CN114605820B - Reinforced semi-aromatic polyamide composition and preparation method and application thereof - Google Patents
Reinforced semi-aromatic polyamide composition and preparation method and application thereof Download PDFInfo
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- CN114605820B CN114605820B CN202210225303.8A CN202210225303A CN114605820B CN 114605820 B CN114605820 B CN 114605820B CN 202210225303 A CN202210225303 A CN 202210225303A CN 114605820 B CN114605820 B CN 114605820B
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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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- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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
- 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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- 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
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- 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
- C08K7/08—Oxygen-containing compounds
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- 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
- C08K7/10—Silicon-containing compounds
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- 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
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Abstract
The reinforced semi-aromatic polyamide composition comprises the following components in parts by weight: 60 parts of semi-aromatic polyamide resin; 15-60 parts of glass fiber; 5-35 parts of fibrous minerals; 15-45wt% of glass fibers and fibrous minerals with a retention length of less than 300 microns, 50-75wt% of glass fibers and fibrous minerals with a retention length of 300-500 microns, and 1-15wt% of glass fibers and fibrous minerals with a retention length of greater than 500 microns, based on the total weight of glass fibers and fibrous minerals. The invention can reduce the orientation of the fibrous matters by controlling the retention length range of the glass fibers and the fibrous minerals, and realize the balance between the reinforcement and the warping resistance of the composition prepared by an SMT method, thereby obtaining the semi-aromatic polyamide composition with low warping and high reinforcement.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a reinforced semi-aromatic polyamide composition, and a preparation method and application thereof.
Background
Polyamide resins have excellent mechanical strength, heat resistance, chemical resistance, abrasion resistance and self-lubricating properties, and low friction coefficient, and are widely used in the fields of electronics and electricity, automobile parts, furniture, building materials, fibers and the like, and have become one of the most important engineering plastics. Materials used as automobile parts and as electronic components are required to have excellent heat resistance, moldability and low water absorption, and therefore various semiaromatic polyamides having higher heat resistance and lower water absorption have been required to be used.
In recent years, as a method for performing high-density mounting, a lead-free solder for surface mounting has been developed from the viewpoint of environmental protection. The reflow temperature of lead-free solders tends to be higher than the solder temperatures that have been widely used before. When such a Surface Mounting Technology (SMT) is employed, the surface-mounted component must be exposed to a high temperature of 250 ℃ or higher, and thus the resin of the electronic component used for the SMT process must have higher heat resistance. In order to meet the requirements of electronic components on mechanical properties, glass fiber reinforced semi-aromatic polyamide materials are generally selected, and meanwhile, in order to achieve good welding effect, high requirements on warping of the materials are provided.
For the improvement of the warping, the following technical schemes are generally adopted: 1. the technical scheme improves the initial warping in the reinforced semi-aromatic polyamide composition by controlling the narrow distribution of the glass fiber limiting length, but the warping is more obvious after the SMT process because the difference of shrinkage stress in the horizontal and vertical directions caused by the glass fiber orientation in the SMT process is larger. 2. The warp is improved by using the special-shaped glass fiber with the non-circular section, and the warp after the initial and SMT processes is improved, but the technical scheme has relatively high cost and limits the application of the method to a great extent.
Disclosure of Invention
The invention aims to provide a reinforced semi-aromatic polyamide composition, which has the advantages of low warpage and high reinforcement.
Another object of the present invention is to provide a process for preparing the reinforced semi-aromatic polyamide composition and its use.
The invention is realized by the following technical scheme:
the reinforced semi-aromatic polyamide composition comprises the following components in parts by weight:
60 parts of semi-aromatic polyamide resin;
15-60 parts of glass fiber;
5-35 parts of fibrous minerals;
15-45wt% of glass fibers and fibrous minerals with a retention length of less than 300 microns, 50-75wt% of glass fibers and fibrous minerals with a retention length of 300-500 microns, and 1-15wt% of glass fibers and fibrous minerals with a retention length of greater than 500 microns, based on the total weight of glass fibers and fibrous minerals.
Preferably, the retained length of glass fibers and fibrous minerals is 25-35wt%, glass fibers and fibrous minerals 300-500 microns are 55-70wt%, and glass fibers and fibrous minerals greater than 500 microns are 5-10wt%, based on the total weight of glass fibers and fibrous minerals.
The test method for reinforcing the retention length distribution of glass fibers and fibrous minerals of the resin matrix of the semi-aromatic polyamide composition comprises the following steps: the reinforced semi-aromatic polyamide composition is subjected to ISO 3451-1 standard to obtain ash content of the composition, the ash content is placed in 100ml of industrial alcohol with the concentration of 95% for ultrasonic dispersion for 2min, then 2ml of the ash content is sucked from the bottom by a pipette and placed on a clean glass slide, the length of glass fiber and fibrous mineral is measured by photographing with an optical microscope at 500 times magnification, and the length, distribution and weight ratio of the glass fiber and the fibrous mineral are calculated by a statistical method.
The semi-aromatic polyamide resin is selected from at least one of PA6T/66, PA6I, PA T/6I, PA T/M5T, PA9T, PA T/66, PA10T, PA T/66, PA10T/10I, PA10T/1010 and PA12T, PA 12I.
The viscosity of the semiaromatic polyamide is not particularly limited in the present invention, and the object of the present invention can be achieved by finding that the semiaromatic polyamide has a relative viscosity in the range of 1.8 to 2.5 through experiments.
The fibrous mineral is at least one selected from alumina fiber, carbon fiber, potassium titanate fiber, boric acid fiber, quartz fiber and wollastonite fiber.
The composition also comprises 0-1 part of dendritic polyamide by weight. For example, a dendrimer is one of the dendrimers, which is a linear polymer with dendron units on each repeating unit. Dendritic units are highly branched structures containing very good geometric symmetry and a large number of surface functional groups. The highly branched structure of the dendritic units results in less intermolecular chain entanglement, with low melt viscosity characteristics. In addition, the regular arrangement of molecular chains can be reduced, so that the crystallization performance of the material is weakened.
The lubricant also comprises 0-2 parts of auxiliary agent according to parts by weight, wherein the auxiliary agent is at least one selected from a lubricant and an antioxidant.
The lubricant may be sodium montanate, stearate, or the like.
A process for preparing a reinforced semi-aromatic polyamide composition comprising the steps of: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, the glass fiber is added by side feeding, the rotating speed of the screw is 200-500 revolutions per minute, and the temperature is 270-330 ℃, so that the reinforced semi-aromatic polyamide composition is obtained.
The application of the reinforced semi-aromatic polyamide composition is used for preparing automobile parts and electronic components by an SMT method.
The invention has the following beneficial effects
The invention can obviously reduce the shrinkage stress difference in the horizontal and vertical directions caused by glass fiber orientation in the SMT process by controlling the size difference of fiber objects and the distribution proportion of a plurality of different glass fiber sizes in the fiber reinforced semi-aromatic polyamide resin composition, and has obvious influence on the warpage of the composition in the initial and SMT processes, so that the reinforced semi-aromatic polyamide composition has the advantages of low warpage and high reinforcement. Further, warpage caused by the SMT process can be significantly improved by adding a dendritic polyamide.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
PA6T/66: relative viscosity 2.1, jinfa technologies, inc., vicnyl 400 NC003;
PA6T/6I: relative viscosity 2.0, jinfa technologies, inc., vicnyl 500 NC003;
PA10T: relative viscosity 2.1, jinfa technologies Co., ltd., vicnyl 700 NC001;
glass fiber: ECS301HP-3-H, length range 3-6 mm, chongqing International;
wollastonite fiber: activated wollastonite mineral fiber, gray-white fiber, with an initial average length of 20 microns, jiangxi Hua Jie Tay mineral fiber technologies Co., ltd;
potassium titanate fiber: TISMO D102, 10-20 microns in length, otsuka chemistry.
And (3) a lubricant: stearate, commercially available, was used in parallel experiments with the same lubricant.
Dendritic polyamide: CYD-816A, wired morning original molecular New Material Co.
Examples and comparative examples enhanced semi-aromatic compositions were prepared: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, the screw is divided into 12 areas, the glass fiber is fed from two sides (the side feeding area is shown in a table), the rotating speed range of the screw is 200-500 r/min, and the temperature range is 110-300-330-320-300-290-280-270-270-280-300-330 ℃, so that the reinforced semi-aromatic polyamide composition is obtained.
The testing method comprises the following steps:
(1) Retention length distribution of glass fibers and fibrous minerals (abbreviated as retention length distribution in the table): the test method for reinforcing the retention length distribution of glass fibers and fibrous minerals of the resin matrix of the semi-aromatic polyamide composition comprises the following steps: the reinforced semi-aromatic polyamide composition is subjected to ISO 3451-1 standard to obtain ash content of the composition, the ash content is placed in 100ml of industrial alcohol with the concentration of 95% for ultrasonic dispersion for 2min, then 2ml of the ash content is sucked from the bottom by a pipette and placed on a clean glass slide, the length of glass fiber and fibrous mineral is measured by photographing with an optical microscope at 500 times magnification, and the length, distribution and weight ratio of the glass fiber and the fibrous mineral are calculated by a statistical method.
(2) Warpage performance test: the composition was injection molded on an injection molding machine to test square plaques of 100mm by 1.5mm at an injection molding temperature of 330℃and a mold temperature of 100 ℃. The square plate is regulated for 24 hours under the environment of 23 ℃/50% R.H., and the initial warping value is tested; the square plates are placed on a horizontal plane, the distances from the other three angles to the horizontal plane are measured by pressing the four angles of the square plates respectively, the maximum distance value is taken as the warpage value of a single square plate, and the average value of 5 square plates is measured in parallel to obtain the warpage value of the composition. The board with the initial warpage value measured is then subjected to a reflow test, the peak temperature of the reflow is 260 ℃, the time above 200 ℃ is about 200s, and the whole reflow period is 300s. And naturally cooling the square board subjected to the reflow soldering test for 2 hours, and then measuring the warpage value of the composition again, wherein the warpage value is the SMT post-warpage value.
(3) Tensile strength: test conditions were determined according to ISO 527-2-2019, temperature 23 ℃; the stretching rate was 10mm/min.
Table 1: examples 1-7 reinforced semiaromatic Polyamide composition component content (parts by weight) and test results
Table 2: examples 8-12 and comparative examples enhanced semiaromatic polyamide composition component content (parts by weight) and test results
From examples 1/8 to 12, it was found that the retention length of the glass fiber and the fibrous mineral was controlled by controlling the addition amount of the glass fiber, the addition amount of the fibrous mineral, the side feeding region and the ratio of the glass fiber, and the screw speed, to obtain a reinforced semiaromatic polyamide composition excellent in warpage, SMT processing resistance, and tensile strength. In particular, although the initial warpage of example 10 was low, since the length content thereof greater than 500mm was too low, the post-SMT warpage was high, and it was found that the fiber amounts of the respective length distributions had a synergistic effect against the initial warpage and the post-SMT warpage.
Continuing with table 2:
as is clear from examples 1/13/14, the dendritic polyamide can significantly improve the warpage and increase the tensile strength.
As is clear from comparative example 1, when the content of the fiber distributed over 500 μm is too low, the difference in shrinkage stress is large, which results in not only high post-SMT warp but also low tensile strength.
As is clear from comparative example 2, when the fiber content of more than 500 μm distribution is too high, the tensile strength is high but the warping property is poor.
As is clear from comparative example 3, even if the length distribution of glass fibers is within the scope of the present invention by adjusting the preparation process without adding mineral fibers, the difference in shrinkage stress in the horizontal and vertical directions due to the orientation of glass fibers during SMT cannot be reduced.
Claims (8)
1. The reinforced semi-aromatic polyamide composition is characterized by comprising the following components in parts by weight:
60 parts of semi-aromatic polyamide resin;
15-60 parts of glass fiber;
5-35 parts of fibrous minerals;
15-45wt% of glass fibers and fibrous minerals with a retention length of less than 300 microns, 50-75wt% of glass fibers and fibrous minerals with a retention length of 300-500 microns, and 1-15wt% of glass fibers and fibrous minerals with a retention length of more than 500 microns, based on the total weight of the glass fibers and fibrous minerals;
the fibrous mineral is at least one selected from alumina fiber, potassium titanate fiber, boric acid fiber, quartz fiber and wollastonite fiber.
2. The reinforced semiaromatic polyamide composition of claim 1, wherein the retained length of glass fibers and fibrous minerals is less than 300 microns by weight, 25-35% by weight, 300-500 microns by weight, 55-70% by weight, and greater than 500 microns by weight, 5-10% by weight, based on the total weight of glass fibers and fibrous minerals.
3. The reinforced semi-aromatic polyamide composition according to claim 1, wherein the semi-aromatic polyamide resin is selected from at least one of PA6T/66, PA6I, PA T/6I, PA T/M5T, PA9T, PA9T/66, PA10T, PA10T/66, PA10T/10I, PA T/1010, PA12T, PA I.
4. The reinforced semi-aromatic polyamide composition according to claim 1, wherein the semi-aromatic polyamide has a relative viscosity ranging from 1.8 to 2.5.
5. The reinforced semiaromatic polyamide composition of claim 1, further comprising 0-1 parts by weight of a dendritic polyamide.
6. The reinforced semi-aromatic polyamide composition according to claim 1, further comprising 0 to 2 parts by weight of an auxiliary agent selected from at least one of a lubricant and an antioxidant.
7. A process for the preparation of a reinforced semi-aromatic polyamide composition according to any one of claims 1 to 6, characterized in that it comprises the following steps: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, the glass fiber is added by side feeding, the rotating speed of the screw is 200-500 revolutions per minute, and the temperature is 270-330 ℃, so that the reinforced semi-aromatic polyamide composition is obtained.
8. Use of the reinforced semi-aromatic polyamide composition according to any one of claims 1 to 6 for the preparation of automotive parts, electronic components.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013571A (en) * | 2008-07-04 | 2010-01-21 | Toyobo Co Ltd | Fiber-reinforced polyamide resin composition |
| CN102321361A (en) * | 2011-08-04 | 2012-01-18 | 金发科技股份有限公司 | Low-warpage halogen-free flame retardant reinforced polyamide composite material |
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN108586733A (en) * | 2018-04-08 | 2018-09-28 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it |
| CN112759923A (en) * | 2020-12-25 | 2021-05-07 | 金发科技股份有限公司 | Glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length and molded product |
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- 2022-03-09 CN CN202210225303.8A patent/CN114605820B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013571A (en) * | 2008-07-04 | 2010-01-21 | Toyobo Co Ltd | Fiber-reinforced polyamide resin composition |
| CN102321361A (en) * | 2011-08-04 | 2012-01-18 | 金发科技股份有限公司 | Low-warpage halogen-free flame retardant reinforced polyamide composite material |
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN108586733A (en) * | 2018-04-08 | 2018-09-28 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it |
| CN112759923A (en) * | 2020-12-25 | 2021-05-07 | 金发科技股份有限公司 | Glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length and molded product |
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