CN109776965B - Heat-resistant polypropylene nano composite material and preparation method thereof - Google Patents
Heat-resistant polypropylene nano composite material and preparation method thereof Download PDFInfo
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- CN109776965B CN109776965B CN201910091959.3A CN201910091959A CN109776965B CN 109776965 B CN109776965 B CN 109776965B CN 201910091959 A CN201910091959 A CN 201910091959A CN 109776965 B CN109776965 B CN 109776965B
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Abstract
The invention discloses a heat-resistant polypropylene nano composite material, which comprises polypropylene, a heat-resistant agent metal-organic framework material MOFs, a dispersing agent, maleic anhydride grafted polypropylene and a processing aid; wherein the MOFs is MOFs taking magnesium as a metal center and taking polycarboxylic organic ligands as organic ligands, and the chemical structural general formula of the dispersing agent is RC6H4SO3‑M+R is CnH2n+1N is not less than 13 and not more than 16, n is an integer, and M is an alkali metal dispersant. According to the heat-resistant polypropylene nano composite material, MOFs (metal-organic frameworks) with a specific metal center and an organic ligand are added into a polypropylene material as a heat-resistant agent, a dispersant with a specific structure and maleic anhydride grafted polypropylene with a specific grafting rate are matched, and the polypropylene composite material has high heat resistance by utilizing the cooperation and synergistic effect of the three.
Description
Technical Field
The invention relates to a polypropylene composite material and a preparation method thereof, in particular to a heat-resistant polypropylene nano composite material and a preparation method thereof, belonging to the technical field of modified high polymer materials.
Background
The polypropylene is a universal plastic which is most widely applied, and compared with other universal plastics, the polypropylene has the advantages of low cost, excellent mechanical property, good chemical resistance, good insulating property, high transparency, low water absorption rate and the like, but the polypropylene also has the problem of poor heat resistance. In order to broaden the application of polypropylene in a higher temperature environment, a great deal of modification research is carried out on the heat resistance of polypropylene in the prior art, and the heat resistance of polypropylene is usually improved by adding various heat stabilizers and the like into a polypropylene composite material. However, heat-resistant polypropylene obtained by using the conventional heat stabilizer to improve the heat resistance of polypropylene still has poor heat resistance, particularly, has poor heat resistance for a long time.
Disclosure of Invention
In order to solve the technical problems, the invention provides a heat-resistant polypropylene nano composite material and a preparation method thereof, and the polypropylene composite material prepared by the preparation method has higher heat resistance.
The technical scheme of the invention is as follows:
the invention discloses a heat-resistant polypropylene nano composite material, which comprises 60-95 parts by weight of polypropylene, 0.1-5.0 parts by weight of heat-resistant agent metal-organic framework material MOFs, 0.5-4.0 parts by weight of dispersant, 2-20 parts by weight of maleic anhydride grafted polypropylene and 0.2-2.0 parts by weight of processing aid.
Wherein the polypropylene has a melt flow rate of 1-100g/10min at 230 ℃/2.16kg, preferably 20-80g/10min at 230 ℃/2.16 kg.
The MOFs is a crystalline porous material which is formed by mutually linking an inorganic metal center and an organic ligand through covalent bonds or ion-covalent bonds and has a regular pore channel or hole structure, has a nanoscale framework type regular pore channel structure, and mainly consists of the metal center and the organic ligand, and has a large specific surface area, a large porosity and a small solid density. The metal-organic framework material MOFs used in the application is at least one of metal-organic framework materials MOFs taking magnesium as a metal center, and the organic ligand of the metal-organic framework material MOFs is a polycarboxylic acid organic ligand, preferably biphenyl-3, 3',5,5' -tetracarboxylic acid.
Wherein the chemical structural general formula of the dispersant is RC6H4SO3-M+(alkylbenzenesulfonate) R is CnH2n+1N is not less than 13 and not more than 16 and n is an integer; m is an alkali metal, preferably one of sodium and potassium, more preferably sodium.
Wherein the maleic anhydride grafted polypropylene is prepared by the following preparation method: 100 parts by weight of dried polypropylene, 2.0-5.0 parts by weight of dried maleic anhydride and 1.0-2.0 parts by weight of dicumyl peroxide are put into a co-rotating twin-screw extruder to be melted, extruded and granulated, and then vacuum drying is carried out for 12-15h to obtain the maleic anhydride grafted polypropylene, wherein the grafting rate of the maleic anhydride grafted polypropylene is 0.2-5.0%. Wherein the processing temperature of the co-rotating twin-screw extruder from the feeding section to the neck ring mold is 35 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 205 ℃ in sequence, and the rotating speed of the twin-screw is 100-120 rpm.
Wherein the processing aid is at least one of low molecular esters, metal soaps, stearic acid composite esters and amides, and the processing aid mainly acts as a lubricant.
The invention also discloses a preparation method of the heat-resistant polypropylene nano composite material, which comprises the following steps:
(1) the maleic anhydride grafted polypropylene is prepared by a double-screw extruder, and the specific process comprises the following steps: putting 100 parts by weight of dried polypropylene, 2.0-5.0 parts by weight of dried maleic anhydride and 1.0-2.0 parts by weight of dicumyl peroxide into a co-rotating double-screw extruder, performing melt extrusion granulation, and performing vacuum drying for 12-15h to obtain maleic anhydride grafted polypropylene; wherein the processing temperature of the co-rotating twin-screw extruder from the feeding section to the neck ring mold is 35 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 205 ℃ in sequence, and the rotating speed of the twin-screw is 100-120 rpm;
(2) weighing 60-95 parts by weight of polypropylene, 0.1-5.0 parts by weight of heat-resistant metal-organic framework material MOFs, 0.5-4.0 parts by weight of dispersant, 2-20 parts by weight of maleic anhydride grafted polypropylene and 0.2-2.0 parts by weight of processing aid, uniformly mixing the heat-resistant metal-organic framework material MOFs and the maleic anhydride grafted polypropylene to obtain a mixture, sequentially putting the mixture, the dispersant, the polypropylene and the processing aid into a mixer, mixing and stirring at 15-50 ℃ at the speed of 400-600r/min for 3-5min to obtain a premix;
(3) and putting the premix into a double-screw extruder, melting, mixing, dispersing, extruding and granulating the premix in the double-screw extruder with the length-diameter ratio of (40-45):1 at the processing temperature of 190-240 ℃ of the double-screw extruder to obtain the heat-resistant polypropylene nanocomposite.
The beneficial technical effects of the invention are as follows: according to the heat-resistant polypropylene nano composite material, MOFs (metal-organic frameworks) with a specific metal center and an organic ligand are added into a polypropylene material as a heat-resistant agent, a dispersant with a specific structure and maleic anhydride grafted polypropylene with a specific grafting rate are matched, and the polypropylene composite material has high heat resistance by utilizing the cooperation and synergistic effect of the three.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The kinds and types of polypropylene, heat-resistant metal-organic framework materials MFOs, dispersant, maleic anhydride-grafted polypropylene, and processing aids selected for the following specific examples and comparative examples are as follows:
polypropylene: m1200 HS.
Heat-resistant agent 1: metal-organic framework materials MFOs having Mg as the metal center and biphenyl-3, 3',5,5' -tetracarboxylic acid as the organic ligand.
Heat-resistant agent 2: metal-organic framework materials MFOs having Ca as the metal center and biphenyl-3, 3',5,5' -tetracarboxylic acid as the organic ligand.
Heat-resistant agent 3: the metal-organic framework material MFOs takes Al as a metal center and takes 1,3, 5-tri (3, 5-m-dicarboxyphenyl) benzene as an organic ligand.
Heat-resistant agent 4: conventional heat stabilizers such as at least one of phenol heat stabilizers, amine heat stabilizers, phosphite heat stabilizers, semi-hindered phenol heat stabilizers, complex heat stabilizers formed by an acryloyl functional group and a thioester, and calixarene heat stabilizers. In the comparative example, pentaerythritol beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was used.
Dispersant 1: sodium hexadecylbenzene sulfonate;
dispersant 2: sodium tridecylbenzenesulfonate;
dispersant, 3: sodium dodecylbenzenesulfonate.
Maleic anhydride grafted polypropylene 1(MAH-g-PP 1): maleic anhydride-grafted polypropylene with a grafting rate of 0.2%;
maleic anhydride grafted polypropylene 2(MAH-g-PP 2): maleic anhydride-grafted polypropylene with a grafting rate of 5.0%;
maleic anhydride grafted polypropylene 3(MAH-g-PP 3): maleic anhydride-grafted polypropylene with a grafting rate of 2.5%;
maleic anhydride grafted polypropylene 4(MAH-g-PP 4): maleic anhydride-grafted polypropylene with a grafting rate of 0.1%;
maleic anhydride grafted polypropylene 5(MAH-g-PP 5): maleic anhydride-grafted polypropylene having a grafting ratio of 6.0%.
Processing aid: and (3) zinc stearate.
The following examples and comparative examples used a co-rotating twin screw extruder model number Berstorff ZE25 with a 40:1 aspect ratio.
The preparation method of the polypropylene nano composite material of the specific embodiment and the comparative example by using the selected components comprises the following steps:
(1) the maleic anhydride grafted polypropylene is prepared by a double-screw extruder, and the preparation process comprises the following steps: putting the dried polypropylene, the dried maleic anhydride and dicumyl peroxide into a co-rotating twin-screw extruder according to a certain proportion, melting, extruding and granulating, and placing in an oven at 80 ℃ for vacuum drying for 12-15h (preferably 12h) to obtain maleic anhydride grafted polypropylene; wherein the processing temperature of the co-rotating twin-screw extruder from the feeding section to the neck ring mold is 35 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 205 ℃ in sequence, and the rotating speed of the twin-screw is 100-120rpm (preferably 100 r/min);
(2) weighing polypropylene, a heat-resistant metal-organic framework material MOFs, a dispersing agent, the maleic anhydride grafted polypropylene and a processing aid according to the formula amount, uniformly mixing the heat-resistant metal-organic framework material MOFs and the maleic anhydride grafted polypropylene to obtain a mixture, and sequentially putting the mixture, the dispersing agent, the polypropylene and the processing aid into a mixer to be mixed and stirred at the speed of 400-600r/min (selected at 600r/min) at the temperature of 15-50 ℃ (selected at 23 ℃) for 3-5min to obtain a premix;
(3) and putting the premix into a double-screw extruder, melting, mixing, dispersing and extruding the premix in the double-screw extruder with the length-diameter ratio of (40-45):1 (preferably 40:1) at the processing temperature of 190 ℃ and 240 ℃ of the double-screw extruder for granulation to obtain the polypropylene nanocomposite.
TABLE 1 EXAMPLES AND COMPARATIVE EXAMPLES the amounts of the respective components (unit: parts by weight)
The polypropylene nanocomposites prepared in the above specific examples and comparative examples were tested for heat resistance, specifically, the prepared polypropylene nanocomposites were press-molded for 5min at 190 ℃ on a flat vulcanizing machine to obtain test pieces with a thickness of about 1mm, and the heat resistance of the material at 150 ℃ was tested according to the test standard VW 440455.14, and the test results are shown in table 2.
TABLE 2 Heat resistance test results of specific examples and comparative examples
From the test results of the above-mentioned specific examples and comparative examples, it can be seen that the use of the heat-resistant agent of specific structure, the dispersant of specific structure and the maleic anhydride-grafted polypropylene of specific grafting ratio described herein in combination can improve the heat resistance of the polypropylene composite material, particularly the powdering time at high temperature.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The heat-resistant polypropylene nano composite material is characterized by comprising 60-95 parts by weight of polypropylene, 0.1-5.0 parts by weight of heat-resistant agent metal-organic framework material MOFs, 0.5-4.0 parts by weight of dispersing agent, 2-20 parts by weight of maleic anhydride grafted polypropylene and 0.2-2.0 parts by weight of processing aid;
wherein, the MOFs is metal center with magnesium and organic ligand with biphenyl-3, 3',5,5' -tetracarboxylic acid;
wherein the dispersant is sodium hexadecylbenzene sulfonate or sodium tridecylbenzene sulfonate;
the maleic anhydride grafted polypropylene is prepared by the following preparation method: 100 parts by weight of dried polypropylene, 2.0-5.0 parts by weight of dried maleic anhydride and 1.0-2.0 parts by weight of dicumyl peroxide are put into a co-rotating twin-screw extruder to be melted, extruded and granulated, and then vacuum drying is carried out for 12-15h to obtain the maleic anhydride grafted polypropylene, wherein the grafting rate of the maleic anhydride grafted polypropylene is 0.2-5.0%.
2. The heat-resistant polypropylene nanocomposite as claimed in claim 1, wherein the processing temperature of the co-rotating twin-screw extruder from the feeding section to the die is 35 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 205 ℃ in this order, and the rotation speed of the twin-screws is 100-120 rpm.
3. The heat-resistant polypropylene nanocomposite according to claim 1, wherein the polypropylene has a melt flow rate of 1 to 100g/10min at 230 ℃/2.16 kg.
4. The heat-resistant polypropylene nanocomposite according to claim 3, wherein the polypropylene has a melt flow rate of 20 to 80g/10min at 230 ℃/2.16 kg.
5. The heat-resistant polypropylene nanocomposite according to claim 1, wherein the processing aid is at least one of low molecular esters, metal soaps, stearic acid complex esters, and amides.
6. A method for preparing a heat-resistant polypropylene nanocomposite as claimed in any one of claims 1 to 5, comprising the steps of:
(1) preparing maleic anhydride grafted polypropylene by a double-screw extruder;
(2) weighing 60-95 parts by weight of polypropylene, 0.1-5.0 parts by weight of heat-resistant metal-organic framework material MOFs, 0.5-4.0 parts by weight of dispersant, 2-20 parts by weight of maleic anhydride grafted polypropylene and 0.2-2.0 parts by weight of processing aid, uniformly mixing the heat-resistant metal-organic framework material MOFs and the maleic anhydride grafted polypropylene to obtain a mixture, sequentially putting the mixture, the dispersant, the polypropylene and the processing aid into a mixer, mixing and stirring at 15-50 ℃ at the speed of 400-600r/min for 3-5min to obtain a premix;
(3) and putting the premix into a double-screw extruder, melting, mixing, dispersing, extruding and granulating the premix in the double-screw extruder at the processing temperature of 190-240 ℃ of the double-screw extruder to obtain the heat-resistant polypropylene nano composite material.
7. The production method according to claim 6, wherein the production of the maleic anhydride-grafted polypropylene by a twin-screw extruder in the step (1) is carried out by: 100 parts by weight of dried polypropylene, 2.0-5.0 parts by weight of dried maleic anhydride and 1.0-2.0 parts by weight of dicumyl peroxide are put into a co-rotating double-screw extruder to be melted, extruded and granulated, and then vacuum-dried for 12-15h to obtain the maleic anhydride grafted polypropylene.
8. The method as claimed in claim 7, wherein the processing temperature of the co-rotating twin-screw extruder from the feeding section to the die is 35 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 205 ℃ in this order, and the rotation speed of the twin-screws is 100-120 rpm.
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| CN106751353A (en) * | 2016-12-26 | 2017-05-31 | 重庆普利特新材料有限公司 | A kind of low-density that can be used for thin-walled property moulding, high-performance polypropylene compound material and preparation method thereof |
| CN107383740A (en) * | 2017-08-25 | 2017-11-24 | 广东壹豪新材料科技股份有限公司 | A kind of PP/COC alloy materials and preparation method thereof of high intensity, low-shrinkage |
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| CN106751353A (en) * | 2016-12-26 | 2017-05-31 | 重庆普利特新材料有限公司 | A kind of low-density that can be used for thin-walled property moulding, high-performance polypropylene compound material and preparation method thereof |
| CN107383740A (en) * | 2017-08-25 | 2017-11-24 | 广东壹豪新材料科技股份有限公司 | A kind of PP/COC alloy materials and preparation method thereof of high intensity, low-shrinkage |
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| "一类新型镁材料——镁基金属有机骨架材料";韩建森等;《化工进展》;20181231;第37卷(第9期);3437-3445 * |
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