CN110655614B - Polypropylene compatibilizer and preparation method thereof, polypropylene modified plastic and preparation method and application thereof - Google Patents
Polypropylene compatibilizer and preparation method thereof, polypropylene modified plastic and preparation method and application thereof Download PDFInfo
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- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a polypropylene compatibilizer and a preparation method thereof, a polypropylene modified plastic and a preparation method and application thereof, and belongs to the technical field of functional materials. The polypropylene compatibilizer provided by the invention is prepared from the following components in parts by mass: 65-70 parts of polypropylene; 35-40 parts of a nucleating agent; 10-15 parts of maleic anhydride; 5-6 parts of an initiator. The polypropylene compatibilizer provided by the invention takes polypropylene as a main body, maleic anhydride is used in a matching manner, and under the combined action of the nucleating agent and the initiator, the grafting rate of the maleic anhydride in the prepared polypropylene compatibilizer is high, so that the compatibility and the dispersibility of a flame retardant, an antioxidant and a stabilizer with the polypropylene can be improved when the polypropylene compatibilizer is used for preparing the polypropylene modified plastic, and the mechanical property and the flame retardant property of the polypropylene modified plastic are obviously improved.
Description
Technical Field
The invention relates to the technical field of functional materials, and particularly relates to a polypropylene compatibilizer and a preparation method thereof, a polypropylene modified plastic and a preparation method and application thereof.
Background
The polypropylene plastic is a thermoplastic resin prepared by polymerizing propylene, has a regular structure, is highly crystallized, and has better heat resistance, corrosion resistance, tensile strength, rigidity and transparency than polyethylene, but the existing polypropylene plastic has poor low-temperature impact resistance, is easy to age and has poor flame retardant property.
The performance of polypropylene plastics can be improved by modifying polypropylene, and common polypropylene modification methods include blending modification, filling modification, fiber reinforced composite material, chemical modification and surface modification, wherein the blending modification is the simplest and most common polypropylene modification method. The compatibility of each component in the blending modification process is the most basic requirement and is one of the important factors for determining the final performance, however, the different components of most blends are not compatible systems in thermodynamics, so macroscopic phase separation occurs in the melt processing process, and the various properties of the blends including mechanical property, thermal stability and the like are not ideal. Therefore, improving the compatibility between the components of the blend is an important issue to be solved for preparing high performance polymer blend materials.
In the prior art, a common compatibilizer for blending and modifying polypropylene is a maleic anhydride grafted polypropylene compatibilizer, but the grafting ratio of maleic anhydride in the conventional maleic anhydride grafted polypropylene compatibilizer is only 0.8-1.2%, the grafting ratio is low, and the performance of modified polypropylene is not ideal when the compatibilizer is applied to the blending and modifying process of polypropylene.
Disclosure of Invention
The invention aims to provide a polypropylene compatibilizer and a preparation method thereof, a polypropylene modified plastic and a preparation method and application thereof. The maleic anhydride grafted polypropylene of the polypropylene compatibilizer provided by the invention has high grafting rate, and can be used as the compatibilizer of polypropylene modified plastics to remarkably improve the mechanical property and flame retardant property of the polypropylene modified plastics.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polypropylene compatibilizer, which is prepared from the following components in parts by mass:
65-70 parts of polypropylene;
35-40 parts of a nucleating agent;
10-15 parts of maleic anhydride;
5-6 parts of an initiator.
Preferably, the polypropylene comprises one or more of PP BJ100N, PP MT20, PP Z30S and PP K7227;
the nucleating agent comprises one or more of polypropylene beta-crystal form nucleating agent, WBG and 8202 CQ;
the initiator comprises dicumyl oxide and/or di-tert-butylperoxydiisopropylbenzene.
The invention provides a preparation method of the polypropylene compatibilizer, which comprises the following steps:
and mixing the polypropylene, the nucleating agent, the maleic anhydride and the initiator, and then extruding and granulating to obtain the polypropylene compatibilizer.
Preferably, the temperature of the extrusion granulation is 160-180 ℃.
The invention provides a polypropylene modified plastic which is prepared from the following components in parts by mass:
75-90 parts of composite polypropylene;
5-7 parts of a polypropylene compatibilizer;
20-25 parts of a flame retardant;
0.1-0.2 part of antioxidant;
0.05-0.1 part of a stabilizer;
the polypropylene compatibilizer is the polypropylene compatibilizer in the technical scheme or the polypropylene compatibilizer prepared by the preparation method in the technical scheme.
Preferably, the composite polypropylene comprises PP BJ100N, PP K8003 and PP BX 3905;
the PP BJ100N, the PP K8003 and the PP BX3905 are in a mass ratio of (5-6): (5-8): (3-4).
Preferably, the flame retardant comprises a phosphorus-nitrogen flame retardant;
the antioxidant comprises a phosphite antioxidant;
the stabilizer comprises a hindered amine light stabilizer.
The invention provides a preparation method of polypropylene modified plastic, which comprises the following steps:
mixing the composite polypropylene, the polypropylene compatibilizer, the antioxidant and the stabilizer to obtain a mixed material;
extruding and granulating the mixed material and the flame retardant to obtain polypropylene modified plastic;
the flame retardant is added in a side feeding mode.
Preferably, the extrusion granulation is performed in a twin-screw extruder, and the temperature of each zone in the twin-screw extruder is respectively as follows: the temperature of the first zone is 155-175 ℃, the temperature of the second zone is 165-185 ℃, the temperature of the third zone is 165-185 ℃, the temperature of the fourth zone is 170-190 ℃, the temperature of the fifth zone is 170-190 ℃, the temperature of the sixth zone is 170-190 ℃, the temperature of the seventh zone is 170-190 ℃, the temperature of the eighth zone is 170-190 ℃, the temperature of the ninth zone is 165-185 ℃ and the temperature of the tenth zone is 165-185 ℃.
The invention also provides the application of the polypropylene modified plastic in the technical scheme or the polypropylene modified plastic prepared by the preparation method in the technical scheme in rail transit.
The invention provides a polypropylene compatibilizer, which is prepared from the following components in parts by mass: 65-70 parts of polypropylene; 35-40 parts of a nucleating agent; 10-15 parts of maleic anhydride; 5-6 parts of an initiator. The polypropylene compatibilizer provided by the invention takes polypropylene as a main body, maleic anhydride is used in a matched manner, strong-polarity side-group maleic anhydride is introduced into a nonpolar molecular main chain of the polypropylene under the combined action of a nucleating agent and an initiator, the grafting ratio of maleic anhydride grafted polypropylene in the prepared polypropylene compatibilizer is higher than 2.3%, and the polypropylene compatibilizer is used for preparing polypropylene modified plastics, can greatly improve the affinity of a flame retardant, an antioxidant and a stabilizer with the polypropylene, and can effectively enhance the dispersibility of the flame retardant, the antioxidant and the stabilizer in the polypropylene, so that the mechanical property and the flame retardant property of the polypropylene modified plastics are obviously improved.
The preparation method of the polypropylene compatibilizer provided by the invention is simple to operate and suitable for industrial production.
The polypropylene modified plastic provided by the invention has excellent mechanical property and flame retardant property, and as shown in the test result of the embodiment, the tensile strength of the polypropylene modified plastic provided by the invention is 16.9-17.4 MPa, the elongation at break is 359-395%, the tensile modulus is 565-605 MPa, the bending strength is 20.6-21.5 MPa, the bending modulus is 987-1147 MPa, the melt index is more than 8.1g/10min, and the impact strength is more than 50kJ/m2The mechanical and processing properties and the stress cracking resistance are excellent; the oxygen index is more than 45%, the calorific value, the toxic gas and the smoke release amount of combustion are low, the combustion grade is V0 grade, the flame spread is 6-12, the flame propagation speed is Class1, the smoke toxicity is 1.5-1.7R, the smoke density is 7.02-7.12, the combustion test completely meets the requirements of BS 6853-.
According to the preparation method of the polypropylene modified plastic, the flame retardant is added in a side feeding manner, the residence time of the flame retardant in a double-screw extruder can be fully ensured, the flame retardant and the mixed materials are fully distributed, mixed and dispersed, the flame retardant is prevented from being carbonized, the coupling rate of resin and the flame retardant can be improved, the flame retardant effect of the polypropylene compatibilizer is further improved, the temperature and technological parameters of extrusion granulation are controlled, the mechanical property and the flame retardant effect of the polypropylene modified plastic can be effectively improved, the operation is simple, and the preparation method is suitable for industrial production.
Drawings
FIG. 1 is a process flow diagram for preparing polypropylene modified plastics.
Detailed Description
The invention provides a polypropylene compatibilizer, which is prepared from the following components in parts by mass:
65-70 parts of polypropylene;
35-40 parts of a nucleating agent;
10-15 parts of maleic anhydride;
5-6 parts of an initiator.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the raw materials for preparing the polypropylene compatibilizer comprise 65-70 parts by weight of polypropylene, preferably 66-70 parts by weight of polypropylene, and more preferably 67 parts by weight, 68 parts by weight, 69 parts by weight or 70 parts by weight of polypropylene. In the present invention, the polypropylene preferably includes one or more of PP BJ100N (nordic chemical limited), PP MT20 (chinese petrochemical central office limited petroleum chemical), PP Z30S (chinese petrochemical group, cyclopentadienyl petrochemical company), and PPK7227 (korean petrochemical limited), more preferably PPBJ100N, PPMT20, PPZ30S, or PPK7227, and most preferably PPBJ 100N.
In the invention, the raw materials for preparing the polypropylene compatibilizer comprise 35-40 parts, preferably 36-40 parts, more preferably 36 parts, 37 parts, 38 parts, 39 parts or 40 parts of a nucleating agent by weight of polypropylene. In the present invention, the nucleating agent preferably includes one or more of polypropylene β -crystal nucleating agent (TMB-5, institute of chemical engineering, shanxi province), WBG (widely weilinna functional materials ltd) and 8202CQ (basf corporation), more preferably TMB-5, WBG or 8202CQ, and most preferably TMB-5.
In the invention, the raw materials for preparing the polypropylene compatibilizer comprise 10-15 parts of maleic anhydride, preferably 11-15 parts of maleic anhydride, and more preferably 11, 12, 13, 14 or 15 parts of maleic anhydride.
In the invention, the raw materials for preparing the polypropylene compatibilizer comprise 5-6 parts of an initiator, preferably 5.5-6 parts by weight of the initiator. In the present invention, the initiator preferably comprises dicumyl peroxide (DCP) and/or di-tert-butylperoxydiisopropylbenzene (BIPB, J.Hunan, J.J.), more preferably DCP or BIPB, and most preferably DCP.
The polypropylene compatibilizer provided by the invention takes polypropylene as a main body, maleic anhydride is used in a matching manner, strong-polarity side group maleic anhydride is introduced into a nonpolar molecular main chain of the polypropylene under the combined action of a nucleating agent and an initiator, the grafting ratio of maleic anhydride grafted polypropylene in the prepared polypropylene compatibilizer is higher than 2.3%, the mechanical property is good, and the polypropylene compatibilizer can be used as a compatibilizer for preparing polypropylene modified plastics, can greatly improve the affinity of a flame retardant, an antioxidant, a stabilizer and the polypropylene, and can effectively enhance the dispersibility of the flame retardant, the antioxidant and the stabilizer in the polypropylene, thereby obviously improving the mechanical property and the flame retardant property of the polypropylene modified plastics.
The invention provides a preparation method of the polypropylene compatibilizer, which comprises the following steps:
and mixing the PPBJ100N, a nucleating agent, maleic anhydride and an initiator, and then extruding and granulating to obtain the polypropylene compatibilizer.
The mixing speed and time in the present invention are not particularly limited, and those known in the art may be used.
In the present invention, the extrusion granulation is preferably carried out in a twin screw extruder, the model of which is preferably SHJ-35 (south kyo hot mechanical equipment limited). In the invention, the temperature of the extrusion granulation is 160-180 ℃, namely, the temperature of the first zone to the tenth zone of the double-screw extruder is independently preferably 160-180 ℃, more preferably 165-175 ℃, and most preferably 170 ℃. In the present invention, the operating parameters of the twin-screw extruder are: the rotating speed of the main machine is preferably 400-550 rpm, more preferably 420-480 rpm, and most preferably 440-460 rpm; the host current is preferably 400-480A, more preferably 420-460A, and most preferably 440A; the number of the membrane pores is preferably 32-40, more preferably 34-38, and most preferably 35-36; the pore diameter of the membrane pores is preferably 4 mm; the number of layers of the filter screen is preferably one, and the aperture of the filter screen is preferably 60 meshes; the vacuum degree is preferably more than or equal to 0.04MPa, namely the vacuum pressure is preferably less than or equal to 0.04 MPa.
In the extrusion granulation process, the polypropylene and the polypropylene compatibilizer are compounded at the screw mixing section of the double-screw extruder to perform a grafting reaction.
The invention provides a polypropylene modified plastic which is prepared from the following components in parts by mass:
75-90 parts of composite polypropylene;
5-7 parts of a polypropylene compatibilizer;
20-25 parts of a flame retardant;
0.1-0.2 part of antioxidant;
0.05-0.1 part of a stabilizer;
the polypropylene compatibilizer is the polypropylene compatibilizer in the technical scheme or the polypropylene compatibilizer prepared by the preparation method in the technical scheme.
In the invention, the raw materials for preparing the polypropylene modified plastic comprise 75-90 parts by weight of composite polypropylene, preferably 76-90 parts by weight, more preferably 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight or 89 parts by weight. In the present invention, the polypropylene preferably comprises a mixture of PP BJ100N (nordic chemical limited), PP K8003 (chinese petrochemical group corporation) and PP BX3905 (korean LG group); the mass ratio of the PP BJ100N to the PPK8003 to the PP BX3905 is preferably (5-6): (5-8): (3-4), more preferably (5.5-6): (5.5-8): (3-4), most preferably (5.5-6): (6-8): (3-4). In the invention, the PP BJ100N, the PP K8003 and the PP BX3905 are used in a matched manner, so that the mechanical property and the flame retardant property of the polypropylene modified plastic can be improved.
In the invention, the raw materials for preparing the polypropylene modified plastic comprise 5-7 parts by weight of polypropylene compatibilizer, preferably 5.5-7 parts by weight, more preferably 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight or 7 parts by weight of composite polypropylene. In the invention, the polypropylene compatibilizer has high grafting rate, can greatly improve the affinity of the flame retardant, the antioxidant and the stabilizer with polypropylene as a compatibilizer for preparing polypropylene modified plastics, and can effectively enhance the dispersibility of the flame retardant, the antioxidant and the stabilizer in the polypropylene, thereby obviously improving the mechanical property and the flame retardant property of the polypropylene modified plastics.
In the invention, the raw materials for preparing the polypropylene modified plastic comprise 20-25 parts of flame retardant, preferably 21-25 parts, more preferably 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts, 24 parts, 24.5 parts or 25 parts by weight of the composite polypropylene; in the present invention, the flame retardant preferably includes a phosphorus nitrogen-based flame retardant, more preferably HS-FP20 (Converous Chemicals, Inc., Guangzhou). The flame retardant adopted by the invention has good flame retardant effect, can be used in combination with other raw materials, can improve the flame retardant resistance and mechanical property of the polypropylene modified plastic, does not contain halogen, and cannot corrode equipment.
In the invention, the raw materials for preparing the polypropylene modified plastic comprise 0.05-0.1 part of stabilizer, preferably 0.06-0.1 part, more preferably 0.06, 0.07, 0.08, 0.09 or 0.1 part by weight of composite polypropylene. In the present invention, the stabilizer preferably includes a hindered amine-based light stabilizer, more preferably 770DF (Basf China Co., Ltd.), HALS, HL-744 (Mitsubishi, Japan), Chimassorb119, Chimassorb2020 (Ciba-Jia Co., Ltd.), GW-628 (Shanxi institute of chemical engineering), 770, 774, GW-540, PDS, and most preferably 770 DF. The hindered amine light stabilizer adopted by the invention has low toxicity, good heat-resistant processability and high light stabilization efficiency, is used together with other raw materials, and can improve the combustion resistance and mechanical property of the polypropylene modified plastic.
In the invention, the raw materials for preparing the polypropylene modified plastic comprise, by weight, 0.1-0.2 part of antioxidant, preferably 0.12-0.2 part, more preferably 0.10 part, 0.11 part, 0.12 part, 0.13 part, 0.14 part, 0.15 part, 0.16 part, 0.17 part, 0.18 part, 0.19 part or 0.2 part of composite polypropylene; in the present invention, the antioxidant preferably includes a phosphite-based antioxidant, and more preferably S-9228A (BASF, China, Inc.). The antioxidant has outstanding high temperature resistance and discoloration resistance, can generate excellent synergistic effect when used together with the antioxidant and the stabilizer, and can improve the weather resistance, discoloration resistance, stress cracking resistance and mechanical property of the polypropylene modified plastic.
The invention provides a preparation method of polypropylene modified plastic, which comprises the following steps:
mixing polypropylene, a polypropylene compatibilizer, an antioxidant and a stabilizer to obtain a mixed material;
extruding and granulating the mixed material and the flame retardant to obtain polypropylene modified plastic;
the flame retardant is added in a side feeding mode.
The process flow diagram for preparing polypropylene modified plastics is shown in figure 1.
The invention mixes polypropylene, polypropylene compatibilizer, antioxidant and stabilizer to obtain a mixed material.
In the invention, the mixing mode is preferably that the polypropylene and the polypropylene compatibilizer are firstly mixed, and the antioxidant and the stabilizer are added for second mixing. In the present invention, the rotation speed of the first mixing is preferably 1500 to 2000rpm, and more preferably 1500 rpm. In the present invention, the time for the first mixing is not particularly limited, and the first mixing may be performed uniformly. In the invention, the rotation speed of the second mixing is preferably 200-300 rpm, and more preferably 200 rpm; the time of the second mixing is preferably 3-5 min, and more preferably 3 min. The invention has no special limitation on the equipment for the first mixing and the second mixing, and the mixing equipment well known in the art can be adopted, such as a high-speed mixer; the temperature of the first mixing and the second mixing is not particularly limited in the present invention, and a mixing temperature well known in the art may be used, specifically, normal temperature. The mixing mode adopted by the invention can ensure the mixing uniformity of all the raw materials, and the temperature of the raw materials is controllable in the mixing process, so that the polypropylene modified plastic is ensured to have excellent stability, mechanical property and flame retardant effect.
After the mixed material is obtained, the mixed material and the flame retardant are extruded and granulated to obtain the polypropylene modified plastic; the flame retardant is added in a side feeding mode.
In the present invention, the extrusion granulation is preferably carried out in a twin screw extruder, the model of which is preferably SHJ-35 (south kyo hot mechanical equipment limited).
In the present invention, the mixed material is preferably placed in a feeding tank of the twin-screw extruder and granulated by the twin-screw extruder.
In the present invention, the temperatures of the zones in the twin-screw extruder are respectively: the first zone is preferably 155-175 ℃, more preferably 160-170 ℃ and most preferably 165 ℃; the second zone is preferably 165-185 ℃, more preferably 170-180 ℃, and most preferably 175 ℃; the preferable three regions are 165-185 ℃, more preferable 170-180 ℃, and most preferable 175 ℃; the preferable temperature of the fourth zone is 170-190 ℃, more preferable temperature is 175-185 ℃, and the most preferable temperature is 180 ℃; the preferable temperature of the fifth area is 170-190 ℃, the more preferable temperature is 175-185 ℃, and the most preferable temperature is 180 ℃; the six areas are preferably 170-190 ℃, more preferably 175-185 ℃ and most preferably 180 ℃; the preferable seven regions are 170-190 ℃, more preferably 175-185 ℃ and most preferably 180 ℃; the preferred temperature of the eight regions is 170-190 ℃, the more preferred temperature is 175-185 ℃, and the most preferred temperature is 180 ℃; the nine zones are preferably 165-185 ℃, more preferably 170-180 ℃, and most preferably 175 ℃; the ten zones are preferably 165-185 ℃, more preferably 170-180 ℃, and most preferably 175 ℃.
In the present invention, the operating parameters of the twin-screw extruder are: the rotating speed of the main machine is preferably 400-550 rpm, more preferably 420-480 rpm, and most preferably 440-460 rpm; the host current is preferably 400-480A, more preferably 420-460A, and most preferably 440A; the number of membrane pores is preferably 32-40, more preferably 34-38, and most preferably 35-36; the pore diameter of the membrane pores is preferably 4 mm; the number of layers of the filter screen is preferably one, and the aperture of the filter screen is preferably 60 meshes; the vacuum degree is preferably more than or equal to 0.04MPa, namely the vacuum pressure is preferably less than or equal to 0.04 MPa.
After the extrusion granulation is completed, the invention preferably further comprises the steps of cooling, granulating and detecting finished products of the obtained granules. The cooling method and operation of the present invention are not particularly limited, and those known in the art may be used. The present invention is not particularly limited to the above-mentioned pellet, and a pellet-forming operation well known in the art may be employed. In the present invention, the particle size of the polypropylene-modified plastic is preferably (3 to 5) mm × (3 to 5) mm, and more preferably 4mm × 4 mm. In the invention, the finished product is preferably used after being detected to be qualified.
According to the preparation method of the polypropylene modified plastic, the flame retardant is added in a side feeding manner, so that the residence time of the flame retardant in a double-screw extruder can be ensured, the flame retardant and a mixed material can be uniformly dispersed, the flame retardant is prevented from being carbonized, the flame retardant effect of the flame retardant can be better protected, and the coupling rate of resin and the flame retardant can be improved, so that the flame retardant effect of the polypropylene compatibilizer is improved, the temperature and the process parameters of extrusion granulation are controlled, the mechanical property and the flame retardant effect of the polypropylene modified plastic can be effectively improved, the operation is simple, and the preparation method is suitable for industrial production.
The invention also provides the application of the polypropylene modified plastic in the technical scheme or the polypropylene modified plastic prepared by the preparation method in the technical scheme in rail transit. In the present invention, the polypropylene modified plastic is preferably applied to rail vehicles, such as passenger trains, trains or high-speed rails. In the present invention, the polypropylene-modified plastic is preferably applied to a battery case of the above-mentioned vehicle.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 65 parts by weight of PP BJ100N, 35 parts by weight of TMB-5 nucleating agent, 10 parts by weight of maleic anhydride and 5 parts by weight of DCP polymerization initiator, and then extruding and granulating by a double-screw extruder, cooling and granulating to obtain a polypropylene compatibilizer (abbreviated as CMG 3001-T);
wherein the temperature of the first zone to the tenth zone of the double-screw extruder is 170 ℃; the working parameters of the double-screw extruder are as follows: the rotating speed of the host is 500rpm, the current of the host is 440A, and the number of membrane pores is 35; the aperture of the membrane hole is 4 mm; the number of the layers of the filter screen is one, and the aperture of the filter screen is 60 meshes; the vacuum pressure was 0.04 MPa.
And testing the grafting rate of the maleic anhydride in the obtained polypropylene compatibilizer by adopting an infrared spectrophotometer method.
Examples 2 to 3
The polypropylene compatibilizer was prepared according to the method of example 1, wherein the amounts of the raw materials and the grafting ratio of maleic anhydride in examples 1 to 3 are shown in table 1:
table 1 examples 1 to 3 each amount (parts by mass) of raw material and graft ratio of maleic anhydride
| Raw materials | PPBJ100N | TMB-5 nucleating agent | Maleic anhydride | DCP polymerization initiators | Percent of grafting% |
| Example 1 | 65 | 35 | 10 | 5 | 2.3 |
| Example 2 | 68 | 37 | 12 | 5.5 | 2.4 |
| Example 3 | 70 | 40 | 15 | 6 | 2.5 |
As can be seen from Table 1, the grafting ratio of the polypropylene compatibilizer prepared by the invention is more than 2.3%, and the grafting ratio is high.
Test example 1
The mechanical properties of the polypropylene compatibilizer prepared in example 1, KT-1 (Shenyangtong plastics Co., Ltd.) and PP GM30 (Ningbo opto New Material science and technology Co., Ltd.) were measured, and the results are shown in Table 2.
TABLE 2 compatibilizer Performance test results
As can be seen from Table 2, the polypropylene compatibilizer prepared by the present invention has better mechanical properties than the commercially available polypropylene compatibilizers KT-1 and PP GM30, and further has better compatibilizing effects as a compatibilizer for polypropylene-modified plastics than the commercially available polypropylene compatibilizers KT-1 and PP GM 30.
Example 4
According to parts by weight, 25 parts of PP BJ100N, 35 parts of PP K8003, 15 parts of PP BX3905 and 5 parts of the polypropylene compatibilizer (CMG3001-T) prepared in example 1 are premixed at 1500rpm, 0.1 part of S-9228A and 0.1 part of 770DF are added and mixed for 3min at 200rpm to obtain a mixed material; adding 20 parts of HS-FP20 in a side feeding manner, uniformly mixing with the mixed material, and extruding and granulating by a double-screw extruder to obtain polypropylene modified plastic;
wherein the temperature of each zone in the double-screw extruder is respectively as follows: a first zone 165 ℃; a second zone is 175 ℃; a third area of 175 ℃; four areas are 180 ℃; five regions are 180 ℃; a sixth zone is 180 ℃; seven regions are 180 ℃; an eighth area is 180 ℃; nine zones at 175 ℃; 175 ℃ in ten areas;
the working parameters of the double-screw extruder are as follows: the rotating speed of the host is 500rpm, the current of the host is 440A, and the number of membrane pores is 35; the aperture of the membrane hole is 4 mm; the number of the layers of the filter screen is one, and the aperture of the filter screen is 60 meshes; the vacuum pressure was 0.04 MPa.
Examples 5 to 8
Polypropylene-modified plastics were prepared according to the method of example 4, and the amounts of the raw materials of examples 5 to 8 are shown in Table 2.
Comparative example 1
Polypropylene-modified plastic was prepared by the method of example 4, except that HS-FP20, S-9228A and 770DF were added simultaneously, and the amounts of the respective raw materials of comparative example 1 were as shown in Table 2.
Table 2 examples 4 to 8 and comparative example 1 each amount (parts by mass) of raw material
| Raw materials | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 |
| PPBJ100N | 25 | 30 | 25 | 25 | 24.5 | 25 |
| PPK8003 | 35 | 25 | 40 | 25 | 26.3 | 35 |
| PPBX3905 | 15 | 15 | 10 | 20 | 20 | 15 |
| CMG3001-T | 5 | 7 | 5 | 8 | 5 | 5 |
| HS-FP20 | 20 | 22 | 25 | 25 | 24 | 20 |
| S-9228A | 0.1 | 0.1 | 0.2 | 0.2 | 0.1 | 0.1 |
| 770DF | 0.1 | 0.05 | 0.1 | 0.1 | 0.1 | 0.1 |
Test example
The polypropylene modified plastics prepared in examples 4 to 8 and comparative example 1 were injection molded to obtain test specimens, wherein the model of an injection molding machine used for injection molding is preferably HTF160W1 (ningbo haitian group ltd), and the size of the test specimens is 80mm × 40mm × 10 mm.
The polypropylene modified plastics prepared in examples 4 to 8 and comparative example 1 were subjected to mechanical property and combustion property tests, and the test results are shown in table 3:
TABLE 3 mechanical Properties and flame retardancy test results of Polypropylene-modified plastics
As can be seen from Table 3, the polypropylene modified plastic provided by the invention has the tensile strength of 16.9-17.4 MPa, the elongation at break of 359-395%, the tensile modulus of 565-605 MPa, the bending strength of 20.6-21.5 MPa, the bending modulus of 987-1147 MPa, the melt index of more than 8.1g/10min, and the impact strength of more than 50kJ/m2The mechanical and processing properties and the stress cracking resistance are excellent; the oxygen index is more than 45%, the calorific value, the toxic gas and the smoke release amount of combustion are low, the combustion grade is V0 grade, the flame spread is 6-12, the flame propagation speed is Class1, the smoke toxicity is 1.5-1.7R, the smoke density is 7.02-7.12, the combustion test completely meets the requirements of BS 6853-. The polypropylene modified plastic provided by the invention has excellent mechanical property and flame retardant property, and has good application effect in rail transit.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The polypropylene compatibilizer is characterized by being prepared from the following components in parts by mass:
65-70 parts of polypropylene;
35-40 parts of a nucleating agent;
10-15 parts of maleic anhydride;
5-6 parts of an initiator.
2. The polypropylene compatibilizer according to claim 1, wherein the polypropylene comprises one or more of PP BJ100N, PP MT20, PP Z30S, and PP K7227;
the nucleating agent comprises one or more of polypropylene beta-crystal form nucleating agent and 8202 CQ; the polypropylene beta-crystalline nucleating agent comprises WBG;
the initiator comprises dicumyl peroxide and/or di-tert-butylperoxydiisopropylbenzene.
3. A method for preparing a polypropylene compatibilizer as claimed in claim 1 or 2, comprising the steps of:
and mixing the polypropylene, the nucleating agent, the maleic anhydride and the initiator, and then extruding and granulating to obtain the polypropylene compatibilizer.
4. The method according to claim 3, wherein the temperature of the extrusion granulation is 160 to 180 ℃.
5. The polypropylene modified plastic is characterized by being prepared from the following components in parts by mass:
75-90 parts of composite polypropylene;
5-7 parts of a polypropylene compatibilizer;
20-25 parts of a flame retardant;
0.1-0.2 part of antioxidant;
0.05-0.1 part of a stabilizer;
the polypropylene compatibilizer is the polypropylene compatibilizer described in any one of claims 1 to 2 or the polypropylene compatibilizer prepared by the preparation method described in any one of claims 3 to 4.
6. The polypropylene-modified plastic of claim 5, wherein the composite polypropylene comprises PP BJ100N, PP K8003, and PP BX 3905;
the mass ratio of the PPBJ100N to the PP K8003 to the PP BX3905 is (5-6): (5-8): (3-4).
7. The polypropylene modified plastic of claim 1, wherein the flame retardant comprises a phosphorus nitrogen based flame retardant;
the antioxidant comprises a phosphite antioxidant;
the stabilizer comprises a hindered amine light stabilizer.
8. A method for preparing polypropylene modified plastic as claimed in any one of claims 5 to 7, comprising the steps of:
mixing the composite polypropylene, the polypropylene compatibilizer, the antioxidant and the stabilizer to obtain a mixed material;
extruding and granulating the mixed material and the flame retardant to obtain polypropylene modified plastic;
the flame retardant is added in a side feeding mode.
9. The method according to claim 8, wherein the extrusion granulation is carried out in a twin-screw extruder in which the temperatures of the respective zones are: the temperature of the first zone is 155-175 ℃, the temperature of the second zone is 165-185 ℃, the temperature of the third zone is 165-185 ℃, the temperature of the fourth zone is 170-190 ℃, the temperature of the fifth zone is 170-190 ℃, the temperature of the sixth zone is 170-190 ℃, the temperature of the seventh zone is 170-190 ℃, the temperature of the eighth zone is 170-190 ℃, the temperature of the ninth zone is 165-185 ℃ and the temperature of the tenth zone is 165-185 ℃.
10. Use of the polypropylene modified plastic according to any one of claims 5 to 7 or the polypropylene modified plastic prepared by the preparation method according to any one of claims 8 to 9 in rail vehicles.
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| WO2009065774A1 (en) * | 2007-11-23 | 2009-05-28 | Basf Se | Grafting of ethylenically unsaturated monomers onto polymers in supercritical carbon dioxide |
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
| CN104592452A (en) * | 2015-01-19 | 2015-05-06 | 洛阳理工学院 | Preparation method of polypropylene modified material with high grafting rate |
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| WO2009065774A1 (en) * | 2007-11-23 | 2009-05-28 | Basf Se | Grafting of ethylenically unsaturated monomers onto polymers in supercritical carbon dioxide |
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
| CN104592452A (en) * | 2015-01-19 | 2015-05-06 | 洛阳理工学院 | Preparation method of polypropylene modified material with high grafting rate |
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