CN115246944A - Anti-aging polypropylene master batch with compact structure and preparation method thereof - Google Patents
Anti-aging polypropylene master batch with compact structure and preparation method thereof Download PDFInfo
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The application relates to the field of high polymer materials, and particularly discloses an anti-aging polypropylene master batch with a compact structure and a preparation method thereof. The anti-aging polypropylene master batch with the compact structure comprises the following raw materials in parts by weight: 30-60 parts of polypropylene powder, 2-3 parts of a dispersing agent, 1-3 parts of a cross-linking agent, 4-6 parts of a functional assistant, 10-20 parts of water and 5-7 parts of an anti-ultraviolet agent, wherein the anti-ultraviolet agent is prepared by dispersing titanium dioxide in polyacrylamide microspheres; the preparation method of the anti-aging polypropylene master batch with compact structure comprises the following steps: s1, preparing raw materials; s2, mixing for the first time; s3, mixing for the second time; s4, extrusion molding; s5, water-cooling and granulating; the aging-resistant polypropylene master batch with the compact structure can improve the compactness of the polypropylene master batch, and further improve the structural strength and the aging resistance of the polypropylene master batch; in addition, the preparation method has the advantages of simplicity, easiness in operation and wide application range.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to an anti-aging polypropylene master batch with a compact structure and a preparation method thereof.
Background
Polypropylene, PP for short, is a colorless, odorless, nontoxic and semitransparent solid substance. Polypropylene is a thermoplastic synthetic resin with excellent performance, and is colorless translucent thermoplastic light general-purpose plastic. The polypropylene has excellent properties of chemical resistance, heat resistance, electrical insulation, high-strength mechanical property, good high-wear-resistance processing property and the like, so that the polypropylene is rapidly and widely developed and applied in a plurality of fields such as machinery, automobiles, electronic and electric appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like since the coming out of the world.
In the related art, for convenience of operation, polypropylene is usually prepared as polypropylene master batch for use. The polypropylene masterbatch is usually prepared by mixing and milling polypropylene powder, required fillers, ultraviolet resistant agents, functional additives and other additives, and then carrying out metering, mixing, melting, extruding, granulating and other processing processes by using equipment such as an extruder.
In view of the above related technologies, the applicant believes that, in the process of preparing the polypropylene master batch, an anti-ultraviolet agent material needs to be added inside the polypropylene master batch to perform anti-aging treatment, and as the added anti-ultraviolet agent material is easy to agglomerate and cannot be effectively dispersed and mixed when the materials are mixed and kneaded, the prepared polypropylene master batch is poor in compactness, so that the structural strength and the anti-aging performance of the polypropylene master batch are affected, and the service life of the polypropylene master batch is further affected.
Disclosure of Invention
In order to improve the dispersibility of the ultraviolet resistant agent and further improve the compactness of the polypropylene master batch, so that the structural strength and the ageing resistance of the polypropylene master batch are improved, the application provides the ageing-resistant polypropylene master batch with the compact structure and the preparation method thereof.
The application provides a compact-structure anti-aging polypropylene master batch and a preparation method thereof, and the technical scheme is as follows:
in a first aspect, the application provides a compact-structure anti-aging polypropylene master batch, which adopts the following technical scheme:
the anti-aging polypropylene master batch with a compact structure is characterized by comprising the following components in parts by weight: 30-60 parts of polypropylene powder, 2-3 parts of dispersing agent, 1-3 parts of cross-linking agent, 4-6 parts of functional assistant, 10-20 parts of water and 5-7 parts of anti-ultraviolet agent; the ultraviolet resistant agent comprises 2-4 parts of titanium dioxide and 4-12 parts of polyacrylamide microspheres.
By adopting the technical scheme, as the adopted ultraviolet resistant agent comprises titanium dioxide and polyacrylamide microspheres, the titanium dioxide is dispersed in the polyacrylamide microspheres to form good combination with the polyacrylamide microspheres. The polypropylene microspheres have good water absorption and good rheological property after water absorption, so the polypropylene microspheres can deform per se and drive titanium dioxide to enter gaps among the components for dispersion filling, the titanium dioxide is uniformly dispersed in the components, the compactness of the polypropylene master batch is improved, and the ageing resistance of the polypropylene master batch is further improved.
Preferably, the polyacrylamide microspheres are nano-sized polyacrylamide microspheres, and the preparation method of the nano-sized polyacrylamide microspheres comprises the following steps:
(1) Preparing an oil phase: mixing and stirring 6-10 parts by weight of sorbitan oleate, 3-5 parts by weight of monooleate, 1-2 parts by weight of azobisisobutyronitrile and 8-12 parts by weight of white oil to obtain an oil phase mixture;
(2) Preparation of a water phase: mixing 30-40 parts of acrylamide, 10-14 parts of 2-acrylamido-2-methylpropanesulfonic acid and 75-85 parts of water according to parts by weight, adding 5-7 parts of disodium ethylene diamine tetraacetate, adjusting the pH value to acidity, and adding 0.1-0.3 part of ammonium persulfate to obtain a water-phase mixture;
(3) Mixing and reacting: mixing 50-60 parts of oil phase mixture and 30-40 parts of water phase mixture according to parts by weight, and adding 2-4 parts of sodium bisulfite solution with the concentration of 0.6-1.4mol/L in nitrogen atmosphere to prepare polymer microsphere emulsion;
(4) Phase inversion: mixing 1-3 parts of phase transfer agent and 7-9 parts of polymer microsphere emulsion, and stirring at a rotating speed of 100-200r/min for 3-5min to obtain nano-grade polyacrylamide microsphere emulsion;
(5) Washing and drying: and washing the polyacrylamide nano microsphere emulsion with absolute ethyl alcohol, then carrying out suction filtration, and drying after suction filtration to obtain the nano-grade polyacrylamide microspheres.
By adopting the technical scheme, the nano-grade polyacrylamide microspheres can be prepared by preparing the oil phase, preparing the water phase, mixing the oil phase and the water phase for reaction, and then performing phase inversion, washing and drying. Compared with micron-sized polyacrylamide microspheres, the nano-sized polyacrylamide microspheres have smaller particle size, and the nano-sized polyacrylamide microspheres after water absorption have good viscoelasticity and better rheological property, and can reduce the viscosity of the nano-sized polyacrylamide microspheres while generating elastic deformation, so that the nano-sized polyacrylamide microspheres are smoother when entering gaps of all components in the raw material, titanium dioxide is convenient to carry to enter more and smaller gaps among all the components, and the compactness and the aging resistance of the polypropylene master batch are further improved.
Preferably, the titanium dioxide comprises porous nano titanium dioxide, and the preparation method of the porous nano titanium dioxide comprises the following steps:
(1) Preparing a pore-forming solution: mixing 6-10 parts of pore-forming agent, 10-14 parts of absolute ethyl alcohol, 20-30 parts of deionized water and 8-10 parts of glacial acetic acid according to parts by weight to obtain pore-forming liquid;
(2) Preparation of gel: according to the weight portion, 30-50 portions of tetra-n-butyl titanate and 60-80 portions of absolute ethyl alcohol are mixed, stirred, added with 10-20 portions of pore-forming liquid, and aged for 20 hours to obtain gel;
(3) Drying and calcining: drying the gel at 60-90 deg.C, grinding, and calcining at 550-650 deg.C for 2-4h to obtain porous nanometer titanium dioxide.
By adopting the technical scheme, the porous nano titanium dioxide is dispersed in the nano polyacrylamide microspheres and then mixed with the raw materials. The nano-grade polyacrylamide microspheres after absorbing the water in the raw materials have good rheological property, so that the self parts can be inserted into the porous structure of the nano titanium dioxide through self deformation, the combination area of the polyacrylamide microspheres and the titanium dioxide is increased, the polyacrylamide microspheres and the nano titanium dioxide are further stably and well combined, the nano-grade polyacrylamide microspheres can conveniently carry the nano titanium dioxide to enter gaps of all components, and the ageing resistance of the polypropylene master batch is further improved.
Preferably, the crosslinking agent is a mixture of 1 to 3 parts by weight of N, N-methylenebisacrylamide and 7 to 13 parts by weight of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
By adopting the technical scheme, the N, N-methylene bisacrylamide can form sol when all components are mixed, so that the lubrication degree is increased, the polyacrylamide microspheres are stably propelled, the polyacrylamide microspheres can conveniently enter gaps among all the components, the gaps among all the components are further plugged, and the compactness of the polypropylene master batch is further improved. And 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane can increase the crosslinking degree of polypropylene and the melt index of the mixture, thereby improving the mechanical property of the material.
Preferably, the preparation steps of the ultraviolet resistant agent are as follows:
according to the weight portion, mixing and grinding half of the nano polyacrylamide microspheres and 2-4 parts of porous nano titanium dioxide for 15-25min to obtain a primary mixed material;
(2) And mixing and grinding the rest half of the nano-grade polyacrylamide microspheres and the primary mixed material for 25-35min to obtain the anti-ultraviolet agent.
By adopting the technical scheme, the nano-polyacrylamide microspheres and the porous nano-titanium dioxide are ground and mixed twice, so that the nano-polyacrylamide microspheres and the porous nano-titanium dioxide are mixed more uniformly and fully, and the uniformity of the ultraviolet resistant agent is improved.
Preferably, the pH is adjusted to acidity in the preparation of the aqueous phase in the step (2) to adjust the pH to 6.8.
By adopting the technical scheme, the polymerization reaction is easy to carry out under the acidic condition, and the stronger the acidity, the easier the polymerization reaction is initiated, so the stronger the acidity, the larger the particle size of the polyacrylamide nano microsphere formed by polymerization is. Therefore, the pH value is adjusted to 6.8, so that the polymerization reaction can be carried out, the polyacrylamide nano microspheres with smaller sizes can be generated, the particle size distribution range of the generated polyacrylamide nano microspheres is narrow, the particle size is uniform, and the polyacrylamide nano microspheres can enter gaps among all components conveniently.
In a second aspect, the application provides a preparation method of an anti-aging polypropylene master batch with a compact structure, which adopts the following technical scheme:
s1, preparing raw materials: taking 50-60 parts of polypropylene powder, 2-3 parts of dispersing agent, 1-3 parts of cross-linking agent, 10-20 parts of water, 4-6 parts of functional auxiliary agent and 5-7 parts of anti-ultraviolet agent for later use;
s2, primary mixing: mixing all the water and the ultraviolet resistant agent to obtain a mixture;
s3, secondary mixing: adding all the polypropylene powder into a temperature-controlled high-speed mixer, then adding all the dispersing agent, the cross-linking agent, the functional assistant and the mixture into the temperature-controlled high-speed mixer, and stirring to obtain a mixed material;
s4, extrusion molding: adding the mixed materials into a double-screw extruder, melting and extruding to obtain an extruded material;
s5, water-cooling pelletizing: and cooling and shaping the extruded material under water, and granulating by a granulator in the cooling process to obtain the polypropylene master batch.
By adopting the technical scheme, the nanoscale polyacrylamide microspheres in the uvioresistant agent are combined with water by one-time mixing, so that the nanoscale polyacrylamide microspheres have good rheological property and viscoelasticity. And then, through secondary mixing and a temperature-controlled high-speed mixer, the polyacrylamide microspheres carrying titanium dioxide are dispersed in each component in the raw material, flow and are filled into the pores among the components in the raw material. The material is then thoroughly dried. And forming a melt from the raw materials by a double-screw extruder, performing water cooling and granulation to obtain a polypropylene master batch blank, dehydrating, sieving, and detecting to be qualified to obtain a polypropylene master batch finished product.
Preferably, in step S3, the stirring process includes: stirring at 200-300rpm for 5min, adjusting the rotation speed of the temperature-controlled high-speed mixer to 1000-1200rpm, and continuing stirring for 25s.
By adopting the technical scheme, the anti-aging agent is stirred at different speeds after being added according to the properties of different materials, the materials are uniformly and thoroughly mixed under low-speed stirring, the high-speed stirring improves the dispersion performance between the anti-aging agent and each component, the anti-aging agent is not easy to agglomerate, the overall performance of the polypropylene master batch is stable and uniform, and the anti-aging performance of the polypropylene master batch is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. because the titanium dioxide is dispersed in the polyacrylamide microspheres to prepare the ultraviolet-resistant agent, and the polypropylene microspheres have good rheological property after absorbing water, the polypropylene microspheres easily carry the titanium dioxide to enter gaps among the components for filling, so that the compactness of the polypropylene master batch is improved, and the titanium dioxide is uniformly dispersed in the components, thereby effectively improving the ageing resistance of the polypropylene master batch;
2. the nano-grade polyacrylamide microspheres are preferably adopted in the application, and have smaller particle size, so that the nano-grade polyacrylamide microspheres after water absorption have good viscoelasticity and better rheological property, the self viscosity is reduced while the nano-grade polyacrylamide microspheres elastically deform, titanium dioxide which is easy to carry enters more and smaller gaps among the components, and the compactness and the aging resistance of the polypropylene master batch are further improved;
3. according to the method, the nanoscale polyacrylamide microspheres in the ultraviolet resistant agent absorb water through primary mixing, the nanoscale polyacrylamide microspheres have rheological property and viscoelasticity, and then are mixed for the second time, the polyacrylamide microspheres carry titanium dioxide to flow and disperse in gaps of components in raw materials through a temperature control high-speed mixer, dispersed materials are fully dried, then the raw materials can form melts through a double-screw extruder, and the polypropylene master batches are obtained through water cooling and grain cutting.
Detailed Description
The present application will be described in further detail with reference to examples.
In the examples of the present application, the equipment used is shown in Table 1:
table 1 instrument device of the embodiment of the present application
In the examples of the present application, the drugs used are shown in table 2:
TABLE 2 pharmaceutical products of the examples of the present application
Preparation examples of raw materials
Preparation of nano-grade polyacrylamide microsphere
Preparation example 1
The following preparation example 1 is taken as an example to illustrate a preparation method of nano-sized polyacrylamide microspheres, which comprises the following steps:
(1) Preparing an oil phase: 60kg of sorbitan oleate, 30kg of monooleate, 10kg of azobisisobutyronitrile and 80kg of white oil are weighed, mixed and stirred for 6min to obtain an oil phase mixture.
(2) Preparation of a water phase: 30kg of acrylamide and 10kg of 2-acrylamido-2-methylpropanesulfonic acid are weighed and mixed, added to 75kg of water, and stirred at normal temperature for 3min to obtain a mixed solution. Adding 5kg of disodium ethylene diamine tetraacetate into the mixed solution, adding 0.1mol/L sodium hydroxide solution to adjust the pH value to 6.8, and adding 0.1kg of ammonium persulfate to obtain a water-phase mixture.
(3) Mixing and reacting: and (3) transferring 50kg of the oil phase mixture into a reactor, adding 30kg of the water phase mixture at the temperature of 20 ℃, stirring for 40min at the rotating speed of 300r/min in the nitrogen atmosphere, adding 2kg of sodium bisulfite, and continuously stirring for 1.5h at the rotating speed of 300r/min in the nitrogen atmosphere to obtain the polymer microsphere emulsion.
(4) Phase inversion: and taking 7kg of polymer microsphere emulsion, adding 1kg of phase inversion agent into the polymer microsphere emulsion, and stirring the polymer microsphere emulsion for 5min at the rotating speed of 300r/min to obtain the polyacrylamide nano microspheres.
(5) Washing and drying: and (4) washing the polyacrylamide nano microsphere emulsion prepared in the step (4) with absolute ethyl alcohol for three times, carrying out suction filtration, and drying at 50 ℃ for 10 hours to prepare the nano-grade polyacrylamide microspheres.
As shown in Table 1, the nano-sized polyacrylamide microspheres of preparation examples 2 to 3 are different from those of preparation example 1 in the component ratio of each step, and are specifically shown in Table 3.
TABLE 3 component proportions in preparation examples 1 to 3
Preparation example 4
The main difference between the nano-sized polyacrylamide microspheres of preparation example 4 is that the pH is adjusted to 3 in the preparation of the aqueous phase in preparation step (2), and the rest of the preparation conditions are the same as those in preparation 2.
Preparation of porous nano titanium dioxide
Preparation example 5
(1) Preparing a pore-forming solution: mixing 6kg of pore-forming agent, 10kg of absolute ethyl alcohol, 20kg of deionized water and 8kg of glacial acetic acid, and magnetically stirring at the rotating speed of 70r/min for 6min at room temperature to obtain a pore-forming solution.
(2) Preparation of the gel: and mixing 30kg of tetra-n-butyl titanate and 60kg of absolute ethyl alcohol, stirring at the rotating speed of 80r/min, adding the pore-forming liquid, and aging for 20 hours after 10 parts of the pore-forming liquid to obtain the gel.
(3) Drying and calcining: and (3) drying the gel in a constant-temperature vacuum drying oven at 60 ℃, grinding, and calcining in a box-type resistance furnace at 550 ℃ for 2h to obtain the first porous nano titanium dioxide.
Preparation examples 6 to 7
As shown in Table 4, the porous titania of production examples 6 to 7 differs from that of production example 5 in the component proportions in the respective steps, as shown in Table 4.
TABLE 4 component proportions in the respective steps in preparation examples 5 to 7
Preparation of anti-ultraviolet agent
Preparation example 8
(1) Taking 4kg of the nano-grade polyacrylamide microspheres obtained in preparation example 1, mixing and grinding half of the mass of the porous nano-titanium dioxide obtained in preparation example 1 and 2kg of the porous nano-titanium dioxide obtained in preparation example 5 for 15min to obtain a primary mixed material;
(2) The remaining preparation example 1 was mixed with the initial mix and ground for 25min.
Preparation examples 9 to 10
As shown in Table 5, the UV inhibitors of preparation examples 9 to 10 are different from those of preparation example 8 in the raw material compounding ratio, specifically, as shown in Table 5.
TABLE 5 compounding ratio of raw materials in preparation examples 8 to 10
Preparation examples 11 to 15
The UV screening agents of preparation examples 11 to 15 are different from those of preparation example 9 in the selection of raw material components, as shown in Table 6.
TABLE 6 starting materials from preparations 11 to 15
Examples
Example 1
Taking example 1 as an example, the preparation method of the aging-resistant polypropylene master batch with a compact structure comprises the following steps:
s1, preparing raw materials: weighing 30kg of polypropylene powder with the fineness of 250 meshes, 2kg of dispersing agent, 1kg of cross-linking agent, 4kg of functional additive, 10kg of water and 5kg of ultraviolet-resistant agent for later use; the crosslinker is a mixture of 1kgN, N-methylenebisacrylamide and 7kg2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the ultraviolet inhibitor is the ultraviolet inhibitor of preparation example 8.
S2, primary mixing: mixing all water in the raw materials with an anti-ultraviolet agent to obtain a mixture;
s3, secondary mixing: adding all polypropylene powder in the raw materials into a temperature-controlled high-speed mixer, then adding all dispersing agents, cross-linking agents and a mixture into the temperature-controlled high-speed mixer, stirring at a low speed of 200rpm for 5min at 30 ℃, adjusting the rotating speed of the temperature-controlled high-speed mixer to a high speed of 1000rpm, and continuously stirring for 3min to obtain a mixed material;
s4, extrusion molding: adding the mixed materials into a double-screw extruder, setting the rotating speed of the double-screw extruder to be 300rpm, and setting the temperature of each temperature zone to be: melting the materials in a 1 st temperature zone of 150 ℃, a 2 nd-9 th temperature zone of 170 ℃ and a 10 th-11 th temperature zone of 160 ℃, and extruding to obtain extruded materials;
s5, water-cooling pelletizing: and cooling and shaping the extruded material under water, and granulating by a granulator in the cooling process to obtain the polypropylene master batch.
Examples 2 to 3
The compact anti-aging polypropylene master batches of examples 2 to 3 are different from those of example 1 in the raw material mixture ratio, and are specifically shown in table 7.
TABLE 7 raw material ratio of anti-aging polypropylene master batch with compact structure in examples 1-3
Examples 4 to 10
The compact anti-aging polypropylene master batches of examples 4 to 10 are different from those of example 2 in the ultraviolet light-resistant agent, and are shown in Table 8.
TABLE 8 UV-resistant agent for anti-aging polypropylene master batches with compact structure in examples 4-10
Examples 11 to 12
Compared with example 8, the difference between the structurally compact anti-aging polypropylene master batches of examples 11 to 12 is that the process parameters in the preparation process of the polypropylene master batches are different, and are specifically shown in table 9.
TABLE 9 table of process parameters of example 8 and examples 11 to 12
Example 13
The preparation conditions and the component ratio are the same as those of example 11 except that commercially available polyacrylamide is used instead of the nano-sized polyacrylamide microspheres of example 11.
Comparative example
Comparative example 1
Commercial titanium dioxide was used as the ultraviolet screening agent in place of the ultraviolet screening agent in example 1, and the preparation conditions were the same as in example 1.
S1, preparing raw materials: weighing 50kg of polypropylene powder with the fineness of 250 meshes, 2kg of dispersing agent, 1kg of cross-linking agent, 4kg of functional additive, 10kg of water and 5kg of ultraviolet-resistant agent for later use; the crosslinker is a mixture of 1kgN, N-methylenebisacrylamide and 7kg2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the ultraviolet resistant agent is titanium dioxide sold in the market.
S2, primary mixing: mixing all water in the raw materials with an anti-ultraviolet agent to obtain a mixture;
s3, secondary mixing: adding all polypropylene powder in the raw materials into a temperature-controlled high-speed mixer, then adding all dispersing agents, cross-linking agents and a mixture into the temperature-controlled high-speed mixer, stirring at a low speed of 200rpm for 5min at 30 ℃, adjusting the rotating speed of the temperature-controlled high-speed mixer to a high speed of 1000rpm, and continuously stirring for 25s to obtain a mixed material;
s4, extrusion molding: adding the mixed materials into a double-screw extruder, setting the rotating speed of the double-screw extruder to be 300rpm, and setting the temperature of each temperature zone to be: melting and extruding the materials at a temperature of 150 ℃ in a 1 st temperature zone, 170 ℃ in a 2 nd-9 st temperature zone and 160 ℃ in a 10 th-11 th temperature zone to obtain extruded materials;
s5, water-cooling pelletizing: and cooling and shaping the extruded material under water, and granulating by a granulator in the cooling process to obtain the polypropylene master batch.
Comparative example 2
The porous titania of preparation example 6 was used as an ultraviolet screening agent in place of the ultraviolet screening agent of example 1, and the preparation conditions were the same as in example 1.
S1, preparing raw materials: weighing 50kg of polypropylene powder with the fineness of 250 meshes, 2kg of dispersing agent, 1kg of cross-linking agent, 4kg of functional additive, 10kg of water and 5kg of ultraviolet-resistant agent for later use; the crosslinker is a mixture of 1kgN, N-methylenebisacrylamide and 7kg2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the ultraviolet resistant agent is the porous nano titanium dioxide in the preparation example 6.
S2, primary mixing: mixing all water in the raw materials with an anti-ultraviolet agent to obtain a mixture;
s3, secondary mixing: adding all polypropylene powder in the raw materials into a temperature-controlled high-speed mixer, then adding all dispersing agents, cross-linking agents and a mixture into the temperature-controlled high-speed mixer, stirring at a low speed of 200rpm for 5min at the temperature of 30 ℃, adjusting the speed of the temperature-controlled high-speed mixer to a high speed of 1000rpm, and continuously stirring for 25s to obtain a mixed material;
s4, extrusion molding: adding the mixed materials into a double-screw extruder, setting the rotating speed of the double-screw extruder to be 300rpm, and setting the temperature of each temperature zone to be: melting the materials in a 1 st temperature zone of 150 ℃, a 2 nd-9 th temperature zone of 170 ℃ and a 10 th-11 th temperature zone of 160 ℃, and extruding to obtain extruded materials;
s5, water-cooling pelletizing: and cooling and shaping the extruded material under water, and granulating by a granulator in the cooling process to obtain the polypropylene master batch.
Comparative example 3
The preparation conditions were the same as in example 1 except that a commercially available silane coupling agent was used in place of the crosslinking agent in example 1.
Performance test
Detection method
Ultraviolet aging resistance: performing a pretreatment experiment on the polypropylene master batch according to GB/T16585-1996, irradiating for 4 hours by ultraviolet light, cooling for 4 hours to form a period, and irradiating and cooling a polypropylene master batch sample for three periods and then taking out. The ultraviolet aging resistance of the polypropylene master batch is reflected by the mechanical property of the polypropylene master batch after being irradiated by ultraviolet light.
Mechanical properties: the tensile stress-strain properties of polypropylene master batches were measured according to GB/T1040-1992 by placing a sample of polypropylene master batches on upper and lower grips uniformly in a tensile tester moving at a constant speed, stretching the sample, and starting the tester to perform the test.
TABLE 10 Performance test Table
Comparing examples 1-3, example 2 has the best resistance to ultraviolet aging because the changes in tensile strength, tensile strength at break and elongation at break before and after ultraviolet irradiation are the smallest, indicating that the raw material ratio in example 2 is the best, indicating that this example is feasible.
Example 4, example 5 and example 2 were compared, with example 2 using the uv blocking agent of preparation 8, example 4 using the uv blocking agent of preparation 9 and example 5 using the uv blocking agent of preparation 10. The difference between the preparation examples 8-10 lies in that the proportion of the nano-polyacrylamide microspheres to the porous nano-titanium dioxide is different when the anti-ultraviolet agent is prepared. The change amounts of tensile strength, tensile strength at break and elongation at break before and after ultraviolet irradiation in example 4 were the smallest, and the ultraviolet aging resistance was the best, which indicates that the component proportions were the best when the ultraviolet resistant agent was prepared in example 4.
When comparing example 6 and example 7 with example 2, and when preparing the anti-uv agent in example 2, example 6 and example 7, the nano-sized polyacrylamide microspheres of preparation examples 1 to 3 were used, respectively, and the nano-sized polyacrylamide microspheres of preparation examples 1 to 3 were different in the component ratios for preparing the nano-sized polyacrylamide microspheres. Example 6 the changes of tensile strength, tensile strength at break and elongation at break before and after uv irradiation were minimal and the uv aging resistance was optimal, which indicates that the component ratios were optimal when preparing the nano-sized polyacrylamide microspheres in example 6.
Comparing example 8, example 9 and example 6, example 8 and example 9 used the porous nano titania in production examples 5 to 7, respectively, and the porous nano titania in production examples 5 to 7 were different in the component distribution ratio for producing the porous nano titania. Example 8 the change amounts of tensile strength, tensile strength at break and elongation at break before and after ultraviolet irradiation were the smallest, and the ultraviolet aging resistance was the best, which shows that the component ratio was the best when the porous nano titanium dioxide was prepared in example 8.
By comparing example 10 with example 8, example 10 uses the anti-ultraviolet agent of preparation 15, and the nano-sized polyacrylamide microsphere of preparation 15 is preparation 4. Example 8 the anti-uv agent of preparation 13 was used, and the nano-sized polyacrylamide microspheres of preparation 13 were preparation 2. Preparation example 4 is different from preparation example 2 in that the aqueous phase of step (2) of preparation example 4 is prepared by adjusting pH to acidity to pH 3, and preparation example 2 is prepared by adjusting pH to 6.8. Example 8 the change amounts of the tensile strength, the tensile strength at break and the elongation at break before and after the ultraviolet irradiation are small, and the ultraviolet aging resistance is the best, which shows that the pH adjustment to acidity is better to be adjusted to pH 6.8 in the preparation of the aqueous phase in the step (2) of the preparation example 2, and the nano-sized polyacrylamide microspheres with small particle size can be prepared.
Comparing examples 11 and 12 with example 8, the differences between examples 11 and 12 and 8 are different in process parameters, while the changes of the tensile strength, the tensile strength at break and the elongation at break before and after the ultraviolet irradiation of example 11 are minimum, the ultraviolet aging resistance is best, and the process parameters for preparing the structure compact type anti-aging polypropylene master batch of example 11 are best.
Comparing example 13 with example 11, example 13 and example 11 are different in that the commercially available polyacrylamide is used in example 13 instead of the nano-sized polyacrylamide microspheres in example 11, and the change amounts of the tensile strength, the tensile strength at break and the elongation at break before and after the ultraviolet irradiation are small in example 11, which shows that the ultraviolet aging resistance of the structure-dense anti-aging polypropylene master batch prepared by using the nano-sized polyacrylamide in example 11 is good.
Comparing comparative example 1 with example 1, comparative example 1 and example 1 are different in that commercial titanium dioxide is used as the anti-ultraviolet agent in comparative example 1 instead of the anti-ultraviolet agent in example 1, and the changes of tensile strength, tensile strength at break and elongation at break before and after ultraviolet irradiation are smaller in example 1, which shows that the polypropylene master batch prepared by using the anti-ultraviolet agent in the examples of the present application has better compactness and better anti-ultraviolet aging performance.
Comparing comparative example 2 with example 1, the difference between comparative example 2 and example 1 is that in comparative example 2, the porous nano titanium dioxide of preparation example 2 is used as the anti-ultraviolet agent instead of the anti-ultraviolet agent in example 1, and the variation of the tensile strength, the tensile strength at break and the elongation at break before and after the ultraviolet irradiation is smaller in example 1, which shows that the polypropylene master batch prepared by the anti-ultraviolet agent used in the examples of the application has better compactness and better anti-ultraviolet aging performance.
Finally, comparing comparative example 3 with example 1, the tensile strength, tensile strength at break and elongation at break of example 10 are higher, and the difference between comparative example 2 and example 1 is that the commercial silane coupling agent is used in place of the crosslinking agent in example 1 in comparative example 2, and the change amounts of the tensile strength, tensile strength at break and elongation at break before and after the ultraviolet irradiation are smaller in example 1, which shows that the polypropylene master batch prepared by using the crosslinking agent in the examples of the present application has better compactness and better ultraviolet aging resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The compact-structure anti-aging polypropylene master batch is characterized by comprising the following components in parts by weight:
30-60 parts of polypropylene powder;
2-3 parts of a dispersing agent;
1-3 parts of a crosslinking agent;
4-6 parts of a functional assistant;
10-20 parts of water;
5-7 parts of an anti-ultraviolet agent; the ultraviolet resistant agent comprises 2-4 parts of titanium dioxide and 4-12 parts of polyacrylamide microspheres.
2. The aging-resistant polypropylene master batch with a compact structure as claimed in claim 1, wherein: the polyacrylamide microsphere is a nano-grade polyacrylamide microsphere, and the preparation method of the nano-grade polyacrylamide microsphere comprises the following steps:
(1) Preparing an oil phase: mixing and stirring 6-10 parts by weight of sorbitan oleate, 3-5 parts by weight of monooleate, 1-2 parts by weight of azobisisobutyronitrile and 8-12 parts by weight of white oil to obtain an oil phase mixture;
(2) Preparation of a water phase: mixing 30-40 parts of acrylamide, 10-14 parts of 2-acrylamido-2-methylpropanesulfonic acid and 75-85 parts of water in parts by weight, adding 5-7 parts of disodium ethylene diamine tetraacetate, adjusting the pH value to acidity, and adding 0.1-0.3 part of ammonium persulfate to obtain a water-phase mixture;
(3) Mixing and reacting: mixing 50-60 parts of oil phase mixture and 30-40 parts of water phase mixture according to parts by weight, and adding 2-4 parts of sodium bisulfite solution with the concentration of 0.6-1.4mol/L in nitrogen atmosphere to prepare polymer microsphere emulsion;
(4) Phase inversion: mixing 1-3 parts of phase transfer agent and 7-9 parts of polymer microsphere emulsion, and stirring at the rotating speed of 100-200r/min for 3-5min to obtain nano-grade polyacrylamide microsphere emulsion;
(5) Washing and drying: washing the polyacrylamide nano microsphere emulsion with absolute ethyl alcohol, then carrying out suction filtration, and carrying out drying treatment after suction filtration to obtain the nano-grade polyacrylamide microspheres.
3. The aging-resistant polypropylene masterbatch with compact structure as claimed in claim 2, wherein: the titanium dioxide is porous nano titanium dioxide, and the preparation method of the porous nano titanium dioxide comprises the following steps:
(1) Preparing a pore-forming solution: mixing 6-10 parts of pore-forming agent, 10-14 parts of absolute ethyl alcohol, 20-30 parts of deionized water and 8-10 parts of glacial acetic acid according to parts by weight to obtain pore-forming liquid;
(2) Preparation of gel: mixing 30-50 parts by weight of tetra-n-butyl titanate and 60-80 parts by weight of absolute ethyl alcohol, stirring at the rotating speed of 150-250r/min, adding 10-20 parts by weight of pore-forming liquid, and aging for 20 hours to obtain gel;
(3) Drying and calcining: drying the gel at 60-90 deg.C, grinding, and calcining at 550-650 deg.C for 2-4h to obtain porous nanometer titanium dioxide.
4. The aging-resistant polypropylene masterbatch with compact structure as claimed in claim 2, wherein: the cross-linking agent is a mixture of 1-3 parts by weight of N, N-methylenebisacrylamide and 7-13 parts by weight of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
5. The aging-resistant polypropylene masterbatch with a compact structure as claimed in claim 3, wherein: the preparation steps of the anti-ultraviolet agent are as follows:
(1) According to the weight portion, mixing and grinding half of the nano polyacrylamide microspheres and 2-4 parts of porous nano titanium dioxide for 15-25min to obtain a primary mixed material;
(2) And mixing and grinding the rest half of the nano-grade polyacrylamide microspheres and the primary mixed material for 25-35min to obtain the anti-ultraviolet agent.
6. The aging-resistant polypropylene masterbatch with a compact structure as claimed in claim 2, wherein: and (3) adjusting the pH to acidity in the preparation of the water phase in the step (2) to be 6.8.
7. The method for preparing the aging-resistant polypropylene master batch with compact structure according to any one of claims 1 to 6, comprising the following steps:
s1, preparing raw materials: weighing polypropylene powder, a dispersing agent, a cross-linking agent, a functional assistant and an anti-ultraviolet agent according to a formula;
s2, primary mixing: mixing all the water and the ultraviolet resistant agent to obtain a mixture;
s3, secondary mixing: adding all the polypropylene powder into a temperature-controlled high-speed mixer, then adding all the dispersing agent, the cross-linking agent, the functional assistant and the mixture into the temperature-controlled high-speed mixer, and stirring to obtain a mixed material;
s4, extrusion molding: adding the mixed materials into a double-screw extruder, and extruding after melting to obtain an extruded material;
s5, water-cooling pelletizing: and cooling and shaping the extruded material under water, and granulating by a granulator in the cooling process to obtain the polypropylene master batch.
8. The preparation method of the aging-resistant polypropylene masterbatch with the compact structure as claimed in claim 7, wherein the preparation method comprises the following steps: the step of the stirring process in step S3 includes: stirring at 200-300rpm for 2-4min, adjusting the rotation speed of the temperature-controlled high-speed mixer to 1000-1200rpm, and continuing stirring for 3-5min.
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| CN115919664A (en) * | 2022-12-27 | 2023-04-07 | 广东普本纳米科技有限公司 | Ultrafine titanium dioxide and preparation method thereof |
| CN115919664B (en) * | 2022-12-27 | 2023-11-28 | 广东普本纳米科技有限公司 | Ultrafine titanium dioxide and preparation method thereof |
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