CN115926287A - Granulating method of compounded agent with melt finger control for polyolefin - Google Patents
Granulating method of compounded agent with melt finger control for polyolefin Download PDFInfo
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Abstract
The invention discloses a granulating method of a compounding agent with melt finger control for polyolefin, which comprises the following specific steps: (1) Adding a surfactant into an organic solvent, gradually heating, adding polyethylene wax, and stirring at a low speed; (2) Adding the modified nano silicon dioxide, stirring at a high speed, and gradually heating until the organic solvent flows back; (3) And adding the composite antioxidant in a reflux state, stirring and refluxing, gradually heating, and then adding the mixture for extrusion granulation to obtain the compounded agent for controlling the melt index of the polyolefin. The compound agent obtained by the granulation method can improve the processing fluidity of the polyolefin resin, produce different polyolefin resin products, improve the product quality and reduce the loss of equipment caused by product molding.
Description
Technical Field
The invention relates to a granulating method of a compounding agent with melt finger control for polyolefin, belonging to the technical field of compounding granulation.
Background
Polyolefin materials are one of the most widely used plastic varieties, wherein the polyolefin resin with high molecular weight, narrow distribution and low melting index has large market demand, because the resin has excellent mechanical property, cracking resistance and creep resistance and high added value, but because of the structural characteristics of the resin, the resin has large load on machine equipment in the granulation or product forming process, so that the machine equipment is seriously abraded and the energy consumption is high; in addition, the melt index of the polyolefin resin required for processing is different according to the structure, molding manner and the like of the product, and if each type of product is manufactured, the polyolefin resin with a specific melt index is purchased or prepared, so that the production cost is high, and the preparation process is different because the polyolefin resins with different melt indexes are produced, so that the production operation is not easy to control, the performance of the polyolefin resin is unstable, and the product quality is also influenced. Therefore, the invention provides a granulating method of the compounding agent for adjusting the low melt index of the polyolefin resin, and the obtained compounding agent with melt index control can improve the processing fluidity and the physical properties of the polyolefin resin so as to produce different polyolefin resin products, improve the product quality and reduce the loss of product molding to equipment.
Disclosure of Invention
In view of the problems of the prior art, the invention provides a granulating method of a compounded agent with melt index control for polyolefin, and the obtained compounded agent can improve the processing fluidity of polyolefin resin, produce different polyolefin resin products, improve the product quality and reduce the loss of equipment for product forming.
In order to achieve the purpose, the invention adopts the following technical scheme: a granulating method of a compounded agent with melt finger control for polyolefin is disclosed, wherein the compounded agent is prepared by taking polyethylene wax, modified nano-silica, a composite antioxidant and a surfactant as raw materials, and comprises the following specific steps:
(1) Adding a surfactant into an organic solvent, gradually heating to 40-45 ℃, maintaining, adding polyethylene wax, and stirring at a low speed for 3-3.5 hours;
(2) Adding the modified nano silicon dioxide, stirring at a high speed, and gradually heating until the organic solvent flows back, wherein the reflux time is 40-45 min;
(3) Adding the composite antioxidant in a reflux state, continuously stirring and refluxing for 30-35 min, gradually heating to 195-210 ℃ to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion granulation, and screening to remove fine powder to obtain the required compounded agent for polyolefin with melt index control;
the compound agent comprises the following components in parts by weight: 45-55% of polyethylene wax, 20-30% of modified nano-silica, 15-25% of composite antioxidant and 8-15% of surfactant;
the modified nano-silica is prepared by modifying nano-silica with maleic anhydride under the action of silane coupling reaction liquid.
Preferably, in step (1) and step (2), the heating rate of gradual heating is 0.5-1 ℃/min.
Preferably, in the step (1), the rotation speed of the low-speed stirring is 500-600 rpm.
Preferably, in the step (2), the rotation speed of the high-speed stirring is 2500-2600 rpm.
Preferably, in the step (3), the temperature rising rate of gradual heating is 1.5 to 2.5 ℃/min.
Preferably, in the step (3), the extrusion temperature in the twin-screw extruder is 165 to 175 ℃ and the rotation speed is 450 to 500rpm.
Preferably, the organic solvent is one of absolute ethyl alcohol or acetone.
Preferably, in step (1), the weight of the organic solvent is 80-110% of the weight of the polyethylene wax.
Preferably, the preparation method of the modified nano-silica comprises the following steps: firstly, heating the nano-silica to 350-400 ℃ under the condition of nitrogen and keeping the temperature for 20-25 min, then placing the nano-silica into silane coupling reaction liquid, hermetically stirring the nano-silica for 1.5-2 h at the temperature of 80-90 ℃ and the pressure of 1.2-1.5 MPa, then adding maleic anhydride and azobisisobutyronitrile, and reacting the mixture for 1-1.5 h at the temperature of 125-135 ℃ and the pressure of 1.5-2 MPa.
Wherein the weight ratio of the nano silicon dioxide, the silane coupling reaction liquid and the maleic anhydride is 1:1.35, and the addition amount of the azobisisobutyronitrile is 0.5-1% of the weight of the maleic anhydride.
Wherein the silane coupling reaction liquid is prepared by mixing 3-aminopropyltriethoxysilane and water according to a volume ratio of 5.
Preferably, the compound antioxidant is prepared by mixing the antioxidant 168, the antioxidant 1076 and the antioxidant 136.
Wherein, the weight ratio of the antioxidant 168 in the composite antioxidant is 59-66%, the weight ratio of the antioxidant 1076 is 21-26%, and the weight ratio of the antioxidant 136 is 13-16%.
Preferably, the surfactant is one of sorbitan fatty acid ester, sorbitol ester polyoxyethylene ether or fatty alcohol polyoxyethylene ether.
Compared with the prior art, the invention has the beneficial effects that:
1. the compounded agent with the melt index control can effectively increase the melt index of the polyolefin on the basis of not reducing other properties of the polyolefin, and improve the processing fluidity of the polyolefin;
2. the compounded agent with the melt index control adjusts the polyolefin to have different melt indexes through different addition amounts so as to meet the production requirements of different polyolefin resin products and improve the product quality;
3. the compounded agent with the melt index control can regulate and control the melt index of the polyolefin on the basis of not reducing other properties of the polyolefin, reduce the difficulty of product processing and reduce the loss of equipment caused by the product processing and forming.
4. The compounded agent with the melt finger control also improves the toughness and the impact strength of the polyolefin.
Detailed Description
In order to more clearly and completely illustrate the present invention, the following examples are given by way of illustration of the present invention, and are not intended to limit the present invention.
In the invention, the raw materials of the compound agent are selected for improving the melt index of the polyolefin, and comprise polyethylene wax, modified nano-silica, a compound antioxidant and a surfactant, wherein the modified nano-silica is prepared by modifying maleic anhydride on the basis of the nano-silica under the action of silane coupling reaction liquid, the compound antioxidant is prepared by mixing an antioxidant 168, an antioxidant 1076 and an antioxidant 136, and the surfactant is one of sorbitan fatty acid ester, sorbitol ester polyoxyethylene ether or fatty alcohol polyoxyethylene ether.
The specific preparation method of the modified nanosilica used in the present invention is as the following preparatory example:
the preparation method of modified nano-silica of the preparative example specifically comprises the following steps:
(1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 350-400 ℃, and then keeping for 20-25 min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 5;
(3) Placing the nano-silica obtained in the step (1) into the silane coupling reaction liquid obtained in the step (2), and hermetically stirring for 1.5-2 h at the temperature of 80-90 ℃ and the pressure of 1.2-1.5 MPa, wherein the weight ratio of the nano-silica to the silane coupling reaction liquid is 1;
(4) Sequentially adding maleic anhydride and azobisisobutyronitrile into the system obtained in the step (3), reacting at 125-135 ℃ and 1.5-2 MPa for 1-1.5 h, wherein the weight ratio of the nano-silica to the maleic anhydride is 1.
Preparative example 1 preparation of modified nanosilica
The method comprises the following specific operations: (1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 350 ℃, and then keeping for 25min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 5;
(3) Placing 100g of the nano silicon dioxide obtained in the step (1) into 135g of the silane coupling reaction liquid obtained in the step (2), and hermetically stirring for 1-2 h at the temperature of 80 ℃ and the pressure of 1.2 MPa;
(4) And (3) sequentially adding 210g of maleic anhydride and 1.05g of azobisisobutyronitrile into the system obtained in the step (3), and reacting at 135 ℃ and 2MPa for 1-1.5 h to obtain the required modified nano silicon dioxide.
Preparative example 2 preparation of modified nanosilica
The method comprises the following specific operations: (1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 375 ℃, and then keeping for 22min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 5;
(3) Placing 100g of the nano silicon dioxide obtained in the step (1) into 135g of the silane coupling reaction liquid obtained in the step (2), and hermetically stirring for 1.5-2 h at the temperature of 85 ℃ and the pressure of 1.35 MPa;
(4) And (4) sequentially adding 210g of maleic anhydride and 1.68g of azobisisobutyronitrile into the system obtained in the step (3), and reacting at 130 ℃ and 1.75MPa for 1-1.5 h to obtain the required modified nano silicon dioxide.
Preparative example 3 preparation of modified nanosilica
The method comprises the following specific operations: (1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 400 ℃, and then keeping for 20min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 5;
(3) Placing 100g of the nano silicon dioxide obtained in the step (1) into 135g of the silane coupling reaction solution obtained in the step (2), and hermetically stirring for 1.5-2 h at the temperature of 90 ℃ and the pressure of 1.5 MPa;
(4) And (3) sequentially adding 210g of maleic anhydride and 2.1g of azobisisobutyronitrile into the system obtained in the step (3), and reacting at 135 ℃ and 2MPa for 1-1.5 h to obtain the required modified nano silicon dioxide.
The above preparatory examples 1 to 3 were used in the following granulation method of the present invention for preparing a compounded agent with melt index control, specifically the following examples:
example 1 preparation of a compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 8g of sorbitan fatty acid ester into 36g of absolute ethyl alcohol, gradually heating to 40 ℃ at the heating rate of 0.5 ℃/min and maintaining, adding 45g of polyethylene wax, and stirring at a low speed of 500rpm for 3.5 hours;
(2) Then adding 25g of the modified nano-silica prepared in preparation example 1, stirring at a high speed of 2500rpm, gradually heating at a heating rate of 0.5 ℃/min until the organic solvent refluxes, wherein the refluxing time is 40min;
(3) Adding 22g of composite antioxidant prepared by mixing 59% of antioxidant 168, 21% of antioxidant 1076 and 16% of antioxidant 136 in percentage by weight under the reflux state, continuously stirring and refluxing for 35min, gradually heating to 195 ℃ at the heating rate of 1.5 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent with melt index control for the polyolefin.
Example 2 preparation of a compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 10g of sorbitan fatty acid ester into 45g of acetone, gradually heating to 43 ℃ at the heating rate of 0.75 ℃/min and maintaining, adding 50g of polyethylene wax, and stirring at a low speed of 550rpm for 3.25h;
(2) Adding 23g of the modified nano-silica prepared in the preparation example 1, stirring at a high speed of 2550pm, and gradually heating at a heating rate of 0.75 ℃/min until the organic solvent reflows, wherein the reflowing time is 43min;
(3) And adding 17g of composite antioxidant prepared by mixing 62 percent of antioxidant 168, 22 percent of antioxidant 1076 and 16 percent of antioxidant 136 in percentage by weight under the reflux state, continuously stirring and refluxing for 33min, gradually heating to 200 ℃ at the heating rate of 2 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent for the polyolefin with melt index control.
EXAMPLE 3 preparation of compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 15g of sorbitol ester polyoxyethylene ether into 48g of acetone, gradually heating to 45 ℃ at the heating rate of 1 ℃/min, maintaining, adding 48g of polyethylene wax, and stirring at a low speed of 600rpm for 3 hours;
(2) Then 20g of the modified nano-silica prepared in preparation example 2 is added, high-speed stirring is carried out at the rotating speed of 2600pm, and the mixture is gradually heated at the heating rate of 1 ℃/min until the organic solvent refluxes, wherein the refluxing time is 45min;
(3) And adding 17g of composite antioxidant prepared by mixing 61 wt% of antioxidant 168, 22 wt% of antioxidant 1076 and 15 wt% of antioxidant 136 in a reflux state, continuously stirring and refluxing for 30min, gradually heating to 210 ℃ at the heating rate of 2.5 ℃/min, completely evaporating the organic solvent to form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent with melt index control for the polyolefin.
Example 4 preparation of compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 8g of fatty alcohol-polyoxyethylene ether into 49.5g of absolute ethanol, gradually heating to 45 ℃ at a heating rate of 0.5 ℃/min, maintaining, adding 45g of polyethylene wax, and stirring at a low speed of 600rpm for 3.5 hours;
(2) Then adding 25g of the modified nano-silica prepared in preparation example 3, stirring at a high speed of 2600pm, and gradually heating at a heating rate of 1 ℃/min until the organic solvent refluxes, wherein the refluxing time is 45min;
(3) Adding 22g of composite antioxidant prepared by mixing 59% of antioxidant 168, 25% of antioxidant 1076 and 16% of antioxidant 136 in percentage by weight under the reflux state, continuously stirring and refluxing for 35min, gradually heating to 205 ℃ at the heating rate of 1.75 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent with melt index control for the polyolefin.
EXAMPLE 5 preparation of compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 8g of behenyl alcohol polyoxyethylene ether into 49.5g of absolute ethyl alcohol, gradually heating to 40 ℃ at a heating rate of 1 ℃/min, maintaining the temperature, adding 55g of polyethylene wax, and stirring at a low speed of 500rpm for 3.5 hours;
(2) Adding 22g of the modified nano-silica prepared in preparation example 2, stirring at a high speed of 2500pm, gradually heating at a heating rate of 0.5 ℃/min until the organic solvent flows back, wherein the reflux time is 40min;
(3) And adding 15g of composite antioxidant formed by mixing 66 percent of antioxidant 168, 21 percent of antioxidant 1076 and 13 percent of antioxidant 136 in a refluxing state, continuously stirring and refluxing for 35min, gradually heating to 205 ℃ at the heating rate of 1.5 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent for polyolefin with melt index control.
EXAMPLE 6 preparation of compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 10g of fatty alcohol-polyoxyethylene ether into 49.5g of acetone, gradually heating to 43 ℃ at the heating rate of 0.5 ℃/min and maintaining, adding 45g of polyethylene wax, and stirring at a low speed of 500rpm for 3.5h;
(2) Then adding 30g of the modified nano-silica prepared in preparation example 3, stirring at a high speed of 2500pm, gradually heating at a heating rate of 0.75 ℃/min until the organic solvent reflows, wherein the reflowing time is 40min;
(3) Adding 15g of composite antioxidant prepared by mixing 59% of antioxidant 168, 26% of antioxidant 1076 and 15% of antioxidant 136 in percentage by weight under the reflux state, continuously stirring and refluxing for 32min, gradually heating to 195 ℃ at the heating rate of 2 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder to perform extrusion granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent for controlling the polyolefin by using the melt index.
Example 7 preparation of a compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 8g of behenyl alcohol polyoxyethylene ether into 46g of propylene absolute ethyl alcohol, gradually heating to 40 ℃ at a heating rate of 1 ℃/min, maintaining the temperature, adding 46g of polyethylene wax, and stirring at a low speed of 500rpm for 3.5 hours;
(2) Then 21g of the modified nano-silica prepared in preparation example 1 is added, high-speed stirring is carried out at the rotating speed of 2500pm, and the mixture is gradually heated at the heating rate of 1 ℃/min until the organic solvent refluxes, wherein the refluxing time is 45min;
(3) Adding 25g of composite antioxidant prepared by mixing 59% of antioxidant 168, 25% of antioxidant 1076 and 16% of antioxidant 136 in percentage by weight under the reflux state, continuously stirring and refluxing for 35min, gradually heating to 210 ℃ at the heating rate of 2.5 ℃/min, completely evaporating the organic solvent to form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent with melt index control for the polyolefin.
EXAMPLE 8 preparation of compounded formulation with melt finger control
The method comprises the following specific operations: (1) Adding 12g of sorbitan fatty acid ester into 36g of absolute ethyl alcohol, gradually heating to 42 ℃ at a heating rate of 0.5 ℃/min and maintaining, adding 45g of polyethylene wax, and stirring at a low speed of 500rpm for 3.5h;
(2) Adding 27g of the modified nano-silica prepared in preparation example 3, stirring at a high speed of 2500pm, gradually heating at a heating rate of 0.5 ℃/min until the organic solvent refluxes, wherein the refluxing time is 45min;
(3) Adding 25g of composite antioxidant prepared by mixing 64 wt% of antioxidant 168, 22 wt% of antioxidant 1076 and 14 wt% of antioxidant 136 under reflux, continuously stirring and refluxing for 30min, gradually heating to 200 ℃ at the heating rate of 1.5 ℃/min to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion and granulation, wherein the extrusion temperature is 165-175 ℃, the rotation speed is 450-500 rpm, and screening to remove fine powder to obtain the required compounded agent with melt index control for polyolefin.
In comparison to the compounded formulation with melt finger control prepared by the granulation process of the present invention, the following comparative examples are provided:
comparative example 1
This comparative example 1 is different from example 2 in that: the nano silicon dioxide added in the step (2) is the same as the rest.
Comparative example 2
This comparative example 2 is different from example 2 in that: the preparation steps of the modified nano silicon dioxide added in the step (2) are as follows: (1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 350 ℃, and then keeping for 25min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 5;
(3) Placing 100g of the nano silicon dioxide obtained in the step (1) in 135g of the silane coupling reaction solution obtained in the step (2), and hermetically stirring for 1-2 h at the temperature of 80 ℃ and the pressure of 1.2 MPa;
(4) Sequentially adding 210g of polymaleic anhydride and 1.05g of azobisisobutyronitrile into the system obtained in the step (3), and reacting at 135 ℃ and 2MPa for 1-1.5 h to obtain the required modified nano-silica;
the rest is identical.
Comparative example 3
This comparative example 3 is different from example 2 in that: the preparation steps of the modified nano silicon dioxide added in the step (2) are as follows: (1) Placing the nano silicon dioxide in a muffle furnace filled with nitrogen, heating to 350 ℃, and then keeping for 25min;
(2) Mixing 3-aminopropyltriethoxysilane with water according to a volume ratio of 6;
(3) 105g of the nano silicon dioxide obtained in the step (1) is placed in 125g of the silane coupling reaction liquid obtained in the step (2), and sealed and stirred for 1-2 h at the temperature of 80 ℃ and the pressure of 1.2 MPa;
(4) Sequentially adding 210g of maleic anhydride and 2.2g of azobisisobutyronitrile into the system obtained in the step (3), and reacting at 135 ℃ and 2MPa for 1-1.5 h to obtain the required modified nano-silica;
the rest is identical.
Comparative example 4
This comparative example 4 is different from example 4 in that: in the step (3), only the antioxidant 168 is used, and the rest is the same.
Comparative example 5
This comparative example 5 is different from example 4 in that: in the step (3), only the antioxidant 1076 is used, and the rest is the same.
Comparative example 6
This comparative example 6 is different from example 4 in that: in the step (3), only the antioxidant 136 is used, and the rest is the same.
Comparative example 7
This comparative example 7 is different from example 4 in that: in the step (3), only the antioxidant 1010 is used, and the rest is completely the same.
Comparative example 8
This comparative example 8 is different from example 4 in that: the composite antioxidant in the step (3) is formed by mixing 59% of antioxidant 168 and 41% of antioxidant 136 in percentage by weight, and the rest is completely the same.
Comparative example 9
This comparative example 9 is different from example 4 in that: the composite antioxidant in the step (3) is prepared by mixing 42% of antioxidant 168, 35% of antioxidant 1076 and 28% of antioxidant 136 in percentage by weight, and the rest is completely the same.
Comparative example 10
This comparative example 10 is different from example 8 in that: the heating in steps (1), (2) and (3) is rapid heating with a heating rate of 10 ℃/min, and the rest is the same.
Comparative example 11
This comparative example 11 is different from example 8 in that: the heating in the steps (1) and (2) is rapid heating, the heating rate is 10 ℃/min, and the rest is completely the same.
Comparative example 12
This comparative example 12 is different from example 8 in that: the heating in step (3) is rapid heating with a temperature rise rate of 10 ℃/min, and the rest is the same.
Comparative example 13
This comparative example 13 is different from example 8 in that: the temperature rise rate of gradual heating in steps (1), (2) and (3) is 0.25 ℃/min, and the rest is the same.
Comparative example 14
This comparative example 14 is different from example 8 in that: the temperature rising rate of gradual heating in the steps (1) and (2) is 2 ℃/min, the temperature rising rate of gradual heating in the step (3) is 3 ℃/min, and the rest is the same.
The effect of compounded agents with melt index control prepared in examples 1 to 8 of the present invention and comparative examples 1 to 14 in polyolefins, specific results are as follows:
effects of the embodiment
1. The compounded agents with melt index control prepared in examples 1 to 8 were uniformly mixed with polyethylene for granulation and extrusion, and the tensile properties and the flow properties were measured and compared with those of polyethylene without the compounded agent, and the results are shown in tables 1, 2, 3 and 4;
table 1 examples 1 to 8 compounding agent 0.5 ‰ was added to polyethylene
Table 2 examples 1 to 8 compounding agents 1 ‰ added to polyethylene
Table 3 example 1 to example 8 compounded agent 2 ‰ added to polyethylene
Table 4 examples 1 to 8 compounding agents 5 ‰ added to polyethylene
From the results shown in tables 1 to 4, it is understood that the compounding agent with melt index control of the present invention can improve the processing flowability of polyolefin without lowering other properties of polyolefin, and improve the toughness and impact strength of polyolefin, and the melt flow rate of polyolefin increases with the increase of the addition amount of the compounding agent with melt index control, that is, the melt index of polyolefin is different depending on the addition amount of the compounding agent with melt index control.
2. The compounded agent prepared in example 2 and having the melt index control, the compounded agents prepared in comparative examples 1 to 3 and polyethylene are uniformly mixed for granulation and extrusion, the tensile property and the flow property are tested, and the compound is compared with the polyethylene granulation and extrusion without the compounded agent, and the result is shown in 5;
table 5 example 2, comparative example 1 to comparative example 3 compounding agent 2 ‰ added to polyethylene
As can be seen from the results of table 5 above, the compounded agent with melt index control prepared from the modified silica prepared by modifying nano-silica with maleic anhydride under the action of the silane coupling reaction solution according to the present invention has a greater effect on the melt flow rate of polyethylene and a more significant increase in the fluidity of polyethylene, and the compounded agent of the present invention prepared from the components in the pre-examined example has a more excellent effect of improving the fluidity of polyethylene melt than the compound prepared from the modified silica prepared in the preparation example of the present invention.
3. The compounded agent prepared in example 4 and prepared in comparative example 5 to comparative example 9 were uniformly mixed with polypropylene for granulation and extrusion, and the tensile properties and the flow properties were measured and compared with those of polypropylene without the compounded agent, and the results are shown in 6;
table 6 example 2, comparative example 5 to comparative example 9 compounding agent 1.5% o was added to polypropylene
As can be seen from the results in table 6 above, the compounded agent prepared from the compound antioxidant of the present invention has a greater effect on the flow rate of the polyethylene melt than the compounded agent prepared from a single antioxidant, the compounded agent prepared from the compound antioxidant prepared from the mixture of the antioxidant 168, the antioxidant 1076 and the antioxidant 136 has a more significant improvement on the flow rate of the polyethylene melt, and the compounded agent prepared from the compound antioxidant prepared from the antioxidant 168, the antioxidant 1076 and the antioxidant 136 in the examples of the present invention has a more excellent improvement on the flow rate of the polyethylene melt, which is preferred to be the compound antioxidant in the examples of the present invention.
4. The compounded agent prepared in example 8 and prepared in comparative example 10 to comparative example 14 were uniformly mixed with polypropylene to perform granulation extrusion, the tensile properties and the flow properties were tested, and the result is shown in 7 when compared with the polypropylene granulation extrusion without the compounded agent;
table 7 example 8, comparative example 10 to comparative example 14 compounding agent 1.5% o was added to polypropylene
From the results of Table 6 above, it can be seen that the improvement of the melt flow rate of polyethylene by the compounded agent of the present invention using the gradual heating method is more remarkable than that of the compounded agent prepared by the rapid heating method, and the improvement of the melt flow rate of polyethylene by the compounded agent prepared at the gradual heating temperature rate of the examples of the present invention, which is preferred, is more excellent.
In conclusion, the compounding agent with melt index control can effectively increase the melt index of the polyolefin on the basis of not reducing other properties of the polyolefin, improve the processing fluidity of the polyolefin and also improve the physical properties of the polyolefin; the difficulty of processing products can be reduced, and the loss of equipment caused by the processing product molding is reduced; the addition amount of the compound agent is regulated and controlled to meet the production requirements of different polyolefin resin products, and the product quality is improved.
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the present invention without departing from the spirit and scope of the present invention, and all modifications or partial substitutions should be covered by the scope of the claims of the present invention.
Claims (10)
1. A granulating method of a compounded agent with melt index control for polyolefin is characterized in that the compounded agent is prepared by taking polyethylene wax, modified nano-silica, a composite antioxidant and a surfactant as raw materials, and comprises the following specific steps:
(1) Adding a surfactant into an organic solvent, gradually heating to 40-45 ℃, maintaining, adding polyethylene wax, and stirring at a low speed for 3-3.5 hours;
(2) Adding the modified nano silicon dioxide, stirring at a high speed, and gradually heating until the organic solvent flows back, wherein the reflux time is 40-45 min;
(3) Adding the composite antioxidant in a reflux state, continuously stirring and refluxing for 30-35 min, gradually heating to 195-210 ℃ to completely evaporate the organic solvent and form a suspension emulsion, adding the suspension emulsion into a double-screw extruder for extrusion granulation, and screening to remove fine powder to obtain the required compounded agent for polyolefin with melt index control;
the compound agent comprises the following components in parts by weight: 45-55% of polyethylene wax, 20-30% of modified nano-silica, 15-25% of composite antioxidant and 8-15% of surfactant;
the modified nano-silica is prepared by modifying nano-silica with maleic anhydride under the action of silane coupling reaction liquid.
2. The method of claim 1, wherein the gradual heating is performed at a temperature increase rate of 0.5 to 1 ℃/min in the steps (1) and (2); in the step (3), the heating rate of gradual heating is 1.5-2.5 ℃/min.
3. The method of claim 1, wherein the modified nanosilica is prepared by a process comprising: firstly, heating the nano silicon dioxide to 350-400 ℃ under the condition of nitrogen and keeping the temperature for 20-25 min, then placing the nano silicon dioxide in silane coupling reaction liquid, hermetically stirring the nano silicon dioxide at the temperature of 80-90 ℃ and the pressure of 1.2-1.5 MPa for 1.5-2 h, then adding maleic anhydride and azobisisobutyronitrile, and carrying out reaction at the temperature of 125-135 ℃ and the pressure of 1.5 MPa-2 MPa for 1-1.5 h.
4. The method of claim 3, wherein the weight ratio of the nanosilicon dioxide, the silane coupling reaction solution and the maleic anhydride is 1:1.35, 2.1, wherein the addition amount of the azobisisobutyronitrile is 0.5-1% of the weight of the maleic anhydride; the silane coupling reaction solution is prepared by mixing 3-aminopropyltriethoxysilane and water according to a volume ratio of 5.
5. The method of claim 1, wherein the antioxidant compound is a mixture of antioxidant 168, antioxidant 1076, and antioxidant 136.
6. The method of claim 5, wherein the antioxidant 168, the antioxidant 1076, and the antioxidant 136 are present in an amount of 59 to 66%, 21 to 26%, and 13 to 16%, respectively.
7. The method of claim 1, wherein the surfactant is one of sorbitan fatty acid ester, sorbitan ester polyoxyethylene ether, or fatty alcohol polyoxyethylene ether.
8. The method of claim 1, wherein the low speed stirring is performed at a speed of 500 to 600rpm; in the step (2), the rotation speed of the high-speed stirring is 2500-2600 rpm.
9. The method of claim 1, wherein the twin-screw extruder is operated at a temperature of 165-175 ℃ and a speed of 450-500 rpm.
10. The method for granulating a compounded agent with melt index control for polyolefin according to claim 1, wherein the weight of the organic solvent is 80-110% of that of the polyethylene wax; the organic solvent is one of absolute ethyl alcohol or acetone.
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| CA2259529A1 (en) * | 1996-08-06 | 1998-02-12 | Exxon Chemical Patents, Inc. | Method of processing polyethylene and polyethylene/elastomer blends |
| WO2004106434A1 (en) * | 2003-05-27 | 2004-12-09 | Toray Industries, Inc. | Resin composition |
| DE102006045812A1 (en) * | 2006-09-28 | 2008-04-03 | Clariant International Limited | Uploaded peroxide masterbatch for targeted degradation or crosslinking reactions in plastics |
| CN104419066A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Polypropylene composition for preparing polypropylene microporous membrane and preparation method of polypropylene composition |
| CN108610763A (en) * | 2016-12-27 | 2018-10-02 | 上海邦中高分子材料有限公司 | A kind of polyethylene powder coating and preparation method thereof of plastic-coated composite pipe high adhesion force and good leveling property |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2259529A1 (en) * | 1996-08-06 | 1998-02-12 | Exxon Chemical Patents, Inc. | Method of processing polyethylene and polyethylene/elastomer blends |
| WO2004106434A1 (en) * | 2003-05-27 | 2004-12-09 | Toray Industries, Inc. | Resin composition |
| DE102006045812A1 (en) * | 2006-09-28 | 2008-04-03 | Clariant International Limited | Uploaded peroxide masterbatch for targeted degradation or crosslinking reactions in plastics |
| CN104419066A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Polypropylene composition for preparing polypropylene microporous membrane and preparation method of polypropylene composition |
| CN108610763A (en) * | 2016-12-27 | 2018-10-02 | 上海邦中高分子材料有限公司 | A kind of polyethylene powder coating and preparation method thereof of plastic-coated composite pipe high adhesion force and good leveling property |
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