds of polymeric amide as claimed in claim 10, is characterized in that:
Described polymeric amide is applied to the manufacture material of Electrical and Electronic equipment, trolley part, office appliance or at home articles for use.
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