CN110845799A - Low-odor scratch-resistant polypropylene composite material and preparation method thereof - Google Patents
Low-odor scratch-resistant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN110845799A CN110845799A CN201911115271.0A CN201911115271A CN110845799A CN 110845799 A CN110845799 A CN 110845799A CN 201911115271 A CN201911115271 A CN 201911115271A CN 110845799 A CN110845799 A CN 110845799A
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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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Abstract
The invention relates to a low-odor scratch-resistant polypropylene composite material which is prepared from the following raw materials in parts by mass: polypropylene: 44.6-96.6%, talcum powder: 0-40%, antioxidant: 0.4-4%, deodorant 1: 1% -5%, deodorant 2: 1% -5%, scratch-resistant auxiliary agent: 1% -5%; the deodorant 1 is one or more of water, hexamethyldisilane, hexamethyldisiloxane, triethylcinnamyl alcohol and octamethyltrisiloxane; the deodorant 2 is mesoporous silica or 13X-type zeolite molecular sieve loaded with at least one of ethylene diamine tetraacetate, methylene triamine pentamethylene phosphoric acid, ethylene diamine tetramethylene phosphoric acid and 2, 4-dinitrophenylhydrazine. The product of the invention has excellent low odor and scratch resistance, reduces the antagonism among odor, emission and scratch resistance, and finally realizes the balance among the odor, the emission and the scratch resistance of the product.
Description
Technical Field
The invention belongs to the field of polypropylene composite materials, and particularly relates to a low-odor scratch-resistant polypropylene composite material and a preparation method thereof.
Background
Under the trend of replacing steel with plastic, the polypropylene can completely meet the requirements of automotive interior parts on material performance through modification effects such as toughening, strengthening and the like. Nowadays, the modified polypropylene material has wide application in automotive interior trim, and is mainly applied to parts such as instrument panels, door protection plates, sub-instrument panels, column protection plates and the like. The polypropylene material is used as a main material applied to automotive upholsteries, has obvious advantages in processability and price, but the polypropylene composite material also has the common defect of being used as a polymer material, namely the material can emit organic small molecular substances in the using process, and the riding environment in a car is seriously influenced; and the surface hardness of the polypropylene composite material is low, so that the surface of a workpiece made of the material is easy to scratch, a user feels low-grade to the material, and the use experience of the user is influenced. Therefore, on the premise of meeting the material performance, the user experience of the user on the product is improved from the material perspective, and the concept of pursuit of higher-quality life of people is better met.
At present, the proposal for improving the scratch resistance of the polypropylene composite material mainly comprises adding an organic silicon substance containing special functional groups, wherein part of organic silicon molecules of the organic silicon substance containing special functional groups play an anchoring role in PP resin, and part of organic silicon molecules of the organic silicon substance are enriched on the surface of the polypropylene material, so that the scratch resistance of the composite material is improved by reducing the surface friction coefficient. The theory of odor, however, suggests that the odor emitted by a substance is closely related to the functional groups that the substance contains. Therefore, while the scratch resistance of the material is improved by adding the scratch resistance aid, the odor and the emission of the material are deteriorated. Therefore, when the comprehensive performance of the material is improved, the antagonism needs to be solved, and the optimal performance of the material in all aspects is realized.
Disclosure of Invention
The invention aims to provide a low-odor scratch-resistant polypropylene composite material and a preparation method thereof, and aims to solve the problems that in the prior art, the polypropylene composite material is large in odor and is not scratch-resistant in the use process of an automobile.
The invention is realized by the following technical scheme:
the invention discloses a low-odor scratch-resistant polypropylene composite material which is characterized by comprising the following raw materials in parts by mass:
polypropylene: 44.6 to 96.6 percent of the total weight of the mixture,
talc powder: 0 to 40 percent of the total weight of the composition,
antioxidant: 0.4 to 4 percent of the total weight of the mixture,
deodorant 1: 1 to 5 percent of the total weight of the mixture,
deodorant 2: 1 to 5 percent of the total weight of the mixture,
scratch-resistant auxiliary: 1% -5%;
the deodorant 1 is one or more of water, hexamethyldisilane, hexamethyldisiloxane, triethylcinnamyl alcohol and octamethyltrisiloxane; the deodorant 2 is mesoporous silica or 13X-type zeolite molecular sieve loaded with at least one of ethylene diamine tetraacetate, methylene triamine pentamethylene phosphoric acid, ethylene diamine tetramethylene phosphoric acid and 2, 4-dinitrophenylhydrazine.
Further, the polypropylene is homo-polypropylene or co-polypropylene, and the melt index of the polypropylene is 2-90 g/10min under the test conditions of 230 ℃ and 2.16 Kg.
Further, the particle size of the talcum powder is more than 400 meshes.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant DSTP.
Furthermore, the scratch-resistant auxiliary agent is silicone master batch with the content of effective components of 20-80%.
The preparation method of the low-odor scratch-resistant polypropylene composite material is characterized by comprising the following steps of:
(1) weighing the polypropylene, the antioxidant, the scratch-resistant auxiliary agent, the deodorant 1 and the deodorant 2, uniformly mixing and drying to obtain a mixture;
(2) placing the mixture in a main feeding bin of an intermeshing co-rotating twin-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, adding the talcum powder into the extruder from a side feeding port, wherein the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the vacuum degree is not lower than-0.08 MPa, and the temperature of each subarea of the machine barrel from a feeding port to a machine head outlet is set as follows: 170-230 ℃ and the rotating speed of a main engine is 450-600 revolutions per minute, and the polypropylene composite material with low odor and scraping resistance is prepared by melt extrusion, cooling, granulation and drying.
Further, the preparation method of the low-odor scratch-resistant polypropylene composite material also comprises a preparation method of the deodorant 2, and comprises the following steps:
preparing at least one of ethylenediamine tetraacetate, methylene triamine pentamethylene phosphoric acid, ethylenediamine tetramethylene phosphoric acid and 2, 4-dinitrophenyl hydrazine into 3% -10% ethanol solution, measuring 1L of the solution, adding 300-450 g of 13X type zeolite molecular sieve, stirring for 2-5 h, then carrying out suction filtration, washing for 2-5 times by using absolute ethanol in the suction filtration process, drying, grinding and sieving to obtain the deodorant 2 loaded with the reaction type porous substance.
The invention focuses on adding other functional additives with different proportions according to specific requirements on the basis of a low-odor and low-VOC substrate material, matching with an extruder of a double-stage vacuumizing device, extruding and granulating under a specific extrusion mixing process, and manufacturing the low-odor, low-VOC and scratch-resistant interior special material in a post-treatment mode.
The low-odor scratch-resistant polypropylene composite material disclosed by the invention has excellent low odor and scratch resistance, and better meets the performance index requirements of automotive interior materials on raw materials under the light weight design of automobiles. According to the invention, two different odor removing agents are added to decompose or chelate the nitrogen hydride, sulfide, oxycarbide and other active reaction groups of small odor molecules which are dissociated from the scratch-resistant agent, so that the dissociated odor substances on the special functional groups of the scratch-resistant agent are captured and fixed in a targeted manner, thereby reducing the antagonistic action among odor, diffusion and scratch resistance, and finally realizing the balance among the odor, diffusion and scratch resistance of the product.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The embodiment of the invention and the raw materials used in the proportion are as follows:
PP: SABIC 511MK40T, copolypropylene, melt index MFR 30g/10min (230 ℃, 2.16 Kg).
Antioxidant: antioxidant Irganox 1010, BASF; antioxidant Irganox 168, BASF.
Talc powder: kingda Industrial BHS-1250.
Scratch-resistant auxiliary: dow Corning silicone master batch MB 50-002.
Experimental example 1
The preparation method of the deodorant 2 comprises the following steps: mixing 2, 4-dinitrophenylhydrazine and ethylene diamine tetramethylene phosphoric acid according to the weight ratio of 1: preparing 10% ethanol solution according to the mass ratio of 1.5, measuring 1L of the solution, adding 450g of 13X type zeolite molecular sieve, stirring for 4h, performing suction filtration, washing with absolute ethanol for 3 times in the suction filtration process, drying, grinding and sieving to obtain a deodorant 2 loaded with a reaction type porous substance, and marking as CWJ-1.
Experimental example 2
The preparation method of the deodorant 2 comprises the following steps: preparing methylene triamine pentamethylene phosphoric acid into an 8% ethanol solution, measuring 1L of the solution, adding 300g of 13X type zeolite molecular sieve, stirring for 5 hours, then carrying out suction filtration, washing with absolute ethanol for 5 times in the suction filtration process, drying, grinding and sieving to obtain a deodorant 2 for loading a reaction type porous substance, and marking the deodorant as CWJ-2.
Experimental example 3
The preparation method of the deodorant 2 comprises the following steps: preparing ethylenediamine tetraacetate into a 3% ethanol solution, measuring 1L of the solution, adding 300g of 13X type zeolite molecular sieve, stirring for 3h, performing suction filtration, washing with absolute ethanol for 2 times in the suction filtration process, drying, grinding and sieving to obtain a deodorant 2 loaded with a reaction type porous substance, and marking as CWJ-3.
Examples 1 to 9
Table 1 shows odorant 1 and odorant 2 used in examples 1 to 9 and comparative examples 1 to 3.
TABLE 1 deodorant in examples 1 to 9 and comparative examples 1 to 3
Tables 2 and 3 show the mass ratios of the respective component ratios in examples 1 to 9 and comparative examples 1 to 3, respectively. The concrete preparation methods of the embodiments 1 to 9 and the comparative examples 1 to 3 are the same, namely, raw materials are weighed according to the component proportions shown in the tables 1 and 2, and the polypropylene, the antioxidant, the scratch-resistant auxiliary agent, the deodorant 1 and the deodorant 2 are uniformly mixed and dried to obtain a mixture; feeding the mixture into a main feeding bin of a meshing co-rotating double-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, adding the talcum powder into the extruder from a side feeding port, wherein the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the vacuum degree is not lower than-0.08 MPa, and the temperature of each subarea of the machine barrel from a feeding port to a machine head outlet is set as follows: and (3) at the temperature of 170-230 ℃, the rotating speed of a main engine is 450-600 revolutions per minute, and the polypropylene composite material with low odor and scraping resistance is prepared by melt extrusion, cooling, granulation and drying.
TABLE 2 component masses (unit: g) of the respective raw materials in examples 1 to 9
The products prepared in examples 1 to 9 and the products prepared in comparative examples 1 to 3 were subjected to performance tests and comparisons, and the parameters of the test performances of the products obtained in examples 1 to 9 and comparative examples 1 to 3 after the tests are shown in table 3.
TABLE 3 Mass of ingredients of comparative examples 1 to 3 (unit: g)
| PP | Talcum powder | Antioxidant agent | Deodorant 1 | Smell removal agent 2 | Scratch-resistant auxiliary | |
| Comparative example 1 | 98.6 | 0 | 0.4 | 1 | 0 | 0 |
| Comparative example 2 | 98.6 | 0 | 0.4 | 0 | 1 | 3 |
| Comparative example 3 | 59.6 | 40 | 0.4 | 0 | 0 | 5 |
The test method comprises the following steps: tensile property: the test is carried out according to ISO527-2 standard, and the test speed is 5 mm/min; bending property: the method IS carried out according to the IS178 standard, the span IS 64mm, and the test speed IS 2 mm/min; impact properties: the method is carried out on a simply supported beam impact tester according to ISO179-1 standard, and a sample strip notch is of an A type; odor grade: testing according to PV3900, wherein the mass of the sample is 50 +/-2 g, the standing temperature is 80 ℃, and the standing time is 2 h; scraping experiment: the test was carried out according to PV 3952 at a test pressure of 10N.
TABLE 4 test Performance results for the products of examples 1-9 and comparative examples 1-3
As can be seen from table 4, odor 1 improved the odor better, while odor 2 improved the TVOC better; when two types of smell removing agents are used in a compounding manner, the smell improving effect and the TVOC controlling effect are more obvious, the smell grade and the TVOC of the polypropylene composite material are in a descending trend along with the increase of the smell removing agents 1 and 2, and the smell grade and the TVOC content of the polypropylene composite material can be obviously improved.
The addition of the scratch resistant auxiliary agent can deteriorate the odor and the emission of the material, but the invention simultaneously adds two kinds of smell removing agents, so that the deterioration effect of the scratch resistant auxiliary agent is better improved, and finally, the polypropylene composite material not only has better scratch resistant performance, but also has lower odor grade and less VOC volatilization.
Claims (7)
1. The low-odor scratch-resistant polypropylene composite material is characterized by comprising the following raw materials in parts by mass:
polypropylene: 44.6 to 96.6 percent of the total weight of the mixture,
talc powder: 0 to 40 percent of the total weight of the composition,
antioxidant: 0.4 to 4 percent of the total weight of the mixture,
deodorant 1: 1 to 5 percent of the total weight of the mixture,
deodorant 2: 1 to 5 percent of the total weight of the mixture,
scratch-resistant auxiliary: 1% -5%;
the deodorant 1 is one or more of water, hexamethyldisilane, hexamethyldisiloxane, triethylcinnamyl alcohol and octamethyltrisiloxane; the deodorant 2 is mesoporous silica or 13X-type zeolite molecular sieve loaded with at least one of ethylene diamine tetraacetate, methylene triamine pentamethylene phosphoric acid, ethylene diamine tetramethylene phosphoric acid and 2, 4-dinitrophenylhydrazine.
2. The polypropylene composite material according to claim 1, wherein the polypropylene is homo-polypropylene or co-polypropylene, and the melt index of the polypropylene is 2-90 g/10min under the test conditions of 230 ℃ and 2.16 Kg.
3. The polypropylene composite according to claim 1, wherein the talc powder has a particle size of 400 mesh or more.
4. The polypropylene composite material according to claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant DSTP.
5. The polypropylene composite material according to claim 1, wherein the scratch-resistant auxiliary agent is silicone master batch with an effective component content of 20-80%.
6. A method for preparing a polypropylene composite material according to any one of claims 1 to 5, comprising the steps of:
(1) weighing the polypropylene, the antioxidant, the scratch-resistant auxiliary agent, the deodorant 1 and the deodorant 2, uniformly mixing and drying to obtain a mixture;
(2) placing the mixture in a main feeding bin of an intermeshing co-rotating twin-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, adding the talcum powder into the extruder from a side feeding port, wherein the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the vacuum degree is not lower than-0.08 MPa, and the temperature of each subarea of the machine barrel from a feeding port to a machine head outlet is set as follows: 170-230 ℃ and the rotating speed of a main engine is 450-600 revolutions per minute, and the polypropylene composite material with low odor and scraping resistance is prepared by melt extrusion, cooling, granulation and drying.
7. The method for preparing polypropylene composite according to claim 1, further comprising the step of preparing the deodorant 2, comprising the steps of:
preparing at least one of ethylenediamine tetraacetate, methylene triamine pentamethylene phosphoric acid, ethylenediamine tetramethylene phosphoric acid and 2, 4-dinitrophenyl hydrazine into 3% -10% ethanol solution, measuring 1L of the solution, adding 300-450 g of 13X type zeolite molecular sieve, stirring for 2-5 h, then carrying out suction filtration, washing for 2-5 times by using absolute ethanol in the suction filtration process, drying, grinding and sieving to obtain the deodorant 2 loaded with the reaction type porous substance.
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| CN111635541A (en) * | 2020-05-21 | 2020-09-08 | 常州可赛成功塑胶材料有限公司 | Preparation method of low-VOC silicone lubricating master batch for polyolefin composite material |
| CN114106539A (en) * | 2021-12-27 | 2022-03-01 | 青岛国恩科技股份有限公司 | Low-odor heat-resistant straw biodegradable material and preparation method thereof |
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| CN114524976A (en) * | 2022-04-13 | 2022-05-24 | 河南大学 | m-SiO2@ EDTMPA composite material and preparation method and application thereof |
| CN114524976B (en) * | 2022-04-13 | 2023-01-13 | 河南大学 | m-SiO 2 @ EDTMPA composite material and preparation method and application thereof |
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