CN106916298A - A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof - Google Patents
A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof Download PDFInfo
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- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
The present invention relates to a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof, environment friendly biological base semi-aromatic PA10T/11 copolymeric materials are made up of the component of following molfraction：Terephthalic acid (TPA) 20, decamethylene diamine 18.5-20,11- aminoundecanoic acid 1-4.5, nucleator 0.05-0.1, catalyst 0.002-0.005, solvent 250-300.Compared with prior art, monomer 11- aminoundecanoic acids in PA10T/11 of the present invention provide flexible segment to the backbone molecule of PA10T/11, so that the compliance of backbone molecule increases, toughness improves, broader process window is made it have, processing and forming difficulty is lower than PA10T, in addition, synthesis material water absorption rate is relatively low, and stability of material is good.The present invention prepares PA10T/11 using a step melt-polycondensation, whole polymerization process is carried out continuously, one step melt-polycondensation has the advantages that processing step is few, polymerization cycle is short, production efficiency is high, low production cost, is that serialization in future industrialized production creates condition.
Description
Technical field
The invention belongs to Polymer Synthesizing field, it is related to a kind of environment friendly biological base semi-aromatic PA10T/11 to be total to
Poly- material and preparation method thereof.
Background technology
With continuing to develop for industrial technology, semiaromatic polyamide composition is increasingly taken seriously, its product category
Also it is more and more.The wherein representative PA4T, the Mitsui chemical industry that have DSM Engineered Plastics
PA6T/66 and Kuraray company PA9T, the semiaromatic adoption of industrialized production at present
In acid amides, PA9T each side combination properties are best.But the monomer nonamethylene diamine of PA9T is by oil
What refining was obtained, oil is non-renewable resources, and nonamethylene diamine complex manufacturing, equipment requirement are high, close
Into technology by Kuraray company monopolizing, the cost and price of PA9T is caused to remain high.
PA10T has not only adhered to good rigid, heat-resisting of PA9T as a kind of new semiaromatic polyamide composition
The advantages of property, dimensional stability, processing characteristics and low water absorption, and also have in terms of cost with environmental protection
Very big advantage.Because the monomer decamethylene diamine of synthesis PA10T is obtained by castor oil refining, castor
Fiber crops are a kind of wide material sources, cheap, environmental protection renewable resource, and decamethylene diamine production technology
Relatively simple, production cost is relatively low, however, PA10T fusing points are up to 320 DEG C or so, its thermal degradation temperature
It is 350 DEG C to spend, and process window (processing temperature scope) is narrower, but high temperature resistant nylon is in actual use,
Maximum temperature is generally 260 DEG C, therefore on the premise of performance is had substantially no effect on, PA10T is carried out
Modification by copolymerization, suitably reduces its fusing point, so as to reduce the processing temperature of PA10T, improves the processing of material
Stability is extremely important.In addition, because rigid phenyl ring content is more in PA10T, therefore
Poor toughness, also limits its application to a certain extent.
The content of the invention
It is an object of the invention to overcome PA10T post-processings to exist, process window is narrow and toughness is poor lacks
Fall into, there is provided a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and its synthetic method so that
The processing temperature of PA10T is obtained and reduced to a certain extent, so that the processing stability of material is improved, and larger journey
Its toughness is improve on degree, the synthetic material water absorption rate is relatively low in addition, therefore good stability of the dimension.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials, by the component system of following molfraction
Into：
Described terephthalic acid (TPA), decamethylene diamine, 11- aminoundecanoic acids purity more than 99.9%, without
Purification processes are carried out again, and wherein decamethylene diamine and 11- aminoundecanoic acids is all from castor oil, environmental protection raw material
Content it is higher, with the value of environmental protection higher, decamethylene diamine is using preceding by smashing micronization processes.
Described nucleator is selected from barium sulfate, titanium dioxide, silica or calcium carbonate, preferably barium sulfate.
Described catalyst is selected from sodium hypophosphite, ortho phosphorous acid potassium, sodium phosphite, ortho phosphorous acid magnesium, secondary
One or more in Arizona bacilli or ortho phosphorous acid zinc, preferably sodium hypophosphite.
Described solvent is selected from deionized water, safety and environmental protection.
A kind of preparation method of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials, comprises the following steps：
(1) by the molfraction of terephthalic acid (TPA) 20, decamethylene diamine 18.5-20 molfractions, nucleator 0.05-0.1
Molfraction, catalyst 0.002-0.005 molfractions are well mixed, and are then added into equipped with high efficiency stirring
Mix in the high pressure polymerisation reactor of device, weigh solvent 250-300 molfractions in reactor, sealing is high
Pressure polymerization reaction kettle, starts stirring and is warming up to 90-120 DEG C, and then constant temperature stirs 1-2h at this temperature
With fully into salt；
(2) reactor is opened, then to the 11- aminoundecanoic acids of 1-4.5 molfractions are added in it, is sealed
High pressure polymerisation reactor, puts body and changes air 3-5 times in kettle using high purity inert gas, and last reserved
The inert gas of 0.05-0.25MPa is used as protective gas；
(3) stirring is opened, heating rate is controlled, 270~290 DEG C is at the uniform velocity warming up to the 1.5-2h times,
And reactor constant pressure is reacted 1-1.5h by delivery systme moisture when pressure is 2.5-3.5MPa in kettle, after
When question response temperature in the kettle rises to 295-305 DEG C, pressure release treatment 1-1.5h is carried out to reactor；
(4) control temperature in the kettle for 310-330 DEG C in pressure leak process, pressure is let out and taken out to normal pressure in kettle
Vacuum reaction 0.5-1h, to being pressurizeed in kettle, 05.-1.2MPa discharges, that is, obtain environment friendly biological base semi-aromatic
PA10T/11 copolymeric materials.
Inert gas described in step (2) is nitrogen, carbon dioxide, argon gas or helium, preferably nitrogen.
Mixing speed is 80-120r/min in each step.
PA10T salt-forming steps and rear polymerization procedure are separately for the accurate decamethylene diamine and right of controlling by the present invention
The usage ratio of phthalic acid, add has some side reactions to occur so as to have a strong impact on decamethylene diamine and to benzene together
The ratio of dioctyl phthalate, ultimately results in target product debris more.
Temperature compares strict with Stress control in preparation method of the present invention, and reason is to suppress 11- amino ten
The polymerization of one acid, needs to keep pressure higher in temperature-rise period, to ensure the presence of large quantity of moisture,
Preventing the forward direction of PA11 polymerisations is carried out, and is carried out in higher temperature, is to make PA10T salt as early as possible
Melting participates in reaction.If temperature, pressure control is bad, 11- aminoundecanoic acids are possible to polymerization in temperature-rise period
Into PA11, and PA10T salt is still unpolymerized, and experiment may finally cannot generate copolymer, or even generation is altogether
Mixed thing, material composition structure has change, performance naturally-occurring great changes.So, suppression is needed in temperature-rise period
The polymerization of PA11 processed, improves the polymerization speed of PA10T to form target product.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) the monomer 11- aminoundecanoic acids in PA10T/11 provide soft to the backbone molecule of PA10T/11
Property segment so that the compliance of backbone molecule increases, toughness improves, and makes it have broader processing
Window, processing and forming difficulty is lower than PA10T；
(2) decamethylene diamine and 11- aminoundecanoic acids in PA10T/11 is all from castor oil, makes green in product
Colour circle guarantor's material content is higher, with the value of environmental protection higher；
(3) PA10T/11 is prepared using a step melt-polycondensation, whole polymerization process is carried out continuously, one
Step melt-polycondensation has the advantages that processing step is few, polymerization cycle is short, production efficiency is high, low production cost,
For serialization in future industrialized production creates condition；
(4) synthesis material water absorption rate is relatively low, and stability of material is good；
(5) polymer solvent uses deionized water, economical and practical, environmental protection.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Below in an example, using following detection method：
Fusing point test carries out test analysis and obtains using differential scanning calorimeter (DSC thermal analyzers).
Tensile property presses ASTM D638-10 tests, rate of extension 5mm/min.
Simply supported beam notch impact strength presses ASTM D6110-10 tests.
Bending strength presses ASTM D790-10 tests, pushes speed 1.25mm/min.
Water absorption rate test：
At room temperature, sample is placed in drier, drier bottom is placed one and fills the saturated common salt aqueous solution
Beaker, maintain drier in relative humidity be 75%, often cross 24h take out sample weigh, be designated as Gi,
(i=1,2,3,4 ...), the sample after weighing still is put back in drier.After 20 days, sample is put into baking oven
Interior drying (70 DEG C, 24h), is subsequently placed in drier and is cooled to room temperature weighing sample, is designated as G0.Press
Formula calculates the water content (W in samplei) %, wherein after the water absorption rate in the present invention is unanimously calculated 10 days
The water absorption rate of (240h)：
Wi=(Gi-G0)/Gi× 100%
Embodiment 1
Take components terephthalic acid 20mol, decamethylene diamine 20mol, nucleator barium sulfate 0.05mol, catalyst
Sodium hypophosphite 0.002mol is well mixed, and is then added into the high pressure polymerisation equipped with Efficient Agitator
In reactor, 250mol solvent deionized waters are weighed in reactor, seal high pressure polymerisation reactor, open
Dynamic to stir and be warming up to 90 DEG C, then constant temperature stirs 2h so that the two is fully into salt at this temperature.
Reactor is again turned on, to the 11- aminoundecanoic acids that 1mol is added in it, sealing high pressure polymerisation reaction
Kettle, puts body and changes air 3 times in kettle, and the last inert gas for reserving 0.05MPa using high purity inert gas
As protective gas.
Stirring is opened, heating rate is controlled, 290 DEG C, and the pressure in kettle are at the uniform velocity warming up to the 2h times
Reactor constant pressure is set to react 1.5h, rear question response temperature in the kettle liter by delivery systme moisture during for 3.5MPa
During to 305 DEG C, pressure release treatment 1.5h is carried out to reactor.
It is 330 DEG C that final temperature in kettle is controlled in pressure leak process, and pressure is let out and vacuumized to normal pressure in kettle
Reaction 0.5h, to being pressurizeed in kettle, 1.2MPa discharges, that is, obtain a kind of environment friendly biological base semi-aromatic PA10T/11
Copolymeric material.
Embodiment 2
Components terephthalic acid 20mol, decamethylene diamine 19.2mol, nucleator titanium dioxide 0.075mol are taken, is urged
Agent Lime Hypophosphate 0.003mol is well mixed, and is then added into the high pressure equipped with Efficient Agitator
In polymerization reaction kettle, 300mol solvent deionized waters are weighed in reactor, seal high pressure polymerisation reactor,
Start stirring and be warming up to 105 DEG C, then constant temperature stirs 1.5h so that the two is fully into salt at this temperature.
Reactor is again turned on, to the 11- aminoundecanoic acids that 3mol is added in it, sealing high pressure polymerisation reaction
Kettle, puts body and changes air 4 times in kettle, and the last inert gas for reserving 0.15MPa using high purity inert gas
As protective gas.
Stirring is opened, heating rate is controlled, 280 DEG C are at the uniform velocity warming up to the 1.75h times, and in kettle internal pressure
Reactor constant pressure is set to react 1.75h, rear question response temperature in the kettle by delivery systme moisture when power is 3.0MPa
When rising to 300 DEG C, pressure release treatment 1.25h is carried out to reactor.
It is 320 DEG C that final temperature in kettle is controlled in pressure leak process, and pressure is let out and vacuumized to normal pressure in kettle
Reaction 0.75h, to being pressurizeed in kettle, 0.8MPa discharges, that is, obtain a kind of environment friendly biological base semi-aromatic
PA10T/11 copolymeric materials.
Embodiment 3
Components terephthalic acid 20mol, decamethylene diamine 18.5mol, nucleator silica 0.1mol are taken, is catalyzed
Agent ortho phosphorous acid potassium 0.005mol is well mixed, and is then added into the high pressure equipped with Efficient Agitator and gathers
Close in reactor, weigh 300mol solvent deionized waters in reactor, seal high pressure polymerisation reactor,
Start stirring and be warming up to 120 DEG C, then constant temperature stirs 1h so that the two is fully into salt at this temperature.
Reactor is again turned on, to the 11- aminoundecanoic acids that 4.5mol is added in it, sealing high pressure polymerisation is anti-
Kettle is answered, body is put using high purity inert gas and is changed air 5 times in kettle, and the last indifferent gas for reserving 0.25MPa
Body is used as protective gas.
Stirring is opened, heating rate is controlled, 270 DEG C, and the pressure in kettle are at the uniform velocity warming up to the 1.5h times
Reactor constant pressure is set to react 2h by delivery systme moisture during for 2.5MPa, rear question response temperature in the kettle rises to
At 295 DEG C, pressure release treatment 1.0h is carried out to reactor.
It is 310 DEG C that final temperature in kettle is controlled in pressure leak process, and pressure is let out and vacuumized to normal pressure in kettle
Reaction 1h, to being pressurizeed in kettle, 0.5MPa discharges, that is, obtain a kind of environment friendly biological base semi-aromatic PA10T/11
Copolymeric material.
Comparative example
Components terephthalic acid 20mol, decamethylene diamine 19.2mol, nucleator barium sulfate 0.075mol are taken, is catalyzed
Agent sodium hypophosphite 0.003mol is well mixed, and is then added into the high pressure equipped with Efficient Agitator and gathers
Close in reactor, seal high pressure polymerisation reactor, put body using high purity inert gas and change air 5 times in kettle,
And the inert gas of last reserved 0.25MPa is used as protective gas.
Start stirring and be warming up to 100 DEG C, then constant temperature stirs 1h so that the two is fully into salt at this temperature.
Insulation terminates, and controls heating rate, and 290 DEG C, and the pressure in kettle are at the uniform velocity warming up to the 2h times
Reactor constant pressure is set to react 1.5h, rear question response temperature in the kettle liter by delivery systme moisture during for 2.7MPa
During to 315 DEG C, pressure release treatment 1.5h is carried out to reactor.
It is 335 DEG C that final temperature in kettle is controlled in pressure leak process, and pressure is let out and vacuumized to normal pressure in kettle
Reaction 0.5h, to being pressurizeed in kettle, 0.9MPa discharges, that is, obtain a kind of bio-based semi-aromatic PA10T materials.
Take the bio-based semi-aromatic PA10T/11 copolymeric materials that synthesize in each embodiment and comparative example synthesis
PA10T carries out injection moulding to obtain standard testing batten, carries out correlated performance test.
The performance test results of embodiment 1-3 and comparative example such as table 1.
Table 1
By the performance test results to each embodiment can be seen that the fusing point of PA10T/11 copolymeric materials all with
The increase of 11- aminoundecanoic acid contents and decline, thus greatly widened its process window.Because
The increase of 11- aminoundecanoic acid contents, makes the construction unit of 11- aminoundecanoic acids in PA10T repeat units
Accounting increase, Chain Flexibility increases, and intermolecular relative motion is easier；11- aminoundecanoic acid contents
Increase destroys the regularity of PA10T molecular structures, and crystallinity reduction, two aspect reasons cause PA10T/11
Fusing point declines with the increase of 11- aminoundecanoic acid contents.Contrasted from conventional mechanical property and found, with 11-
The increase of aminoundecanoic acid content, the tensile strength of PA10T/11 copolymeric materials, elongation at break, impact
Intensity increases, and shows that overall stiffness declines, and toughness rises, and meets theoretical rule.Water absorption rate data
See, with the increase of 11- aminoundecanoic acid contents, the water absorption rate change of PA10T/11 copolymeric materials is little,
Because the water absorption rate of polyamide depends on the density of amide groups in strand, amide groups has hydrophily, acyl
Amido density is bigger, and the water absorption rate of polyamide is higher.After polyamide water suction, intermolecular force can be caused
Weaken, dimensional stability declines etc..But compared with PA6 (water absorption rate 1.8%), PA66 (water absorption rate 2.8%)
It is Deng fatty polyamide or much lower, therefore dimension stability is preferable.
The above-mentioned description to embodiment is understood that and makes for ease of those skilled in the art
With invention.Person skilled in the art obviously easily can make various modifications to these embodiments,
And General Principle described herein is applied in other embodiment without by performing creative labour.Cause
This, the invention is not restricted to above-described embodiment, those skilled in the art's announcement of the invention does not depart from this
The improvement and modification that invention category is made all should be within protection scope of the present invention.
Claims (9)
1. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials, it is characterised in that rubbed by following
You are made the component of number：
2. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 1,
Characterized in that, the purity of described terephthalic acid (TPA), decamethylene diamine, 11- aminoundecanoic acids 99.9% with
On.
3. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 1,
Characterized in that, described decamethylene diamine passes through smashing micronization processes using preceding.
4. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 1,
Characterized in that, described nucleator is selected from barium sulfate, titanium dioxide, silica or calcium carbonate, preferably
Barium sulfate.
5. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 1,
Characterized in that, described catalyst is selected from sodium hypophosphite, ortho phosphorous acid potassium, sodium phosphite, secondary phosphorous
One or more in sour magnesium, Lime Hypophosphate or ortho phosphorous acid zinc, preferably sodium hypophosphite.
6. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 1,
Characterized in that, described solvent is selected from deionized water.
7. a kind of system of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials as claimed in claim 1
Preparation Method, it is characterised in that comprise the following steps：
(1) by the molfraction of terephthalic acid (TPA) 20, decamethylene diamine 18.5-20 molfractions, nucleator 0.05-0.1
Molfraction, after the mixing of catalyst 0.002-0.005 molfractions, is added to the reactor with agitating device
In, solvent 250-300 molfractions are weighed in reactor, sealed reactor starts stirring and is warming up to
90-120 DEG C, then constant temperature stirs 1-2h with fully into salt at this temperature；
(2) reactor is opened, then to the 11- aminoundecanoic acids of 1-4.5 molfractions are added in it, is sealed
Reactor, puts body and changes air 3-5 times in kettle, and finally reserve the lazy of 0.05-0.25MPa using inert gas
Property gas is used as protective gas；
(3) stirring is opened, heating rate is controlled, 270~290 DEG C is at the uniform velocity warming up to the 1.5-2h times,
And reactor constant pressure is reacted 1-1.5h by delivery systme moisture when pressure is 2.5-3.5MPa in kettle, after
When question response temperature in the kettle rises to 295-305 DEG C, pressure release treatment 1-1.5h is carried out to reactor；
(4) control temperature in the kettle for 310-330 DEG C in pressure leak process, pressure is let out and taken out to normal pressure in kettle
Vacuum reaction 0.5-1h, to being pressurizeed in kettle, 05.-1.2MPa discharges, that is, obtain environment friendly biological base semi-aromatic
PA10T/11 copolymeric materials.
8. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 7
Preparation method, it is characterised in that the inert gas described in step (2) is nitrogen, carbon dioxide, argon
Gas or helium, preferably nitrogen.
9. a kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials according to claim 7
Preparation method, it is characterised in that mixing speed is 80-120r/min in each step.
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| CN114181390A (en) * | 2021-12-23 | 2022-03-15 | 北京化工大学 | Bio-based high-temperature-resistant polyamide and preparation method thereof |
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| CN113072699A (en) * | 2021-03-09 | 2021-07-06 | 东莞市华盈新材料有限公司 | Low-hygroscopicity PA10T and synthesis method thereof |
| CN113072699B (en) * | 2021-03-09 | 2022-03-01 | 东莞市华盈新材料有限公司 | Low-hygroscopicity PA10T and synthesis method thereof |
| WO2022188597A1 (en) * | 2021-03-09 | 2022-09-15 | 东莞市华盈新材料有限公司 | Low-hygroscopicity pa10t and synthesis method therefor |
| CN113667115A (en) * | 2021-09-03 | 2021-11-19 | 五行科技股份有限公司 | Semi-aromatic high-temperature-resistant PA6T/11 material and preparation method thereof |
| CN113999389A (en) * | 2021-11-19 | 2022-02-01 | 四川大学 | Film of copolymer of long-chain nylon and biuret and preparation method thereof |
| CN113999389B (en) * | 2021-11-19 | 2022-12-06 | 四川大学 | Film of copolymer of long-chain nylon and biuret and preparation method thereof |
| CN114181390A (en) * | 2021-12-23 | 2022-03-15 | 北京化工大学 | Bio-based high-temperature-resistant polyamide and preparation method thereof |
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