CN105330846B - Bio-based heat resistant polyamide and its synthetic method - Google Patents
Bio-based heat resistant polyamide and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of bio-based heat resistant polyamide and its synthetic method, the bio-based heat resistant polyamide has following structure shown in formula I：In formula I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide.Bio-based heat resistant polyamide of the present invention has a mechanical property and heat resistance higher, low water absorption, and processing characteristics is excellent and characteristic with biogenetic derivation, can be applied to field of electronics, LED field, automotive field, Aero-Space and military industry field etc..
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of bio-based heat resistant polyamide and its synthetic method.
Background technology
In recent years, in order to meet the requirement of the higher performance in fields such as electronics, electrical equipment, automobiles, in particular with surface
The development of mounting technique (Surface Mount Technology, abbreviation SMT), common thermostability engineering plastic polyphenylene sulfide
And the heat resistance of liquid crystal polymer (LCP) can not fully meet its requirement, therefore exploitation heat resistance engineering higher (PPS)
Plastics just turn into inevitable.
Semiaromatic polyamide composition is typically by aliphatic diamines or diacid and diacid or diamines with aromatic rings, through polycondensation
And be obtained, due to having imported aromatic rings on polyamide molecule main chain, its heat resistance and mechanical property are improved, and inhale
Water rate is reduced, and with preferable superiority of effectiveness, it is mainly used in automobile and electric and electronic industry.Industrialized semiaromatic
Polyamide mainly has polyamide 6 T (copolymer), polyamide 9T, polyamide 10T etc..But, the fusing point of polyamide 6 T resins is
370 DEG C or so, it alreadys exceed decomposition temperature, actually can not carry out melt-processed, it is necessary to add the list of third component
Body makes the melt temperature of polymer be down to less than 320 DEG C.
Solid phase (Solid state Polymerization) refers to solid (or crystalline phase) monomer below its fusing point
The polymerisation of generation, or the polymerization carried out more than monomer fusing point but below the melt temperature of the polymer for being formed is anti-
Should.Due to solid phase it is general below the fusing point of prepolymer 15~30 DEG C carry out, its reaction rate relatively slow, reaction time compared with
It is long, and the production process of solid phase is more, flow is complicated, and higher to device parameter requirement, reaction also needs to guarantee functional group
Proportioning close to 1:1, the thickening stage needs vacuum or air-flow to accelerate the discharge of small molecular by product, so as to improve polycondensation product
The molecular weight of thing, therefore, conditions above limits the large-scale promotion of solid phase.Melt polymerization (Melt
Polymerization refer to) polymerization process that monomer and polymer are under molten condition, the method process route is simple,
Can continuously produce, it is also possible to Batch Process.Reaction needs to carry out at high temperature, and the reaction time is shorter, and the pair such as hydrone
Product discharge is easy.At present, some researchs, such as Chinese patent have been done in the synthesis in the prior art to semiaromatic polyamide composition
CN102153741A disclose a kind of homopolymers of Long carbon chain semiaromatic heat resistant polyamide and the synthetic method of copolymer and its
The polymerizate for obtaining, the polymerizate is mainly and is obtained by the method for solid phase；Chinese patent CN103360599A is public
A kind of semi-aromatic and fatty polyamide block copolymer are opened, the molar percentage of wherein semiaromatic polyamide composition block contains
Measure as the mole percent level of 40%~99%, fatty polyamide block is 1~60%, the polymerizate is mainly and passes through
The method of solid phase is obtained；Chinese patent CN101948619A discloses a kind of poly-paraphenylene terephthalamide's nonamethylene diamine material and its system
Preparation Method；Chinese patent CN1106842A discloses polyamide 9T, 9M-T and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of mechanical property and heat resistance higher, low water absorption, processing characteristics is excellent
Different bio-based heat resistant polyamide, can be applied to field of electronics, LED field, automotive field, Aero-Space and military project neck
Domain etc..
To reach above-mentioned purpose, the present invention uses following scheme：
A kind of bio-based heat resistant polyamide, it has following structure shown in formula I：
In formula I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has
Such as Formula Il structure：
In Formula II, x=10~200, y=10~200, z=10~100；
The bio-based heat resistant polyamide is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is that mol ratio is 1:
0.55~0.8:0.2~0.45 hexamethylene diamine, terephthalic acid (TPA) and decanedioic acid, and hexamethylene diamine and terephthalic acid (TPA) and decanedioic acid two
The mol ratio of person's consumption sum is 1, and the addition of the polyesteramide is the 1~8% of the gross weight of the monomer 1.
Wherein in some embodiments, the addition of the polyesteramide is the 2~6% of the gross weight of the monomer 1.
Wherein in some embodiments, the inherent viscosity of the bio-based heat resistant polyamide is 0.7~1.0dL/g, glass
Glass temperature Tg>=110 DEG C, melt temperature TmIt is 302~315 DEG C.
Wherein in some embodiments, the polyesteramide is formed by the copolymerization of monomer 2, and the monomer 2 is that mol ratio is 1:
0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones and 2,2'- (1,3- phenylenes)-bisoxazoline.
Wherein in some embodiments, the polyesteramide is obtained by following synthetic method：(1) by the institute after vacuum drying
State monomer 2 to be added in stirring-type polymer reactor, while adding the titanium compound of the 0.1~2% of the gross weight of the monomer 2 to make
For catalyst, add suitable quantity of water (medium of mass-and heat-transfer)；Then 3~10min is vacuumized, leads to 3~10min of inert gas, such as
This circulation 5~10 times, makes in the environment that reactant is present under inert gas shielding, controls in the stirring-type polymer reactor
System pressure is 0.1~0.5MPa；
(2) by the stirring-type polymer reactor airtight heating to 240~260 DEG C, the stirring-type polymerisation is adjusted
The mixing speed of device is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 210 DEG C, it is deflated to
1.6MPa, and maintain pressure in 1.6MPa, after reacting 0.5~4 hour, normal pressure is deflated to, continue to react at 240~260 DEG C
After 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas；The titanium compound is butyl titanate, isopropyl titanium
One or more mixture in acid esters, propyl titanate, acrylic titanate esters.
It is a further object of the present invention to provide the synthetic method of above-mentioned bio-based heat resistant polyamide, comprise the following steps：
(1) monomer 1 is added in stirring-type polymer reactor, while adding the polyesteramide, molecular weight to adjust
Section agent, antioxidant, water (medium of mass-and heat-transfer)；Then 3~10min is vacuumized, leads to 3~10min of inert gas, so circulation
5~10 times, make in the environment that reactant is present under inert gas shielding, control system pressure in the stirring-type polymer reactor
Power is 0.1~0.5MPa；The monomer 1 is that mol ratio is 1:0.55~0.8:0.2~0.45 hexamethylene diamine, terephthalic acid (TPA) and
Decanedioic acid, and hexamethylene diamine and both terephthalic acid (TPA) and decanedioic acid consumption and mol ratio be 1, the addition of the polyesteramide
It is the 1~8% of the gross weight of the monomer 1；, the polyesteramide forms by the copolymerization of monomer 2, and the monomer 2 is that mol ratio is 1:
0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones and 2,2'- (1,3- phenylenes)-bisoxazoline；
(2) by the stirring-type polymer reactor airtight heating to 275~290 DEG C, the stirring-type polymerisation is adjusted
The mixing speed of device is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to
2.0MPa, and maintain pressure in 2.0MPa, after reacting 0.5~4 hour, normal pressure is deflated to, while being warming up at 316~330 DEG C
After continuing to react 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas.
Logical inert gas purpose is to reduce the probability that side reaction occurs before reaction；The purpose vacuumized in course of reaction is handle
The water produced in polymerisation is removed, and is conducive to polymerisation forward direction to carry out.
Wherein in some embodiments, the synthetic method of the bio-based heat resistant polyamide is comprised the following steps：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulated 5~7 times, made anti-
Answer in the environment that thing is present under nitrogen protection, it is 0.2~0.3MPa to control system pressure in the stirring-type polymer reactor；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 280~290 DEG C, adjust institute
The mixing speed of stirring-type polymer reactor is stated for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
At 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 316~326 DEG C, constant temperature is persistently vacuumized 0.3~1 hour, and reaction terminates, and is supplemented in discharging
Nitrogen.
Wherein in some embodiments, the polyesteramide is obtained by following synthetic method：(1) by the institute after vacuum drying
State monomer 2 to be added in stirring-type polymer reactor, while adding the titanium compound of the 0.1~2% of the gross weight of the monomer 2 to make
For catalyst, add suitable quantity of water；Then 3~10min is vacuumized, leads to 3~10min of inert gas, so circulated 5~10 times, made
Reactant is present in the environment under inert gas shielding, control in the stirring-type polymer reactor system pressure be 0.1~
0.5MPa；
(2) by the stirring-type polymer reactor airtight heating to 240~260 DEG C, the stirring-type polymerisation is adjusted
The mixing speed of device is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 210 DEG C, it is deflated to
1.6MPa, and maintain pressure in 1.6MPa, after reacting 0.5~4 hour, normal pressure is deflated to, continue to react at 240~260 DEG C
After 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas；The titanium compound is butyl titanate, isopropyl titanium
One or more mixture in acid esters, propyl titanate, acrylic titanate esters.
Wherein in some embodiments, the molecular weight regulator be that addition is the gross weight of the monomer 1 0.1~
8% organo montmorillonite and addition is the benzoic acid of the 0.1~3% of the gross weight of the monomer 1；The antioxidant is to add
Measure the N for the 0.1~0.3% of the gross weight of the monomer 1, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diformazans
Acid amides.
Wherein in some embodiments, the addition of the polyesteramide is the 2~6% of the gross weight of the monomer 1；It is described
The addition of organo montmorillonite is the 0.5~5% of the gross weight of the monomer 1, and the addition of the benzoic acid is that the monomer 1 is total
The 0.5~2.5% of weight.
Principle of the invention is as follows：
Too high in order to solve the problems, such as polyamide 6 T melting point resins, the present invention has carried out the design of new resinous molecular structure,
The fusing point of copolymer is reduced by adding decanedioic acid, at the same add polyesteramide come improve copolymer notch impact strength and
Antistatic effect, adds N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides to process polymerization process
In xanthochromia problem.
Polyesteramide has ether epoxide, and it can be combined with free electric charge, and electric charge can be in the way of combination
It is mobile, ionic conduction release electrostatic lotus is carried out along polyesteramide backbone, so as to reach anlistatig effect.Further, since ether oxygen
The bond angle of key is larger, and segment compliance preferably, therefore can improve the notch impact strength of copolymer.
Organo montmorillonite belongs to polyhydroxy inorganic matter, by terminal hydroxy group and the bio-based heat resistant polyamide of organo montmorillonite
End group reaction, reach the purpose of Molecular regulator amount.Further, since organo montmorillonite has nanometer small-size effect, it can be with
The modulus and anti-flammability of copolymer are improved, shrinkage factor and water absorption rate is reduced.
Benzoic acid belongs to the organic matter of simple function group, the end carboxyl of benzoic acid and the resistance to height of bio-based in melt polymerization process
After the Amino End Group reaction of warm polyamide, its reaction for no longer carrying out chain growth, so as to play a part of Molecular regulator amount.
The fusing point of N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides is 272 DEG C, boiling point>360
DEG C, the better heat stability in bio-based heat resistant polyamide building-up process, its amide group can be with biological based high-temp-resistant
The end group of polyamide reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dyeing of copolymer
Property.
Bio-based heat resistant polyamide provided by the present invention and its synthetic method have advantages below：
(1) the present inventor has carried out new molecular resin for the too high problem of existing polyamide 6 T melting point resins
The design of structure, the fusing point of copolymer is reduced by adding decanedioic acid, while adding polyesteramide to improve lacking for copolymer
Mouth impact strength and antistatic effect, add N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides to come
Xanthochromia problem in treatment polymerization process；Bio-based heat resistant polyamide of the present invention has mechanical property and heat resistance higher
Can, low water absorption, processing characteristics is excellent and characteristic with biogenetic derivation, can be applied to field of electronics, LED field,
Automotive field, Aero-Space and military industry field etc..
(2) preparation method of the present invention using one-step polymerization method, it has a reduction operation, shortens flow, reduces cost,
Put forward large-duty advantage；Preparation technology of the present invention is easy, and polymerization process is easy to operate, is easy to management and control, can be fully achieved institute
It is required that polymerizing condition, facilitate its industrialized realization；And do not use any organic solvent in the course of the polymerization process, to human body and
Environment is not dangerous, and security is good.
(3) decanedioic acid used in raw material of the present invention is prepared by the castor oil of nature, therefore, present invention system
The standby bio-based heat resistant polyamide for obtaining is a kind of bio-based materials, the characteristic with environmental protection.
Brief description of the drawings
Fig. 1 show the synthesis process flow diagram of bio-based heat resistant polyamide of the present invention；
Fig. 2 show the nonisothermal crystallization melting curve figure of the bio-based heat resistant polyamide of the gained of the embodiment of the present invention 5.
Specific embodiment
It is specific purposes, the function that can further appreciate that feature of the invention, technological means and reached, parses this hair
Bright advantage and spirit, by following examples, the present invention is further elaborated.
Bio-based heat resistant polyamide of the present invention has following structure shown in formula I：
In formula I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has
Such as Formula Il structure：
In Formula II, x=10~200, y=10~200, z=10~100；
The reaction mechanism of bio-based heat resistant polyamide of the present invention is following (synthesis process flow diagram is see Fig. 1)：
Reaction mechanism
It is the Amino End Group of hexamethylene diamine, the end carboxyl of terephthalic acid (TPA), the end carboxyl of decanedioic acid, poly- from above-mentioned reaction equation
The Amino End Group and end carboxyl of esteramides, these groups can react to each other and obtain biological based high-temp-resistant polyamides of the present invention
Amine.
And the reaction mechanism of the polyesteramide added in above-mentioned bio-based heat resistant polyamide course of reaction is as follows：
Reaction mechanism
From above-mentioned reaction equation, its ester group after 6- caprolactone open loops, the Amino End Group of 11- aminoundecanoic acids, 2,2'- (1,
3- phenylenes)-bisoxazoline oxazoline group, these three groups can react to each other and obtain the polyester acyl that is added of the present invention
Amine, the inherent viscosity of the polyesteramide that the present invention is added is 0.7~1.0dL/g, glass transition temperature Tg>=80 DEG C, melt temperature
TmIt is 215~225 DEG C.
The raw material that the embodiment of the present invention is used is as follows：
Hexamethylene diamine, selected from Wuxi Yinda Nylon Co., Ltd.；
Terephthalic acid (TPA), selected from Beijing Yanshan Petrochemical Co.；
Decanedioic acid, selected from Shandong Guang Yin new materials Co., Ltd；
Polyesteramide, self-control, the 6- caprolactones in raw material, selected from the rich bamboo grove chemistry Science and Technology Ltd. in Wuhan；
11- aminoundecanoic acids, selected from Taiyuan Zhong Lianze agrochemicals Co., Ltd；
2,2'- (1,3- phenylene)-bisoxazolines, selected from Nanjing colon medication chemistry Co., Ltd；
Butyl titanate, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Organo montmorillonite, selected from Zhejiang Fenghong New Material Co., Ltd.；
Benzoic acid, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, selected from Chinese medicines group chemical reagent
Co., Ltd.
The present invention is described in detail below in conjunction with specific embodiment.
Polyesteramide in following examples is disliked by 11- aminoundecanoic acids, 6- caprolactones, 2,2'- (1,3- phenylenes)-two
Oxazoline copolymerization is formed, and 11- aminoundecanoic acids, 6- caprolactones, the mol ratio of 2,2'- (1,3- phenylene)-bisoxazoline are 1:0.5
~1:0.1~0.4.
Synthetic method is as follows：
(1) by the monomer 2 after vacuum drying：11- aminoundecanoic acids, 6- caprolactones, 2,2'- (1,3- phenylenes)-two are disliked
Oxazoline is added in stirring-type polymer reactor by above-mentioned mol ratio, while adding the 0.1~2% of the gross weight of monomer 2 titanizing
Compound as catalyst, add appropriate water as the medium of mass-and heat-transfer；Then 3~10min is vacuumized, leads to inert gas 3
~10min, so circulates 5~10 times, makes in the environment that reactant is present under inert gas shielding, and control stirring-type polymerization is anti-
It is 0.1~0.5MPa to answer system pressure in device；
(2) by stirring-type polymer reactor airtight heating to 240~260 DEG C, the stirring of stirring-type polymer reactor is adjusted
Speed is 0~100r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to, and maintain
Pressure after reacting 0.5~4 hour, is deflated to normal pressure in 1.6MPa, after continuing to react 0.5~4 hour at 240~260 DEG C,
Constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas of selection is nitrogen or argon gas；The titanium compound of selection is butyl titanate, isopropyl
One or more mixture in base titanate esters, propyl titanate, acrylic titanate esters.
Embodiment 1
The raw material of the polyesteramide used in the present embodiment is constituted and synthesis step is as follows：
(1) by the monomer 2 after vacuum drying：1006.6g (5mol) 11- aminoundecanoic acids, 456.6g (4mol) 6- are in oneself
Ester, 270.3g (1.25mol) 2,2'- (1,3- phenylene)-bisoxazoline are added in stirring-type polymer reactor, while adding
The butyl titanate (17.3g) of the 1% of the gross weight of monomer 2 as catalyst, add 500mL water as mass-and heat-transfer medium；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times makes in the environment that reactant is present under nitrogen protection, and control is stirred
It is 0.2MPa to mix system pressure in formula polymer reactor；
(2) in 2.5 hours by the closed constant-speed heating of stirring-type polymer reactor to 250 DEG C, regulation stirring-type polymerization is anti-
The mixing speed of device is answered for 40r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to,
And maintain pressure in 1.6MPa, and after reacting 1.5 hours, normal pressure is deflated to, after continuing to react 1.5 hours at 250 DEG C, constant temperature is held
Continuous to vacuumize 0.5 hour, reaction terminates, and nitrogen is supplemented in discharging.
A kind of synthetic method of bio-based heat resistant polyamide of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：116.2g (1mol) hexamethylene diamine, 132.9g (0.8mol) terephthalic acid (TPA),
40.5g (0.2mol) decanedioic acid is added in stirring-type polymer reactor, while adding 1% (2.9g's) of the gross weight of monomer 1
Polyesteramide, the organo montmorillonite of 0.1% (0.3g), the benzoic acid of 0.1% (0.3g), the N of 0.1% (0.3g), N`- bis- (2,
2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, add 100mL water as mass-and heat-transfer medium；Then take out true
Empty 5min, leads to nitrogen 5min, and so circulation 6 times makes in the environment that reactant is present under nitrogen protection, controls stirring-type polymerization
System pressure is 0.3MPa in reactor；
(2) in 4 hours by the closed constant-speed heating of stirring-type polymer reactor to 290 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 0.5 hour, be deflated to normal pressure, while after continuing to react 0.5 hour at being warming up to 330 DEG C,
Constant temperature is persistently vacuumized 2 hours, and reaction terminates, and nitrogen is supplemented in discharging.
Embodiment 2
The raw material of polyesteramide used is constituted and synthesis step is with embodiment 1 in the present embodiment.
A kind of synthetic method of bio-based heat resistant polyamide of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：116.2g (1mol) hexamethylene diamine, 91.4g (0.55mol) terephthalic acid (TPA),
91.0g (0.45mol) decanedioic acid is added in stirring-type polymer reactor, while adding 8% (23.9g) of the gross weight of monomer 1
Polyesteramide, the organo montmorillonite of 8% (23.9g), the benzoic acid of 3% (9.0g), the N of 0.3% (0.9g), N`- bis- (2,2,
6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, add 100mL water as mass-and heat-transfer medium；Then vacuumize
5min, leads to nitrogen 5min, and so circulation 6 times makes in the environment that reactant is present under nitrogen protection, and control stirring-type polymerization is anti-
It is 0.2MPa to answer system pressure in device；
(2) in 2 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 4 hours, be deflated to normal pressure, while after continuing to react 4 hours at being warming up to 316 DEG C, constant temperature
Persistently vacuumize 0.1 hour, reaction terminates, nitrogen is supplemented in discharging.
Embodiment 3
The raw material of polyesteramide used is constituted and synthesis step is with embodiment 1 in the present embodiment.
A kind of synthetic method of bio-based heat resistant polyamide of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：116.2g (1mol) hexamethylene diamine, 116.3g (0.7mol) terephthalic acid (TPA),
60.7g (0.3mol) decanedioic acid is added in stirring-type polymer reactor, while adding 2% (5.9g's) of the gross weight of monomer 1
Polyesteramide, the organo montmorillonite of 0.5% (1.5g), the benzoic acid of 0.5% (1.5g), the N of 0.2% (0.6g), N`- bis- (2,
2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, add 100mL water as mass-and heat-transfer medium；Then take out true
Empty 5min, leads to nitrogen 5min, and so circulation 6 times makes in the environment that reactant is present under nitrogen protection, controls stirring-type polymerization
System pressure is 0.3MPa in reactor；
(2) in 3.5 hours by the closed constant-speed heating of stirring-type polymer reactor to 290 DEG C, regulation stirring-type polymerization is anti-
The mixing speed of device is answered for 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to,
And maintain pressure in 2.0MPa, after reacting 1 hour, normal pressure is deflated to, while after continuing to react 1 hour at being warming up to 326 DEG C, it is permanent
Temperature is persistently vacuumized 1 hour, and reaction terminates, and nitrogen is supplemented in discharging.
Embodiment 4
The raw material of polyesteramide used is constituted and synthesis step is with embodiment 1 in the present embodiment.
A kind of synthetic method of bio-based heat resistant polyamide of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：116.2g (1mol) hexamethylene diamine, 99.7g (0.6mol) terephthalic acid (TPA),
80.9g (0.4mol) decanedioic acid is added in stirring-type polymer reactor, while adding 6% (17.8g's) of the gross weight of monomer 1
Polyesteramide, the organo montmorillonite of 5% (14.8g), the benzoic acid of 2.5% (7.4g), the N of 0.2% (0.6g), N`- bis- (2,2,
6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, add 100mL water as mass-and heat-transfer medium；Then vacuumize
5min, leads to nitrogen 5min, and so circulation 6 times makes in the environment that reactant is present under nitrogen protection, and control stirring-type polymerization is anti-
It is 0.3MPa to answer system pressure in device；
(2) in 2.5 hours by the closed constant-speed heating of stirring-type polymer reactor to 280 DEG C, regulation stirring-type polymerization is anti-
The mixing speed of device is answered for 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to,
And maintain pressure in 2.0MPa, after reacting 2 hours, normal pressure is deflated to, while after continuing to react 2 hours at being warming up to 316 DEG C, it is permanent
Temperature is persistently vacuumized 0.3 hour, and reaction terminates, and nitrogen is supplemented in discharging.
Embodiment 5
The raw material of polyesteramide used is constituted and synthesis step is with embodiment 1 in the present embodiment.
A kind of synthetic method of bio-based heat resistant polyamide of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：116.2g (1mol) hexamethylene diamine, 108.0g (0.65mol) terephthalic acid (TPA),
70.8g (0.35mol) decanedioic acid is added in stirring-type polymer reactor, while adding 4% (11.8g) of the gross weight of monomer 1
Polyesteramide, the organo montmorillonite of 3% (8.8g), the benzoic acid of 1.5% (4.4g), the N of 0.2% (0.6g), N`- bis- (2,
2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, add 100mL water as mass-and heat-transfer medium；Then take out true
Empty 5min, leads to nitrogen 5min, and so circulation 6 times makes in the environment that reactant is present under nitrogen protection, controls stirring-type polymerization
System pressure is 0.3MPa in reactor；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 285 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 320 DEG C,
Constant temperature is persistently vacuumized 0.5 hour, and reaction terminates, and nitrogen is supplemented in discharging.
The nonisothermal crystallization melting curve figure of the bio-based heat resistant polyamide obtained by the present embodiment is as shown in Fig. 2 in figure
The melting peak-to-peak temperature (i.e. melt temperature) for showing the bio-based heat resistant polyamide is 307.47 DEG C.
Below for the raw material of embodiment 1~5 constitutes list：
The embodiment raw material of table 1 constitutes list
The made sample of above-described embodiment is carried out into following performance test：
Tensile property：By GB/T1040-2006 standard testings, rate of extension 50mm/min；
Impact property：By GB/T1843-2008 standard testings, batten thickness is 3.2mm；
Water absorption rate：By GB/T1034-2008 standard testings, thickness of test piece 2mm；
Inherent viscosity：By GB/T1632-2008 standard testings, the solvent concentrated sulfuric acid；
Glass transition temperature：By GB/T19466.2-2004 standard testings；
Melt temperature：By GB/T19466.3-2004 standard testings.
Results of property is see following table：
The embodiment performance list of table 2
As can be seen from the above embodiments, the addition of decanedioic acid is more, the tensile strength of bio-based heat resistant polyamide,
Glass transition temperature and melt temperature are lower, and impact strength is higher；The water absorption rate change of each embodiment is little；With molecular weight
The addition of conditioning agent (organo montmorillonite and benzoic acid) increases, and its inherent viscosity diminishes.Wherein, the combination property of embodiment 5
Most preferably.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of bio-based heat resistant polyamide, it is characterised in that it has following structure shown in formula I：
In formula I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has as follows
Formula II structure：
In Formula II, x=10~200, y=10~200, z=10~100；
The bio-based heat resistant polyamide is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is that mol ratio is 1:0.55
~0.8:0.2~0.45 hexamethylene diamine, terephthalic acid (TPA) and decanedioic acid, and hexamethylene diamine uses with both terephthalic acid (TPA) and decanedioic acid
The mol ratio for measuring sum is 1, and the addition of the polyesteramide is the 1~8% of the gross weight of the monomer 1.
2. bio-based heat resistant polyamide according to claim 1, it is characterised in that the addition of the polyesteramide is
The 2~6% of the gross weight of the monomer 1.
3. bio-based heat resistant polyamide according to claim 1, it is characterised in that the bio-based heat resistant polyamide
Inherent viscosity be 0.7~1.0dL/g, glass transition temperature Tg>=110 DEG C, melt temperature TmIt is 302~315 DEG C.
4. bio-based heat resistant polyamide according to claim 1, it is characterised in that the polyesteramide is total to by monomer 2
Poly- to form, the monomer 2 is that mol ratio is 1:0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones and 2,2'- (1,
3- phenylenes)-bisoxazoline.
5. bio-based heat resistant polyamide according to claim 4, it is characterised in that the polyesteramide is synthesized by following
Method is obtained：(1) by vacuum drying after the monomer 2 be added in stirring-type polymer reactor, while adding the monomer 2
The titanium compound of the 0.1~2% of gross weight is used as catalyst, addition suitable quantity of water；Then 3~10min is vacuumized, leads to inert gas
3~10min, so circulates 5~10 times, makes in the environment that reactant is present under inert gas shielding, controls the stirring-type
System pressure is 0.1~0.5MPa in polymer reactor；
(2) by the stirring-type polymer reactor airtight heating to 240~260 DEG C, the stirring-type polymer reactor is adjusted
Mixing speed is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 210 DEG C, it is deflated to
1.6MPa, and maintain pressure in 1.6MPa, after reacting 0.5~4 hour, normal pressure is deflated to, continue to react at 240~260 DEG C
After 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas；The titanium compound is butyl titanate, isopropyl metatitanic acid
One or more mixture in ester, propyl titanate, acrylic titanate esters.
6. the synthetic method of the bio-based heat resistant polyamide described in a kind of claim 1, it is characterised in that including following step
Suddenly：
(1) monomer 1 is added in stirring-type polymer reactor, at the same add the polyesteramide, molecular weight regulator,
Antioxidant, water；Then 3~10min is vacuumized, leads to 3~10min of inert gas, so circulated 5~10 times, there is reactant
In the environment under inert gas shielding, it is 0.1~0.5MPa to control system pressure in the stirring-type polymer reactor；It is described
Monomer 1 is that mol ratio is 1:0.55~0.8:0.2~0.45 hexamethylene diamine, terephthalic acid (TPA) and decanedioic acid, and hexamethylene diamine with it is right
The mol ratio of both phthalic acid and decanedioic acid consumption sum is 1, and the addition of the polyesteramide is the gross weight of the monomer 1
1~8%；, the polyesteramide forms by the copolymerization of monomer 2, and the monomer 2 is that mol ratio is 1:0.5~1:0.1~0.4 11-
Aminoundecanoic acid, 6- caprolactones and 2,2'- (1,3- phenylenes)-bisoxazoline；
(2) by the stirring-type polymer reactor airtight heating to 275~290 DEG C, the stirring-type polymer reactor is adjusted
Mixing speed is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to
2.0MPa, and maintain pressure in 2.0MPa, after reacting 0.5~4 hour, normal pressure is deflated to, while being warming up at 316~330 DEG C
After continuing to react 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas.
7. synthetic method according to claim 6, it is characterised in that comprise the following steps：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while add the polyesteramide,
Molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to afterwards, so circulated 5~7 times, made anti-
Answer in the environment that thing is present under nitrogen protection, it is 0.2~0.3MPa to control system pressure in the stirring-type polymer reactor；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 280~290 DEG C, regulation described in stir
The mixing speed of formula polymer reactor is mixed for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1~2 hour, normal pressure is deflated to, while being warming up to 316
After continuing to react 1~2 hour at~326 DEG C, constant temperature is persistently vacuumized 0.3~1 hour, and reaction terminates, and nitrogen is supplemented in discharging
Gas.
8. the synthetic method according to claim 6 or 7, it is characterised in that the polyesteramide is by following synthetic method system
：(1) by vacuum drying after the monomer 2 be added in stirring-type polymer reactor, while adding the gross weight of the monomer 2
0.1~2% titanium compound as catalyst, add suitable quantity of water；Then 3~10min is vacuumized, logical inert gas 3~
10min, so circulates 5~10 times, makes in the environment that reactant is present under inert gas shielding, controls the stirring-type polymerization
System pressure is 0.1~0.5MPa in reactor；
(2) by the stirring-type polymer reactor airtight heating to 240~260 DEG C, the stirring-type polymer reactor is adjusted
Mixing speed is 0~100r/min, wherein, when the stirring-type polymer reactor temperature reaches 210 DEG C, it is deflated to
1.6MPa, and maintain pressure in 1.6MPa, after reacting 0.5~4 hour, normal pressure is deflated to, continue to react at 240~260 DEG C
After 0.5~4 hour, constant temperature is persistently vacuumized 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas；The titanium compound is butyl titanate, isopropyl metatitanic acid
One or more mixture in ester, propyl titanate, acrylic titanate esters.
9. the synthetic method according to claim 6 or 7, it is characterised in that the molecular weight regulator is that addition is institute
The organo montmorillonite and addition of stating the 0.1~8% of the gross weight of monomer 1 are the 0.1~3% of the gross weight of the monomer 1 benzene
Formic acid；The antioxidant is addition is the gross weight of the monomer 1 0.1~0.3% N, N`- bis- (2,2,6,6- tetramethyls-
4- piperidyls) -1,3- benzenedicarboxamides.
10. synthetic method according to claim 9, it is characterised in that the addition of the polyesteramide is the monomer 1
The 2~6% of gross weight；The addition of the organo montmorillonite is the 0.5~5% of the gross weight of the monomer 1, the benzoic acid
Addition is the 0.5~2.5% of the gross weight of the monomer 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937315A (en) * | 1988-06-15 | 1990-06-26 | Rhone-Poulenc Chimie | Transparent amorphous polyamide having high Tg from hindered aromatic diamine and branched chain aliphatic diamine |
| CN101020746A (en) * | 2007-03-19 | 2007-08-22 | 北京化工大学 | Prepn process of biodegradable polyamidoester |
| CN102079814A (en) * | 2010-12-21 | 2011-06-01 | 北京化工大学 | Preparation method of aliphatic polyester amide containing short polyamide segment |
| CN102775601A (en) * | 2012-08-03 | 2012-11-14 | 中北大学 | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937315A (en) * | 1988-06-15 | 1990-06-26 | Rhone-Poulenc Chimie | Transparent amorphous polyamide having high Tg from hindered aromatic diamine and branched chain aliphatic diamine |
| CN101020746A (en) * | 2007-03-19 | 2007-08-22 | 北京化工大学 | Prepn process of biodegradable polyamidoester |
| CN102079814A (en) * | 2010-12-21 | 2011-06-01 | 北京化工大学 | Preparation method of aliphatic polyester amide containing short polyamide segment |
| CN102775601A (en) * | 2012-08-03 | 2012-11-14 | 中北大学 | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer |
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