CN113881144A - Polypropylene/ethylene propylene diene monomer/rice hull ash composite material and preparation method thereof - Google Patents
Polypropylene/ethylene propylene diene monomer/rice hull ash composite material and preparation method thereof Download PDFInfo
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- CN113881144A CN113881144A CN202111329979.3A CN202111329979A CN113881144A CN 113881144 A CN113881144 A CN 113881144A CN 202111329979 A CN202111329979 A CN 202111329979A CN 113881144 A CN113881144 A CN 113881144A
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- 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
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Abstract
The invention provides a polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material, and belongs to the technical field of high polymer materials. The composite material comprises the following components in percentage by weight: 60-85% of polypropylene resin, 6-14% of Ethylene Propylene Diene Monomer (EPDM) -g-Glycidyl Methacrylate (GMA) and 30-5% of rice hull ash, wherein the rice hull ash is treated by a silane coupling agent. The invention also provides a preparation method and application of the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material. The polypropylene composite material has the advantages of light weight, low cost, good mechanical property and processability, and wide application, and can be used in the fields of flexible packaging, textiles, buildings, furniture, automobiles and the like. The polypropylene/ethylene propylene diene monomer/rice hull ash composite material has the advantages of simple preparation method, easy implementation of production process and cost saving.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material and a preparation method thereof.
Background
The global Production of Polypropylene (PP) in 2018 is about 5600 ten thousand tons, the composite growth rate in the coming years will be kept at 5.84%, and the global PP production in 2025 is expected to reach 8300 ten thousand tons. On the background, the pursuit of lightweight and high-strength PP products is a constant theme in all industrial application fields driven by economic and social benefits such as cost saving, environmental protection, sustainable development and the like, so that the research on how to manufacture lightweight PP products without sacrificing performance has a broad prospect in both academic and industrial fields. Ethylene-propylene-diene monomer (EPDM) is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, is one of ethylene-propylene rubbers, has excellent heat resistance, weather resistance and other aging resistance performances because a main chain of the EPDM consists of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in side chains, and has a similar structure with PP, so that the EPDM has better compatibility. The rice hull ash generated by burning the rice hulls is a resource waste material, the main component of the waste material is silicon dioxide, the silicon dioxide is used as a filler, the effects of reducing the cost and improving the mechanical properties such as elastic modulus, strength and the like can be achieved, and besides the silicon dioxide, other components are carbon and a small amount of metal oxide, and the influence on the environment is avoided. The invention adopts engineering plastic PP resin, EPDM rubber and resource waste rice hull ash as raw materials, prepares a polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material by a chemical modification method and a melt blending technology, and the composite material has the advantages of light weight, excellent performance, low cost and wide application prospect.
Disclosure of Invention
The invention aims to provide a polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material and a preparation method thereof. In order to achieve the above purpose, the invention provides the following technical scheme:
the invention firstly provides a polypropylene/ethylene propylene diene monomer/rice hull ash composite material, which comprises the following components in percentage by weight: 60-85% of PP matrix resin, 6-14% of EPDM-g-GMA and 30-5% of modified rice hull ash;
wherein the EPDM-g-GMA comprises the following components in percentage by weight: 80-89% EPDM and 20-11% GMA;
preferably, the preparation method of the EPDM-g-GMA comprises the following steps:
firstly, cleaning and drying EPDM, then, melting and blending the dried EPDM, GMA, an initiator DCP and an antioxidant 1010 according to the weight ratio to obtain EPDM-g-GMA, and drying for 12 h;
preferably, the ratio of EPDM to GMA is (4-8): 1, the melt blending time is 6-10 min;
the invention also provides a preparation method of the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material, which comprises the following steps: weighing PP matrix resin, EPDM-g-GMA and modified rice hull ash, and carrying out melt blending to obtain the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material.
Preferably, the melt blending temperature is 210 ℃, and the melt blending time is 7-11 min.
The invention has the advantages of
The invention firstly provides a polypropylene/ethylene propylene diene monomer/rice hull ash composite material, which comprises the following components in percentage by weight: 60-85% of PP matrix resin, 6-14% of EPDM-g-GMA and 30-5% of modified rice hull ash; wherein the EPDM-g-GMA comprises the following components in percentage by weight: 80-89% EPDM and 20-11% GMA. Compared with the prior art, the polypropylene composite material is prepared by melt blending of polypropylene, EPDM-g-GMA and modified rice hull ash, and has good toughness and rigidity. The experimental results show that: the impact strength of the polypropylene composite material can reach 696J/m, and the modulus can reach 892 Mpa.
The invention also provides a preparation method of the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material, the preparation method is simple in process and easy in obtaining of raw materials, and the prepared composite material has good toughness and rigidity.
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 firstly provides a polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material, which comprises the following components in percentage by weight: 60-85% PP matrix resin, preferably 70-85%, more preferably 75-85%; 6-14% EPDM-g-GMA, preferably 8-14%, more preferably 10-14%; 30-5% of modified rice hull ash, preferably 20-5%, more preferably 15-5%.
Wherein the EPDM-g-GMA comprises the following components in percentage by weight: 80-89% EPDM, preferably 83-89%, more preferably 86%; 11-20% GMA, preferably 17-11%, more preferably 14%.
The PP matrix resin, EPDM, GMA and rice hull ash according to the present invention are commercial products commonly used by those skilled in the art.
The process for the preparation of EPDM-g-GMA according to the invention preferably comprises:
EPDM at 60 degrees C drying for 12 hours. Then dry EPDM and GMA react and blend, wash and dry for 12 hours at 60 ℃ after grafting;
according to the invention, the EPDM to GMA ratio is preferably (4-8): 1, more preferably (5-7): 1, more preferably 6: 1; the time for melt blending is 6 to 10min, more preferably 7 to 9min, and still more preferably 8 min.
The invention also provides a preparation method of the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material, which comprises the following steps: weighing a polypropylene resin matrix, EPDM-g-GMA and modified rice hull ash, and carrying out melt blending to obtain the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material. The melt blending temperature is preferably 210 ℃, and the melt blending time is preferably 7-11 min.
The present invention will be further illustrated in detail by the following examples, but it should be noted that these examples should not be construed as limiting the scope of the present invention in any way.
Example 1
Preparation of EPDM-g-GMA:
firstly, the EPDM is put into drying equipment, the drying temperature is set to be 60 ℃, and the EPDM is dried for 12 hours. And then putting the pretreated EPDM and GMA into an internal mixer for reaction and blending, wherein the ratio of the EPDM to the GMA is 6: 1, fixing the mixing temperature to 170 ℃, mixing for 8min, then cleaning EPDM-g-GMA, firstly washing with clear water for 3-4 times to ensure that the surface of the EPDM-g-GMA is clean, finally washing with deionized water for one time, putting into drying equipment after cleaning, setting the drying temperature to be 60 ℃, and drying for 12 hours for later use.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 2
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 85 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 5 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃ and the mixing time is 9min, so as to obtain the polypropylene/ethylene propylene diene monomer/rice hull ash composite material. The physical properties of the composite material are shown in Table 1.
Example 3
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 75 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 15 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 4
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 70 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 20 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so as to obtain the polypropylene/ethylene propylene diene monomer/rice hull ash composite material. The physical properties of the composite material are shown in Table 1.
Example 5
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 65 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 25 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so as to obtain the polypropylene/ethylene propylene diene monomer/rice hull ash composite material. The physical properties of the composite material are shown in Table 1.
Example 6
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
60 parts by weight of PP matrix resin, 30 parts by weight of EPDM-g-GMA10 and 30 parts by weight of modified rice hull ash are weighed and melt blended, the mixing temperature is fixed at 210 ℃, the mixing time is 9min, and the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 7
Preparation of EPDM-g-GMA:
firstly, the EPDM is put into drying equipment, the drying temperature is set to be 60 ℃, and the EPDM is dried for 12 hours. And then putting the pretreated EPDM and GMA into an internal mixer for reaction and blending, wherein the ratio of the EPDM to the GMA is 4: 1, fixing the mixing temperature to 170 ℃, mixing for 8min, then cleaning EPDM-g-GMA, firstly washing with clear water for 3-4 times to ensure that the surface of the EPDM-g-GMA is clean, finally washing with deionized water for one time, putting into drying equipment after cleaning, setting the drying temperature to be 60 ℃, and drying for 12 hours for later use.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 8
Preparation of EPDM-g-GMA:
firstly, the EPDM is put into drying equipment, the drying temperature is set to be 60 ℃, and the EPDM is dried for 12 hours. And then putting the pretreated EPDM and GMA into an internal mixer for reaction and blending, wherein the ratio of the EPDM to the GMA is 8: 1, fixing the mixing temperature to 170 ℃, mixing for 8min, then cleaning EPDM-g-GMA, firstly washing with clear water for 3-4 times to ensure that the surface of the EPDM-g-GMA is clean, finally washing with deionized water for one time, putting into drying equipment after cleaning, setting the drying temperature to be 60 ℃, and drying for 12 hours for later use.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 9
Preparation of EPDM-g-GMA:
firstly, the EPDM is put into drying equipment, the drying temperature is set to be 60 ℃, and the EPDM is dried for 12 hours. And then putting the pretreated EPDM and GMA into an internal mixer for reaction and blending, wherein the ratio of the EPDM to the GMA is 6: 1, fixing the mixing temperature to 170 ℃, mixing for 6min, then cleaning EPDM-g-GMA, firstly washing with clear water for 3-4 times to ensure that the surface of the EPDM-g-GMA is clean, finally washing with deionized water for one time, putting into drying equipment after cleaning, setting the drying temperature to be 60 ℃, and drying for 12 hours for later use.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 10
Preparation of EPDM-g-GMA:
firstly, the EPDM is put into drying equipment, the drying temperature is set to be 60 ℃, and the EPDM is dried for 12 hours. And then putting the pretreated EPDM and GMA into an internal mixer for reaction and blending, wherein the ratio of the EPDM to the GMA is 6: 1, fixing the mixing temperature to 170 ℃, mixing for 10min, then cleaning EPDM-g-GMA, firstly washing with clear water for 3-4 times to ensure that the surface of the EPDM-g-GMA is clean, finally washing with deionized water for one time, putting into drying equipment after cleaning, setting the drying temperature to be 60 ℃, and drying for 12 hours for later use.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 11
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 7min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 12
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 80 parts by weight of PP matrix resin, 10 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 11min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 13
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 84 parts by weight of PP matrix resin, 6 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃, and the mixing time is 9min, so that the polypropylene/ethylene propylene diene monomer/rice hull ash composite material is obtained. The physical properties of the composite material are shown in Table 1.
Example 14
Preparation of EPDM-g-GMA:
same as in example 1.
Preparation of polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material:
weighing 76 parts by weight of PP matrix resin, 14 parts by weight of EPDM-g-GMA and 10 parts by weight of modified rice hull ash, and carrying out melt blending, wherein the mixing temperature is fixed at 210 ℃ and the mixing time is 9min, thus obtaining the polypropylene/ethylene propylene diene monomer/rice hull ash composite material. The physical properties of the composite material are shown in Table 1.
TABLE 1 physical Properties of the composites made in examples 1-14
| Serial number | PP/EPDM-g-GMA/RHA(wt/wt/wt) | Impact Strength (J/m) | Tensile Strength (MPa) | Modulus (MPa) |
| Example 1 | 80/10/10 | 475 | 28 | 777 |
| Example 2 | 85/10/5 | 696 | 32 | 623 |
| Example 3 | 75/10/15 | 328 | 25 | 784 |
| Example 4 | 70/10/20 | 218 | 21 | 796 |
| Example 5 | 65/10/25 | 154 | 19 | 826 |
| Example 6 | 60/10/30 | 95 | 17 | 892 |
| Example 7 | 80/10/10 | 428 | 27 | 753 |
| Example 8 | 80/10/10 | 446 | 28 | 746 |
| Example 9 | 80/10/10 | 461 | 25 | 737 |
| Example 10 | 80/10/10 | 457 | 29 | 682 |
| Example 11 | 80/10/10 | 463 | 27 | 761 |
| Example 12 | 80/10/10 | 472 | 28 | 759 |
| Example 13 | 84/6/10 | 348 | 26 | 857 |
| Example 14 | 76/14/10 | 492 | 29 | 634 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and modifications and variations thereof within the spirit and scope of the invention will be apparent to those skilled in the art.
Claims (7)
1. The polypropylene/ethylene propylene diene monomer/rice hull ash composite material and the preparation method thereof are characterized by comprising the following components in percentage by weight: 60-85% of polypropylene resin, 6-14% of EPDM-g-GMA and 30-5% of rice hull ash;
the EPDM-g-GMA comprises the following components in percentage by weight: 80-89% EPDM and 20-11% GMA;
the preparation method of the EPDM-g-GMA comprises the following steps: firstly, cleaning and drying EPDM, then carrying out melt blending on the dried EPDM, GMA, an initiator DCP and an antioxidant 1010 according to the weight ratio of the EPDM, the GMA, the initiator DCP and the antioxidant 1010 to obtain EPDM-g-GMA, and drying the EPDM-g-GMA;
the preparation method of the modified rice hull ash comprises the following steps: firstly, cleaning and drying rice hull ash, then putting the dried rice hull ash into a silane coupling agent ethanol solution, soaking and stirring, and cleaning and drying after modification is finished;
the preparation method of the polypropylene/ethylene propylene diene monomer/rice hull ash comprises the following steps: and (3) carrying out melt blending on the PP resin, EPDM-g-GMA and the modified rice hull ash to prepare the polypropylene/ethylene propylene diene monomer rubber/rice hull ash composite material.
2. The method for preparing polypropylene/EPDM/rice husk ash composite material according to claim 1, wherein the EPDM is dried at 60 ℃ for 12 hours.
3. The method for preparing polypropylene/EPDM/rice husk ash composite material according to claim 1, wherein the ratio of EPDM to GMA is (4-8): 1, the reaction blending time is 6-10 min.
4. The method for preparing polypropylene/EPDM/rice husk ash composite material according to claim 1, wherein the EPDM-g-GMA reaction blending temperature is 170 ℃.
5. The method for preparing polypropylene/EPDM/rice husk ash composite material according to claim 1, wherein the EPDM-g-GMA is dried at 60 ℃ for 12 hours.
6. The preparation method of the polypropylene/ethylene propylene diene monomer/rice hull ash composite material according to claim 1, wherein the melt blending time is 7-11 min.
7. The method for preparing polypropylene/EPDM/rice husk ash composite material according to claim 1, wherein the melt blending temperature is 210 ℃.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509241A (en) * | 2012-06-27 | 2014-01-15 | 上海杰事杰新材料(集团)股份有限公司 | Rice hull ash modified polypropylene material and preparation method thereof |
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2021
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509241A (en) * | 2012-06-27 | 2014-01-15 | 上海杰事杰新材料(集团)股份有限公司 | Rice hull ash modified polypropylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Y HE ETAL.: ""EEPDM-G-GMA Toughening off Straw /Polypropylene Composites：Mechanical Properties ,Thermal Stabillity and Rheologicall Properties"", 《INTERNATIONAL POLYMER PROCESSING》 * |
| 李海东等: ""熔融法制备EPDM-g-GMA及其对PEN脆韧转变的研究"", 《2004年中国工程塑料加工应用技术研讨会》 * |
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