CN105330852B - Long-carbon-chain transparent nylon and its synthetic method - Google Patents
Long-carbon-chain transparent nylon and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of long-carbon-chain transparent nylon and its synthetic method, the long-carbon-chain transparent nylon 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.Long-carbon-chain transparent nylon of the invention has mechanical property and light transmittance higher, low water absorption, processing characteristics is excellent and characteristic with biogenetic derivation, can be applied to the fields such as surrounding mechanical part and electro mechanical component, precision optical instrument, pressure-resistant form, peephole, extraordinary light fixture outer cover, food product packing film, the high-grade sports equipment of fuel and oil.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of long-carbon-chain transparent nylon and its synthetic method.
Background technology
Transparent polyamide (transparent nylon) is a kind of macromolecular material of excellent combination property.It not only has mechanical strength
The advantages of high, heat endurance good, excellent corrosion resistance, also with easy processing and forming, dimensional stability, linear expansion coefficient
Small, cost performance is high, electrical insulating property and resistance to ag(e)ing is excellent, nontoxic, odorless, easily forms alloy with other amorphous or hemihedral crystal polyamide
The advantages of；It is not only transparent excellent (transparency is even more than PC, close to PMMA), and in tenable environment stress cracking, oil resistant
Property solvent, it is resistance to scratch, the aspect such as wear-resistant it is more more superior than general transparent polymer material (such as PS, PC, PMMA).
Transparent polyamide has been widely used for the periphery of fuel and oil and electrically waits mechanical part (such as lighter fluid now
Groove, flowmeter set, strainer cover, filter bowl, breaker and Shells of High Voltage Switches etc.) in, especially in precision optical instrument, pressure-resistant
The application in the fields such as form, peephole, extraordinary light fixture outer cover, food product packing film, high-grade sports equipment is other materials institute nothing
What method was substituted.
Because polyamide belongs to crystalline polymer, the polyamide for wanting to produce possesses light transmittance very high, can be with
From from the aspect of three below：(1) crystallizing power of polyamide is reduced, so as to obtain amorphous product；(2) crystalline region crystal is reduced
Size, makes the diameter of crystal less than visible light wave wavelength, and this method is otherwise known as controlled micro crystallization method；(3) by blending, copolymerization etc.
Method adjusts the refractive index of amorphous area and crystalline region to be modified to polyamide, them is had identical refraction index.
Solid phase (Solid state Polymerization) refers to solid (or crystalline phase) monomer below its fusing point
The polymerisation of generation, or more than monomer fusing point, but the polymerization carried out 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, and in the thickening stage need vacuum or air-flow and accelerate the discharge of small molecular by product, so as to improve contracting
The molecular weight of poly- product, therefore, conditions above limits the large-scale promotion of solid phase.
Melt polymerization (Melt Polymerization) refers to the polymerization that monomer and polymer are under molten condition
Journey, the method process route is simple, can continuously produce, it is also possible to Batch Process.Reaction needs to carry out at high temperature, during reaction
Between it is shorter, and the discharge of the accessory substance such as hydrone is easy.
At present, some researchs have been done in the synthesis in the prior art to transparent polyamide, for example：Chinese patent CN1041957A
A kind of transparent thermoplastic polyamide is disclosed, its structure is by cycloaliphatic diamine, the lactams of at least 7 carbon atoms or corresponding
Amino acid, and terephthalic acid (TPA) or the terephthalic acid (TPA) containing more than 50% terephthalic acid (TPA) and M-phthalic acid mixture
Group is constituted.This kind of polyamide is by lactams or amino-acid compound and terephthalic acid (TPA) or terephthalic acid (TPA) by the first step
Mixture with M-phthalic acid reacts, and resulting diacid oligomer and cycloaliphatic diamine reaction are obtained second step, should
Patent is two step method.Chinese patent CN101372531A discloses a kind of transparent co-polyamide and preparation method thereof, with domestic
Cheap dimeric dibasic acid, aromatic acid and acyclic straight diamine are raw material, and melt polycondensation obtains a kind of copolyamide, this
The light transmittance of copolymer is planted up to more than 90%, while having heat resistance higher not only but also with preferable moulding processability.
Chinese patent CN103073717A discloses a kind of preparation method of Semi-aromatic transparent polyamide, comprises the following steps：Will be right
Phthalic acid and 2,2,4- trimethylhexane diamines (TMD) are added in organic solvent, it is fully reacted prepared paraphenylene terephthalamide three
Methyl hexamethylene diamine salt (TMDT salt)；Paraphenylene terephthalamide's trimethylhexane diamine salt (TMDT salt), 11- amino ten are added in a kettle.
One acid, nucleator and deionized water, are purged using nitrogen and cleaned, and a kind of Semi-aromatic transparent polyamide is obtained.Chinese patent
CN103435796A discloses a kind of Semi-aromatic transparent polyamide material and preparation method thereof, and the material is by semi-aromatic acid amides
Salt is constituted with the random copolymer and necessary auxiliary agent of aliphatic amide salt.Chinese patent CN103483581A discloses a kind of saturating
Bright polyamide and its synthetic method, first prepare amorphous polyamide salt and fatty polyamide salt, then by the amorphous poly
Amidic-salt and fatty polyamide salt react under conditions of catalyst and antioxidant are present, and transparent polyamide is obtained.
The content of the invention
There is higher force performance and light transmittance it is an object of the invention to provide one kind, low water absorption, processing characteristics is excellent
Long-carbon-chain transparent nylon different and with biogenetic derivation, the long-carbon-chain transparent nylon can be applied to fuel and
The surrounding mechanical part of oil, electro mechanical component, precision optical instrument, pressure-resistant form, peephole, extraordinary light fixture outer cover, food
In the fields such as packing film, high-grade sports equipment.
To reach above-mentioned purpose, the present invention uses following scheme：
A kind of long-carbon-chain transparent nylon, with 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 long-carbon-chain transparent nylon is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is for mol ratio
1:0.65~0.99:0.01~0.35 decamethylene diamine, M-phthalic acid, adipic acid, and the decamethylene diamine and M-phthalic acid and
The mol ratio of both adipic acids 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 long-carbon-chain transparent nylon is 0.7~1.0dL/g,
Flow temperature TfIt is 214~229 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；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.
It is a further object of the present invention to provide the synthetic method of above-mentioned long-carbon-chain transparent nylon, including following step
Suddenly：
(1) monomer 1 is added in stirring-type polymer reactor, while adding the polyesteramide, crystallization to promote
Agent, molecular weight regulator, antioxidant, water (medium of mass-and heat-transfer)；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；The monomer 1 is that mol ratio is 1:0.65~0.99:0.01~0.35 last of the ten Heavenly stems
Diamines, M-phthalic acid, adipic acid, the addition of the polyesteramide are the 1~8% of the gross weight of the monomer 1；The polyester
Acid amides 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- oneself
Lactone and 2,2'- (1,3- phenylenes)-bisoxazoline；
(2) by the stirring-type polymer reactor airtight heating to 214~224 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, while being warming up at 230~244 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 above-mentioned long-carbon-chain transparent nylon 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, crystallization promoter, molecular weight regulator, antioxidant, suitable quantity of water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so
Circulation 5~7 times, makes in the environment that reactant is present under nitrogen protection, controls system pressure in the stirring-type polymer reactor
Power is 0.2~0.3MPa；The addition of the polyesteramide is the 2~6% of the gross weight of the monomer 1；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 216~222 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 210 DEG C, 1.6MPa is deflated to, and maintains pressure in 1.6MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 232~242 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 crystallization promoter be that addition is the gross weight of the monomer 1 0.1~
0.3% Long carbon chain carboxylic acid calcium salt, the carbon number of the Long carbon chain carboxylic acid calcium salt is 10~40；The molecular weight regulator is to add
Measure the benzoic acid for the 0.1~2% of the gross weight of the monomer 1；The antioxidant is that addition is the gross weight of the monomer 1
0.1~0.3% N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides.
Wherein in some embodiments, the crystallization promoter is the Long carbon chain carboxylic acid calcium salt that carbon number is 15~35；It is described
Molecular weight regulator is addition is the gross weight of the monomer 1 0.5~1.5% benzoic acid.
Principle of the invention is as follows：
The present invention prepares long-carbon-chain with cheap M-phthalic acid, decamethylene diamine, adipic acid, polyesteramide as raw material
Transparent nylon, the symmetry of polyamide molecule chain and regular is destroyed using the dissymmetrical structure and adipic acid of M-phthalic acid
Property, the locomitivity of polyamide molecule chain is reduced by the rigid benzene ring structure in M-phthalic acid, reduce poly- so as to reach
The purpose of acid amides crystallizing power.Also, reduce the size of polyamide crystalline region crystal by adding crystallization promoter, make polyamides
The Crystallization microstructure of the crystal region of polyimide resin, and the presence of microstructure makes material have more preferable mechanical strength, it is resistance to
Chemicals and anti-stress cracking, while assigning material low water absorbable and pliability.Meanwhile, polyesteramide is added to improve altogether
The notch impact strength and antistatic effect of polymers, add N, N`- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene two
Acid amides processes 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 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.
Benzoic acid belongs to the organic matter of simple function group, the end carboxyl of benzoic acid and bio-based carbon long in melt polymerization process
After the Amino End Group reaction of chain transparent nylon, 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- benzene diamides is 272 DEG C, boiling point>360
DEG C, the better heat stability in long-carbon-chain transparent nylon building-up process, its amide group can be with bio-based carbon long
The end group of chain transparent nylon reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dye of copolymer
Color.
The present invention compares the advantage of prior art and has the beneficial effect that：
(1) a kind of long-carbon-chain transparent nylon of the invention, with cheap M-phthalic acid, decamethylene diamine, adipic acid,
Polyesteramide is prepared for raw material.The invention is reached using M-phthalic acid and adipic acid reduces polyamide crystallizing power
Purpose, makes the Crystallization microstructure of the crystal region of polyamide, by adding polyester acyl by adding crystallization promoter
Amine improves the notch impact strength and antistatic effect of copolymer, by adding N, (2,2,6, the 6- tetramethyl -4- piperazines of N`- bis-
Piperidinyl) -1,3- benzene diamides processes the xanthochromia problem in polymerization process.
The long-carbon-chain transparent nylon has higher force performance and light transmittance, and low water absorption, processing characteristics is excellent
The characteristics of.The long-carbon-chain transparent nylon can be applied to surrounding mechanical part, electro mechanical component, the precision of fuel and oil
In the fields such as optical instrument, pressure-resistant form, peephole, extraordinary light fixture outer cover, food product packing film, high-grade sports equipment.
(2) synthetic method of long-carbon-chain transparent nylon of the invention using one-step polymerization method, it has and subtracts
Lack operation, shortened flow, reduced cost, improve the advantage of productivity ratio；Preparation technology of the invention is easy, is polymerized
Journey is easy to operate, is easy to management and control, can be fully achieved required polymerizing condition, facilitates its industrialized realization.Also, poly-
Any organic solvent is not used during conjunction, not dangerous to human body and environment, security is good.
(3) decamethylene diamine used in raw material of the present invention is prepared by the castor oil of nature, therefore, present invention system
The standby long-carbon-chain transparent nylon 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 long-carbon-chain transparent nylon of the present invention.
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.
A kind of long-carbon-chain transparent nylon of the invention, with 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.
Synthesizing the reaction mechanism of long-carbon-chain transparent nylon of the invention, following (synthesis process flow diagram is see figure
1)：
Reaction mechanism
It is the Amino End Group of decamethylene diamine, the end carboxyl of M-phthalic acid, the end carboxyl of adipic 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 the transparent Buddhist nun of long-carbon-chain of the present invention
Dragon.
The reaction mechanism for synthesizing the polyesteramide added in above-mentioned long-carbon-chain transparent nylon 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：
Decamethylene diamine, selected from Wuxi Yinda Nylon Co., Ltd.；
M-phthalic acid, selected from Beijing Yanshan Petrochemical Co.；
Adipic acid, selected from Shandong Guang Yin new materials Co., Ltd；
Polyesteramide, self-control；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；
Long carbon chain carboxylic acid calcium salt, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
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 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 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.
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 long-carbon-chain transparent nylon 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) M-phthalic acid,
1.5g (0.01mol) adipic acid is added in stirring-type polymer reactor, while adding 1% (3.4g's) of the gross weight of monomer 1
Polyesteramide, the Long carbon chain carboxylic acid calcium salt 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- benzene diamides, 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 224 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to, and
Maintain pressure in 1.6MPa, after reacting 0.5 hour, be deflated to normal pressure, while after continuing to react 0.5 hour at being warming up to 244 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.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, is comprised the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 108.0g (0.65mol) M-phthalic acid,
51.1g (0.35mol) adipic acid is added in stirring-type polymer reactor, while adding 8% (26.5g) of the gross weight of monomer 1
Polyesteramide, the Long carbon chain carboxylic acid calcium salt of 0.3% (1.0g), the benzoic acid of 2% (6.6g), the N of 0.3% (1.0g), N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, 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 0.2MPa in reactor；
(2) in 2 hours by the closed constant-speed heating of stirring-type polymer reactor to 214 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to, and
Maintain pressure in 1.6MPa, after reacting 4 hours, be deflated to normal pressure, while after continuing to react 4 hours at being warming up to 230 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.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, is comprised the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 149.5g (0.9mol) M-phthalic acid,
14.6g (0.1mol) adipic acid is added in stirring-type polymer reactor, while adding 2% (6.7g's) of the gross weight of monomer 1
Polyesteramide, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the benzoic acid of 0.5% (1.7g), the N of 0.2% (0.7g), N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, 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 222 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, after reacting 1 hour, normal pressure is deflated to, while after continuing to react 1 hour at being warming up to 242 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.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, is comprised the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 116.3g (0.7mol) M-phthalic acid,
43.8g (0.3mol) adipic acid is added in stirring-type polymer reactor, while adding 6% (19.9g's) of the gross weight of monomer 1
Polyesteramide, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the benzoic acid of 1.5% (5.0g), the N of 0.2% (0.7g), N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, 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 2.5 hours by the closed constant-speed heating of stirring-type polymer reactor to 216 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, after reacting 2 hours, normal pressure is deflated to, while after continuing to react 2 hours at being warming up to 232 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.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, is comprised the following steps：
(1) by the monomer 1 after vacuum drying：172.3g (1mol) decamethylene diamine, 132.9g (0.8mol) M-phthalic acid,
29.2g (0.2mol) adipic acid is added in stirring-type polymer reactor, while adding 4% (13.4g's) of the gross weight of monomer 1
Polyesteramide, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the benzoic acid of 1.0% (3.3g), the N of 0.2% (0.7g), N`- bis-
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, 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 219 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 210 DEG C, 1.6MPa is deflated to, and
Maintain pressure in 1.6MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 237 DEG C,
Constant temperature is persistently vacuumized 0.5 hour, and reaction terminates, and nitrogen is supplemented in discharging.
It is below embodiment 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；
Light transmittance：By GB/T2410-2008 standard testings；
Flow temperature：Tested using digital micro-analysis melting point apparatus.
The embodiment performance list of table 2
As can be seen from the above embodiments, the addition of adipic acid is more, and the stretching of long-carbon-chain transparent nylon is strong
Degree, light transmittance and flow temperature are lower, and impact strength is higher；The water absorption rate change of each embodiment is little；With molecular-weight adjusting
The addition of agent benzoic acid increases, and its inherent viscosity diminishes.Wherein, the combination property of embodiment 5 is optimal.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of long-carbon-chain transparent nylon, it is characterised in that with 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 long-carbon-chain transparent nylon is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is that mol ratio is 1:
0.65~0.99:0.01~0.35 decamethylene diamine, M-phthalic acid, adipic acid, and the decamethylene diamine and M-phthalic acid and oneself
The mol ratio of both diacid consumption sum is 1, and the addition of the polyesteramide is the 1~8% of the gross weight of the monomer 1.
2. long-carbon-chain transparent nylon according to claim 1, it is characterised in that the addition of the polyesteramide
It is the 2~6% of the gross weight of the monomer 1.
3. long-carbon-chain transparent nylon according to claim 1, it is characterised in that the long-carbon-chain is transparent
The inherent viscosity of nylon is 0.7~1.0dL/g, flow temperature TfIt is 214~229 DEG C.
4. the long-carbon-chain transparent nylon according to claim any one of 1-3, it is characterised in that the polyesteramide
Formed by the copolymerization of monomer 2, the monomer 2 is that mol ratio is 1:0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones
With 2,2'- (1,3- phenylenes)-bisoxazoline.
5. long-carbon-chain transparent nylon according to claim 4, it is characterised in that the polyesteramide is by following conjunction
It is obtained into method：(1) by vacuum drying after the monomer 2 be added in stirring-type polymer reactor, while adding the list
The titanium compound of the 0.1~2% of the gross weight of body 2 is used as catalyst, addition suitable quantity of water；Then 3~10min is vacuumized, leads to inertia
3~10min of gas, so circulates 5~10 times, makes in the environment that reactant is present under inert gas shielding, is stirred described in control
It is 0.1~0.5MPa to mix system pressure in formula 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 be butyl titanate, propyl titanate,
One or more mixture in acrylic titanate esters.
6. the synthetic method of the long-carbon-chain transparent nylon 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, while adding the polyesteramide, crystallization promoter, dividing
Son amount conditioning agent, antioxidant, 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；The monomer 1 is that mol ratio is 1:0.65~0.99:0.01~0.35 decamethylene diamine, M-phthalic acid, adipic acid,
The addition of the polyesteramide is the 1~8% of the gross weight of the monomer 1；The polyesteramide is formed by the copolymerization of monomer 2, institute
Monomer 2 is stated for mol ratio is 1:0.5~1:0.1~0.4 11- aminoundecanoic acids, 6- caprolactones and 2,2'- (1,3- Asias benzene
Base)-bisoxazoline；
(2) by the stirring-type polymer reactor airtight heating to 214~224 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, while being warming up at 230~244 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,
Crystallization promoter, molecular weight regulator, antioxidant, suitable quantity of water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so followed
Ring 5~7 times, makes in the environment that reactant is present under nitrogen protection, controls system pressure in the stirring-type polymer reactor
It is 0.2~0.3MPa；The addition of the polyesteramide is the 2~6% of the gross weight of the monomer 1；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 216~222 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 210
DEG C when, be deflated to 1.6MPa, and maintain pressure in 1.6MPa, after reaction 1~2 hour, normal pressure is deflated to, while being warming up to 232
After continuing to react 1~2 hour at~242 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 be butyl titanate, propyl titanate,
One or more mixture in acrylic titanate esters.
9. the synthetic method according to claim 6 or 7, it is characterised in that the crystallization promoter is that addition is described
The Long carbon chain carboxylic acid calcium salt of the 0.1~0.3% of the gross weight of monomer 1, the carbon number of the Long carbon chain carboxylic acid calcium salt is 10~40；It is described
Molecular weight regulator is addition is the gross weight of the monomer 1 0.1~2% benzoic acid；The antioxidant is that addition is
The N of 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 diamides.
10. synthetic method according to claim 9, it is characterised in that the crystallization promoter is that carbon number is 15~35
Long carbon chain carboxylic acid calcium salt；The molecular weight regulator is addition is the gross weight of the monomer 1 0.5~1.5% benzoic acid.
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