CN111592755B - Enhanced bio-based polyamide 56 composition and preparation method thereof - Google Patents
Enhanced bio-based polyamide 56 composition and preparation method thereof Download PDFInfo
- Publication number
- CN111592755B CN111592755B CN201910131033.2A CN201910131033A CN111592755B CN 111592755 B CN111592755 B CN 111592755B CN 201910131033 A CN201910131033 A CN 201910131033A CN 111592755 B CN111592755 B CN 111592755B
- Authority
- CN
- China
- Prior art keywords
- composition
- bio
- based polyamide
- polyamide
- temperature
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention provides a reinforced bio-based polyamide 56 composition and a preparation method thereof, wherein the reinforced bio-based polyamide 56 composition comprises the following components in parts by weight: 120 portions of polyamide 5680 and 5 to 45 portions of mineral component. The enhanced bio-based polyamide 56 provided by the invention not only adopts renewable substances as main raw materials, is green and environment-friendly, but also has good mechanical properties, heat resistance and dimensional stability. The mineral filler is added to enhance the strength of the polyamide 56, and the polyamide has stable size, does not warp, and has wide application prospect in electronic and electrical connecting pieces and plug-in components.
Description
Technical Field
The invention relates to PA56 resin, in particular to a reinforced bio-based polyamide 56 composition and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Polyamides are widely used as engineering plastics due to their excellent mechanical properties and moldability. The glass fiber reinforced nylon has excellent performance, so that the product is widely applied to daily life and production. With the increasing use amount and demand of reinforced nylon, mineral reinforced nylon is receiving increasing attention. The mineral reinforced nylon is filled reinforced plastic prepared by adding mineral filler into nylon resin and mixing the mixture by an extruder at a temperature higher than the melting point and lower than the decomposition temperature of the resin. Has better rigidity, heat resistance, low shrinkage and lower cost than pure nylon resin, and has better shape stability, namely inflexibility than fiber reinforced nylon.
With the increasing exhaustion of energy sources and the high price of petroleum, the mineral used for reinforcing the bio-based polyamide 56 is an effective way for reducing the cost and protecting the environment.
Disclosure of Invention
The invention provides a reinforced bio-based polyamide 56 composition and a preparation method thereof, wherein renewable substances are used as main raw materials, so that the composition is green and environment-friendly, and has the advantages of high dimensional stability, high heat resistance and high mechanical strength.
It is an object of the present invention to provide a composition for enhancing bio-based polyamide 56.
The reinforced bio-based polyamide 56 composition comprises the following components in parts by weight: 120 portions of polyamide 5680-containing additive and 5-45 portions of mineral components, wherein the mineral components comprise any one or combination of more of montmorillonite, talcum powder, calcium carbonate, calcium sulfate whisker, titanium dioxide and silicon dioxide.
Further, the reinforcing bio-based polyamide 56 composition comprises the following components in parts by weight: 120 portions of polyamide 5680-one, 5-45 portions of mineral components, 0.05-1 portion of lubricant and 0.05-0.5 portion of antioxidant, wherein the mineral components comprise any one or combination of more of montmorillonite, talcum powder, calcium carbonate, calcium sulfate whisker, titanium dioxide and silicon dioxide.
Further, the reinforcing bio-based polyamide 56 composition comprises the following components in parts by weight: 120 portions of polyamide 5680-one, 10 portions to 30 portions of mineral components, 0.05 portion to 1 portion of lubricant and 0.05 portion to 0.5 portion of antioxidant, wherein the mineral components comprise any one or the combination of more of montmorillonite, talcum powder, calcium carbonate, calcium sulfate whisker, titanium dioxide and silicon dioxide.
Further, the reinforcing bio-based polyamide 56 composition comprises the following components in parts by weight: 120 portions of polyamide 5680-one, 10-23 portions of mineral components, 0.05-1 portion of lubricant and 0.05-0.5 portion of antioxidant, wherein the mineral components comprise any one or combination of more of montmorillonite, talcum powder, calcium carbonate, calcium sulfate whisker, titanium dioxide and silicon dioxide.
The types of matrix resin and the types and the contents of mineral components have different influences on the extrusion performance and the injection molding performance of the mineral reinforced plastic and the mechanical performance, the thermal stability, the smoothness and the dimensional stability of an injection molding product. How to improve processability, thermal stability, dimensional stability, etc. while maintaining mechanical properties of nylon has been a problem that those skilled in the art have been trying to solve.
The main raw material adopted by the invention is polyamide 56, PA56 for short, which is prepared by taking pentanediamine from biomass as a raw material and performing a biological fermentation method, for example, lysine is subjected to decarboxylation under the action of decarboxylase. Meanwhile, the PA56 at least partially comprises organic carbon with renewable sources which conforms to the standard of ASTM D6866. Therefore, the polyamide 56 used as the main raw material for the preparation of the present invention is more environmentally friendly. Secondly, PA56 has good mechanical strength, and a certain amount of mineral is added, so that the composition of the bio-based polyamide 56 has high strength, and the rigidity and the strength of the bio-based polyamide 56 are further improved.
The mineral components in the raw materials are distributed in a disordered manner in the matrix and can serve as a nucleating agent, so that the mechanical strength of the enhanced bio-based polyamide 56 composition can be obviously improved, and the crystallization of the bio-based polyamide can be promoted, so that the enhanced bio-based polyamide 56 composition has good dimensional stability after injection molding.
Further, the relative viscosity number of the polyamide 56 is 2.0 to 4.0, preferably 2.5 to 3.5, more preferably 2.5 to 3.0. The relative viscosity number of polyamide 56 was measured using the concentrated sulfuric acid method with an Ubbelohde viscometer: a dried polyamide resin sample (0.5. + -. 0.0002 g) was accurately weighed, dissolved by adding 50mL of concentrated sulfuric acid (98 wt%), and the flow time t0 of the concentrated sulfuric acid and the flow time t of the polyamide resin solution were measured and recorded in a constant temperature water bath at 25 ℃. Relative viscosity calculation formula: relative viscosity η r ═ t/t0 where: t: the solution flow time; t 0: the solvent was run through time.
By controlling the relative viscosity number of the polyamide 56, the mechanical strength of the substrate can be further controlled.
Further, the enhanced bio-based polyamide 56 composition according to any of the above, the mineral component has a particle size of 50 mesh or less, preferably 100 mesh or less, more preferably 200 mesh or less, more preferably 400 mesh or less.
According to some embodiments of the present invention, the mineral component is a combination of calcium sulfate and montmorillonite, and the mass ratio of calcium sulfate to montmorillonite is (1:1) - (6:1), preferably (1:1) - (4:1), and more preferably (2:1) - (3: 1).
According to some embodiments of the invention, the lubricant is selected from any one or a combination of several of montan wax (clariant chemical, model Licowax-e), amide wax (clariant chemical, model Licowax-c), calcium stearate, and Ethylene Bis Stearamide (EBS). When the lubricant of the present invention is a mixture of the above-mentioned substances, the present invention does not limit the ratio between the respective substances.
According to some embodiments of the present invention, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228. When the antioxidant of the present invention is a mixture of the above-mentioned plural substances, the present invention does not limit the ratio between the respective substances.
Further, the composition of the reinforcing bio-based polyamide 56 can be added with other additives according to actual needs, including: any one or a combination of a plurality of light stabilizer, coupling agent, weather resisting agent, anti-hydrolysis stabilizer, pigment, gloss enhancer, delustering agent, plasticizer, antistatic agent, flame retardant, catalyst, end capping agent and anti-ultraviolet absorbent.
The invention also aims to provide a preparation method of the reinforced bio-based polyamide 56 composition, which comprises the following steps:
1) weighing the components in parts by weight, and mixing to obtain a premix;
2) and (3) melting and mixing the premix by using a double-screw extruder, extruding, cooling and granulating to obtain the reinforced bio-based polyamide 56 composition.
In the step 1), after the materials are prepared according to the limited weight part ratio, the components can be uniformly mixed at normal temperature to obtain the premix.
In specific operation, the melt kneading is performed by using a twin-screw extruder, and the mixture is extruded from a nozzle of the twin-screw extruder to obtain a molten strand of the reinforced bio-based polyamide 56 composition. And cooling the molten reinforcing bio-based polyamide 56 composition strand by adopting a water cooling mode to obtain a solid strand, and then cutting the solid strand into particles to obtain the reinforcing bio-based polyamide 56 composition. Further, melt-kneading is carried out by using a twin-screw extruder, and after 3 to 20 minutes, preferably after 5 to 10 minutes, the mixture is extruded from a nozzle of the twin-screw extruder to obtain a molten strand of the reinforced bio-based polyamide 56 composition.
The temperature for melting and mixing in the step 2) is 210-300 ℃.
According to some embodiments of the invention, in the melting and mixing step 2), the twin-screw extruder is in a seven-zone heating mode, the temperature of the first zone is 210-260 ℃, and/or the temperature of the second zone is 240-270 ℃, and/or the temperature of the third zone is 250-280 ℃, and/or the temperature of the fourth zone is 250-280 ℃, and/or the temperature of the fifth zone is 250-290 ℃, and/or the temperature of the sixth zone is 250-290 ℃, and/or the temperature of the seventh zone is 255-285 ℃; wherein the direction from the first area to the seventh area is the direction from the feeding port to the die port. And/or the temperature of the die orifice of the double-screw extruder is 255-285 ℃; and/or the main feeding speed of the double-screw extruder is 15-50 r/min; and/or the screw rotating speed of the double-screw extruder is 250-700 r/min; and/or the length-diameter ratio of the double-screw extruder is 1 (30-50).
The implementation of the invention has at least the following advantages:
1. the composition of the invention takes bio-based PA56 as a main raw material, thereby improving the environmental friendliness. The addition of mineral components to PA56 enhances the mechanical strength and heat resistance of the bio-based polyamide.
2. The mineral component used in the invention can be used as a nucleating agent, so that the crystallization property of PA56 is improved, the demoulding is easy in the injection molding process, the production period is shortened, and the production cost is reduced.
3. The mineral component used in the present invention can improve the flatness of the product.
4. The enhanced preparation method of the enhanced bio-based polyamide 56 composition is simple, the process parameters are easy to control, large instruments are not needed for assistance, and the quantitative production is convenient to carry out.
5. Due to the addition of the mineral filler, the polyamide 56 composition has the advantages of enhanced strength, stable dimension, no warping, application in electronic and electric connectors and inserts, easier connection and easier assembly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The reinforced bio-based polyamide 56 composition of this example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
Montmorillonite: 20 portions (grain size 600 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part
Antioxidant 1098: 0.2 part
The preparation method of the enhanced bio-based polyamide 56 composition of this example comprises the following steps:
1) preparing materials according to the proportion;
2) mixing PA56, mineral component, lubricant and antioxidant to obtain a premix;
3) and (3) melting and mixing the premix by a double-screw extruder, extruding a molten strand by the double-screw extruder after 5-10min, cooling the strand by taking water as a cooling medium to obtain a solid strand, and pelletizing to obtain the reinforced bio-based polyamide 56 composition of the embodiment.
Wherein the double-screw extruder adopts a seven-zone heating mode, and the temperatures of the first zone to the seventh zone (feeding to a die orifice) are 250 ℃, 260 ℃, 275 ℃, 260 ℃, 265 ℃ and 265 ℃ in sequence;
the temperature of the die orifice is 265 ℃;
the main feeding speed is 18 r/min;
the rotating speed of the screw is 480 r/min;
the length-diameter ratio of the double-screw extruder is 1: 40.
The reinforced bio-based polyamide 56 composition of this example was tested as follows:
1. the crystallization peak temperature of the enhanced bio-based polyamide 56 composition will be determined by differential scanning calorimetry (TA, Q2000), wherein the non-isothermal crystallization conditions are: firstly, the temperature is increased from room temperature to 300 ℃ at the speed of 10 ℃/min, the temperature is reduced to the room temperature at the speed of 10 ℃/min after the temperature is kept for 2min, and then the temperature is increased from the room temperature to 300 ℃ at the speed of 10 ℃/min. The test results are shown in Table 1.
2. Also, the reinforced biobased polyamide 56 composition was subjected to mechanical property tests including tensile strength, flexural properties and impact properties tests, wherein the dumbbell test piece size for tensile strength was 170X 10X 4mm (ISO527), the test piece size for flexural strength was 80X 10X 4mm (ISO178), and the test piece notch for impact strength was 2mm impact (ISO 197). The test results are shown in Table 1.
3. The reinforced bio-based polyamide 56 composition was injection molded and the samples obtained from the injection molding were subjected to a heat distortion temperature test (ISO 75-2, 1.8 MPa). The specific test results are shown in table 1.
4. The reinforced bio-based polyamide 56 composition was injection molded and the molded specimens were subjected to the mold shrinkage test (ISO 294.4). The specific test results are shown in table 1.
5, carrying out a thermal decomposition temperature test on the enhanced bio-based polyamide 56 composition, raising the temperature from 30 ℃ to 700 ℃ at 20 ℃/min, and recording the temperature at which the thermal decomposition rate is the fastest, wherein the test result is shown in table 1.
Example 2
The reinforced bio-based polyamide 56 composition of the embodiment comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
Talc powder: 20 portions (grain size 800 mesh)
Montan wax: 0.15 part of
Amide wax: 0.2 part
Antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Example 3
The reinforced bio-based polyamide 56 composition of this example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.75): 100 portions of
CaCO3: 20 portions (grain size 600 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part
The antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Example 4
The reinforced bio-based polyamide 56 composition of the embodiment comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
CaSO4Whisker: 20 portions (grain diameter 600 meshes)
Montan wax: 0.15 part
Amide wax: 0.2 part
Antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Example 5
The reinforced bio-based polyamide 56 composition of this example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
CaSO4Whisker: 15 portions (grain size 600 mesh)
Montmorillonite: 5 portions (grain size 600 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part
The antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Example 6
The reinforced bio-based polyamide 56 composition of this example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
TiO2: 25 parts (grain size 1200 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part of
The antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Example 7
The reinforced bio-based polyamide 56 composition of the embodiment comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
SiO2: 30 portions (grain size 1000 meshes)
Montan wax: 0.15 part
Amide wax: 0.2 part
The antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1 and the results are shown in table 1.
Comparative example 1
The reinforced bio-based polyamide 56 composition of this comparative example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
Montan wax: 0.15 part
Amide wax: 0.2 part
Antioxidant 1098: 0.2 part.
The method of making the enhanced bio-based polyamide 56 composition of this comparative example comprises the steps of:
1) preparing materials according to the proportion;
2) mixing PA56, a lubricant and an antioxidant to obtain a premix;
3) the premix was melt-kneaded by a twin-screw extruder for 5 to 10 minutes, and then a strand was extruded by the twin-screw extruder, and the strand was cooled to a temperature not higher than the melting point of PA56 using water as a cooling medium and cut to obtain the reinforced bio-based polyamide 56 composition of the present example.
Wherein the double-screw extruder adopts a seven-zone heating mode, and the temperatures of the first zone to the seventh zone (feeding to a die orifice) are 250 ℃, 260 ℃, 275 ℃, 260 ℃, 265 ℃ and 265 ℃ in sequence;
the temperature of the die orifice is 265 ℃;
the main feeding speed is 18 r/min;
the rotating speed of the screw is 480 r/min;
the length-diameter ratio of the double-screw extruder is 1: 40.
The enhanced bio-based polyamide 56 composition of this comparative example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1, and the results are shown in table 1. The injection-molded sample of comparative example 1 had a surface that warped significantly and could not be used for electronic and electrical connectors and inserts that had high requirements for dimensional stability and flatness.
Comparative example 2
The enhanced bio-based polyamide 56 composition of this comparative example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
CaSO4Whisker: 50 parts (grain diameter 600 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part
The antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this comparative example was prepared in the same manner as in example 1.
The reinforced bio-based polyamide 56 composition of this comparative example was subjected to the same tests as the reinforced bio-based polyamide 56 composition of example 1, and the results are shown in table 1.
Comparative example 3
The enhanced bio-based polyamide 56 composition of this comparative example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
Montmorillonite: 50 portions (grain size 600 mesh)
Montan wax: 0.15 part
Amide wax: 0.2 part of
Antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this comparative example was prepared in the same manner as in example 1.
The reinforced bio-based polyamide 56 composition of this comparative example was subjected to the same tests as the reinforced bio-based polyamide 56 composition of example 1, and the results are shown in table 1.
Comparative example 4
The enhanced bio-based polyamide 56 composition of this comparative example comprises the following components in parts by weight:
polyamide PA56 (relative viscosity number: 2.80): 100 portions of
CaSO4Whisker: 36 parts (grain size 600 mesh)
Montmorillonite: 12 portions (grain diameter 600 meshes)
Montan wax: 0.15 part
Amide wax: 0.2 part
Antioxidant 1098: 0.2 part.
The reinforced bio-based polyamide 56 composition of this comparative example was prepared in the same manner as in example 1.
The enhanced bio-based polyamide 56 composition of this comparative example was subjected to the same tests as the enhanced bio-based polyamide 56 composition of example 1, and the results are shown in table 1.
Table 1 enhanced bio-based polyamide 56 composition performance test results table
The heat distortion temperature reflects the heat resistance of the material, and the higher the heat distortion temperature is, the better the heat resistance is. As can be seen from Table 1: the addition of the mineral component according to the invention increases the heat distortion temperature of the polyamide 56 compared with comparative example 1. When less than 25 parts of the mineral component was added to examples 1 to 7, the mechanical strength was higher than that of comparative example 1, particularly in that the improvement in flexural strength was significant, as compared with comparative example 1. Although the tensile strength and impact strength of PA56 are slightly reduced when 25 parts and 30 parts of minerals are added in examples 6 and 7, respectively, compared with comparative example 1, the heat resistance of PA56 is obviously improved, and the economic cost is reduced by filling and reinforcing PA56 with the cheap minerals.
In addition, the crystallization peak temperatures of examples 1 to 7 were increased and the half-widths were significantly reduced as compared with comparative example 1. The mineral component added in the invention is used as a nucleating agent in the polyamide matrix, and the crystallization rate of PA56 is improved. The mold is easy to demould in the injection molding process of PA56, and the production period is shortened. The mineral component content in comparative examples 2-4 is high, which leads to difficult demoulding in the injection molding process and long production period, and is not beneficial to mass industrial production. The agglomeration behavior of the resin in the melt extrusion process is influenced by different addition amounts or types of minerals, and for the polyamide resin which is easy to agglomerate, stress concentration and fracture occur in the stretching process, and the impact strength and the tensile strength are reduced, and meanwhile, the gate brittle fracture easily occurs in the injection molding process.
In addition, compared with the comparative example 1, the reinforced bio-based polyamide 56 compositions of examples 1 to 7 have significantly reduced molding shrinkage, improved injection molding sample precision, smooth surface and no warpage, and can meet the requirement of injection molding for a material for electronic and electrical plug-in components with high dimensional stability.
The reinforced bio-based polyamide 56 composition provided by the invention can improve the mechanical strength of the bio-based polyamide PA56, and also improves the heat resistance of the bio-based polyamide PA56, and the crystallization performance and the size are more stable. In addition, the mineral components are added, so that the cost is reduced, the processing technology is simple, and the production is easy.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. The reinforced bio-based polyamide 56 composition is characterized by comprising the following components in parts by weight: 120 parts of polyamide 5680-montmorillonite, and 5-45 parts of a mineral component, wherein the mineral component is a combination of calcium sulfate whisker and montmorillonite, and the mass ratio of the calcium sulfate whisker to the montmorillonite is (1:1) - (6: 1).
2. The enhanced bio-based polyamide 56 composition of claim 1, wherein the composition further comprises: 0.05-1 part of lubricant and 0.05-0.5 part of antioxidant according to parts by weight.
3. The enhanced bio-based polyamide 56 composition of claim 1 or 2, wherein said polyamide 56 has a relative viscosity number of 2.0-4.0.
4. The reinforced bio-based polyamide 56 composition as claimed in claim 1 or 2, wherein the mass ratio of the calcium sulfate whisker to the montmorillonite is (1:1) - (4: 1).
5. The reinforced bio-based polyamide 56 composition as claimed in claim 4, wherein the mass ratio of the calcium sulfate whisker to the montmorillonite is (2:1) - (3: 1).
6. The enhanced bio-based polyamide 56 composition of claim 2, wherein said lubricant is selected from the group consisting of montan wax, amide wax, calcium stearate, and ethylene bis-stearamide in any one or combination of several.
7. The enhanced bio-based polyamide 56 composition as claimed in claim 2, wherein said antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228.
8. The method of preparing the enhanced bio-based polyamide 56 composition of any of claims 1-7, comprising the steps of:
1) weighing the components in parts by weight, and mixing to obtain a premix;
2) and (3) melting and mixing the premix by using a double-screw extruder, extruding, cooling and granulating to obtain the enhanced bio-based polyamide 56.
9. The preparation method of claim 8, wherein in the step 2), the premix is melted, mixed and extruded by a twin-screw extruder to obtain a molten reinforcing bio-based polyamide 56 composition strand; and water-cooling the molten reinforcing bio-based polyamide 56 composition strand, and pelletizing to obtain the reinforcing bio-based polyamide 56 composition.
10. The method as claimed in claim 8 or 9, wherein the temperature for melt-kneading in step 2) is 210-300 ℃.
11. The production method according to claim 8 or 9, wherein the twin-screw extruder is a seven-zone heating mode in which,
the temperature of one zone is 210-260 ℃,
and/or, the temperature of the second zone is 240- & ltSUB & gt and 270- & lt SUB & gt,
and/or the temperature of the three zones is 250-280 ℃,
and/or, the temperature of the four zones is 250-280 ℃,
and/or, the five-zone temperature is 250- & ltSUB & gt 290- & ltSUB & gt,
and/or, the six-zone temperature is 250- & ltSUB & gt 290- & ltSUB & gt,
and/or the temperature of the seven zones is 255-285 ℃;
and/or the temperature of the die orifice of the double-screw extruder is 255-285 ℃;
and/or the main feeding speed of the double-screw extruder is 15-50 r/min;
and/or the screw rotating speed of the double-screw extruder is 250-700 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131033.2A CN111592755B (en) | 2019-02-21 | 2019-02-21 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131033.2A CN111592755B (en) | 2019-02-21 | 2019-02-21 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111592755A CN111592755A (en) | 2020-08-28 |
| CN111592755B true CN111592755B (en) | 2022-07-19 |
Family
ID=72190669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910131033.2A Active CN111592755B (en) | 2019-02-21 | 2019-02-21 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111592755B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881374A (en) * | 2014-03-13 | 2014-06-25 | 上海凯赛生物技术研发中心有限公司 | Reinforced polyamide resin composite material |
| CN104031263A (en) * | 2013-03-08 | 2014-09-10 | 上海凯赛生物技术研发中心有限公司 | Nylon manufacturing method |
| CN105295367A (en) * | 2014-06-27 | 2016-02-03 | 上海凯赛生物技术研发中心有限公司 | Toughened polyamide resin composite material and preparation method therefor |
| CN106147047A (en) * | 2015-03-25 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Elastic composition and preparation method thereof |
| CN106479173A (en) * | 2016-10-28 | 2017-03-08 | 上海耐特复合材料制品有限公司 | Good print performance fire-retardant nylon composite and preparation method thereof |
| CN106867249A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | One kind enhancing static resistant polyamide composite and preparation method thereof |
| CN107915839A (en) * | 2016-10-11 | 2018-04-17 | 东丽先端材料研究开发（中国）有限公司 | A kind of polyamide and preparation method thereof |
| CN108239395A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight reinforced polyamide composition and preparation method thereof |
| CN108239394A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight halogen-free fire-retarding reinforced polyamide composition and preparation method thereof |
| CN108239393A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight daiamid composition and preparation method thereof |
| CN108795033A (en) * | 2017-04-28 | 2018-11-13 | 上海凯赛生物技术研发中心有限公司 | A kind of Flameproof polyamide 5X compositions and preparation method thereof having compared with high fluidity |
| CN108795034A (en) * | 2017-04-28 | 2018-11-13 | 上海凯赛生物技术研发中心有限公司 | A kind of polyamide 5X compositions and preparation method thereof |
| CN109181297A (en) * | 2018-08-31 | 2019-01-11 | 上海凯赛生物技术研发中心有限公司 | 56 resin combination of high fluidity biological poly amide and preparation method thereof |
| CN109306179A (en) * | 2018-09-30 | 2019-02-05 | 杭州本松新材料技术股份有限公司 | Purposes of the polyamide 5X as enhancing thermoplastic compounds apparent mass improver |
| CN109337361A (en) * | 2018-07-27 | 2019-02-15 | 会通新材料股份有限公司 | Daiamid composition with improved appearance and warping characteristic and include the product of the composition |
| CN110054891A (en) * | 2018-01-19 | 2019-07-26 | 上海凯赛生物技术研发中心有限公司 | A kind of 56 master batch of delustring polyamide, delustering fibre and preparation method |
-
2019
- 2019-02-21 CN CN201910131033.2A patent/CN111592755B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031263A (en) * | 2013-03-08 | 2014-09-10 | 上海凯赛生物技术研发中心有限公司 | Nylon manufacturing method |
| CN103881374A (en) * | 2014-03-13 | 2014-06-25 | 上海凯赛生物技术研发中心有限公司 | Reinforced polyamide resin composite material |
| CN105295367A (en) * | 2014-06-27 | 2016-02-03 | 上海凯赛生物技术研发中心有限公司 | Toughened polyamide resin composite material and preparation method therefor |
| CN106147047A (en) * | 2015-03-25 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Elastic composition and preparation method thereof |
| CN107915839A (en) * | 2016-10-11 | 2018-04-17 | 东丽先端材料研究开发（中国）有限公司 | A kind of polyamide and preparation method thereof |
| CN106479173A (en) * | 2016-10-28 | 2017-03-08 | 上海耐特复合材料制品有限公司 | Good print performance fire-retardant nylon composite and preparation method thereof |
| CN108239394A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight halogen-free fire-retarding reinforced polyamide composition and preparation method thereof |
| CN108239395A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight reinforced polyamide composition and preparation method thereof |
| CN108239393A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of lightweight daiamid composition and preparation method thereof |
| CN106867249A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | One kind enhancing static resistant polyamide composite and preparation method thereof |
| CN108795033A (en) * | 2017-04-28 | 2018-11-13 | 上海凯赛生物技术研发中心有限公司 | A kind of Flameproof polyamide 5X compositions and preparation method thereof having compared with high fluidity |
| CN108795034A (en) * | 2017-04-28 | 2018-11-13 | 上海凯赛生物技术研发中心有限公司 | A kind of polyamide 5X compositions and preparation method thereof |
| CN110054891A (en) * | 2018-01-19 | 2019-07-26 | 上海凯赛生物技术研发中心有限公司 | A kind of 56 master batch of delustring polyamide, delustering fibre and preparation method |
| CN109337361A (en) * | 2018-07-27 | 2019-02-15 | 会通新材料股份有限公司 | Daiamid composition with improved appearance and warping characteristic and include the product of the composition |
| CN109181297A (en) * | 2018-08-31 | 2019-01-11 | 上海凯赛生物技术研发中心有限公司 | 56 resin combination of high fluidity biological poly amide and preparation method thereof |
| CN109306179A (en) * | 2018-09-30 | 2019-02-05 | 杭州本松新材料技术股份有限公司 | Purposes of the polyamide 5X as enhancing thermoplastic compounds apparent mass improver |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111592755A (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110452502B (en) | Low-warpage good-appearance high-heat-resistance polyester composite material and preparation method thereof | |
| CN102453306A (en) | High-fluidity PVC/ABS alloy material and preparation method thereof | |
| CN102993668A (en) | Polycarbonate/acrylonitrile-butadiene-styrene (ABS)/polypropylene ternary alloy material and preparation method thereof | |
| CN111621123A (en) | Low-warpage PET/PBT composite material and preparation method thereof | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN111763383B (en) | Good-touch glass fiber reinforced polypropylene composite and preparation method thereof | |
| CN113321873B (en) | Low-shrinkage high-toughness modified polypropylene material and preparation method thereof | |
| CN101469115B (en) | High flowability and high tenacity polycarbonate composition | |
| CN113429781A (en) | Long glass fiber reinforced bio-based polyamide 56, alloy and preparation method thereof | |
| CN112662143A (en) | PBT composition with high elongation at break and preparation method thereof | |
| CN107501717B (en) | Polypropylene filling master batch and preparation method thereof | |
| CN111592755B (en) | Enhanced bio-based polyamide 56 composition and preparation method thereof | |
| CN109438905B (en) | Quaternary blending modified ABS material and preparation method thereof | |
| CN111057376A (en) | Polyphenylene sulfide composite material with low flash | |
| CN110760129A (en) | Polypropylene material with low linear expansion coefficient and preparation method thereof | |
| WO2023160155A1 (en) | Pbt/pet alloy, and preparation method therefor and use thereof | |
| WO2023160154A1 (en) | Pbt/pet composite material, and preparation method therefor and use thereof | |
| CN108795033B (en) | Flame-retardant polyamide 5X composition with high fluidity and preparation method thereof | |
| CN111004476B (en) | Engineering plastic composition and preparation method thereof | |
| CN111057374A (en) | Low-flash rapid crystalline polyphenylene sulfide composite material | |
| CN102516755A (en) | Nylon-based high filling master batch and preparation method thereof | |
| CN111057375A (en) | Polyphenylene sulfide composite material with high strength and low flash | |
| CN114591608B (en) | Glass fiber reinforced PET composition easy to release and preparation method and application thereof | |
| CN112480630A (en) | Good-appearance halogen-free flame-retardant polycarbonate composition for high-speed rail and preparation method thereof | |
| CN112795162A (en) | Easily-sprayed high-rigidity alloy material 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 |