CN111363293B - Preparation method of auxiliary agent system for producing high-rigidity high-toughness polypropylene thin-wall injection molding material - Google Patents
Preparation method of auxiliary agent system for producing high-rigidity high-toughness polypropylene thin-wall injection molding material Download PDFInfo
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Abstract
The invention discloses a method for preparing an auxiliary agent system for producing high-rigidity high-toughness polypropylene thin-wall injection molding materials, which comprises a styrene-butadiene-styrene block copolymer, a styrene-acrylonitrile copolymer, an antioxidant, an organic modified filler stiffening agent, a carboxymethyl cellulose dispersing agent, a modified sorbitol nucleating agent, an elastomer toughening agent, a slipping agent and a microstructure adjusting auxiliary agent, and the preparation method comprises the following steps: the surface of the filler stiffening agent is activated and modified to prepare the organic modified filler stiffening agent, and the sorbitol nucleating agent is subjected to auxiliary synergistic treatment, wherein the components are sequentially subjected to high-speed stirring treatment in a reactor under the conditions of no solvent through nitrogen protection and oil bath heating, and are subjected to melt mixing and extrusion granulation to prepare the auxiliary agent system. The auxiliary agent system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material is prepared, so that the rigidity and toughness of the polypropylene thin-wall injection molding material are improved, and the haze of the polypropylene thin-wall injection molding material is reduced.
Description
Technical Field
The invention relates to a preparation method of an auxiliary agent system for producing high-rigidity high-toughness polypropylene thin-wall injection molding materials, belonging to the technical field of auxiliary agent systems for producing polypropylene.
Background
The polypropylene is one of five common plastics with the largest production consumption, and has the advantages of no toxicity, no harm, low cost, easy processing and the like. The polypropylene special material has wide application prospect in the fields of food packaging, medicine and health, electronic and electric appliances, daily necessities, mechanical devices and the like, and can be used for producing packaging products such as fresh-keeping boxes, medicine boxes, take-out products and the like, plastic containers such as sorting boxes, storage cabinets and the like, mechanical devices such as picking-up pieces, stacking and the like, and high-precision devices such as mobile phone rear covers and the like. In recent years, packaging products, plastic containers, mechanical devices, high-precision devices and the like gradually develop to thin walls and even ultra-thin walls, the rigidity of manufactured parts is seriously reduced due to the reduction of the wall thickness in thin-wall injection molding, and currently, the addition of a stiffening assistant is the most common, simplest and most effective method for changing the rigidity of polypropylene thin-wall injection molding materials, but the toughness of the polypropylene thin-wall injection molding materials is greatly lost, and the defects of insufficient impact resistance, low transparency, easiness in crushing at low temperature and the like exist. Some auxiliary agent systems on the market can only solve the problem of single rigidity, and the mixed inorganic stiffening agent, nucleating agent and the like are physically mixed, so that the performance of the auxiliary agent system is influenced by uneven mixing, and the requirement on the rigidity cannot be met. Therefore, the auxiliary agent system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material and the preparation method thereof are needed, the auxiliary agent system can reduce the haze of the polypropylene thin-wall injection molding material, improve the transparency and the impact resistance of the polypropylene thin-wall injection molding material, and has the advantages of difficult deformation and difficult brittle fracture.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of an auxiliary agent system for producing a high-rigidity high-toughness polypropylene thin-wall injection molding material, so that the auxiliary agent system can simultaneously improve the rigidity and toughness of the polypropylene thin-wall injection molding material and reduce the haze of the polypropylene thin-wall injection molding material, thereby improving the transparency and impact resistance of the polypropylene thin-wall injection molding material, and being not easy to deform and brittle fracture.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of an auxiliary agent system for producing high-rigidity high-toughness polypropylene thin-wall injection molding materials comprises the following components: styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, organic modified filler stiffening agent, elastomer toughening agent, modified sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjusting auxiliary agent; the microstructure adjusting aid consists of a hydroxyl phosphate aluminum salt nucleating agent and magnesium sulfate whiskers in a weight ratio of 1:1.2, the slipping agent consists of magnesium stearate or calcium stearate and glyceryl monostearate in a weight ratio of 2:1.3, and the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a weight ratio of 2.5: 1;
the organic modified filler stiffening agent is prepared by performing surface activation modification treatment on the filler stiffening agent through a coupling agent and carboxyl latex;
the modified sorbitol nucleating agent is prepared by mixing the sorbitol nucleating agent with anthraquinone disperse dye for auxiliary synergistic treatment;
the preparation method of the auxiliary agent system comprises the following steps:
(1) under the protection of nitrogen, adding a styrene-butadiene-styrene block copolymer and a styrene-acrylonitrile copolymer in a weight ratio of 3: 2-3: 2.5 into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at a speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8-10% of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing the mixture;
(2) then adding an organic modified filler stiffening agent which accounts for 153-165% of the weight of the styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding a carboxymethyl cellulose dispersing agent which accounts for 2-4% of the weight of the organic modified filler stiffening agent and a modified sorbitol nucleating agent which accounts for 43-47% of the weight of the organic modified filler stiffening agent, and mixing for 15-20 min;
(3) adding an elastomer toughening agent accounting for 33-38% of the weight of the organic modified filler stiffening agent until the organic modified filler stiffening agent is completely melted, uniformly mixing, adding a slipping agent accounting for 3-6% of the weight of the elastomer toughening agent, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 5-7% of the weight of the elastomer toughening agent, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(4) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Preferably, the organic modified filler stiffening agent is prepared, the coupling agent is an aluminate coupling agent, and the carboxyl latex is carboxyl styrene-butadiene latex; adding a filler stiffening agent and water in a weight ratio of 5: 3.5-5: 4 into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2-2.5% of the weight of the filler stiffening agent, mixing for 15-20 min, adding a carboxylic styrene-butadiene latex accounting for 35-45% of the weight of the filler stiffening agent, mixing for 45-55 min, then adding a slipping agent accounting for 1.5-2.2% of the weight of the filler stiffening agent, mixing for 15-18 min, heating in a water bath to 50-55 ℃, removing for 7-12 min, taking out and drying to obtain the organic modified filler stiffening agent.
Preferably, the modified sorbitol nucleating agent is prepared by putting anthraquinone disperse dyes into a grinding machine to be ground until the particle size is smaller than 50 microns, adding sorbitol nucleating agents and ethanol with water content of 60% in a weight ratio of 4: 7-4: 9 into a No. 2 three-neck flask, stirring and mixing for 10-15 min under the condition that the speed is 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agents accounting for 0.05-0.07% of the weight of the sorbitol nucleating agents and ground anthraquinone disperse dyes accounting for 0.07-0.12% of the weight of the sorbitol nucleating agents, mixing for 15-20 min, then heating in a water bath to 45-50 ℃, distilling to recover ethanol water solution, taking out and drying to obtain the modified sorbitol nucleating agent.
Preferably, the filler stiffening agent is selected from nano montmorillonite, nano talcum powder or nano mica.
Preferably, the elastomer toughening agent is ethylene-butene copolymer or ethylene-octene copolymer.
The invention has the beneficial effects that:
1) the invention adopts styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, organic modified filler stiffening agent, elastomer toughening agent, modified sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjustment auxiliary agent as raw materials, the raw materials are stirred at high speed in a reactor, and are melted and mixed under the conditions of no solvent through nitrogen protection and oil bath heating, the process is simple, the process condition is easy to control, the auxiliary agent system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material is prepared, the problem that some conventional auxiliary agents can only solve single rigidity can be solved, the rigidity and toughness of the polypropylene thin-wall injection molding material are improved, the haze of the polypropylene thin-wall injection molding material is reduced, and the transparency and the impact resistance of the polypropylene thin-wall injection molding material are improved, the product is not easy to deform and brittle failure;
2) the filler stiffening agent is prepared into an organic modified filler stiffening agent by carrying out surface activation modification treatment on an aluminate coupling agent and carboxylic styrene-butadiene latex, so that the transparency of the polypropylene thin-wall injection molding material can be prevented from being reduced when the rigidity of an auxiliary agent system in the polypropylene thin-wall injection molding material is further improved;
3) mixing a small amount of anthraquinone disperse dye in the sorbitol nucleating agent for modification treatment to prepare the modified sorbitol nucleating agent, wherein the anthraquinone disperse dye assists the sorbitol nucleating agent to ensure that the microcrystalline structure of the polypropylene thin-wall injection molding material prepared by an auxiliary agent system is uniformly distributed, so that the transparency of the polypropylene thin-wall injection molding material is further improved;
4) the preparation method comprises the steps of sequentially adding a styrene-butadiene-styrene block copolymer, a styrene-acrylonitrile copolymer, an antioxidant, an organic modified filler stiffening agent, a carboxymethyl cellulose dispersing agent, a modified sorbitol nucleating agent, an elastomer toughening agent, a slipping agent and a microstructure adjusting aid into a preparation aid system, wherein the stability is good, the addition of the aid system can improve the rigidity and toughness of the polypropylene thin-wall injection molding material when the polypropylene thin-wall injection molding material is prepared, and the prepared polypropylene thin-wall injection molding material has the advantages of good rigidity, good toughness and good transparency, and is resistant to high temperature, low temperature, difficult to deform and difficult to break.
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.
The auxiliary agent system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material comprises the following components in parts by weight: styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, organic modified filler stiffening agent, elastomer toughening agent, modified sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjusting auxiliary agent; the microstructure adjusting aid consists of a hydroxyl phosphate aluminum salt nucleating agent and magnesium sulfate whiskers in a weight ratio of 1:1.2, the slipping agent consists of magnesium stearate or calcium stearate and glyceryl monostearate in a weight ratio of 2:1.3, and the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a weight ratio of 2.5: 1.
Example 1
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano montmorillonite, wherein the weight ratio of water to the nano montmorillonite is 3.7:5, adding the nano montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.02% of the weight of the nano montmorillonite, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 35.2% of the weight of the nano montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.51% of the weight of the nano montmorillonite, mixing for 15-18 min, heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano montmorillonite;
(2) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 7.8:4 into a 2# three-neck flask, stirring and mixing for 10-15 min at the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.051% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.071% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, then heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(3) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.48:3, putting the mixture into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 9.8 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(4) adding 154% of organic modified nano montmorillonite by weight of styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding 2.3% of carboxymethyl cellulose dispersing agent by weight of organic modified nano montmorillonite and 43.2% of modified sorbitol nucleating agent by weight of organic modified nano montmorillonite, and mixing for 15-20 min;
(5) adding an ethylene-butylene copolymer accounting for 33.4 percent of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding a slipping agent accounting for 3.1 percent of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 5.2 percent of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(6) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Example 2
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano montmorillonite, wherein the weight ratio of water to the nano montmorillonite is 3.8:5, adding the nano montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.25% of the weight of the nano montmorillonite, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 37.8% of the weight of the nano montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.72% of the weight of the nano montmorillonite, mixing for 15-18 min, then heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano montmorillonite;
(2) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding the ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 8.1:4 into a 2# three-neck flask, stirring and mixing for 10-15 min at the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.056% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.083% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(3) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.36:3, putting the mixture into a reactor, heating the mixture in an oil bath to 250-255 ℃, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 9.2 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(4) adding 157.3% of organic modified nano montmorillonite in weight of styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding 3.1% of carboxymethyl cellulose dispersing agent in weight of organic modified nano montmorillonite and 44.6% of modified sorbitol nucleating agent in weight of organic modified nano montmorillonite, and mixing for 15-20 min;
(5) adding ethylene-butylene copolymer accounting for 35.1% of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding slipping agent accounting for 4.05% of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding microstructure adjusting aid accounting for 5.92% of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(6) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Example 3
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano-montmorillonite, wherein the weight ratio of water to the nano-montmorillonite is 3.82:5, adding the nano-montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.38% of the weight of the filler stiffening agent, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 42.3% of the weight of the nano-montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.84% of the weight of the nano-montmorillonite, mixing for 15-18 min, heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano-montmorillonite;
(2) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 8.3:4 into a 2# three-neck flask, stirring and mixing for 10-15 min at the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.063% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.105% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(3) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.18:3, putting the mixture into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8.6 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(4) adding organic modified nano montmorillonite which accounts for 161.5 percent of the weight of the styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding carboxymethyl cellulose dispersing agent which accounts for 3.7 percent of the weight of the organic modified nano montmorillonite and modified sorbitol nucleating agent which accounts for 45.8 percent of the weight of the organic modified nano montmorillonite, and mixing for 15-20 min;
(5) adding an ethylene-butylene copolymer accounting for 36.4% of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding a slipping agent accounting for 5.1% of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 6.57% of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(6) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Example 4
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano montmorillonite, wherein the weight ratio of water to the nano montmorillonite is 3.82:5, adding the nano montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.48% of the weight of the nano montmorillonite, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 44.3% of the weight of the nano montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.99% of the weight of the nano montmorillonite, mixing for 15-18 min, then heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano montmorillonite;
(2) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 8.32:4 into a 2# three-neck flask, stirring and mixing for 10-15 min under the condition of the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.069% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.12% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, then heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(3) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.01:3, putting the mixture into a reactor, heating the mixture in an oil bath to 250-255 ℃, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8.1 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(4) adding organic modified nano montmorillonite accounting for 164.7 percent of the weight of the styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding carboxymethyl cellulose dispersing agent accounting for 3.9 percent of the weight of the organic modified nano montmorillonite and modified sorbitol nucleating agent accounting for 47 percent of the weight of the organic modified nano montmorillonite, and mixing for 15-20 min;
(5) adding an ethylene-butylene copolymer accounting for 37.9% of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding a slipping agent accounting for 6% of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 6.96% of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(6) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Example 5
This example is identical to example 3 in step, except that: the organic modified filler stiffening agent in the step (1) is different from the filler stiffening agent selected:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano talcum powder, adding water and the nano talcum powder in a weight ratio of 3.82:5 into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2% of the weight of the nano talcum powder, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 35.2% of the weight of the nano talcum powder, mixing for 45-55 min, then adding a slipping agent accounting for 1.51% of the weight of the nano talcum powder, mixing for 15-18 min, heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano talcum powder.
Example 6
This example is identical to example 3 in step, except that: the organic modified filler stiffening agent in the step (1) is different from the filler stiffening agent selected:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano mica, wherein the weight ratio of water to the nano mica is 3.82:5, adding the nano mica into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2% of the weight of the nano mica, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 35.2% of the weight of the nano mica, mixing for 45-55 min, then adding a slipping agent accounting for 1.51% of the weight of the nano mica, mixing for 15-18 min, heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano mica.
Example 7
This example is identical to example 3 in step, except that: the elastomer toughening agents added in the step (5) are different:
(5) and then adding an ethylene-octene copolymer accounting for 36.4% of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding a slipping agent accounting for 3.1% of the weight of the ethylene-octene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 5.2% of the weight of the ethylene-octene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen.
Comparative example 1
This comparative example differs from example 3 in that: the selected filler stiffening agent is not modified, and the assistant system comprises the following components: styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, nano montmorillonite, elastomer toughening agent, modified sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjusting auxiliary agent; the microstructure adjusting aid consists of a hydroxyl phosphate aluminum salt nucleating agent and magnesium sulfate whiskers in a weight ratio of 1:1.2, the slipping agent consists of magnesium stearate or calcium stearate and glyceryl monostearate in a weight ratio of 2:1.3, and the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a weight ratio of 2.5: 1.
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 8.3:4 into a 2# three-neck flask, stirring and mixing for 10-15 min at the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.063% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.105% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(2) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.18:3, putting the mixture into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8.6 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(3) adding 110% of nano montmorillonite by weight of styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding 3.7% of carboxymethyl cellulose dispersing agent by weight of elastomer toughening agent and 45.8% of modified sorbitol nucleating agent by weight of organic modified filler stiffening agent, and mixing for 15-20 min;
(4) adding an ethylene-butylene copolymer accounting for 36.4% of the weight of the nano montmorillonite until the ethylene-butylene copolymer is completely melted, uniformly mixing, adding a slipping agent accounting for 5.1% of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 6.57% of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(5) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Comparative example 2
This comparative example differs from example 3 in that: the sorbitol nucleating agent is not modified, and the assistant system comprises the following components: styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, organic modified filler stiffening agent, elastomer toughening agent, sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjusting auxiliary agent; the microstructure adjusting aid consists of a hydroxyl phosphate aluminum salt nucleating agent and magnesium sulfate whiskers in a weight ratio of 1:1.2, the slipping agent consists of magnesium stearate or calcium stearate and glyceryl monostearate in a weight ratio of 2:1.3, and the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a weight ratio of 2.5: 1.
The preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano montmorillonite, wherein the weight ratio of water to the nano montmorillonite is 3.82:5, adding the nano montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.38% of the weight of the nano montmorillonite, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 42.3% of the weight of the nano montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.84% of the weight of the nano montmorillonite, mixing for 15-18 min, then heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano montmorillonite;
(2) under the protection of nitrogen, taking 100g of styrene-butadiene-styrene block copolymer, wherein the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.18:3, putting the mixture into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8.6 percent of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing;
(3) adding an organic modified filler stiffening agent accounting for 161.5 percent of the weight of the styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding a carboxymethyl cellulose dispersing agent accounting for 3.7 percent of the weight of the elastomer stiffening agent and a sorbitol nucleating agent accounting for 45.72 percent of the weight of the organic modified filler stiffening agent, and mixing for 15-20 min;
(4) adding an ethylene-butylene copolymer accounting for 36.4% of the weight of the organic modified nano montmorillonite until the mixture is completely melted, uniformly mixing, adding a slipping agent accounting for 5.1% of the weight of the ethylene-butylene copolymer, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 6.57% of the weight of the ethylene-butylene copolymer, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(5) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
Comparative example 3
This comparative example differs from example 3 in that: the preparation method is different:
the preparation method of the auxiliary agent system comprises the following steps:
(1) preparing an organic modified filler stiffening agent, taking 150g of nano montmorillonite, wherein the weight ratio of water to the nano montmorillonite is 3.82:5, adding the nano montmorillonite into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2.38% of the weight of the nano montmorillonite, mixing for 15-20 min, adding carboxylic styrene-butadiene latex accounting for 42.3% of the weight of the nano montmorillonite, mixing for 45-55 min, then adding a slipping agent accounting for 1.84% of the weight of the nano montmorillonite, mixing for 15-18 min, then heating to 50-55 ℃ in a water bath, removing for 7-12 min, taking out and drying to obtain the organic modified nano montmorillonite;
(2) preparing a modified sorbitol nucleating agent, namely putting anthraquinone disperse dye into a grinding machine to be ground until the particle size is smaller than 50 mu m, taking 85g of sorbitol nucleating agent, adding ethanol with water content of 60% and the sorbitol nucleating agent in a weight ratio of 8.3:4 into a 2# three-neck flask, stirring and mixing for 10-15 min at the speed of 200-250 rpm, continuously adding carboxymethyl cellulose dispersing agent accounting for 0.063% of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.105% of the weight of the sorbitol nucleating agent, mixing for 15-20 min, heating in a water bath to 45-50 ℃, distilling to recover ethanol aqueous solution, taking out and drying to obtain the modified sorbitol nucleating agent;
(3) under the condition of nitrogen protection, 100g of styrene-butadiene-styrene block copolymer is taken, the weight ratio of the styrene-acrylonitrile copolymer to the styrene-butadiene-styrene block copolymer is 2.18:3, the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are put into a reactor, the styrene-acrylonitrile copolymer and the styrene-butadiene-styrene block copolymer are heated to 250-255 ℃ in an oil bath, the stirring is carried out under the condition of the speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and then organic modified nano montmorillonite which accounts for 161.5 percent of the weight of the styrene-butadiene-styrene block copolymer, ethylene-butylene copolymer which accounts for 36.4 percent of the weight of the organic modified nano montmorillonite, carboxymethyl cellulose dispersant which accounts for 3.7 percent of the weight of the organic modified nano montmorillonite, and modified sorbitol nucleating agent which accounts for 45.8 percent of the weight of the organic modified nano montmorillonite are respectively added, A slipping agent accounting for 5.1 percent of the weight of the ethylene-butylene copolymer, an antioxidant accounting for 8.6 percent of the weight of the styrene-butadiene-styrene block copolymer and a microstructure adjusting aid accounting for 6.57 percent of the weight of the ethylene-butylene copolymer are stirred and cooled until the mixture is completely melted and uniformly mixed until the temperature is reduced to 190-200 ℃, and then the nitrogen is stopped being filled;
(4) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
4.2 g of the additive systems prepared in the above examples 1 to 7 and comparative examples 1 to 3 are respectively mixed with 100g of polypropylene to prepare a standard thin-wall sample sheet by an injection molding machine, and the polypropylene without the additive system is used as a blank to prepare the standard thin-wall sample sheet by the injection molding machine, and the haze value, the tensile yield strength and the flexural modulus of the thin-wall sample sheet are tested after the sample sheet is treated in a standard environment, and the test results are as follows:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Blank example | |
| Haze value | 9.7% | 9.3% | 8.4% | 9.8% | 8.3% | 8.5% | 8.3% | 35.3% | 34.2% | 23.1% | 54.3% |
| Tensile yield strength (MPa) | 39.8 | 39.7 | 42.6 | 40.3 | 42.1 | 42.5 | 41.9 | 36.5 | 36.8 | 38.6 | 32.5 |
| Flexural modulus (MPa) | 1512 | 1545 | 1628 | 1579 | 1622 | 1629 | 1620 | 1350 | 1368 | 1456 | 1125 |
The table shows that: the auxiliary agent system prepared by the invention is used for producing the polypropylene thin-wall injection molding material, has good rigidity and toughness, can improve the rigidity and toughness of the polypropylene thin-wall injection molding material and reduce the haze of polypropylene, thereby improving the transparency and impact resistance of the polypropylene thin-wall injection molding material, and is not easy to deform and brittle fracture. The automatic stacking machine can be applied to mechanical manual picking and stacking; take-out packaging boxes, frozen storage boxes, etc. for food.
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 (8)
1. The preparation method of the auxiliary agent system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material is characterized in that the auxiliary agent system comprises the following components: styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, organic modified filler stiffening agent, elastomer toughening agent, modified sorbitol nucleating agent, carboxymethyl cellulose dispersing agent, slipping agent, antioxidant and microstructure adjusting auxiliary agent; the microstructure adjusting aid consists of a hydroxyl phosphate aluminum salt nucleating agent and magnesium sulfate whiskers in a weight ratio of 1:1.2, the slipping agent consists of magnesium stearate and glyceryl monostearate in a weight ratio of 2:1.3 or consists of calcium stearate and glyceryl monostearate in a weight ratio of 2:1.3, and the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a weight ratio of 2.5: 1;
the organic modified filler stiffening agent is prepared by performing surface activation modification treatment on the filler stiffening agent through a coupling agent and carboxyl latex;
the modified sorbitol nucleating agent is prepared by mixing the sorbitol nucleating agent with anthraquinone disperse dye for auxiliary synergistic treatment;
the preparation method of the auxiliary agent system comprises the following steps:
(1) under the protection of nitrogen, adding a styrene-butadiene-styrene block copolymer and a styrene-acrylonitrile copolymer in a weight ratio of 3: 2-3: 2.5 into a reactor, heating the mixture to 250-255 ℃ in an oil bath, stirring the mixture at a speed of 1500-1800 rpm until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, adding an antioxidant accounting for 8-10% of the weight of the styrene-butadiene-styrene block copolymer until the styrene-butadiene-styrene block copolymer and the styrene-acrylonitrile copolymer are completely melted, and uniformly mixing the mixture;
(2) then adding an organic modified filler stiffening agent which accounts for 153-165% of the weight of the styrene-butadiene-styrene block copolymer, mixing for 25-30 min, adding a carboxymethyl cellulose dispersing agent which accounts for 2-4% of the weight of the organic modified filler stiffening agent and a modified sorbitol nucleating agent which accounts for 43-47% of the weight of the organic modified filler stiffening agent, and mixing for 15-20 min;
(3) adding an elastomer toughening agent accounting for 33-38% of the weight of the organic modified filler stiffening agent until the organic modified filler stiffening agent is completely melted, uniformly mixing, adding a slipping agent accounting for 3-6% of the weight of the elastomer toughening agent, mixing for 10-15 min, adding a microstructure adjusting aid accounting for 5-7% of the weight of the elastomer toughening agent, mixing for 20-25 min, then cooling while stirring until the temperature is reduced to 190-200 ℃, and stopping filling nitrogen;
(4) and then adding the mixture into an extruder, and extruding, cooling and granulating at the temperature of 180-225 ℃ to obtain an auxiliary agent system.
2. The preparation method of the additive system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to claim 1, wherein the preparation method of the organic modified filler stiffening agent is characterized in that an aluminate coupling agent is selected as the coupling agent, and carboxylated styrene-butadiene latex is selected as the carboxylated latex; adding a filler stiffening agent and water in a weight ratio of 5: 3.5-5: 4 into a No. 1 three-neck flask, stirring and mixing for 8-12 min under the condition that the speed is 300-400 rpm, continuously adding an aluminate coupling agent accounting for 2-2.5% of the weight of the filler stiffening agent, mixing for 15-20 min, adding a carboxylic styrene-butadiene latex accounting for 35-45% of the weight of the filler stiffening agent, mixing for 45-55 min, then adding a slipping agent accounting for 1.5-2.2% of the weight of the filler stiffening agent, mixing for 15-18 min, heating in a water bath to 50-55 ℃, removing for 7-12 min, taking out and drying to obtain the organic modified filler stiffening agent.
3. The preparation method of the additive system used for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to claim 1, the preparation method is characterized in that the modified sorbitol nucleating agent is prepared by putting anthraquinone disperse dye into a grinder to be ground until the particle size is less than 50 mu m, adding the sorbitol nucleating agent and ethanol with water content of 60% in a weight ratio of 4: 7-4: 9 into a No. 2 three-neck flask, stirring and mixing for 10-15 min under the condition that the speed is 200-250 rpm, continuously adding a carboxymethyl cellulose dispersing agent accounting for 0.05-0.07 percent of the weight of the sorbitol nucleating agent and ground anthraquinone disperse dye accounting for 0.07-0.12 percent of the weight of the sorbitol nucleating agent, mixing for 15-20 min, and then heating to 45-50 ℃ in a water bath, distilling to recover an ethanol water solution, taking out and drying to obtain the modified sorbitol nucleating agent.
4. The method for preparing the assistant system used for producing the high rigidity and high toughness polypropylene thin wall injection molding compound in claim 1, wherein the weight of the antioxidant is 8.6% of the weight of the styrene-butadiene-styrene block copolymer, the weight of the organic modified filler stiffening agent is 161.5% of the weight of the styrene-butadiene-styrene block copolymer, the weight of the carboxymethyl cellulose dispersant is 3.7% of the weight of the organic modified filler stiffening agent, the weight of the modified sorbitol type nucleating agent is 45.8% of the weight of the organic modified filler stiffening agent, the weight of the elastomer toughening agent is 36.4% of the weight of the organic modified filler stiffening agent, the weight of the microstructure adjusting assistant is 6.57% of the weight of the elastomer toughening agent, and the weight of the slip agent is 5.1% of the weight of the elastomer toughening agent.
5. The method for preparing the assistant system used for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to claim 2, wherein the weight of the aluminate coupling agent is 2.38% of that of the filler stiffening agent, and the weight of the carboxylated styrene-butadiene latex is 42.3% of that of the filler stiffening agent.
6. The preparation method of the assistant system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to claim 3, wherein the anthraquinone type disperse dye accounts for 0.105 percent of the weight of the sorbitol type nucleating agent.
7. The method for preparing the additive system for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to the claim 1 or 2, characterized in that the filler stiffening agent is selected from nano montmorillonite, nano talcum powder or nano mica.
8. The method for preparing the auxiliary agent system used for producing the high-rigidity high-toughness polypropylene thin-wall injection molding material according to claim 1, wherein the elastomer toughening agent is ethylene-butylene copolymer or ethylene-octene copolymer.
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| CN103183870A (en) * | 2011-12-29 | 2013-07-03 | 合肥杰事杰新材料股份有限公司 | Polyolefin/styrene based resin composition and preparation method thereof |
| CN103724807A (en) * | 2013-12-17 | 2014-04-16 | 浙江普利特新材料有限公司 | Polypropylene composite material with low after shrinkage, high modulus and high impact resistance and preparation method thereof |
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| US20180208753A1 (en) * | 2017-01-25 | 2018-07-26 | Nano And Advanced Materials Institute Limited | Mechanically reinforced, transparent, anti-biofouling thermoplastic resin composition and manufacturing method thereof |
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