CN112143224A - Anti-yellowing high-heat-resistance high-dimensional-stability PPA material and preparation method thereof - Google Patents

Anti-yellowing high-heat-resistance high-dimensional-stability PPA material and preparation method thereof Download PDF

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CN112143224A
CN112143224A CN202011035544.3A CN202011035544A CN112143224A CN 112143224 A CN112143224 A CN 112143224A CN 202011035544 A CN202011035544 A CN 202011035544A CN 112143224 A CN112143224 A CN 112143224A
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resistant
yellowing
parts
dimensional stability
ppa
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曾方岑
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XIANGTAN LINHAI MACHINERY MANUFACTURING CO LTD
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XIANGTAN LINHAI MACHINERY MANUFACTURING CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/03—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
    • 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
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a PPA material with yellowing resistance, high heat resistance and high dimensional stability and a preparation method thereof, and the PPA material is a composite material discussed in the invention; the composition comprises the following components in parts by weight: 100 parts by weight of polyphthalamide raw material, 0.5-40 parts by weight of polyamide 66, 0.3-60 parts by weight of filling reinforcing agent, 4-20 parts by weight of titanium dioxide, 5-40 parts by weight of main flame retardant, 0.5-20 parts by weight of auxiliary flame retardant, 0.1-50 parts by weight of lubricant and the balance of ultramarine, toughening agent, antioxidant, stabilizer and coupling agent; the preparation method comprises the steps of high-speed mixing, melt extrusion, injection molding and the like; the product prepared by the invention has yellowing resistance, high heat resistance and high dimensional stability. The material can be widely applied to the fields of LED lamp supports, heat-resistant electric appliance shells and the like.

Description

Anti-yellowing high-heat-resistance high-dimensional-stability PPA material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a PPA material with yellowing resistance, high heat resistance and high dimensional stability and a preparation method thereof.
Background
Polyphthalamide (PPA) is semi-aromatic polyamide which takes terephthalic acid or phthalic acid as raw materials, is semi-crystalline thermoplastic aromatic polyamide, is commonly called aromatic high-temperature nylon, is a high-temperature resistant material, and has a melting point of 310-325 ℃. PPA has the following basic properties: 1. stronger and harder than fatty polyamides such as PA 66; 2. lower sensitivity to moisture and better thermal performance; 3. creep resistance, fatigue resistance and chemical resistance are excellent; 4. the PPA resin reinforced by the glass fiber has very high heat distortion temperature and can resist the short-term action of very high temperature; 5. under normal environmental conditions, PPA resins generally exhibit good resistance to aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, esters, ketones, alcohols, and most aqueous solutions.
The appearance of PPA fills the gap between traditional engineering plastics and high-cost special polymers in cost and performance. The thermal deformation temperature of PPA is up to more than 300 ℃, and the continuous use temperature can reach 170 ℃. Pure PPA is opaque and white, and the PPA product is in a crystalline state and an amorphous state, and the maximum crystallinity is 20.3%. The PPA resin modified by glass fiber, carbon fiber or other inorganic fillers has good mechanical properties and can maintain the properties in a wide temperature range. Therefore, the PPA serving as an excellent engineering plastic capable of replacing metal has a very wide application prospect in the industries of electronics, electric appliances, automobiles and the like.
LED lamp supports, heat-resistant electrical appliance shells and the like are the main application fields of PPA materials, and the whiteness requirements of the materials of the products are strict. However, the processing temperature of PPA is above 300 ℃, so that thermal oxidation aging is easy to occur during the processing process, which causes the PPA product to turn yellow and the mechanical property to be poor.
Disclosure of Invention
The invention aims to provide a PPA material with good dimensional stability, easy processing, yellowing resistance, high heat resistance and high dimensional stability and a preparation method thereof, aiming at the defects of the prior art.
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following raw materials in parts by weight (1 part is 100 g, the same below):
Figure BDA0002704969600000011
Figure BDA0002704969600000021
watch 1
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the polyphthalamide is semi-crystalline resin.
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the filling reinforcing agent is alkali-free glass fiber. Because the reinforcing effect of the short glass fiber on the material is not as good as that of the long glass fiber, the long glass fiber is preferred for obtaining better mechanical property.
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the main flame retardant is a halogen-free flame retardant, and preferably hypophosphite.
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the auxiliary flame retardant is anhydrous zinc borate.
In the above-mentioned yellowing-resistant, high-heat-resistant and high-dimensional stability PPA material, the antioxidant is a composite antioxidant: h3373, inorganic phosphate antioxidant; h10, compound antioxidant; at least one of KBG 779.
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the coupling agent is a silane coupling agent KH-550.
In the PPA material with yellowing resistance, high heat resistance and high dimensional stability, the ultramarine pigment is the oldest and most bright blue pigment, is non-toxic and environment-friendly, and belongs to the category of inorganic pigments. It is used for whitening and eliminating yellow light in white paint or other white pigment.
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the lubricant is Wacker silicone or EBS (ethylene bis stearamide).
In the yellowing-resistant, high-heat-resistant and high-dimensional-stability PPA material, the toughening agent is ethylene-methyl acrylate-glycidyl methacrylate terpolymer (GMA).
In the PPA material with yellowing resistance, high heat resistance and high dimensional stability, the stabilizer is PA nylon multifunctional stabilizer SEED.
The preparation method of the yellowing-resistant high-heat-resistance high-dimensional stability PPA material comprises the following steps: the preparation method comprises the following steps of firstly, dry-mixing the raw materials in a high-speed mixer for 10-12 minutes, and then putting the mixture into a double-screw extruder to be subjected to melt extrusion, cooling, grain cutting and packaging to obtain a finished product; the temperature of a first area of the double-screw extruder is 200-220 ℃, the temperature of a second area is 300-320 ℃, the temperature of a third area is 300-320 ℃, the temperature of a fourth area is 280-300 ℃, the temperature of a fifth area is 275-325 ℃, the residence time is 1-2 minutes, and the pressure is 10-15 MPa.
Compared with the prior art, the invention mainly has the following main advantages: the processing rheological property, the high temperature resistance and the dimensional stability of the PPA material are improved, the yellowing resistance of the PPA material in a high-temperature environment is improved, and the surface appearance of the PPA material is improved.
Detailed Description
Example one
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following components in percentage by weight:
Figure BDA0002704969600000022
Figure BDA0002704969600000031
watch two
Pouring the prepared components into a stirrer, uniformly stirring, placing into a double-screw extruder, rotating the screw at 40Hz, and setting the temperature as follows: extruding and granulating at the temperature of 210 ℃ in the first zone, 320 ℃ in the second zone, 310 ℃ in the third zone, 290 ℃ in the fourth zone and 325 ℃ in the fifth zone to obtain the yellowing-resistant PPA material with high heat resistance and high dimensional stability.
And (3) performance test results:
Figure BDA0002704969600000032
watch III
Example two
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following components in percentage by weight:
Figure BDA0002704969600000033
Figure BDA0002704969600000041
watch four
Pouring the prepared components into a stirrer, uniformly stirring, placing into a double-screw extruder, rotating the screw at 40Hz, and setting the temperature as follows: extruding and granulating at the temperature of 210 ℃ in the first zone, 320 ℃ in the second zone, 310 ℃ in the third zone, 290 ℃ in the fourth zone and 325 ℃ in the fifth zone to obtain the yellowing-resistant PPA material with high heat resistance and high dimensional stability.
And (3) performance test results:
Figure BDA0002704969600000042
watch five
EXAMPLE III
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following components in percentage by weight:
Figure BDA0002704969600000043
Figure BDA0002704969600000051
watch six
Pouring the prepared components into a stirrer, uniformly stirring, placing into a double-screw extruder, rotating the screw at 40Hz, and setting the temperature as follows: extruding and granulating at the temperature of 210 ℃ in the first zone, 320 ℃ in the second zone, 310 ℃ in the third zone, 290 ℃ in the fourth zone and 325 ℃ in the fifth zone to obtain the yellowing-resistant PPA material with high heat resistance and high dimensional stability.
And (3) performance test results:
Figure BDA0002704969600000052
watch seven
The invention adopts a proper compatilizer, improves the compatibility between PPA and glass fiber, and optimizes the processing performance of the alloy material. Compared with the prior art, the three samples are bright and white in color and have no obvious yellowing phenomenon, so that the yellowing phenomenon of the product is solved, and the size stability and the heat resistance of the PPA are improved.
Comparative example I (without addition of antioxidant)
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following components in percentage by weight:
Figure BDA0002704969600000053
Figure BDA0002704969600000061
table eight
Pouring the prepared components into a stirrer, uniformly stirring, placing into a double-screw extruder, rotating the screw at 40Hz, and setting the temperature as follows: extruding and granulating at the temperature of 210 ℃ in the first zone, 320 ℃ in the second zone, 310 ℃ in the third zone, 290 ℃ in the fourth zone and 325 ℃ in the fifth zone to obtain the yellowing-resistant PPA material with high heat resistance and high dimensional stability.
And (3) performance test results:
Figure BDA0002704969600000062
watch nine
Compared with the first to third examples, the antioxidant is not contained in the formula, the melt index of the PPA is slightly improved, the PPA is partially degraded, and the properties such as impact strength, bending strength and tensile strength are reduced, so that the antioxidant used in the invention is obviously helpful for the mechanical properties of the PPA composition.
Comparative example two (No flame retardant added)
The PPA material with yellowing resistance, high heat resistance and high dimensional stability comprises the following components in percentage by weight:
Figure BDA0002704969600000063
Figure BDA0002704969600000071
watch ten
Pouring the prepared components into a stirrer, uniformly stirring, placing into a double-screw extruder, rotating the screw at 40Hz, and setting the temperature as follows: extruding and granulating at the temperature of 210 ℃ in the first zone, 320 ℃ in the second zone, 310 ℃ in the third zone, 290 ℃ in the fourth zone and 325 ℃ in the fifth zone to obtain the yellowing-resistant PPA material with high heat resistance and high dimensional stability.
And (3) performance test results:
Figure BDA0002704969600000072
watch eleven
Compared with the first to third examples, the flame retardant is not added in the formula, and the flame retardant performance of the PPA blending material is obviously reduced and can only reach the HB level.
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 PPA material with yellowing resistance, high heat resistance and high dimensional stability is characterized by comprising the following components in parts by mass: 100 parts of polyphthalamide raw material, 0.5-40 parts of polyamide 66, 0.3-60 parts of filling reinforcing agent, 4-20 parts of titanium dioxide, 5-40 parts of main flame retardant, 0.5-20 parts of auxiliary flame retardant, 0.1-50 parts of lubricant and the balance of ultramarine, toughening agent, antioxidant, stabilizer and coupling agent.
2. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 1, wherein: the polyphthalamide is semi-crystalline resin.
3. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 2, wherein: the filling reinforcing agent is alkali-free glass fiber. Because the reinforcing effect of the short glass fiber on the material is not as good as that of the long glass fiber, the long glass fiber is preferred for obtaining better mechanical property.
4. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 3, wherein: the main flame retardant is a halogen-free flame retardant, preferably hypophosphite; the auxiliary flame retardant is anhydrous zinc borate.
5. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 4, wherein: the antioxidant is a compound antioxidant: h3373, inorganic phosphate antioxidant; h10, compound antioxidant; at least one of KBG 779.
6. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 5, wherein: the coupling agent is a silane coupling agent KH-550.
7. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 6, wherein: the ultramarine pigment is the oldest and most bright blue pigment, is non-toxic and environment-friendly, and belongs to the category of inorganic pigments. It is used for whitening and eliminating yellow light in white paint or other white pigment.
8. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 7, wherein: the lubricant is Wacker Silicone, EBS (ethylene bis stearamide).
9. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 8, wherein: the toughening agent is ethylene-methyl acrylate-glycidyl methacrylate terpolymer (GMA).
10. The yellowing-resistant, high heat-resistant, high dimensional stability PPA material of claim 9, wherein: the stabilizer is PA nylon multifunctional stabilizer SEED.
CN202011035544.3A 2020-09-27 2020-09-27 Anti-yellowing high-heat-resistance high-dimensional-stability PPA material and preparation method thereof Withdrawn CN112143224A (en)

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