CN103965466A - Semi-aromatic biological nylon and preparation method thereof - Google Patents
Semi-aromatic biological nylon and preparation method thereof Download PDFInfo
- Publication number
- CN103965466A CN103965466A CN201310028089.8A CN201310028089A CN103965466A CN 103965466 A CN103965466 A CN 103965466A CN 201310028089 A CN201310028089 A CN 201310028089A CN 103965466 A CN103965466 A CN 103965466A
- Authority
- CN
- China
- Prior art keywords
- reactor
- nylon
- aromatic
- acid
- semi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a semi-aromatic biological nylon and a preparation method thereof, belonging to the field of synthesis of a high polymer material--nylon. The nylon is prepared from the following components by mol: 10.20 to 11.22 mol of aromatic diacid, 9.80 to 10.78 mol of aliphatic diacid, 19.60 to 21.65 mol of aliphatic diamine, 0.015 to 0.03 mol of a catalyst and 220 to 300 mol of deionized water. The semi-aromatic biological nylon synthesized in the invention has moderate viscosity and good fluidity, is easy to discharge, can be directly used for drawing and granulation after cooling, is convenient to package, transport and store and is directly applicable to molding after drying, a product shape is stable, and no tedious post-processing is needed. The synthesized semi-aromatic biological nylon has performance better than those of nylon 6 and nylon 66 and has certain properties comparable to those of nylon 612 and nylon 12.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material nylon, relate to biological nylon of a kind of semi-aromatic and preparation method thereof.
Background technology
Nylon (polymeric amide) is the outer most widely used a kind of thermoplastic engineering plastic of Present Domestic, it has the excellent specific properties such as tough wear-resisting, shock-resistant, antifatigue, corrosion-resistant, oil resistant, be widely used in the industries such as auto-parts, electronic apparatus, machinery, over 60 years, steady-state growth in the cut-throat competition of engineering plastics, its demand occupies the first place of five large-engineering plastics so far always.
Semi-aromatic nylon is by aliphatie diamine or diacid and is with aromatic diacid or diamines, through polycondensation, makes.Owing to importing aliphatic chain in fully aromatic polyamide molecular backbone chain, thereby forming process and solvability etc. have been improved.Compare with aliphatics nylon, the maximum feature of semi-aromatic nylon is fine heat-resisting performance, and second-order transition temperature is generally more than 100 ℃, and fusing point is generally more than 250 ℃, mostly all near 300 ℃.Heat aging property is good, and mechanical property is little to the dependency of temperature, in wide temperature range, can keep stable performance.Water-intake rate is low, and size and the mechanical property of goods changes little after moisture absorption.The chemical drugs moral character such as organic solvent-resistant and various vehicle fuel, oil plant, deicing fluid are good, and some has good barrier properties for gases, and electrical insulation capability is good, also has outstanding arc resistance agent tracking.Shrinkability, deformability, creep properties are very little, and rigidity and intensity are generally better than general aliphatics nylon.The main raw material sebacic acid synthetic due to this nylon makes by Viscotrol C alkaline hydrolysis, and Viscotrol C is present in the seed of biological castor-oil plant, is therefore referred to as biological nylon.
Through the literature search of prior art is found, Chinese patent 200910072711.9 has been announced the method for preparing nylon-610, and the main raw material of its use is hexanolactam, does not have biologically, has use tolylene diisocyanate simultaneously, and risk level is higher; Patent US4022756, CN200610147391, US6156869, US566328 etc. disclose the preparation method of semi-aromatic nylon, in these preparation technologies, prepolymer nylon salt is first prepared in employing mostly, again prepolymer is obtained to the nylon finally needing through solid-phase tack producing to improve nylon molecular weight, so synthesis technique is comparatively loaded down with trivial details.
Summary of the invention
The object of the invention is to provide biological nylon of a kind of semi-aromatic and preparation method thereof for overcoming the defect of prior art.
For achieving the above object, the present invention is by the following technical solutions:
By the biological nylon of the synthetic semi-aromatic of preparation method of the present invention, do not exist first synthetic nylon salt at polymeric kettle, to carry out again the loaded down with trivial details techniques such as polymerization, but add reactor directly to carry out polymerization raw material, so its synthesis technique is simple, generated time is shorter; Meanwhile, solvent for use is deionized water, safer environmental protection; By the method, synthesize the biological properties of nylons of semi-aromatic and be better than nylon 6 and nylon 66, and can compare favourably with nylon 612 and nylon 12 in some properties, the biological nylon of synthetic semi-aromatic is particular plastics, and molecular weight is higher, is applicable to industrialization promotion and produces.
The biological nylon of semi-aromatic, by the component that comprises following mole number, made:
Described aromatic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, 4, one or more in 4'-biphenyl dicarboxylic acid, naphthalic acid, preferably terephthalic acid.
Described aliphatic diamine is selected from one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably hexanediamine.
Described aliphatic dibasic acid is selected from one or more in the aliphatic dibasic acid that contains 4-13 carbon atom in molecular chain main chain, the sebacic acid of preferably producing from Viscotrol C.
Described catalyzer is selected from one or more in ortho phosphorous acid potassium, sodium phosphite, phosphorous acid magnesium, phosphorous acid calcium, zinc phosphite, potassiumphosphate, trimagnesium phosphate, calcium phosphate, zinc phosphate, ortho phosphorous acid potassium, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate or ortho phosphorous acid zinc, preferably inferior sodium phosphate.
A preparation method for the biological nylon of above-mentioned semi-aromatic, comprises the following steps:
(1) according to the above ratio by polymerization single polymerization monomer 10.20-11.22mol aromatic acid, 19.60-21.65mol aliphatic diamine, 9.80-10.78mol aliphatic dibasic acid and 0.015-0.03mol catalyst mix are even, then joined in the 25L high pressure polymerisation reactor that whipping appts is housed, take 220-300mol aqueous solvent in reactor, start agitator (rotating speed 60r/min) and be filled with appropriate rare gas element in reactor, vacuumize, at least repeat 3 times, to get rid of, be reserved in the air in reactor, finally reserved 0.01Mpa-0.03Mpa rare gas element is as protection gas,
(2) by circulating heat conduction oil, reactor is carried out to heat temperature raising, then to being incubated in reactor still, so that polymerization single polymerization monomer is dissolved in solvent completely;
(3) insulation finishes, reactor is continued to heat up, now reacting kettle inner pressure rises, by delivery systme, react the moisture realization producing reactor is carried out to pressurize, maintain constant voltage, and reactor is continued to heating, when reactor temperature reaches 260-270 ℃ by the time, agitator speed is doubled (rotating speed rises to 120r/min), by circulating heat conduction oil, continue rising temperature of reaction kettle, when question response temperature in the kettle rises to 305-315 ℃, under the precondition that keeps temperature of reaction kettle not decline, be that holding temperature is not higher than 315 ℃, reactor is carried out to release, when the pressure in reactor unloads to normal pressure by the time, reduce agitator speed (rotating speed is down to 12r/min), to reactor, be filled with rare gas element, discharging obtains having the biological nylon material of semi-aromatic of better mobility.
In described step (1) or (2), rare gas element is nitrogen, carbonic acid gas, argon gas or helium, preferred nitrogen.
In described step (2), the intensification temperature of reactor is 120-140 ℃, preferably 125-135 ℃; Soaking time is 1.5-2.5 hour, preferably 2.0 hours.
In described step (3), reacting kettle inner pressure is 2.3-2.8MPa, preferred 2.5MPa, and constant voltage time is 0.5-1.5 hour, preferably 1 hour.
In described step (3), in reactor, the amount of pouring of rare gas element is 0.3-1.2MPa.
The present invention compared with the existing technology, has the following advantages:
(1) reactions steps is simple, and the equipment cost of reacting used is cheap, and simultaneous reactions condition is comparatively gentle without High Temperature High Pressure, to the requirement of equipment, be not therefore very high, and its energy consumption is also less.
(2) solvent used is deionized water, there is no toxicity, wide material sources, and environmental protection, for alleviating environmental stress, protection of the environment aspect is extremely important.
(3) the modest viscosity mobility of the biological nylon of synthetic semi-aromatic is better, and discharging is convenient, through cooling, can directly draw granulation, is convenient to encapsulation transportation and storage, after oven dry, can be directly used in forming process, and shape of product is stable without loaded down with trivial details last handling process.
(4) the biological properties of nylons of synthetic semi-aromatic is better than nylon 6 and nylon 66, and can compare favourably with nylon 612 and nylon 12 in some properties.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
In following embodiment, adopt following detection method:
Melt flow rate (MFR) (MFR) is pressed ASTM D1238-10, at 300 ℃, under 2.16kg condition, tests.
Tensile property is pressed ASTM D638-10 test, rate of extension 5mm/min.
Simply supported beam notched Izod impact strength is pressed ASTM D6110-10 test.
Flexural strength is pressed ASTM D790-10 test, presses down speed 1.25mm/min.
Rockwell hardness is pressed ASTM D785-08 test.
Embodiment 1
Weigh in proportion terephthalic acid 1694.526(and be roughly equal to 10.20mol), sebacic acid 1982.05g(is roughly equal to 9.80mol), hexanediamine 2277.716g(is roughly equal to 19.60mol), inferior sodium phosphate 1.2896g(is roughly equal to 0.015mol), mix and be poured in 25L reactor, inject 3.96kg deionized water (being roughly equal to 220mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.02MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 120 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 260 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 310 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make there is pressure in reactor be 0.3MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 2
Weigh in proportion terephthalic acid 1694.526(and be roughly equal to 10.20mol), sebacic acid 1982.05g(is roughly equal to 9.80mol), hexanediamine 2280.0402g(is roughly equal to 19.62mol), inferior sodium phosphate 1.5g(is roughly equal to 0.01744mol), mix and be poured in 25L reactor, inject 4.14kg deionized water (being roughly equal to 230mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.03MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 125 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 265 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 315 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.6MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 3
Weigh in proportion terephthalic acid 1694.526(and be roughly equal to 10.20mol), sebacic acid 1982.05g(is roughly equal to 9.80mol), hexanediamine 2282.3644g(is roughly equal to 19.64mol), inferior sodium phosphate 2.2g(is roughly equal to 0.02559mol), mix and be poured in 25L reactor, inject 4.5kg deionized water (being roughly equal to 250mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.02MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 125 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 315 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.5MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 4
Weigh in proportion terephthalic acid 1694.526(and be roughly equal to 10.20mol), sebacic acid 1982.05g(is roughly equal to 9.80mol), hexanediamine 2284.6886g(is roughly equal to 19.66mol), inferior sodium phosphate 2.4g(is roughly equal to 0.02791mol), mix and be poured in 25L reactor, inject 4.68kg deionized water (being roughly equal to 260mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.01MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 130 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 315 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.8MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 5
Weigh in proportion terephthalic acid 1863.9786g(and be roughly equal to 11.22mol), sebacic acid 2180.255g(is roughly equal to 10.78mol), hexanediamine 2508.0442g(is roughly equal to 21.582mol), inferior sodium phosphate 2.5g(is roughly equal to 0.029mol), mix and be poured in 25L reactor, inject 4.86kg deionized water (being roughly equal to 270mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.03MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 125 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 315 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 1.1MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 6
Weigh in proportion terephthalic acid 1863.9786g(and be roughly equal to 11.22mol), sebacic acid 2180.255g(is roughly equal to 10.78mol), hexanediamine 2510.6008g(is roughly equal to 21.604mol), inferior sodium phosphate 2.5g(is roughly equal to 0.029mol), mix and be poured in 25L reactor, inject 5.04kg deionized water (being roughly equal to 280mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.02MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 135 ℃ and be incubated 2.0 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 315 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.9MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 7
Weigh in proportion terephthalic acid 1863.9786g(and be roughly equal to 11.22mol), sebacic acid 2180.255g(is roughly equal to 10.78mol), hexanediamine 2513.1575(is roughly equal to 21.626mol), inferior sodium phosphate 2.5788g(is roughly equal to 0.03mol), mix and be poured in 25L reactor, inject 5.22kg deionized water (being roughly equal to 290mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.025MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 130 ℃ and be incubated 2.0 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 320 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, be filled with nitrogen and make reacting kettle inner pressure 1.2MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 8
Weigh in proportion terephthalic acid 1863.9786g(and be roughly equal to 11.22mol), sebacic acid 2180.255g(is roughly equal to 10.78mol), hexanediamine 2515.7141g(is roughly equal to 21.648mol), inferior sodium phosphate 2.5788g(is roughly equal to 0.03mol), mix and be poured in 25L reactor, inject 5.4kg deionized water (being roughly equal to 300mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.02MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 135 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 275 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 320 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.7MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
The performance test results of embodiment 1-8 is as table 1.
Table 1
Embodiment 9
Weigh in proportion m-phthalic acid 1694.526g(and be roughly equal to 10.2mol), succinic acid 1157.282g(is roughly equal to 9.8mol), butanediamine 1727.74g(is roughly equal to 19.6mol), ortho phosphorous acid potassium 1.5612g(is roughly equal to 0.015mol), mix and be poured in 25L reactor, inject 3.96kg deionized water (being roughly equal to 220mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.02MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 135 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 275 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 320 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.65MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 10
Weigh in proportion phthalic acid 1777.591g(and be roughly equal to 10.70mol), hexanodioic acid 1512.549g(is roughly equal to 10.35mol), decamethylene diamine 3549.792g(is roughly equal to 20.60mol), phosphorous acid magnesium 3.40g(is roughly equal to 0.02mol), mix and be poured in 25L reactor, inject 4.5kg deionized water (being roughly equal to 250mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.03MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 125 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finish to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature
When degree arrives 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 320 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.75MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 11
Weigh in proportion phthalic acid 1863.9786g(and be roughly equal to 11.22mol), undecane dicarboxylic acid 2633.8774g(is roughly equal to 10.78mol), tridecane diamines 4597.9148g(is roughly equal to 21.65mol), ortho phosphorous acid magnesium 2.6182g(is roughly equal to 0.03mol), mix and be poured in 25L reactor, inject 5.4kg deionized water (being roughly equal to 300mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, get rid of and be reserved in the air in still, and reserved 0.015MPa nitrogen is as protection gas.
By circulating heat conduction oil, make reactor temperature rise to 130 ℃ and be incubated 2 hours, make polymerization single polymerization monomer be dissolved in solvent completely;
Insulation finishes to continue rising reactor temperature, until reacting kettle inner pressure carries out pressurize while being 2.5MPa, and pressurize edge height temperature of reaction kettle in limit is until temperature while arriving 270 ℃, strengthen mixing speed to 120r/min, continue rising temperature of reaction kettle until temperature is 325 ℃, keep temperature of reaction kettle not decline under prerequisite, carry out release until pressure unloads to normal pressure, reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.8MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Comparative example 1～4
Choose other serial nylon, the nylon that embodiment 1～4 chooses is respectively nylon 6, nylon 66, nylon 12, nylon 612, in 110 ℃ of-135 ℃ of baking ovens, dry 24h, then injection moulding on injection moulding machine, the interval temperature of injection moulding is 290 ℃, 295 ℃, 295 ℃, obtain for correlated performance testing standard nylon batten, and compare with the average behaviour of above-mentioned synthetic nylon 610T.
Embodiment NYLON610 T and other nylon series the performance test results is to such as table 2.
Table 2
By the implementation process of each embodiment, the known ratio that can conveniently be regulated aliphatic diamine and aliphatic dibasic acid and aromatic acid by preparation method of the present invention, thereby provide a very easy method for obtaining the biological nylon of a kind of semi-aromatic of required particular requirement, and the present invention has fed in raw material rear directly synthetic, simple for process, solvent used is deionized water simultaneously, there is no toxicity, safety and environmental protection.Through performance comparative analysis is simultaneously known, is better than nylon 6 and nylon 66, and can compares favourably with nylon 612 and nylon 12 in some properties with the most of performance of the biological nylon of the synthetic semi-aromatic of the method, therefore has broad application prospects.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. the biological nylon of semi-aromatic, is characterized in that: by the component that comprises following mole number, made:
2. the biological nylon of semi-aromatic according to claim 1, it is characterized in that: described aromatic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, 4, one or more in 4'-biphenyl dicarboxylic acid or naphthalic acid, preferably terephthalic acid.
3. the biological nylon of semi-aromatic according to claim 1, is characterized in that: described aliphatic diamine is selected from one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably hexanediamine.
4. the biological nylon of semi-aromatic according to claim 1, it is characterized in that: described aliphatic dibasic acid is selected from one or more in the aliphatic dibasic acid that contains 4-13 carbon atom in molecular chain main chain the sebacic acid of preferably producing from Viscotrol C.
5. the biological nylon of semi-aromatic according to claim 1, it is characterized in that: described catalyzer is selected from one or more in ortho phosphorous acid potassium, sodium phosphite, phosphorous acid magnesium, phosphorous acid calcium, zinc phosphite, potassiumphosphate, trimagnesium phosphate, calcium phosphate, zinc phosphate, ortho phosphorous acid potassium, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate or ortho phosphorous acid zinc, preferably inferior sodium phosphate.
6. a preparation method for the biological nylon of arbitrary described semi-aromatic in the claims 1-5, is characterized in that: comprise the following steps:
(1) in ratio claimed in claim 1 by polymerization single polymerization monomer 10.20-11.22mol aromatic acid, 19.60-21.65mol aliphatic diamine, 9.80-10.78mol aliphatic dibasic acid and 0.015-0.03mol catalyst mix are even, then joined in the 25L high pressure polymerisation reactor that whipping appts is housed, take 220-300mol aqueous solvent in reactor, the rotating speed that starts agitator is 60r/min and is filled with appropriate rare gas element in reactor, vacuumize, at least repeat 3 times, to get rid of, be reserved in the air in reactor, finally reserved 0.01Mpa-0.03Mpa rare gas element is as protection gas,
(2) by circulating heat conduction oil, reactor is carried out to heat temperature raising, then to being incubated in reactor still, so that polymerization single polymerization monomer is dissolved in solvent completely;
(3) insulation finishes, reactor is continued to heat up, now reacting kettle inner pressure rises, by delivery systme, react the moisture realization producing reactor is carried out to pressurize, maintain constant voltage, and reactor is continued to heating, when reactor temperature reaches 260-270 ℃ by the time, agitator speed is doubled to 120r/min, by circulating heat conduction oil, continue rising temperature of reaction kettle, when question response temperature in the kettle rises to 305-315 ℃, under the precondition that keeps temperature of reaction kettle not decline, be that holding temperature is not higher than 315 ℃, reactor is carried out to release, when the pressure in reactor unloads to normal pressure by the time, reduction agitator speed is 12r/min, to reactor, be filled with rare gas element, discharging obtains the biological nylon material of semi-aromatic.
7. preparation method according to claim 6, is characterized in that: in described step (1) or (3), rare gas element is nitrogen, carbonic acid gas, argon gas or helium, preferred nitrogen.
8. preparation method according to claim 6, is characterized in that: in described step (2), the intensification temperature of reactor is 120-140 ℃, preferably 125-135 ℃; Soaking time is 1.5-2.5 hour, preferably 2.0 hours.
9. preparation method according to claim 6, is characterized in that: in described step (3), reacting kettle inner pressure is 2.3-2.8MPa, preferred 2.5MPa, and constant voltage time is 0.5-1.5 hour, preferably 1 hour.
10. preparation method according to claim 6, is characterized in that: in described step (3), in reactor, the amount of pouring of rare gas element is 0.3-1.2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028089.8A CN103965466A (en) | 2013-01-25 | 2013-01-25 | Semi-aromatic biological nylon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028089.8A CN103965466A (en) | 2013-01-25 | 2013-01-25 | Semi-aromatic biological nylon and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103965466A true CN103965466A (en) | 2014-08-06 |
Family
ID=51235500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310028089.8A Pending CN103965466A (en) | 2013-01-25 | 2013-01-25 | Semi-aromatic biological nylon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965466A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589351A (en) * | 2015-10-14 | 2017-04-26 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic transparent nylon material PA6I and preparing method thereof |
| CN106928452A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of semi-aromatic nylon material of Long carbon chain containing naphthalene nucleus and preparation method thereof |
| CN112724400A (en) * | 2020-12-29 | 2021-04-30 | 南京开创新材料科技有限公司 | Semi-aromatic polyamide resin with high CTI value and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5245005A (en) * | 1992-04-10 | 1993-09-14 | Monsanto Company | Process for the production of linear amorphous polyamides with excess diamine |
| CN1590461A (en) * | 2003-08-05 | 2005-03-09 | 阿托菲纳公司 | Semi-aromatic polyamides with low moisture regain |
| CN102070902A (en) * | 2009-11-23 | 2011-05-25 | Ems专利股份公司 | Semi-aromatic moulding masses and their applications |
-
2013
- 2013-01-25 CN CN201310028089.8A patent/CN103965466A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5245005A (en) * | 1992-04-10 | 1993-09-14 | Monsanto Company | Process for the production of linear amorphous polyamides with excess diamine |
| CN1590461A (en) * | 2003-08-05 | 2005-03-09 | 阿托菲纳公司 | Semi-aromatic polyamides with low moisture regain |
| CN102070902A (en) * | 2009-11-23 | 2011-05-25 | Ems专利股份公司 | Semi-aromatic moulding masses and their applications |
Non-Patent Citations (1)
| Title |
|---|
| 顾亮 等: "半芳香族尼龙的制备方法", 《聚酯工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589351A (en) * | 2015-10-14 | 2017-04-26 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic transparent nylon material PA6I and preparing method thereof |
| CN106928452A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of semi-aromatic nylon material of Long carbon chain containing naphthalene nucleus and preparation method thereof |
| CN112724400A (en) * | 2020-12-29 | 2021-04-30 | 南京开创新材料科技有限公司 | Semi-aromatic polyamide resin with high CTI value and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104231262B (en) | A kind of preparation method of organophosphor copolymerization fire-retardant polyamide material | |
| CN104163918A (en) | High-temperature-resistant nylon PA66T material and preparation method thereof | |
| CN102159620B (en) | Polyamide resin | |
| US8802810B2 (en) | Process for the manufacture of a solution of salts of diacids/diamine(s) | |
| CN103694468B (en) | A kind of nylon resin and preparation method thereof | |
| WO2018120702A1 (en) | Method for producing semi-aromatic polyamide and semi-aromatic polyamide | |
| CN104250377A (en) | Low-water absorption biological nylon material PA610T and preparation method thereof | |
| CN110669216B (en) | Bio-based semi-aromatic polyamide and preparation method thereof | |
| CN104072756A (en) | Low-melting-point biological nylon material and preparation method thereof | |
| CN108383996A (en) | A kind of highly crystalline rate polyamide and its preparation method and application | |
| CN103965466A (en) | Semi-aromatic biological nylon and preparation method thereof | |
| CN109517165A (en) | A kind of semi-aromatic biological poly amide and preparation method thereof | |
| CN102850541A (en) | Biomass based polyamide resin | |
| CN103539935B (en) | A kind of method improving polymeric amide whiteness | |
| CN108424641A (en) | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening | |
| CN108148200A (en) | Water-soluble polyamide resins and preparation method thereof | |
| CN111518510B (en) | Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups | |
| CN107446129B (en) | Preparation method of anti-aging semi-aromatic nylon resin | |
| CN106232676A (en) | For being impregnated with composition and the method for the composite of the semicrystalline polyamides obtained by prepolymer and chain extender | |
| CN104774454B (en) | A kind of high temperature resistant nylon PA66T materials and preparation method thereof | |
| CN109575273A (en) | A kind of high temperature resistant semiaromatic copolymer nylon and preparation method thereof | |
| CN103910878A (en) | Lysine-synthesized semi-aromatic nylon and its synthesizing method | |
| CN105143351A (en) | Polyamide resin composition, and molded article | |
| CN103435796A (en) | Semi-aromatic transparent polyamide material and preparation method thereof | |
| JPH02115225A (en) | Branched (co)polyamide made by polycondensation in the presence of lysine component/polycarboxylic acid mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140806 |