CN110054772A - A kind of Long Carbon Chain Polyamide resin and preparation method thereof - Google Patents
A kind of Long Carbon Chain Polyamide resin and preparation method thereof Download PDFInfo
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- CN110054772A CN110054772A CN201810052832.6A CN201810052832A CN110054772A CN 110054772 A CN110054772 A CN 110054772A CN 201810052832 A CN201810052832 A CN 201810052832A CN 110054772 A CN110054772 A CN 110054772A
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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 present invention provides a kind of long-carbon-chain polyamide and preparation method thereof; the raw materials for production of Long Carbon Chain Polyamide resin include 1; 5- pentanediamine, long carbochain biatomic acid, end-capping reagent and other additives; preparation process is as follows: under nitrogen or inert gas shielding; reaction raw materials are added in reaction vessel; polyamide salt aqueous solution is prepared, polyamide salt aqueous solution is transferred in polymeric kettle, carries out polycondensation reaction.By optimizing polymerization technique, including control polymer raw and regulation reaction condition, can get heretofore described Long Carbon Chain Polyamide, fluctuated with viscosity number it is small, the features such as easy processing, superior performance.
Description
Technical field
The invention belongs to polyamide material technical fields, and in particular to a kind of Long Carbon Chain Polyamide resin and its preparation side
Method.
Background technique
In general, we call the carbon chain lengths in polyamide molecule between 2 amide groups in 10 or more polyamide
Long Carbon Chain Polyamide.Many performances of polyamide are strongly depend on the concentration of amide groups in polyamide, and carbon in polyamide molecule
The length of chain directly determines amide groups concentration again, and carbochain is longer, and the concentration of amide groups is with regard to smaller.With carbon chain lengths
Increase, polyamide performance changes.Long Carbon Chain Polyamide applies involved automobile, electronic apparatus, machinery, military equipment etc.
Every field.For a long time, important to one in the research and development of Long Carbon Chain Polyamide always polyamide new product development
And popular project.
Long Carbon Chain Polyamide removes for example good mechanical property of most of versatilities, wearability, profit with common polyamide
Slip, solvent resistance and easily molded processability etc., also have following unique performance: (1) water absorption rate is low.Polyamide water suction is main
It is since polar amide groups in polyamide molecule and water have very strong affinity.Amide groups in long carbon chain nylon molecule is dense
Degree is smaller than common polyamide, therefore its water absorption rate is low, if the water absorption rate of polyamide 12 is only 0.25%, and the water suction of polyamide 6
Rate is 1.8%.(2) good stability of the dimension.Since the water absorption rate of Long Carbon Chain Polyamide is low, also can in a humidity environment
Higher toughness and hardness are kept, too big change will not occur for mechanical property.The component made of Long Carbon Chain Polyamide, ruler
Very little stability is good, and precision is high, can be used for the occasion of precise requirements height, humid environment.(3) toughness and flexibility are good.Long carbon chain
Polyamide molecule have can free extension and rotation methine long-chain, therefore, toughness and flexibility are good, and rebound degree is high, i.e.,
Make also impact flexibility and flexibility with higher at quite low temperatures, flexible products and cold-resistant component can be made.(4) wear-resisting
Damage is had excellent performance.The abrasion coefficient of Long Carbon Chain Polyamide is small, and abrasion loss is low, such as under the same conditions, polyamide 11, polyamide
12, polyamide 6, polyamide 66 abrasion amount be respectively 9.9mg, 8.2mg, 35.0mg, 27.0mg (Wang Duoren, nylon 11 and Buddhist nun
Application [J] the synthesis material aging of dragon 12 and application, 1996 (3): 17).It will not be generated when rubbing with smooth metal surface
It is serious to wear and occur apparent abrasive dust, so Long Carbon Chain Polyamide is particularly suitable for production wear parts.(5) electrical property is excellent
It is different.The long carbon chain structure of Long Carbon Chain Polyamide imparts its excellent electric property.Since the water imbibition of Long Carbon Chain Polyamide is small,
Although still having excellent dielectric properties in a humid environment, this be the short carbon chains such as polyamide 6, polyamide 66 polyamide institute not
The characteristic having.
Current polyamide product is essentially all to be made using the derivative of petroleum as raw material, and general synthesis technology is multiple
It is miscellaneous, and there is certain pollution.For a long time, people wait in expectation using can be come what is grown by the absorbing carbon dioxide from air again
Plant resource as starting material, come prepare with the comparable biological poly amide of existing kind polyamide performance, solve to non-
Circular Society Construction is built in the dependence of the renewable sources of energy.In this context, triumphant match biology takes the lead in obtaining by lysine decarboxylation
1,5- pentanediamine simultaneously realizes volume production (referring to patent CN102851307B), and using it as a series of biology base polyamides of Material synthesis
Amine, polyamide 5X (PA5X) (referring to patent CN103145979B).Wherein PA510 is shortest as carbochain in Long Carbon Chain Polyamide
Polyamide, there are many special performances.But when in the course of the polymerization process, being polymerize using conventional polymerization process, before and after pelletizing process
The viscosity number difference being sliced obtained by phase is very big, and this viscosity number difference has seriously affected it and answered in injection molding, spinning, membrane field
With.
Summary of the invention
It is excessive in order to solve to fluctuate using the long-carbon-chain polyamide viscosity number of conventional polymerization process production, it influences
The problem of post-processing and performance, present inventor is by optimization polymerization technique, including control polymer raw and regulation are instead
Condition is answered, the viscosity number undulated control of Long Carbon Chain Polyamide resin can be less than 15mL/g, even less than 6mL/g.
The present invention provides a kind of Long Carbon Chain Polyamide resin, and the Long Carbon Chain Polyamide resin includes following structural formula:
-NH-(CH2)5-NH-CO-R-CO-
Wherein, R is the alkylidene of C8~C10.Preferably, R is the alkylidene of C8 or the alkylidene of C10.
The viscosity number fluctuation of Long Carbon Chain Polyamide resin is less than 15mL/g in the present invention, and preferably viscosity number fluctuation is less than 10mL/g,
More preferable viscosity number fluctuation is less than 6mL/g.
The viscosity number of Long Carbon Chain Polyamide resin is 120-300mL/g, preferably 125-220mL/g in the present invention.
The terminal amino group content of Long Carbon Chain Polyamide resin is 11-39mol/ton, preferably 13-35mol/ in the present invention
Ton, more preferably 15-33mol/ton.
The raw materials for production of Long Carbon Chain Polyamide resin include 1,5- pentanediamine (i.e. pentanediamine or cadaverine, pentamethylene two
Amine), long carbochain biatomic acid and end-capping reagent.
Above-mentioned long carbochain biatomic acid be aliphatic long carbochain biatomic acid, pentanediamine and/or aliphatic long carbochain biatomic acid by
Bioanalysis is prepared.Mentioned here prepared by bioanalysis includes through bioconversion method using organism-based raw material (as fermented
Method, enzyme transforming process) produce product (such as pentanediamine, long-chain biatomic acid etc.)；Or using petroleum-based feedstock through bioconversion side
Method produces product (such as long-chain biatomic acid)；Or product (such as decanedioic acid etc.) is produced through chemical method using organism-based raw material.
Alternatively, pentanediamine and/or aliphatic long carbochain biatomic acid contain the organic carbon for meeting the renewable source of ASTM D6866 standard.
Aliphatic long carbochain biatomic acid is preferably decanedioic acid, eleven carbon diacids, any one in dodecanedicarboxylic acid
Or several combinations, more preferably decanedioic acid or dodecanedicarboxylic acid.
End-capping reagent includes any compound reacted with Amino End Group, carboxyl end group, preferably contains carboxyl compounds, more preferable second
Acid, any one in adipic acid or two kinds.
The quality of end-capping reagent account for the 2% of Long Carbon Chain Polyamide production of resins raw material pentanediamine and binary acid gross mass hereinafter,
It is preferred that 1% or less.
The raw materials for production of Long Carbon Chain Polyamide resin can also include additive, and the quality of additive accounts for Long Carbon Chain Polyamide
The 40% of the raw materials for production gross mass of resin is hereinafter, it is preferred that account for 20% or less.
The present invention also provides the preparation methods of above-mentioned Long Carbon Chain Polyamide resin, include the following steps:
1) under nitrogen or inert gas shielding, reaction raw materials are added in reaction vessel, prepare polyamide salt aqueous solution；
2) polyamide salt aqueous solution obtained by step 1) is transferred in polymeric kettle, carries out polycondensation reaction.
PH value is 6.60-8.75 when polyamide salt concentration of aqueous solution is 10wt% in step 1), preferably 6.70~7.42,
More preferably 6.80~7.15.
Preferably, the pH value of polyamide salt aqueous solution is adjusted with pentanediamine or long carbochain biatomic acid.
It further includes that end-capping reagent is added that polyamide salt aqueous solution is prepared in step 1).
Preferably, end-capping reagent is acetic acid, any one in adipic acid or two kinds in step 1), and the additional amount of end-capping reagent is length
Carbochain polyamide raw materials for production gross mass pentanediamine and binary acid 2% are hereinafter, it is preferred that 1% or less.
It further includes that additive is added that polyamide salt aqueous solution is prepared in step 1).
Preferably, additive is antioxidant in step 1).
The mass concentration of polyamide salt aqueous solution is 30%-80% in step 1), and preferred mass concentration is 40-70%.
Polymerization technique listed by step 2) is conventional polycondensation technique, reaction condition are as follows: be heated to pressure in reaction vessel and rise to
0.5~3.0MPa starts to be vented and keep the pressure, when system temperature rises to 200~320 DEG C, makes pressure in reaction vessel
It is gradually down to normal pressure, is further continued for 25~120min of reaction, preferably 40~80min.
It preferably, further include carrying out depressurization steps after pressure is down to normal pressure in reaction vessel in step 2).
It is highly preferred that pressure is down to normal pressure in reaction vessel in step 2), it further include the step for rising to normal pressure again after decompression
Suddenly.
The pressure limit of above-mentioned decompression is -0.01~-0.1MPa (gauge pressure).
By adopting the above scheme, the beneficial effects of the present invention are:
The present invention is passed through using raw material 1,5- pentanediamine, aliphatic long carbochain biatomic acid, end-capping reagent and various additives
The polymerization technique of optimization has obtained the long-carbon-chain polyamide that viscosity number fluctuation is less than 15mL/g.It overcomes and utilizes tradition
Long carbon chain biological poly amide resin viscosity number obtained by polymerization technique fluctuates larger disadvantage.Excessive viscosity number fluctuation can cause to add
There are many problems during work, such as feeds unsmooth, spinning and fracture of wire, product mechanical property variation occur, without film forming processability
Energy.
In addition, one of raw material used in the present invention or a variety of derived from reproducible plant, belongs to environmentally friendly material on the whole
Material, alleviates the dependence to non-renewable energy, is conducive to build Circular Society Construction.
Specific embodiment
Heretofore described Long Carbon Chain Polyamide resin includes following structural formula:
-NH-(CH2)5-NH-CO-R-CO-
Wherein, R is the alkylidene of C8~C10.Preferably, R is the alkylidene of C8 or the alkylidene of C10.
The viscosity number fluctuation of heretofore described Long Carbon Chain Polyamide resin is less than 15mL/g, and preferably viscosity number fluctuation is less than
10mL/g, more preferable viscosity number fluctuation are less than 6mL/g.
Viscosity number fluctuation, which refers in the same batch wise polymerization of slice or packaging bag, arbitrarily takes multiple samples, detects viscosity number respectively, appoints
The maximum difference of meaning sample room viscosity number.Pentanediamine, which is carried out, using conventional polymerization process polymerize resulting long carbon with long carbochain biatomic acid
The viscosity number fluctuation of chain polyamide can be in 20mL/g or more, which can seriously affect Long Carbon Chain Polyamide and add in downstream
Use in work, appearance charging is unsmooth such as on screw rod, and molten drop occurs in spinning process, cannot be processed film, while can serious shadow
Ring properties of product.Can be controlled in 15mL/g using the obtained long-carbon-chain nylon viscosity number fluctuation of this patent method hereinafter,
Even 6mL/g is can be controlled in hereinafter, fully meeting requirement of the downstream client to machinability and mechanical property.
The viscosity number of Long Carbon Chain Polyamide resin of the invention is 120-300mL/g, preferably 125-220mL/g.
Index of the viscosity number as molecular weight, the molecular weight of higher representation polymer is higher, the more high then polyamide of molecular weight
Intensity it is higher.This is because the amount of molecule chain end existing for per unit is smaller if molecular weight is higher, then may be
The defect of fiber is fewer.Simultaneously as strand is longer, (such as physics twines each strand with more strands generation interaction
Knot, hydrogen bond, Van der Waals force etc.), uniformly to shift various stress, therefore strand is uniformly directed in process.Another party
Face, the viscosity number in sulfuric acid preferably remain in proper range, because excessively high viscosity number will lead to melt flow decline, influence sample
Product appearance and processing efficiency, therefore viscosity number is more preferably 125-220mL/g.
The terminal amino group content of Long Carbon Chain Polyamide resin of the invention can be 11-39mol/ton, preferably 13-
35mol/ton, more preferably 15-33mol/ton.The reason is as follows that: we have found that when terminal amino group content is lower, the viscosity number of product
Fluctuation range is smaller, and the too low viscosity number that will affect gained polyamide of terminal amino group content is promoted, and being unable to get has and can answer
With the Long Carbon Chain Polyamide resin of value.
The raw materials for production of Long Carbon Chain Polyamide resin include 1,5- pentanediamine, long carbochain biatomic acid and end-capping reagent.
Pentanediamine (i.e. 1,5- pentanediamine or cadaverine, five methylene diamine) can be prepared by bioanalysis, can also be with
It is prepared by chemical method, and the organic carbon for the renewable source for meeting ASTM D6866 standard can be contained.This field skill
Art personnel know, by lysine or lysine salt under the action of lysine decarboxylase (such as EC 4.1.1.18), slough both ends
After carboxyl, pentanediamine is produced.Such as " make lysine decarboxylase property and application study " (Jiang Lili, Nanjing University, master
Paper) in disclose the method that specific bioanalysis prepares pentanediamine.For another example " microorganism conversion L-lysine is grinding for cadaverine
Study carefully " method that specific bioanalysis prepares pentanediamine is also disclosed in (Zhu Jing, University Of Science and Technology Of Tianjin, Master's thesis, 2009.3).
Binary acid is aliphatic long carbochain biatomic acid.Aliphatic long carbochain biatomic acid can also be by bioanalysis or chemical legal system
It is standby to form, and the organic carbon for the renewable source for meeting ASTM D6866 standard can also be contained.As long as guarantee pentanediamine and
At least one of aliphatic long carbochain biatomic acid is biobased products.
Aliphatic long carbochain biatomic acid can be any one in decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid
Or several combinations, preferably decanedioic acid or dodecanedicarboxylic acid.
End-capping reagent includes any compound reacted with Amino End Group, carboxyl end group, preferably contains carboxyl compounds, more preferable second
Acid, adipic acid.
The quality of end-capping reagent accounts for 2% or less Long Carbon Chain Polyamide production of resins raw material pentanediamine and binary acid gross mass.
In experiment find end-capping reagent can be effectively controlled Long Carbon Chain Polyamide resin viscosity number fluctuation, but after excessive addition meeting so that Long carbon chain
Polyamide viscosity number is too low and loses application value, therefore it is preferred that 1% or less.
The raw materials for production of Long Carbon Chain Polyamide resin of the invention can also include additive, and the quality of additive accounts for long carbon
The 40% of the raw materials for production gross mass of chain polyamide is hereinafter, it is preferred that account for 20% or less.
Additive can for antioxidant, heat-resisting stabilizing agent, weather resisting agent, pigment, gloss enhancer, dyestuff, crystal nucleating agent,
Delustering agent, plasticizer, antistatic agent, any one or the combination of several of them in fire retardant.
Wherein, heat-resisting stabilizing agent includes but is not limited to the compound based on hindered phenol, the compound based on quinhydrones, is based on thiophene
The compound of azoles, the compound (such as phenyl-phosphonic acid) based on phosphorus, compound (such as 2-mercaptobenzimidazole) based on imidazoles and its
Substitution product, copper halide and iodine compound etc..
Weather resisting agent includes but is not limited to resorcinol, salicylate, benzotriazole, benzophenone and hindered amine etc..
Pigment includes but is not limited to cadmium sulfide, phthalocyanine and carbon black etc..
Gloss enhancer includes but is not limited to titanium oxide and calcium carbonate etc..
Dyestuff includes but is not limited to Ni Gehei and nigrosine etc..
Crystal nucleating agent includes but is not limited to talcum, silica, kaolin and clay etc..
Plasticizer includes but is not limited to oxybenzoic acid monooctyl ester and N-butylbenzenesulfonamide etc..
Antistatic agent include but is not limited to alkyl sulphate type anionic antioxidant, quaternary ammonium salt cationic type resist it is quiet
Electric agent, non-ionic antistatic agent (such as polyoxyethylene sorbitan monostearate) and both sexes based on glycine betaine are antistatic
Agent etc..
Fire retardant includes but is not limited to melamine cyanurate, hydroxide (such as magnesium hydroxide or aluminium hydroxide), more
Ammonium phosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin, by any fire retardant based on bromine
The combination etc. constituted with antimony oxide.
The invention also discloses a kind of methods for preparing above-mentioned Long Carbon Chain Polyamide resin, include the following steps:
1) under nitrogen or inert gas shielding, reaction raw materials are added in reaction vessel, prepare polyamide salt aqueous solution；
2) polyamide salt aqueous solution obtained by step 1) is transferred in polymeric kettle, carries out polycondensation reaction.It is prepared in step 1)
Polyamide salt aqueous solution further includes that end-capping reagent is added.In experiment we have found that in the case where end-capping reagent is not added Long carbon chain polyamides
The viscosity number fluctuation of polyimide resin is very big, even if adjusting various technological parameters, viscosity number is also difficult to control within the scope of compared with minor swing,
This is because end-capping reagent reduces polymerization goal platform, is conducive to polymerization system and is rapidly achieved equilibrium state, however end-capping reagent is added
It is too low and lose industrial application value that amount excessively will lead to Long Carbon Chain Polyamide viscosity number, therefore the additional amount of end-capping reagent need to be controlled accurately
System is in suitable range.
Preferably, end-capping reagent can be acetic acid, adipic acid in step 1), and the additional amount of end-capping reagent is Long Carbon Chain Polyamide tree
Rouge raw materials for production pentanediamine and binary acid gross mass 2% are hereinafter, it is preferred that 1% or less.
Step 1) further includes the pH value that solution is adjusted with pentanediamine or long carbochain biatomic acid after obtaining polyamide salt aqueous solution
To 6.60-8.75.It is unbalance that excessively high, too low pH value will lead to end group, influences viscosity of polyamides and mechanical property.
Preferably, the pH value of solution be 6.70-7.42, more preferably 6.80~7.15, initial polyamide salt aqueous solution
PH value is larger to the viscosity number influence of fluctuations of Long Carbon Chain Polyamide resin, and at higher ph values, by the way that end-capping reagent is added, viscosity number can
Control is within the scope of compared with minor swing, but span of control limit of control is little, and reason may be since Long Carbon Chain Polyamide 5X is with extraordinary
Advise the polymerizing power of nylon, if pH value is not serious relatively low, polymerization process can not reduction of speed, therefore, to obtain viscosity number
Smaller Long Carbon Chain Polyamide is fluctuated, pH value has to be lower than the pH value for preparing conventional polyamide.However pH value is too low, gained is long
The mechanical property of carbochain polyamide will receive influence, this may be to cause since the degree of polymerization is relatively low, by accurately controlling
PH value processed, can be by viscosity number undulated control in smaller range.
In order not to introduce other impurity, pentanediamine can be selected or long carbochain biatomic acid adjusts the pH of polyamide salt aqueous solution
Value.
It can also include that additive is added that polyamide salt aqueous solution is prepared in step 1).
Preferably, additive is antioxidant in step 1).
The mass concentration of polyamide salt aqueous solution is 30%-80% in step 1), and preferred mass concentration is 40-70%, because
It is limited for one side concentration by upper solubility limit, and concentration is too low, and it is higher to will lead to energy consumption, therefore concentration selects 30%-80%
It is advisable.
Polymerization technique listed by step 2) is conventional polycondensation technique, reaction condition are as follows: be heated to pressure in reaction vessel and rise to
0.5~3.0MPa starts to be vented and keep the pressure, when system temperature rises to 200~320 DEG C, makes pressure in reaction vessel
It is gradually down to normal pressure, is further continued for 25~120min of reaction, preferably 40~80min.
It preferably, further include carrying out depressurization steps after pressure is down to normal pressure in reaction vessel in step 2).
It is highly preferred that pressure is down to normal pressure in reaction vessel in step 2), it further include the step for rising to normal pressure again after decompression
Suddenly.
The pressure limit of above-mentioned decompression is -0.01~-0.1MPa (gauge pressure).
We have found that experience depressurizes or first depressurizes polymerization under atmospheric pressure certain time again after polymerization system is down to normal pressure, can also have
Effect reduces the fluctuation of product viscosity number.Through analyzing, it is believed that polymerization pressure determines rate of polymerization and reaction end platform, decompression process
Be conducive to rate of polymerization promotion, and terminal pressure decides that system moisture platform and reaction end platform, terminal pressure are closer
Normal pressure, reaction end platform are more accessible to, therefore the present invention most preferably first depressurizes again the process of normal pressure.In addition can also pass through
Polymerization time makes polymerization system reach reaction end platform after extension.
The present invention is further illustrated with comparative example with reference to embodiments.
Following embodiments use following characterizing method and have carried out performance characterization to Long Carbon Chain Polyamide resin:
(1) viscosity number
Pass through Ubbelohde viscometer sulphate method: the polyamide sample (such as PA510) 0.25 after precise is dry is viscous
Degree meter sulphate method:, the 50mL concentrated sulfuric acid (96%) dissolution is added, measures and records the concentrated sulfuric acid in 25 DEG C of constant temperature water baths and flows through
Time t0With polyamide sample (such as PA66) solution flow time t.
Viscosity number calculation formula: viscosity number VN=(t/t0-1)/C；
T1 solution flow time；
t0- solvent flow time；
The concentration (g/mL) of C agent polymer.
(2) Amino End Group
By 1g polyamide slice be dissolved under shake at 30 DEG C 50 milliliters of phenol/alcohol mixed solutions (phenol/
Ethyl alcohol=80/20) in, and with the 0.02mol/L hydrochloric acid acid-base titration solution.Determine the amount of 0.02mol/L hydrochloric acid used.It is empty
It is white to use the above-mentioned phenol/alcohol mixed solvent of 0.02mol/L titration with hydrochloric acid, and determine the amount of 0.02mol/L hydrochloric acid.By between amount
Difference obtains the terminal amino group content in every 1 ton of polyamide sample.
(3) pH value
Polyamide salt solution is diluted to 10wt%, is detected at 30 DEG C using pH meter.
1 polyamide 510 of embodiment
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 15kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 23.25kg (115.2mol) decanedioic acid is added, pH value is adjusted to 8.71 (30 DEG C with a small amount of pentanediamine and decanedioic acid
Salting liquid is diluted to 10% testing result), 350g adipic acid is added, adds 25g antioxidant H10, it is water-soluble that polyamide salt is made
Liquid.
2) under nitrogen environment, oil bath temperature gradually rises to 289 DEG C, and pressure rises to 1.7MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 240 DEG C, pressure in reaction vessel is made gradually to be down to normal pressure, temperature in the kettle up to 262 DEG C, maintain normal pressure after
Continuous reaction 38min, is made polyamide 510.
2 polyamide 510 of embodiment
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 20kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 23.25kg (115.2mol) decanedioic acid is added, pH value is adjusted to 8.21 (30 DEG C with a small amount of pentanediamine and decanedioic acid
Salting liquid is diluted to 10% testing result), 175g adipic acid is added, polyamide salt aqueous solution is made.
2) under nitrogen environment, oil bath temperature gradually rises to 285 DEG C, and pressure rises to 1.5MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 245 DEG C, pressure in reaction vessel is made gradually to be down to normal pressure, temperature in the kettle up to 268 DEG C, be evacuated to-
0.07MPa keeps vacuum degree 28min, and polyamide 510 is made.
3 polyamide 510 of embodiment
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 15kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 23.25kg (115.2mol) decanedioic acid is added, pH value is adjusted to 7.42 (30 DEG C with a small amount of pentanediamine and decanedioic acid
Salting liquid is diluted to 10% testing result), 35g adipic acid is added, polyamide salt aqueous solution is made.
2) under nitrogen environment, oil bath temperature gradually rises to 293 DEG C, and pressure rises to 1.7MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 238 DEG C, pressure in reaction vessel is made gradually to be down to normal pressure, temperature in the kettle up to 265 DEG C, be evacuated to-
0.06MPa keeps vacuum degree 55min, and polyamide 510 is made.
4 polyamide 511 of embodiment
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 15kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 24.865kg (115.2mol) eleven carbon diacids is added, is adjusted pH value with a small amount of pentanediamine and 11 carbon diacid
To 7.29 (30 DEG C of salting liquids are diluted to 10% testing result), 35g acetic acid is added, adds 20g antioxidant H10, polyamides is made
Amine salt aqueous solution.
2) under nitrogen environment, oil bath temperature gradually rises to 286 DEG C, and pressure rises to 1.7MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 235 DEG C, pressure in reaction vessel is made gradually to be down to normal pressure, temperature in the kettle up to 267 DEG C, be evacuated to-
0.08Mpa, keeps vacuum degree 28min, and rear inflated with nitrogen to normal pressure continues to stir 20min, polyamide 511 is made.
5 polyamide 512 of embodiment
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 25kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 26.47kg (115.2mol) dodecanedicarboxylic acid is added, is adjusted pH value with a small amount of pentanediamine and dodecanedicarboxylic acid
To 6.96 (30 DEG C of salting liquids are diluted to 10% testing result), 3.5g adipic acid is added, adds 50g antioxidant H10, is made poly-
Amide saline solution.
2) under nitrogen environment, oil bath temperature gradually rises to 290 DEG C, and pressure rises to 1.5MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 245 DEG C, pressure in reaction vessel is made gradually to be down to normal pressure, temperature in the kettle up to 272 DEG C, be evacuated to-
0.07Mpa, keeps vacuum degree 36min, and rear inflated with nitrogen to normal pressure continues to stir 30min, polyamide 512 is made.
1 polyamide 510 of comparative example
1) 100 liters of polymeric kettles (K/SY166-2007 type) is used into nitrogen displaced air, 15kg pure water is added into reaction kettle,
Then 11.75kg (115.2mol) pentanediamine (organic carbon comprising meeting the renewable source of ASTM D6866 standard) is added,
After stirring, 23.25kg (115.2mol) decanedioic acid is added, pH value is adjusted to 7.89 (30 DEG C with a small amount of pentanediamine and decanedioic acid
Salting liquid is diluted to 10% testing result), polyamide salt aqueous solution is made.
2) under nitrogen environment, oil bath temperature gradually rises to 285 DEG C, and pressure rises to 1.7MPa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 262 DEG C, it is evacuated to -0.06MPa, keeps vacuum degree 30min, polyamide 510 is made.
After polyamide is made, it is filled with nitrogen into polymeric kettle and starts melting discharging to pressure 0.4MPa, and utilizes and cuts
Grain machine is granulated, and pelletizing process takes a sample every about 8kg, takes four samples altogether, and viscosity number fluctuation is to appoint in this four samples
Maximum difference between both meanings viscosity number.Plastic sealing pack after 110 DEG C of dryings are dried in vacuo 24 hours.Slice testing result is shown in table
1。
Each embodiment sample detection data of table 1
Table 1 is statistics indicate that the viscosity number fluctuation of long-carbon-chain polyamide obtained by this patent is significantly less than conventional polymerization process
Obtained long-carbon-chain nylon, the pH value of polymerization process nylon salt, the addition of end-capping reagent and polycondensation vacuum condition
Selection is extremely important to viscosity number control, the biological poly amide adaptation Downstream processing of this patent, function admirable, and market prospects are huge
Greatly.
This hair can be understood and used the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments,
Those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in this hairs
Within bright protection scope.
Claims (12)
1. a kind of Long Carbon Chain Polyamide resin, which is characterized in that the Long Carbon Chain Polyamide resin includes following structural formula:
-NH-(CH2)5-NH-CO-R-CO-
Wherein, R is the alkylidene of C8~C10, and the viscosity number fluctuation of the Long Carbon Chain Polyamide resin is less than 15mL/g, preferably viscosity number
Fluctuation is less than 10mL/g, and more preferable viscosity number fluctuation is less than 6mL/g.
2. Long Carbon Chain Polyamide resin according to claim 1, the viscosity number of the Long Carbon Chain Polyamide resin is 120-
300mL/g, preferably 125-220mL/g.
3. Long Carbon Chain Polyamide resin according to claim 1 or 2, the terminal amino group content of the Long Carbon Chain Polyamide resin
For 11-39mol/ton, preferably 13-35mol/ton, more preferably 15-33mol/ton.
4. Long Carbon Chain Polyamide resin according to claim 1-3, the production of the Long Carbon Chain Polyamide resin
Raw material includes 1,5- pentanediamine and long carbochain biatomic acid, and the long carbochain biatomic acid includes decanedioic acid, eleven carbon diacids, 12
Any one or a few in carbon dicarboxylic acid.
5. Long Carbon Chain Polyamide resin according to claim 1-4, the production of the Long Carbon Chain Polyamide resin
Raw material further includes end-capping reagent, and the end-capping reagent includes any compound reacted with Amino End Group, carboxyl end group, preferably class containing carboxyl
Object is closed, any one in more preferable acetic acid, adipic acid or two kinds.
6. Long Carbon Chain Polyamide resin according to claim 5, the quality of the end-capping reagent account for Long Carbon Chain Polyamide resin
Raw materials for production pentanediamine and binary acid gross mass 2% hereinafter, it is preferred that 1% or less.
7. a kind of method for preparing Long Carbon Chain Polyamide resin as claimed in any one of claims 1 to 6, which is characterized in that described
Preparation method the following steps are included:
1) under nitrogen or inert gas shielding, reaction raw materials are added in reaction vessel, prepare polyamide salt aqueous solution；
2) polyamide salt aqueous solution obtained by step 1) is transferred in polymeric kettle, carries out polycondensation reaction.
8. preparation method according to claim 7, the mass concentration of polyamide salt aqueous solution is 30%- in step 1)
80%.
9. preparation method according to claim 7, pH value is when polyamide salt concentration of aqueous solution is 10wt% in step 1)
6.60-8.75, preferably 6.70~7.42, more preferably 6.80~7.15；Preferably, with pentanediamine or long carbochain biatomic acid tune
Save the pH value of polyamide salt aqueous solution.
10. preparation method according to claim 7, polycondensation reaction condition described in step 2) are as follows: be heated to reaction vessel
Interior pressure rises to 0.5~3.0MPa, starts to be vented and keep the pressure, when system temperature rises to 200~320 DEG C, makes to react
Container inner pressure is gradually down to normal pressure, is further continued for 25~120min of reaction, preferably 40~80min.
11. preparation method according to claim 10, after pressure is down to normal pressure in reaction vessel in step 2), further include into
Row depressurization steps, it is preferable that pressure is down to normal pressure in reaction vessel in step 2), further includes the step for rising to normal pressure again after decompression
Suddenly.
12. preparation method according to claim 11, the pressure limit of the decompression is -0.01~-0.1MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066393A (en) * | 2018-01-23 | 2019-07-30 | 凯赛(乌苏)生物技术有限公司 | A kind of Long Carbon Chain Polyamide resin and preparation method thereof |
| CN112759760A (en) * | 2019-11-02 | 2021-05-07 | 上海凯赛生物技术股份有限公司 | High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| CN113214471A (en) * | 2020-01-21 | 2021-08-06 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin, preparation method thereof and high-strength high-modulus fiber |
| CN113651957A (en) * | 2020-09-17 | 2021-11-16 | 上海恒什塑料技术有限公司 | Black-spot-free polyamide composition and polymerization process thereof |
| CN115725074A (en) * | 2021-08-27 | 2023-03-03 | 上海凯赛生物技术股份有限公司 | Bio-based long carbon chain polyamide elastomer and preparation method thereof |
| CN115725068A (en) * | 2021-08-27 | 2023-03-03 | 上海凯赛生物技术股份有限公司 | Polyamide elastomer based on pentamethylene diamine and preparation method and application thereof |
| CN115725068B (en) * | 2021-08-27 | 2024-07-05 | 上海凯赛生物技术股份有限公司 | Pentanediamine-based polyamide elastomer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011207979A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Chemicals Corp | Polyamide resin composition excellent in low temperature impact property, and molded article thereof |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104031263A (en) * | 2013-03-08 | 2014-09-10 | 上海凯赛生物技术研发中心有限公司 | Nylon manufacturing method |
| CN106555250A (en) * | 2015-09-30 | 2017-04-05 | 上海凯赛生物技术研发中心有限公司 | Long Carbon Chain Polyamide fiber and preparation method thereof |
-
2018
- 2018-01-19 CN CN201810052832.6A patent/CN110054772B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011207979A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Chemicals Corp | Polyamide resin composition excellent in low temperature impact property, and molded article thereof |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104031263A (en) * | 2013-03-08 | 2014-09-10 | 上海凯赛生物技术研发中心有限公司 | Nylon manufacturing method |
| CN106555250A (en) * | 2015-09-30 | 2017-04-05 | 上海凯赛生物技术研发中心有限公司 | Long Carbon Chain Polyamide fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴立峰 等: "《合成纤维着色技术》", 31 January 1996, 北京：中国石化出版社 * |
| 赵振河: "《高分子化学和物理》", 30 September 2003, 北京：中国纺织出版社 * |
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| CN110066393A (en) * | 2018-01-23 | 2019-07-30 | 凯赛(乌苏)生物技术有限公司 | A kind of Long Carbon Chain Polyamide resin and preparation method thereof |
| CN110066393B (en) * | 2018-01-23 | 2022-08-02 | 凯赛(乌苏)生物技术有限公司 | Long-carbon-chain polyamide resin and preparation method thereof |
| CN112759760A (en) * | 2019-11-02 | 2021-05-07 | 上海凯赛生物技术股份有限公司 | High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| CN112759760B (en) * | 2019-11-02 | 2023-09-22 | 上海凯赛生物技术股份有限公司 | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| CN113214471A (en) * | 2020-01-21 | 2021-08-06 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin, preparation method thereof and high-strength high-modulus fiber |
| CN113214471B (en) * | 2020-01-21 | 2023-11-17 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin, preparation method thereof and high-strength high-modulus fiber |
| CN113651957A (en) * | 2020-09-17 | 2021-11-16 | 上海恒什塑料技术有限公司 | Black-spot-free polyamide composition and polymerization process thereof |
| CN115725074A (en) * | 2021-08-27 | 2023-03-03 | 上海凯赛生物技术股份有限公司 | Bio-based long carbon chain polyamide elastomer and preparation method thereof |
| CN115725068A (en) * | 2021-08-27 | 2023-03-03 | 上海凯赛生物技术股份有限公司 | Polyamide elastomer based on pentamethylene diamine and preparation method and application thereof |
| CN115725068B (en) * | 2021-08-27 | 2024-07-05 | 上海凯赛生物技术股份有限公司 | Pentanediamine-based polyamide elastomer and preparation method and application thereof |
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