CN105295033B - Long carbon chain semiaromatic polyamide composition and its synthetic method - Google Patents
Long carbon chain semiaromatic polyamide composition and its synthetic method Download PDFInfo
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Abstract
The present invention relates to a kind of Long carbon chain semiaromatic polyamide composition and its synthetic method.The Long carbon chain semiaromatic polyamide composition has such as following formula I structure：In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide.Long carbon chain semiaromatic polyamide composition of the present invention has higher mechanical property and heat resistance, low water absorption, processing characteristics is excellent and has the characteristic of biological source, 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 Long carbon chain semiaromatic polyamide composition and its synthetic method.
Background technology
In recent years, in order to meet the requirement in the higher performance in the fields such as electronics, electrical equipment, automobile, in particular with surface
The development of mounting technique (Surface Mount Technology, abbreviation SMT), common thermostability engineering plastic polyphenylene sulfide
(PPS) and the heat resistance of liquid crystal polymer (LCP) can not fully meet its requirement, therefore develop the higher engineering of heat resistance
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 made, 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 has preferable superiority of effectiveness, and 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 10T resins
For 320 DEG C or so, it is more or less the same with decomposition temperature, processing temperature narrow limits, easily causes polymer in process
Decompose, so the methods of generally use and other copolyamides reduces its melting temperature.
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 melting temperature of the polymer of formation are anti-
Should.15~30 DEG C of progress typically below the fusing point of prepolymer due to solid phase, its reaction rate is relatively slow, the reaction time compared with
It is long, and the production process of solid phase is more, flow is complicated, requires higher to device parameter, reaction also needs to ensure 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 production
The molecular weight of thing, therefore, conditions above limit the large-scale promotion of solid phase.Melt polymerization (Melt
Polymerization) referring to monomer and polymer is in polymerization process under molten condition, this method process route is simple,
Can be with continuous production, can also 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 homopolymer of Long carbon chain semiaromatic heat resistant polyamide and the synthetic method of copolymer and its
Obtained polymerizate, the polymerizate are mainly 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
The mole percent level measured as 40%~99%, fatty polyamide block is 1~60%, and the polymerizate mainly passes through
The method of solid phase obtains；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 higher mechanical property and heat resistance, low water absorption, processing characteristics are excellent
Long carbon chain semiaromatic polyamide composition different and with biological source, it can be applied to field of electronics, LED field, automobile neck
Domain, Aero-Space and military industry field etc..
To reach above-mentioned purpose, the present invention uses following scheme：
A kind of Long carbon chain semiaromatic polyamide composition, it has such as following formula I structure：
I
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has
Such as Formula Il structure：
II
Wherein, x=10~200, y=10~200, z=10~100；
The Long carbon chain semiaromatic polyamide composition is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is for mol ratio
1:0.7~0.99:0.01~0.3 decamethylene diamine, terephthalic acid (TPA), dodecanedioic acid, and the decamethylene diamine and terephthalic acid (TPA)
Mol ratio with both dodecanedioic acids dosage sum is 1, the addition of the polyesteramide for the gross weight of monomer 1 1~
8%.
In wherein some embodiments, the addition of the polyesteramide is the 2~6% of the gross weight of monomer 1.
In wherein some embodiments, the inherent viscosity of the Long carbon chain semiaromatic polyamide composition is 0.7~1.0dL/g,
Glass transition temperature Tg>=100 DEG C, melting temperature TmFor 290~305 DEG C.
In wherein some embodiments, the polyesteramide is copolymerized by monomer 2 and formed, 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.
In wherein some embodiments, the polyesteramide is made by following synthetic method：(1) by the institute after vacuum drying
State monomer 2 to be added in stirring-type polymer reactor, while 0.1~2% titanium compound for adding the gross weight of monomer 2 is made
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 reactant be present in the environment 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 reaction 0.5~4 hour, normal pressure is deflated to, continues to react at 240~260 DEG C
After 0.5~4 hour, constant temperature persistently vacuumizes 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 kinds of mixtures 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 Long carbon chain semiaromatic polyamide composition, including following step
Suddenly：
(1) monomer 1 is added in stirring-type polymer reactor, while adds the polyesteramide, molecular weight tune
Save 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, reactant is present in the environment 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 1:0.7~0.99:0.01~0.3 decamethylene diamine, terephthalic acid (TPA),
Dodecanedioic acid, and the decamethylene diamine and both terephthalic acid (TPA) and dodecanedioic acid dosage and mol ratio be 1, the polyester
The addition of acid amides is the 1~8% of the gross weight of monomer 1；The polyesteramide is copolymerized by monomer 2 and formed, and the monomer 2 is
Mol ratio is 1:0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones and 2,2'- (1,3- phenylenes)-dioxazole
Quinoline；
(2) by the stirring-type polymer reactor airtight heating to 270~285 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 reaction 0.5~4 hour, normal pressure is deflated to, while be warming up at 306~325 DEG C
After continuing reaction 0.5~4 hour, constant temperature persistently vacuumizes 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 purpose of leading to inert gas before reaction is to reduce the probability that side reaction occurs；The purpose vacuumized in course of reaction is handle
Caused water removes in polymerisation, is advantageous to the positive progress of polymerisation.
In wherein some embodiments, above-mentioned synthetic method comprises the following steps：
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while adds the polyester acyl
Amine, molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, is so circulated 5~7 times, is made anti-
Thing is answered to be present in the environment 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 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 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 reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After continuing reaction at 310~320 DEG C 1~2 hour, constant temperature persistently vacuumizes 0.3~1 hour, and reaction terminates, and is supplemented in discharging
Nitrogen.
In wherein some embodiments, the polyesteramide is made by following synthetic method：(1) by the institute after vacuum drying
State monomer 2 to be added in stirring-type polymer reactor, while 0.1~2% titanium compound for adding the gross weight of monomer 2 is made
For catalyst, add suitable quantity of water；Then 3~10min is vacuumized, leads to 3~10min of inert gas, so circulates 5~10 times, makes
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 reaction 0.5~4 hour, normal pressure is deflated to, continues to react at 240~260 DEG C
After 0.5~4 hour, constant temperature persistently vacuumizes 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 kinds of mixtures in acid esters, propyl titanate, acrylic titanate esters.
In wherein some embodiments, the molecular weight regulator be addition be the gross weight of monomer 1 0.1~
8% organo montmorillonite and addition is 0.1~3% benzoic acid of the gross weight of monomer 1；The antioxidant is to add
Measure as 0.1~0.3% N of the gross weight of monomer 1, the acyl of N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene two
Amine.
In wherein some embodiments, the addition of the polyesteramide is the 2~6% of the gross weight of monomer 1；It is described
The addition of organo montmorillonite is the 0.5~5% of the gross weight of monomer 1, and the addition of the benzoic acid is total for the monomer 1
The 0.5~2.5% of weight.
The principle of the present invention is as follows：
In order to solve the defects of polyamide 10T resin processing temperature narrow limits, the present invention has carried out new molecular resin knot
The design of structure, the fusing point of copolymer is reduced by adding dodecanedioic acid, while add polyesteramide to improve copolymer
Notch impact strength and antistatic effect, add N, and N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides comes
Handle the xanthochromia problem in polymerization process.
Polyesteramide has ether epoxide, and it can be combined with free electric charge, and electric charge can be in a manner 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 is preferable, therefore can improve the notch impact strength of copolymer.
Organo montmorillonite belongs to polyhydroxy inorganic matter, passes through terminal hydroxy group and the Long carbon chain semi-aromatic polyamides of organo montmorillonite
The end group reaction of amine, reach the purpose of regulation molecular weight.Further, since organo montmorillonite has nanometer small-size effect, it can
To improve the modulus of copolymer and anti-flammability, shrinkage factor and water absorption rate are reduced.
Benzoic acid belongs to the organic matter of simple function group, the end carboxyl of benzoic acid and the virtue of Long carbon chain half in melt polymerization process
After the Amino End Group reaction of fragrant polyamide, it no longer carries out the reaction of chain growth, so as to play a part of adjusting molecular weight.
The fusing point of N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides is 272 DEG C, boiling point>360
DEG C, the better heat stability in Long carbon chain semiaromatic polyamide composition building-up process, its amide group can be with the virtue of Long carbon chain half
The end group of fragrant polyamide is reacted to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dye of copolymer
Color.
Compared with prior art, the invention has the advantages that：
(1) the defects of present invention is directed to existing polyamide 10T resin processing temperature narrow limits, has carried out new molecular resin
The design of structure, the fusing point of copolymer is reduced by adding dodecanedioic acid, while add polyesteramide to improve copolymer
Notch impact strength and antistatic effect, add N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides
To handle the xanthochromia problem in polymerization process, gained Long carbon chain semiaromatic polyamide composition has higher mechanical property and heat resistance
Can, low water absorption, processing characteristics it is excellent and with biological source characteristic, can be applied to field of electronics, LED field,
Automotive field, Aero-Space and military industry field etc..
(2) method that synthetic method of the invention uses one-step polymerization, it shortens flow with process is reduced, and drops
Low cost, the advantages of improving productivity ratio, preparation technology is easy, and polymerization process is easy to operate, is easy to management and control, can fully reach
To required polymerizing condition, facilitate its industrialized realization；And in the course of the polymerization process without using any organic solvent, to people
Body and environment are not dangerous, and security is good.
(3) decamethylene diamine used in the present invention is prepared by the castor oil of nature, and therefore, the present invention is prepared
Long carbon chain semiaromatic polyamide composition is a kind of bio-based materials, has green characteristic.
Brief description of the drawings
Fig. 1 show the synthesis process flow diagram of Long carbon chain semiaromatic polyamide composition of the present invention；
Fig. 2 show the nonisothermal crystallization melting curve of the Long carbon chain semiaromatic polyamide composition of the gained of the embodiment of the present invention 5
Figure.
Embodiment
For the feature of the present invention, technological means and the specific purposes reached, function can be further appreciated that, this hair is parsed
The advantages of bright and spirit, by following examples, the present invention is further elaborated.
Long carbon chain semiaromatic polyamide composition of the present invention, it has such as following formula I structure：
I
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has
Such as Formula Il structure：
II
Wherein, x=10~200, y=10~200, z=10~100.
The reaction mechanism of Long carbon chain semiaromatic polyamide composition of the present invention is following (synthesis process flow diagram is see Fig. 1)：
Reaction mechanism
From above-mentioned reaction equation, the Amino End Group of decamethylene diamine, the end carboxyl of terephthalic acid (TPA), the end carboxylic of dodecanedioic acid
The Amino End Group and end carboxyl of base, polyesteramide, these groups can react to each other to obtain Long carbon chain semiaromatic of the present invention
Polyamide.
And the reaction mechanism of the polyesteramide added in above-mentioned Long carbon chain semiaromatic polyamide composition 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 to obtain the polyester acyl that the present invention is added
Amine, the inherent viscosity for the polyesteramide that the present invention is added is 0.7~1.0dL/g, glass transition temperature Tg>=80 DEG C, melting temperature
TmFor 215~225 DEG C.
Raw material is as follows used in the embodiment of the present invention：
Decamethylene diamine, selected from Wuxi Yinda Nylon Co., Ltd.；
Terephthalic acid (TPA), selected from Beijing Yanshan Petrochemical Co.；
Dodecanedioic acid, selected from Shandong Guang Yin new materials Co., Ltd；
Polyesteramide, make by oneself, 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- benzene diamides, has selected from Chinese medicines group chemical reagent
Limit company.
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 forms, 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 adds 0.1~2% titanizing of the gross weight of monomer 2
Medium of the compound water appropriate as catalyst, addition as mass-and heat-transfer；Then 3~10min is vacuumized, leads to inert gas 3
~10min, so circulate 5~10 times, reactant is present in the environment under inert gas shielding, 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 reaction 0.5~4 hour, is deflated to normal pressure in 1.6MPa, after continuing reaction at 240~260 DEG C 0.5~4 hour,
Constant temperature persistently vacuumizes 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 kinds of mixtures in acid esters, propyl titanate, acrylic titanate esters.
Embodiment 1
The raw material of polyesteramide used in the present embodiment is formed 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, added simultaneously
1% butyl titanate (17.3g) of the gross weight of monomer 2 is as the medium of catalyst, addition 500mL water as mass-and heat-transfer；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, 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 for answering device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to,
And pressure is maintained in 1.6MPa, after reaction 1.5 hours, normal pressure is deflated to, after continuing reaction at 250 DEG C 1.5 hours, constant temperature is held
Continuous to vacuumize 0.5 hour, reaction terminates, and nitrogen is supplemented in discharging.
A kind of synthetic method of Long carbon chain semiaromatic polyamide composition of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 164.5g (0.99mol) terephthalic acid (TPA),
2.3g (0.01mol) dodecanedioic acid is added in stirring-type polymer reactor, while adds 1% (3.4g) of single 1 gross weight
Polyesteramide, 0.1% (0.3g) organo montmorillonite, 0.1% (0.3g) benzoic acid, 0.1% (0.3g) N, N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add medium of the 100mL water as mass-and heat-transfer；Then take out true
Empty 5min, lead to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, control 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 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
Pressure is maintained in 2.0MPa, after reaction 0.5 hour, is deflated to normal pressure, while after being warming up at 325 DEG C and continuing reaction 0.5 hour,
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 formed in the present embodiment and synthesis step is the same as embodiment 1.
A kind of synthetic method of Long carbon chain semiaromatic polyamide composition of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 116.3g (0.7mol) terephthalic acid (TPA),
69.1g (0.3mol) dodecanedioic acid is added in stirring-type polymer reactor, while adds 8% (28.6g) of single 1 gross weight
Polyesteramide, 8% (28.6g) organo montmorillonite, 3% (10.7g) benzoic acid, 0.3% (1.1g) N, N`- bis- (2,
2,6,6- tetramethyl -4- piperidyls) medium of -1,3- benzene diamides, addition 100mL water as mass-and heat-transfer；Then vacuumize
5min, lead to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, 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 270 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
Pressure is maintained in 2.0MPa, after reaction 4 hours, is deflated to normal pressure, while after being warming up at 306 DEG C and continuing reaction 4 hours, constant temperature
Persistently vacuumize 0.1 hour, reaction terminates, and nitrogen is supplemented in discharging.
Embodiment 3
The raw material of polyesteramide used is formed in the present embodiment and synthesis step is the same as embodiment 1.
A kind of synthetic method of Long carbon chain semiaromatic polyamide composition of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 149.5g (0.9mol) terephthalic acid (TPA),
23.0g (0.1mol) dodecanedioic acid is added in stirring-type polymer reactor, while adds 2% (6.9g) of single 1 gross weight
Polyesteramide, 0.5% (1.7g) organo montmorillonite, 0.5% (1.7g) benzoic acid, 0.2% (0.7g) N, N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add medium of the 100mL water as mass-and heat-transfer；Then take out true
Empty 5min, lead to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, control 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 280 DEG C, regulation stirring-type polymerization is anti-
The mixing speed for answering device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to,
And pressure is maintained in 2.0MPa, after reaction 1 hour, normal pressure is deflated to, while after being warming up at 320 DEG C and continuing reaction 1 hour, 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 formed in the present embodiment and synthesis step is the same as embodiment 1.
A kind of synthetic method of Long carbon chain semiaromatic polyamide composition of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 132.9g (0.8mol) terephthalic acid (TPA),
46.1g (0.2mol) dodecanedioic acid is added in stirring-type polymer reactor, while adds 6% (21.1g) of single 1 gross weight
Polyesteramide, 5% (17.6g) organo montmorillonite, 2.5% (8.8g) benzoic acid, 0.2% (0.7g) N, N`- bis- (2,
2,6,6- tetramethyl -4- piperidyls) medium of -1,3- benzene diamides, addition 100mL water as mass-and heat-transfer；Then vacuumize
5min, lead to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, 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 272 DEG C, regulation stirring-type polymerization is anti-
The mixing speed for answering device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to,
And pressure is maintained in 2.0MPa, after reaction 2 hours, normal pressure is deflated to, while after being warming up at 310 DEG C and continuing reaction 2 hours, 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 formed in the present embodiment and synthesis step is the same as embodiment 1.
A kind of synthetic method of Long carbon chain semiaromatic polyamide composition of the present embodiment, comprises the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 146.2g (0.88mol) terephthalic acid (TPA),
27.6g (0.12mol) dodecanedioic acid is added in stirring-type polymer reactor, while adds the 4% of single 1 gross weight
The polyesteramide of (13.8g), 3% (10.4g) organo montmorillonite, 1.5% (5.2g) benzoic acid, 0.2% (0.7g) N, N
`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add medium of the 100mL water as mass-and heat-transfer；Then
5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, reactant is present in the environment under nitrogen protection, control stirring-type
System pressure is 0.3MPa in polymer reactor；
(2) in 3 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
Pressure is maintained in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while after being warming up at 315 DEG C and continuing reaction 1.5 hours,
Constant temperature is persistently vacuumized 0.5 hour, and reaction terminates, and nitrogen is supplemented in discharging.
The nonisothermal crystallization melting curve figure of Long carbon chain semiaromatic polyamide composition obtained by the present embodiment is as shown in Fig. 2 figure
In show the Long carbon chain semiaromatic polyamide composition melting peak peak temperature (i.e. melting temperature) be 299.68 DEG C.
It is embodiment list below：
The embodiment raw material of table 1 forms list
The made sample of above-described embodiment is subjected to 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；
Melting temperature：By GB/T19466.3-2004 standard testings.
The embodiment performance list of table 2
As can be seen from the above embodiments, the addition of dodecanedioic acid is more, the drawing of Long carbon chain semiaromatic polyamide composition
Stretch that intensity, glass transition temperature and melting temperature are lower, and impact strength is higher；The water absorption rate change of each embodiment is little；With
The addition for molecular weight regulator (organo montmorillonite and benzoic acid) increases, and its inherent viscosity diminishes.Wherein, embodiment 5
Combination property is optimal.
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 that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come 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 the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. a kind of Long carbon chain semiaromatic polyamide composition, it is characterised in that it has such as following formula I structure：
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, R is polyesteramide, and it has as follows
Formula II structure：
Wherein, x=10~200, y=10~200, z=10~100；
The Long carbon chain semiaromatic polyamide composition is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is that mol ratio is 1:
0.7~0.99:0.01~0.3 decamethylene diamine, terephthalic acid (TPA), dodecanedioic acid, and the decamethylene diamine and terephthalic acid (TPA) and
The mol ratio of both dodecanedioic acids dosage sum is 1, the addition of the polyesteramide for the gross weight of monomer 1 1~
8%；
The polyesteramide is copolymerized by monomer 2 and formed, and the monomer 2 is that mol ratio is 1:0.5~1:0.1~0.4 11- amino
Undecanoic acid, 6- caprolactones and 2,2'- (1,3- phenylenes)-bisoxazoline；
The polyesteramide is made by following synthetic method：(1) monomer 2 after vacuum drying is added to stirring-type polymerization
In reactor, while 0.1~2% titanium compound of the gross weight of monomer 2 is added as catalyst, addition suitable quantity of water；So
After vacuumize 3~10min, lead to inert gas 3~10min, so circulate 5~10 times, reactant is present in inert gas guarantor
In environment under shield, it is 0.1~0.5MPa to control system pressure in the stirring-type 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 reaction 0.5~4 hour, normal pressure is deflated to, continues to react at 240~260 DEG C
After 0.5~4 hour, constant temperature persistently vacuumizes 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 kinds of mixtures in ester, propyl titanate, acrylic titanate esters.
2. Long carbon chain semiaromatic polyamide composition according to claim 1, it is characterised in that the addition of the polyesteramide
For the 2~6% of the gross weight of monomer 1.
3. Long carbon chain semiaromatic polyamide composition according to claim 1, it is characterised in that the Long carbon chain semiaromatic adoption
The inherent viscosity of acid amides is 0.7~1.0dL/g, glass transition temperature Tg>=100 DEG C, melting temperature TmFor 290~305 DEG C.
4. the synthetic method of the Long carbon chain semiaromatic polyamide composition 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 circulates 5~10 times, reactant be present
In 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 1:0.7~0.99:0.01~0.3 decamethylene diamine, terephthalic acid (TPA), dodecanedioic acid, and the last of the ten Heavenly stems two
Amine and both terephthalic acid (TPA) and dodecanedioic acid dosage and mol ratio be 1, the addition of the polyesteramide is the list
The 1~8% of the gross weight of body 1；The polyesteramide is copolymerized by monomer 2 and formed, 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 270~285 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 reaction 0.5~4 hour, normal pressure is deflated to, while be warming up at 306~325 DEG C
After continuing reaction 0.5~4 hour, constant temperature persistently vacuumizes 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is nitrogen or argon gas.
5. synthetic method according to claim 4, it is characterised in that comprise the following steps：
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, at the same add the polyesteramide,
Molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulates 5~7 times, makes reaction
Thing is present in the environment under nitrogen protection, and 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 272~280 DEG C, stirred described in regulation
The mixing speed for mixing formula polymer reactor is 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, be deflated to normal pressure, while be warming up to 310
After continuing reaction at~320 DEG C 1~2 hour, constant temperature is persistently vacuumized 0.3~1 hour, and reaction terminates, and nitrogen is supplemented in discharging
Gas.
6. the synthetic method according to claim 4 or 5, it is characterised in that the polyesteramide is by following synthetic method system
：(1) monomer 2 after vacuum drying is added in stirring-type polymer reactor, while adds the gross weight of 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 circulate 5~10 times, reactant is present in the environment under inert gas shielding, control the stirring-type to polymerize
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 reaction 0.5~4 hour, normal pressure is deflated to, continues to react at 240~260 DEG C
After 0.5~4 hour, constant temperature persistently vacuumizes 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 kinds of mixtures in ester, propyl titanate, acrylic titanate esters.
7. the synthetic method according to claim 4 or 5, it is characterised in that the molecular weight regulator is addition for institute
0.1~8% organo montmorillonite and the addition for stating the gross weight of monomer 1 are 0.1~3% benzene of the gross weight of monomer 1
Formic acid；The antioxidant be addition be the gross weight of monomer 1 0.1~0.3% N, N`- bis- (2,2,6,6- tetramethyls-
4- piperidyls) -1,3- benzene diamides.
8. synthetic method according to claim 7, 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 monomer 1, the benzoic acid
Addition is the 0.5~2.5% of the gross weight of monomer 1.
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