CN103910878A - Lysine-synthesized semi-aromatic nylon and its synthesizing method - Google Patents
Lysine-synthesized semi-aromatic nylon and its synthesizing method Download PDFInfo
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Abstract
The invention relates to the synthesis field of polymer material nylon, and relates to a synthesizing method of semi-aromatic nylon. The semi-aromatic nylon comprises the following components by molar: 10.65-15.05mol of aromatic dicarboxylic acid; 10.55-14.60mol of aliphatic diamine; 1.49-4.90mol of lysine, 0.015-0.03mol of a catalyst and 220-300mol of a solvent. The method is simple in reaction steps, low in cost of equipment for the reaction, relatively mild in reaction conditions, not very high in equipment requirements for the reason of being in no need of high temperature and high pressure, and low in energy consumption. The synthesized semi-aromatic nylon is high in melt index, good in fluidity and convenient in discharging, can be directly dragged for granulation after cooling, is easy to package, transport and store, and after drying can be directly used for forming processing, and the product is stable in shape, in no need of cumbersome aftertreatment processes, and also ideal in mechanical properties.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material nylon, relate to a kind of semi-aromatic nylon and preparation method thereof.
Technical background
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 occupy 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, makes through polycondensation.Owing to importing aliphatic chain in fully aromatic polyamide molecular backbone chain, thereby forming process and solvability etc. are improved.Compared 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.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.
Through the literature search of prior art is found, Chinese patent 200910227658.5 discloses a kind of preparation method of semi-aromatic nylon, but this technological reaction time is longer, technique is comparatively loaded down with trivial details (first obtains synthetic nylon salt, and then carry out polymerization to reactor), and solvent for use is alcohols or ketone solution, dangerous environmental protection.The defects such as Chinese patent 200580023100.5 relates to by Methionin synthesis of caprolactam, and solvent for use is alcohol solution, has equally dangerous environmental protection, and reactions steps is loaded down with trivial details.
Summary of the invention
An object of the present invention is provides a kind of semi-aromatic nylon and preparation method thereof for the deficiencies in the prior art.This semi-aromatic nylon is particular plastics, and performance is comparatively desirable, is applicable to suitability for industrialized production.
The method of synthetic semi-aromatic nylon provided by the invention, does not exist first synthetic nylon salt to carry out the loaded down with trivial details techniques such as polymerization at polymeric kettle again, but adds reactor directly to carry out polymerization raw material, and therefore its synthesis technique is simple, and generated time is shorter; In addition, the present invention can adopt deionized water as solvent, and many costs have also been saved in therefore safer environmental protection simultaneously.
For achieving the above object, the present invention is by the following technical solutions:
A kind of semi-aromatic nylon, made by the component that comprises following mole number:
Aromatic acid 10.65-15.05mol;
Aliphatic diamine 10.55-14.60mol;
Methionin 1.49-4.90mol;
Catalyzer 0.015-0.03mol;
Solvent 220-300mol;
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;
Described aliphatic diamine is one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably decamethylene diamine;
Described catalyzer is 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;
Described solvent is deionized water, organic alcohol solvent, organic ketone solvent, and wherein Organic Alcohol is selected from methyl alcohol or ethanol; Organic ketone solvent is selected from acetone, the preferred deionized water of the present invention.
A method for the synthetic semi-aromatic nylon of above-mentioned Methionin, comprises the following steps:
(1) take aromatic acid 10-15mol, aliphatic diamine 10-14mol, Methionin 1.0-5.0mol, catalyzer 0.015-0.03mol and solvent 220-300mol according to above-mentioned mole number proportioning;
By even to aromatic acid, aliphatic diamine, Methionin and catalyst mix, then joined in the polymerization reaction kettle of whipping appts, add solvent, stir above-mentioned reaction mixture and to being filled with rare gas element in reactor, vacuumizing to get rid of the air being reserved in reactor;
(2) reacting by heating still insulation, 120 ℃-130 ℃ of heat-preserving ranges, are dissolved in solvent polymerization single polymerization monomer completely;
Insulation finishes, reactor is continued to heat up, the temperature range heating up is 130 ℃-335 ℃, now reacting kettle inner pressure rises, until still internal pressure is while reaching 2.5MPa, reactor is carried out to pressurize, and when reactor is continued to be heated to 260-270 ℃, agitator speed is doubled (agitator speed rises to 120r/min), continue rising temperature of reaction kettle to 315-320 ℃ by circulating heat conduction oil (being equivalent to the oil bath of flowing), under the precondition that keeps temperature of reaction kettle not decline, reactor is carried out to release;
By the time when the pressure in reactor unloads to normal pressure, reduce agitator speed (it is following that agitator speed is down to 12r/min), be filled with rare gas element with the pressure within the scope of 0.3-1.2MPa in reactor, discharging to reactor, cooling and dicing, obtains having semi-aromatic nylon pellet.
Power of agitator in described step (1) is 60r/min.
In described step (1) or step (2), rare gas element is nitrogen, carbonic acid gas, argon gas or helium, preferred nitrogen.
In described step (2), the temperature of reacting by heating is 120-130 ℃,
In described step (2), semi-aromatic nylon material dries 24h in 110 ℃ of-135 ℃ of baking ovens, then injection moulding on injection moulding machine, and the interval temperature of injection moulding is 290 ℃, 295 ℃, 295 ℃, obtains for correlated performance testing standard nylon batten.
In described step (2), before discharging, determine and the size of material viscosity in still further determine whether to vacuumize tackify step according to stirring the watt level showing: when power of agitator is during lower than 1100w, vacuumize processing; In the time that power of agitator is 1100w-1250w, without vacuumizing.
The method of synthetic semi-aromatic nylon provided by the invention, does not exist first synthetic nylon salt to carry out the loaded down with trivial details techniques such as polymerization at polymeric kettle again, but adds reactor directly to carry out polymerization raw material, and therefore its synthesis technique is simple, and generated time is shorter; In addition, the present invention can adopt deionized water as solvent, and many costs have also been saved in therefore safer environmental protection simultaneously.
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, be not therefore very high to the requirement of equipment, 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) melting index of synthetic semi-aromatic nylon is higher, and mobility is better, and discharging is convenient, can directly draw granulation through cooling, 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.Meanwhile, its mechanical property is also comparatively desirable.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are only for the present invention is described, and are not intended to limit the scope of the invention.Technician makes according to the present invention in actual applications improvement and adjustment, still belong to protection scope of the present invention.
In following embodiment, adopt following detection method:
The melting index of nylon is pressed GB/T3682-2000, at 300 ℃, under 2.16kg condition, tests.
Tensile property is pressed GB/T1040.1-20O6 test, and rate of extension 5mm/min tests under fixed temperature and humidity experiment condition.
Simply supported beam notched Izod impact strength is pressed GB/T1043 test, under fixed temperature and humidity experiment condition, tests.
Flexural strength GB/T9341-2008 test, presses down speed 1.25mm/min, under fixed temperature and humidity experiment condition, tests.
Embodiment 1
Weigh in proportion terephthalic acid (purity 100%) 2460.8118g(and be roughly equal to 14.8126mol), decamethylene diamine (purity 99%) 2320.4560g(is roughly equal to 13.3313mol), Methionin (purity 99%) 217.9631g(is roughly equal to 1.4813mol), inferior sodium phosphate 1.2894g(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, gets rid of the air being reserved in still;
Insulation finishes, reactor is continued to heat up, make reactor temperature rise to 120 ℃ and be incubated 2 hours by circulating heat conduction oil, polymerization single polymerization monomer is dissolved in solvent completely, insulation finishes to continue rising reactor temperature to 235 ℃, now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and limit pressurize edge height temperature of reaction kettle until temperature arrive 260 ℃ time, 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, now power of agitator is 1189w, without vacuumizing.Reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 0.3MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 2
Weigh in proportion terephthalic acid (purity 100%) 2499.9065g(and be roughly equal to 15.0479mol), decamethylene diamine (purity 99%) 1833.4718g(is roughly equal to 10.5335mol), Methionin (purity 99%) 666.6216g(is roughly equal to 4.5144mol), inferior sodium phosphate 2.0g(is roughly equal to 0.02326mol), mix and be poured in 25L reactor, inject 4.3kg deionized water (being roughly equal to 238.89mol) in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, gets rid of the air being reserved in still;
Insulation finishes, and reactor is continued to heat up, and makes reactor temperature rise to 122 ℃ and be incubated 2 hours by circulating heat conduction oil, and polymerization single polymerization monomer is dissolved in solvent completely; Insulation finishes to continue rising reactor temperature to 237 ℃, now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and pressurize edge height temperature of reaction kettle in limit, until temperature arrives 262 ℃ time, strengthens mixing speed to 120r/min, continues 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, now power of agitator is 1212w, without vacuumizing.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 3
Weigh in proportion terephthalic acid 2429.1803g(and be roughly equal to 14.6222mol), decamethylene diamine 2349.3627g(is roughly equal to 13.4974mol), Methionin 221.4571g(is roughly equal to 1.4997mol), catalyzer 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, gets rid of the air being reserved in still;
Insulation finishes, reactor is continued to heat up, make reactor temperature rise to 125 ℃ and be incubated 2 hours by circulating heat conduction oil, polymerization single polymerization monomer is dissolved in solvent completely, insulation finishes to continue rising reactor temperature to 237 ℃, now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and limit pressurize edge height temperature of reaction kettle until temperature arrive 265 ℃ time, 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, now power of agitator is 1021w, vacuumize process 5 minutes to power of agitator be 1160w.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 4
Weigh in proportion terephthalic acid 1766.2614g(and be roughly equal to 10.6318mol), decamethylene diamine 2535.9773g(is roughly equal to 14.5695mol), Methionin 697.7613g(is roughly equal to 4.7252mol), inferior sodium phosphate 2.4g(is roughly equal to 0.02792mol), mixing and be poured in 25L reactor, inject 4.8kg(and be roughly equal to 266.66mol) deionized water is in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, gets rid of the air being reserved in still;
Insulation finishes, reactor is continued to heat up, make reactor temperature rise to 125 ℃ and be incubated 2 hours by circulating heat conduction oil, polymerization single polymerization monomer is dissolved in solvent completely, insulation finishes to continue rising reactor temperature to 234 ℃, now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and limit pressurize edge height temperature of reaction kettle until temperature arrive 265 ℃ time, 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, now power of agitator is 1141w, without vacuumizing.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.
Embodiment 5
Weigh in proportion terephthalic acid 2396.7507g(and be roughly equal to 14.4270mol), decamethylene diamine 2378.9987g(is roughly equal to 13.6676mol), Methionin 224.2506g(is roughly equal to 1.5186mol), inferior sodium phosphate 2.5g(is roughly equal to 0.02908mol), mixing and be poured in 25L reactor, inject 5.0kg(and be roughly equal to 277.77mol) deionized water is in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, gets rid of the air being reserved in still;
Insulation finishes, reactor is continued to heat up, make reactor temperature rise to 125 ℃ and be incubated 2 hours by circulating heat conduction oil, polymerization single polymerization monomer is dissolved in solvent completely, insulation finishes to continue rising reactor temperature to 236 ℃, now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and limit pressurize edge height temperature of reaction kettle until temperature arrive 265 ℃ time, 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, now power of agitator is 1201w, without vacuumizing.Reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 1.0MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
Embodiment 6
Weigh in proportion terephthalic acid 2297.2044g(and be roughly equal to 13.8277mol), decamethylene diamine 1982.1257g(is roughly equal to 11.3875mol), Methionin 720.6699g(is roughly equal to 4.8804mol), inferior sodium phosphate 2.5788g(is roughly equal to 0.03mol), mixing and be poured in 25L reactor, inject 5.4kg(and be roughly equal to 300mol) deionized water is in reactor.Opening whipping appts rotating speed is 60r/min, is filled with nitrogen and vacuumizes, and repeats 3 times, gets rid of the air being reserved in still;
Insulation finishes, reactor is continued to heat up, make reactor temperature rise to 130 ℃ and be incubated 2 hours by circulating heat conduction oil, polymerization single polymerization monomer is dissolved in solvent completely, insulation finishes to continue rising reactor temperature to 239 ℃, , now reacting kettle inner pressure increases to 2.5MPa, reactor is carried out to pressurize, and limit pressurize edge height temperature of reaction kettle until temperature arrive 270 ℃ time, 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, now power of agitator is 980w, vacuumize process 11 minutes to power of agitator be 1145w.Reduce mixing speed to 12r/min, being filled with nitrogen, to make reacting kettle inner pressure be 1.2MPa, discharging, obtain continuity better cooling after the direct semi-aromatic nylon material of pelletizing.
The performance test results of embodiment 1-6 is as table 1.
Table 1
| ? | Melting index (g/10min) | Tensile strength (MPa) | Shock strength (KJ/m 2） | Flexural strength (MPa) |
| Embodiment 1 | 172.3 | 54.87 | 8.35 | 120.30 |
| Embodiment 2 | 174.5 | 50.90 | 7.81 | 118.28 |
| Embodiment 3 | 172.2 | 48.79 | 8.48 | 111.09 |
| Embodiment 4 | 172.8 | 56.86 | 7.79 | 114.30 |
| Embodiment 5 | 177.3 | 60.04 | 8.75 | 119.94 |
| Embodiment 6 | 173.6 | 49.98 | 7.17 | 122.86 |
By implementation process and the performance test results of the various embodiments described above, the known molar ratio that can conveniently be regulated aliphatic diamine and aromatic acid and Methionin by preparation method of the present invention, thereby provide a very easy method for obtaining a kind of semi-aromatic nylon of required good mechanical performance, 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.
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. a semi-aromatic nylon, is characterized in that: be made up of the component that comprises following mole number:
Aromatic acid 10.65-15.05mol;
Aliphatic diamine 10.55-14.60mol;
Methionin 1.49-4.90mol;
Catalyzer 0.015-0.03mol;
Solvent 220-300mol.
2. semi-aromatic nylon 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. semi-aromatic nylon according to claim 1, is characterized in that: described aliphatic diamine is one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably decamethylene diamine.
4. semi-aromatic nylon according to claim 1, it is characterized in that: described catalyzer is 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.
5. semi-aromatic nylon according to claim 1, is characterized in that: described solvent is deionized water, organic alcohol solvent, organic ketone solvent, preferably deionized water.
6. semi-aromatic nylon according to claim 5, is characterized in that: described Organic Alcohol is selected from methyl alcohol or ethanol; Or organic ketone solvent is selected from acetone.
7. a method for arbitrary described synthetic semi-aromatic nylon in the claims 1-6, is characterized in that: comprise the following steps:
(1) take each component materials of following weight part according to mole number proportioning claimed in claim 1: aromatic acid 10-15mol, aliphatic diamine 10-14mol, Methionin 1.0-5.0mol, catalyzer 0.015-0.03mol and solvent 220-300mol;
By even to aromatic acid, aliphatic diamine, Methionin and catalyst mix, then joined in the polymerization reaction kettle of whipping appts, add solvent, stir above-mentioned reaction mixture and to being filled with rare gas element in reactor, vacuumizing to get rid of the air being reserved in reactor;
(2) reacting by heating still insulation, 120 ℃-130 ℃ of heat-preserving ranges, are dissolved in solvent polymerization single polymerization monomer completely; Insulation finishes, reactor is continued to heat up, the temperature range heating up is 130 ℃-335 ℃, now reacting kettle inner pressure rises, until still internal pressure while reaching 2.5MPa, is carried out pressurize to reactor, and when reactor is continued to be heated to 260-270 ℃, agitator speed is risen to 120r/min, continue rising temperature of reaction kettle to 315-320 ℃ by circulating heat conduction oil, under the precondition that keeps temperature of reaction kettle not decline, reactor is carried out to release;
By the time when the pressure in reactor unloads to normal pressure, reduce agitator speed to 12r/min, be filled with rare gas element with the pressure within the scope of 0.3-1.2MPa in reactor to reactor, discharging, cooling and dicing, obtains semi-aromatic nylon pellet.
8. preparation method according to claim 7, is characterized in that: the agitator speed in described step (1) is 60r/min; Or rare gas element is nitrogen, carbonic acid gas, argon gas or helium in described step (1) or step (2), preferred nitrogen.
9. preparation method according to claim 7, is characterized in that: in described step (2), the temperature of reacting by heating is 120-130 ℃;
Or in described step (2), before discharging, when power of agitator is during lower than 1100w, vacuumize processing.
10. preparation method according to claim 7, it is characterized in that: in described step (2), semi-aromatic nylon material dries 24h in 110 ℃ of-135 ℃ of baking ovens, then injection moulding on injection moulding machine, the interval temperature of injection moulding is 290 ℃, 295 ℃, 295 ℃, obtains for correlated performance testing standard nylon batten.
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| CN104710613A (en) * | 2015-03-12 | 2015-06-17 | 中国科学院理化技术研究所 | Solvent-thermal preparation method for semi-aromatic polyamide |
| CN104817693A (en) * | 2015-05-21 | 2015-08-05 | 郑州大学 | Semi-aromatic polyamide PA11T and preparation method thereof |
| CN106916298A (en) * | 2015-12-25 | 2017-07-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof |
| CN108659527A (en) * | 2018-05-02 | 2018-10-16 | 山东冬瑞高新技术开发有限公司 | A kind of high-strength glass fiber composite material and preparation method thereof |
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| CN106916298A (en) * | 2015-12-25 | 2017-07-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof |
| CN108659527A (en) * | 2018-05-02 | 2018-10-16 | 山东冬瑞高新技术开发有限公司 | A kind of high-strength glass fiber composite material and preparation method thereof |
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Denomination of invention: Lysine-synthesized semi-aromatic nylon and its synthesizing method Effective date of registration: 20191223 Granted publication date: 20180102 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980001220 |
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