CN105295032A - Long-carbon-chain semi-aromatic nylon and synthetic method thereof - Google Patents
Long-carbon-chain semi-aromatic nylon and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to long-carbon-chain semi-aromatic nylon and a synthetic method thereof. The long-carbon-chain semi-aromatic nylon has a structure in a formula I (shown in the specification), wherein 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 long-carbon-chain semi-aromatic nylon has the characteristics of relatively high mechanical property and heat resistance, low water absorption rate, excellent processing performance and biogenetic derivation and can be applied to the fields of electronic and electric appliances, LED, automobiles, aerospace, war industry and the like.
Description
Technical field
The present invention relates to Material Field, particularly relate to a kind of Long carbon chain semi-aromatic nylon and synthetic method thereof.
Background technology
In recent years, in order to meet the more high performance requirement in fields such as electronics, electrical equipment, automobiles, particularly along with surface mounting technique (SurfaceMountTechnology, be called for short SMT) development, common thermostability engineering plastic polyphenylene sulfide (PPS) and the thermotolerance of liquid crystalline polymers (LCP) can not meet its requirement completely, and therefore developing the higher engineering plastics of thermotolerance just becomes inevitable.
Semiaromatic polyamide composition is normally by diacid or the diamines of aliphatic diamines or diacid and band aromatic nucleus, obtain through polycondensation, owing to having imported aromatic nucleus on polyamide molecule main chain, its thermotolerance and mechanical property are improved, and water-intake rate is reduced, have good superiority of effectiveness, it is mainly used in automobile and electric and electronic industry.Industrialized semiaromatic polyamide composition mainly contains polyamide 6 T (multipolymer), polyamide 9T, polymeric amide 10T etc.But the fusing point of polymeric amide 10T resin is about 320 DEG C, and itself and decomposition temperature are more or less the same, and processing temperature narrow limits, easily causes polymer unwinds in the course of processing, reduce its melt temperature so usually adopt with the method for other copolyamide.
Solid state polymerization (SolidstatePolymerization) refers to the polyreaction that solid (or crystalline phase) monomer occurs below its fusing point, or the polyreaction of carrying out more than monomer fusing point but 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 the thickening stage needs vacuum or air-flow to accelerate the discharge of small molecular by product, 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 semiaromatic polyamide composition, the polymerisate that such as Chinese patent CN102153741A discloses a kind of homopolymer of Long carbon chain semiaromatic heat resistant polyamide and the synthetic method of multipolymer and obtains, this polymerisate is mainly obtained by the method for solid state polymerization; Chinese patent CN103360599A discloses a kind of semi-aromatic and fatty polyamide block copolymer, wherein the mole percent level of semiaromatic polyamide composition block is 40% ~ 99%, the mole percent level of fatty polyamide block is 1 ~ 60%, and this polymerisate is mainly obtained by the method for solid state polymerization; Chinese patent CN101948619A discloses a kind of poly-paraphenylene terephthalamide's nonamethylene diamine material and preparation method thereof; Chinese patent CN1106842A discloses polyamide 9T, 9M-T and preparation method thereof.
Summary of the invention
The object of the present invention is to provide a kind of higher mechanical property and resistance toheat, low water absorption, processing characteristics is excellent and have the Long carbon chain semi-aromatic nylon of a step melt polymerization of biogenetic derivation, can be applicable to field of electronics, LED field, automotive field, aerospace and military industry field etc.
For achieving the above object, the present invention adopts following scheme:
A kind of Long carbon chain semi-aromatic nylon, it has following structure shown in formula I:
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:
II
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100;
Described Long carbon chain semi-aromatic nylon is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 for mol ratio be the decamethylene diamine of 1:0.7 ~ 0.99:0.01 ~ 0.3, terephthalic acid and hexanodioic acid, and described decamethylene diamine and terephthalic 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 semi-aromatic nylon is 0.7 ~ 1.0dL/g, second-order transition temperature T
g>=100 DEG C, melt temperature T
mit is 294 ~ 305 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 (medium of mass-and heat-transfer); 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 semi-aromatic nylon, comprises the following steps:
(1) described monomer 1 is joined in stirring-type polymerization reactor, add described polyesteramide, 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, terephthalic acid, the hexanodioic acid of 1:0.7 ~ 0.99:0.01 ~ 0.3, and described decamethylene diamine and terephthalic 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; Described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be 11-aminoundecanoic acid, 6-caprolactone, 2,2'-(1,3-phenylene)-bisoxazoline of 1:0.5 ~ 1:0.1 ~ 0.4;
(2) 270 ~ 285 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 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 0.5 ~ 4 hour, venting is to normal pressure, continue reaction at being warming up to 306 ~ 325 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, above-mentioned synthetic method comprises the following steps:
(1) the described monomer 1 after vacuum-drying is joined in stirring-type polymerization reactor, add described polyesteramide, molecular weight regulator, oxidation inhibitor, 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;
(2) in 2 ~ 4 hours by described airtight constant-speed heating to 272 ~ 280 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 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 1 ~ 2 hour, venting is to normal pressure, continue reaction at being warming up to 310 ~ 320 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 organo montmorillonite of described molecular weight regulator to be add-on be 0.1 ~ 8% of described monomer 1 gross weight and add-on are the phenylformic acid of 0.1 ~ 3% 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, the add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight; The add-on of described organo montmorillonite is 0.5 ~ 5% of described monomer 1 gross weight, and described benzoic add-on is 0.5 ~ 2.5% of described monomer 1 gross weight.
Principle of the present invention is as follows:
In order to solve the defect of polymeric amide 10T resin processing temperature narrow limits, invention has been the design of new resinous molecular structure, the fusing point of multipolymer is reduced by adding hexanodioic acid, add polyesteramide to improve notched Izod impact strength and the antistatic effect of multipolymer simultaneously, add N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide processes 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.
Organo montmorillonite belongs to poly-hydroxy inorganics, is reacted, reach the object of Molecular regulator amount by the terminal hydroxy group of organo montmorillonite and the end group of Long carbon chain semi-aromatic nylon.In addition, because organo montmorillonite has nanometer small-size effect, it can improve modulus and the flame retardant resistance of multipolymer, reduces shrinking percentage and water-intake rate.
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 semi-aromatic 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 semi-aromatic nylon building-up process, its amide group can react to improve consistency with the end group of Long carbon chain semi-aromatic 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) inventor is for the defect of existing polymeric amide 10T resin processing temperature narrow limits, carry out the design of new resinous molecular structure, and the fusing point of multipolymer is reduced by adding hexanodioic acid, add polyesteramide to improve notched Izod impact strength and the antistatic effect of multipolymer simultaneously, add N, N`-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzene diamide processes xanthochromia problem in polymerization process.Long carbon chain semi-aromatic nylon of the present invention has higher mechanical property and resistance toheat, low water absorption, processing characteristics is excellent and have the characteristic of biogenetic derivation, can be applicable to field of electronics, LED field, automotive field, aerospace and military industry field etc.
(2) preparation method of the present invention adopts the method for one-step polymerization, and it has minimizing operation, shortens flow process, reduces costs, the advantage boosted 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; And 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, it is a kind of bio-based materials that the present invention prepares Long carbon chain semi-aromatic nylon, has the characteristic of environmental protection.
Accompanying drawing explanation
Figure 1 shows that the synthesis process flow diagram of Long carbon chain semi-aromatic nylon of the present invention;
Figure 2 shows that the nonisothermal crystallization melting curve figure of the Long carbon chain semi-aromatic nylon of the embodiment of the present invention 5 gained.
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.
Long carbon chain semi-aromatic nylon of the present invention, it has following structure shown in formula I:
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:
II
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100.
The reaction mechanism following (synthesis process flow diagram asks for an interview Fig. 1) of Long carbon chain semi-aromatic nylon of the present invention:
Reaction mechanism
From above-mentioned reaction formula, the Amino End Group of decamethylene diamine, the end carboxyl of terephthalic 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 semi-aromatic nylon of the present invention.
And the reaction mechanism of the polyesteramide added in above-mentioned Long carbon chain semi-aromatic 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.;
Terephthalic acid, is selected from Beijing Yanshan Petrochemical Co.;
Hexanodioic acid, is selected from Shandong Guang Yin novel material company limited;
Polyesteramide, self-control, the 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;
Organo montmorillonite, is selected from Zhejiang Fenghong New Material Co., Ltd.;
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 semi-aromatic nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 164.5g (0.99mol) terephthalic 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 organo montmorillonite 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 285 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 0.5 hour, exit to normal pressure, continue reaction at being warming up to 325 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 synthetic method of a kind of Long carbon chain semi-aromatic nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 116.3g (0.7mol) terephthalic acid, 43.8g (0.3mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 8% (26.6g) of monomer 1 gross weight, the organo montmorillonite of 8% (26.6g), the phenylformic acid of 3% (10.0g), 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 270 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 4 hours, exit to normal pressure, continue reaction at being warming up to 306 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 synthetic method of a kind of Long carbon chain semi-aromatic nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 149.5g (0.9mol) terephthalic 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 organo montmorillonite of 0.5% (1.7g), 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 280 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 1 hour, exit to normal pressure, continue reaction at being warming up to 320 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 synthetic method of a kind of Long carbon chain semi-aromatic nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 132.9g (0.8mol) terephthalic acid, 29.2g (0.2mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 6% (20.1g) of monomer 1 gross weight, the organo montmorillonite of 5% (16.7g), the phenylformic acid of 2.5% (8.4g), 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 272 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 2 hours, exit to normal pressure, continue reaction at being warming up to 310 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 synthetic method of a kind of Long carbon chain semi-aromatic nylon of the present embodiment, comprises the following steps:
(1) monomer 1:172.3g (1mol) decamethylene diamine after vacuum-drying, 144.5g (0.87mol) terephthalic acid, 19.0g (0.13mol) hexanodioic acid are joined in stirring-type polymerization reactor, add the polyesteramide of 4% (13.4g) of monomer 1 gross weight, the organo montmorillonite of 3% (10.1g), 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 3 hours by airtight for stirring-type polymerization reactor constant-speed heating to 275 DEG C, the stirring velocity regulating stirring-type polymerization reactor is 40r/min, wherein, when stirring-type polyreaction actuator temperature reaches 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 1.5 hours, exit to normal pressure, continue reaction at being warming up to 315 DEG C after 1.5 hours simultaneously, constant temperature continues to vacuumize 0.5 hour, and reaction terminates, and supplements nitrogen when discharging.
As shown in Figure 2, the melting peak-to-peak temperature (i.e. melt temperature) showing this Long carbon chain semi-aromatic nylon in figure is 301.24 DEG C to the nonisothermal crystallization melting curve figure of the Long carbon chain semi-aromatic nylon of the present embodiment gained.
Be below embodiment 1 ~ 5 raw material composition 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;
Second-order transition temperature: by GB/T19466.2-2004 standard testing;
Melt temperature: by GB/T19466.3-2004 standard testing.
Results of property please see the following form:
Table 2 embodiment performance table look-up
As can be seen from Table 2, the addition of hexanodioic acid is more, and the tensile strength of Long carbon chain semi-aromatic nylon, second-order transition temperature and melt temperature are lower, and shock strength is higher; The water-intake rate change of each embodiment is little; Along with the addition of molecular weight regulator (organo montmorillonite and phenylformic acid) increases, its limiting viscosity diminishes.Wherein, the over-all properties of embodiment 5 is best.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification sheets is recorded.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.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 semi-aromatic nylon, is characterized in that, it has following structure shown in formula I:
In formula I, a=10 ~ 100, b=10 ~ 200, c=10 ~ 100, d=10 ~ 100, R is polyesteramide, and it has as shown in the formula II structure:
In formula II, x=10 ~ 200, y=10 ~ 200, z=10 ~ 100;
Described Long carbon chain semi-aromatic nylon is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 for mol ratio be the decamethylene diamine of 1:0.7 ~ 0.99:0.01 ~ 0.3, terephthalic acid and hexanodioic acid, and described decamethylene diamine and terephthalic 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 semi-aromatic 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 semi-aromatic nylon according to claim 1, is characterized in that, the limiting viscosity of described Long carbon chain semi-aromatic nylon is 0.7 ~ 1.0dL/g, second-order transition temperature T
g>=100 DEG C, melt temperature T
mit is 294 ~ 305 DEG C.
4. Long carbon chain semi-aromatic nylon according to claim 1, 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 semi-aromatic 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 semi-aromatic 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, 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, terephthalic acid, the hexanodioic acid of 1:0.7 ~ 0.99:0.01 ~ 0.3, and described decamethylene diamine and terephthalic 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; Described polyesteramide is formed by monomer 2 copolymerization, described monomer 2 for mol ratio be 11-aminoundecanoic acid, 6-caprolactone, 2,2'-(1,3-phenylene)-bisoxazoline of 1:0.5 ~ 1:0.1 ~ 0.4;
(2) 270 ~ 285 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 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 0.5 ~ 4 hour, venting is to normal pressure, continue reaction at being warming up to 306 ~ 325 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, molecular weight regulator, oxidation inhibitor, 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;
(2) in 2 ~ 4 hours by described airtight constant-speed heating to 272 ~ 280 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 215 DEG C, venting is to 2.0MPa, and maintain pressure at 2.0MPa, react after 1 ~ 2 hour, venting is to normal pressure, continue reaction at being warming up to 310 ~ 320 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 organo montmorillonite of described molecular weight regulator to be add-on be 0.1 ~ 8% of described monomer 1 gross weight and add-on are the phenylformic acid of 0.1 ~ 3% 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, the add-on of described polyesteramide is 2 ~ 6% of described monomer 1 gross weight; The add-on of described organo montmorillonite is 0.5 ~ 5% of described monomer 1 gross weight, and described benzoic add-on is 0.5 ~ 2.5% of described monomer 1 gross weight.
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| WO2021218648A1 (en) * | 2020-04-30 | 2021-11-04 | 成都肆零壹科技有限公司 | Process for polymerizing polyesteramide |
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| WO2021218648A1 (en) * | 2020-04-30 | 2021-11-04 | 成都肆零壹科技有限公司 | Process for polymerizing polyesteramide |
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