CN115011036A - Surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material and preparation method thereof - Google Patents
Surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material and preparation method thereof Download PDFInfo
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- CN115011036A CN115011036A CN202210668869.8A CN202210668869A CN115011036A CN 115011036 A CN115011036 A CN 115011036A CN 202210668869 A CN202210668869 A CN 202210668869A CN 115011036 A CN115011036 A CN 115011036A
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- calcium sulfate
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- 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
- C08L23/12—Polypropene
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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
Abstract
The invention relates to a surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material, which mainly comprises the following raw materials in parts by weight: 66-97 parts of polypropylene, 1-30 parts of modified calcium sulfate whisker, 1-3 parts of compatilizer, 0.4-0.6 part of dispersant and 0.4-0.6 part of antioxidant; the modified calcium sulfate whisker is obtained by surface treatment under the action of a catalyst, and the modifier is methacrylic acid; the filler in the composite material has good compatibility with resin, the rigidity, the strength and the heat resistance of the obtained product are greatly improved, and the toughness is also good; the product of the invention can be used in the fields of automobiles and household appliances with higher requirements on product performance.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material and a preparation method thereof.
Background
Polypropylene is one of the most active plastic materials at present, and particularly, modified PP is layered endlessly and tends to replace low-end engineering plastics. The PP has light weight, no toxicity, good performance, capability of steam disinfection and wider application range. In the aspects of household daily necessities and household appliances, the medical instrument can also be used; automotive parts, pipes; a container; in addition, it can be used as building material, various implements for agriculture, forestry, animal husbandry, subsidiary industry and fishery, rope and fishing net, etc.
Although PP has many excellent properties, it still has many disadvantages, mainly including poor low-temperature impact strength, easy embrittlement, poor weather resistance, high static electricity, poor dyeability, and the like.
The calcium sulfate whisker can be called as gypsum whisker, is one kind of whisker, has the advantages of high strength, high modulus, heat resistance, light weight and the like of the whisker, and is a whisker with rich resources. Not only a great deal of gypsum mine exists in nature, but also with the development of industrial technology, the method for preparing the gypsum whisker by treating industrial waste gas with limestone is mature day by day. Therefore, the calcium sulfate whiskers are widely used in the fields of high polymer materials, rubber materials, paper reinforcement and the like. In order to improve the compatibility between the gypsum whiskers and the resin and to allow better bonding between the two, thereby enhancing the properties of the composite, the whiskers are typically surface treated.
For example, chinese patent CN102504409A discloses a method for reinforcing polypropylene with calcium sulfate whiskers, which comprises mixing polypropylene, calcium sulfate whiskers, and stearic acid at a certain ratio, and extruding to obtain excellent composite particles, wherein stearic acid is a modifier of calcium sulfate whiskers. Chinese patent CN102070842B discloses a high heat-resistant low-density high-performance polypropylene composition for vehicles and a preparation method thereof, the components of the composite material are polypropylene, a toughening agent, whiskers, talcum powder and a coupling agent which are mixed according to a certain proportion and then extruded to obtain excellent composite material particles, wherein the coupling agent is epoxy resin, hydrogenated butadiene and monostearyl alcohol glycerol ester. Chinese patent CN101693776B discloses a high-strength high-heat-resistance polypropylene modified composite material and a preparation method thereof, and the composite material comprises the components of polypropylene, calcium sulfate whiskers, glass fibers, polypropylene grafted maleic anhydride, a nucleating agent, an antioxidant and a lubricant which are mixed according to a certain proportion and then extruded to obtain excellent composite material particles.
However, the surface treatment of the calcium sulfate whiskers in the above patents is rough, and although the compatibility between the whiskers and the matrix resin can be improved to a certain extent, the compatibility between the whiskers and the polypropylene resin is still poor, and the whisker agglomeration phenomenon is easily caused, so that the performance of the composite material is affected. In the invention, proper amount of modified calcium sulfate whiskers are added into polypropylene, so that the related performance of the composite material can be greatly improved.
Disclosure of Invention
In order to solve the problems, the invention discloses a surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material comprises the following components in parts by weight: 66-97 parts of polypropylene, 1-30 parts of modified calcium sulfate whisker, 1-3 parts of compatilizer, 0.4-0.6 part of dispersant and 0.4-0.6 part of antioxidant.
Further, the polypropylene is one or more of homo-polypropylene and co-polypropylene.
Further, the compatilizer is maleic anhydride grafted polypropylene, and the grafting rate is 0.8%.
Further, the dispersing agent is one or more of silicone powder, zinc stearate, calcium stearate, stearic acid and ethylene bisstearamide.
Further, the antioxidant is prepared by compounding hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to the weight ratio of 1: 2.
Furthermore, the average diameter of the modified calcium sulfate whisker is 3-10 μm, and the average length of the modified calcium sulfate whisker is 50-80 μm.
Further, the preparation method of the modified calcium sulfate whisker comprises the following steps:
(1) in a three-neck round-bottom flask provided with a magnetic stirring rotor, benzene is taken as a solvent, and a certain amount of calcium sulfate whiskers are dispersed in the benzene;
(2) then, sequentially adding excessive methacrylic acid and adding a proper amount of p-toluenesulfonic acid and hydroquinone;
(3) heating the mixture until benzene refluxes, and separating water from the reaction product by adopting a condensation pipe and a water separator, wherein the reaction lasts for 5 hours;
(4) after the reaction is finished, filtering, washing and vacuum drying the product at 80 ℃ for 6h to obtain the modified crystal whisker.
Further, the weight ratio of the calcium sulfate whisker to the solvent in the step (1) is 1: 2-5; the weight ratio of the methacrylic acid, the p-toluenesulfonic acid, the hydroquinone in the step (2) to the calcium sulfate whisker in the step (1) is 20-80: 0.8-1.5: 0.3-0.8: 100 respectively.
The reaction mechanism of the methacrylic acid modified whisker is shown in figure 1.
The preparation method of the surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material comprises the following steps: premixing the polypropylene and the components except the modified calcium sulfate whisker in a high-speed mixer, transferring the mixed material into a double-screw extruder, adding the modified calcium sulfate whisker into the double-screw extruder from a side feed, and performing melt extrusion granulation to obtain the surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material.
Further, the rotating speed of the high-speed mixer is 800-1000 r/min, the temperature of the double-screw extruder is 70-210 ℃, and the rotating speed of the screws is 200-400 r/min.
The invention has the beneficial effects that:
the whisker modification method adopted in the formula can greatly improve the compatibility between the whisker and the polypropylene resin and improve the bonding capacity of the whisker and the matrix resin, thereby improving the relevant performance of the material, simultaneously the added compatilizer can further improve the compatibility between the whisker and the resin, and the dispersant can improve the dispersion effect of the whisker and the processing performance of the composite material.
Drawings
FIG. 1 is a reaction mechanism diagram of methacrylic acid and calcium sulfate whisker;
FIG. 2 is an infrared spectrum before and after modification of calcium sulfate whiskers;
FIG. 3 is an SEM image of an impact cross-section of a polypropylene composite; b. unmodified whiskers; c. and modifying the crystal whisker.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
Preparation of modified calcium sulfate whisker
In a three-neck round bottom flask equipped with a magnetic stirring rotor, using benzene as a solvent, firstly weighing 20g of calcium sulfate whiskers to be dispersed in 40g of benzene, and then adding excessive 10g of methacrylic acid, 0.2g of p-toluenesulfonic acid and 0.1g of hydroquinone in sequence. The mixture was heated to benzene reflux and water was separated from the reaction product using a condenser and trap and the reaction was continued for 5 h. And after the reaction is finished, filtering, washing and drying the product in vacuum at 80 ℃ for 6 hours to obtain the modified calcium sulfate whisker.
The infrared spectra before and after modification of the whisker are shown in FIG. 2, from which it can be seen that the modified calcium sulfate whisker is 2919cm -1 ～2851cm -1 Smaller absorption peaks appear in the range, which should be C-H stretching vibration absorption peaks, and the C-H bonds only possibly come from the modifier methacrylic acid. Meanwhile, the crystal whisker modified by methacrylic acid is at 1727cm -1 ，1685cm -1 Two parts also go outNew absorption peaks are now present, which are characteristic of C ═ O and C ═ C, respectively, indicating that methacrylic acid has successfully modified the whiskers.
Examples 2-5 and comparative example
Weighing the raw materials according to the formula table of table 1, premixing the polypropylene and the components except the modified calcium sulfate whisker in a high-speed mixer at the rotating speed of 800 r/min; then transferring the mixed material to a double-screw extruder, adding the modified calcium sulfate whisker into the double-screw extruder from a side feed, and controlling the temperature of the extruder to be as follows: the temperature is 70-210 ℃, and the rotating speed of the screw is 350 r/min. And (4) performing melt extrusion granulation to obtain a sample.
Table 1 formula table
| Example 2 | Example 3 | Example 4 | Example 5 | Comparative example | |
| Polypropylene | 97 | 88 | 77 | 66 | 66 |
| Unmodified calcium sulfate whiskers | 30 | ||||
| Modified calcium sulfate whisker | 1 | 10 | 20 | 30 | |
| Polypropylene grafted maleic anhydride | 1 | 1 | 2 | 3 | 3 |
| Dispersing agent | 0.4 | 0.4 | 0.5 | 0.6 | 0.6 |
| Antioxidant agent | 0.6 | 0.6 | 0.5 | 0.4 | 0.4 |
The injection molding test properties of the prepared samples are shown in table 2:
table 2 table of performance testing data
From the table comparing examples 2 to 5, the density, tensile strength, flexural modulus and heat distortion temperature of the material are all improved with the increase of the addition amount of the modification whisker, while the toughness of the material is decreased, and from example 2, it is found that the performance of the material is greatly improved when the addition amount of the modification whisker is only 1%. Comparing example 5 with the comparative example, it can be seen that the performance of example 5 is higher than that of the comparative example, and it can be proved that the modified whiskers have better material modification effect than the unmodified whiskers, so that the modified whiskers have better dispersion effect in the matrix resin than the unmodified whiskers.
The SEM images of the impact cross-sections of the polypropylene composites of comparative example and example 4 are shown in fig. 3, and after the unmodified calcium sulfate whiskers were added, the fracture surface was irregular and the appearance of ridges and ravines appeared as shown in fig. b, but it was also clear that significant cracks existed between the calcium sulfate whiskers and the polypropylene resin due to their poor compatibility. However, as can be seen from the graph c, the modified calcium sulfate whiskers and the polypropylene resin are fully fused together, and the grooves left by pulling or breaking the calcium sulfate whiskers out of the polypropylene resin can also be observed, so that the whole broken surface becomes more wrinkled and uneven, which can indicate that the polypropylene resin and the modified calcium sulfate whiskers absorb a large amount of external stress during the breaking process of the sample strips added with the modified calcium sulfate whiskers, and which also microscopically proves the improvement of the material strength.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (10)
1. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material is characterized by comprising the following components in parts by weight:
66-97 parts of polypropylene, 1-30 parts of modified calcium sulfate whisker, 1-3 parts of compatilizer, 0.4-0.6 part of dispersant and 0.4-0.6 part of antioxidant.
2. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 1, wherein the polypropylene is one or more of homo-polypropylene and co-polypropylene.
3. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 1, wherein the compatibilizer is maleic anhydride-grafted polypropylene, and the grafting ratio is 0.8%.
4. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 1, wherein the dispersant is one or more of silicone powder, zinc stearate, calcium stearate, stearic acid, and ethylene bis stearamide.
5. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 1, wherein the antioxidant is an antioxidant prepared by compounding a hindered phenol antioxidant 1010 and a phosphite antioxidant 168 in a weight ratio of 1: 2.
6. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 1, wherein the modified calcium sulfate whiskers have an average diameter of 3 to 10 μm and an average length of 50 to 80 μm.
7. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 6, wherein the preparation method of the modified calcium sulfate whisker comprises the following steps:
(1) in a three-neck round-bottom flask provided with a magnetic stirring rotor, benzene is taken as a solvent, and a certain amount of calcium sulfate whiskers are dispersed in the benzene;
(2) then, sequentially adding excessive methacrylic acid and adding a proper amount of p-toluenesulfonic acid and hydroquinone;
(3) heating the mixture until benzene refluxes, and separating water from the reaction product by adopting a condensation pipe and a water separator, wherein the reaction lasts for 5 hours;
(4) after the reaction is finished, filtering, washing and vacuum drying the product at 80 ℃ for 6h to obtain the modified crystal whisker.
8. The surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 7, wherein the weight ratio of the calcium sulfate whiskers to the solvent in step (1) is 1: 2-5; the mass ratio of the methacrylic acid, the p-toluenesulfonic acid and the hydroquinone in the step (2) to the calcium sulfate whisker in the step (1) is 20-80: 0.8-1.5: 0.3-0.8: 100.
9. The preparation method of the surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in any one of claims 1 to 8, comprising the following steps: premixing the polypropylene and the components except for the modified calcium sulfate whisker in a high-speed mixer, transferring the mixed material into a double-screw extruder, adding the modified calcium sulfate whisker into the double-screw extruder from side feeding, and performing melt extrusion granulation to obtain the surface modified calcium sulfate whisker reinforced and toughened polypropylene composite material.
10. The preparation method of the surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material as claimed in claim 8, wherein the rotation speed of the high-speed mixer is 800-1000 r/min, the temperature of the twin-screw extruder is 70-210 ℃, and the rotation speed of the screws is 250-400 r/min.
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| CN202210668869.8A CN115011036A (en) | 2022-06-14 | 2022-06-14 | Surface-modified calcium sulfate whisker reinforced and toughened polypropylene composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850857A (en) * | 2022-12-16 | 2023-03-28 | 广东圆融新材料有限公司 | Whisker reinforced polypropylene composite material and preparation method thereof |
| CN117209898A (en) * | 2023-11-07 | 2023-12-12 | 一夫科技股份有限公司 | Calcium sulfate filled high-strength polypropylene material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693776A (en) * | 2009-09-18 | 2010-04-14 | 苏州禾盛新型材料股份有限公司 | Novel high-intensity high heat-resistance polypropylene modified composite material and preparation method thereof |
| WO2020199350A1 (en) * | 2019-03-30 | 2020-10-08 | 厦门大学 | High-performance calcium sulfate whisker material and preparation process therefor |
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- 2022-06-14 CN CN202210668869.8A patent/CN115011036A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693776A (en) * | 2009-09-18 | 2010-04-14 | 苏州禾盛新型材料股份有限公司 | Novel high-intensity high heat-resistance polypropylene modified composite material and preparation method thereof |
| WO2020199350A1 (en) * | 2019-03-30 | 2020-10-08 | 厦门大学 | High-performance calcium sulfate whisker material and preparation process therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850857A (en) * | 2022-12-16 | 2023-03-28 | 广东圆融新材料有限公司 | Whisker reinforced polypropylene composite material and preparation method thereof |
| CN117209898A (en) * | 2023-11-07 | 2023-12-12 | 一夫科技股份有限公司 | Calcium sulfate filled high-strength polypropylene material and preparation method thereof |
| CN117209898B (en) * | 2023-11-07 | 2024-02-13 | 一夫科技股份有限公司 | Calcium sulfate filled high-strength polypropylene material and preparation method thereof |
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