CN112661954B - Star polyamide and application thereof - Google Patents
Star polyamide and application thereof Download PDFInfo
- Publication number
- CN112661954B CN112661954B CN201910982633.XA CN201910982633A CN112661954B CN 112661954 B CN112661954 B CN 112661954B CN 201910982633 A CN201910982633 A CN 201910982633A CN 112661954 B CN112661954 B CN 112661954B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- star
- dianhydride
- polymerization
- carbon material
- 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.)
- Active
Links
Images
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a star polyamide and its use, add dianhydride as initiator or amide exchanger into the polymerization process of polyamide, through initiating monomer polymerization or amide exchange, get star polyamide, the add amount of dianhydride is 0.5-10% of the weight of the polymerized monomer. The star polyamide is used in preparing fluorescent material, polyamide modifier or carbon material solubilizer. The polyamide modifier is used as a lubricant to reduce the viscosity of the polyamide and enable the polyamide to have higher fluidity. The carbon material solubilizer improves the compatibility of the carbon material with the polyamide matrix interface. According to the invention, the dianhydride is added as an initiator or an amide exchanger, and the star-shaped polyamide is obtained by initiating the polymerization or the amide exchange of the monomer, so that the performance of the polyamide is improved, the composite material with excellent performance is prepared, and the application of a polyamide product is expanded.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and relates to star polyamide and application thereof.
Background
Since the last 30 th century polyamide was developed by dupont in the united states, it has been widely used in various fields of automobiles, electronics, construction, machinery, energy sources, etc., due to its excellent electrical and mechanical properties, and good solvent resistance, abrasion resistance, self-lubrication, and processability. Polyamides play an increasingly important role in saving energy, replacing metals, and the like. As one of the five major engineering plastics, it plays a significant role in the economic development.
However, in order for the polyamide to be applied in more prominent positions, it is necessary to further reinforce and toughen the polyamide. The problem to be solved by strengthening, toughening and modification is the compatibility of interfaces. In the past, reinforcing modification is carried out on polyamide, and coupling agents such as silane coupling agents, titanate coupling agents and aluminate coupling agents are mainly added to improve interface compatibility. And the toughening modification is mainly added with solubilizers such as maleic anhydride grafted ABS and maleic anhydride grafted SEBS. The principle of the two methods is similar, and the added auxiliary agents are polar groups which contain hydroxyl, carboxyl, epoxy groups and the like at one end and can be subjected to chemical reaction with polyamide, and the other end can be compatible with filling materials or other resins, so that the compatibility of interfaces is obviously improved.
The polyamide modified by glass fiber, carbon fiber, graphite ore, carbon black and other materials has important breakthrough in the aspects of increasing the strength of the composite material and reducing the cost. However, as these inorganic fillers continue to increase, the processability of the composite materials is also decreasing. If the star polyamide with high fluidity can be added in the modification process, the mechanical processing property of the star polyamide can be greatly modified, the cost is further reduced, and the strength of the composite material is increased.
Disclosure of Invention
The invention aims to provide star polyamide, improve the performance of polyamide, prepare composite materials with excellent performance and expand the application of polyamide products. It is another object of the present invention to provide uses for preparing fluorescent materials, polyamide modifiers and solubilizers for carbon materials.
The technical scheme of the invention is that star polyamide is obtained by adding dianhydride as an initiator or an amide exchanger into a polyamide polymerization process and initiating monomer polymerization or amide exchange, wherein the addition amount of the dianhydride is 0.5-10% of the weight of a polymerization monomer. The preparation method of the star polyamide comprises the following steps:
adding dianhydride into an organic solvent, and ultrasonically mixing 1-2 h at 60-80 ℃ to obtain a dianhydride solution;
and (3) adding the dianhydride solution obtained in the step (c) into a reaction system for preparing the polyamide, wherein the adding mode is adding in the early stage, the middle stage or the later stage of polymerization, and reacting at 140-160 ℃ for 3-5 h to obtain the star-shaped polyamide. The structural formula of the star polyamide is as follows:
the organic solvent is dimethyl sulfoxide (DMSO), and the mass concentration of the dianhydride solution is 10-60 mg/mL. The polymerization process is polycondensation or anionic polymerization.
The polyamide is polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 46, polyamide 1010, poly (p-phenylene terephthalamide), poly (m-phenylene terephthalamide), or poly (p-phenylene terephthalamide) or copolymers thereof.
The polyamide monomer is caprolactam, adipic acid, hexamethylenediamine, sebacic acid, decanediamine, 1, 4-butanediamine, terephthalic acid or terephthalamide. The dianhydride is pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, perylene-3, 4,9, 10-tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, hexafluoroisopropyl phthalic anhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride or 4,4' -oxydiphthalic anhydride. The structural formula of the compound is as follows:
pyromellitic dianhydride：
；
1,4,5, 8-naphthalene tetracarboxylic dianhydride:
；
perylene-3, 4,9, 10-tetracarboxylic dianhydride:
；
3,3', 4' -benzophenone tetracarboxylic dianhydride:
；
hexafluoroisopropyl phthalic anhydride:
；
3,3', 4' -biphenyltetracarboxylic dianhydride:
；
3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride:
and
4,4' -oxydiphthalic anhydride:
。
the star polyamide of the invention is used for preparing fluorescent materials (glass fiber/polyamide materials), polyamide modifiers and carbon material solubilizers. The polyamide modifier is used as a lubricant to reduce the viscosity of the polyamide and enable the polyamide to have higher fluidity. The carbon material solubilizer improves the compatibility of the carbon material with the polyamide matrix interface.
The preparation method of the polyamide modifier comprises the following steps: the star polyamide and the polyamide are mixed by a double screw extruder according to the weight ratio of 30-50 percent to 50-70 percent, and then are granulated by a granulator to obtain the polyamide modifier. The preparation method of the fluorescent material comprises the following steps: the prepared polyamide modifier and glass fiber are mixed with auxiliary agent in the weight ratio of 60-80% to 20-40% in a double screw extruder at 230-260 deg.c, and pelletized in a pelletizer to obtain glass fiber/polyamide material. The auxiliary agent is a coupling agent KH550, and the dosage of the auxiliary agent is 2-8% of the weight of the glass fiber. The preparation method of the carbon material solubilizer comprises the following steps: the star polyamide, polyamide and carbon material are mixed in a double screw extruder in the weight ratio of 5-10% to 50-75% to 20-40% at 230-260 deg.c, and pelletized in a pelletizer to obtain the carbon material/polyamide composite material. The carbon material is fullerene, carbon nanotube, graphene, carbon black, graphene oxide, graphite mineral powder or coal gangue powder.
The invention adopts a polycondensation or anion polymerization method, and single dianhydride or a mixture thereof is added in the pre-polymerization stage, the middle polymerization stage or the late polymerization stage to prepare the star-shaped polyamide. And (3) adopting a melt blending extrusion mode to blend star-shaped polyamide with corresponding polyamide, glass fiber, graphene and other carbon materials according to a certain proportion, so as to prepare the glass fiber/polyamide composite material and the carbon material/polyamide composite material with excellent performance.
The invention adds dianhydride as initiator or amide exchanger in the early, middle or late polymerization of polyamide, and obtains star polyamide by initiating monomer polymerization or amide exchange, thus improving the performance of polyamide and preparing composite material with excellent performance. The fluorescent material, the polyamide modifier or the carbon material prepared from the star polyamide has good performance, and the application of the polyamide product is expanded.
Drawings
FIG. 1 is a fluorescent appearance of star polyamide under 365nm light irradiation;
FIG. 2 is a fluorescent appearance of star polyamide without 365nm light;
FIG. 3 is a fluorescence spectrum of star polyamide;
FIG. 4 is a fluorescent appearance of perylene anhydride/polyamide 6 star polymer under 365nm light irradiation;
FIG. 5 is a fluorescent appearance of perylene anhydride/polyamide 6 star polymer without 365nm light irradiation.
Detailed Description
The present invention will be described in detail with reference to examples and drawings. The scope of the invention is not limited to the examples, and any modifications within the scope of the claims are within the scope of the invention.
Example 1:
adding 1,4,5, 8-naphthalene tetracarboxylic dianhydride into DMSO, and ultrasonically mixing 2h at 70+/-2 ℃ to prepare dianhydride solution with the mass concentration of 20 mg/mL;
and (3) adding the dianhydride solution obtained in the step (A) into a polymerization reactor of the polyamide 6 in the early stage of polymerization, namely, before the polymerization reaction starts, wherein the addition amount is 2% of the weight of the raw materials of the polymerization monomers. Reacting 3 h at 150+ -5deg.C to obtain star polyamide 6;
thirdly, blending the star-shaped polyamide 6 obtained in the step (II) and the polyamide 6 in a weight ratio of 30% to 70% by using a double-screw extruder at the extrusion temperature of 230 ℃, and granulating by using a granulator to obtain a polyamide modifier, namely a high-fluidity polyamide material;
fourthly, adding an auxiliary agent into the high-fluidity polyamide material obtained from the step and the glass fiber according to the weight ratio of 60 percent to 40 percent, blending by a double-screw extruder at the extrusion temperature of 260 ℃, and granulating by a granulator to obtain the glass fiber/polyamide material; the auxiliary agent is a coupling agent KH550, and the dosage of the auxiliary agent is 8% of the weight of the glass fiber.
Example 2
Adding perylene-3, 4,9, 10-tetracarboxylic dianhydride into DMSO, and ultrasonically mixing for 1.5 hours at 75+/-2 ℃ to prepare dianhydride solution with the mass concentration of 30 mg/mL;
adipic acid and hexamethylenediamine are added into a reaction kettle, polymerization is carried out through a polycondensation mechanism, and the dianhydride solution obtained in the step (A) is added into a polymerization reactor of polyamide 66 in the middle polymerization stage, namely, 2 hours after the polymerization reaction starts, wherein the addition amount is 5% of the weight of the raw materials of the polymerization monomers. Reacting 4 h at 145+ -5deg.C to obtain star polyamide 66;
thirdly, blending the star-shaped polyamide 66 obtained in the step (II) and polyamide 66 in a weight ratio of 40% to 60% by using a double-screw extruder at the extrusion temperature of 240 ℃, and granulating by using a granulator to obtain a polyamide modifier, namely a high-fluidity polyamide material;
fourthly, adding an auxiliary agent into the high-fluidity polyamide material obtained from the step and glass fiber according to the weight ratio of 70 percent to 30 percent, blending by a double-screw extruder at the extrusion temperature of 260 ℃, and granulating by a granulator to obtain the glass fiber/polyamide material; the auxiliary agent is a coupling agent KH550, and the dosage of the auxiliary agent is 5% of the weight of the glass fiber.
Example 3
Adding 3,3', 4' -benzophenone tetracarboxylic dianhydride into DMSO, and carrying out ultrasonic mixing for 1.5 hours at 75+/-2 ℃ to prepare dianhydride solution with the mass concentration of 40 mg/mL;
the method comprises the steps of adding adipic acid and decamethylene diamine into a reaction kettle, polymerizing through an anionic polymerization mechanism, and adding the dianhydride solution obtained in the step into a polymerization reactor of poly-paraphenylene terephthalamide in the later polymerization stage, namely, adding the dianhydride solution into the polymerization reactor at the moment when the polymerization reaction is about to end, wherein the addition amount is 8% of the weight of a polymerization monomer raw material. Reacting 5h at 155+ -5deg.C to obtain star polyamide 610;
thirdly, blending the star-shaped polyamide 610 obtained in the step (II) and the polyamide 610 in a weight ratio of 50% to 50% by using a double-screw extruder at the extrusion temperature of 240 ℃, and granulating by using a granulator to obtain a polyamide modifier, namely a high-fluidity polyamide material;
fourthly, adding an auxiliary agent into the high-fluidity polyamide material obtained from the step and glass fiber according to the weight ratio of 80 percent to 20 percent, blending by a double-screw extruder at the extrusion temperature of 260 ℃, and granulating by a granulator to obtain the glass fiber/polyamide material; the auxiliary agent is a coupling agent KH550, and the dosage of the auxiliary agent is 2% of the weight of the glass fiber.
The high-flowability polyamide materials prepared in examples 1 to 3 were tested for melt index according to the international standard ISO 1133, the test results are shown in Table 1, and the test results of the polyamides PA6, PA66 and PA610 used are shown in Table 1 together. The glass fiber/polyamide materials prepared in examples 1 to 3 were tested for tensile strength according to national standard GB/T1040-2006, the test results are shown in Table 2, and the test results of the polyamides PA6, PA66 and PA610 used are shown in Table 2 together.
TABLE 1 high flow Polyamide materials prepared in examples 1-3 and comparative example Performance test results
| Performance index | Test standard | Example 1 | Example 2 | Example 3 | PA6 | PA66 | PA610 |
| Melt index (g/10 min) | ISO 1133 | 47 | 45 | 52 | 35 | 32 | 37 |
TABLE 2 glass fiber/polyamide materials prepared in examples 1-3 and comparative example Performance test results
| Performance index | Test standard | Example 1 | Example 2 | Example 3 | PA6 | PA66 | PA610 |
| Tensile Strength (MPa) | GB/T1040-2006 | 185 | 190 | 150 | 80 | 85 | 60 |
| Flexural Strength (MPa) | GB/T9341-2006 | 252 | 245 | 210 | 128 | 133 | 90 |
| Notched impact Strength (kJ/m) 2 ） | GB/T1043-2008 | 15 | 13 | 11 | 5.5 | 5 | 5.5 |
The data in tables 1 and 2 show that the technical indexes of the star polyamide of the invention, namely the tensile strength, the bending strength and the notch impact strength, are obviously higher than those of the PA6 PA66 PA610 in the prior art. The star polyamide prepared in example 1 nylon 6 was subjected to a fluorescent irradiation test, and the star polyamide was not irradiated with 365nm light, as shown in FIG. 1, and was irradiated with 365nm light, as shown in FIG. 2. FIG. 3 is a fluorescence spectrum of star polyamide. FIGS. 4 and 5 are fluorescent appearance diagrams of perylene anhydride/nylon 6 star polymer, wherein: FIG. 4 shows luminescence under 365nm light irradiation, and FIG. 5 shows no luminescence under 365nm light irradiation.
Example 4
Adding hexafluoroisopropyl phthalic anhydride into DMSO, and ultrasonically mixing for 1.5 hours at 75+/-2 ℃ to prepare dianhydride solution with the mass concentration of 20 mg/mL;
and (3) adding the dianhydride solution obtained in the step (A) into a polymerization reactor of the polyamide 6 in the early stage of polymerization, namely, before the polymerization reaction starts, wherein the addition amount is 2% of the weight of the raw materials of the polymerization monomers. Reacting 3 h at 150+ -5deg.C to obtain star polyamide 6;
thirdly, blending the star-shaped polyamide 6, polyamide 6 and graphene in a weight ratio of 5-10% by using a double-screw extruder at the extrusion temperature of 250 ℃, and granulating by using a granulator to obtain the carbon material/polyamide composite material.
Example 5
Adding 3,3', 4' -biphenyl tetracarboxylic dianhydride into DMSO, and ultrasonically mixing for 1.5 hours at 75+/-2 ℃ to prepare dianhydride solution with the mass concentration of 30 mg/mL;
adding adipic acid and hexamethylenediamine into a reaction kettle, and polymerizing by a polycondensation mechanism; the dianhydride solution obtained in the step (A) is added into a polymerization reactor of polyamide 66 in the middle polymerization stage, namely, 2h after the polymerization reaction starts, and the addition amount is 4% of the weight of the raw materials of the polymerized monomers. Reacting 4 h at 150+ -5deg.C to obtain star polyamide 66;
thirdly, mixing the star-shaped polyamide 66 obtained in the step II, polyamide 66 and carbon nano tubes in a weight ratio of 8-82-10% by using a double-screw extruder, extruding at the temperature of 250 ℃, and granulating by using a granulator to obtain the carbon material/polyamide composite material.
Example 6:
adding 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride into DMSO, and ultrasonically mixing for 1.5 hours at 67+/-2 ℃ to prepare a dianhydride solution with the mass concentration of 40 mg/mL;
adding terephthalic acid and hexamethylenediamine into a reaction kettle, and polymerizing by an anionic polymerization mechanism; the dianhydride solution obtained in the step (A) is added into a polymerization reactor of poly (p-phenylene terephthamide) in the later period of polymerization, namely, the dianhydride solution is added when the polymerization reaction is about to be finished, and the addition amount is 6% of the weight of the raw materials of the polymerized monomers. Reacting 5h at 145+ -5deg.C to obtain star polyamide;
thirdly, blending the star-shaped polyamide obtained in the step II, the poly-p-phenylene terephthamide and the graphite ore in a weight ratio of 10-60-30%, using a double-screw extruder to obtain a blend, extruding at the temperature of 250 ℃, and granulating by a granulator to obtain the carbon material/polyamide composite material.
Example 7:
adding pyromellitic dianhydride and 4,4' -oxydiphthalic anhydride into DMSO, and ultrasonically mixing for 1.5 hours at 67+/-2 ℃ to prepare a dianhydride solution with the mass concentration of 50 mg/mL;
adding adipic acid and decanediamine into a reaction kettle, and polymerizing by a polycondensation mechanism; the dianhydride solution obtained in the step (A) is added into a polyamide 610 polymerization reactor in the middle polymerization stage, namely, after the polymerization reaction is carried out by 2.5. 2.5 h, and the addition amount is 8% of the weight of the raw materials of the polymerized monomers. Reacting 5h at 155+ -2deg.C to obtain star polyamide 610;
thirdly, blending the star-shaped polyamide 610, polyamide 610 and carbon black which are obtained in the step according to the weight ratio of 10 percent to 55 percent to 35 percent by using a double-screw extruder, wherein the extrusion temperature is 260 ℃, and granulating by using a granulator to obtain the carbon material/polyamide composite material.
Example 8
Adding perylene-3, 4,9, 10-tetracarboxylic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride into DMSO, and ultrasonically mixing for 1.5 hours at 65+/-2 ℃ to prepare a dianhydride solution with the mass concentration of 50 mg/mL;
adding terephthalic acid and hexamethylenediamine into a reaction kettle, and polymerizing by a polycondensation mechanism; the dianhydride solution obtained in the step (A) is added into a poly (hexamethylene terephthalamide) polymerization reactor in the middle polymerization stage, namely, after the polymerization reaction (2), and the addition amount is 10% of the weight of the raw materials of the polymerized monomers. Reacting 5h at 155+ -2deg.C to obtain star-shaped poly (hexamethylene terephthalamide);
thirdly, mixing the star-shaped poly (hexamethylene terephthalamide) obtained in the step II with poly (hexamethylene terephthalamide) and carbon black in a weight ratio of 10% to 55% to 35% by using a double-screw extruder, wherein the extrusion temperature is 260 ℃, and granulating by using a granulator to obtain the carbon material/polyamide composite material.
The carbon material/polyamide composite materials prepared in examples 4 to 8 were tested for tensile strength according to national standard GB/T1040-2006, flexural strength according to GB/T9341-2006, notched impact strength according to GB/T1043-2008, and the test results are shown in Table 3.
TABLE 3 Polyamide materials prepared in examples 4-7 and comparative examples provide the results of performance tests
| Performance index | Test standard | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Tensile Strength (MPa) | GB/T1040-2006 | 132 | 128 | 120 | 112 | 137 |
| Flexural Strength (MPa) | GB/T9341-2006 | 175 | 182 | 190 | 150 | 201 |
| Notched impact Strength (kJ/m) 2 ） | GB/T1043-2008 | 14.5 | 16 | 9 | 11 | 9.5 |
Claims (5)
1. A star polyamide characterized by: adding dianhydride as an initiator or an amide exchanger into a polyamide polymerization process, and obtaining star polyamide by initiating monomer polymerization or amide exchange; the preparation method of the star polyamide comprises the following steps:
adding dianhydride into an organic solvent, and performing ultrasonic dispersion for 1-2 hours at 60-80 ℃ to obtain a dianhydride solution;
adding the dianhydride solution obtained in the step (A) into the reaction system for preparing the polyamide, wherein the adding mode is adding in the early stage of polymerization, adding in the middle stage of polymerization or adding in the later stage of polymerization, and reacting for 3-5 h at 140-160 ℃ to obtain star-shaped polyamide; the organic solvent is DMSO; the mass concentration of the dianhydride solution is 10-60 mg/mL; the polymerization method is polycondensation or anionic polymerization; the structural formula of the star polyamide is as follows:
the application of the star polyamide is as follows: for preparing fluorescent materials, polyamide modifiers and solubilizers for carbon materials; the polyamide modifier is used as a lubricant to reduce the viscosity of polyamide, so that the polyamide has higher fluidity; the carbon material solubilizer improves the compatibility of the carbon material and the polyamide matrix interface; the application method of the polyamide modifier comprises the following steps: blending star polyamide and polyamide in a weight ratio of 30-50% to 50-70% by using a double screw extruder, extruding at 230-260 ℃, and granulating by a granulator to obtain a polyamide modifier; the preparation method of the carbon material solubilizer comprises the following steps: mixing star polyamide, polyamide and carbon material in the weight ratio of 5-10% to 50-75% to 20-40% in a double screw extruder at 230-260 deg.c, and pelletizing in a pelletizer to obtain carbon material/polyamide composite material; the dianhydride is pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, perylene-3, 4,9, 10-tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, hexafluoroisopropyl phthalic anhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride or 4,4' -oxydiphthalic anhydride.
2. Star polyamide according to claim 1, characterized in that: the polyamide is polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 46, polyamide 1010, poly (p-phenylene terephthalamide), poly (m-phenylene terephthalamide), or poly (hexamethylene terephthalamide), and copolymers thereof.
3. Star polyamide according to claim 1, characterized in that: the polyamide monomer is caprolactam, adipic acid, hexamethylenediamine, sebacic acid, decanediamine, 1, 4-butanediamine, terephthalic acid or p-xylylenediamine.
4. Star polyamide according to claim 1, characterized in that: the preparation method of the fluorescent material comprises the following steps: adding an auxiliary agent into a polyamide modifier and glass fiber according to the weight ratio of 60-80 percent to 20-40 percent, blending by a double screw extruder, extruding at the temperature of 230-260 ℃, and granulating by a granulator to obtain a glass fiber/polyamide material; the auxiliary agent is a coupling agent KH550, and the dosage of the auxiliary agent is 2-8% of the weight of the glass fiber.
5. Star polyamide according to claim 1, characterized in that: the carbon material is fullerene, carbon nanotube, graphene, carbon black, graphene oxide, graphite mineral powder or coal gangue powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982633.XA CN112661954B (en) | 2019-10-16 | 2019-10-16 | Star polyamide and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982633.XA CN112661954B (en) | 2019-10-16 | 2019-10-16 | Star polyamide and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112661954A CN112661954A (en) | 2021-04-16 |
| CN112661954B true CN112661954B (en) | 2023-05-05 |
Family
ID=75400161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910982633.XA Active CN112661954B (en) | 2019-10-16 | 2019-10-16 | Star polyamide and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661954B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191012B (en) * | 2006-11-21 | 2011-10-26 | 上海普利特复合材料有限公司 | High glazing and high liquidity long glass fiber-reinforced polyamide composite material and preparation method thereof |
| FR2950626B1 (en) * | 2009-09-30 | 2013-11-08 | Rhodia Operations | POLYAMIDES WITH HIGH FLUIDITY |
| CN103665373B (en) * | 2013-11-12 | 2016-08-17 | 金发科技股份有限公司 | A kind of PA10T polyamide and consisting of daiamid composition |
| CN104927085B (en) * | 2015-06-15 | 2018-03-16 | 浙江俊尔新材料股份有限公司 | A kind of multifunctional assistant and preparation method thereof and the application in polyamide compoiste material is prepared |
| CN107987273B (en) * | 2016-10-26 | 2020-07-21 | 中国石油化工股份有限公司 | Polyamide and preparation method and application thereof |
-
2019
- 2019-10-16 CN CN201910982633.XA patent/CN112661954B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112661954A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI395789B (en) | Filled polyamide molding materials showing a reduced water absorption | |
| CN106928413A (en) | A kind of method of styrene maleic anhydride copolymer graft modification Graphene | |
| US4755552A (en) | Impact-resistant polyamide molding compounds | |
| US20140018469A1 (en) | Composite material containing carbon nanotubes and particles having a core-shell structure | |
| CN1712451A (en) | Polymer mixture of aliphatic polyamides and partially aromatic polyamides, moulded articles thereof and use thereof | |
| CN108587146B (en) | Heat-resistant long glass fiber reinforced nylon composite material and preparation method thereof | |
| KR101815577B1 (en) | Polyamide based polymer compositions comprising hyperbranched polyamide having enhanced flowability and preparation method thereof | |
| CN108912659B (en) | Preparation method of crosslinked three-dimensional carbon nano composite polyurethane material | |
| CN112661954B (en) | Star polyamide and application thereof | |
| CN112662169A (en) | High-impact-strength PA6 composite material and preparation method thereof | |
| CN101457019A (en) | Carbon nanotube/polysulfonamide nano composite material and preparation method thereof | |
| CN110835412B (en) | Hyperbranched polymer, preparation method thereof and epoxy resin composition | |
| CN110684347B (en) | Conductive polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN110240805B (en) | Graphene modified polyphenylene sulfide material, preparation method thereof and heat-conducting plastic pipe | |
| CN113831732A (en) | Low-water-absorption high-toughness high-temperature nylon composite material and preparation method thereof | |
| CN102190849B (en) | PA 6 (polyamide 6)/EVA (ethylene-vinyl acetate)/OMMT (organic montmorillonite) super-toughness vibration damping material and manufacturing method thereof | |
| CN109320898B (en) | Nano montmorillonite modified PA6/ABS alloy and preparation method thereof | |
| CN113336980B (en) | Self-reinforcing and toughening polyamide material and preparation method thereof | |
| CN109422957A (en) | A kind of 6 composition of polypropylene/Nylon and preparation method thereof | |
| CN115058074B (en) | Special material for steel pipe lining for hot water pipe and preparation method thereof | |
| JP2021519377A (en) | Polyamide composition, its production method, usage method and articles | |
| CN114196203B (en) | Red phosphorus flame-retardant compound and preparation method and application thereof | |
| CN115044196B (en) | Preparation method of nylon alloy | |
| CN113897038B (en) | High-heat-resistance PBT composition, and preparation method and application thereof | |
| CN115785662B (en) | Composition of polyamide hose for cooling pipe and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |