CN103539936A - Polyamide, synthesis method and application thereof, and polyamide product - Google Patents
Polyamide, synthesis method and application thereof, and polyamide product Download PDFInfo
- Publication number
- CN103539936A CN103539936A CN201210227226.6A CN201210227226A CN103539936A CN 103539936 A CN103539936 A CN 103539936A CN 201210227226 A CN201210227226 A CN 201210227226A CN 103539936 A CN103539936 A CN 103539936A
- Authority
- CN
- China
- Prior art keywords
- acid
- polymeric amide
- synthetic method
- diamine
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyamides (AREA)
Abstract
The invention discloses a polyamide, a synthesis method and application thereof, and a polyamide product. The synthesis method comprises the following steps: feeding: proportionally adding dibasic acid monomer, diamine monomer and other reaction assistants into a reaction kettle; 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 60-100 vol% of CO2; heating the reaction kettle to perform prepolymerization reaction on the mixture in the reaction kettle, discharging after the prepolymerization reaction is finished, drying the prepolymerization product, and carrying out solid-phase tackification to obtain the polyamide. The terminal amino content and terminal carboxyl content in the polyamide prepared by the synthesis method are low. The polyamide disclosed by the invention is applicable to a manufacturing material of electric and electronic equipment, automobile part, office supply or home supply. The invention also discloses 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, 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, 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.
When carboxyl that polymeric amide comprises high-content, this product is easily degraded when its melting or modification, thereby damages its mechanical property and final impact is used.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 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.
Further, be also necessary to provide a kind of manufacture material, trolley part, office appliance or household supplies of Electrical and Electronic equipment.
The technical solution adopted in the present invention is that a kind of synthetic method of polymeric amide, is characterized in that, comprises the following steps:
Reinforced: raw material is joined in reactor, fully mix and obtain mixture, described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
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 60-66.7 or 66.7-100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, prepolymerization reaction completes after discharging, and solid-phase tack producing after described prepolymer product is dried, 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, and described rare gas element is selected from one or more in helium, neon, argon gas, Krypton, xenon, radon gas.
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 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 is selected from one or more 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.
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 in described diamine monomer, the ratio of the shared amount of substance of 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 reacting by heating still under agitation, and reacting by heating still is to 210-220 ℃, 220-250 ℃ or 250-260 ℃, 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.
, the polymeric amide obtaining by above-mentioned method.
Wherein, described polymeric amide is 20-110mol/t with its content of carboxyl end group of autopotentiometric titrator titration, described polymeric amide is 5-50mol/t with its terminal amino group content of autopotentiometric titrator titration, mol/t mean per ton in containing end carboxyl or hold amino mol amount.
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 equipment, trolley part, office appliance or household supplies, comprise above-mentioned polymeric amide.
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; can keep the stable end amino of prepolymer and/or carboxyl ratio; can suppress the loss of diamine; can be in the situation that reducing diamine consumption; thereby the end amino and/or the carboxyl that are finally conducive to the follow-up solid-phase tack producing stage are controlled; obtain holding amino and/or the controlled polyamide resin of carboxyl-content height, thereby make the viscosity increased of polymeric amide.
Embodiment
The synthetic method that the invention discloses a kind of polymeric amide, is characterized in that, comprises the following steps:
Reinforced: raw material is joined in reactor, fully mix and obtain mixture, described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
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 60-66.7 or 66.7-100%;
Pre-polymerization: reacting by heating still, makes the mixture in reactor carry out prepolymerization reaction.
Wherein, prepolymerization reaction completes after discharging, and solid-phase tack producing after described prepolymer product is dried, 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, and described rare gas element is selected from one or more in helium, neon, argon gas, Krypton, xenon, radon gas.
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 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 is selected from one or more 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.
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 in described diamine monomer, the ratio of the shared amount of substance of 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 reacting by heating still under agitation, and reacting by heating still is to 210-220 ℃, 220-250 ℃ or 250-260 ℃, 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.
, the polymeric amide obtaining by above-mentioned method.
Wherein, described polymeric amide is 20-110mol/t with its content of carboxyl end group of autopotentiometric titrator titration, and described polymeric amide is 5-50mol/t with its terminal amino group content of autopotentiometric titrator titration.
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 equipment, trolley part, office appliance or household supplies, comprise above-mentioned polymeric amide.
Test respectively the relative viscosity of gained prepolymer 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 η r that concentration is the polymeric amide of 0.25g/dl in 98% the vitriol oil of 25 ± 0.01 ℃.Adopt the NCY-2 automatic viscometer that Shanghai Si Erda scientific instrument company limited produces to measure.
The fusing point of test gained polymeric amide, its testing method is with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry.
Test gained polymeric amide terminal amino group content, with Metrohm 848 Titrino plus autopotentiometric titrator titration sample terminal amino group contents.Get 0.5g polymkeric substance, add phenol 45ml and anhydrous methanol 3ml, reflux, after observation sample dissolves completely, is chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content of having demarcated.
Test gained polymeric amide content of carboxyl end group, with Metrohm 848 Titrino plus autopotentiometric titrator titration sample content of carboxyl end group.Get 0.5g polymkeric substance, add ortho-cresol 50ml, reflux and dissolve, let cool the rear 400 μ L formaldehyde solutions that add rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having 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; 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 content adding is also preferred content of the present invention, adopts the nylon salt of cited other of the present invention and other interpolation scope to be also applicable to the present invention, at this, is not enumerating.
What the reaction promoter adding in following embodiment was chosen at this is sodium hypophosphite, and with its comparatively 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
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.2mol, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.1MPa.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 and polymeric amide are detected, the results are shown in Table 1 for it.
Embodiment 2
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.2mol, 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 and polymeric amide are detected, the results are shown in Table 1 for it.
Embodiment 3
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.2mol, fill CO after vacuumizing
2to normal pressure, after repeating to vacuumize, fill CO
2process three times, finally by CO
2pressure rises to 0.5MPa.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 and polymeric amide are detected, the results are shown in Table 1 for it.
Embodiment 4
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.2mol, 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 and polymeric amide are detected, the results are shown in Table 1 for it.
Comparative example 1
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.2mol, vacuumize, and fills 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 and polymeric amide are detected, the results are shown in Table 1 for it.
Comparative example 2
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.4mol, vacuumize, and fills 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 and polymeric amide are detected, the results are shown in Table 1 for it.
Comparative example 3
The 1，10-diaminodecane, 74.8g phenylformic acid, the 6.98g sodium hypophosphite that in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, 20.8mol, vacuumize, and fills N
2pressure to reactor is 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 ℃, 50kPa vacuum condition, obtains polyamide resin.
According to above-mentioned testing method, prepolymer and polymeric amide are detected, the results are shown in Table 1 for it.
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, 20.2mol, 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.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 and polymeric amide are detected, the results are shown in Table 2 for it.
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, 20.2mol, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g 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 and polymeric amide are detected, the results are shown in Table 2 for it.
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, 20.2mol, the nylon salt of 10-decamethylene diamine, 2mol, 78.6g phenylformic acid, 7.53g 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 and polymeric amide are detected, the results are shown in Table 2 for it.
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, 20.2mol, the nylon salt of 10-decamethylene diamine, 5mol, 78.6g phenylformic acid, 7.53g 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 and polymeric amide are detected, the results are shown in Table 2 for it.
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, 20.2mol, the nylon salt of 10-decamethylene diamine, 10mol, 78.6g phenylformic acid, 7.53g 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 and polymeric amide are detected, the results are shown in Table 2 for it.
Comparative example 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, 20.2mol, 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
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 and polymeric amide are detected, the results are shown in Table 2 for it.
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, 20.2mol, 8-octamethylenediamine, 61.1g phenylformic acid, 5.3g 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 and polymeric amide are detected, the results are shown in Table 3 for it.
Comparative example 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, 20.2mol, 8-octamethylenediamine, 61.1g phenylformic acid, 5.3g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
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 and polymeric amide are detected, the results are shown in Table 3 for it.
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, 20.2mol, 12-12 carbon diamines, 85.5g phenylformic acid, 7.42g 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 and polymeric amide are detected, the results are shown in Table 3 for it.
Comparative example 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, 20.2mol, 12-12 carbon diamines, 85.5g phenylformic acid, 7.42g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
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 and polymeric amide are detected, the results are shown in Table 3 for it.
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, 20.2mol, 13-13 carbon diamines, 97.7g phenylformic acid, 8.48g 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 and polymeric amide are detected, the results are shown in Table 3 for it.
Comparative example 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, 20.2mol, 13-13 carbon diamines, 97.7g phenylformic acid, 8.48g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
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 PA12T resin.
According to above-mentioned testing method, prepolymer and polymeric amide are detected, the results are shown in Table 3 for it.
Embodiment 13
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1 of 18mol terephthalic acid, 2mol, 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.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 and polymeric amide are detected, the results are shown in Table 3 for it.
Comparative example 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 18mol terephthalic acid, 2mol, 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.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 and polymeric amide are detected, the results are shown in Table 3 for it.
Embodiment 14
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, 16.16mol, 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.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 and polymeric amide are detected, the results are shown in Table 3 for it.
Comparative example 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, 16.16mol, 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.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 and polymeric amide are detected, 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 be found at pre-polymerization stage CO
2while making protection gas, end amino and the content of carboxyl end group of the polymeric amide of gained have all obtained obvious control, the larger raising that the viscosity number of polymeric amide also obtains.From the comparison of embodiment 1-4 and comparative example 1-4, can find out, when reducing diamine consumption, use CO
2make protection gas, can obtain with diamine excessive higher but do not use CO
2the polymeric amide of identical viscosities level while making protection gas.
It should be noted that, with reference to embodiment 1 and comparative example 1, in the situation that 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 at least one being 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, and described diamine monomer is included as 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, 2,2,4-trimethylhexamethylenediamine, 2,4, at least one in 4-trimethylhexamethylenediamine, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 diamines, 12 diamines, 13 diamines.End amino and the content of carboxyl end group of the polymeric amide that it makes have also all obtained 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 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 (19)
1. a synthetic method for polymeric amide, is characterized in that, comprises the following steps:
Reinforced: raw material is joined in reactor, fully mix and obtain mixture, described raw material comprises (a) diprotic acid, and (b) diamine, and optional (c) other components;
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 60-66.7 or 66.7-100%;
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, and solid-phase tack producing after described prepolymer product is dried, 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 0.1-0.3MPa, 0.3-0.5MPa or 0.5-1.0MPa.
4. the synthetic method of polymeric amide according to claim 1, is characterized in that:
Described protection gas also comprises nitrogen and/or rare gas element, and described rare gas element is selected from one or more in helium, neon, argon gas, Krypton, xenon, radon 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 more than twice.
6. according to the synthetic method of the arbitrary described polymeric amide of claim 1-5, it is characterized in that:
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%.
7. the synthetic method of polymeric amide according to claim 6, is characterized in that:
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 is selected from one or more 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.
8. according to the synthetic method of the polymeric amide one of claim 1-5 Suo Shu, it is characterized in that:
Described (b) diamine is C
2-13binary aliphatic amine monomers.
9. according to the synthetic method of the polymeric amide one of claim 1-5 Suo Shu, it is characterized in that:
Described (b) diamine monomer comprises (b1) 1，10-diaminodecane and optional (b2) other diamines, and in described diamine monomer, the ratio of the shared amount of substance of 1，10-diaminodecane is 70-100mol%.
10. the synthetic method of polymeric amide according to claim 9, is characterized in that:
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.
The synthetic method of 11. polymeric amide according to claim 10, is characterized in that:
Described (c) other components comprise one or more in (c1) nylon salt, (c2) molecular weight regulator, (c3) catalyzer.
The synthetic method of 12. polymeric amide 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.
The synthetic method of 13. 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 is to 210-220 ℃, 220-250 ℃ or 250-260 ℃, reaction 1-3 hour.
The synthetic method of 14. polymeric amide according to claim 1, is characterized in that:
Described (c2) molecular weight regulator is monoprotic acid or monoamine.
The synthetic method of 15. polymeric amide according to claim 1, is characterized in that:
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.
16. 1 kinds of polymeric amide, is characterized in that:
The polymeric amide being obtained by the arbitrary described method of claim 1-15.
17. polymeric amide according to claim 16, is characterized in that:
Described polymeric amide is 20-110mol/t with its content of carboxyl end group of autopotentiometric titrator titration, and described polymeric amide is 5-50mol/t with its terminal amino group content of autopotentiometric titrator titration.
The application of 18. 1 kinds of polymeric amide as claimed in claim 16, is characterized in that:
Described polymeric amide is applied to manufacture material, trolley part, office appliance or the household supplies of Electrical and Electronic equipment.
The manufacture material of 19. 1 kinds of Electrical and Electronic equipment, trolley part, office appliance or household supplies, is characterized in that: comprise the polymeric amide that claim 16 limits.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227226.6A CN103539936B (en) | 2012-07-03 | 2012-07-03 | A kind of polymeric amide and synthetic method thereof and application and polyamide article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227226.6A CN103539936B (en) | 2012-07-03 | 2012-07-03 | A kind of polymeric amide and synthetic method thereof and application and polyamide article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103539936A true CN103539936A (en) | 2014-01-29 |
| CN103539936B CN103539936B (en) | 2016-04-20 |
Family
ID=49963829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210227226.6A Active CN103539936B (en) | 2012-07-03 | 2012-07-03 | A kind of polymeric amide and synthetic method thereof and application and polyamide article |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539936B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108424641A (en) * | 2018-04-08 | 2018-08-21 | 中国科学院理化技术研究所 | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening |
| 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 |
| 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 |
| 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 |
| CN109503829A (en) * | 2018-10-10 | 2019-03-22 | 华峰集团有限公司 | There is light shaped silk spinning-grade polyamide 66 resin and preparation method thereof |
| CN111217995A (en) * | 2020-03-16 | 2020-06-02 | 珠海派锐尔新材料有限公司 | Polymerization method of polyamide |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH07228695A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Production of new polyamide |
| CN101016378A (en) * | 2007-02-12 | 2007-08-15 | 南京工业大学 | Process of producing dimer acid amide nylon |
| CN101215375A (en) * | 2008-01-11 | 2008-07-09 | 郑州大学 | Long carbon chain condensed ring semi-fragrant nylon and synthesis technique thereof |
| CN101372531A (en) * | 2008-10-17 | 2009-02-25 | 华南理工大学 | Transparent co-polyamide and preparation thereof |
| CN101456949A (en) * | 2007-12-14 | 2009-06-17 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
| CN101768266A (en) * | 2009-12-25 | 2010-07-07 | 郑州大学 | Method for preparing semi-aromatic nylon |
-
2012
- 2012-07-03 CN CN201210227226.6A patent/CN103539936B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH07228695A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Production of new polyamide |
| CN101016378A (en) * | 2007-02-12 | 2007-08-15 | 南京工业大学 | Process of producing dimer acid amide nylon |
| CN101456949A (en) * | 2007-12-14 | 2009-06-17 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
| CN101215375A (en) * | 2008-01-11 | 2008-07-09 | 郑州大学 | Long carbon chain condensed ring semi-fragrant nylon and synthesis technique thereof |
| 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 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN108424641A (en) * | 2018-04-08 | 2018-08-21 | 中国科学院理化技术研究所 | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening |
| 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 |
| 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 |
| 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 |
| CN109503829A (en) * | 2018-10-10 | 2019-03-22 | 华峰集团有限公司 | There is light shaped silk spinning-grade polyamide 66 resin and preparation method thereof |
| 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 |
| CN111217995A (en) * | 2020-03-16 | 2020-06-02 | 珠海派锐尔新材料有限公司 | Polymerization method of polyamide |
| CN111217995B (en) * | 2020-03-16 | 2023-02-17 | 珠海派锐尔新材料有限公司 | Polymerization method of polyamide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103539936B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539936B (en) | A kind of polymeric amide and synthetic method thereof and application and polyamide article | |
| CN103539935B (en) | A kind of method improving polymeric amide whiteness | |
| CN110218311B (en) | Flame-retardant semi-aromatic polyamide and preparation method thereof | |
| CN101492534A (en) | Process for preparing semi-aromatic polyamides | |
| CN101759853A (en) | Method for preparing semi-aromatic polyamide | |
| US20050165211A1 (en) | Polyamides | |
| CN103119083A (en) | Polyamide resin | |
| CN113817159B (en) | Furandioic polyamide resin, preparation method thereof and polyamide molding composition | |
| WO2023000871A1 (en) | Method for preparing high molecular weight furan polyamide | |
| CN101759851B (en) | Semi-aromatic polyamide and preparation method thereof | |
| CN1315912C (en) | Block copolyamide and preparation thereof | |
| WO2020224377A1 (en) | Flame-retardant semi-aromatic polyamide and preparation method therefor | |
| CN113896886B (en) | Furandioic acid-based polyamide, preparation method thereof and furandioic acid-based polyamide composition | |
| KR20140086769A (en) | Crystalline polyamide ester resin, method for preparing the same, and article comprising the same | |
| CN101759852A (en) | Preparation method of semi-aromatic polyamide | |
| CN113683638A (en) | Phosphorus-containing organic acid alkenyl amine salt and preparation method and application thereof | |
| JP2017088708A (en) | Polyamide resin and manufacturing method of polyamide resin | |
| CN102964590B (en) | Polyamide and preparation method and application thereof | |
| CN106380594A (en) | Preparation method of anti-yellowing polyamide | |
| WO2023185517A1 (en) | Bio-based high-temperature-resistant polyamide with high binding force, method for preparing same, and use thereof | |
| CN108003828B (en) | Preparation method of copolyamide hot melt adhesive | |
| KR101570562B1 (en) | Polyamide resin, method for preparing the same, and article comprising the same | |
| CN105153417A (en) | Halogen-free flame-retardant high-temperature nylon | |
| CN103539937B (en) | The application of a kind of polyamide, its synthetic method and this polyamide | |
| US5015680A (en) | Production of a thermoplastically processable, aromatic polyamide using a 4-phenoxypyridine stabilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
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 |
|
| CB03 | Change of inventor or designer information |