CN106928451A - High temperature resistant PA6T copolymers and preparation method thereof - Google Patents
High temperature resistant PA6T copolymers and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of high temperature resistant PA6T copolymers and preparation method thereof；The raw materials for production of high temperature resistant PA6T copolymers contain：100 parts of terephthalic acid (TPA)s, 67-70 parts of hexamethylene diamine, 55-157 parts of amorphous nylon salt, 0.3-0.55 parts of nucleator, 0.1-0.3 parts of catalyst and 160-220 parts of deionized waters；Preparation method includes：Said components are added in reactor; continuously stirred with the mixing speed of 75-150r/min during the course of the reaction; carry out first time intensification, insulation, second liter of gentle pressure release successively to reactor under the protection of inert gas, be then charged with inert gas and obtain high temperature resistant PA6T copolymers after discharging；PA6T copolymers of the invention have the advantages that light weight, high temperature resistant, excellent in mechanical performance, size are stablized relatively, polymerization technique is simple, with short production cycle and are more adapted to commercial introduction.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, it is related to a kind of PA6T copolymers and its preparation method and application.
Background technology
Polyamide (PA) is the general name of the thermoplastic resin containing the amide group for repeating on molecular backbone, although there is excellent mechanical property, friction and wear behavior, self lubricity, shock-absorbing noise reduction, oil resistant, alkaline-resisting, weak acid resistant and general organic solvent is tolerated, but also have the shortcomings that water imbibition is big, so as to influence its dimensional stability and electrical property to a certain degree.
Polyamide common at present includes：Nylon 46 (PA46), poly- hexamethylene terephthalamide (PA6T), poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T) and poly- paraphenylene terephthalamide's decamethylene diamine (PA10T) etc..
Wherein, although PA46 crystallinity is high, crystalline rate is fast, excellent in mechanical performance, because its amide group content is high, therefore water absorption rate is also high, its range of application is subject to a definite limitation.PA9T has good toughness in high temperature environments, while also there is relatively low water absorption rate, but it is complicated due to synthesizing the raw material nonamethylene diamine technology path of PA9T, limit its large-scale promotion.PA10T is the high temperature resistant PA new varieties that domestic development gets up, its fusing point is up to 315 DEG C, water absorption rate is similar with PA9T, and its raw materials for production decamethylene diamine comes from castor oil, belong to bio-based environment-friendly materials, the very strong market competitiveness is shown, but decamethylene diamine price is higher, causes PA10T production costs high.Although PA6T costs are relatively low, water absorption rate is moderate, because its fusing point is higher than its heat decomposition temperature, it is difficult to carry out melt-processed shaping, therefore, these all have impact on further applying for above-mentioned polyamide to a certain extent.
The content of the invention
It is a primary object of the present invention to provide a kind of high temperature resistant PA6T copolymers.
It is another object of the present invention to provide a kind of preparation method of above-mentioned high temperature resistant PA6T copolymers.
To reach above-mentioned purpose, solution of the invention is：
A kind of high temperature resistant PA6T copolymers, its raw materials for production contains following components and the weight portion of every kind of component is as follows：
Wherein, amorphous nylon salt can be selected from PA66, PA610 and caprolactam in any one or a few.
Nucleator can be selected from barium sulfate, calcium carbonate, titanium dioxide and silica in any one or a few.
Catalyst can be selected from sodium phosphite, sodium hypophosphite, ortho phosphorous acid potassium, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc in any one or a few.
A kind of method for preparing above-mentioned high temperature resistant PA6T copolymers, it comprises the following steps：
(1) it is added in reactor after, being well mixed 100 parts of terephthalic acid (TPA)s, 67-70 parts of hexamethylene diamine, 55-157 portions of amorphous nylon salt, 0.3-0.55 portions of nucleator and 0.1-0.3 parts of catalyst, 160-220 parts of deionized water is eventually adding, is continuously stirred with the mixing speed of 75-150r/min during the course of the reaction；
(2) first time intensification, is carried out to reactor under the protection of inert gas, the temperature in the kettle of question response kettle is incubated when reaching 85-150 DEG C, and soaking time is 0.5-2.0h；The heating rate for heating up for the first time is 8-12 DEG C/min；
(3) after, insulation terminates, second intensification is carried out to reactor, second heating rate of temperature-rise period is 2-5 DEG C/min, and constant pressure when pressure in the kettle of the reactor reaches 2.0-3.0MPa continues to heat up reactor in constant voltage process；The heating rate of constant voltage process is 2-5 DEG C/min；Second heating rate of temperature-rise period is equal to the heating rate of constant voltage process.
(4) pressure release is carried out when, the temperature in the kettle of question response kettle reaches 310-320 DEG C and after constant-voltage phase terminates, it is 330-350 DEG C that temperature in the kettle is controlled in pressure leak process；
(5) mixing speed to 4-12r/min, is reduced when pressure in kettle reaches atmospheric pressure, inert gas is filled with to reactor, discharging obtains high temperature resistant PA6T copolymers.
Wherein, the inert gas in step (2) is any one in nitrogen, carbon dioxide, argon gas and helium.
The pressure of the inert gas in step (2) is 0.05-0.08MPa.
The pressure of the inert gas in step (5) is 0.3-1.2MPa.
Due to using such scheme, the beneficial effects of the invention are as follows：
Firstth, low-melting component (such as amorphous nylon salt) is with the addition of in polymerization system of the invention, copolymerization is participated in so as to reduce the fusing point of PA6T by low-melting component, so as to improve the processing characteristics of PA6T, the high temperature resistant PA6T copolymers of easy melt-processed shaping have been finally given.
The preparation method polymerization technique of high temperature resistant PA6T copolymers the secondth, of the invention is simple, with short production cycle, is more adapted to commercial introduction.
3rd, the preparation method of high temperature resistant PA6T copolymers of the invention avoids into the operation links such as salt crystallisation by cooling, and reactions steps are simple, and the equipment cost for often walking involved by reaction is cheap, and energy consumption is also smaller, is adapted to industrialization promotion production.
4th, the solvent used by the preparation method of high temperature resistant PA6T copolymers of the invention is only deionized water, and environmental pollution is small, beneficial to environmental protection.
5th, the PA6T copolymers that melting copolymerization of the invention is obtained are rigid radical due to there is phenyl ring, phenyl ring in strand, and Chain Flexibility is bad, therefore PA6T copolymers are not very big, and density is smaller, is a kind of light material.
6th, PA6T copolymers of the invention are irregular because strand is arranged, therefore its impact property etc. is preferably.
7th, polyamide material is belonged to due to PA6T, because the presence of amide groups causes nylon to there is certain water imbibition, so as to influence its dimensional stability, and amide groups concentration is relatively low in PA6T copolymers of the present invention, therefore water imbibition is much smaller than amorphous nylon, so the size of material is stablized relatively.
Brief description of the drawings
Fig. 1 is the schematic diagram in each stage of the preparation method of high temperature resistant PA6T copolymers of the invention.
Specific embodiment
The invention provides a kind of high temperature resistant PA6T copolymers and its preparation method and application.
<High temperature resistant PA6T copolymers>
A kind of high temperature resistant PA6T copolymers, its raw materials for production contains following components and the weight portion of every kind of component is as follows：
Wherein, hexamethylene diamine is selected from Henan China Shenma Group Co., Ltd., and technical parameter is as follows：Water white transparency, content >=99.85%, moisture≤0.15%, fusing point≤41.5 DEG C, colourity≤5APHA, polarogram value≤200m-molIBA/T-HMD, total volatile alkaline：≤ 4.0100gHMD consumes 0.005mol/LH2SO4Ml, false nitric acid：≤ 20mg/Kg, false DACH：≤10mg/Kg.
Amorphous nylon salt can be selected from PA66, PA610 and caprolactam in any one or a few.
Nucleator can be selected from barium sulfate, calcium carbonate, titanium dioxide and silica in any one or a few.
Catalyst can be selected from sodium phosphite, sodium hypophosphite, ortho phosphorous acid potassium, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc in any one or a few.
In high temperature resistant PA6T copolymers of the invention, because with the addition of low-melting component (such as amorphous nylon salt), copolymerization is participated in so as to reduce the fusing point of PA6T by low-melting component, so as to improve the processing characteristics of PA6T.
<The preparation method of high temperature resistant PA6T copolymers>
The preparation method of above-mentioned high temperature resistant PA6T copolymers comprises the following steps：
(1), the preparatory stage
By 100 parts of terephthalic acid (TPA)s, 67-70 parts of hexamethylene diamine, 55-157 portions of amorphous nylon salt, it is added in the reactor with agitating device (i.e. 25L high pressure polymerisations reactor) after 0.3-0.55 portions of nucleator and 0.1-0.3 parts of catalyst are well mixed, it is last that 160-220 parts of deionized water is added in the reactor, opening agitating device and making the agitating device carries out continuous and continual stirring in whole course of reaction with the mixing speed of 75-150r/min, use the air two to four times in inert gas replacement reactor, the air in reactor is reserved in abundant exclusion, the inert gas of 0.05-0.08MPa is finally reserved as protection gas；
(2), first stage (temperature rise period first time)
Reactor is heated using the Heat-conduction oil circulation system (including circulating heat conduction oil) being built in the reactor, its temperature in the kettle is raised under the protection of inert gas, temperature-rise period is stopped when temperature in the kettle reaches 85-150 DEG C；The heating rate in this stage is 8-12 DEG C/min；
(3), second stage (holding stage)
After temperature rise period first time terminates, insulating process is carried out, holding temperature is 85-150 DEG C, and soaking time is 0.5-2.0h；The effect in the stage is polymerized monomer (such as terephthalic acid (TPA), hexamethylene diamine) completely into salt (such as nylon 6T salt)；
(4), phase III (second temperature rise period)
After holding stage terminates, second temperature-rise period is carried out to reactor, now the pressure of reactor is also increased, second temperature-rise period is stopped when pressure in the kettle of the reactor reaches 2.0-3.0MPa；Second speed of temperature-rise period is 2-5 DEG C/min, and the second PA6T salt and amorphous nylon salt for being second stage formation is caused for the carrying out of copolyreaction that heats up is copolymerized；Second heating rate of temperature-rise period is equal to the heating rate of constant voltage process.
(5), fourth stage (constant-voltage phase)
After second temperature-rise period terminates, the moisture produced by release reaction system carries out constant voltage process to reactor, continue to heat up reactor with certain heating rate in constant voltage process, the pressure of constant pressure is 2.0-3.0MPa, and the time of constant pressure is about 1.0-2.0h (change is adjusted according to the difference of heating rate)；The heating rate in this stage is 2-5 DEG C/min, and the stage heating rate is to carry out more abundant to be polymerized more slowly, if being also unfavorable for that vapor fully discharges system as the first stage heats up so soon；
(6), the 5th stage (the pressure release stage)
Pressure release is carried out when the temperature in the kettle of question response kettle reaches 310-320 DEG C and after constant-voltage phase terminates, stop pressure leak process when pressure in kettle reaches atmospheric pressure (1atm), continue to heat up reactor in pressure leak process, but should keep control temperature in the kettle all the time in the range of 330-350 DEG C；
(7), the 6th stage (aeration phase)
The pressure release stage reduces mixing speed to 4-12r/min after terminating, and inert gas is filled with to reactor, and the charge of inert gas should ensure that the pressure of the inert gas in reactor is 0.3-1.2MPa (i.e. the charge of inert gas is 0.3-1.2MPa)；This stage opens valve discharging immediately after inert gas is filled with, and being filled with for inert gas is, in order to be pressurizeed to system, to be easy to discharging.
(8), the 7th stage (discharging stage)
Discharging, obtains high temperature resistant PA6T copolymers.
In step (1), inert gas is any one in nitrogen, carbon dioxide, argon gas and helium.
Wherein, as shown in figure 1, the abscissa and ordinate of Fig. 1 are not offered as specific physical parameter, its broken line does not indicate that the variation tendency of certain physical quantity to above-mentioned preparation method yet, it is only for distinguish each stage.
In step (1), the stirring that course of reaction refers in step (2) to step (7), therefore step (2) to step (8) is uninterruptedly to carry out, and the speed of stirring can be 75-150rpm.Inert gas can be selected from any one in nitrogen, carbon dioxide, argon gas and helium.
AB sections of step (2) (i.e. temperature rise period first time) corresponding diagram 1, A points are the starting point of temperature rise period first time, and B points are the terminal of temperature rise period first time, the temperature T of B pointsb=85-150 DEG C.The heating rate of reactor can be 8-12 DEG C/min.Conduction oil in Heat-conduction oil circulation system is in heated condition always, but the temperature in the kettle of reactor is that, by related inlet valve manual control, each step can correspond to a specific temperature.
BC sections of step (3) (i.e. holding stage) corresponding diagram 1, B points also can be considered the starting point of insulating process, and C points are the terminal of insulating process.Insulating process duration tbc=0.5-2.0h.The effect of insulating process is to make relevant polymerization monomer (i.e. terephthalic acid (TPA) and hexamethylene diamine) fully into salt, and this stage amorphous nylon also has neither part nor lot in reaction.
CD sections of step (4) (i.e. second temperature rise period) corresponding diagram 1, C points also can be considered second starting point of temperature rise period, and D points are the terminal of second intensification.The pressure P of D pointsd=2.0-3.0MPa.
DE sections of step (5) (i.e. constant-voltage phase) corresponding diagram 1, D points also can be considered the starting point of constant-voltage phase, and E points are the terminal of constant-voltage phase.Constant-voltage phase duration is about tde=1.0-2.0h.Pressure is maintained by the interior vapor for reacting generation of continuous release reaction kettle to realize in kettle, the purpose of constant pressure is to react condensation polymerization to occur to positive direction as far as possible, so as to produce more products, (product herein is the oligomer of PA6T copolymers, for example：If what is added is 66 salt, its product is PA6T/66 oligomer).
EF sections of step (6) (i.e. pressure release stage) corresponding diagram 1, E points are the starting point of pressure leak process, and F points are the terminal of pressure leak process.The temperature T of E pointse=310-320 DEG C, the pressure P of F pointsf=1atm.
FG sections of step (7) (i.e. aeration phase) corresponding diagram 1.
GH sections of step (8) (i.e. discharging stage) corresponding diagram 1, the product obtained by H points is high temperature resistant PA6T copolymers.
The preparation method step of high temperature resistant PA6T copolymers of the invention is simple therefore production cost is relatively low, is adapted to industrialization generation；In addition, only with deionized water as solvent in engineering is synthesized, without using solvents with larger toxic and side effect such as organic solvents, being conducive to environmental protection.
<The application of high temperature resistant PA6T copolymers>
High temperature resistant PA6T copolymers of the invention can be used for making the parts of electronic and electrical equipment, such as auxiliary component of automobile engine, it is also possible to be used under hot environment for making high temperature-resistant part.
The present invention is further illustrated with reference to embodiments.
The method of testing that the present invention is used is as follows：
(1), fusing point test：Test analysis are carried out using differential scanning calorimeter (DSC thermal analyzers) to obtain.
(2), tensile property：Tested by ASTM D638-10, rate of extension 5mm/min.
(3), simply supported beam notch impact strength：Tested by ASTM D6110-10.
(4), bending strength：Tested by ASTM D790-10, push speed 1.25mm/min.
Embodiment one
The raw materials for production of high temperature resistant PA6T copolymers are as shown in table 1 in the present embodiment：
The raw materials for production component table of the high temperature resistant PA6T copolymers of the embodiment of table 1
| Component | Weight portion |
| Terephthalic acid (TPA) | 100 |
| Hexamethylene diamine | 67 |
| Amorphous nylon salt (nylon salt) | 129.2 |
| Nucleator (barium sulfate) | 0.3 |
| Catalyst (sodium hypophosphite) | 0.1 |
| Deionized water | 160 |
The preparation method of high temperature resistant PA6T copolymers is as follows in the present embodiment：
(1), the preparatory stage
By 100 parts of terephthalic acid (TPA)s, 67 parts of hexamethylene diamines, 129.2 portions of salt of amorphous nylon 66, it is added in the reactor with agitating device (i.e. 25L high pressure polymerisations reactor) after 0.3 portion of nucleator and 0.1 part of catalyst are well mixed, it is last that 160 parts of deionized waters are added in the reactor, opening agitating device and making the agitating device carries out continuous and continual stirring in whole course of reaction with the mixing speed of 75r/min, use the air three times in inert gas (nitrogen) replacement reaction kettle, the air in reactor is reserved in abundant exclusion, the inert gas of 0.05MPa is finally reserved as protection gas；
(2), first stage (temperature rise period first time)
Reactor is heated using the Heat-conduction oil circulation system (including circulating heat conduction oil) being built in the reactor, its temperature in the kettle is raised under the protection of inert gas, temperature-rise period is stopped when temperature in the kettle reaches 80 DEG C；The heating rate in this stage is 8 DEG C/min；
(3), second stage (holding stage)
After temperature rise period first time terminates, insulating process is carried out, holding temperature is 80 DEG C, and soaking time is 2.0h；The effect in the stage is that polymerized monomer is dissolved completely in solvent and forms nylon salt；The polymerized monomer in this stage is terephthalic acid (TPA), hexamethylene diamine, and what synthesis was obtained is nylon 6T salt；
(4), phase III (second temperature rise period)
After holding stage terminates, second temperature-rise period is carried out to reactor, now the pressure of reactor is also increased, second temperature-rise period is stopped when pressure in the kettle of the reactor reaches 2.0MPa；Second heating rate of temperature-rise period is 2 DEG C/min；
(5), fourth stage (constant-voltage phase)
After second temperature-rise period terminates, the moisture produced by release reaction system carries out constant voltage process to reactor, continue to heat up reactor with certain heating rate in constant voltage process, the pressure of constant pressure is 2.0MPa, and the time of constant pressure is about 2.0h (changing according to the difference of heating rate)；The heating rate in this stage is 2 DEG C/min；
(6), the 5th stage (the pressure release stage)
Pressure release is carried out when the temperature in the kettle of question response kettle reaches 320 DEG C and after constant-voltage phase terminates, stop pressure leak process when pressure in kettle reaches atmospheric pressure (1atm), continue to heat up reactor in pressure leak process, but should keep control temperature in the kettle all the time in the range of 350 DEG C；
(7), the 6th stage (aeration phase)
The pressure release stage reduces mixing speed to 4r/min after terminating, and inert gas is filled with to reactor, and the charge of inert gas should ensure that the pressure of the inert gas in reactor is 1.2MPa (i.e. the charge of inert gas is 1.2MPa)；Valve discharging is opened immediately after being filled with inert gas, and being filled with for inert gas is, in order to be pressurizeed to system, to be easy to discharging；
(8), the 7th stage (discharging stage)
Discharging, obtains high temperature resistant PA6T copolymers.
The performance of the high temperature resistant PA6T copolymers of the present embodiment is as shown in table 4.
Embodiment two
The raw materials for production of high temperature resistant PA6T copolymers are as shown in table 2 in the present embodiment：
The raw materials for production component table of the high temperature resistant PA6T copolymers of the embodiment of table 2
| Component | Weight portion |
| Terephthalic acid (TPA) | 100 |
| Hexamethylene diamine | 70 |
| Amorphous nylon salt (NYLON610 salt) | 157 |
| Nucleator (talcum powder) | 0.55 |
| Catalyst (Lime Hypophosphate) | 0.3 |
| Deionized water | 220 |
The preparation method of high temperature resistant PA6T copolymers is as follows in the present embodiment：
(1), the preparatory stage
By 100 parts of terephthalic acid (TPA)s, 70 parts of hexamethylene diamines, 157 portions of salt of amorphous nylon 610, it is added in the reactor with agitating device (i.e. 25L high pressure polymerisations reactor) after 0.55 portion of nucleator and 0.3 part of catalyst are well mixed, it is last that 220 parts of deionized waters are added in the reactor, opening agitating device and making the agitating device carries out continuous and continual stirring in whole course of reaction with the mixing speed of 120r/min, use the air three times in inert gas (carbon dioxide) replacement reaction kettle, the air in reactor is reserved in abundant exclusion, the inert gas of 0.08MPa is finally reserved as protection gas；
(2), first stage (temperature rise period first time)
Reactor is heated using the Heat-conduction oil circulation system (including circulating heat conduction oil) being built in the reactor, its temperature in the kettle is raised under the protection of inert gas, temperature-rise period is stopped when temperature in the kettle reaches 120 DEG C；The heating rate in this stage is 12 DEG C/min；
(3), second stage (holding stage)
After temperature rise period first time terminates, insulating process is carried out, holding temperature is 120 DEG C, and soaking time is 1.0h；The effect in the stage is that polymerized monomer is dissolved completely in solvent and forms nylon salt；The polymerized monomer in this stage is terephthalic acid (TPA), hexamethylene diamine, and what synthesis was obtained is nylon 6T salt；
(4), phase III (second temperature rise period)
After holding stage terminates, second temperature-rise period is carried out to reactor, now the pressure of reactor is also increased, second temperature-rise period is stopped when pressure in the kettle of the reactor reaches 2.8MPa；Second heating rate of temperature-rise period is 5 DEG C/min；
(5), fourth stage (constant-voltage phase)
After second temperature-rise period terminates, the moisture produced by release reaction system carries out constant voltage process to reactor, continue to heat up reactor with certain heating rate in constant voltage process, the pressure of constant pressure is 2.8MPa, and the time of constant pressure is about 1.0h (changing according to the difference of heating rate)；The heating rate in this stage is 5 DEG C/min；
(6), the 5th stage (the pressure release stage)
The temperature in the kettle of question response kettle reaches 315 DEG C and carries out pressure release after constant-voltage phase terminates, stop pressure leak process when pressure in kettle reaches atmospheric pressure (1atm), continue to heat up reactor in pressure leak process, but should keep control temperature in the kettle all the time in the range of 340 DEG C；
(7), the 6th stage (aeration phase)
The pressure release stage reduces mixing speed to 8r/min after terminating, and inert gas is filled with to reactor, and the charge of inert gas should ensure that the pressure of the inert gas in reactor is 0.8MPa (i.e. the charge of inert gas is 0.8MPa)；Valve discharging is opened immediately after being filled with inert gas, and being filled with for inert gas is, in order to be pressurizeed to system, to be easy to discharging；
(8), the 7th stage (discharging stage)
Discharging, obtains high temperature resistant PA6T copolymers.
The performance of the high temperature resistant PA6T copolymers of the present embodiment is as shown in table 4.
Embodiment three
The raw materials for production of high temperature resistant PA6T copolymers are as shown in table 3 in the present embodiment：
The raw materials for production component table of the high temperature resistant PA6T copolymers of the embodiment of table 3
| Component | Weight portion |
| Terephthalic acid (TPA) | 100 |
| Hexamethylene diamine | 69 |
| Amorphous nylon salt (caprolactam) | 55 |
| Nucleator (silica) | 0.45 |
| Catalyst (ortho phosphorous acid potassium) | 0.2 |
| Deionized water | 195 |
The preparation method of high temperature resistant PA6T copolymers is as follows in the present embodiment：
(1), the preparatory stage
By 100 parts of terephthalic acid (TPA)s, 69 parts of hexamethylene diamines, 55 parts of amorphous nylon salt (caprolactam), it is added in the reactor with agitating device (i.e. 25L high pressure polymerisations reactor) after 0.45 portion of nucleator and 0.2 part of catalyst are well mixed, it is last that 195 parts of deionized waters are added in the reactor, opening agitating device and making the agitating device carries out continuous and continual stirring in whole course of reaction with the mixing speed of 150r/min, use the air three times in inert gas (argon gas) replacement reaction kettle, the air in reactor is reserved in abundant exclusion, the inert gas of 0.07MPa is finally reserved as protection gas；
(2), first stage (temperature rise period first time)
Reactor is heated using the Heat-conduction oil circulation system (including circulating heat conduction oil) being built in the reactor, its temperature in the kettle is raised under the protection of inert gas, temperature-rise period is stopped when temperature in the kettle reaches 150 DEG C；The heating rate in this stage is 10 DEG C/min；
(3), second stage (holding stage)
After temperature rise period first time terminates, insulating process is carried out, holding temperature is 150 DEG C, and soaking time is 1.5h；The effect in the stage is that polymerized monomer is dissolved completely in solvent and forms nylon salt；The polymerized monomer in this stage is terephthalic acid (TPA), hexamethylene diamine, and what synthesis was obtained is nylon 6T salt；
(4), phase III (second temperature rise period)
After holding stage terminates, second temperature-rise period is carried out to reactor, now the pressure of reactor is also increased, second temperature-rise period is stopped when pressure in the kettle of the reactor reaches 3.0MPa；Second heating rate of temperature-rise period is 3.5 DEG C/min；
(5), fourth stage (constant-voltage phase)
After second temperature-rise period terminates, the moisture produced by release reaction system carries out constant voltage process to reactor, continue to heat up reactor with certain heating rate in constant voltage process, the pressure of constant pressure is 3.0MPa, and the time of constant pressure is about 1.5h (changing according to the difference of heating rate)；The heating rate in this stage is 3.5 DEG C/min；
(6), the 5th stage (the pressure release stage)
Pressure release is carried out when the temperature in the kettle of question response kettle reaches 310 DEG C and after constant-voltage phase terminates, stop pressure leak process when pressure in kettle reaches atmospheric pressure (1atm), continue to heat up reactor in pressure leak process, but should keep control temperature in the kettle all the time in the range of 330 DEG C；
(7), the 6th stage (aeration phase)
The pressure release stage reduces mixing speed to 10r/min after terminating, and inert gas is filled with to reactor, and the charge of inert gas should ensure that the pressure of the inert gas in reactor is 1.2MPa (i.e. the charge of inert gas is 1.2MPa)；Valve discharging is opened immediately after being filled with inert gas, and being filled with for inert gas is, in order to be pressurizeed to system, to be easy to discharging；
(8), the 7th stage (discharging stage)
Discharging, obtains high temperature resistant PA6T copolymers.
The performance of the high temperature resistant PA6T copolymers of the present embodiment is as shown in table 4.
The performance test results of the high temperature resistant PA6T copolymers that above-described embodiment is obtained are as shown in table 4：
The test result table of table 4
To sum up, the preparation method of high temperature resistant PA6T copolymer materials of the invention includes：The components such as terephthalic acid (TPA), hexamethylene diamine, amorphous nylon salt, nucleator, catalyst and deionized water are added in reactor; continuously stirred with the mixing speed of 75-150r/min during the course of the reaction; carry out first time intensification, insulation, second liter of gentle pressure release successively to reactor under the protection of inert gas, be then charged with inert gas and obtain high temperature resistant PA6T copolymers after discharging；PA6T copolymers of the invention have the advantages that light weight, high temperature resistant, excellent in mechanical performance, size are stablized relatively, polymerization technique is simple, with short production cycle and are more adapted to commercial introduction, therefore can be widely used in general hot environment with substituted metal material, such as be used to make high temperature-resistant part.
The above-mentioned description to embodiment is to be understood that and use the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be within protection scope of the present invention.
Claims (8)
1. a kind of high temperature resistant PA6T copolymers, it is characterised in that：Its raw materials for production contains following components and the weight portion of every kind of component is as follows：
2. high temperature resistant PA6T copolymers according to claim 1, it is characterised in that：The amorphous nylon salt be selected from PA66, PA610 and caprolactam in any one or a few.
3. high temperature resistant PA6T copolymers according to claim 1, it is characterised in that：The nucleator be selected from barium sulfate, calcium carbonate, titanium dioxide and silica in any one or a few.
4. high temperature resistant PA6T copolymers according to claim 1, it is characterised in that：The catalyst be selected from sodium phosphite, sodium hypophosphite, ortho phosphorous acid potassium, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc in any one or a few.
5. a kind of method of the high temperature resistant PA6T copolymers prepared as described in any in Claims 1-4, it is characterised in that comprise the following steps：
(1) it is added in reactor after, being well mixed 100 parts of terephthalic acid (TPA)s, 67-70 parts of hexamethylene diamine, 55-157 portions of amorphous nylon salt, 0.3-0.55 portions of nucleator and 0.1-0.3 parts of catalyst, 160-220 parts of deionized water is eventually adding, is continuously stirred with the mixing speed of 75-150r/min during the course of the reaction；
(2) first time intensification, is carried out to the reactor under the protection of inert gas, the temperature in the kettle of question response kettle is incubated when reaching 85-150 DEG C, and soaking time is 0.5-2.0h；
(3) after, insulation terminates, second intensification is carried out to the reactor, constant pressure when pressure in the kettle of the reactor reaches 2.0-3.0MPa continues to heat up the reactor in constant voltage process；
(4) pressure release is carried out when, the temperature in the kettle of question response kettle reaches 310-320 DEG C, it is 330-350 DEG C that temperature in the kettle is controlled in pressure leak process；
(5) mixing speed to 4-12r/min, is reduced when pressure in kettle reaches atmospheric pressure, inert gas is filled with to the reactor, discharging obtains high temperature resistant PA6T copolymers.
6. method according to claim 5, it is characterised in that：Inert gas in step (2) is any one in nitrogen, carbon dioxide, argon gas and helium.
7. method according to claim 5, it is characterised in that：The pressure of the inert gas in step (2) is 0.05-0.08MPa.
8. method according to claim 5, it is characterised in that：The pressure of the inert gas in step (5) is 0.3-1.2MPa..
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| CN113087896A (en) * | 2021-04-12 | 2021-07-09 | 东莞市华盈新材料有限公司 | High-temperature-resistant PA6T and synthesis method thereof |
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