CN110951169B - Light-shading low-linear-expansion-coefficient polypropylene composite material and preparation method thereof - Google Patents
Light-shading low-linear-expansion-coefficient polypropylene composite material and preparation method thereof Download PDFInfo
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- CN110951169B CN110951169B CN201911285794.XA CN201911285794A CN110951169B CN 110951169 B CN110951169 B CN 110951169B CN 201911285794 A CN201911285794 A CN 201911285794A CN 110951169 B CN110951169 B CN 110951169B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
- 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
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention provides a light-shading low-linear-expansion-coefficient polypropylene composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 100 parts of polypropylene copolymer; 0.5-1 part of a nucleating system; 10-20 parts of titanium dioxide; 1-5 parts of carbon nanotubes; 5-10 parts of basalt fibers; 10-30 parts of glass fiber; 10-30 parts of talcum powder; 5-10 parts of a compatilizer. The polypropylene composite material prepared by the invention can achieve the effect of full shading by more than 1mm in thickness, has extremely low linear expansion coefficient, does not crack after long-term use, and does not crack after being circulated for 5000 hours at the high and low temperatures of-20-85 ℃.
Description
Technical Field
The invention relates to a polypropylene composite material and a preparation method thereof, in particular to a light-shading low-linear expansion coefficient polypropylene composite material and a preparation method thereof.
Background
The LED is used as a fourth-generation light source, has the advantages of long service life, energy conservation, environmental protection, safety, rich colors and the like, has important application in the aspects of display, illumination, signal indication, medical treatment and the like, has great economic benefit and social significance, and is known to be one of the high technical fields with the development prospect in the 21 st century.
With the wider application of LEDs, materials for LEDs are becoming hot spots for material development. In the field of high-power lamps, as more heat is generated in the use process of the high-power lamps, better heat reduction quantity is needed to be LED out in the use process, a metal part, usually aluminum, is additionally arranged at the bottom of the LED, and the aluminum cup stand needs a layer of plastic to be coated to achieve the appearance and structural effects. The coating plastic is a PBT fiber-added material, and the material has brittle performance and higher price. As a material with excellent price ratio, polypropylene (PP) material is a hot spot in the research of LED field.
However, the difficulty of using PP as the aluminum-clad material is that: firstly, PP is an easily crystallized polymer, has very large shrinkage rate and slow crystallization speed, and has large change of the shrinkage rate along with the change of temperature, namely, the linear expansion coefficient is large, so that when an LED lamp is used, the plastic material and the metal aluminum have inconsistent shrinkage along with the change of temperature, and a workpiece is easy to crack; secondly, the crystalline PP has certain light transmittance, so that light leakage can be caused in the using process of a workpiece, the light reflectivity is low, and the luminous flux of the whole lamp is influenced.
According to the search, the prior patent document CN103756144A discloses a polypropylene composite material with low linear expansion, scraping resistance and high gloss, which is prepared from 50-80 parts of polypropylene, 10-50 parts of phenolic resin, 1-5 parts of curing agent, 10-40 parts of compatilizer, 0.1-0.4 part of antioxidant, 0.1-0.3 part of nucleating agent, 0.1-0.3 part of lubricant and 0-5 parts of other auxiliary agents in parts by weight. However, the composite material has no shading effect and cannot meet the application in the field of LEDs.
Prior patent document CN 107501750a discloses a composite material comprising: 50-70 parts of polypropylene, 10-20 parts of chopped glass fiber, 20-30 parts of inorganic filler, 5-10 parts of graft compatilizer, 0.2-0.8 part of antioxidant, 0.5-2.0 parts of lubricant, 0.1-1.0 part of nucleating agent and 0.5-2.0 parts of rare earth oxide. The composite material has a low linear expansion coefficient and excellent dimensional stability. But it also has no light-shielding effect and cannot be applied to the field of LEDs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a light-shielding polypropylene composite material with a low linear expansion coefficient and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the invention provides a light-shielding polypropylene composite material with a low linear expansion coefficient, which comprises the following components in parts by weight:
100 parts of polypropylene copolymer;
0.5-1 part of a nucleating system;
10-20 parts of titanium dioxide;
1-5 parts of carbon nanotubes;
5-10 parts of basalt fibers;
10-30 parts of glass fiber;
10-30 parts of talcum powder;
5-10 parts of a compatilizer.
Preferably, the MI of the co-polypropylene under 230 ℃ by 2.16kg is in the range of 10-15g/10 min. The polypropylene copolymer in the melt finger range has proper molecular weight, too low melt finger is not beneficial to the dispersion of minerals and fibers, too high melt finger is too high, the shrinkage is larger after the molecular weight is higher, the ductility of the product is poor, and the product performance is influenced.
Preferably, the nucleating system is a sodium salt of a polyacrylic acid. The nucleation system is added to provide nucleation points, accelerate the formation of crystal nuclei and the completion of crystallization, and reduce post-shrinkage.
Preferably, the titanium dioxide is rutile titanium dioxide which has excellent light reflection capability and achieves the purpose of effective shading. And because the carbon nano tube has excellent light absorption capacity, the light escaping after being reflected by the titanium dioxide can be absorbed, and the carbon nano tube and the titanium dioxide are compounded to generate extremely excellent synergistic effect so as to achieve the effect of total shading.
Preferably, the fiber diameter of the basalt fiber is 12-15 micrometers, and the length-diameter ratio is more than or equal to 6. It can generate a synergistic effect with the glass fiber to control the shrinkage anisotropy of the composite material.
Preferably, the glass fiber is alkali-free glass fiber, the fiber diameter is 10-13 microns, and the shrinkage anisotropy of the composite material can be controlled.
Preferably, the particle size of the talcum powder is 1-5 microns, and the talcum powder can generate a synergistic effect with the glass fiber and the basalt fiber to control the shrinkage anisotropy of the composite material.
Preferably, the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is 0.8-1.2%, and the dispersing agent and the interface bonding force of fibers, minerals and PP resin can be improved.
The invention also provides a preparation method of the light-shading low-linear expansion coefficient polypropylene composite material, which comprises the following steps:
mixing the raw materials in proportion, adding the mixture into a double-screw extruder, performing melt blending extrusion, bracing, water cooling, drying and granulating to obtain the light-shading low-linear expansion coefficient polypropylene composite material.
Preferably, double vacuum is opened in the front conveying section and the rear conveying section in the extrusion process, and the vacuum degree is less than or equal to-0.08 MPa;
the rotating speed of the double-screw extruder is 200-300 r/min, and the temperature of each zone is controlled to be 210-230 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polypropylene composite material prepared by the invention can achieve the effect of full shading when the thickness is more than 1mm, namely, the light transmittance is 0%;
(2) the polypropylene composite material prepared by the invention has extremely low linear expansion coefficient which is not more than 2.5 x 10-5 mm/mm DEG C, and the linear expansion coefficient of the metal aluminum is 2.32 x 10-5 mm/mm DEG C, so that the two materials have excellent matching performance;
(3) the polypropylene composite material prepared by the invention does not crack after long-term use, does not crack after being cycled at 40 ℃ below zero to 85 ℃ for 5000 hours, does not crack for 3000 cycles, can enable the lamp to be normally used for more than five years according to industrial lamp tests and use experiences, and can realize the service life cycle of the lamp to be free from cracking for more than 5000 cycles.
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 invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention provides a light-shielding polypropylene composite material with a low linear expansion coefficient, which comprises the following components in parts by weight:
100 parts of polypropylene copolymer;
0.5-1 part of a nucleating system;
10-20 parts of titanium dioxide;
1-5 parts of carbon nanotubes;
5-10 parts of basalt fibers;
10-30 parts of glass fiber;
10-30 parts of talcum powder;
5-10 parts of a compatilizer.
The MI of the copolymerized polypropylene under the condition of 230 ℃ by 2.16kg is in the range of 10-15g/10 min.
The nucleating system is sodium polypropylenecarboxylate.
The titanium dioxide is rutile type titanium dioxide.
The basalt fiber has a fiber diameter of 12-15 microns and a length-diameter ratio of more than or equal to 6.
The glass fiber is alkali-free glass fiber, and the fiber diameter is 10-13 microns.
The particle size of the talcum powder is 1-5 microns.
The compatilizer is maleic anhydride grafted polypropylene, and the grafting rate is 0.8-1.2%.
The light-shading polypropylene composite material with low linear expansion coefficient can be prepared by adopting the components and the content range under the conditions.
In the following examples and comparative examples, the polypropylene copolymer specifically used was 4084 manufactured by Ningbo Teplast corporation, and had a melt index of 10.0g/10min (230 ℃ C. by 2.16 kg); the adopted nucleation system is HPN-68L produced by Milliken company; the adopted titanium dioxide is rutile type titanium dioxide; the adopted basalt fiber is commercially available, the diameter of the fiber is 13 micrometers, and the length of the fiber is 6 mm; the adopted alkali-free glass fiber is 249A produced by the European Committee of science, and the fiber diameter is 12 mu m; the adopted talcum powder has the grain diameter of 1-5 microns and is sold in the market; the adopted compatilizer maleic anhydride grafted polypropylene is preferably easy 5001-T, and the grafting rate is 1%.
Examples 1 to 4 and comparative examples 1 to 7
The components and the weight parts of the light-shielding polypropylene composite material with low linear expansion coefficient are shown in the table 1.
The preparation method comprises the following steps:
mixing the raw materials in proportion, adding the mixture into a double-screw extruder, performing melt blending extrusion, bracing, water cooling, drying and granulating to obtain the light-shading low-linear expansion coefficient polypropylene composite material.
Double vacuum is opened in the front conveying section and the rear conveying section in the extrusion process, and the vacuum degree is less than or equal to-0.08 MPa;
the rotating speed of the double-screw extruder is 200-300 r/min, and the temperature of each zone is controlled to be 210-230 ℃.
Wherein, comparative examples 1, 3 and 5 are the same as the preparation conditions of example 1; comparative examples 2, 4, 7 were prepared under the same conditions as in example 3; comparative example 6 was prepared under the same conditions as in example 2.
TABLE 1
Comparative example 8
This comparative example is essentially the same as the feed composition of example 1, except that: the comparative example uses mica powder instead of talc.
Effect verification:
the polypropylene composites prepared in examples 1-4 and comparative examples 1-8 above were tested for their properties by the following methods: testing light transmittance, namely performing injection molding on the composite material at 200 ℃ to form a 1mm double-sided polishing plate, and testing according to GB/T2410-2008 standard; the linear expansion coefficient is tested according to GB/T1036; and (2) performing high-low temperature cycle test, namely performing injection molding on the composite material at the temperature of 200 ℃ to obtain an actual product part, testing in a high-low temperature cycle test box according to a GB/T2423.4-2001 method, circulating the product part to 5000 cycles at the cycle temperature of-40-85 ℃, and respectively keeping the temperature of-40 ℃ and 85 ℃ for 1h, visually observing the cracking state of the product part, and recording the number of cracking cycles.
The test results are shown in Table 2.
TABLE 2
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (9)
1. The light-shielding polypropylene composite material with the low linear expansion coefficient is characterized by comprising the following components in parts by weight:
100 parts of polypropylene copolymer;
0.5-1 part of a nucleating system;
10-20 parts of titanium dioxide;
1-5 parts of carbon nanotubes;
5-10 parts of basalt fibers;
10-30 parts of glass fiber;
10-30 parts of talcum powder;
5-10 parts of a compatilizer;
the MI of the copolymerized polypropylene under the condition of 230 ℃ by 2.16kg is in the range of 10-15g/10 min.
2. The light-blocking low coefficient of linear expansion polypropylene composite of claim 1 wherein the nucleating system is a sodium salt of a polyacrylic acid.
3. The light-shielding polypropylene composite material with low linear expansion coefficient according to claim 1, wherein the titanium dioxide is rutile type titanium dioxide.
4. The light-shielding polypropylene composite material with low linear expansion coefficient as claimed in claim 1, wherein the basalt fiber has a fiber diameter of 12-15 μm and an aspect ratio of 6 or more.
5. The light-blocking low linear expansion coefficient polypropylene composite material according to claim 1, wherein the glass fiber is alkali-free glass fiber, and the fiber diameter is 10-13 μm.
6. The light-blocking low linear expansion coefficient polypropylene composite according to claim 1, wherein the talc powder has a particle size of 1 to 5 μm.
7. The light-shielding low linear expansion coefficient polypropylene composite material as claimed in claim 1, wherein the compatibilizer is maleic anhydride grafted polypropylene, and the grafting ratio is 0.8-1.2%.
8. A method for preparing the light-screening low linear expansion coefficient polypropylene composite material according to claim 1, comprising the following steps:
mixing the raw materials in proportion, adding the mixture into a double-screw extruder, performing melt blending extrusion, bracing, water cooling, drying and granulating to obtain the light-shading low-linear expansion coefficient polypropylene composite material.
9. The method for preparing the light-shielding polypropylene composite material with low linear expansion coefficient according to claim 8, wherein the extrusion process is characterized in that double vacuum is opened at the front conveying section and the rear conveying section, and the vacuum degree is less than or equal to-0.08 MPa;
the rotating speed of the double-screw extruder is 200-300 r/min, and the temperature of each zone is controlled to be 210-230 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000219753A (en) * | 1999-02-03 | 2000-08-08 | Kuraray Plast Co Ltd | Light-shielding film |
| WO2002052059A1 (en) * | 2000-12-22 | 2002-07-04 | Samsung General Chemicals Co., Ltd. | Flame retardant polypropylene resin composition |
| CN105670101A (en) * | 2014-11-20 | 2016-06-15 | 重庆界威模具股份有限公司 | Polypropylene modified material |
| CN107513225A (en) * | 2017-09-26 | 2017-12-26 | 上海日之升科技有限公司 | A kind of LED high shading high reflection PP composite materials and preparation method thereof |
| CN110240754A (en) * | 2019-07-17 | 2019-09-17 | 福建鑫邦新材料科技有限公司 | Modified polypropene and preparation method thereof |
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- 2019-12-13 CN CN201911285794.XA patent/CN110951169B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000219753A (en) * | 1999-02-03 | 2000-08-08 | Kuraray Plast Co Ltd | Light-shielding film |
| WO2002052059A1 (en) * | 2000-12-22 | 2002-07-04 | Samsung General Chemicals Co., Ltd. | Flame retardant polypropylene resin composition |
| CN105670101A (en) * | 2014-11-20 | 2016-06-15 | 重庆界威模具股份有限公司 | Polypropylene modified material |
| CN107513225A (en) * | 2017-09-26 | 2017-12-26 | 上海日之升科技有限公司 | A kind of LED high shading high reflection PP composite materials and preparation method thereof |
| CN110240754A (en) * | 2019-07-17 | 2019-09-17 | 福建鑫邦新材料科技有限公司 | Modified polypropene and preparation method thereof |
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