A kind of Long Carbon Chain Polyamide resin and preparation method thereof
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
In order to which the long-carbon-chain polyamide viscosity number fluctuation for solving conventional polymerization process production is excessive, add after influencing
The problem of work and performance, the present invention have obtained one by optimization polymerization technique, the pH value of especially regulation polyamide salt aqueous solution
Kind viscosity number fluctuation is less than the Long carbon chain biological poly amide of 15mL/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 15-35mol/ in the present invention
Ton, more preferably 17-33mol/ton.
The raw materials for production of Long Carbon Chain Polyamide resin include 1,5- pentanediamine (i.e. pentanediamine or cadaverine, five in the present invention
Methylene diamine) and long carbochain biatomic acid, it can also include additive, the quality of additive accounts for the Long Carbon Chain Polyamide resin
Raw materials for production gross mass 40% hereinafter, the quality of preferable additives accounts for the raw materials for production gross mass of Long Carbon Chain Polyamide resin
20% or less.
Above-mentioned long carbochain biatomic acid is aliphatic long carbochain biatomic acid, 1,5- pentanediamine and/or aliphatic Long carbon chain binary
Acid is prepared by bioanalysis.It is mentioned here by bioanalysis preparation include using organism-based raw material through bioconversion method (such as
Fermentation method, enzyme transforming process) produce product (such as pentanediamine, long-chain biatomic acid etc.);Or turned using petroleum-based feedstock through biology
Change method produces product (such as long-chain biatomic acid);Or using organism-based raw material through chemical method production product (such as decanedioic acid
Deng).Alternatively, 1,5- pentanediamine and/or aliphatic long carbochain biatomic acid contain the renewable source for meeting ASTM D6866 standard
Organic carbon.
Aliphatic long carbochain biatomic acid is preferably decanedioic acid, eleven carbon diacids, any one in dodecanedicarboxylic acid
Or several, more preferably decanedioic acid or dodecanedicarboxylic acid.
The present invention also provides 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,
PH is adjusted with pentanediamine or long carbochain biatomic acid;
2) polyamide salt aqueous solution obtained by step 1) is transferred in polymeric kettle, carries out polycondensation reaction.
The pH value of polyamide salt aqueous solution is adjusted in step 1) to 6.60-7.49, preferably 6.80-7.42.
The mass concentration of polyamide salt aqueous solution is 30%-80% in step 1), and preferred mass concentration is 40-70%.
It further includes that additive is added that polyamide salt aqueous solution is prepared in step 1).
Preferably, additive is antioxidant in step 1).
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
1.3~3.0Mpa starts to be vented and keep the pressure, when system temperature rises to 230~320 DEG C, makes pressure in reaction vessel
It is down to 0~-0.1Mpa (gauge pressure), keeps 5~120min of the vacuum degree.
Using the above scheme, the beneficial effects of the present invention are:
The present invention passes through optimization using raw material 1,5- pentanediamine and aliphatic long carbochain biatomic acid and various additives
Polymerization technique has obtained the long-carbon-chain polyamide that viscosity number fluctuation is less than 15mL/g.It overcomes and utilizes conventional polymeric work
Long carbon chain biological poly amide viscosity number obtained by skill fluctuates larger disadvantage.Excessive viscosity number fluctuation can cause to go out in process
Existing many problems, such as feed unsmooth, spinning and fracture of wire, product mechanical property variation occur, without film forming processing performance.
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 refers to any number of samples in the same batch wise polymerization of slice or packaging bag, detects viscosity number respectively, arbitrarily
The maximum difference of sample room viscosity number.Pentanediamine, which is carried out, using conventional polymerization process polymerize resulting Long carbon chain with long carbochain biatomic acid
The viscosity number of polyamide is fluctuated in 20mL/g or more, which can seriously affect Long Carbon Chain Polyamide resin under
Use in trip processing, appearance charging is unsmooth such as on screw rod, and molten drop occurs in spinning process, cannot be processed film, while can be tight
Ghost image rings properties of product.15mL/g is can be controlled in using the obtained long-carbon-chain nylon viscosity number fluctuation of method in the present invention
Hereinafter, even caning be controlled in 6mL/g 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 15-
35mol/ton, more preferably 17-33mol/ton.The reason is as follows that: we have found that when terminal amino group content is higher, 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 valence can be applied by being unable to get to have
The Long Carbon Chain Polyamide resin of value.
The raw materials for production of Long Carbon Chain Polyamide resin of the invention include 1,5- pentanediamine and long carbochain biatomic acid.
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 " L-lysine decarboxylation enzymatic property and application study " (Jiang Lili, Nanjing University, master's opinion
Text) in disclose the method that specific bioanalysis prepares pentanediamine.For another example " research that microorganism conversion L-lysine is cadaverine "
The method that specific bioanalysis prepares pentanediamine is also disclosed in (Zhu Jing, University Of Science and Technology Of Tianjin, Master's thesis, 2009.3).
Long carbochain biatomic acid is aliphatic long carbochain biatomic acid.Aliphatic long carbochain biatomic acid can also be by bioanalysis or change
Method is prepared, and can also contain the organic carbon for the renewable source for meeting ASTM D6866 standard.As long as guaranteeing penta
At least one of diamines and aliphatic long carbochain biatomic acid are 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.
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, the quality of preferable additives accounts for the life of Long Carbon Chain Polyamide resin
Produce 20% or less total mass of raw material.
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.
Preferably, the additive is antioxidant.
The present invention also provides 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,
PH value is adjusted with a small amount of pentanediamine or long carbochain biatomic acid;
2) polyamide salt aqueous solution obtained by step 1) is transferred in polymeric kettle, carries out polycondensation reaction.
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.
The pH value of polyamide salt aqueous solution is adjusted to 6.60-7.49, preferably 6.80-7.42, initial polyamide in step 1)
The pH value of saline solution is very big to the viscosity number influence of fluctuations of Long Carbon Chain Polyamide resin, at higher ph values, even if adjusting
Various technological parameters, viscosity number are also difficult to control within the scope of compared with minor swing, and reason may be due to Long Carbon Chain Polyamide 5X
Polymerizing power with unconventional nylon, if pH value is not serious relatively low, polymerization process can not reduction of speed, therefore, to
It obtains viscosity number and fluctuates lesser Long Carbon Chain Polyamide, pH value has to be lower than the pH value for preparing conventional polyamide.However pH value mistake
Low, the mechanical property of gained Long Carbon Chain Polyamide resin will receive influence, this may be to cause since the degree of polymerization is relatively low, pH
Value needs to be accurately controlled in suitable range.
One or more additives can be added in step 1) as needed.
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
1.3~3.0Mpa starts to be vented and keep the pressure, when system temperature rises to 230~320 DEG C, makes pressure in reaction vessel
It is down to 0~-0.1Mpa (gauge pressure), keeps 5~120min of the vacuum degree.It can be specifically adjusted according to polymerization situation.
The present invention is further illustrated with comparative example with reference to embodiments.
Performance characterization has been carried out to Long Carbon Chain Polyamide resin using following characterizing method:
(1) viscosity number
Pass through Ubbelohde viscometer sulphate method: polyamide sample (such as PA66) 0.25 after precise is dry ±
0.0002g is added the 50mL concentrated sulfuric acid (96%) dissolution, concentrated sulfuric acid flow time t is measured and recorded in 25 DEG C of constant temperature water baths0
With polyamide sample (such as PA66) solution flow time t.
Viscosity number calculation formula: viscosity number VN=(t/t0-1)/C;
T-solution flow time;
t0- solvent flow time;
C-polymer concentration (g/mL).
(2) terminal amino group content
1g polyamide slice is dissolved under shake in 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.Blank is used
Above-mentioned phenol/the alcohol mixed solvent of 0.02mol/L titration with hydrochloric acid, and determine the amount of 0.02mol/L hydrochloric acid.By the difference between amount
Value obtains the terminal amino group content in every 1 ton of polyamide sample.
(3) pH value
Polyamide salt aqueous solution is diluted to 10%wt, 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 7.49 (30 DEG C with a small amount of pentanediamine or 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 292 DEG C, and pressure rises to 2.0Mpa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 265 DEG C, it is evacuated to -0.08Mpa, keeps vacuum degree 35min, polyamide 510 is made.
2 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 7.40 (30 DEG C with a small amount of pentanediamine or 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.
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 7.19 (30 DEG C with a small amount of pentanediamine or 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 288 DEG C, and pressure rises to 2.5Mpa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 260 DEG C, it is evacuated to -0.07Mpa, keeps vacuum degree 28min, polyamide 510 is made.
4 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 6.60 (30 DEG C with a small amount of pentanediamine or decanedioic acid
Salting liquid is diluted to 10% testing result), 25g antioxidant H10 is added, polyamide salt aqueous solution is made.
2) under nitrogen environment, oil bath temperature gradually rises to 290 DEG C, and pressure rises to 1.0Mpa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 270 DEG C, it is evacuated to -0.08Mpa, keeps vacuum degree 30min, polyamide 510 is made.
5 polyamide 512 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, 26.47kg (115.2mol) decanedioic acid is added, pH value is adjusted to 7.23 with a small amount of pentanediamine or dodecanedioic acid
Polyamide salt aqueous solution is made in (30 DEG C of salting liquids are diluted to 10% testing result).
2) under nitrogen environment, oil bath temperature gradually rises to 288 DEG C, and pressure rises to 1.5Mpa in kettle to be polymerized, starts to be vented,
When temperature in the kettle reaches 262 DEG C, it is evacuated to -0.07Mpa, keeps vacuum degree 35min, 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 7.70 (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 present invention gained long-carbon-chain polyamide is significantly less than conventional polymeric
Long-carbon-chain polyamide obtained by technique, the pH value by adjusting polymerization process polyamide salt aqueous solution can be by viscosity number wave
Dynamic to control in lesser range, biological poly amide adaptation Downstream processing of the invention, function admirable, market prospects are huge.
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.