CN103539936B - A kind of polymeric amide and synthetic method thereof and application and polyamide article - Google Patents
A kind of polymeric amide and synthetic method thereof and application and polyamide article Download PDFInfo
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- CN103539936B CN103539936B CN201210227226.6A CN201210227226A CN103539936B CN 103539936 B CN103539936 B CN 103539936B CN 201210227226 A CN201210227226 A CN 201210227226A CN 103539936 B CN103539936 B CN 103539936B
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Abstract
The invention discloses a kind of polymeric amide and synthetic method thereof and application and polyamide article.Synthetic method of the present invention comprises reinforced: dicarboxylic acid monomer, diamine monomer and other reaction promoters are joined in proportion in reactor; In reactor, be filled with protection gas, the pressure in reactor is added to 0.2-1.0MPa, containing CO in described protection gas
2, CO
2the volume content accounting for described protection gas is 60-100%; Reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction, after prepolymerization reaction completes discharging, carries out solid-phase tack producing, obtain polymeric amide after described prepolymer product drying.The polymeric amide that synthetic method of the present invention is obtained, its Amino End Group and content of carboxyl end group are all lower.Polymeric amide disclosed by the invention is applied to the manufacture material of Electrical and Electronic equipment, trolley part, office appliance or articles for use at home.The invention also discloses a kind of manufacture material, trolley part, office appliance or household supplies of Electrical and Electronic equipment.
Description
Technical field
The present invention relates to polymeric amide synthesis field, particularly a kind of polymeric amide and synthetic method thereof and application and polyamide article.
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, improving 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.
When polymeric amide comprises the carboxyl of high-content, this product is easily degraded when its melting or modification, thus damages its mechanical property and finally affect use.When polymeric amide comprises high-content amino, this product has crosslinked trend in follow-up use procedure, makes it be difficult to obtain a kind of full-bodied polymeric amide.
Summary of the invention
In view of the above, the present invention is necessary the synthetic method providing a kind of polymeric amide.
Further, there is a need to provide a kind of polymeric amide.
Further, there is a need to the application that a kind of polymeric amide is provided.
Further, there is a need to manufacture material, trolley part, office appliance or household supplies that a kind of Electrical and Electronic equipment is provided.
The technical solution adopted in the present invention is, a kind of synthetic method of polymeric amide, is characterized in that, comprises the following steps:
Reinforced: to be joined by raw material in reactor, fully mixing obtains mixture, and described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
Inflation: be filled with protection gas in reactor, containing CO in wherein said protection gas
2, CO
2the volume content accounting for described protection gas is 60-66.7 or 66.7-100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, after prepolymerization reaction completes discharging, described prepolymer product carries out the rear solid-phase tack producing of drying, obtains polymeric amide.
Wherein, in described aeration step, the pressure in reactor is added to 0.1-0.3MPa, 0.3-0.5MPa or 0.5-1.0MPa.
Wherein, described protection gas also comprises nitrogen and/or rare gas element, described rare gas element be selected from helium, neon, argon gas, Krypton, xenon, radon gas one or more.
Wherein, also comprise steps A: vacuumized by reactor before described aeration step, be then filled with protection gas to normal pressure, described steps A repeats more than twice.
Wherein, described (a) diprotic acid comprises (a1) aromatic acid and optional (a2) aliphatic dibasic acid, and wherein the ratio of aromatic acid is 70-100mol%, and the ratio of aliphatic dibasic acid is 0-30mol%.
Wherein, described (a1) aromatic acid is selected from terephthalic acid, m-phthalic acid or 2, at least one in 6-naphthalene dicarboxylic acids or multiple, described (a2) aliphatic dibasic acid be selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid and 14 diacid one or more.
Wherein, described (b) diamine is C
2-13binary aliphatic amine monomers.
Wherein, described (b) diamine monomer comprises (b1) 1，10-diaminodecane and optional (b2) other diamines, and the ratio of the amount of substance in described diamine monomer shared by 1，10-diaminodecane is 70-100mol%.
Wherein, described (b2) other diamines are selected from quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2-methyl octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2, one or more in 4,4-trimethylhexamethylenediamine, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 diamines, 12 diamines, 13 diamines.
Wherein, described (c) other components comprise one or more in (c1) nylon salt, (c2) molecular weight regulator, (c3) catalyzer.
Wherein, described (c1) 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.
Wherein, described prepolymerization reaction is under agitation reacting by heating still, and reacting by heating still is to 210-220 DEG C, 220-250 DEG C or 250-260 DEG C, reaction 1-3 hour.
Wherein, described (c2) molecular weight regulator is monoprotic acid or monoamine.
Wherein, described (c3) catalyzer is selected from one or more in phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphenylic acid, phenyl-phosphinic acid, phosphoric acid salt, phosphite, hypophosphite, phosphniline hydrochlorate, phenyl-phosphinic acid salt, triphenylphosphate, triphenyl phosphite.
A kind of polymeric amide, the polymeric amide obtained by above-mentioned method.
Wherein, its content of carboxyl end group of described polymeric amide autopotentiometric titrator titration is 20-110mol/t, its terminal amino group content of described polymeric amide autopotentiometric titrator titration to be 5-50mol/t, mol/t be represent per ton in containing the mol amount of end carboxyl or Amino End Group.
An application for polymeric amide, described polymeric amide is applied to manufacture material, trolley part, office appliance or the household supplies of Electrical and Electronic equipment.
A manufacture material for Electrical and Electronic equipment, trolley part, office appliance or household supplies, comprise above-mentioned polymeric amide.
The synthetic method of polymeric amide of the present invention, partly or entirely uses CO at precondensation stage
2as the protection gas in prepolymerization reaction stage; the Amino End Group that prepolymer can be kept stable and/or carboxyl ratio; the loss of diamine can be suppressed; can when reducing diamine consumption; thus be finally conducive to Amino End Group and/or the carboxyl control in follow-up solid-phase tack producing stage; obtain Amino End Group and/or the controlled polyamide resin of carboxyl-content height, thus the viscosity of polymeric amide is increased.
Embodiment
The invention discloses a kind of synthetic method of polymeric amide, it is characterized in that, comprise the following steps:
Reinforced: to be joined by raw material in reactor, fully mixing obtains mixture, and described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
Inflation: be filled with protection gas in reactor, containing CO in wherein said protection gas
2, CO
2the volume content accounting for described protection gas is 60-66.7 or 66.7-100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, after prepolymerization reaction completes discharging, described prepolymer product carries out the rear solid-phase tack producing of drying, obtains polymeric amide.
Wherein, in described aeration step, the pressure in reactor is added to 0.1-0.3MPa, 0.3-0.5MPa or 0.5-1.0MPa.
Wherein, described protection gas also comprises nitrogen and/or rare gas element, described rare gas element be selected from helium, neon, argon gas, Krypton, xenon, radon gas one or more.
Wherein, also comprise steps A: vacuumized by reactor before described aeration step, be then filled with protection gas to normal pressure, described steps A repeats more than twice.
Wherein, described (a) diprotic acid comprises (a1) aromatic acid and optional (a2) aliphatic dibasic acid, and wherein the ratio of aromatic acid is 70-100mol%, and the ratio of aliphatic dibasic acid is 0-30mol%.
Wherein, described (a1) aromatic acid is selected from terephthalic acid, m-phthalic acid or 2, at least one in 6-naphthalene dicarboxylic acids or multiple, described (a2) aliphatic dibasic acid be selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid and 14 diacid one or more.
Wherein, described (b) diamine is C
2-13binary aliphatic amine monomers.
Wherein, described (b) diamine monomer comprises (b1) 1，10-diaminodecane and optional (b2) other diamines, and the ratio of the amount of substance in described diamine monomer shared by 1，10-diaminodecane is 70-100mol%.
Wherein, described (b2) other diamines are selected from quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2-methyl octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2, one or more in 4,4-trimethylhexamethylenediamine, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 diamines, 12 diamines, 13 diamines.
Wherein, described (c) other components comprise one or more in (c1) nylon salt, (c2) molecular weight regulator, (c3) catalyzer.
Wherein, described (c1) 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 under agitation reacting by heating still, and reacting by heating still is to 210-220 DEG C, 220-250 DEG C or 250-260 DEG C, reaction 1-3 hour.
Wherein, described (c2) molecular weight regulator is monoprotic acid or monoamine.
Wherein, described (c3) catalyzer is selected from one or more in phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphenylic acid, phenyl-phosphinic acid, phosphoric acid salt, phosphite, hypophosphite, phosphniline hydrochlorate, phenyl-phosphinic acid salt, triphenylphosphate, triphenyl phosphite.
A kind of polymeric amide, the polymeric amide obtained by above-mentioned method.
Wherein, its content of carboxyl end group of described polymeric amide autopotentiometric titrator titration is 20-110mol/t, and its terminal amino group content of described polymeric amide autopotentiometric titrator titration is 5-50mol/t.
An application for polymeric amide, described polymeric amide is applied to manufacture material, trolley part, office appliance or the household supplies of Electrical and Electronic equipment.
A manufacture material for Electrical and Electronic equipment, trolley part, office appliance or household supplies, comprise above-mentioned polymeric amide.
Test the relative viscosity of gained prepolymer and polymeric amide respectively, its man of testing method reference People's Republic of China (PRC) standard GB12006.1-89, polymeric amide viscosity number measuring method.
Concrete testing method is in the vitriol oil of 25 ± 0.01 DEG C 98%, measure the relative viscosity η r that concentration is the polymeric amide of 0.25g/dl.The NCY-2 automatic viscometer adopting Shanghai Si Erda scientific instrument company limited to produce is measured.
The fusing point of test gained polymeric amide, its testing method is with reference to ASTMD3418-2003, StandardTestMethodforTransitionTemperaturesofPolymersByD ifferentialScanningCalorimetry.
Test gained polymeric amide terminal amino group content, with Metrohm848Titrinoplus autopotentiometric titrator titration sample end amino content.Get 0.5g polymkeric substance, add phenol 45ml and anhydrous methanol 3ml, reflux, after observation sample dissolves completely, be chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content demarcated.
Test gained polymeric amide content of carboxyl end group, with Metrohm848Titrinoplus autopotentiometric titrator titration sample end carboxyl-content.Get 0.5g polymkeric substance, add ortho-cresol 50ml, backflow is dissolved, and lets cool and adds rapidly 400 μ L formaldehyde solutions afterwards, with the KOH-ethanolic soln titration content of carboxyl end group demarcated.
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; other temperature of reaction in the scope that the present invention protects is applicable to the present invention too, will not enumerate at this.
What the nylon salt added in following embodiment was chosen is nylon66 fiber-salt, and the content added also is preferred content of the present invention, adopts other the nylon salt cited by the present invention and other interpolation scope to be also applicable to the present invention, is not enumerating at this.
What the reaction promoter added in following embodiment was chosen at this is sodium hypophosphite, and with its comparatively preferred content, adopts other the reaction promoter cited by the present invention and other interpolation scope to be also applicable to the present invention, do not enumerating at this.
Embodiment 1
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.2mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.1MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Embodiment 2
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.2mol, 74.8g phenylformic acid, 6.98g 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.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Embodiment 3
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.2mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.5MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Embodiment 4
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.2mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 1MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Comparative example 1
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.2mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, vacuumize, fill N
2be 0.3MPa to the pressure in reactor.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50kPa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Comparative example 2
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.4mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, vacuumize, fill N
2be 0.3MPa to the pressure in reactor.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50kPa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Comparative example 3
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, vacuumize, fill N
2be 0.6MPa to the pressure in reactor.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50kPa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 1 for it.
Embodiment 5
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill CO
2three times, finally by CO
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Embodiment 6
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2rise to after 0.2MPa until pressure, then be filled with high-purity N wherein
20.3MPa is risen to pressure.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Embodiment 7
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2rise to after 0.18MPa until pressure, then be filled with high-purity N wherein
20.3MPa is risen to pressure.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.Reacting and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer product, and prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Embodiment 8
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 5mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2rise to after 0.18MPa until pressure, then be filled with high-purity N wherein
20.3MPa is risen to pressure.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.Reacting and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer product, and prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Embodiment 9
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 10mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill CO
2three times, finally fill CO
2rise to after 0.18MPa until pressure, then be filled with high-purity N wherein
20.3MPa is risen to pressure.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.Reacting and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer product, and prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Comparative example 4
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.2mol 1, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, vacuumize, fill N
2three times, last high-purity N
20.3MPa is risen to pressure.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.Reacting and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water.Reacted rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer product, and prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 2 for it.
Embodiment 10
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 1, the 8-octamethylenediamine of 20.2mol, 61.1g phenylformic acid, 5.3g 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.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Comparative example 5
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 1, the 8-octamethylenediamine of 20.2mol, 61.1g phenylformic acid, 5.3g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Embodiment 11
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,12-ten two carbon diamines, 85.5g phenylformic acid, the 7.42g sodium hypophosphite of 20mol terephthalic acid, 20.2mol, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Comparative example 6
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,12-ten two carbon diamines, 85.5g phenylformic acid, the 7.42g sodium hypophosphite of 20mol terephthalic acid, 20.2mol, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Embodiment 12
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,13-ten three carbon diamines, 97.7g phenylformic acid, the 8.48g sodium hypophosphite of 20mol terephthalic acid, 20.2mol, after vacuumizing, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Comparative example 7
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,13-ten three carbon diamines, 97.7g phenylformic acid, the 8.48g sodium hypophosphite of 20mol terephthalic acid, 20.2mol, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains PA12T resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Embodiment 13
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 18mol terephthalic acid, 2mol 1,1 of 10-sebacic acid, 20.2mol, 10-decamethylene diamine, 110g phenylformic acid, 9.54g sodium hypophosphite, vacuumize, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times three times, finally by CO
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Comparative example 8
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 18mol terephthalic acid, 2mol 1,1 of 10-sebacic acid, 20.2mol, 10-decamethylene diamine, 100g phenylformic acid, 9.54g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Embodiment 14
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 16.16mol 1,1 of 10-decamethylene diamine, 4.04mol, 6-hexanediamine, 76.2g phenylformic acid, 6.39g sodium hypophosphite, vacuumize, fill CO
2to normal pressure, after repeating to vacuumize, fill CO
2process three times three times, finally by CO
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, the results are shown in Table 3 for it.
Comparative example 9
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 16.16mol 1,1 of 10-decamethylene diamine, 4.04mol, 6-hexanediamine, 76.2g phenylformic acid, 6.39g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, constant pressure is kept by removing formed water, react rear discharging, prepolymer vacuum-drying 24 hours at 80 DEG C, obtain prepolymer product, described prepolymer product, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.
Detect prepolymer and polymeric amide according to above-mentioned testing method, it the results are shown in following table 3.
The test result of table 1 embodiment 1-4 and comparative example 1-3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Terephthalic acid/mol | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| 1，10-diaminodecane/mol | 20.2 | 20.2 | 20.2 | 20.2 | 20.2 | 20.4 | 20.8 |
| CO 2Pressure/MPa | 0.1 | 0.3 | 0.5 | 1 | 0 | 0 | 0 |
| N 2Pressure/MPa | 0 | 0 | 0 | 0 | 0.3 | 0.3 | 0.6 |
| Prepolymer terminal amino group content mol/t | 1620 | 1600 | 1550 | 1520 | 1650 | 1620 | 1580 |
| Prepolymer content of carboxyl end group mol/t | 1790 | 1590 | 1520 | 1500 | 1980 | 1810 | 1550 |
| Polymeric amide fusing point T m/℃ | 316 | 317 | 316 | 317 | 317 | 317 | 316 |
| Terminal amino group content mol/t | 30 | 36 | 38 | 29 | 12 | 25 | 36 |
| Content of carboxyl end group mol/t | 150 | 87 | 90 | 82 | 205 | 190 | 89 |
| Polymeric amide relative viscosity | 2.149 | 2.241 | 2.255 | 2.251 | 1.785 | 2.013 | 2.226 |
The test result of table 2 embodiment 5-9 and comparative example 4
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 4 | |
| Terephthalic acid/mol | 20 | 20 | 20 | 20 | 20 | 20 |
| 1，10-diaminodecane/mol | 20.2 | 20.2 | 20.2 | 20.2 | 20.2 | 20.2 |
| Nylon salt/mol | 2.2 | 2.2 | 2.2 | 1.1 | 4.0 | 2.2 |
| CO 2Volume content | 100 | 66.7% | 60% | 60% | 60% | 0 |
| Pressure/the MPa of protection gas | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Prepolymer terminal amino group content/mol/t | 1250 | 1280 | 1320 | 1380 | 1080 | 1210 |
| Prepolymer content of carboxyl end group/mol/t | 1210 | 1290 | 1350 | 1390 | 1100 | 1590 |
| Polymeric amide fusing point T m/℃ | 293 | 293 | 292 | 303 | 277 | 293 |
| Terminal amino group content mol/t | 32 | 21 | 20 | 25 | 30 | 12 |
| Content of carboxyl end group mol/t | 76 | 82 | 89 | 92 | 95 | 132 |
| Polymeric amide relative viscosity | 2.242 | 2.239 | 2.235 | 2.233 | 2.244 | 1.736 |
The test result of table 3 different sorts polymeric amide
| Dicarboxylic acid monomer 20mol | Diamine monomer 20.2mol | CO 2Pressure/MPa | N 2Pressure/MPa | Prepolymer terminal amino group content/mol/t | Prepolymer content of carboxyl end group/mol/t | Melting point polymer T m/℃ | Terminal amino group content mol/t | Content of carboxyl end group mol/t | Polymeric amide relative viscosity | |
| Embodiment 10 | Terephthalic acid | 1,8-octamethylenediamine | 0.3 | 0 | 1590 | 1570 | 332 | 35 | 88 | 2.240 |
| Comparative example 5 | Terephthalic acid | 1,8-octamethylenediamine | 0 | 0.3 | 1380 | 1970 | 333 | 12 | 150 | 1.856 |
| Embodiment 11 | Terephthalic acid | 1,12-12 carbon diamines | 0.3 | 0 | 1250 | 1210 | 310 | 26 | 78 | 2.234 |
| Comparative example 6 | Terephthalic acid | 1,12-12 carbon diamines | 0 | 0.3 | 1080 | 1520 | 311 | 10 | 132 | 1.952 |
| Embodiment 12 | Terephthalic acid | 1,13-13 carbon diamines | 0.3 | 0 | 1130 | 1090 | 302 | 30 | 95 | 2.299 |
| Comparative example 7 | Terephthalic acid | 1,13-13 carbon diamines | 0 | 0.3 | 960 | 1420 | 301 | 15 | 120 | 1.963 |
| Embodiment 13 | Terephthalic acid: sebacic acid=9 ﹕ 1 | 1，10-diaminodecane | 0.3 | 0 | 1210 | 1180 | 305 | 38 | 89 | 2.251 |
| Comparative example 8 | Terephthalic acid: sebacic acid=9 ﹕ 1 | 1，10-diaminodecane | 0 | 0.3 | 1100 | 1630 | 306 | 14 | 140 | 1.811 |
| Embodiment 14 | Terephthalic acid | 1，10-diaminodecane: 1,6-hexanediamine=4 ﹕ 1 | 0.3 | 0 | 1450 | 1420 | 311 | 29 | 75 | 2.248 |
| Comparative example 9 | Terephthalic acid | 1，10-diaminodecane: 1,6-hexanediamine=4 ﹕ 1 | 0 | 0.3 | 1330 | 1890 | 310 | 11 | 136 | 1.766 |
Detected result comparison from table 1 to table 3 can find at precondensation stage CO
2when making protection gas, the Amino End Group of the polymeric amide of gained and content of carboxyl end group are obtained for obvious control, the larger raising that the viscosity number of polymeric amide also obtains.From comparing of embodiment 1-4 and comparative example 1-4, can find out, while minimizing diamine consumption, use CO
2make protection gas, can obtain excessive higher but do not use CO with diamine
2make the polymeric amide of identical levels of viscosity during protection gas.
It should be noted that, with reference to embodiment 1 and comparative example 1, when other condition is constant, only change all kinds of of dicarboxylic acid monomer and diamine monomer, described dicarboxylic acid monomer comprises aromatic acid and aliphatic dibasic acid, the monomer of wherein said aliphatic dibasic acid is selected from least one in oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid and 14 diacid, and described diamine monomer comprises for C
2-13binary aliphatic amine monomers, described diamine monomer comprises 1,10-decamethylene diamine, also comprise quadrol, propylene diamine, slough amine, cadaverine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2-methyl octamethylenediamine, 2,2, at least one in 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamines, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 diamines, 12 diamines, 13 diamines.The Amino End Group of its obtained polymeric amide and content of carboxyl end group are also obtained for obvious control.
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 the scope of the claims of the present invention is limited; every equivalent transformation utilizing 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 (14)
1. reduce the method that diamine consumption controls polymeric amide Amino End Group and content of carboxyl end group, it is characterized in that, adopt containing CO in polyamide prepolymer polymerization process
2protection gas, polymeric amide building-up process comprises the following steps:
Reinforced: to be joined by raw material in reactor, fully mixing obtains mixture, and described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
Inflation: be filled with protection gas in reactor, containing CO in wherein said protection gas
2, CO
2the volume content accounting for described protection gas be 60 ?66.7 or 66.7 ?100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction; After prepolymerization reaction completes discharging, described prepolymer product carries out the rear solid-phase tack producing of drying, obtains polymeric amide;
Its content of carboxyl end group of described polymeric amide autopotentiometric titrator titration be 20 ?110mol/t, its terminal amino group content of described polymeric amide autopotentiometric titrator titration be 5 ?50mol/t.
2. method according to claim 1, is characterized in that:
Described prepolymerization reaction is under agitation reacting by heating still, reacting by heating still to 210 ?220 DEG C, 220 ?250 DEG C or 250 ?260 DEG C, react 1 ?3 hours.
3. method according to claim 1, is characterized in that:
In described aeration step, the pressure in reactor is added to 0.1 ?0.3MPa, 0.3 ?0.5MPa or 0.5 ?1.0MPa.
4. method according to claim 1, is characterized in that:
Described protection gas also comprises nitrogen and/or rare gas element, described rare gas element be selected from helium, neon, argon gas, Krypton, xenon, radon gas one or more.
5. method according to claim 1, is characterized in that:
Also comprise steps A before described aeration step: vacuumized by reactor, be then filled with protection gas to normal pressure, described steps A repeats more than twice.
6. according to claim 1 ?5 arbitrary described methods, it is characterized in that:
Described (a) diprotic acid comprises (a1) aromatic acid and optional (a2) aliphatic dibasic acid, wherein the ratio of aromatic acid be 70 ?100mol%, the ratio of aliphatic dibasic acid be 0 ?30mol%.
7. method according to claim 6, is characterized in that:
Described (a1) aromatic acid is selected from terephthalic acid, m-phthalic acid or 2,6 ?at least one or multiple in naphthalene dicarboxylic acids, described (a2) aliphatic dibasic acid be selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2 ?one or more in methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid and 14 diacid.
8. according to claim 1 ?one of 5 described methods, it is characterized in that:
Described (b) diamine is C
2 ?13binary aliphatic amine monomers.
9. according to claim 1 ?one of 5 described methods, it is characterized in that:
Described (b) diamine monomer comprise (b1) 1,10 ?decamethylene diamine and optional (b2) other diamines, in described diamine monomer 1,10 ?the ratio of amount of substance shared by decamethylene diamine be 70 ?100mol%.
10. method according to claim 9, is characterized in that:
Described (b2) other diamines be selected from quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 ?making methylpentamethylenediamine diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2 ?methyl octamethylenediamine, 2,2,4 ?trimethylhexamethylenediamine, 2,4,4 ?trimethylhexamethylenediamine, 5 ?Jia Ji ?nonamethylene diamine, nonamethylene diamine, 11 diamines, 12 diamines, one or more in 13 diamines.
11. methods according to claim 10, is characterized in that:
Described (c) other components comprise in (c1) nylon salt, (c2) molecular weight regulator, (c3) catalyzer one or more.
12. methods according to claim 11, is characterized in that:
Described (c1) 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.
13. methods according to claim 11, is characterized in that:
Described (c2) molecular weight regulator is monoprotic acid or monoamine.
14. methods according to claim 11, is characterized in that:
Described (c3) catalyzer be selected from phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphenylic acid, phenyl-phosphinic acid, phosphoric acid salt, phosphite, hypophosphite, phosphniline hydrochlorate, phenyl-phosphinic acid salt, triphenylphosphate, triphenyl phosphite one or more.
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| CN105885036A (en) * | 2016-05-13 | 2016-08-24 | 东华大学 | Polyamide resin and preparation method thereof |
| CN105968346A (en) * | 2016-05-13 | 2016-09-28 | 东华大学 | Polyamide resin, composition containing polyamide resin and preparation method of polyamide resin |
| CA3075401A1 (en) | 2017-09-28 | 2019-04-04 | Dupont Polymers, Inc. | Polymerization process |
| CN108586733A (en) * | 2018-04-08 | 2018-09-28 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it |
| CN108559076A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108424641A (en) * | 2018-04-08 | 2018-08-21 | 中国科学院理化技术研究所 | Random copolymerization toughened semi-aromatic polyamide and preparation method thereof |
| CN108559075A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN109503829B (en) * | 2018-10-10 | 2021-07-09 | 华峰集团有限公司 | Spinning-grade polyamide 66 resin for bright profiled yarn and preparation method thereof |
| CN111217995B (en) * | 2020-03-16 | 2023-02-17 | 珠海派锐尔新材料有限公司 | Polymerization method of polyamide |
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Inventor after: Huang Xianbo Inventor after: Zhang Chuanhui Inventor after: Cai Tongmin Inventor after: Zeng Xiangbin Inventor after: Cao Min Inventor after: Xia Shiyong Inventor after: Ye Nanbiao Inventor after: Chen Dahua Inventor before: Zhang Chuanhui Inventor before: Cai Tongmin Inventor before: Zeng Xiangbin Inventor before: Cao Min Inventor before: Xia Shiyong Inventor before: Ye Nanbiao Inventor before: Chen Dahua |