CN110819105A - Nylon composite material and preparation method and application thereof - Google Patents
Nylon composite material and preparation method and application thereof Download PDFInfo
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- CN110819105A CN110819105A CN201910949494.0A CN201910949494A CN110819105A CN 110819105 A CN110819105 A CN 110819105A CN 201910949494 A CN201910949494 A CN 201910949494A CN 110819105 A CN110819105 A CN 110819105A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a nylon composite material and a preparation method and application thereof. The nylon composite material is prepared from the following raw materials in percentage by weight: 80-90% of polyhexamethylene adipamide, 5-15% of compound toughening agent, 0.1-2% of organic copper salt and 1.5-5% of auxiliary agent; the compound toughening agent is formed by mixing at least two of maleic anhydride grafted polyoctene, ethylene acrylic acid copolymer and polybutene. The nylon composite material can resist high temperature and aging for a long time, can be used as a ribbon material on the periphery of an engine, and has a remarkable shearing and thinning phenomenon, thereby being beneficial to producing ribbon products with complicated injection molding structures and long and narrow flow knives.
Description
Technical Field
The invention relates to the field of polymer composite materials, in particular to a nylon composite material and a preparation method and application thereof.
Background
Nylon (PA66) materials have a superior combination of properties, for example, excellent mechanical strength, stiffness, toughness, mechanical damping and abrasion resistance, as well as good electrical insulation and chemical resistance. This makes the PA66 material a "universal grade" material that can be used in the manufacture of mechanical structural parts and service parts.
At present, a plurality of modified PA66 materials appear on the market, which are good materials for replacing metals such as steel, iron, copper and the like, are also important engineering plastics, can widely replace wear-resistant parts of mechanical equipment and manufacture wear-resistant part transmission structural members, and at present, the shadow of modified PA66 material products can be found in the aspects of household appliances, automobile manufacturing, chemical equipment, mechanical parts and the like.
The automobile cable tie is also an important field of application of nylon materials, however, the cable ties at different positions have different requirements on the performance of the materials, the cable tie at the position far away from an engine has general requirements on the comprehensive performance of the materials, and the cable tie required by the periphery of the engine needs to have long-term high-temperature aging resistance, so that the requirements on the performance of the modified PA66 material are more strict. Meanwhile, for some complex injection molding structures, for example: the single-gate injection mold and the 1 mold 36 are used for rolling the belt, the problem that the nylon material cannot be fully rolled easily occurs when the conventional modified PA66 material passes through the mold, and if pressure is further increased, the grooves of the belt rolling clamp are easily subjected to flash.
Disclosure of Invention
Based on the above, the invention provides a nylon composite material, and a preparation method and application thereof. The nylon composite material can resist high temperature and aging for a long time, can be used as a ribbon material on the periphery of an engine, and has a remarkable shearing thinning phenomenon, thereby being beneficial to producing ribbon products with complicated injection molding structures and long and narrow flow knives.
The specific technical scheme is as follows:
the nylon composite material is prepared from the following raw materials in percentage by weight:
the compound toughening agent is formed by mixing at least two of maleic anhydride grafted polyoctene, ethylene acrylic acid copolymer and polybutene.
The invention also provides a preparation method of the nylon composite material.
The specific technical scheme is as follows:
a preparation method of a nylon composite material comprises the following steps:
and uniformly mixing the polyhexamethylene adipamide, the compound toughening agent, the organic copper salt and the auxiliary agent, and extruding and granulating to obtain the composite material.
Compared with the prior art, the invention has the following beneficial effects:
the nylon composite material is added with a compound toughening agent formed by mixing at least two of maleic anhydride grafted polyoctene, ethylene acrylic acid copolymer and polybutene, and is matched with organic copper salt as a heat-resistant agent, so that the prepared nylon composite material has good mechanical property, and the mechanical residual rate of the material is more than 85% after the material is aged at the high temperature of 140 ℃/1000 h. The high-temperature-resistant and aging-resistant ribbon material can resist high temperature and aging for a long time, can be used as a ribbon material around an engine, and meanwhile, the addition of the compound toughening agent, especially the ethylene acrylic acid copolymer and the polybutylene with a specific proportion is beneficial to enhancing the shearing and thinning phenomena of the nylon composite material, the flowability is good during injection molding, the problems that the existing nylon material cannot be fully injected during injection molding, the pressure ribbon clamping groove is increased, and the flash is easy to occur are solved, and the production of a ribbon product with a complex injection molding structure and long and narrow flow knife is facilitated.
Drawings
FIG. 1 is a graph of shear viscosity versus shear rate for each example and comparative example.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
All the raw materials in the following embodiments are commercially available unless otherwise specified.
The nylon composite material is prepared from the following raw materials in percentage by weight:
the compound toughening agent is formed by mixing at least two of maleic anhydride grafted polyoctene (POE-g-MAH), ethylene acrylic acid copolymer (EAA) and polybutene (PB-1).
It can be understood that the formulation of the compounded toughening agent can have the following conditions:
(1) the compound toughening agent is formed by mixing POE-g-MAH and EAA, preferably, the weight ratio of POE-g-MAH to EAA is 1: (0.5-2), more preferably, the weight ratio of the maleic anhydride grafted polyoctene and the ethylene acrylic acid copolymer is 1: 1.
(2) the compound toughening agent is formed by mixing EAA and PB-1, preferably, the weight ratio of the EAA to the PB-1 is 1: (0.5-2), more preferably, the weight ratio of EAA to PB-1 is 1: 1.
(3) the compound toughening agent is formed by mixing POE-g-MAH and EAA, preferably, the weight ratio of POE-g-MAH to EAA is 1: (0.5-2), more preferably, the weight ratio of POE-g-MAH to EAA is 1: 1.
(4) the compound toughening agent is formed by mixing POE-g-MAH, EAA and PB-1, and preferably, the weight ratio of POE-g-MAH to EAA to PB-1 is (1: 3): (0.5-2): 1, more preferably, the weight ratio of POE-g-MAH to EAA to PB-1 is 2: 1: 1.
the POE-g-MAH can be purchased from Jiangsu Limited company which is a good easy compatilizer, and the product model is CMG 5805L.
The PB-1 is available from Mitsui chemical company under the product model number P5050.
Preferably, the compound toughening agent in the formula (2) is adopted, so that the prepared nylon composite material has more remarkable performance advantage.
In some preferred embodiments, the nylon composite material is prepared from the following raw materials in percentage by weight:
the above-mentioned organic copper salt is used as a heat-resistant agent, and the meaning of the organic copper salt includes organic copper salt and its derivatives. Preferably, the organic copper salt is selected from products produced by Bluggeman, more preferably, the organic copper salt is Bluggeman H3336.
Preferably, polyhexamethylene adipamide (PA66) has a relative viscosity of 2.4 to 2.7, available from Invitrogen corporation as U4800.
It is understood that the nylon material may also be added with an auxiliary agent.
The auxiliary agent is selected from one or more of an antioxidant, a lubricant and a colorant.
Preferably, the antioxidant is prepared by mixing phosphite ester (168) and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (1098).
Lubricants include, but are not limited to, oxidized polyethylene waxes, silicones, and siloxanes. Preferably, the lubricant is selected from oxidized polyethylene wax AC-540A available from Honeywell.
The colorant may be a high temperature resistant toner including, but not limited to, carbon black and titanium dioxide.
After the compound toughening agent and the organic copper salt are added into the PA66, the prepared nylon composite material has good mechanical property, and the mechanical residual rate of the material is more than 85% after the material is aged at the high temperature of 140 ℃/1000 h. Can be high temperature aging resistant for a long time, can regard as the peripheral ribbon material of engine, simultaneously, nylon combined material still has the shear thinning phenomenon that is showing, and mobility is good when moulding plastics, has solved current nylon material and can't beat fully when moulding plastics, increases the problem of pressure ribbon draw-in groove easy overlap again, is favorable to producing ribbon product that injection moulding structure is complicated, the stream sword is long and narrow.
A preparation method of a nylon composite material comprises the following steps:
the PA66, the compound toughening agent, the organic copper salt and the auxiliary agent are uniformly mixed according to a proportion and are placed in a main machine cylinder of a double-screw extruder (the diameter of a screw is 35mm, and the length-diameter ratio L/D is 36), the temperature of the main machine cylinder is controlled to be 230 ℃, 250 ℃, 260 ℃, 270 ℃ and 270 ℃ in nine sections (from a feed inlet to a machine head outlet), the rotating speed of the double screw is 300 revolutions per minute, and extruded material strips are cooled by a water tank and then cut into granules to obtain the product.
The product performance testing method comprises the following steps:
charpy notched impact strength: according to ISO 179-1 method, the specification of the test specimen is as follows: 80 x 10 x 4 mm.
Tensile strength: tested according to ISO527 standard, type 1A.
The aging evaluation means was Q/JL J124010-2016.
The test temperature (140 +/-2) DEG C and the aging time (1000 +/-5) h. After ageing, the specimens were stored for at least 16h in dry conditions (in a drying dish). Spline size: tensile strength 1A type, simple beam notch impact strength (80 +/-2) mmX (10 +/-0.2) mmX (4 +/-0.2) mm (machining notch before aging test).
Rheological properties: measuring viscosity change at different shear rates by Malvern rheometer, and setting the shear rate at 50-4000s at 280 deg.C-1Change in shear viscosity under conditions.
The following is a further description with reference to specific examples.
Examples 1 to 4
Examples 1-4 provide 4 composite tougheners, respectively, and the preparation method comprises mixing the raw materials uniformly according to the formula in table 1.
Table 1 formulation units of compounded tougheners: the weight percentage is%
| Example 1 | Example 2 | Example 3 | Example 4 | |
| POE-g-MAH | 50 | 0 | 50 | 50 |
| EAA | 50 | 50 | 0 | 25 |
| PB-1 | 0 | 50 | 50 | 25 |
Examples 5-8, comparative example 1 and Performance test
The nylon composite materials of examples 5-8 and comparative example 1 were prepared as follows:
the dried PA66, organic copper salt, compound toughening agent, antioxidant, lubricant and colorant are uniformly mixed according to the formula in Table 2, then the mixture is placed in a main machine cylinder of a double-screw extruder (the diameter of a screw is 35mm, and the length-diameter ratio L/D is 36), the temperature of the main machine cylinder is controlled to be 230 ℃, 250 ℃, 260 ℃, 270 ℃ and 270 ℃ in nine sections, the rotating speed of the double screws is 300 r/min, and extruded strips are cooled by a water tank and then cut into particles to obtain the product. After drying the product in a forced air oven at 110 ℃ for 4 hours, the particles were taken for rheology test, the test results are shown in Table 3 and FIG. 1, and the rest were injection molded into standard sample bars at an injection temperature of 250 ℃ and 280 ℃. The injection molded sample bars were immediately placed in a glass desiccator and placed at room temperature for at least 24 hours before performance, long term high temperature aging tests. The test results are shown in Table 2.
Table 2 nylon composite formulations and performance units: the weight percentage is%
As can be seen from Table 2, the nylon materials of examples 5-8 adopt the compound toughening agents of examples 1-4 respectively, and are matched with PA66 and organic copper salt with specific viscosity, and after long-term high-temperature aging resistance experiments, the mechanical retention rate of the product is more than 85%, so that the performance requirements of the ribbon around the engine are met.
Compared with the nylon material in the comparative example 1, the POE-g-MAH is used as the toughening agent, and the organic copper salt heat-resistant agent is not added, so that the long-term high-temperature aging resistance of the product is obviously poor.
The data show that the specific compound toughening agent and the organic copper salt have mutual support and interaction relationship, and the long-term high-temperature aging resistance of the nylon material is improved under the combined action of the specific compound toughening agent and the organic copper salt.
TABLE 3 shear viscosity vs shear rate relationship for nylon composites
As can be seen from table 3 and fig. 1, the reduction of the shear viscosity of the nylon materials of examples 5 to 8 is more obvious along with the increase of the shear rate, especially, the nylon material of example 6 has a very significant shear thinning phenomenon, such a property can solve the problems that the existing nylon material cannot be fully filled during injection molding, and the pressure ribbon clamping groove is increased and is easy to overlap, and has more obvious advantages when the injection molding structure is complex, one mold has more parts, and the flow channel is long and narrow.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The nylon composite material is characterized by being prepared from the following raw materials in percentage by weight:
the compound toughening agent is formed by mixing at least two of maleic anhydride grafted polyoctene, ethylene acrylic acid copolymer and polybutene.
2. The nylon composite material of claim 1, which is prepared from the following raw materials in percentage by weight:
3. the nylon composite material of claim 1, wherein the compounded toughening agent is prepared by mixing an ethylene acrylic acid copolymer and polybutene.
4. The nylon composite of claim 3, wherein the weight ratio of ethylene acrylic acid copolymer to polybutylene is 1: (0.5-2).
5. The nylon composite of claim 1, wherein the polyhexamethylene adipamide has a relative viscosity of 2.4 to 2.7.
6. The nylon composite of any one of claims 1-5, wherein the auxiliary agent is selected from one or more of an antioxidant, a lubricant, and a colorant.
7. The nylon composite of claim 6, wherein the antioxidant is a mixture of phosphite and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
8. The nylon composite of claim 6, wherein the lubricant is selected from one or more of oxidized polyethylene wax, silicone, and siloxane; and/or the presence of a catalyst in the reaction mixture,
the colorant is selected from one of carbon black and titanium dioxide.
9. A method of preparing a nylon composite as claimed in any one of claims 1 to 8, comprising the steps of:
and uniformly mixing the polyhexamethylene adipamide, the compound toughening agent, the organic copper salt and the auxiliary agent, and extruding and granulating to obtain the composite material.
10. Use of the nylon composite of any one of claims 1-8 in automotive cable ties.
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| CN106519663A (en) * | 2016-11-21 | 2017-03-22 | 上海金发科技发展有限公司 | Flame-retardant and high temperature-resistant polyimide compound and preparation method thereof |
| CN108070253A (en) * | 2017-11-29 | 2018-05-25 | 合肥圆融新材料有限公司 | A kind of daiamid composition of high temperature heat-resistant oxygen aging and preparation method thereof |
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2019
- 2019-10-08 CN CN201910949494.0A patent/CN110819105B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858113A (en) * | 2006-03-30 | 2006-11-08 | 上海大学 | Tenacity reinforced nylon and its preparing method |
| CN102115591A (en) * | 2010-12-31 | 2011-07-06 | 广州鹿山新材料股份有限公司 | Toughened nylon blend and preparation method thereof |
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