CN105330852A - Bio-based long-carbon-chain transparent nylon and synthesis method thereof - Google Patents
Bio-based long-carbon-chain transparent nylon and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses bio-based long-carbon-chain transparent nylon and a synthesis method thereof. The bio-based long-carbon-chain transparent nylon has the structure shown in formula I as described in the description, wherein in the formula I, a is equal to 10-100, b is equal to 10-200, c is equal to 10-100, d is equal to 10-100, and R represents polyesteramide. The bio-based long-carbon-chain transparent nylon has the advantages that mechanical performance and light transmittance are high, the water absorption rate is low, the machining performance is excellent, biological sources are achieved, and the bio-based long-carbon-chain transparent nylon can be applied to the fields of surrounding mechanical parts and electrical and mechanical parts of fuel and oil, precision optical instruments, pressure-proof view windows, observation mirrors, special lamp outer covers, food packaging thin films, high-grade sports equipment and the like.
Description
Technical field
The present invention relates to Material Field, particularly relate to a kind of long-carbon-chain transparent nylon and synthetic method thereof.
Background technology
Transparent polyamide (transparent nylon) is a kind of macromolecular material of excellent combination property.It not only has the advantages such as physical strength is high, Heat stability is good, excellent erosion resistance, also there is easy forming process, dimensional stability, linear expansivity be little, cost performance is high, electrical insulating property and ageing resistance is excellent, nontoxic, odorless, easily and other amorphous or hemihedral crystal polymeric amide form the advantages such as alloy; Not only (transparency is even more than PC for transparency excellence, close to PMMA), and at tenable environment stress cracking, oil-proofness solvent, resistance toly to scratch, wear-resistant etc. in transparent polymer material (as PS, PC, PMMA etc.) than general more superior.
Transparent polyamide has been widely used in now the periphery of fuel and oil and has electrically waited in mechanical part (as lighter oil groove, under meter cover, strainer cover, filter bowl, isolating switch and Shells of High Voltage Switches etc.), is especially that other materials institute is irreplaceable in the application in the fields such as precision optical instrument, withstand voltage form, sight glass, extraordinary light fixture outer cover, food product packing film, high-grade sports equipment.
Because polymeric amide belongs to crystalline polymer, the polymeric amide wanting to produce possesses very high transmittance, can from the viewpoint of following three: (1) reduces the crystallizing power of polymeric amide, thus obtains amorphous product; (2) reduce the size of crystalline region crystal, make the diameter of crystal be less than visible optical wavelength, this method is otherwise known as micritization method; (3) by methods such as blended, copolymerization, modification is carried out to polymeric amide, regulate the specific refractory power of non-crystalline region and crystalline region, make them have identical refractive index.
Solid state polymerization (SolidstatePolymerization) refers to the polyreaction that solid (or crystalline phase) monomer occurs below its fusing point, or more than monomer fusing point, but the polyreaction of carrying out below the melt temperature of the polymkeric substance formed.Due to solid state polymerization generally below the fusing point of prepolymer 15 ~ 30 DEG C carry out, its speed of reaction is comparatively slow, the reaction times is longer, and the production process of solid state polymerization is many, flow process is complicated, require higher to device parameter, reaction also needs to ensure that the proportioning of functional group is close to 1:1, and needs vacuum or air-flow to accelerate the discharge of small molecular by product in the thickening stage, thus improves the molecular weight of polycondensation product, therefore, above condition limits the large-scale promotion of solid state polymerization.
Melt polymerization (MeltPolymerization) refer to monomer and polymkeric substance be all in molten state under polymerization process, the method operational path is simple, can continuous seepage, also can batch production.Reaction needed is at high temperature carried out, and the reaction times is shorter, and the by product such as water molecules is discharged easily.
At present, in prior art, some researchs are done to the synthesis of transparent polyamide, such as: Chinese patent CN1041957A discloses a kind of transparent thermoplastic polymeric amide, its structure is by the lactan of cycloaliphatic diamine, at least 7 carbon atoms or corresponding amino acid, and terephthalic acid or the group composition containing the terephthalic acid of more than 50% terephthalic acid and the mixture of m-phthalic acid.This kind of polymeric amide is by the mixture reaction of the first step by lactan or amino-acid compound and terephthalic acid or terephthalic acid and m-phthalic acid, and obtained diacid oligomer and cycloaliphatic diamine are reacted obtained by second step, and this patent is two step method.Chinese patent CN101372531A discloses a kind of transparent co-polyamide and preparation method thereof, with the dimeracid of domestic cheapness, aromatic acid and acyclic straight diamine for raw material, melt phase polycondensation obtains a kind of copolyamide, the transmittance of this multipolymer reaches more than 90%, has higher resistance toheat not only but also have good moulding processability simultaneously.Chinese patent CN103073717A discloses a kind of preparation method of Semi-aromatic transparent polyamide, comprise the following steps: terephthalic acid and 2,2,4-trimethylhexane diamine (TMD) adds in organic solvent, makes it fully react obtained paraphenylene terephthalamide's trimethylhexane diamine salt (TMDT salt); Add paraphenylene terephthalamide's trimethylhexane diamine salt (TMDT salt), 11-aminoundecanoic acid, nucleator and deionized water in a kettle., use nitrogen purging to clean, obtained a kind of Semi-aromatic transparent polyamide.Chinese patent CN103435796A discloses a kind of Semi-aromatic transparent polyamide material and preparation method thereof, and this material is made up of semi-aromatic amide salt and the random copolymers of aliphatic amide salt and the auxiliary agent of necessity.Chinese patent CN103483581A discloses a kind of transparent polyamide and synthetic method thereof, first prepare amorphous polyamide salt and fatty polyamide salt, again this amorphous polyamide salt and fatty polyamide salt are reacted under catalyzer and oxidation inhibitor existent condition, obtained transparent polyamide.
Summary of the invention
One is the object of the present invention is to provide to have higher force performance and transmittance, low water absorption, processing characteristics is excellent and have the long-carbon-chain transparent nylon of biogenetic derivation, and this long-carbon-chain transparent nylon can be applicable in the field such as surrounding mechanical parts, electro mechanical component, precision optical instrument, withstand voltage form, sight glass, extraordinary light fixture outer cover, food product packing film, high-grade sports equipment of fuel and oil.
For achieving the above object, the present invention adopts following scheme:
A kind of 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, and it has as shown in the formula II structure:
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100;
Described long-carbon-chain transparent nylon is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 for mol ratio be decamethylene diamine, m-phthalic acid, the hexanodioic acid of 1:0.65 ~ 0.99:0.01 ~ 0.35, and described decamethylene diamine and m-phthalic acid and hexanodioic acid consumption and mol ratio be 1, the add-on of described polyesteramide is 1 ~ 8% of described monomer 1 gross weight.
Wherein in some embodiments, the add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight.
Wherein in some embodiments, the limiting viscosity of described long-carbon-chain transparent nylon is 0.7 ~ 1.0dL/g, flow temperature T
fit is 214 ~ 229 DEG C.
Wherein in some embodiments, described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be the 11-aminoundecanoic acid of 1:0.5 ~ 1:0.1 ~ 0.4,6-caprolactone and 2,2'-(1,3-phenylene)-bisoxazoline.
Wherein in some embodiments, described polyesteramide is obtained by following synthetic method: the described monomer 2 after vacuum-drying joins in stirring-type polymerization reactor by (1), add simultaneously the titanium compound of 0.1 ~ 2% of described monomer 2 gross weight as catalyzer, add suitable quantity of water; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa;
(2) 240 ~ 260 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, exit to normal pressure, reaction is continued after 0.5 ~ 4 hour at 240 ~ 260 DEG C, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas; Described titanium compound is one or more the mixture in tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate, propenyl titanic acid ester.
Another object of the present invention is to provide the synthetic method of above-mentioned long-carbon-chain transparent nylon, comprises the following steps:
(1) described monomer 1 is joined in stirring-type polymerization reactor, add described polyesteramide, crystallization promoter, molecular weight regulator, oxidation inhibitor, water (medium of mass-and heat-transfer) simultaneously; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa; Described monomer 1 for mol ratio be decamethylene diamine, m-phthalic acid, the hexanodioic acid of 1:0.65 ~ 0.99:0.01 ~ 0.35, the add-on of described polyesteramide is 1 ~ 8% of described monomer 1 gross weight; Described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be the 11-aminoundecanoic acid of 1:0.5 ~ 1:0.1 ~ 0.4,6-caprolactone and 2,2'-(1,3-phenylene)-bisoxazoline;
(2) 214 ~ 224 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, venting is to normal pressure, continue reaction at being warming up to 230 ~ 244 DEG C after 0.5 ~ 4 hour simultaneously, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas.
Before reaction, logical rare gas element object reduces the probability of side reaction generation; The object vacuumized in reaction process is the water removing producing in polyreaction, is conducive to polyreaction forward and carries out.
Wherein in some embodiments, the synthetic method of above-mentioned long-carbon-chain transparent nylon comprises the following steps:
(1) the described monomer 1 after vacuum-drying is joined in stirring-type polymerization reactor, add described polyesteramide, crystallization promoter, molecular weight regulator, oxidation inhibitor, suitable quantity of water simultaneously; Then vacuumize 4 ~ 6min, logical nitrogen 4 ~ 6min, so circulate 5 ~ 7 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in described stirring-type polymerization reactor is 0.2 ~ 0.3MPa; The add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight;
(2) in 2 ~ 4 hours by described airtight constant-speed heating to 216 ~ 222 DEG C of stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 30 ~ 50r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 1 ~ 2 hour, venting is to normal pressure, continue reaction at being warming up to 232 ~ 242 DEG C after 1 ~ 2 hour simultaneously, constant temperature continues to vacuumize 0.3 ~ 1 hour, and reaction terminates, and supplements nitrogen when discharging.
Wherein in some embodiments, described polyesteramide is obtained by following synthetic method: the described monomer 2 after vacuum-drying joins in stirring-type polymerization reactor by (1), add simultaneously the titanium compound of 0.1 ~ 2% of described monomer 2 gross weight as catalyzer, add suitable quantity of water; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa;
(2) 240 ~ 260 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, exit to normal pressure, reaction is continued after 0.5 ~ 4 hour at 240 ~ 260 DEG C, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas; Described titanium compound is one or more the mixture in tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate, propenyl titanic acid ester.
Wherein in some embodiments, the Long carbon chain carboxylic acid calcium salt of described crystallization promoter to be add-on be 0.1 ~ 0.3% of described monomer 1 gross weight, the carbon number of described Long carbon chain carboxylic acid calcium salt is 10 ~ 40; The phenylformic acid of described molecular weight regulator to be add-on be 0.1 ~ 2% of described monomer 1 gross weight; The N of described oxidation inhibitor to be add-on be 0.1 ~ 0.3% of described monomer 1 gross weight, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide.
Wherein in some embodiments, described crystallization promoter to be carbon number be 15 ~ 35 Long carbon chain carboxylic acid calcium salt; The phenylformic acid of described molecular weight regulator to be add-on be 0.5 ~ 1.5% of described monomer 1 gross weight.
Principle of the present invention is as follows:
The present invention prepares long-carbon-chain transparent nylon with the m-phthalic acid of cheapness, decamethylene diamine, hexanodioic acid, polyesteramide for raw material, utilize the unsymmetrical structure of m-phthalic acid and hexanodioic acid to destroy symmetry and the regularity of polyamide molecule chain, reduced the motor capacity of polyamide molecule chain by the rigidity benzene ring structure in m-phthalic acid, thus reach the object reducing polymeric amide crystallizing power.And, the size of polyamide resin crystalline region crystal is reduced by adding crystallization promoter, make the crystal formation microlitic structure of the crystallizing field of polyamide resin, and the existence of microlitic structure makes material have better physical strength, chemical-resistant resistance and anti-stress cracking, give material low water absorbable and snappiness simultaneously.Meanwhile, add polyesteramide to improve notched Izod impact strength and the antistatic effect of multipolymer, add N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide processes the xanthochromia problem in polymerization process.
Polyesteramide has ether oxygen base, and it can combine with free electric charge, and electric charge can move in the mode of combination, carries out ionic conduction release electrostatic lotus along polyesteramide backbone, thus reaches anlistatig effect.In addition, because the bond angle of ether-oxygen bond is comparatively large, segment kindliness is better, therefore can improve the notched Izod impact strength of multipolymer.
Phenylformic acid belongs to the organism of simple function group, and after in melt polymerization process, the Amino End Group of benzoic end carboxyl and long-carbon-chain transparent nylon reacts, it no longer carries out the reaction of chainpropagation, thus plays the effect of Molecular regulator amount.
N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl) fusing point of-1,3-benzene diamide 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 react to improve consistency with the end group of long-carbon-chain transparent nylon, and hindered piperidine base can provide antioxygenation and improve the dyeability of multipolymer.
The present invention compares the advantage of prior art and beneficial effect is:
(1) a kind of long-carbon-chain transparent nylon of the present invention, prepares for raw material with the m-phthalic acid of cheapness, decamethylene diamine, hexanodioic acid, polyesteramide.This invention utilizes m-phthalic acid and hexanodioic acid to reach the object reducing polymeric amide crystallizing power, the crystal formation microlitic structure of the crystallizing field of polyamide resin is made by adding crystallization promoter, notched Izod impact strength and the antistatic effect of multipolymer is improved by adding polyesteramide, by adding N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide processes xanthochromia problem in polymerization process.
This long-carbon-chain transparent nylon has higher force performance and transmittance, low water absorption, the feature of processing characteristics excellence.This long-carbon-chain transparent nylon can be applicable in the field such as surrounding mechanical parts, electro mechanical component, precision optical instrument, withstand voltage form, sight glass, extraordinary light fixture outer cover, food product packing film, high-grade sports equipment of fuel and oil.
(2) synthetic method of long-carbon-chain transparent nylon of the present invention adopts the method for one-step polymerization, and it has and decreases operation, shortens flow process, reduces cost, improve the advantage of productivity; Preparation technology of the present invention is easy, and polymerization process is easy to operate, is convenient to management and control, can reach required polymerizing condition fully, facilitates its industrialized realization.Further, do not use any organic solvent in the course of the polymerization process, to human body and environment not dangerous, security is good.
(3) decamethylene diamine used in raw material of the present invention is prepared by natural Viscotrol C and obtains, and therefore, the long-carbon-chain transparent nylon that the present invention prepares is a kind of bio-based materials, has the characteristic of environmental protection.
Accompanying drawing explanation
Figure 1 shows that the synthesis process flow diagram of long-carbon-chain transparent nylon of the present invention.
Embodiment
For understanding feature of the present invention, technique means and the specific purposes reached, function further, resolve the advantages and spirit of the present invention, by following examples, the present invention is further elaborated.
A kind of long-carbon-chain transparent nylon 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 as shown in the formula II structure:
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100.
Synthesize the reaction mechanism following (synthesis process flow diagram asks for an interview Fig. 1) of long-carbon-chain transparent nylon of the present invention:
Reaction mechanism
From above-mentioned reaction formula, the Amino End Group of decamethylene diamine, the end carboxyl of m-phthalic acid, the end carboxyl of hexanodioic acid, the Amino End Group of polyesteramide and end carboxyl, these groups can react to each other and obtain long-carbon-chain transparent nylon of the present invention.
The reaction mechanism of synthesizing the polyesteramide added in above-mentioned long-carbon-chain transparent nylon reaction process is as follows:
Reaction mechanism
From above-mentioned reaction formula, the Amino End Group, 2 of its ester group, 11-aminoundecanoic acid after the open loop of 6-caprolactone, 2'-(1,3-phenylene) the oxazoline group of-bisoxazoline, these three kinds of groups can react to each other and obtain the polyesteramide that the present invention adds, the limiting viscosity of the polyesteramide that the present invention adds is 0.7 ~ 1.0dL/g, second-order transition temperature T
g>=80 DEG C, melt temperature T
mit is 215 ~ 225 DEG C.
The raw material that the embodiment of the present invention uses is as follows:
Decamethylene diamine, is selected from Wuxi Yinda Nylon Co., Ltd.;
M-phthalic acid, is selected from Beijing Yanshan Petrochemical Co.;
Hexanodioic acid, is selected from Shandong Guang Yin novel material company limited;
Polyesteramide, self-control; 6-caprolactone in raw material, is selected from Wuhan rich bamboo grove chemistry Science and Technology Ltd.;
11-aminoundecanoic acid, is selected from Lian Zenong Chemical Co., Ltd. in Taiyuan;
2,2'-(1,3-phenylene)-bisoxazoline, is selected from colon, Nanjing medication chemistry company limited;
Tetrabutyl titanate, is selected from Chemical Reagent Co., Ltd., Sinopharm Group;
Long carbon chain carboxylic acid calcium salt, is selected from Chemical Reagent Co., Ltd., Sinopharm Group;
Phenylformic acid, is selected from Chemical Reagent Co., Ltd., Sinopharm Group;
N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, is selected from Chemical Reagent Co., Ltd., Sinopharm Group.
The present invention is described in detail below in conjunction with specific embodiment.
Polyesteramide in following examples is by 11-aminoundecanoic acid, 6-caprolactone, 2,2'-(1,3-phenylene)-bisoxazoline copolymerization forms, 11-aminoundecanoic acid, 6-caprolactone, 2, the mol ratio of 2'-(1,3-phenylene)-bisoxazoline is 1:0.5 ~ 1:0.1 ~ 0.4.
Synthetic method is as follows:
(1) by monomer 2:11-aminoundecanoic acid, the 6-caprolactone, 2 after vacuum-drying, 2'-(1,3-phenylene)-bisoxazoline joins in stirring-type polymerization reactor by above-mentioned mol ratio, add simultaneously the titanium compound of 0.1 ~ 2% of monomer 2 gross weight as catalyzer, add the medium of appropriate water as mass-and heat-transfer; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulates 5 ~ 10 times, and in the environment under making reactant be present in protection of inert gas, controlling system pressure in stirring-type polymerization reactor is 0.1 ~ 0.5MPa;
(2) 240 ~ 260 DEG C are heated to by airtight for stirring-type polymerization reactor, the stirring velocity regulating stirring-type polymerization reactor is 0 ~ 100r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, exit to normal pressure, reaction is continued after 0.5 ~ 4 hour at 240 ~ 260 DEG C, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas; Described titanium compound is one or more the mixture in tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate, propenyl titanic acid ester.
Embodiment 1:
The raw material of the polyesteramide used in the present embodiment form and synthesis step as follows:
(1) by monomer 2:1006.6g (5mol) the 11-aminoundecanoic acid after vacuum-drying, 456.6g (4mol) 6-caprolactone, 270.3g (1.25mol) 2,2'-(1,3-phenylene)-bisoxazoline joins in stirring-type polymerization reactor, add simultaneously the tetrabutyl titanate (17.3g) of 1% of monomer 2 gross weight as catalyzer, add the medium of 500mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.2MPa;
(2) in 2.5 hours by airtight for stirring-type polymerization reactor constant-speed heating to 250 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 1.5 hours, exit to normal pressure, reaction is continued after 1.5 hours at 250 DEG C, constant temperature continues to vacuumize 0.5 hour, and reaction terminates, and supplements nitrogen when discharging.
The synthetic method of a kind of long-carbon-chain transparent nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 164.5g (0.99mol) m-phthalic acid, 1.5g (0.01mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 1% (3.4g) of monomer 1 gross weight, the Long carbon chain carboxylic acid calcium salt of 0.1% (0.3g), the phenylformic acid of 0.1% (0.3g), the N of 0.1% (0.3g) simultaneously, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, add the medium of 100mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.3MPa;
(2) in 4 hours by airtight for stirring-type polymerization reactor constant-speed heating to 224 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 hour, exit to normal pressure, continue reaction at being warming up to 244 DEG C after 0.5 hour simultaneously, constant temperature continues to vacuumize 2 hours, and reaction terminates, and supplements nitrogen when discharging.
Embodiment 2:
The raw material formation of polyesteramide used in the present embodiment and synthesis step are with embodiment 1.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 108.0g (0.65mol) m-phthalic acid, 51.1g (0.35mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 8% (26.5g) of monomer 1 gross weight, the Long carbon chain carboxylic acid calcium salt of 0.3% (1.0g), the phenylformic acid of 2% (6.6g), the N of 0.3% (1.0g) simultaneously, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, add the medium of 100mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.2MPa;
(2) in 2 hours by airtight for stirring-type polymerization reactor constant-speed heating to 214 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 4 hours, exit to normal pressure, continue reaction at being warming up to 230 DEG C after 4 hours simultaneously, constant temperature continues to vacuumize 0.1 hour, and reaction terminates, and supplements nitrogen when discharging.
Embodiment 3:
The raw material formation of polyesteramide used in the present embodiment and synthesis step are with embodiment 1.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 149.5g (0.9mol) m-phthalic acid, 14.6g (0.1mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 2% (6.7g) of monomer 1 gross weight, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the phenylformic acid of 0.5% (1.7g), the N of 0.2% (0.7g) simultaneously, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, add the medium of 100mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.3MPa;
(2) in 3.5 hours by airtight for stirring-type polymerization reactor constant-speed heating to 222 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 1 hour, exit to normal pressure, continue reaction at being warming up to 242 DEG C after 1 hour simultaneously, constant temperature continues to vacuumize 1 hour, and reaction terminates, and supplements nitrogen when discharging.
Embodiment 4:
The raw material formation of polyesteramide used in the present embodiment and synthesis step are with embodiment 1.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 116.3g (0.7mol) m-phthalic acid, 43.8g (0.3mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 6% (19.9g) of monomer 1 gross weight, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the phenylformic acid of 1.5% (5.0g), the N of 0.2% (0.7g) simultaneously, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, add the medium of 100mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.3MPa;
(2) in 2.5 hours by airtight for stirring-type polymerization reactor constant-speed heating to 216 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 2 hours, exit to normal pressure, continue reaction at being warming up to 232 DEG C after 2 hours simultaneously, constant temperature continues to vacuumize 0.3 hour, and reaction terminates, and supplements nitrogen when discharging.
Embodiment 5:
The raw material formation of polyesteramide used in the present embodiment and synthesis step are with embodiment 1.
The present embodiment is a kind of synthetic method of long-carbon-chain transparent nylon, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 132.9g (0.8mol) m-phthalic acid, 29.2g (0.2mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 4% (13.4g) of monomer 1 gross weight, the Long carbon chain carboxylic acid calcium salt of 0.2% (0.7g), the phenylformic acid of 1.0% (3.3g), the N of 0.2% (0.7g) simultaneously, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide, add the medium of 100mL water as mass-and heat-transfer; Then vacuumize 5min, logical nitrogen 5min, so circulation 6 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in stirring-type polymerization reactor is 0.3MPa;
(2) in 3 hours by airtight for stirring-type polymerization reactor constant-speed heating to 219 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 1.5 hours, exit to normal pressure, continue reaction at being warming up to 237 DEG C after 1.5 hours simultaneously, constant temperature continues to vacuumize 0.5 hour, and reaction terminates, and supplements nitrogen when discharging.
Be below embodiment table look-up:
Table 1 embodiment raw material composition table look-up
Made for above-described embodiment sample is carried out following performance test:
Tensile property: by GB/T1040-2006 standard testing, rate of extension 50mm/min;
Impact property: by GB/T1843-2008 standard testing, batten thickness is 3.2mm;
Water-intake rate: by GB/T1034-2008 standard testing, thickness of test piece 2mm;
Limiting viscosity: by GB/T1632-2008 standard testing, the solvent vitriol oil;
Transmittance: by GB/T2410-2008 standard testing;
Flow temperature: use digital micro-analysis melting point apparatus to test.
Table 2 embodiment performance table look-up
As can be seen from the above embodiments, the addition of hexanodioic acid is more, and the tensile strength of long-carbon-chain transparent nylon, transmittance and flow temperature are lower, and shock strength is higher; The water-intake rate change of each embodiment is little; Along with the benzoic addition of molecular weight regulator increases, its limiting viscosity diminishes.Wherein, the over-all properties of embodiment 5 is best.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a long-carbon-chain transparent nylon, is characterized in that, 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 shown in the formula II structure:
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100;
Described long-carbon-chain transparent nylon is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 for mol ratio be decamethylene diamine, m-phthalic acid, the hexanodioic acid of 1:0.65 ~ 0.99:0.01 ~ 0.35, and described decamethylene diamine and m-phthalic acid and hexanodioic acid consumption and mol ratio be 1, the add-on of described polyesteramide is 1 ~ 8% of described monomer 1 gross weight.
2. long-carbon-chain transparent nylon according to claim 1, is characterized in that, the add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight.
3. long-carbon-chain transparent nylon according to claim 1, is characterized in that, the limiting viscosity of described long-carbon-chain transparent nylon is 0.7 ~ 1.0dL/g, flow temperature T
fit is 214 ~ 229 DEG C.
4. the long-carbon-chain transparent nylon according to any one of claim 1-3, it is characterized in that, described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be 11-aminoundecanoic acid, the 6-caprolactone and 2 of 1:0.5 ~ 1:0.1 ~ 0.4,2'-(1,3-phenylene)-bisoxazoline.
5. long-carbon-chain transparent nylon according to claim 4, it is characterized in that, described polyesteramide is obtained by following synthetic method: the described monomer 2 after vacuum-drying joins in stirring-type polymerization reactor by (1), add simultaneously the titanium compound of 0.1 ~ 2% of described monomer 2 gross weight as catalyzer, add suitable quantity of water; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa;
(2) 240 ~ 260 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, exit to normal pressure, reaction is continued after 0.5 ~ 4 hour at 240 ~ 260 DEG C, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas; Described titanium compound is one or more the mixture in tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate, propenyl titanic acid ester.
6. a synthetic method for long-carbon-chain transparent nylon according to claim 1, is characterized in that, comprise the following steps:
(1) described monomer 1 is joined in stirring-type polymerization reactor, add described polyesteramide, crystallization promoter, molecular weight regulator, oxidation inhibitor, water simultaneously; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa; Described monomer 1 for mol ratio be decamethylene diamine, m-phthalic acid, the hexanodioic acid of 1:0.65 ~ 0.99:0.01 ~ 0.35, the add-on of described polyesteramide is 1 ~ 8% of described monomer 1 gross weight; Described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be the 11-aminoundecanoic acid of 1:0.5 ~ 1:0.1 ~ 0.4,6-caprolactone and 2,2'-(1,3-phenylene)-bisoxazoline;
(2) 214 ~ 224 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, venting is to normal pressure, continue reaction at being warming up to 230 ~ 244 DEG C after 0.5 ~ 4 hour simultaneously, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas.
7. synthetic method according to claim 6, is characterized in that, comprises the following steps:
(1) the described monomer 1 after vacuum-drying is joined in stirring-type polymerization reactor, add described polyesteramide, crystallization promoter, molecular weight regulator, oxidation inhibitor, suitable quantity of water simultaneously; Then vacuumize 4 ~ 6min, logical nitrogen 4 ~ 6min, so circulate 5 ~ 7 times, in the environment under making reactant be present in nitrogen protection, controlling system pressure in described stirring-type polymerization reactor is 0.2 ~ 0.3MPa; The add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight;
(2) in 2 ~ 4 hours by described airtight constant-speed heating to 216 ~ 222 DEG C of stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 30 ~ 50r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 1 ~ 2 hour, venting is to normal pressure, continue reaction at being warming up to 232 ~ 242 DEG C after 1 ~ 2 hour simultaneously, constant temperature continues to vacuumize 0.3 ~ 1 hour, and reaction terminates, and supplements nitrogen when discharging.
8. the synthetic method according to claim 6 or 7, it is characterized in that, described polyesteramide is obtained by following synthetic method: the described monomer 2 after vacuum-drying joins in stirring-type polymerization reactor by (1), add simultaneously the titanium compound of 0.1 ~ 2% of described monomer 2 gross weight as catalyzer, add suitable quantity of water; Then vacuumize 3 ~ 10min, logical rare gas element 3 ~ 10min, so circulate 5 ~ 10 times, in the environment under making reactant be present in protection of inert gas, controlling system pressure in described stirring-type polymerization reactor is 0.1 ~ 0.5MPa;
(2) 240 ~ 260 DEG C are heated to by airtight for described stirring-type polymerization reactor, the stirring velocity of described stirring-type polymerization reactor is regulated to be 0 ~ 100r/min, wherein, when described stirring-type polyreaction actuator temperature reaches 210 DEG C, venting is to 1.6MPa, and maintain pressure at 1.6MPa, react after 0.5 ~ 4 hour, exit to normal pressure, reaction is continued after 0.5 ~ 4 hour at 240 ~ 260 DEG C, constant temperature continues to vacuumize 0.1 ~ 2 hour, and reaction terminates, the topping up when discharging;
In above-mentioned steps, described rare gas element is nitrogen or argon gas; Described titanium compound is one or more the mixture in tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate, propenyl titanic acid ester.
9. the synthetic method according to claim 6 or 7, is characterized in that, the Long carbon chain carboxylic acid calcium salt of described crystallization promoter to be add-on be 0.1 ~ 0.3% of described monomer 1 gross weight, and the carbon number of described Long carbon chain carboxylic acid calcium salt is 10 ~ 40; The phenylformic acid of described molecular weight regulator to be add-on be 0.1 ~ 2% of described monomer 1 gross weight; The N of described oxidation inhibitor to be add-on be 0.1 ~ 0.3% of described monomer 1 gross weight, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide.
10. synthetic method according to claim 9, is characterized in that, described crystallization promoter to be carbon number be 15 ~ 35 Long carbon chain carboxylic acid calcium salt; The phenylformic acid of described molecular weight regulator to be add-on be 0.5 ~ 1.5% of described monomer 1 gross weight.
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