CN111484737A - High-impact-resistance and high-modulus nylon composite material and preparation method thereof - Google Patents
High-impact-resistance and high-modulus nylon composite material and preparation method thereof Download PDFInfo
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- CN111484737A CN111484737A CN201911322075.0A CN201911322075A CN111484737A CN 111484737 A CN111484737 A CN 111484737A CN 201911322075 A CN201911322075 A CN 201911322075A CN 111484737 A CN111484737 A CN 111484737A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
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- 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
- C08K2003/3045—Sulfates
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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Abstract
The invention discloses a high-impact-resistance and high-modulus nylon composite material which is prepared from the following raw materials in percentage by mass: PA 6655-65%; 25-35% of glass fiber filler; 5-10% of mineral filler; 0.2-1% of a lubricant; 0.4-1% of antioxidant is added into the light-colored product to avoid the yellowing problem of the material in the production process. The PA66 composite material prepared by the method not only retains the characteristics of high modulus, high strength, high hardness and self-lubrication of the original nylon, but also obviously improves the impact strength of the material, meanwhile, the appearance of the product does not have the condition that glass fibers are exposed, and the PA66 composite material can be widely used for automobile intake manifolds and bearings and can also be used as stress parts such as gears and the like due to the excellent surface and dimensional stability of the PA66 composite material. The product of the invention has simple preparation process and lower cost, and is easy to carry out large-scale industrial production.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-impact-resistance and high-modulus nylon composite material and a preparation method thereof.
Background
PA66 has excellent mechanical strength, heat resistance, wear resistance and self-lubricating property, and products are widely used as various mechanical and electrical appliance parts, wherein the parts comprise bearings, gears, pulley pump impellers, blades, high-pressure sealing rings, gaskets, valve seats, bushings, oil conveying pipes, oil reservoirs, ropes, transmission belts, grinding wheel adhesives, battery boxes, electrical coils, cable joints and the like, and with further improvement of national requirements on energy conservation and emission reduction and high-speed development of the Chinese automobile industry, automobile lightweight becomes an important way for energy conservation and emission reduction of automobiles and becomes a mainstream of automobile development, steel is replaced by plastic in one of important directions for automobile lightweight development, original weight is reduced, material use strength is satisfied, and glass fiber reinforced PA66 becomes a first choice for replacing steel.
Problems faced by conventional glass fiber reinforced PA 66: because the notch impact strength of the raw material PA66 is not high, after the reinforced filling is introduced, the notch impact strength of the reinforced plastic is obviously short in all mechanical properties, and a product is damaged due to too low notch, so that the advantage of comparing with other types of reinforced plastics is lost; the surface of the product may lose the self-lubricating property of PA66 along with the increase of the glass fiber filling proportion, and when parts such as gears and the like which need low friction, dimensional stability and the like are manufactured, the PA66 has extremely strong hygroscopicity, so that the dimensional stability is not facilitated after the material absorbs water for a long time; the addition of the filler can effectively improve the dimensional stability, and meanwhile, the coating capability of the filler by the material after the filling proportion is increased is considered.
In view of the above, there is a need for a high impact resistant, high modulus nylon composite.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a high-impact-resistance and high-modulus nylon composite material. The material has high modulus, high impact resistance, high heat resistance, dimensional stability, wear resistance and surface self-lubrication, meets the performance requirements of gears, and has obviously improved notch impact strength and smoother surface of products under the same ash content condition compared with the traditional reinforced PA 66; the traditional compatible toughening agent is not used, the smell of the product is lower, and the product can be used as an automotive interior trim part; and the preparation process is simple, the cost is lower, and the large-scale industrial production is easy to carry out. The technical scheme adopted by the invention is as follows:
the detailed formula of the raw materials comprises the following components in percentage by mass:
PA66 55～65%
25-35% of glass fiber filler
Mineral filler 5-10%
0.2 to 1 percent of lubricant
And adding 0.4-1% of antioxidant into the light-colored product.
1. The PA66 poly hexamethylene adipamide, the notch impact strength of the raw material is 4 KJ/square meter.
2. The glass fiber filler is short glass fiber and comprises continuous fiber and discontinuous fiber.
3. The mineral filler is at least one of carrier-free talcum powder, wollastonite, mica powder and precipitated barium sulfate.
4. The lubricant is one or more of calcium stearate, EBS and PETS.
5. The antioxidant is prepared by compounding hexamethylene dipropionamide antioxidant and isocyanuric acid antioxidant according to the proportion of 1: 1.
6. The preparation process comprises the following steps: adding PA66, a mineral filler, a lubricant and an antioxidant into respective independent hoppers of a main feed in proportion, setting parameters after calculation, adding the materials into a double-screw extruder from the main feed, adding a glass fiber filler from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and glass fiber-exposure-free nylon fiber-added composite material, wherein the processing temperature is 255-270 ℃.
7. The invention has the beneficial effects that:
(1) the glass fiber reinforced PA66 material prepared by the invention has high modulus, high heat resistance, wear resistance and surface self-lubricating property; compared with the traditional glass fiber reinforced PA66, the notch impact of the product is obviously improved, the odor grade of the material can be reduced under the same notch impact strength, and the glass fiber occlusion effect on the surface of the product can reach the best under the same glass fiber filling proportion,
(2) the preparation process is simple, the cost is low, and the large-scale industrial production is easy to carry out.
Detailed Description
The high-impact-resistance and high-modulus nylon composite material comprises the following components in percentage by mass:
PA66 55～65%
25-35% of glass fiber filler
Mineral filler 5-10%
0.2 to 1 percent of lubricant
And adding 0.4-1% of antioxidant into the light-colored product.
1. Preferably, the PA66 raw material needs higher melt mass flow rate, the notch impact strength of the raw material is generally 4 KJ/square meter, more preferably the flat-topped Amur horse PA66(PER27), and the melt mass flow rate is 75g/10 min.
2. Preferably, the glass fiber filler is short glass fiber, and comprises continuous fiber and discontinuous fiber, more preferably, the glass fiber filler is continuous short fiber of giant rock GF, and the monofilament diameter is about 10 microns.
3. Preferably, the mineral filler is at least one of carrier-free talcum powder, wollastonite, mica powder and precipitated barium sulfate, and more preferably, the mineral filler is precipitated barium sulfate with aggregated particles, and the ignition loss is 99%.
4. Preferably, the lubricant is one or more of calcium stearate, EBS and PETS, further preferably PETS from shanghai.
5. Preferably, the antioxidant is prepared by compounding hexamethylene dipropionamide antioxidant and isocyanuric acid antioxidant according to the proportion of 1:1, and further preferably a linaloon antioxidant 1098 and a American Saint Laike antioxidant 3114.
6. Preferably, the preparation process comprises: adding PA66, a mineral filler, a lubricant and an antioxidant into respective independent hoppers of a main feed in proportion, setting parameters after calculation, adding the materials into a double-screw extruder from the main feed, adding a glass fiber filler from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and glass fiber-exposure-free nylon fiber-added composite material, wherein the processing temperature is 255-270 ℃.
The present invention will be further described with reference to specific examples.
The formulation compositions of the examples and comparative examples are shown in Table 1
TABLE 1 formulation composition (in mass%) of examples and comparative examples
| Raw materials | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| PA66 | 58.4 | 58.4 | 58.4 | 58.4 |
| Glass fiber | 40 | 35 | 25 | 30 |
| Mineral substance | 0 | 5 | 15 | 10 |
| Lubricant agent | 1 | 1 | 1 | 1 |
| Antioxidant agent | 0.6 | 0.6 | 0.6 | 0.6 |
In Table 1, PA66 used was PA66(EPR27), glass fiber was chopped continuous fiber of macrostone GF, mineral filler was precipitated barium sulfate of 10 μm, lubricant was PETS, and antioxidant used was 1098 and 3114 in a ratio of 1: 1.
The lubricant and the antioxidant are mixed in proportion, three main feeding hoppers of the equipment are PA66, mineral substances and auxiliary materials (the lubricant and the antioxidant), weightless scale parameters are set in proportion, the main feeding hoppers are added into a double-screw extruder, glass fibers are added from side position materials, the high-modulus, high-strength, high-hardness and high-notch impact glass fiber reinforced nylon composite material is obtained after melting, mixing, extruding, bracing and water cooling granulation, and the processing temperature is 255-270 ℃.
The composite materials obtained after processing were tested by the test standards shown in table two, and table 3 shows the test results of the corresponding examples and comparative examples.
| Detecting items | Unit of | Test standard |
| Tensile strength | Mpa | ISO527-2 |
| Bending strength | Mpa | ISO 178 |
| Flexural modulus | Mpa | ISO 178 |
| Fuse finger | g/10min | ISO 1133 |
| Shrinkage rate | % | ISO 2577 |
| Notched impact strength of cantilever beam | Kj/m2 | ISO 180 |
| Detecting items | Example 1 | Example 2 | Examples3 | Comparative example 1 |
| Tensile strength | 188 | 182 | 151 | 185 |
| Bending strength | 225 | 211 | 195 | 207 |
| Flexural modulus | 10500 | 10200 | 8700 | 9880 |
| Fuse finger | 28 | 29 | 40 | 33 |
| Shrinkage rate | 0.4 | 0.4 | 0.6 | 0.4 |
| Notched impact strength of cantilever beam | 7.5 | 9 | 20 | 18 |
As can be seen from table 3, it can be seen from the detection performance that, when 30% GF and 10% mineral substance are added to a material under the same 40% ash content, the mechanical properties of the material are relatively average, and the surface of a sample piece is observed when the sample piece is manufactured, as the proportion of precipitated barium sulfate is increased, the glass fiber occlusion property on the surface of the product is better, the notch impact strength of the material is higher, but the tensile strength, the bending strength and the modulus are continuously reduced, the data of the comparative example can reach a relatively perfect performance data, the shrinkage rate and the surface effect of the sample piece, in the production of the natural-color glass fiber reinforced product, the color influence of the production process on the natural-color product needs to be noticed, and the yellowing problem of the product can be effectively avoided by considering the low.
It should be understood by those skilled in the art that various changes and modifications can be made to the above embodiments without departing from the scope of the present invention, and any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention are within the scope of the present invention.
Claims (7)
1. A high impact resistant, high modulus nylon composite characterized by: the material is composed of the following raw materials by mass percent:
PA66 55～65%
25-35% of glass fiber filler
Mineral filler 5-10%
0.2 to 1 percent of lubricant
And adding 0.4-1% of antioxidant into the light-colored product.
2. A high impact, high modulus nylon composite according to claim 1, characterized by: the PA66 famous polyhexamethylene adipamide has the notch impact strength of 4KJ per square meter of single raw material.
3. A high impact, high modulus nylon composite according to claim 1, characterized by: the glass fiber filler is short glass fiber.
4. A high impact, high modulus nylon composite according to claim 1, characterized by: the mineral filler is at least one of carrier-free talcum powder, wollastonite, mica powder and precipitated barium sulfate.
5. A high impact, high modulus nylon composite according to claim 1, characterized by: the lubricant is one or more of calcium stearate, EBS and PETS.
6. A high impact, high modulus nylon composite according to claim 1, characterized by: the antioxidant is prepared by compounding hexamethylene dipropionamide antioxidant and isocyanuric acid antioxidant according to the proportion of 1: 1.
7. A high impact, high modulus nylon composite as claimed in any one of claims 1 to 6 wherein: the preparation method comprises the following preparation processes: adding PA66, a mineral filler, a lubricant and an antioxidant into respective independent hoppers of a main feed in proportion, setting parameters after calculation, adding the materials into a double-screw extruder from the main feed, adding a glass fiber filler from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and glass fiber-exposure-free nylon fiber-added composite material, wherein the processing temperature is 255-270 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3173214D1 (en) * | 1980-11-21 | 1986-01-23 | Allied Corp | High impact molding compositions |
| DE4035611A1 (en) * | 1990-11-09 | 1992-05-14 | Basf Ag | Thermoplastic moulding materials |
| CN101875780A (en) * | 2009-11-19 | 2010-11-03 | 深圳市科聚新材料有限公司 | Polyamide composite material and preparation method thereof |
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| CN104672892A (en) * | 2015-03-12 | 2015-06-03 | 苏州隆阁新材料有限公司 | Dedicated nylon composite material for automobile engine cylinder head cover and preparation method thereof |
| CN105504798A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Glass fiber reinforced nylon composite material |
-
2019
- 2019-12-20 CN CN201911322075.0A patent/CN111484737A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3173214D1 (en) * | 1980-11-21 | 1986-01-23 | Allied Corp | High impact molding compositions |
| DE4035611A1 (en) * | 1990-11-09 | 1992-05-14 | Basf Ag | Thermoplastic moulding materials |
| CN101875780A (en) * | 2009-11-19 | 2010-11-03 | 深圳市科聚新材料有限公司 | Polyamide composite material and preparation method thereof |
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| CN104672892A (en) * | 2015-03-12 | 2015-06-03 | 苏州隆阁新材料有限公司 | Dedicated nylon composite material for automobile engine cylinder head cover and preparation method thereof |
| CN105504798A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Glass fiber reinforced nylon composite material |
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Application publication date: 20200804 |