CN106893096B - A kind of biological poly amide and preparation method thereof - Google Patents
A kind of biological poly amide and preparation method thereof Download PDFInfo
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- CN106893096B CN106893096B CN201710092536.4A CN201710092536A CN106893096B CN 106893096 B CN106893096 B CN 106893096B CN 201710092536 A CN201710092536 A CN 201710092536A CN 106893096 B CN106893096 B CN 106893096B
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- azelaic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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Abstract
The invention discloses a kind of biological poly amides and preparation method thereof, the biology base 1 that the present invention uses renewable biological source to prepare, 9- azelaic acid and 1,6- hexamethylene diamine are monomer, biological poly amide, specially biological poly azelaic acid acyl hexamethylene diamine can be obtained by direct melt polycondensation reaction.It is solvent that water is used only in the entire synthesis process of the present invention, without using any organic solvent and additive, it both can avoid changing the physico-chemical parameter and performance of monomer and amine salt in polymerization process because of organic solvent and being introduced into for additive in this way, to influence entire polymerization technique process.The present invention takes water as a solvent clean and environmental protection, meets the objective of the environmentally protective recyclable regenerative of biology base high molecular material, and the present invention takes water as a solvent and provides reaction medium for polymerization process, is convenient for energy transmission, charging and subsequent reactions.
Description
Technical field
The present invention relates to biology base polymeric material fields, and in particular to a kind of biological poly amide and preparation method thereof,
In particular to a kind of biological poly azelaic acid acyl hexamethylene diamine and preparation method thereof.
Background technique
Since early 20th century, the rudiment of high molecular material open the mankind material science is probed into and is applied it is new
Chapter, the source of high molecular material also from incipient natural macromolecular material (such as rubber, animal, plant fiber etc.) gradually
Development is transitioned into fossil resources, and while meeting the mankind using material, sustainable development, which is undoubtedly, is badly in need of that thinking is gone to visit
Rope and practicing solves the problems, such as.
Polyamide (Polyamide), abbreviation PA, industrially referred to as nylon, is developed so far existing more than 80 years.Polyamide with
A kind of most commonly used thermoplastic engineering plastic of domestic and international application is had become by means of its excellent comprehensive performance, while being also to be only second to
The second-biggest-in-the-world fibrous material of polyester fiber (terylene).
Currently, the guidance and environmentally protective theory with domestic and foreign policies are rooted in the hearts of the people, it is renewable to greatly develop circulation
Biological poly amide products have become polyamide production and research field hot spot.The biological poly amide material developed
Material includes biology base PA610, PA11, PA1010, PA10T, PA1012, PA410 etc., they theoretically can be almost complete
Substitute petroleum-based similar product, to reduce human society depending on unduly for petroleum chemicals, while reduce environment and
Pressure on Energy, thus become most potential one of the developing direction of current polyamide high polymer material.
Biological poly amide PA69 is a kind of important biomolecule based high-polymer material for being currently in conceptual phase.Currently,
It can extract unsaturated fat pinolenic acid, linoleic acid from the natural reproducibles plant such as castor oil, Chinese tallow, soybean oil, then pass through
Biology base azelaic acid monomer can be obtained in oxicracking, this technology is very mature by the development utilization of many years.It is same with this
When, industrialized hexamethylene diamine is still generated by petroleum cracking.Foreign study scholar attempts to prepare biology with glucose fermentation
Base hexamethylene diamine mainly passes through Escherichia coli and converts glucose into 3- dehydroshikimate, then, is further converted to
It is suitable, cis- muconic acid.Finally, by suitable, cis- muconic acid carry out under high pressure hydrogenation obtain biology base oneself
Biology base adipic acid is carried out subsequent nitrilation and amination treatment, biology base hexamethylene diamine can be obtained by diacid monomer.In addition, grape
Sugar can be also converted into suitable, cis- muconic acid by the soil bacteria with a variety of metabolic capabilities, then be hydrogenated to
Adipic acid.Finally, biology base adipic acid is carried out subsequent nitrilation and amination treatment, biology base hexamethylene diamine can be obtained.Therefore, mesh
Preceding domestic and international biology base hexamethylene diamine monomer is also in conceptual phase, and there are no the reports of related industry.
Currently, the research of domestic and international polyamide PA69 is also limited only to basic research, research contents also essentially consist in crystallization,
Thermal degradation, blending etc..Biology base PA69 flexibility and good stability of the dimension, it is solvent resistant, wear-resistant, corrosion-resistant, low temperature resistant
Impact, electrical insulation capability is excellent, can be widely applied to fibre, extrusion, mechanograph, cable prepuce etc., it is also possible to cure
With biomimetic material, slightly higher 5~10 degree of its glass transition temperature are compared compared with PA11, and base carbon atom number structural unit is electroactive
Be conducive to ostosis.Therefore, vast market prospect will be possessed in following industrial circle.
Prior art head in the synthesis process of PA69 is required to azelaic acid, hexamethylene diamine monomer is first dissolved in ethyl alcohol etc. has
In solvent, reaction is remixed into salt, the later period also needs by subsequent treatment process systems such as sub-cooled, rotary evaporation, dryings
Standby corresponding amidic-salt.Then, then amidic-salt is added in polymerization equipment and prepares polyamide PA69 high polymer.Such reaction
It is normally thought of as being divided into the progress of two steps, one side operating procedure and process flow are many and diverse, consumption of raw materials and equipment requirement phase
To higher；The monomers such as reaction are dissolved using ethyl alcohol equal solvent, a large amount of organic solvent can be consumed, while being unfavorable for environmental protection
Increase the difficulty of post-processing work；On the other hand, operation, meeting is exhausted under the conditions ofs high temperature and pressure etc. in polycondensation phase needs
Monomer in reaction system is caused seriously to escape, monomer ratio is unbalance.Therefore, during the reaction, hexamethylene diamine monomer was required to
Amount about 5% or so, and monomer excessively can play the role of sealing end, lead to molecular weight and the performance decline of polymer.Therefore, how
The excellent biological poly amide PA69 of environmentally friendly, efficient processability is the current technical issues that need to address.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of biological poly amide PA69 and its preparation side
Method.It is solvent without using any organic solvent and additive that water is used only in the entire synthesis process of the present invention, can both be kept away in this way
Exempt to change the physico-chemical parameter and performance of monomer and amine salt in polymerization process because of organic solvent and being introduced into for additive, to influence
Entire polymerization technique process.The present invention takes water as a solvent clean and environmental protection, and it is environmentally protective recyclable to meet biology base high molecular material
Regenerated objective, and the present invention takes water as a solvent and provides reaction medium for polymerization process, convenient for energy transmission, charging and after
Continuous reaction.
For achieving the above object, using following technical scheme:
A kind of preparation method of biological poly amide, 1,9- azelaic acid and 1,6- hexamethylene diamine are prepared by melt polycondensation reaction
Biological poly amide specially prepares biological poly azelaic acid acyl hexamethylene diamine, comprising the following steps:
(1) 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution are prepared: 1,6- hexamethylene diamine is added (before use in deionized water
It is liquid that low-grade fever, which melts it by crystal) with stirred in the mixture of 1,9- azelaic acid, mixed solution is made；Hexamethylene diamine is liquid
Body, azelaic acid is powdered, and hexamethylene diamine is dissolved in water azelaic acid and is slightly soluble in water under room temperature, added after the two mixing water will form it is transparent
Solution system.
(2) prepare poly- azelaic acid acyl hexamethylene diamine: by 1,6- hexamethylene diamine and 1,9- azelaic acid mixed solution is added in reactor,
Then the atmosphere in reactor is replaced into inert atmosphere, then under stirring, above-mentioned mixed solution in reactor into
Poly- azelaic acid acyl hexamethylene diamine is made in row melt polycondensation reaction；
1, the 9- azelaic acid is biology base 1,9- azelaic acid, by crude vegetal or soybean grease by saponification, acid
Changing separation can be obtained oleic acid, then make the fracture of its double bond can 1,9- nonyl two into the present invention oleic acid progress oxicracking
Acid；1,6- hexamethylene diamine in the present invention is mainly prepared by the product adiponitrile of petroleum cracking by catalytic hydrogenation method.
The melt polycondensation reaction divides four-stage to carry out, and the reaction temperature of first stage is 110~140 DEG C, reactor
Interior pressure is 0.1~0.4MPa, and stirring rate is 100~300r/min, while during the reaction, being constantly discharged in reactor
Steam, the vapour quantity of discharge are to stop exhaust when being initially added the 75~95% of water total volume；The reaction temperature of second stage
It is 180~230 DEG C, reactor pressure is 0.5~2.5MPa, and stirring rate is 150~250r/min, and the reaction time is 1~4
Hour；The reaction temperature of phase III is 220~280 DEG C, reactor pressure 0MPa, and stirring rate is 100~200r/
Min, reaction time are 20~120 minutes；The reaction temperature of fourth stage is 230~270 DEG C, and pressure is -0.1MPa, stirring speed
Rate is 50~150r/min, and the reaction time is 20~150 minutes.
The present invention is as follows by 1,9- azelaic acid and the reaction equation of 1,6- hexamethylene diamine synthesising biological based polyamide PA69:
The technology of the present invention first reacted under the conditions of low-temp low-pressure by (i.e. first stage of reaction of melt polycondensation reaction),
1,9- azelaic acid and 1 in the process, two kinds of monomers of 6- hexamethylene diamine carry out quick salt-forming reaction in polymerization reaction kettle, while
Constantly steam is discharged during heating, regulates and controls pressure in kettle.First stage of reaction of melt polycondensation reaction is low in the present invention
When pressure gas, it is reversible that this phase temperature is below the fusing point of amide small molecule salt and the generation of amide small molecule salt in reaction system
The boiling point of the acid, amine monomers that generate is reacted, therefore not will cause the evolution of monomeric small molecule substantially.Then it is protected in the present invention
(i.e. second stage of reaction) is reacted in warm pressure maintaining, and pressure needed for this elementary reaction is adjusted in first stage of reaction without row
Gas, it is possible to prevente effectively from this high temperature and pressure stage monomer (wherein, the boiling point of 1,6- hexamethylene diamine is about 200 DEG C) is due to steam is discharged
Evolution is decomposed, monomer is caused to be lost and match unevenness, eventually leads to molecular weight and the comprehensive performance decline of polymer.
And be all made of two-step method in synthesis process of the prior art about polyamide PA69: selection organic solvent is molten first
Agent prepares corresponding small molecule amine salt, then again by small molecule amine salt under the conditions ofs high temperature and pressure etc. (relative in the application
Second stage of reaction of melt polycondensation reaction) progress melt polycondensation synthesizes the heat-insulation pressure keeping reaction in reaction process, and press at this time
Power must also control in a certain range, solvent be discharged to adjust phase therefore it is necessary to be exhausted under high-temperature and high-pressure conditions
The pressure value answered, so that it is guaranteed that later period amidic-salt melt polycondensation reaction is gone on smoothly.But it is inevitable to have two o'clock at this time
Defect, first: if this stage is exhausted, kettle internal solvent can be largely discharged, and temperature in the kettle can generate certain fluctuation, influence
Reaction rate；Second: this stage is exhausted, and the temperature in kettle is higher than the fusing point and corresponding amides of small molecule amine salt at this time
Salt (the small molecule amine salt of addition has reversible reaction in a solvent, generates the monomers such as corresponding small molecule acid, amine) generates small
The fusing point of molecule monomer adds condition of high voltage, and amine salt can decompose in exhaust process, and the relatively low amine monomers of boiling point are opposite to be escaped
It is more, cause reaction monomers proportion unbalance.So during the reaction, corresponding amine monomers are required to excessive about 5% or so,
And monomer excessively can play the role of sealing end, lead to molecular weight and the performance decline of polymer.The present invention is in first stage of reaction
It is just exhausted, so that it may effectively avoid such problems, monomer ratio is uniform in reaction system, convenient for preferably carrying out subsequent contracting
Poly- reaction, further increases the molecular weight and comprehensive performance of polymer.The present invention optimizes the preparation process of traditional polyamide, can be with
Synthesize that molecular weight is higher and performance more preferably polyamide high polymer.
As a preferred technical scheme:
The preparation method of biological poly amide as described above, the yield of the biological poly azelaic acid acyl hexamethylene diamine are 85
~95%.
The preparation method of biological poly amide as described above, the reactor are polymeric kettle, 1,9- azelaic acid and 1,6-
The gross mass of hexamethylene diamine and the mass ratio of deionized water are 1:0.2~1.0,1, the 9- azelaic acid and 1, the monomer of 6- hexamethylene diamine
Mol ratio is 1:1~1.01.
The preparation method of biological poly amide as described above, the reaction temperature of the melt polycondensation reaction first stage are
120~130 DEG C, pressure is 0.15~0.25MPa in kettle, and stirring rate is 150~250r/min, while during the reaction,
Steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 80~90% of water total volume；The
The reaction temperature of two-stage is 200~210 DEG C, and pressure is 1.3~1.7MPa in kettle, and stirring rate is 150~200r/min, instead
It is 2~3 hours between seasonable；The reaction temperature of phase III is 240~250 DEG C, and pressure is 0MPa, stirring rate 100 in kettle
~150r/min, reaction time are 40~90 minutes；The reaction temperature of fourth stage be 240~250 DEG C, in kettle pressure be-
0.1MPa, reaction time are 30~90 minutes, and stirring rate is 50~100r/min.
The same deionized water of the preparation method of biological poly amide as described above, 1,9- azelaic acid and 1,6- hexamethylene diamine is mixed
After conjunction, mixing time is 1~10 minute；Stirring rate is 100~400r/min.
The preparation method of biological poly amide as described above, when melt polycondensation reaction carries out first stage reaction, polymerization
The measurement method for the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle, from
And obtain the vapour quantity of discharge；When melt polycondensation reaction carries out fourth stage reaction, pressure in polymeric kettle is made to be negative the method for pressure
It is to be vacuumized to closed polymeric kettle, makes to generate negative pressure in it.
The preparation method of biological poly amide as described above, the method that the atmosphere in polymeric kettle is replaced into inert atmosphere
Be vacuumize 1 to closed polymeric kettle~after twenty minutes, be passed through and inert gas be discharged 1~10 minute；The inert gas is
Nitrogen.
As above the biological poly amide that any preparation method is prepared, the molecular formula of poly- azelaic acid acyl hexamethylene diamine
Are as follows:Wherein, n is integer, and the value range of n is 80~180.
Biological poly amide as described above, the melting temperature of the poly- azelaic acid acyl hexamethylene diamine are 210~220 DEG C.
Biological poly amide as described above, the bio-based matter ratio of the poly- azelaic acid acyl hexamethylene diamine are 61.8%, i.e.,
For part biological based polyamide material.
The utility model has the advantages that
(1) the biology base PA69 prepared by the present invention is biological based high molecular material, and the exploitation for biological based polyamide mentions
New product is supplied.The biological poly amide PA69 that the present invention synthesizes is beneficial to alleviate what current traditional polyamide industrial circle faced
The increasingly depleted awkward situation of fossil resource, also the sustainable development for polyamide industry provides completely new thinking.
(2) the technology of the present invention is a step melt polycondensation reaction, does not add any organic solvent in synthesis process, safety, nothing
Poison, environmental protection, meets the objective of biology base high molecular material sustainable development.Biological poly is prepared by direct melt polycondensation reaction
Amide PA69, simplifies salification process, optimizes and improves the existing synthetic technology about PA69, further improve PA69's
Relative viscosity and molecular weight keep its comprehensive performance more superior.
(3) synthetic method of the invention is simpler convenient, effectively reduces the energy consumption and equipment requirement, meanwhile, it improves
Product efficiency and comprehensive performance, are conducive to processing and forming and study on the modification, have established for its industrialized realization good in later period
Theory and practice basis.
(4) between 1.6~1.7, viscosity and molecular weight need the relative viscosity range of the PA69 of prior art synthesis
It further increases；And the relative viscosity of PA69 synthesized in the technology of the present invention can reach 2.4, number-average molecular weight can reach
40000 or more.Finally, high polymer is flowed out after polymerization reaction with melt form in this technology invention, compared with the prior art
More conducively molding and following process modification.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.3, and it is molten that mixing is made after stirring 2 minutes with the rate of 400r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.008；
Then the atmosphere in polymeric kettle is replaced into nitrogen atmosphere, is to close by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
It after the polymeric kettle closed vacuumizes 1 minute, is passed through and inert gas is discharged 10 minutes, then under stirring, above-mentioned mixing is molten
Liquid carries out melt polycondensation reaction in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out,
The reaction temperature of first stage is 110 DEG C, and pressure is 0.13MPa, stirring rate 100r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 75% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 185 DEG C, and pressure is 1.0MPa in kettle, and the reaction time is 1 small
When, stirring rate 150r/min；The reaction temperature of phase III is 220 DEG C, and pressure is 0MPa in kettle, and the reaction time is 30 points
Clock, stirring rate 100r/min；The reaction temperature of fourth stage is 230 DEG C, and pressure is -0.1MPa, and the reaction time is 30 points
Clock, stirring rate 60r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in it negative
Pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 90
~100, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 210~215 DEG C, yield 85%.
Embodiment 2
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.9, and obtained mixing is molten after ten minutes with the stirring of the rate of 100r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.01；So
The atmosphere in polymeric kettle is replaced into nitrogen atmosphere afterwards, is to closed by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
Polymeric kettle vacuumize after twenty minutes, be passed through and inert gas be discharged 2 minutes, then under stirring, above-mentioned mixed solution
Melt polycondensation reaction is carried out in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out, the
The reaction temperature in one stage is 140 DEG C, and pressure is 0.35MPa, stirring rate 300r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 95% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 230 DEG C, and pressure is 2.4MPa in kettle, and the reaction time is 4 small
When, stirring rate 200r/min；The reaction temperature of phase III is 270 DEG C, and pressure is 0MPa in kettle, and the reaction time is 60 points
Clock, stirring rate 200r/min；The reaction temperature of fourth stage is 270 DEG C, and pressure is -0.1MPa, and the reaction time is 60 points
Clock, stirring rate 100r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in it negative
Pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 100
~110, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 210~215 DEG C, yield 89%.
Embodiment 3
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.7, and it is molten that mixing is made after stirring 8 minutes with the rate of 150r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.005；
Then the atmosphere in polymeric kettle is replaced into nitrogen atmosphere, is to close by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
It after the polymeric kettle closed vacuumizes 15 minutes, is passed through and inert gas is discharged 5 minutes, then under stirring, above-mentioned mixing is molten
Liquid carries out melt polycondensation reaction in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out,
The reaction temperature of first stage is 120 DEG C, and pressure is 0.2MPa, stirring rate 250r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 90% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 195 DEG C, and pressure is 1.4MPa, reaction time 1.5 in kettle
Hour, stirring rate 200r/min；The reaction temperature of phase III is 230 DEG C, and pressure is 0MPa, reaction time 45 in kettle
Minute, stirring rate 150r/min；The reaction temperature of fourth stage is 240 DEG C, and pressure is -0.1MPa, reaction time 90
Minute, stirring rate 120r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in its
Negative pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 130
~140, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 215~220 DEG C, yield 91%.
Embodiment 4
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.5, and obtained mixing is molten after five minutes with the stirring of the rate of 200r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.001；
Then the atmosphere in polymeric kettle is replaced into nitrogen atmosphere, is to close by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
The polymeric kettle closed vacuumizes after ten minutes, is passed through and inert gas is discharged 6 minutes, and then under stirring, above-mentioned mixing is molten
Liquid carries out melt polycondensation reaction in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out,
The reaction temperature of first stage is 125 DEG C, and pressure is 0.23MPa, stirring rate 150r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 80% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 200 DEG C, and pressure is 1.5MPa, reaction time 2.5 in kettle
Hour, stirring rate 175r/min；The reaction temperature of phase III is 240 DEG C, and pressure is 0MPa, reaction time 75 in kettle
Minute, stirring rate 120r/min；The reaction temperature of fourth stage is 245 DEG C, and pressure is -0.1MPa, reaction time 70
Minute, stirring rate 75r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in its
Negative pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 140
~160, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 215~220 DEG C, yield 95%.
Embodiment 5
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.6, and it is molten that mixing is made after stirring 7 minutes with the rate of 250r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.003；
Then the atmosphere in polymeric kettle is replaced into nitrogen atmosphere, is to close by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
It after the polymeric kettle closed vacuumizes 12 minutes, is passed through and inert gas is discharged 8 minutes, then under stirring, above-mentioned mixing is molten
Liquid carries out melt polycondensation reaction in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out,
The reaction temperature of first stage is 130 DEG C, and pressure is 0.25MPa, stirring rate 200r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 85% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 210 DEG C, and pressure is 1.6MPa in kettle, and the reaction time is 2 small
When, stirring rate 180r/min；The reaction temperature of phase III is 245 DEG C, and pressure is 0MPa in kettle, and the reaction time is 70 points
Clock, stirring rate 135r/min；The reaction temperature of fourth stage is 250 DEG C, and pressure is -0.1MPa, and the reaction time is 75 points
Clock, stirring rate 80r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in it negative
Pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 160
~170, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 215~220 DEG C, yield 93%.
Embodiment 6
A kind of preparation method of biological poly amide, comprising the following steps:
It prepares 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution: (melting it by crystal using preceding low-grade fever 1,6- hexamethylene diamine
Turn to liquid) be added in 1,9- azelaic acid, according to reaction monomers (i.e. 1,9- azelaic acid and 1, the quality summation of 6- hexamethylene diamine) and
The mass ratio of deionized water is that deionized water is added in 1:0.4, and it is molten that mixing is made after stirring 4 minutes with the rate of 150r/min
Liquid.
Prepare poly- azelaic acid acyl hexamethylene diamine: by the mixed solution of 1,6- hexamethylene diamine and 1,9- azelaic acid adding by polymeric kettle
After material mouth is added in polymeric kettle, polymeric kettle is sealed, the monomer molar proportion of 1,9- azelaic acid and 1,6- hexamethylene diamine is 1:1.006；
Then the atmosphere in polymeric kettle is replaced into nitrogen atmosphere, is to close by the method that the atmosphere in polymeric kettle is replaced into nitrogen atmosphere
After the polymeric kettle closed vacuumizes 8 minutes, it is passed through and inert gas is discharged 4 minutes, then under stirring, above-mentioned mixed solution
Melt polycondensation reaction is carried out in polymeric kettle, and poly- azelaic acid acyl hexamethylene diamine is made；Melt polycondensation reaction divides four-stage to carry out, the
The reaction temperature in one stage is 115 DEG C, and pressure is 0.18MPa, stirring rate 175r/min in kettle, while in reaction process
In, steam is constantly discharged in polymeric kettle, the vapour quantity of discharge is to stop exhaust when being initially added the 90% of water total volume, is gathered
The measurement method for closing the vapour quantity being discharged in kettle is that volume is collected through condensing unit and measured to the steam that will be discharged in polymeric kettle,
To obtain the vapour quantity of discharge；The reaction temperature of second stage is 190 DEG C, and pressure is 1.3MPa in kettle, and the reaction time is 3 small
When, stirring rate 160r/min；The reaction temperature of phase III is 250 DEG C, and pressure is 0MPa in kettle, and the reaction time is 90 points
Clock, stirring rate 140r/min；The reaction temperature of fourth stage is 255 DEG C, and pressure is -0.1MPa, and the reaction time is 45 points
Clock, stirring rate 50r/min, making the be negative method of pressure of pressure in polymeric kettle is vacuumized to polymeric kettle, makes to generate in it negative
Pressure.
The biological poly azelaic acid acyl hexamethylene diamine prepared by the above method is biological poly amide material, poly- nonyl two
The molecular formula of sour acyl hexamethylene diamine are as follows:Wherein, n is integer, and the value range of n is 110
~130, the melting temperature of poly- azelaic acid acyl hexamethylene diamine is 210~215 DEG C, yield 86%.
The preparation-obtained biological poly amide PA69 of 1-6 of the embodiment of the present invention is subjected to following performance test:
(1) number-average molecular weight: being the gel permeation chromatography of solvent phase by hexafluoroisopropanol, and the number for measuring polymer is divided equally
Son amount；
(2) relative viscosity: according to GB12006.1-89 standard testing；
(3) tensile property: according to ASTM-D638 standard testing；
(4) bending property: according to ASTM-D790 standard testing；
(5) notched impact properties: according to ASTM-D256 standard testing；
(6) melting temperature: according to ASTM-D3418 standard testing；
The physical mechanical property of the biological poly amide PA69 of embodiment 1-6 preparation is as shown in table 1:
The physical mechanical property of the biological poly amide PA69 of 1 embodiment 1-6 of table synthesis
Find out from upper table, the comprehensive performance of biological poly amide PA69 prepared by embodiment 4 and 5 is better than other embodiments
The biological poly amide PA69 being prepared, the biological poly amide PA69 comprehensive performance that embodiment 5 is prepared are best.
Claims (9)
1. a kind of preparation method of biological poly amide, it is characterized in that: 1,9- azelaic acid and 1,6- hexamethylene diamine passes through melt polycondensation
Reaction prepares biological poly amide, specially prepares biological poly azelaic acid acyl hexamethylene diamine, comprising the following steps:
(1) 1,6 hexamethylene diamines and 1,9- azelaic acid mixed solution are prepared: 1,6- hexamethylene diamine and 1,9- azelaic acid is added in deionized water
Mixture in stir, be made mixed solution；
(2) prepare poly- azelaic acid acyl hexamethylene diamine: by 1,6- hexamethylene diamine and 1,9- azelaic acid mixed solution is added in reactor, then
Atmosphere in reactor is replaced into inert atmosphere, then under stirring, above-mentioned mixed solution is melted in reactor
Melt polycondensation reaction, poly- azelaic acid acyl hexamethylene diamine is made；
The 1,9- azelaic acid is biology base 1,9- azelaic acid；
The melt polycondensation reaction divides four-stage to carry out, and the reaction temperature of first stage is 110~140 DEG C, reactor internal pressure
Power is 0.1~0.4MPa, and stirring rate is 100~300r/min, while during the reaction, water being constantly discharged in reactor
Vapour, the vapour quantity of discharge are to stop exhaust when being initially added the 75~95% of water total volume；The reaction temperature of second stage is
180~230 DEG C, reactor pressure is 0.5~2.5MPa, and stirring rate is 150~250r/min, and the reaction time is 1~4 small
When；The reaction temperature of phase III is 220~280 DEG C, reactor pressure 0MPa, and stirring rate is 100~200r/min,
Reaction time is 20~120 minutes；The reaction temperature of fourth stage is 230~270 DEG C, and reactor pressure is -0.1MPa, is stirred
Mixing rate is 50-150r/min, and the reaction time is 20~150 minutes.
2. the preparation method of biological poly amide according to claim 1, which is characterized in that the biological poly azelaic acid
The yield of acyl hexamethylene diamine is 85~95%.
3. the preparation method of biological poly amide according to claim 1, which is characterized in that the reactor is polymerization
Kettle, 1,9- azelaic acid and 1, the gross mass of 6- hexamethylene diamine and the mass ratio of deionized water are 1:0.2~1.0,1, the 9- nonyl two
The monomer molar proportion of acid and 1,6- hexamethylene diamine is 1:1~1.01.
4. the preparation method of biological poly amide according to claim 3, which is characterized in that the melt polycondensation reaction
The reaction temperature in one stage is 120~130 DEG C, and pressure is 0.15~0.25MPa in kettle, and stirring rate is 150~250r/min,
Simultaneously during the reaction, be constantly discharged steam in polymeric kettle, the vapour quantity of discharge be initially added water total volume 80~
When 90%, stop exhaust；The reaction temperature of second stage is 200~210 DEG C, and pressure is 1.3~1.7MPa, stirring rate in kettle
For 150~200r/min, the reaction time is 2~3 hours；The reaction temperature of phase III is 240~250 DEG C, and pressure is in kettle
0MPa, stirring rate are 100~150r/min, and the reaction time is 40~90 minutes；The reaction temperature of fourth stage be 240~
250 DEG C, pressure is -0.1MPa in kettle, and the reaction time is 30~90 minutes, and stirring rate is 50~100r/min.
5. the preparation method of biological poly amide according to claim 1, which is characterized in that mixing time in step (1)
It is 1~10 minute；Stirring rate is 100~400r/min.
6. the preparation method of biological poly amide according to claim 3, which is characterized in that melt polycondensation reaction carries out the
When one elementary reaction, the measurement method for the vapour quantity being discharged in polymeric kettle is that the steam that will be discharged in polymeric kettle is received through condensing unit
Collect and measure volume, to obtain the vapour quantity of discharge；When melt polycondensation reaction carries out fourth stage reaction, make in polymeric kettle
Pressure is that the method for negative pressure is vacuumized to closed polymeric kettle, makes to generate negative pressure in it.
7. the preparation method of biological poly amide according to claim 3, which is characterized in that set the atmosphere in polymeric kettle
The method for being changed to inert atmosphere be vacuumize 1 to closed polymeric kettle~after twenty minutes, be passed through and be discharged 1~10 point of inert gas
Clock；The inert gas is nitrogen.
8. the preparation method of biological poly amide according to claim 1, it is characterized in that: the poly- azelaic acid acyl of preparation oneself two
The molecular formula of amine are as follows:Wherein, n is integer, and the value range of n is 80~180.
9. the preparation method of biological poly amide according to claim 8, it is characterized in that: the poly- azelaic acid acyl hexamethylene diamine
Melting temperature be 210~220 DEG C.
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