CN113388192B - High-toughness low-temperature-resistant high-gloss regenerated PP modified material and preparation method thereof - Google Patents
High-toughness low-temperature-resistant high-gloss regenerated PP modified material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The high-toughness low-temperature-resistant high-gloss regenerated PP modified material is prepared from the following components in parts by weight: recovering the PP resin: 100 parts; UHMWPE resin: 30-50 parts of a lubricant; and (3) a compatilizer: 5-15 parts; nano barium sulfate: 20-30 parts of a lubricant; coupling agent: 0.5-1.5 parts; and (3) a modifier: 1-2 parts; stabilizing agent: 1-2 parts; an antioxidant: 1-2 parts; and (3) a lubricant: 1-3 parts; high-efficiency dispersing agent: 0.5-1 part. The regenerated PP modified material overcomes the defects in the prior art and has the advantages of high toughness, low temperature resistance, high light resistance and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-toughness low-temperature-resistant high-gloss regenerated PP modified material and a preparation method thereof.
Background
PP (polypropylene) is a thermoplastic material, is a polymer formed by the addition polymerization of propylene, is one of the varieties with the largest dosage in general thermoplastic resins, and is widely applied to various fields of industrial production. Polypropylene is a white wax-like material, transparent and light in appearance, and has a specific gravity of about 0.9, and a use temperature ranging from-30 to 140 ℃, and is resistant to acids, alkalis, salt solutions and various organic solvents. However, polypropylene is decomposed under the action of high temperature and oxidation, extrusion granulation and high temperature and high shear of injection molding process, and the ultraviolet light used in daily life of the product can cause degradation of the product to different degrees. When the polypropylene regenerated material is recycled, the strength and toughness are reduced to a greater extent, and the polypropylene regenerated material is fragile and easy to crack especially at low temperature, so that the use of the polypropylene regenerated material is limited.
UHMWPE (ultra high molecular weight polyethylene) is unbranched linear polyethylene with molecular weight of more than 100 ten thousand, is thermoplastic engineering plastic with a linear structure and excellent comprehensive performance, and has extremely excellent ductility and toughness, stable chemical property and strong ageing resistance. However, ultra-high molecular weight polyethylene has extremely high viscosity in a molten state and extremely poor fluidity, so that it is difficult to use a general injection molding method, which limits its use in bathroom products.
Because PP and PE are both polyolefin and non-polar materials, the blending of the two is not mutually exclusive. However, the compatibility between the two is gradually reduced due to the expansion of the molecular weight difference, and the two cannot be effectively combined. For example, the UHMWPE (ultra high molecular weight polyethylene) is polyethylene with molecular weight more than 100 ten thousand, the molecular weight is several times or even tens times larger than that of common homopolymerized PP, and the melt viscosity difference is large, so that a compatilizer is needed to improve the binding force of the UHMWPE and the PP. The addition of the common compatilizer (such as OBC) can not effectively restrict the flowing states of PP and UHMWPE in the processing process, as a non-Newtonian fluid, the great difference of viscosity can cause that PP with good fluidity can form a peak in UHMWPE with poor fluidity, a large amount of PP is rapidly filled at the tail end part of an injection molding product, and UHMWPE is retained at the front end of the product and even at a gate, so that the reinforcing effect of the material cannot be well reflected on the injection molding product.
In recent years, with the importance of China on environmental protection, environmental protection requirements are continuously improved, and recycling and regeneration of plastic products are increasingly important under the large environments of energy conservation, emission reduction, plastic restriction and the like. As one of the varieties with the largest dosage in the general thermoplastic resin, the polypropylene has the remarkable generation quantity of waste products, and the means of natural degradation can not solve the environmental damage caused by the polypropylene, so that the regeneration and the utilization of the polypropylene are urgent. But the molecular chain bond energy of polypropylene is not high, and the mechanical properties of the recovered product are greatly reduced when the polypropylene is subjected to light, heat and oxygen aging in a series of processing and product use processes. Therefore, a scheme is urgently needed to recycle the recovered PP on the premise of keeping good performance and appearance of the PP. Chinese invention CN 105542297B discloses a regenerated composite material for automobile parts and a preparation process thereof, wherein long glass fibers are added based on recovered PP material to obtain high strength of the material, but at the same time, the appearance is rough due to the presence of the glass fibers; the invention CN 106046537B discloses a special material for a regenerated HDPE compatible modified regenerated PP drainage corrugated pipe and a preparation method thereof, wherein a large amount of stiffening master batch is calcium carbonate, so that the glossiness of the material is greatly reduced while the strength of the material is improved; the Chinese invention CN 105504508B discloses a high-impact matt modified regenerated PP material and a preparation method thereof, and uses calcium carbonate and wollastonite as fillers, so that the glossiness of the material is poor, the glossiness is lower than 40, the tensile strength is also very low, and the highest implementation case is not more than 20MPa.
Disclosure of Invention
The invention aims to solve the problems of overcoming the defects in the prior art and providing a high-toughness low-temperature-resistant high-gloss regenerated PP modified material and a preparation method thereof.
In order to achieve the above object, the solution of the present invention is:
the high-toughness low-temperature-resistant high-gloss regenerated PP modified material is prepared from the following components in parts by weight:
recovering the PP resin: 100 parts;
UHMWPE resin: 30-50 parts of a lubricant;
and (3) a compatilizer: 5-15 parts;
nano barium sulfate: 20-30 parts of a lubricant;
coupling agent: 0.5-1.5 parts;
and (3) a modifier: 1-2 parts;
stabilizing agent: 1-2 parts;
an antioxidant: 1-2 parts;
and (3) a lubricant: 1-3 parts;
high-efficiency dispersing agent: 0.5-1 part.
Further, the compatilizer is compounded by OBC, POE and ethylene propylene diene monomer.
Further, the recovered PP resin is a homo-polypropylene.
Further, the coupling agent is a titanium aluminate coupling agent.
Further, the modifier is a compound of ethoxylated trimethylolpropane triacrylate and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
Further, the stabilizer is compounded by carbodiimide and terephthalamide.
Further, the antioxidant is compounded by an antioxidant 168 and an antioxidant 1010.
Further, the lubricant is vinyl bis-stearamide.
Further, the efficient dispersing agent is
A homopolymer.
The preparation method of the high-toughness low-temperature-resistant high-gloss regenerated PP modified material comprises the following steps:
step 1, weighing the raw materials of all components in the high-toughness low-temperature-resistant high-light regenerated PP modified material according to a proportion, then dripping a coupling agent into nano barium sulfate, and stirring to obtain treated nano barium sulfate;
step 2, stirring and recycling PP resin, UHMWPE resin and compatilizer, fully mixing, adding white mineral oil, stirring uniformly, wherein the addition amount of the white mineral oil is 0.5% -1% of the total weight of each component, adding a lubricant and a high-efficiency dispersing agent, stirring uniformly, sequentially adding a modifier, a stabilizer and an antioxidant, stirring uniformly, and finally adding the treated nano barium sulfate, and stirring to obtain a mixture;
and step 3, adding the mixture into a granulator, heating, extruding, volatilizing white mineral oil in the extrusion process, and then cooling and granulating to obtain the regenerated PP modified material.
In the step 3, the granulator is a parallel extrusion granulator with the same direction.
Further, in the step 3, the extrusion temperature of the granulator is 200-230 ℃ and the screw rotation speed is 200-500 rpm.
After the structure is adopted, the regenerated PP modified material prepared by the invention has excellent comprehensive performance and mechanical strength superior to the recovered PP before modification, the strength and toughness of the prepared closestool cover plate can reach the level of the material for the common closestool cover plate, the toughness is improved compared with that of the common recovered PP material, the glossiness is also kept good, and the recovered PP is recycled on the premise of keeping good performance and appearance of the PP.
Detailed Description
The invention discloses a high-toughness low-temperature-resistant high-gloss regenerated PP modified material, which comprises the following raw materials: the method comprises the steps of recovering PP resin, UHMWPE resin, compatilizer, nano barium sulfate, coupling agent, modifier, stabilizer, antioxidant, lubricant and efficient dispersing agent.
Specifically, the high-toughness low-temperature-resistant high-gloss regenerated PP modified material is prepared from the following components in parts by weight:
recovering the PP resin: 100 parts;
UHMWPE resin: 30-50 parts of a lubricant;
and (3) a compatilizer: 5-15 parts;
nano barium sulfate: 20-30 parts of a lubricant;
coupling agent: 0.5-1.5 parts;
and (3) a modifier: 1-2 parts;
stabilizing agent: 1-2 parts;
an antioxidant: 1-2 parts;
and (3) a lubricant: 1-3 parts;
high-efficiency dispersing agent: 0.5-1 part.
The recycled PP resin adopted by the invention can be homo-polypropylene so as to ensure the glossiness of the modified material, and the recycled material of the toilet cover plate can be adopted when the recycled PP resin is used for preparing the toilet cover plate, is produced by homo-polypropylene, and is subjected to mixing and stirring treatment on a large amount of recycled material, so that the whole batch of the recycled PP resin is more uniform and stable. After modification, the polypropylene with high glossiness can be obtained, and the requirement of the toilet cover plate is met.
The invention adopts UHMWPE as the toughening and reinforcing component of the modified material. The UHMWPE added content in the formula is 30-50 parts, because the mechanical properties of the UHMWPE to the material are greatly improved within 50 parts, otherwise, too much UHMWPE can cause the strength of the material to be greatly reduced, and too much UHMWPE has too high viscosity, so that the fluidity of the system is poor, and the injection molding processing is difficult.
The compatilizer adopted by the invention is compounded by OBC, POE and ethylene propylene diene monomer. Because the molecular structure of the compound block polymer has ethylene, propylene, butylene and octene chain segments, namely the compound block polymer is compatible with propylene and ethylene chain segments, the compound block polymer has very good compatibility with PP resin and UHMWPE resin, can be used as a compatilizer for the PP resin and the UHMWPE, provides stronger compatibility for the PP and the UHMWPE, improves the low-temperature toughness and the fluidity of the material, improves the performance of the composite material, is beneficial to the processing and forming of the composite material, and obtains a product with excellent appearance. The three block copolymers are matched together, so that excellent toughness can be kept, meanwhile, the compatibility between different olefins is greatly improved, and the compatibility between UHMWPE and PP is effectively improved. Meanwhile, because the molecular weight distribution of the OBC, POE and ethylene propylene diene monomer is different, the compatilizer system covers a wider molecular weight region, forms stepped distribution, fills the molecular weight gap between the PP and the UHMWPE, ensures that the molecular weight distribution in the modified material is more uniform and continuous, and does not generate larger faults. Therefore, compared with the common compatilizer in the processing process, the compatilizer in the patent can enable PP and UHMWPE to be better compatible, flow is mutually restricted in injection molding processing, the defect of flow layering can not occur, and each part of a final injection molding product can be effectively reinforced.
Moreover, the price of POE and ethylene propylene diene monomer is a greater advantage over OBC. And finally, the mass ratio of the OBC/POE/ethylene propylene diene monomer is 2 after multiple times of proportion adjustment: 1:1, compatibility and toughness are considered, and the cost performance is high.
This patent uses high-efficiency dispersing agent as
The homopolymer is used as a lubricating dispersant, is a product of Honeswell Honeywell company, is A-C polyethylene wax, is obtained by polymerization reaction of ethylene monomers, has relatively concentrated molecular weight, has more effective parts compared with common polyethylene wax, has more excellent lubricating performance, and can provide ultra-strong external lubricating performance. Specifically, the product of the model number Honeywell A-C617A can be used as a high-efficiency dispersant. Due to the high-efficiency lubricant, the processability of the modified material can be greatly improved, particularly the fluidity of UHMWPE is improved, so that the UHMWPE cannot stay at the tail end of an injection molding product to form layering with PP, and the components of the modified material can be uniformly distributed in the injection molding product.
In the present invention, the coupling agent may be a titanium aluminate coupling agent.
The stabilizer can be carbodiimide and terephthalamide.
The antioxidant can be compounded from antioxidant 168 and antioxidant 1010.
The lubricant may be vinyl bis-stearamide.
The modifier can be a combination of ethoxylated trimethylolpropane triacrylate (ETPTA) and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (DBPH). The compound system can partially chain-extend and crosslink the degraded chain segments in the recycled PP material, so that the molecular weight of the material is increased, and the strength of the material is improved.
The nano barium sulfate treated by the titanium aluminate coupling agent is well compatible with a material main body, so that the strength of the material is improved, the crystallization of PP is promoted, and the strength and glossiness of the material are further improved. By adding the efficient dispersant, the filler can be sufficiently dispersed and uniformly dispersed. In addition, the formula is added with a lubricant, and the lubricant can be vinyl bis-stearamide. The efficient dispersing agent can be used as an external lubricant, and the lubricant vinyl bis-stearamide can be used as an internal lubricant, so that the lubricity of the surface of the material is improved during processing, and the mechanical shearing force of the material is reduced, so that the material is easier to process and form; the internal lubricant can reduce the internal friction of the polymer, increase the melting rate and the melt deformability of the plastic, reduce the melt viscosity and improve the plasticizing performance. The efficient dispersing agent and the lubricant are matched for use, so that the problem that after UHMWPE and OBC are added, the fluidity of the modified material is poor can be effectively solved, the modified material is easier to process, the fluidity of the system is further improved, and the processing and forming of the product are ensured.
The addition amount of the compatilizer in the formula is 5-15 parts, because the addition amount of the compatilizer is less than 5 parts, the compatibility of the PP resin and the UHMWPE resin is not obviously improved, and when the addition amount exceeds 15 parts, uneven dispersion can occur, and meanwhile, the cost is too high.
The addition amount of the nano barium sulfate in the formula is 20-30 parts, and as the addition amount of the nano barium sulfate is less than 20 parts, the effect of improving the glossiness of the material is not obvious, and when the addition amount exceeds 30 parts, uneven dispersion and embrittlement can occur. Meanwhile, the addition amount of more than 20 parts can play a good role of a nucleating agent and promote the crystallization of the PP material.
The invention also discloses a method for regenerating the PP modified material with high toughness, low temperature resistance and high light, which comprises the following steps:
step 1, weighing the raw materials of all components in the high-toughness low-temperature-resistant high-light regenerated PP modified material according to a proportion, then dripping a coupling agent into nano barium sulfate, and stirring to obtain treated nano barium sulfate;
step 2, stirring and recycling PP resin, UHMWPE resin and compatilizer, fully mixing, adding white mineral oil, stirring uniformly, wherein the addition amount of the white mineral oil is 0.5% -1% of the total weight of each component, adding a lubricant and a high-efficiency dispersing agent, stirring uniformly, sequentially adding a modifier, a stabilizer and an antioxidant, stirring uniformly, and finally adding the treated nano barium sulfate, and stirring to obtain a mixture;
and step 3, adding the mixture into a granulator, heating, extruding, volatilizing white mineral oil in the extrusion process, and then cooling and granulating to obtain the regenerated PP modified material.
Further, in the step 3, the granulator is a parallel extrusion granulator in the same direction.
Further, the extrusion temperature of the granulator in the step 3 is 200-230 ℃, and the rotating speed of the screw is 200-500 rpm.
In the preparation method, the nano barium sulfate is firstly treated by using the coupling agent, and the dispersing effect and the compatibility of the nano barium sulfate can be improved after the treatment; if the coupling agent treatment is not carried out, the nano barium sulfate is easy to generate uneven dispersion, thereby causing poor fluidity and reduced product performance.
In the preparation method, the addition amount of the white mineral oil is very small and is 0.5-1% of the total weight of each component, the white mineral oil can be gradually decomposed and volatilized in granulation, and powdery auxiliary agents such as lubricants can be uniformly adhered to polymer particles to play a role in stirring and dispersing. The addition amount of other additives is small, and the addition amount of the modifier, the stabilizer, the antioxidant, the lubricant and the efficient dispersing agent in the formula is within 3 parts. The stabilizer and the antioxidant can effectively improve the processing performance of the material, so that the material is not easy to be oxidized and degraded, and meanwhile, the weather resistance of the material is greatly improved.
After the scheme is adopted, the regenerated PP modified material with high toughness, low temperature resistance and high light is prepared through reasonable design of each component of the regenerated PP modified material and simple operation steps, so that the application field of the regenerated PP material is expanded, and the regenerated PP modified material has popularization value.
The technical scheme of the invention is further described below by combining examples. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The formulation of this example is shown in Table 1, wherein the recycled PP resin is the recycled broken material of the toilet cover plate, the UHMWPE resin is formed by compounding German import GUR 5113, the compatilizer is formed by compounding OBC (American import INFUSE 9530), POE (American import DOW 8003) and ethylene propylene diene monomer, the nano barium sulfate is nano-grade high whiteness barium sulfate, the coupling agent is titanium aluminate, the modifier is formed by compounding ethoxylated trimethylolpropane triacrylate ETPTA and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane DBPH according to 1/2, the stabilizer is formed by compounding carbodiimide and terephthalamide according to 1/1, the antioxidant is formed by compounding antioxidant 168 and antioxidant 1010 according to 1/1, the lubricant is vinyl bis stearamide, and the efficient dispersing agent is formed by compounding American import HoneywellA-C617A.
TABLE 1 regenerated PP modified materials formulation
And (3) a filler manufacturing step:
1) Pouring nano barium sulfate into a stirring barrel, uniformly dripping a titanium aluminate coupling agent, stirring for 20min, and finally pouring out powder; putting the corresponding recovered PP resin into a designated drying tower according to the formula amount, wherein the drying temperature is 80 ℃, the drying time is about 3 hours, and testing the water content until the water content is within 0.3%;
2) Stirring the recovered PP resin, UHMWPE resin and a compatilizer, adding white mineral oil, stirring for 5min, adding a lubricant and a high-efficiency dispersing agent, stirring for 15min, adding a modifier, a stabilizer and an antioxidant, stirring for 5min, and finally adding treated nano barium sulfate, stirring for 10min to obtain a mixture;
3) Extruding the mixture, wherein the extruding equipment is a parallel extruding granulator with the extruding temperature of 220 ℃ and the screw rotating speed of 400 revolutions per minute, then cooling, and finally granulating to obtain the regenerated PP modified material.
The performance of the prepared material is detected as shown in the following table 2, and as can be seen from the table 2, the modified material has excellent comprehensive performance and high glossiness, and can be directly used for producing toilet cover plates.
TABLE 2 regenerated PP modified materials Performance test Table
Example 2
The formulation of this example is shown in Table 3, wherein the recycled PP resin is the recycled broken material of the toilet cover plate, the UHMWPE resin is formed by compounding German import GUR 5113, the compatilizer is formed by compounding OBC (American import INFUSE 9530), POE (American import DOW 8003) and ethylene propylene diene monomer, the nano barium sulfate is nano-grade high whiteness barium sulfate, the coupling agent is titanium aluminate, the modifier is formed by compounding ethoxylated trimethylolpropane triacrylate ETPTA and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane DBPH according to 1/2, the stabilizer is formed by compounding carbodiimide and terephthalamide according to 1/1, the antioxidant is formed by compounding antioxidant 168 and antioxidant 1010 according to 1/1, the lubricant is vinyl bis stearamide, and the efficient dispersing agent is formed by compounding American import HoneywellA-C617A.
TABLE 3 regenerated PP modified materials formulation
And (3) a filler manufacturing step:
1) Pouring nano barium sulfate into a stirring barrel, uniformly dripping a titanium aluminate coupling agent, stirring for 20min, and finally pouring out powder; putting the corresponding recovered PP resin into a designated drying tower according to the formula amount, wherein the drying temperature is 80 ℃, the drying time is about 3 hours, and testing the water content until the water content is within 0.3%;
2) Stirring the recovered PP resin, UHMWPE resin and a compatilizer, adding white mineral oil, stirring for 5min, adding a lubricant and a high-efficiency dispersing agent, stirring for 15min, adding a modifier, a stabilizer and an antioxidant, stirring for 5min, and finally adding treated nano barium sulfate, stirring for 10min to obtain a mixture;
3) Extruding the mixture, wherein the extruding equipment is a parallel extruding granulator with the extruding temperature of 220 ℃ and the screw rotating speed of 400 revolutions per minute, then cooling, and finally granulating to obtain the regenerated PP modified material.
The performance of the prepared material is tested as shown in the following table 4, and as can be seen from the table 4, the modified material has excellent comprehensive performance and high glossiness, and can be directly used for producing toilet cover plates.
TABLE 4 regenerated PP modified materials Performance test Table
| Test item | Performance data |
| Tensile strength, MPa | 33 |
| Notched impact strength, 23℃and kJ/m 2 | 28 |
| Notched impact strength, -10 ℃, kJ/m 2 | 9.5 |
| Melt index, g/10min (230 ℃,2.16 kg) | 11 |
| Gloss, incident light angle 60 DEG | 88 |
Example 3
The formulation of this example is shown in Table 5, wherein the recycled PP resin is the recycled broken material of the toilet cover plate, the UHMWPE resin is formed by compounding German import GUR 5113, the compatilizer is formed by compounding OBC (American import INFUSE 9530), POE (American import DOW 8003) and ethylene propylene diene monomer, the nano barium sulfate is nano-grade high whiteness barium sulfate, the coupling agent is titanium aluminate, the modifier is formed by compounding ethoxylated trimethylolpropane triacrylate ETPTA and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane DBPH according to 1/2, the stabilizer is formed by compounding carbodiimide and terephthalamide according to 1/1, the antioxidant is formed by compounding antioxidant 168 and antioxidant 1010 according to 1/1, the lubricant is vinyl bis stearamide, and the efficient dispersing agent is formed by compounding American import HoneywellA-C617A.
Table 5 regenerated PP modified materials formulation table
| Raw material name | Parts by mass (portions) |
| Recovered PP resin | 100 |
| UHMWPE | 50 |
| Compatibilizing agent | 15 |
| Nanometer barium sulfate | 30 |
| Coupling agent | 1.2 |
| Modifying agent | 1.5 |
| Stabilizing agent | 1.2 |
| Antioxidant | 1.2 |
| Lubricant | 2 |
| High-efficiency dispersing agent | 0.7 |
And (3) a filler manufacturing step:
1) Pouring nano barium sulfate into a stirring barrel, uniformly dripping a titanium aluminate coupling agent, stirring for 20min, and finally pouring out powder; putting the corresponding recovered PP resin into a designated drying tower according to the formula amount, wherein the drying temperature is 80 ℃, the drying time is about 3 hours, and testing the water content until the water content is within 0.3%;
2) Stirring the recovered PP resin, UHMWPE resin and a compatilizer, adding white mineral oil, stirring for 5min, adding a lubricant and a high-efficiency dispersing agent, stirring for 15min, adding a modifier, a stabilizer and an antioxidant, stirring for 5min, and finally adding treated nano barium sulfate, stirring for 10min to obtain a mixture;
3) Extruding the mixture, wherein the extruding equipment is a parallel extruding granulator with the extruding temperature of 220 ℃ and the screw rotating speed of 400 revolutions per minute, then cooling, and finally granulating to obtain the regenerated PP modified material.
The performance of the prepared material is detected as shown in the following table 6, and as can be seen from the table 6, the modified material has excellent comprehensive performance and high glossiness, and can be directly used for producing toilet cover plates.
TABLE 6 regenerated PP modified materials Performance test Table
| Test item | Performance data |
| Tensile strength, MPa | 36 |
| Notched impact strength, 23℃and kJ/m 2 | 25 |
| Notched impact strength, -10 ℃, kJ/m 2 | 9 |
| Melt index, g/10min (230 ℃,2.16 kg) | 11 |
| Gloss, incident light angle 60 DEG | 92 |
Example 4
The formulation of this example is shown in Table 7, wherein the recycled PP resin is the recycled broken material of the toilet cover plate, the UHMWPE resin is formed by compounding German import GUR 5113, the compatilizer is formed by compounding OBC (American import INFUSE 9530), POE (American import DOW 8003) and ethylene propylene diene monomer, the nano barium sulfate is nano-grade high whiteness barium sulfate, the coupling agent is titanium aluminate, the modifier is formed by compounding ethoxylated trimethylolpropane triacrylate ETPTA and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane DBPH according to 1/2, the stabilizer is formed by compounding carbodiimide and terephthalamide according to 1/1, the antioxidant is formed by compounding antioxidant 168 and antioxidant 1010 according to 1/1, the lubricant is vinyl bis stearamide, and the efficient dispersing agent is formed by compounding American import Honeywell A-C617A.
TABLE 7 regenerated PP modified materials formulation
| Raw material name | Parts by mass (portions) |
| Recovered PP resin | 100 |
| UHMWPE | 40 |
| Compatibilizing agent | 10 |
| Nanometer barium sulfate | 20 |
| Coupling agent | 0.8 |
| Modifying agent | 1.5 |
| Stabilizing agent | 1.2 |
| Antioxidant | 1.2 |
| Lubricant | 1.7 |
| High-efficiency dispersing agent | 0.7 |
And (3) a filler manufacturing step:
1) Pouring nano barium sulfate into a stirring barrel, uniformly dripping a titanium aluminate coupling agent, stirring for 20min, and finally pouring out powder; putting the corresponding recovered PP resin into a designated drying tower according to the formula amount, wherein the drying temperature is 80 ℃, the drying time is about 3 hours, and testing the water content until the water content is within 0.3%;
2) Stirring the recovered PP resin, UHMWPE resin and a compatilizer, adding white mineral oil, stirring for 5min, adding a lubricant and a high-efficiency dispersing agent, stirring for 15min, adding a modifier, a stabilizer and an antioxidant, stirring for 5min, and finally adding treated nano barium sulfate, stirring for 10min to obtain a mixture;
3) Extruding the mixture, wherein the extruding equipment is a parallel extruding granulator with the extruding temperature of 220 ℃ and the screw rotating speed of 400 revolutions per minute, then cooling, and finally granulating to obtain the regenerated PP modified material.
The performance of the prepared material is detected as shown in the following table 8, and as can be seen from the table 8, the modified material has excellent comprehensive performance and high glossiness, and can be directly used for producing toilet cover plates.
Table 8 regenerated PP modified material performance test table
| Test item | Performance data |
| Tensile strength, MPa | 34 |
| Notched impact strength, 23℃and kJ/m 2 | 23 |
| Notched impact strength, -10 ℃, kJ/m 2 | 7.5 |
| Melt index, g/10min (230 ℃,2.16 kg) | 12 |
| Gloss, incident light angle 60 DEG | 87 |
Example 5
The formulation of this example is shown in Table 9, wherein the recycled PP resin is the recycled broken material of the toilet cover plate, the UHMWPE resin is formed by compounding German import GUR 5113, the compatilizer is formed by compounding OBC (American import INFUSE 9530), POE (American import DOW 8003) and ethylene propylene diene monomer, nano barium sulfate and a coupling agent are not added in this example, the modifier is formed by compounding ethoxylated trimethylolpropane triacrylate ETPTA with 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane DBPH according to 1/2, the stabilizer is formed by compounding carbodiimide and terephthalamide according to 1/1, the antioxidant is formed by compounding antioxidant 168 and antioxidant 1010 according to 1/1, the lubricant is vinyl bis stearamide, and the efficient dispersant is formed by compounding American import HoneywellA-C617A.
Table 9 regenerated PP modified materials formulation table
| Raw material name | Parts by mass (portions) |
| Recovered PP resin | 100 |
| UHMWPE | 50 |
| Compatibilizing agent | 15 |
| Nanometer barium sulfate | 0 |
| Coupling agent | 0 |
| Modifying agent | 1.5 |
| Stabilizing agent | 1.2 |
| Antioxidant | 1.2 |
| Lubricant | 1.5 |
| High-efficiency dispersing agent | 0.7 |
And (3) a filler manufacturing step:
1) Putting the corresponding recovered PP resin into a designated drying tower according to the formula amount, wherein the drying temperature is 80 ℃, the drying time is about 3 hours, and testing the water content until the water content is within 0.3%;
2) Stirring the recovered PP resin, UHMWPE resin and a compatilizer, adding white mineral oil, stirring for 5min, adding a lubricant and a high-efficiency dispersing agent, stirring for 15min, adding a modifier, a stabilizer and an antioxidant, and stirring for 5min to obtain a mixture;
3) Extruding the mixture, wherein the extruding equipment is a parallel extruding granulator with the extruding temperature of 220 ℃ and the screw rotating speed of 400 revolutions per minute, then cooling, and finally granulating to obtain the regenerated PP modified material.
The performance of the prepared material is tested as shown in the following table 10, and the modified material has excellent comprehensive performance and high glossiness, and can be directly used for producing toilet cover plates.
Table 10 regenerated PP modified material performance test table
| Test item | Performance data |
| Tensile strength, MPa | 31 |
| Notched impact strength, 23℃and kJ/m 2 | 29 |
| Notched impact strength, -10 ℃, kJ/m 2 | 11 |
| Melt index, g/10min (230 ℃,2.16 kg) | 14 |
| Gloss, incident light angle 60 DEG | 79 |
From the above-mentioned reformulation formula, it can be seen that the gloss of the material is greatly affected without the addition of barium sulfate.
As a comparative example, table 11 below shows a material property test table for the recovered PP material.
Comparative example 1
Table 11 Performance test Table for recovered PP Material
As can be seen from the performance tables shown in the table 2, table 4, table 6, table 8, table 10 and table 11, the regenerated PP modified material has excellent comprehensive performance, mechanical strength is superior to the recovered PP before modification, strength and toughness reach the level of the material for the common closestool cover plate, meanwhile, the toughness at the low temperature of-10 ℃ is improved compared with that of the common recovered PP material, the regenerated PP modified material is not easy to become brittle and crack at the low temperature, and the glossiness is also kept good. The tensile strength of the regenerated PP modified material is larger than that of the modified regenerated PP material in the prior art, the glossiness of the regenerated PP modified material is far better than that of the material in the prior art, and the regenerated PP is recycled on the premise of keeping good performance and appearance of the PP.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (10)
1. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material is characterized by being prepared from the following components in parts by weight:
recovering the PP resin: 100 parts;
UHMWPE resin: 30-50 parts of a lubricant;
and (3) a compatilizer: 5-15 parts;
nano barium sulfate: 20-30 parts of a lubricant;
coupling agent: 0.5-1.5 parts;
and (3) a modifier: 1-2 parts;
stabilizing agent: 1-2 parts;
an antioxidant: 1-2 parts;
and (3) a lubricant: 1-3 parts;
high-efficiency dispersing agent: 0.5-1 part;
wherein the compatilizer is compounded by OBC, POE and ethylene propylene diene monomer; the modifier is the combination of ethoxylated trimethylol propane triacrylate and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane.
2. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the recycled PP resin is homopolypropylene.
3. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the coupling agent is titanium aluminate coupling agent.
4. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the stabilizer is compounded by carbodiimide and terephthalamide.
5. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the antioxidant is compounded by an antioxidant 168 and an antioxidant 1010.
6. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the lubricant is vinyl bis-stearamide.
7. The high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 1, wherein the modified PP modified material is characterized in that: the efficient dispersing agent is A-C homopolymer.
8. The preparation method of the high-toughness low-temperature-resistant high-gloss regenerated PP modified material comprises the following steps:
step 1, weighing the raw materials of all components in the high-toughness low-temperature-resistant high-light regenerated PP modified material in any one of claims 1 to 7 according to a proportion, then dripping a coupling agent into nano barium sulfate, and stirring to obtain treated nano barium sulfate;
step 2, stirring and recycling PP resin, UHMWPE resin and compatilizer, fully mixing, adding white mineral oil, stirring uniformly, wherein the addition amount of the white mineral oil is 0.5% -1% of the total weight of each component, adding a lubricant and a high-efficiency dispersing agent, stirring uniformly, sequentially adding a modifier, a stabilizer and an antioxidant, stirring uniformly, and finally adding the treated nano barium sulfate, and stirring to obtain a mixture;
and step 3, adding the mixture into a granulator, heating, extruding, volatilizing white mineral oil in the extrusion process, and then cooling and granulating to obtain the regenerated PP modified material.
9. The method for preparing the high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 8, which is characterized in that: in the step 3, the granulator is a parallel extrusion granulator in the same direction.
10. The method for preparing the high-toughness low-temperature-resistant high-gloss regenerated PP modified material according to claim 9, which is characterized by comprising the following steps: in the step 3, the extrusion temperature of the granulator is 200-230 ℃ and the screw rotating speed is 200-500 revolutions per minute.
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