CN110294928B - High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof - Google Patents
High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof Download PDFInfo
- Publication number
- CN110294928B CN110294928B CN201910642993.5A CN201910642993A CN110294928B CN 110294928 B CN110294928 B CN 110294928B CN 201910642993 A CN201910642993 A CN 201910642993A CN 110294928 B CN110294928 B CN 110294928B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- glass
- mineral
- fiber
- gloss
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the field of composite materials, and discloses a polyamide material with high glass mineral fiber content and high gloss, and a preparation raw material, a preparation method and an application thereof. The preparation method of the high-glass mineral fiber high-gloss polyamide material comprises the following steps: s1, uniformly mixing the hydrogen bond inhibitor with optional lubricant and antioxidant in advance to obtain a powder packet; uniformly mixing semi-crystalline polyamide, amorphous polyamide and a powder package to obtain a main material; and S2, feeding the main materials from a main feeding port of the double-screw extruder in a weightless scale metering manner, feeding the glass mineral fibers from a side feeding port of the double-screw extruder in a weightless scale metering manner, and performing melt extrusion, water cooling and grain cutting on the materials in the double-screw extruder to obtain the high-glass mineral fiber high-gloss polyamide material. The polyamide material obtained by the method provided by the invention has high mechanical strength and high glossiness, and is very suitable for being used as a shell type structural component with high requirements on visual sensory effect of the glossiness.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a polyamide material with high glass mineral fiber content and high gloss, and a preparation raw material, a preparation method and an application thereof.
Background
Polyamide (nylon, PA) is an engineering plastic with excellent comprehensive performance. Nylon has high mechanical strength, heat resistance, abrasion resistance, chemical resistance and electrical insulation. The nylon material has wide application in various fields such as automobile industry, electronic and electrical industry, transportation, machinery, aerospace and the like. The high-gloss nylon can obtain excellent appearance effects of products, such as high gloss, metal effect and the like, through direct injection molding. The nylon base material is modified to obtain high mechanical strength and high gloss effect, and can replace part of metal parts, toy parts, household kitchen and bathroom parts and other shell products with good gloss requirement.
Currently, the most commercially used polyamide materials are semi-crystalline polyamide materials such as PA6 and PA 66. The PA6 and PA66 adopt glass fiber, needle-shaped or whisker mineral and other glass mineral fibers for reinforcing, filling and modifying, and can obviously improve the rigidity, heat resistance and mechanical strength of modified materials.
However, in the prior art, modifying materials generally require the addition of large amounts of glass-mineral fibers in order to achieve higher rigidity, heat resistance and mechanical strength. However, the addition of a large amount of glass-mineral fibers, particularly when the amount of glass-mineral fibers added exceeds 50wt%, not only results in a severe deterioration in the surface appearance of the polyamide material, and the occurrence of undesirable phenomena such as fiber floating, but also results in a significant reduction in the gloss of the polyamide material. The existing methods for improving the effect of improving the glossiness of the floating fiber comprise the following steps: 1) the fluidity of the material is improved by using low-viscosity polyamide or a chain scission agent or a branched resin viscosity reducer and the like, so that the phenomenon of fiber floating caused by insufficient fluidity can be avoided to a greater extent; 2) the appearance is improved by reducing the melting point of the semicrystalline polyamide using a low melting point copolymerized polyamide or amorphous polyamide; 3) the use of flat glass fibers also improves the appearance of the product to some extent. However, the modified polyamide materials obtained by the above methods have a drawback that they cannot satisfy both high mechanical strength (e.g., high tensile strength and high notched impact strength) and high gloss.
For example, CN1329448C discloses a polyamide material for high gloss and rigidity, which contains a polyamide mixture of a semi-crystalline linear polyamide, a specific branched graft polyamide, an amorphous polyamide, a reinforcing material and conventional additives. However, although the gloss of the polyamide material obtained by this process is better, it is necessary to add more than 9% or more of branched graft polyamide or amorphous polyamide material to the mixture, and the addition of such materials results in a more pronounced reduction in the dry tensile strength and notched impact strength of the material. For example, CN105419315A discloses a reinforced nylon material with high glass fiber content, which contains 5 to 10% by weight of nylon copolymer and 0.05 to 1% by weight of star-shaped branching agent. However, although the polyamide material obtained by the method has better fluidity and low fiber floating effect, the star-shaped branching agent has negative effects on the dry tensile strength and the notch impact strength of the polyamide material while the viscosity of the nylon is obviously reduced, and the prepared material has lower glossiness. For example, CN108676355A discloses a low-floating-fiber high-gloss glass fiber reinforced polyamide composition, which contains 0.1-10% by mass of nano-filler and 0.08-5.0% by mass of rheology modifier. Although the polyamide material obtained by the method has high fluidity and low fiber floating, the used rheological control agent also adopts hyperbranched resin to reduce viscosity of polyamide so as to achieve the purpose of improving the fluidity of the polyamide material, and the polyamide material is reduced in viscosity through the hyperbranched resin, so that the notch impact strength of the polyamide material in a dry state can be negatively influenced actually.
Disclosure of Invention
The invention aims to overcome the defect that the existing polyamide material with high glass mineral fiber content cannot simultaneously obtain high tensile strength, high notch impact strength and high glossiness, and provides a polyamide material with high glass mineral fiber content and high glossiness, a preparation raw material, a preparation method and an application thereof.
Fiber reinforced polyamides with high glass mineral fiber content can be used to replace parts of metal parts due to their high mechanical strength, rigidity and heat resistance. For example, when the addition amount of the glass-mineral fiber reaches 50% or more, the corresponding glass-mineral fiber polyamide material can obtain high rigidity and tensile strength approaching or even exceeding that of a part of metal. For visual appearance parts, housing type structural parts having high requirements for visual sensory effects of glossiness need to satisfy both high mechanical strength and high glossiness. However, as described above, when the amount of the glass mineral fiber added in the polyamide material reaches 50% or more, the polyamide material obtained by the conventional modification method is inferior in both appearance effect and glossiness effect, or is improved either by sacrificing mechanical strength. The inventors of the present invention have conducted extensive studies and found that modification of a polyamide material having a high fiber content with a metal compound capable of inhibiting hydrogen bonding between the molecular chains of a semicrystalline polyamide can simultaneously achieve high mechanical properties (such as high tensile strength and notched impact strength), high rigidity, and unexpectedly good appearance and gloss effects. Based on this, the present invention has been completed.
The raw materials for preparing the high-glass-mineral-fiber-content high-gloss polyamide material comprise 15-85 wt% of semi-crystalline polyamide, 0-10 wt% of amorphous polyamide, 10-80 wt% of glass mineral fiber and 0.1-5 wt% of a hydrogen bond inhibitor, wherein the hydrogen bond inhibitor is a metal compound capable of inhibiting hydrogen bonds formed between semi-crystalline polyamide molecular chains.
Further, the raw materials for preparing the high-glass-mineral-fiber-content high-gloss polyamide material comprise the following components: 19.5-84 wt% of semi-crystalline polyamide, 0-8 wt% of amorphous polyamide, 15-70 wt% of glass mineral fiber, 0.5-1.5 wt% of hydrogen bond inhibitor, 0.3-0.5 wt% of lubricant and 0.2-0.5 wt% of antioxidant.
Further, the raw materials for preparing the high-glass-mineral-fiber-content high-gloss polyamide material comprise the following components: 20-50 wt% of semi-crystalline polyamide, 0.5-8 wt% of amorphous polyamide, 45-70 wt% of glass mineral fiber, 0.5-1.5 wt% of hydrogen bond inhibitor, 0.3-0.5 wt% of lubricant and 0.2-0.5 wt% of antioxidant.
Further, the semi-crystalline polyamide is at least one selected from the group consisting of PA6, PA66, PA11, PA12, PA46, PA56, PA610, PA612, and PA1010, and preferably is PA 6.
Further, the amorphous polyamide is PA6I and/or PA MACM12, preferably PA 6I.
Further, the relative viscosity R.V. of the semi-crystalline polyamide and the relative viscosity R.V. of the amorphous polyamide are respectively and independently 2.4-2.8.
Further, the glass mineral fiber is selected from at least one of glass fiber, needle-shaped wollastonite and calcium sulfate whisker.
Furthermore, the diameter of the glass mineral fiber is 7-13 mu m, and the length of the glass mineral fiber is 0.2-5 mm.
Furthermore, the glass mineral fibers are chopped glass fibers with the diameter of 7-13 mu m and the length of 3-5 mm.
Further, the hydrogen bond inhibitor is at least one selected from lithium chloride, calcium chloride, zinc chloride and zinc sulfide, and is preferably a compound of zinc chloride and zinc sulfide according to a mass ratio of 1 (5-10).
Further, the lubricant is selected from at least one of stearate, ethylene acrylic acid copolymer and amide lubricant.
Further, the antioxidant is selected from at least one of 1098, 168, 9228, 1010 and H161.
The invention also provides a preparation method of the high-glass-mineral-fiber-content high-gloss polyamide material, wherein the preparation method takes the preparation raw material of the high-glass-mineral-fiber-content high-gloss polyamide material as a raw material and comprises the following steps:
s1, mixing materials: uniformly mixing the hydrogen bond inhibitor with optional lubricant and antioxidant in advance to obtain a powder packet; uniformly mixing the semi-crystalline polyamide, the amorphous polyamide and the powder package to obtain a main material;
s2, melt extrusion granulation: the main material is fed from a main feeding port of the double-screw extruder through a weightlessness scale in a metering manner, the glass mineral fiber is fed from a side feeding port of the double-screw extruder through a weightlessness scale in a metering manner, and the high glass mineral fiber high-gloss polyamide material is obtained after the materials are subjected to melt extrusion, water cooling and grain cutting in the double-screw extruder.
The invention also provides the polyamide material with high glass mineral fiber content and high gloss prepared by the method.
In addition, the invention also provides application of the high-glass-mineral-fiber-content high-gloss polyamide material as a raw material for preparing shell products.
The invention has the following beneficial effects:
according to the invention, the hydrogen bond inhibitor is added into the polyamide material, and the proportion of the materials is reasonably controlled, so that the mechanical property of the reinforced polyamide material can be fully maintained under the conditions of not breaking polyamide molecular chains and reducing the molecular weight, meanwhile, because the hydrogen bonds among the polyamide molecular chains are partially inhibited, the crystallization capacity of the polyamide is reduced, and the glossiness of the polyamide material can be greatly improved. That is, the reinforced polyamide material with high glass mineral fiber content provided by the invention can simultaneously obtain high mechanical properties (such as high tensile strength and notch impact strength), high rigidity and unexpected good appearance and glossiness effects, and can be used for replacing housing products with good glossiness requirements, such as partial metal parts, toy parts, household kitchen and bathroom parts and the like. The reason for this is presumed to be due to: the addition of the hydrogen bond inhibitor can inhibit hydrogen bonds from forming among partial semicrystalline polyamide molecular chains, so that the crystallization speed of the semicrystalline polyamide material can be reduced, the crystallinity of the polyamide is reduced, the flowing and the dispersion of glass mineral fibers in polyamide resin are facilitated, and the fiber floating phenomenon and the glossiness of the polyamide with high fiber content can be improved on the basis of not influencing the mechanical strength of the polyamide material.
Detailed Description
In the present invention, the kinds of the semicrystalline polyamide and the amorphous polyamide are not particularly limited. The semicrystalline polyamide may be a partially crystalline polymer containing an amide group in a repeating unit of a main chain of various macromolecules, and specific examples thereof include, but are not limited to: at least one of PA6, PA66, PA11, PA12, PA46, PA56, PA610, PA612, PA1010 and the like, preferably PA 6. The amorphous polyamide may be a non-crystalline polymer containing amide groups in the repeating units of the main chain of various macromolecules, and specific examples thereof include, but are not limited to: PA6I and/or PA MACM12, preferably PA 6I. The relative viscosity R.V. of the semi-crystalline polyamide and the relative viscosity R.V. of the amorphous polyamide are preferably 2.4-2.8 independently. In the present invention, the test conditions for the relative viscosity include a temperature of 25 ℃ and a reference medium of sulfuric acid with a concentration of 98% by weight. In addition, the content of the semicrystalline polyamide is 15 to 85wt%, preferably 19.5 to 84wt%, and more preferably 20 to 50 wt%. The content of the amorphous polyamide is 0-10 wt%, preferably 0-8 wt%, and more preferably 0.5-8 wt%.
In the present invention, the glass-mineral fibers may be various existing glass fibers and/or mineral fibers capable of being used as a polyamide reinforcing material, and specific examples thereof include, but are not limited to: at least one of glass fiber, needle-shaped wollastonite and calcium sulfate whisker. The diameter of the glass mineral fiber is preferably 7-13 mu m, and the length of the glass mineral fiber is preferably 0.2-5 mm. The glass mineral fiber is particularly preferably chopped glass fiber special for nylon, the diameter of the glass mineral fiber is preferably 7-13 mu m, and the length of the glass mineral fiber is preferably 3-5 mm. In addition, the content of the glass mineral fibers is 10-80 wt%, preferably 15-70 wt%, and more preferably 45-70 wt%.
In the invention, the hydrogen bond inhibitor is a metal compound capable of inhibiting the semi-crystalline polyamide material from forming hydrogen bonds, preferably at least one selected from lithium chloride, calcium chloride, zinc chloride and zinc sulfide, more preferably a compound of zinc chloride and zinc sulfide, and most preferably a compound of zinc chloride and zinc sulfate according to a mass ratio of 1 (5-10). The hydrogen bond inhibitor can slow down the crystallization speed of the polyamide material and reduce the crystallinity of the polyamide, is beneficial to the flowing and the dispersion of glass mineral fibers in the polyamide resin, and further can improve the fiber floating phenomenon and the glossiness of the polyamide material with high fiber content. In addition, the content of the hydrogen bond inhibitor is 0.1-5 wt%, preferably 0.5-1.5 wt%.
The type of the lubricant is not particularly limited in the present invention, and may be various additives capable of improving the lubricating performance of the polyamide material, and specific examples thereof include, but are not limited to: at least one of a stearate, an ethylene acrylic acid copolymer, and an amide-based lubricant. The content of the lubricant is preferably 0.3-0.5 wt%.
In the present invention, the antioxidant may be selected from at least one of 1098, 168, 9228, 1010 and H161. The content of the antioxidant is preferably 0.2-0.5 wt%.
The preparation method of the high-glass mineral fiber high-gloss polyamide material provided by the invention comprises the following steps:
s1, mixing materials: uniformly mixing the hydrogen bond inhibitor with optional lubricant and antioxidant in advance to obtain a powder packet; uniformly mixing the semi-crystalline polyamide, the amorphous polyamide and the powder package to obtain a main material;
s2, melt extrusion granulation: the main material is fed from a main feeding port of the double-screw extruder through a weightlessness scale in a metering manner, the glass mineral fiber is fed from a side feeding port of the double-screw extruder through a weightlessness scale in a metering manner, and the high glass mineral fiber high-gloss polyamide material is obtained after the materials are subjected to melt extrusion, water cooling and grain cutting in the double-screw extruder.
The lubricant and the antioxidant may be selectively added according to actual conditions, and when the lubricant and the antioxidant are not required to be added, the semi-crystalline polyamide, the amorphous polyamide and the hydrogen bond inhibitor may be directly and uniformly mixed in step S1 to obtain the main material.
In step S1, the mixing may be performed by manually stirring or by mechanical mixing using various conventional mixing devices (e.g., high-speed stirrer, low-speed stirrer, etc.). The mixing conditions are such that the above components form a homogeneous system. The purpose of uniformly mixing the semicrystalline polyamide, the amorphous polyamide, the hydrogen bond inhibitor and the optional antioxidant and lubricant before melt extrusion is to ensure that the hydrogen bond inhibitor is sufficiently and uniformly dispersed in the polyamide base stock so as to avoid too high local concentration, thereby being more beneficial to obtain a reasonably controllable ratio of hydrogen bond inhibition effect.
In step S2, the twin-screw extruder includes a main feeding port located at a front section of the twin-screw extruder and a side feeding port located at a generally middle section of the twin-screw extruder. For example, when the twin screw extruder is a twin screw extruder comprising eleven zones to thirteen zones, the main feed port is typically located in one zone and the side feed ports are typically located in five or six zones. The main materials are obtained after polyamide and powder bags are uniformly mixed, and are accurately fed from a main feeding port in a metering weightlessness mode through a scale, and the glass mineral fibers are accurately fed from a side feeding port in a metering weightlessness mode through a scale.
The invention also provides the polyamide material with high glass mineral fiber content and high gloss prepared by the method. The polyamide material with high glass mineral fiber content and high gloss has high mechanical properties (such as high tensile strength and notch impact strength), high rigidity and unexpected good appearance and gloss effects, and can be used for replacing shell products with good gloss requirements, such as partial metal parts, toy parts, household kitchen and bathroom parts and the like.
In addition, the invention also provides application of the high-glass-mineral-fiber-content high-gloss polyamide material as a raw material for preparing shell products.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples and comparative examples: the semicrystalline polyamide was PA6 having a relative viscosity r.v. of 2.4, and the amorphous polyamide was PA6I having a relative viscosity of 2.4. The glass mineral fiber is a chopped glass fiber with a monofilament diameter of 10-13 mu m and a length of 3-5 mm. The hydrogen bond inhibitor is a compound consisting of zinc chloride and zinc sulfide according to the mass ratio of 1: 9. The lubricant is calcium stearate. The antioxidant is 1098. The double-screw extruder is a double-screw extruder with a main feeding port and a side feeding port, in particular to a Ruizian RXT-65 with the length-diameter ratio of 40:1, and comprises eleven zones, wherein the main feeding port is positioned in one zone, and the side feeding port is positioned in five zones.
Examples 1 to 4
S1, mixing materials: putting the hydrogen bond inhibitor, the lubricant and the antioxidant into a high-speed stirrer, mixing for 2min at the rotating speed of 600r/min, and fully and uniformly mixing to form a powder packet for later use; putting PA6, PA6I and the powder packet into a low-speed stirrer, mixing for 5min at the rotating speed of 100r/min, and fully and uniformly mixing to form a main material for later use;
s2, melt extrusion granulation: the main materials are metered and fed from a main feeding port of the double-screw extruder through a weightlessness scale, and the chopped glass fibers are metered and fed from a side feeding port of the double-screw extruder separately through the weightlessness scale; the temperature of each section of the double-screw extruder is respectively as follows: 210 ℃, 235 ℃, 250 ℃, 245 ℃, 235 ℃, 225 ℃, 250 ℃ and 225 ℃, the head temperature is 250 ℃, and the screw rotation speed is 400 r/min; the materials are fully fused under the shearing, mixing and conveying of a screw, and finally the high glass fiber content high gloss polyamide material granules are prepared after extrusion, bracing, water cooling and grain cutting. Wherein the amounts of the components are shown in table 1.
Comparative example 1
Pellets of a polyamide material having a high glass mineral fiber content and a high gloss were prepared according to the method of example 1, except that the hydrogen bond inhibitor was replaced with the same weight part of PA6 resin, and the remaining conditions were the same as in example 1, to obtain pellets of a polyamide material having a high glass mineral fiber content and a high gloss. Wherein the amounts of the components are shown in table 1.
Comparative example 2
Pellets of a polyamide material having a high glass mineral fiber content and a high gloss were prepared according to the method of example 4, except that the hydrogen bond inhibitor was replaced with the same weight part of PA6I resin, and the remaining conditions were the same as in example 4, to obtain pellets of a polyamide material having a high glass mineral fiber content and a high gloss. Wherein the amounts of the components are shown in table 1.
Comparative examples 3 to 4
The preparation method of the high-glass-mineral-fiber-content high-gloss polyamide material granules according to the embodiments 1 to 4 is different from the preparation method of the high-glass-mineral-fiber-content high-gloss polyamide material granules, wherein the gloss is improved mainly by adding amorphous polyamide PA6I and a hyperbranched resin viscosity reducer with a three-dimensional structure (which can reduce entanglement among molecular chains, specifically a morning-source resin-shaped nylon lubricant, and the trademark CYD-701D), and the preparation method comprises the following specific steps:
s1, mixing materials: putting an antioxidant, a lubricant and CYD-701D into a high-speed stirrer, mixing for 2min at the rotating speed of 600r/min, and fully and uniformly mixing to form a powder packet for later use; putting PA6, PA6I and the powder packet into a low-speed stirrer, mixing for 5min at the rotating speed of 100r/min, and fully and uniformly mixing to form a main material for later use;
s2, melt extrusion granulation: the main materials are metered and fed from a main feeding port of the double-screw extruder through a weightlessness scale, and the chopped glass fibers are metered and fed from a side feeding port of the double-screw extruder separately through the weightlessness scale; the temperature of each section of the double-screw extruder is respectively as follows: 210 ℃, 235 ℃, 250 ℃, 245 ℃, 235 ℃, 225 ℃, 250 ℃ and 225 ℃, the head temperature is 250 ℃, and the screw rotation speed is 400 r/min; the materials are fully fused under the shearing, mixing and conveying of the screw, and finally the materials are extruded, pulled into strips, cooled by water and cut into granules to prepare the polyamide material granules with high content of high-gloss glass mineral fibers. Wherein the amounts of the components are shown in table 1.
Test example
The high-glass-mineral-fiber-content high-gloss polyamide material granules obtained in the examples 1 to 4 and the high-glass-mineral-fiber-content high-gloss polyamide material granules obtained in the comparative examples 1 to 4 are dried in a 90 ℃ blast dryer for 4 hours, and then the dried granules are respectively subjected to injection molding at the temperature of 245 to 270 ℃ to obtain test sample bars, wherein the relevant performance test and test method of the test sample bars and the obtained results are shown in table 2.
TABLE 1 amounts of the components (wt%)
TABLE 2
Remarking: in Table 2, + is good, the more + the better; -to a poor degree, -the more and the less good.
As can be seen from the data in Table 2, the samples with the same thickness are prepared in the examples 1-4 and the comparative examples 1-4 by the same injection molding process, and the samples have higher visual transparency due to the addition of the hydrogen bond inhibitor in the examples 1-4, which also shows that the crystallization capacity of the material is reduced after the hydrogen bond inhibitor is added, the crystal growth is limited, and the transparency is increased. Examples 1-4 addition of the hydrogen bond inhibitor partially inhibited the formation of hydrogen bonds between polyamide PA6 molecular chains to some extent, and after the formation of hydrogen bonds was inhibited, the polyamide wasThe crystallization ability of PA6 is also diminished, and the crystallization rate and crystallinity are reduced. The modified polyamide materials obtained in the examples 1-4 have obviously better anti-floating fiber effect and obviously higher 60-degree angle glossiness. In addition, the crystallization peak T of the ordinary 50% glass fiber reinforced PA6 in comparative example 1cThe temperature was about 179 ℃ and the addition of the hydrogen bond inhibitor in example 1 reduced the crystallization peak temperature and crystallization onset temperature of the semicrystalline polyamide PA6 by 6 ℃ and increased the crystallization half-peak width of example 1 by 3 ℃. From the results of comparative examples 2 to 4, it can be seen that the addition of the amorphous polyamide material PA6I and the addition of the viscosity reducer have certain effects on improving the glossiness of the polyamide material, but have great influence on the impact strength of the modified material, and generally improve the glossiness effect. In conclusion, the hydrogen bond inhibitor added in the embodiments 1 to 4 can obtain high glossiness of the high fiber reinforced polyamide material while keeping the toughness of the material to the maximum extent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (13)
1. The raw materials for preparing the high-glass-mineral-fiber-content high-gloss polyamide material are characterized by comprising 15-85 wt% of semi-crystalline polyamide, 0-10 wt% of amorphous polyamide, 10-80 wt% of glass mineral fibers and 0.1-5 wt% of a hydrogen bond inhibitor, wherein the hydrogen bond inhibitor is a metal compound capable of inhibiting hydrogen bonds formed between semi-crystalline polyamide molecular chains, and the hydrogen bond inhibitor is a compound of zinc chloride and zinc sulfide according to a mass ratio of 1 (5-10).
2. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material according to claim 1, wherein the raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material consists of the following components:
semi-crystalline polyamide: 19.5 to 84 wt%;
amorphous polyamide: 0-8 wt%;
glass mineral fiber: 15 to 70wt%
Hydrogen bond inhibitors: 0.5-1.5 wt%;
lubricant: 0.3-0.5 wt%;
antioxidant: 0.2 to 0.5 wt%.
3. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material according to claim 2, wherein the raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material consists of the following components:
semi-crystalline polyamide: 20 to 50 wt%;
amorphous polyamide: 0.5-8 wt%;
glass mineral fiber: 45 to 70wt%
Hydrogen bond inhibitors: 0.5-1.5 wt%;
lubricant: 0.3-0.5 wt%;
antioxidant: 0.2 to 0.5 wt%.
4. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in any one of claims 1 to 3, wherein the semi-crystalline polyamide is at least one selected from PA6, PA66, PA11, PA12, PA46, PA56, PA610, PA612 and PA1010, and the amorphous polyamide is PA6I and/or PA MACM 12; the relative viscosity R.V. of the semi-crystalline polyamide and the relative viscosity R.V. of the amorphous polyamide are respectively and independently 2.4-2.8.
5. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in claim 4, wherein the semi-crystalline polyamide is selected from PA 6.
6. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in claim 4, wherein the amorphous polyamide is PA 6I.
7. The raw material for preparing the high-glass-mineral-fiber high-gloss polyamide material as claimed in any one of claims 1 to 3, wherein the glass mineral fibers are at least one selected from glass fibers, acicular wollastonite and calcium sulfate whiskers.
8. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in claim 7, wherein the glass mineral fibers have a diameter of 7-13 μm and a length of 0.2-5 mm.
9. The raw material for preparing the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in claim 7, wherein the glass-mineral fibers are chopped glass fibers with a diameter of 7-13 μm and a length of 3-5 mm.
10. The raw material for producing the high glass mineral fiber high gloss polyamide material according to claim 2 or 3, characterized in that the lubricant is selected from at least one of stearate, ethylene acrylic acid copolymer and amide-based lubricant; the antioxidant is selected from at least one of 1098, 168, 9228, 1010 and H161.
11. A preparation method of a high-glass-mineral-fiber-content high-gloss polyamide material is characterized in that the preparation method takes the preparation raw material of the high-glass-mineral-fiber-content high-gloss polyamide material as claimed in any one of claims 1 to 7 as a raw material and comprises the following steps:
s1, mixing materials: uniformly mixing the hydrogen bond inhibitor with optional lubricant and antioxidant in advance to obtain a powder packet; uniformly mixing the semi-crystalline polyamide, the amorphous polyamide and the powder package to obtain a main material;
s2, melt extrusion granulation: the main material is fed from a main feeding port of the double-screw extruder through a weightlessness scale in a metering manner, the glass mineral fiber is fed from a side feeding port of the double-screw extruder through a weightlessness scale in a metering manner, and the high glass mineral fiber high-gloss polyamide material is obtained after the materials are subjected to melt extrusion, water cooling and grain cutting in the double-screw extruder.
12. The high glass mineral fiber high gloss polyamide material produced by the method of claim 11.
13. Use of the high glass mineral fiber high gloss polyamide material according to claim 12 as a raw material for the production of shell-like products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910642993.5A CN110294928B (en) | 2019-07-17 | 2019-07-17 | High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910642993.5A CN110294928B (en) | 2019-07-17 | 2019-07-17 | High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110294928A CN110294928A (en) | 2019-10-01 |
| CN110294928B true CN110294928B (en) | 2022-01-21 |
Family
ID=68031292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910642993.5A Active CN110294928B (en) | 2019-07-17 | 2019-07-17 | High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110294928B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322033B (en) * | 2020-10-13 | 2022-08-09 | 天津金发新材料有限公司 | Low-crystallization-temperature high-performance polyamide composite material |
| CN113755006A (en) * | 2021-08-06 | 2021-12-07 | 深圳市骏鼎达新材料股份有限公司 | High-gloss flame-retardant polyamide material and preparation method thereof |
| KR20230166753A (en) * | 2022-05-31 | 2023-12-07 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded product manufactured by the same |
| CN115926452B (en) * | 2022-12-21 | 2024-05-14 | 上海金发科技发展有限公司 | Thin-wall high-light-transmittance flame-retardant nylon composite material and preparation method and application thereof |
| CN116478476B (en) * | 2023-05-06 | 2023-11-28 | 青岛中新华美塑料有限公司 | PP/PA alloy and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000345032A (en) * | 1999-04-02 | 2000-12-12 | Toyobo Co Ltd | Inorganic reinforced polyamide resin composition |
| CN101314672A (en) * | 2008-06-30 | 2008-12-03 | 上海日之升新技术发展有限公司 | High-gloss, low-smell, reinforced nylon composite material and preparation method thereof |
| CN103160117A (en) * | 2011-12-16 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | High-gloss extrusion-grade glass-fiber-reinforced nylon 66 composite material and preparation method thereof |
| CN106700535A (en) * | 2017-02-13 | 2017-05-24 | 上海跃贝塑化科技有限公司 | Glass fiber-reinforced polyamide 66 and semi-aromatic nylon composite material for vehicular structural member and preparation method |
| CN106751793A (en) * | 2016-11-18 | 2017-05-31 | 江苏沃特新材料科技有限公司 | High surface gloss high-dimensional stability polyamide compoiste material and preparation method thereof |
| CN106905693A (en) * | 2017-03-30 | 2017-06-30 | 湖南华曙高科技有限责任公司 | For laser sintered polyamide 6 powder material preparation method |
| CN108676355A (en) * | 2018-05-23 | 2018-10-19 | 江苏金发科技新材料有限公司 | Low floating fine high glaze fiber glass reinforced polyamide composition |
| CN109135276A (en) * | 2018-08-23 | 2019-01-04 | 上海金发科技发展有限公司 | That resist warping high temperature resistant reinforced polyamide composition and preparation method thereof |
| CN109825077A (en) * | 2019-03-14 | 2019-05-31 | 金旸（厦门）新材料科技有限公司 | One kind is heat-resisting to be exempted to spray bloom nylon material and preparation method thereof |
-
2019
- 2019-07-17 CN CN201910642993.5A patent/CN110294928B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000345032A (en) * | 1999-04-02 | 2000-12-12 | Toyobo Co Ltd | Inorganic reinforced polyamide resin composition |
| CN101314672A (en) * | 2008-06-30 | 2008-12-03 | 上海日之升新技术发展有限公司 | High-gloss, low-smell, reinforced nylon composite material and preparation method thereof |
| CN103160117A (en) * | 2011-12-16 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | High-gloss extrusion-grade glass-fiber-reinforced nylon 66 composite material and preparation method thereof |
| CN106751793A (en) * | 2016-11-18 | 2017-05-31 | 江苏沃特新材料科技有限公司 | High surface gloss high-dimensional stability polyamide compoiste material and preparation method thereof |
| CN106700535A (en) * | 2017-02-13 | 2017-05-24 | 上海跃贝塑化科技有限公司 | Glass fiber-reinforced polyamide 66 and semi-aromatic nylon composite material for vehicular structural member and preparation method |
| CN106905693A (en) * | 2017-03-30 | 2017-06-30 | 湖南华曙高科技有限责任公司 | For laser sintered polyamide 6 powder material preparation method |
| CN108676355A (en) * | 2018-05-23 | 2018-10-19 | 江苏金发科技新材料有限公司 | Low floating fine high glaze fiber glass reinforced polyamide composition |
| CN109135276A (en) * | 2018-08-23 | 2019-01-04 | 上海金发科技发展有限公司 | That resist warping high temperature resistant reinforced polyamide composition and preparation method thereof |
| CN109825077A (en) * | 2019-03-14 | 2019-05-31 | 金旸（厦门）新材料科技有限公司 | One kind is heat-resisting to be exempted to spray bloom nylon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110294928A (en) | 2019-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110294928B (en) | High-glass mineral fiber content high-gloss polyamide material and preparation raw materials, preparation method and application thereof | |
| CN102108206B (en) | High-performance nylon resin/calcium sulfate whisker composite material and preparation method thereof | |
| CN107057339A (en) | A kind of activeness and quietness nylon material and its preparation method and application | |
| CN102391432B (en) | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof | |
| CN108034215B (en) | High-low temperature alternating-resistant modified polyester alloy material and preparation method thereof | |
| CN109438975B (en) | High-strength nylon composite material and preparation method thereof | |
| CN111040440B (en) | Low-density high-wear-resistance nylon composite material and preparation method and application thereof | |
| CN104448597A (en) | Preparation method of glass fiber reinforced AS resin | |
| CN111073273A (en) | Glass fiber reinforced PA6 composite material for improving floating fiber and high surface smoothness and preparation method thereof | |
| CN102093705A (en) | High fatigue resistance glass fiber reinforced nylon material and preparation method thereof | |
| CN109401302A (en) | Good surface high impact nylon/POK alloy and preparation method thereof | |
| CN107778853A (en) | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof | |
| CN113429781A (en) | Long glass fiber reinforced bio-based polyamide 56, alloy and preparation method thereof | |
| CN102286201A (en) | High-strength nylon complex and preparation method thereof | |
| CN113980459A (en) | High-rigidity glass fiber reinforced nylon composite material and preparation method thereof | |
| CN1966564A (en) | Reinforced toughening anti-aging polypropylene/nano calcium carbonate composite material and its preparation method | |
| CN102942736B (en) | High-glass fiber content reinforced polypropylene material and preparation method thereof | |
| CN114316586B (en) | Aramid fiber reinforced polyamide composite material and preparation method thereof | |
| CN110746771A (en) | High-flexibility flexible reinforced nylon material and preparation method thereof | |
| CN112745667B (en) | Composite reinforced nylon material and preparation method thereof | |
| CN104629356A (en) | Enhanced semi-aromatic nylon/liquid crystal polymer alloy material and preparation method thereof | |
| CN112662076B (en) | Polypropylene composite material and preparation method thereof | |
| CN105968801A (en) | High-performance modified polyamide composite material and preparation method thereof | |
| CN103571182A (en) | High-fluidity toughened filling nylon and preparation method thereof | |
| CN112812562A (en) | Low-fiber-floating low-warpage high-glass-fiber-content reinforced polyphenylene sulfide composite 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 |