CN113845737B - Polypropylene composite material and preparation method and application thereof - Google Patents
Polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN113845737B CN113845737B CN202111219472.2A CN202111219472A CN113845737B CN 113845737 B CN113845737 B CN 113845737B CN 202111219472 A CN202111219472 A CN 202111219472A CN 113845737 B CN113845737 B CN 113845737B
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- polypropylene resin
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- resistant agent
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- -1 Polypropylene Polymers 0.000 title claims abstract description 138
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 137
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 239000003999 initiator Substances 0.000 claims abstract description 43
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 34
- 238000001125 extrusion Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000006078 metal deactivator Substances 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 29
- 238000001556 precipitation Methods 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000000740 bleeding effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- JQIBHSDQYRKBLC-UHFFFAOYSA-N 2-ethynylperoxy-2-methylpropane Chemical group C(C)(C)(C)OOC#C JQIBHSDQYRKBLC-UHFFFAOYSA-N 0.000 description 1
- LRRBANSQUYNJTH-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CC(C)(C)OOC(C)(C)C LRRBANSQUYNJTH-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FEHDLMJLTHKGJQ-UHFFFAOYSA-N C1(CC(=O)OC(C2=CC=CC=C2)O1)=O.N1=NN=CC=C1 Chemical compound C1(CC(=O)OC(C2=CC=CC=C2)O1)=O.N1=NN=CC=C1 FEHDLMJLTHKGJQ-UHFFFAOYSA-N 0.000 description 1
- 241001212699 Pinctada martensii Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- 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
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The application discloses a polypropylene composite material, a preparation method and application thereof, and relates to the technical field of high polymer materials. The application provides a polypropylene composite material which comprises the following components in parts by weight: comprises the following components in parts by weight: 65-90 parts of modified polypropylene resin and 0.2-0.6 part of antioxidant; wherein, the modified polypropylene resin is grafted with copper-damage resistant agent by grafting initiator; the weight ratio of the polypropylene resin to the grafting initiator to the copper-damage-resistant agent is as follows: polypropylene resin: grafting initiator: copper pest resistance = 99.7-99.9:0.05-0.15:0.01-0.15; the decomposition temperature of the grafting initiator is 165-175 ℃. The application provides a polypropylene composite material, which is prepared by grafting a copper-damage-resistant agent onto polypropylene, so that the heat aging resistance of a product in contact with metal can be obviously improved, and the product keeps excellent precipitation-resistant and sticky performance.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a polypropylene composite material and a preparation method and application thereof.
Background
Compared with other general thermoplastic resins, the polypropylene resin has the advantages of small relative density, low price, good processability, good comprehensive performance and the like, but also has the defects of poor heat aging resistance, especially poor copper damage resistance and aging resistance and the like. In the practical application of polypropylene materials, in order to improve the ageing resistance of polypropylene when contacting with metal, copper-resistant agents are usually added, but the copper-resistant agents are easy to separate out, so that the product has very serious sticky phenomenon of separating out on the surface of the product under the high temperature or illumination condition, thereby greatly limiting the application field of polypropylene composite materials.
Disclosure of Invention
Based on the above, the application aims to overcome the defects of the prior art and provide a polypropylene composite material, and a preparation method and application thereof. According to the application, the copper-damage-resistant agent is grafted to the polypropylene, so that the polypropylene composite material is provided, the heat aging resistance of the product when the product contacts with metal can be obviously improved, and the product keeps excellent precipitation-resistant and sticky performance.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows: the polypropylene composite material comprises the following components in parts by weight: 65-90 parts of modified polypropylene resin and 0.2-0.6 part of antioxidant; wherein, the modified polypropylene resin is grafted with copper-damage resistant agent by grafting initiator; the weight ratio of the polypropylene resin to the grafting initiator to the copper-damage-resistant agent is as follows: polypropylene resin: grafting initiator: copper pest resistance = 99.7-99.9:0.05-0.15:0.01-0.15; the decomposition temperature of the grafting initiator is 165-175 ℃.
In the process of preparing the polypropylene composite material, the copper-resistant agent is grafted to polypropylene, modified polypropylene resin is generated first, the heat aging resistance of the prepared polypropylene composite material is obviously improved when the polypropylene composite material contacts with metal, and the problem of precipitation and stickiness of the copper-resistant agent is avoided.
When the modified polypropylene resin is prepared, the content of a grafting initiator is too small, a good grafting effect cannot be formed, and the existence of the free copper-resistant agent causes serious precipitation and stickiness; too much grafting initiator content, too much peroxide, results in accelerated degradation, a significant decrease in the ageing properties of the material and severe bleeding-out and stickiness due to the presence of the free copper-hazard-resistant agent.
The decomposition temperature of the grafting initiator is 165-175 ℃, and the applicant discovers in the practical experiment process that the initiator with low decomposition temperature has the effect of not playing the role of the initiator because the melting point of polypropylene is about 165 ℃ and the processing temperature is required to be more than 165 ℃, so that the activity of the initiator with low decomposition temperature is too high to cause oxidization; initiators with high decomposition temperatures, which require high processing temperatures, increase the risk of degradation of the polypropylene itself at high temperatures, and in addition to the peroxidation, cause degradation.
Preferably, the polypropylene composite material comprises the following components in parts by weight: 70-80 parts of modified polypropylene resin and 0.3-0.5 part of antioxidant. In the practical experimental process, the applicant finds that the selection of the weight parts of the modified polypropylene resin and the antioxidant also affects the precipitation and stickiness resistance of the final polypropylene composite material, and the prepared polypropylene composite material has better heat aging resistance and precipitation and stickiness resistance in the weight part range.
Preferably, the polypropylene resin is at least one of copolymerized polypropylene and homo-polymerized polypropylene; it is further preferred that the melt mass flow rate of the polypropylene resin is 5-90g/10min, the melt mass flow rate of the polypropylene resin being measured according to astm d1238 using a weight of 2.16kg and at a temperature of 230 ℃.
Preferably, the grafting initiator is dicumyl peroxide.
Preferably, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.
Preferably, the copper-damage tolerant agent is a metal deactivator having a hydrazide structure.
Preferably, the polypropylene composite further comprises 10 to 30 parts by weight of filler and 0.1 to 0.3 parts by weight of weather-resistant agent.
The filler is calcium carbonate and/or talcum powder; the weather-proof agent is at least one of hindered amine, benzotriazole, benzophenone and triazine benzylidene malonate. The inventor finds that the filler and the weather-proof agent hardly affect the heat aging resistance and the precipitation-resistant and sticky performance in the practical experiment process, and only improve the physical properties after use.
Preferably, the preparation method of the polypropylene composite material comprises the following steps:
(1) Mixing polypropylene resin, a grafting initiator and a copper-resistant agent in proportion, placing the mixture into a double-screw extruder, and extruding, cooling and granulating the mixture to obtain modified polypropylene resin;
(2) Uniformly stirring the modified polypropylene resin, the filler, the antioxidant and the weather-resistant agent according to a proportion, putting the mixture into a double-screw extruder, and extruding, cooling and granulating the mixture to obtain the polypropylene composite material.
Preferably, in the step (1), the stirring temperature is 60-70 ℃ and the stirring rotating speed is 120-140r/min; the extrusion temperature of the double-screw extruder is 170-180 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1, a step of; in the step (2), the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1.
when the modified polypropylene resin is prepared by the application, the extrusion temperature of the double screw extruder is 170-180 ℃. The degradation is accelerated in the preparation process of the copper-damage-resistant polypropylene due to the overhigh temperature, the ageing performance of the material is obviously reduced, and the sticky phenomenon is seriously precipitated due to the existence of the free copper-damage-resistant agent; too low a temperature does not allow good grafting, and the presence of free copper-based agents results in severe bleeding and stickiness.
Furthermore, the application provides application of the polypropylene composite material in preparing decorative parts for automobiles.
Compared with the prior art, the application has the beneficial effects that: the application provides a polypropylene composite material, which is prepared by grafting a copper-damage-resistant agent onto polypropylene, so that the heat aging resistance of a product in contact with metal can be obviously improved, and the product keeps excellent precipitation-resistant and sticky performance. The application also provides a preparation method of the polypropylene composite material, which has simple operation steps and can realize industrialized mass production. The application also provides application of the polypropylene composition in preparing decorative parts for automobiles.
Drawings
FIG. 1 is a synthetic view of a modified polypropylene resin.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to the following specific examples and the accompanying drawings. In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
The following description of the raw materials used in the examples and comparative examples is provided, but is not limited to these materials:
polypropylene resin:
polypropylene resin a: a copolymerized polypropylene resin, exxon BX3800, having a melt mass flow rate of 30g/10min, measured according to astm d1238 using a weight of 2.16kg and a temperature of 230 ℃;
polypropylene resin B: a copolymerized polypropylene resin, exxon BX3900, having a melt mass flow rate of 60g/10min, measured according to astm d1238 using a weight of 2.16kg and a temperature of 230 ℃;
polypropylene resin C: a homo-polypropylene resin, medium petrochemical Z30S, melt mass flow rate of 30g/10min measured according to ASTMD1238 using a weight of 2.16kg and a temperature of 230 ℃;
polypropylene resin D: a copolymerized polypropylene resin, exxon 7033N, having a melt mass flow rate of 8g/10min, measured according to astm d1238 using a weight of 2.16kg and a temperature of 230 ℃;
polypropylene resin E: a copolymerized polypropylene resin, exxon BX3920, having a melt mass flow rate of 95g/10min, measured according to astm d1238 using a weight of 2.16kg and a temperature of 230 ℃;
polypropylene resin F: a copolymerized polypropylene resin, K8003, having a melt mass flow rate of 3g/10min, measured according to ASTMD1238 using a weight of 2.16kg and a temperature of 230 ℃;
copper damage resistant agent:
copper damage resistant agent: basf MD-1024, n' -bis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, manufactured by basf corporation, germany;
grafting initiator:
grafting initiator A: dicumyl peroxide, with a decomposition temperature of 171 ℃, purchased from aledine;
grafting initiator B: tert-butyl peroxybenzoate having a decomposition temperature of 166 ℃ and purchased from sea in thailand;
grafting initiator C: benzoyl peroxide, at a decomposition temperature of 133 ℃, purchased from sea volence in thailand;
grafting initiator D: (2-ethylhexanoate) -tert-butyl peroxide, with a decomposition temperature of 135 ℃, purchased from thousand chemicals;
grafting initiator E:2, 5-dimethyl-2, 5-bis (t-butylperoxy) acetylene, with a decomposition temperature of 193 ℃, purchased from sea in thailand;
an antioxidant:
antioxidant A: ai Dike A hindered phenol antioxidant AO-330 (1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene), produced by Japanese Ai Dike;
and (3) an antioxidant B: phosphite antioxidant 168 (tris [2, 4-di-t-butylphenyl ] phosphite), manufactured by basf, germany;
talc powder: talcum powder provided by Pinctada martensii supply chain management Co., ltd, north sea additive source TYT-777A model product, wherein the talcum powder is 3000 meshes;
weather-resistant agent: hindered amine weather resistant agent UV-3808PP5, manufactured by Sorve company, USA.
Examples 1 to 17 and comparative examples 1 to 10
The components and parts by weight of the polypropylene composite materials of examples 1 to 17 and comparative examples 1 to 10 are shown in tables 1 and 2;
table 1 Components and weight part selections
Table 2 selection of Components and parts by weight
The polypropylene composites of examples 1-17 and comparative examples 1-10 were prepared as follows:
(1) Mixing polypropylene resin, a grafting initiator and a copper-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, the stirring rotating speed is 120-140r/min, and placing the mixture into a double-screw extruder, the extrusion temperature of the double-screw extruder is 170-180 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1, extruding, cooling and granulating to obtain the modified polypropylene resin; the synthesis of the modified polypropylene resin is shown in figure 1;
(2) Uniformly stirring the modified polypropylene resin, the filler, the antioxidant and the weather-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Comparative examples 11 to 15
Meanwhile, according to different preparation methods, the polypropylene composite material of the comparative examples 11-15 is prepared by setting the components and the weight parts of the polypropylene composite material of the comparative examples 11-15 to be completely the same as those of the example 2, and the preparation methods are only different, and the specific preparation methods are as follows:
comparative example 11
(1) Mixing polypropylene resin, a grafting initiator and a copper-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, the stirring rotating speed is 120-140r/min, and placing the mixture into a double-screw extruder, the extrusion temperature of the double-screw extruder is 155-165 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1, extruding, cooling and granulating to obtain the modified polypropylene resin;
(2) Uniformly stirring the modified polypropylene resin, the filler, the antioxidant and the weather-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Comparative example 12
(1) Mixing polypropylene resin, a grafting initiator and a copper-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, the stirring rotating speed is 120-140r/min, and placing the mixture into a double-screw extruder, the extrusion temperature of the double-screw extruder is 185-195 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1, extruding, cooling and granulating to obtain the modified polypropylene resin;
(2) Uniformly stirring the modified polypropylene resin, the filler, the antioxidant and the weather-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Comparative example 13
Uniformly stirring polypropylene resin, a copper-damage-resistant agent, a filler, an antioxidant and a weather-resistant agent in proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Comparative example 14
Uniformly stirring polypropylene resin, a grafting initiator, a copper-damage-resistant agent, a filler, an antioxidant and a weather-resistant agent according to a proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Comparative example 15
Uniformly stirring polypropylene resin, a grafting initiator, a copper-damage-resistant agent, a filler, an antioxidant and a weather-resistant agent according to a proportion, wherein the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; putting the mixture into a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 170-180 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36: and 1, extruding, cooling and granulating to obtain the polypropylene composite material.
Performance testing
The polypropylene composites prepared in examples 1-16 and comparative examples 1-15 were subjected to the relevant performance test, and the specific test methods are as follows:
(1) Aging time: injecting 100 x 2mm plates of each product, binding and fixing the plates and the copper plates with the same size together by copper wires, then placing the plates into a 150 ℃ oven, and recording the time for starting degradation;
(2) The precipitation is sticky: a test standard PV1306, wherein the higher the grade, the more serious the stickiness is precipitated;
the test results are shown in tables 3 and 4 below;
table 3 test results
Table 4 test results
As can be seen from comparison of examples 1-4, the modified polypropylene resin is prepared in advance within the protection range of the polypropylene resin, the grafting initiator and the copper-damage-resistant agent provided by the application, and the finally prepared polypropylene composite material has excellent heat aging resistance and precipitation-sticky resistance.
As is clear from comparison of examples 2 and examples 5 to 9, the kind and melt mass flow rate of the polypropylene resin hardly affect the heat aging resistance and the bleeding-tack resistance of the final polypropylene composite within the range provided by the present application, and the melt fingers of examples 8 to 9 are not within the preferable range, and the final heat aging resistance is slightly inferior.
As is clear from the comparison of example 2 and example 10, the kind of the grafting initiator has a great influence on the final heat aging resistance, and the inventor of the present application has found from practical experiments that the heat aging resistance of the finally obtained polypropylene composite material is better when dicumyl peroxide is used at a decomposition temperature of 165-175 ℃.
As is evident from the comparison of examples 2 and examples 11 to 14, the parts by weight of the modified polypropylene resin and the antioxidant have a large influence on the final heat aging resistance and the bleeding and sticking resistance. When 70-80 parts of modified polypropylene resin and 0.3-0.5 part of antioxidant are used, the heat aging resistance of the finally obtained polypropylene composite material is better.
As is evident from the comparison of examples 2 and 15 to 17, the weight parts of the modified filler and the weather-resistant agent hardly affect the final heat aging resistance and the bleeding-out and sticking resistance.
As is evident from the comparison of example 2 and comparative examples 1 to 3, the decomposition temperature of the grafting initiator has a great influence on the heat aging resistance and the bleeding-out tackiness resistance of the final polypropylene composite material, and the heat aging resistance and the bleeding-out tackiness resistance are not significantly reduced in the range of the decomposition temperature of the grafting initiator selected in the present application.
As is clear from the comparison of example 2 and comparative examples 4 to 5, the reduction of the grafting initiator content does not result in a good grafting effect, and the presence of the free copper-hazard-resistant agent results in severe bleeding and stickiness; the content of the grafting initiator is increased, the degradation is accelerated due to excessive peroxide, the ageing performance of the material is obviously reduced, and the precipitation and stickiness are serious due to the existence of free copper-resistant agents.
As is clear from the comparison of example 2 and comparative examples 6 to 7, when the parts by weight of the modified polypropylene resin are out of the range provided by the present application, the heat aging resistance and the bleeding-out tackiness resistance are significantly reduced, and the amount of the modified polypropylene of comparative example 7 is reduced, the content of the relative antioxidant is increased, the aging performance is not significantly changed, but the bleeding-out is severe due to the increase of the content of the relative antioxidant.
As is clear from the comparison of example 2 and comparative examples 8 to 10, the selection of the weight parts of the antioxidant has a great influence on the final heat aging resistance and the anti-precipitation tackiness performance, and too low an antioxidant content can reduce the aging property of the material and too high an antioxidant content can cause serious precipitation phenomenon.
As is clear from comparison of example 2 and comparative examples 11 and 12, the extrusion temperature of the twin-screw extruder during the preparation of the modified polypropylene resin has a large influence on the heat aging resistance and the bleeding and stickiness resistance of the final polypropylene composite. The extrusion temperature is reduced, a good grafting effect cannot be formed, and the existence of the free copper-resistant agent causes serious precipitation and stickiness; the extrusion temperature is increased, so that degradation is accelerated in the preparation process of the copper-damage-resistant polypropylene, the ageing performance of the material is obviously reduced, and the free copper-damage-resistant agent exists, so that the bleeding out and stickiness are serious.
As is clear from comparison of example 2 and comparative examples 13-15, the preparation process for preparing the polypropylene composite material by the two-step method provided by the application has great influence on the heat aging resistance and the precipitation and stickiness resistance of the finally obtained polypropylene composite material. Comparative example 13 the copper harm resistant agent was directly added to the polypropylene composite material, and the aging resistance was improved, but the bleeding-out and sticking phenomenon was very serious. Comparative example 14 the modified polypropylene resin was prepared without the two-step process of the present application, and the grafting initiator was directly added at the stage of the modification mixing, which failed to form a good grafting effect, and the addition of peroxide resulted in accelerated degradation, a significant decrease in the aging properties of the material, and severe bleeding and stickiness due to the presence of the free copper-hazard-resistant agent. Comparative example 15 the modified polypropylene resin was prepared without the two-step process of the present application, and the grafting initiator was directly added at the stage of the modification mixing, even if the extrusion temperature was lowered and the extrusion temperature of the modified polypropylene resin was kept consistent, a good grafting effect could not be formed as well, and the bleeding was severe due to the presence of the free copper-hazard-resistant agent.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present application.
Claims (9)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight: 65-90 parts of modified polypropylene resin and 0.2-0.6 part of antioxidant; wherein, the modified polypropylene resin is grafted with copper-damage resistant agent by grafting initiator; the weight ratio of the polypropylene resin to the grafting initiator to the copper-damage-resistant agent is as follows: polypropylene resin: grafting initiator: copper pest resistance = 99.7-99.9:0.05-0.15:0.01-0.15; the decomposition temperature of the grafting initiator is 165-175 ℃; the copper-resistant agent is a metal deactivator with a hydrazide structure;
the modified polypropylene resin is obtained by mixing and extruding polypropylene resin, a grafting initiator and a copper-resistant agent, and the extrusion temperature is 170-180 ℃.
2. The polypropylene composite material according to claim 1, comprising the following components in parts by weight: 70-80 parts of modified polypropylene resin and 0.3-0.5 part of antioxidant.
3. The polypropylene composite material according to claim 1, wherein the polypropylene resin is at least one of a copolymerized polypropylene and a homopolypropylene.
4. A polypropylene composite material according to claim 3, wherein the polypropylene resin has a melt mass flow rate of 5-90g/10min, the melt mass flow rate of the polypropylene resin being measured according to astm d1238 using a weight of 2.16kg and at a temperature of 230 ℃.
5. The polypropylene composite material according to claim 1, wherein the grafting initiator is dicumyl peroxide.
6. The polypropylene composite of claim 1, wherein the polypropylene composite further comprises 10 to 30 parts by weight filler and 0.1 to 0.3 parts by weight weatherproofing agent.
7. A method of preparing the polypropylene composite of claim 6, comprising the steps of:
(1) Mixing polypropylene resin, a grafting initiator and a copper-resistant agent in proportion, placing the mixture into a double-screw extruder, and extruding, cooling and granulating the mixture to obtain modified polypropylene resin;
(2) Uniformly stirring the modified polypropylene resin, the filler, the antioxidant and the weather-resistant agent according to a proportion, putting the mixture into a double-screw extruder, and extruding, cooling and granulating the mixture to obtain the polypropylene composite material.
8. The method for producing a polypropylene composite material according to claim 7, wherein in the step (1), the stirring temperature is 60 to 70 ℃ and the stirring speed is 120 to 140r/min; the extrusion temperature of the double-screw extruder is 170-180 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1, a step of; in the step (2), the stirring temperature is 60-70 ℃, and the stirring rotating speed is 120-140r/min; the extrusion temperature of the double-screw extruder is 190-210 ℃, the screw rotating speed of the double-screw extruder is 170-190r/min, and the length-diameter ratio of the screw is more than or equal to 36:1.
9. use of a polypropylene composite according to any one of claims 1 to 6 for the preparation of decorative parts for automobiles.
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