CN117384452A - High-strength impact-resistant polyvinyl chloride injection molding material composition and preparation method thereof - Google Patents

High-strength impact-resistant polyvinyl chloride injection molding material composition and preparation method thereof Download PDF

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CN117384452A
CN117384452A CN202311234095.9A CN202311234095A CN117384452A CN 117384452 A CN117384452 A CN 117384452A CN 202311234095 A CN202311234095 A CN 202311234095A CN 117384452 A CN117384452 A CN 117384452A
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injection molding
polyvinyl chloride
molding material
material composition
chloride injection
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高虎
任仰省
从宪玲
寻之玉
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Shandong Lutai Holding Group Co Ltd
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Shandong Lutai Holding Group Co Ltd
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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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention relates to the technical field of PVC modification, in particular to a high-strength impact-resistant polyvinyl chloride injection molding material composition and a preparation method thereof. The preparation method comprises the following steps: mixing PVC resin powder, a heat stabilizer, an internal lubricant and a solid plasticizer, and heating; step two: adding an external lubricant, a brightening agent, a processing aid, an antioxidant, a light stabilizer and a composite toughening agent for mixing; step three: adding inorganic filler; step four: cooling and discharging; step five: granulating, hot cutting, and cooling. The composition and the preparation method thereof provided by the invention endow the polyvinyl chloride injection molding material with excellent impact strength, bending property and impact resistance.

Description

High-strength impact-resistant polyvinyl chloride injection molding material composition and preparation method thereof
Technical Field
The invention relates to the technical field of PVC modification, in particular to a high-strength impact-resistant polyvinyl chloride injection molding material composition and a preparation method thereof.
Background
Thermoplastic plastics are plastics which have plasticity at a certain temperature, solidify after cooling and can be recycled and remolded. Thermoplastic plastics can be classified into general plastics, engineering plastics and special plastics according to performance characteristics, application universality and molding technology universality, wherein the general plastics comprise five general plastics such as Polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) and the like. Polyvinyl chloride, which is one of five general-purpose plastics, has been successfully used in the fields of light industry, construction industry, packaging industry, electric and electronic elements by virtue of excellent insulation, self-flame retardance, processability, corrosion resistance, good compatibility with modifiers, low production cost, mature synthetic process and the like.
In recent years, with the increasing market demands of industries such as building industry, municipal engineering, hydraulic engineering, agriculture, industry and the like, plastic pipes are rapidly developed, PVC materials become dominant products of the plastic pipes, the PVC materials are plastics obtained by extrusion molding or injection molding after being matched with polyvinyl chloride resin, a stabilizer, a lubricant and the like, and the tensile strength of the PVC materials is high, but the impact strength and the impact resistance are poor, and the phenomenon of pipe bursting easily occurs in the using process.
In order to improve the strength of the PVC material, inorganic fillers such as calcium carbonate are often required to be added into the PVC material, however, the mechanical properties of the PVC material are greatly reduced due to the addition of the inorganic fillers, and especially the tensile strength and the impact strength are obviously reduced, and the main reasons are that the compatibility of the PVC resin and the calcium carbonate is poor, the fluidity of the PVC is poor, the plasticizing peak and the balance torque are improved, the processability is poor, and the surface of the product has no glossiness. The coupling agent is added into the PVC material, so that the filler and the polymer are tightly connected to achieve good mechanical strength, and the dispersibility of the filler in the polymer can be improved after the filler is treated by the coupling agent, so that the fluidity of a filler polymer system is improved. However, most of the coupling agents contain heavy metals, and have high requirements on the use environment, which is not beneficial to environmental protection and mass production.
In order to comprehensively improve the mechanical properties and strength of the PVC material, the prior art generally adopts a mode of blending PVC resin and an impact modifier to improve the impact strength of the PVC material, and the impact modifier adopts ACR resin to improve the comprehensive properties of the PVC material. The main action mechanism of the ACR resin for improving the impact strength to the PVC material is as follows: the cross-linked rubber particles are distributed in the PVC matrix in the form of dispersed particles, and when the PVC material receives impact, silver lines or shear bands can be generated, so that the impact strength of the PVC material is improved by absorbing impact energy. Although the impact strength of the PVC material can be improved by blending the ACR resin and the PVC resin, the influence of the ACR resin on the bending performance and the impact resistance of the PVC material is not disclosed in the prior art, and the ACR resin contains a crosslinked structure, so that the recovery and the reutilization of the PVC material are not facilitated, and the adverse effect on the environment is caused.
Disclosure of Invention
Aiming at the problem that the comprehensive properties of the PVC material such as impact strength, bending property and impact resistance are unbalanced in the prior art, the invention provides the high-strength impact-resistant polyvinyl chloride injection molding material composition and the preparation method thereof, and the polyvinyl chloride injection molding material composition is endowed with excellent impact strength, bending property and impact resistance, so that the polyvinyl chloride injection molding material composition can be recycled.
In a first aspect, the invention provides a high-strength impact-resistant polyvinyl chloride injection molding material composition, which comprises the following components in parts by weight: 100 parts of PVC resin powder, 1.5-4 parts of heat stabilizer, 1-3 parts of solid plasticizer, 1.5-3.5 parts of processing aid, 4-6 parts of composite toughening agent, 6-20 parts of inorganic filler, 0.5-2.5 parts of external lubricant, 1.5-4 parts of internal lubricant, 0.2-0.5 part of light stabilizer, 0.1-0.4 part of antioxidant and 0.1-1 part of brightening agent.
Wherein the solid plasticizer is at least one of glutaric acid type polyester plasticizer, azelaic acid type polyester plasticizer or sebacic acid type polyester plasticizer. The molecular weight of the solid plasticizer is 8000-12000g/mol.
Further, the PVC resin powder is a PVC resin synthesized by a general ethylene method, and the polymerization degree of the PVC resin is 650-750.
Further, the preparation method of the composite toughening agent comprises the following steps:
step (1): respectively weighing PVC resin powder and ABS high-glue powder, and adding the PVC resin powder and the ABS high-glue powder into a high-speed mixer for stirring;
step (2): respectively weighing chlorinated polyethylene, white oil and a dispersing agent, adding the chlorinated polyethylene, the white oil and the dispersing agent into the high-speed mixer in the step (1), stirring and mixing, and heating in the stirring process;
step (3): and (3) weighing nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing, heating in the stirring process, and then cooling under low-speed stirring to obtain the composite toughening agent.
Further, the mass ratio of the ABS high rubber powder, the PVC resin powder, the chlorinated polyethylene, the nano activated calcium carbonate, the white oil and the dispersing agent in each weight part of the composite toughening agent is 50:50:5-10:3-8:1-3:0.1-0.4.
Further, the ABS high rubber powder comprises 10% -14% of Acrylonitrile (AN), butadiene (BD) and 26% -30% of Styrene (SM).
Further, in the step (1), the stirring time is 1-2min.
Further, in the step (2), the stirring speed of stirring and mixing is 1000-1500rpm, and the stirring time is 2-5min; the temperature is raised to 60 ℃ during the stirring process, and the stirring speed is 1000-1500rpm.
Further, in the step (3), the stirring speed of stirring and mixing is 1000-1500rpm, and the stirring time is 5-10min; heating to 100-120 deg.c during stirring; the stirring speed of low-speed stirring is 500-800rpm, and the mixture is cooled to 40-50 ℃.
Further, the heat stabilizer is at least one of isooctyl dithioglycolate, isooctyl dimethyldithioglycolate and di-n-octyl beta-mercaptopropionate. The tin heat stabilizer adopted by the invention is a nontoxic and efficient environment-friendly heat stabilizer, wherein the di-n-octyl tin of isooctyl dimercaptoacetate has excellent transparency.
Further, the processing aid is an acrylic copolymer. Processing aids include, but are not limited to, acrylate copolymers having viscosity numbers 201, 401, 20, 40. The acrylic ester copolymer is a polymer with a linear structure, and the acrylic ester copolymer with the linear structure has good compatibility with the polyvinyl chloride injection molding material composition, so that the melting of each component in the polyvinyl chloride injection molding material composition can be quickened, the plasticizing time is shortened, the uniformity of the polyvinyl chloride injection molding material composition is improved, and the polyvinyl chloride injection molding material composition is not easy to crack.
Further, the inorganic filler is at least one of nano active calcium carbonate and nano active barium sulfate. The nano active calcium carbonate can increase the strength and volume of the polyvinyl chloride injection molding material composition and reduce the cost; the nano active barium sulfate is an inorganic filler with an environment-friendly function, not only can the impact strength, the bending strength and the bending modulus of the polyvinyl chloride injection molding material composition be increased on the premise of not reducing the impact strength of the polyvinyl chloride injection molding material composition, but also the cost can be reduced, the glossiness of the polyvinyl chloride injection molding material composition is improved, the polyvinyl chloride injection molding material composition has excellent weather resistance, the application range of the polyvinyl chloride injection molding material composition is enlarged, and meanwhile, the polyvinyl chloride injection molding material composition is endowed with high thermal conductivity and rheological property, and the molding period of the material is shortened.
Further, the external lubricant is polyethylene wax and low-density oxidized polyethylene wax, and the weight ratio of the polyethylene wax to the low-density oxidized polyethylene wax is 2-4:1, the polyethylene wax adopts an ethylene synthesis method with the molecular weight of 1000-1500 g/mol. The polyethylene wax floats on the surface of the polyvinyl chloride injection molding material composition in a microcrystalline form at normal temperature, so that the demolding of the polyvinyl chloride injection molding material composition is facilitated, meanwhile, the viscosity and the compatibility of the polyvinyl chloride injection molding material composition can be increased, and the processability of the material is improved; the low-density oxidized polyethylene wax can reduce the precipitation of tin heat stabilizers, improve the extrusion speed of the polyvinyl chloride injection molding material composition, and increase the appearance glossiness of the polyvinyl chloride injection molding material composition. The invention combines polyethylene wax and low-density oxidized polyethylene wax, thereby reducing the surface precipitation of the polyvinyl chloride injection molding material composition and the dosage of the low-density oxidized polyethylene wax.
Further, the internal lubricant is glycerin fatty acid ester and calcium stearate, and the weight ratio of the glycerin fatty acid ester to the calcium stearate is 3-5:1. the calcium stearate can accelerate plasticization when being used alone, improve melt viscosity, synergistically strengthen lubrication when being matched with an external lubricant, and reduce the torque value of the polyvinyl chloride injection molding material composition; the calcium stearate can also be used to absorb hydrogen chloride generated by heating chlorinated polyethylene in the melt. The calcium stearate and the glycerin fatty acid ester can be uniformly dispersed among melt molecular chains under the combined action of the calcium stearate and the glycerin fatty acid ester, so that the internal friction of the molecular chains is reduced, the melt fluidity is improved, and the surface smoothness of the polyvinyl chloride injection molding material composition is improved. The inner lubricant and the outer lubricant can make up for the defect of the heat stabilizer and the processing aid in the aspect of lubricity.
Further, the light stabilizer is benzophenone UV531, the antioxidant is antioxidant tetraphenol 1010, the dispersing agent is vinyl bis-stearamide, the kinematic viscosity of the white oil is 4-5cst, and the brightening agent is pentaerythritol stearate.
In a second aspect, the invention provides a method for preparing the high-strength impact-resistant polyvinyl chloride injection molding material composition, which comprises the following steps:
step one: adding PVC resin powder, a heat stabilizer, an internal lubricant and a solid plasticizer into a high-speed mixer for mixing, and heating in the mixing process;
step two: adding an external lubricant, a brightening agent, a processing aid, an antioxidant, a light stabilizer and a composite toughening agent into a high-speed mixer in the first step, and heating and mixing;
step three: adding inorganic filler into the high-speed mixer in the second step, stirring and mixing, and heating in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling and discharging;
step five: and (3) adding the mixture obtained in the step (IV) into a conical double-screw extruder, extruding, granulating and hot cutting the granules, and cooling the granules to obtain the high-strength impact-resistant polyvinyl chloride injection molding material composition.
Further, in the first step, the temperature is raised to 60 ℃ in the mixing process.
In the second step, the temperature is raised to 90-100 ℃ and then mixed in the temperature range.
Further, in the third step, the rotation speed of stirring and mixing is controlled to be 1000-1500rpm, and the temperature is raised to 115-125 ℃ in the mixing process.
Further, in the fourth step, the temperature is reduced and cooled to 40-50 ℃.
Further, in the fifth step, the extrusion temperature of the conical twin-screw extruder is 160-185 ℃, and the rotating speed of the conical twin-screw extruder is 40-400r/min.
The invention has the beneficial effects that:
the PVC resin is modified by utilizing the coordination effect among the composite toughening agent, the heat stabilizer, the solid plasticizer, the processing aid, the inorganic filler, the external lubricant, the internal lubricant, the light stabilizer, the antioxidant and the brightening agent, so that the impact strength, the bending strength and the bending modulus of the PVC injection molding material composition are comprehensively improved. The invention avoids the 'anti-plasticization' effect of the liquid plasticizer on the polyvinyl chloride injection molding material composition by adding the solid plasticizer, improves the compatibility between the PVC resin and the inorganic filler, and has the advantages of uniform components and stable performance.
According to the invention, the composite toughening agent is used, the ABS high rubber powder, the PVC resin powder and the chlorinated polyethylene are pretreated, the chlorinated polyethylene is used for assisting the ABS high rubber powder with a sea-island structure to increase the toughness of the polyvinyl chloride injection molding material composition, and the compatibility between the PVC resin, the inorganic filler and the ABS high rubber powder is improved, the inorganic filler and the ABS high rubber powder are promoted to be uniformly dispersed in the PVC resin, and the processability and the impact resistance of the polyvinyl chloride injection molding material composition are further improved, so that the components of the polyvinyl chloride injection molding material composition are uniformly distributed, and the performance is stable. Meanwhile, the ABS high rubber powder can play a role in increasing the toughness of the polyvinyl chloride injection molding material composition, and is beneficial to improving the notch impact strength of the cantilever beam of the polyvinyl chloride injection molding material composition; the ABS high-rubber powder has good processability and fluidity. Finally, by adjusting the proportion of the elastic structure of the copolymer in the composite toughening agent, the finally prepared composite toughening agent has a core-shell structure, and the inorganic filler is coated by a composite system formed by ABS, PVC and chlorinated polyethylene, so that the composite toughening agent can be better and tightly combined with the PVC matrix resin and the filler, and the defects of poor dispersibility and poor compatibility between the inorganic filler and the PVC and between the inorganic filler and the single toughening agent are overcome.
The invention can solve the contradiction that the strength and the impact resistance of the polyvinyl chloride injection molding material composition can not be compatible by regulating and controlling the components and the preparation method of the polyvinyl chloride injection molding material composition without using a coupling agent.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The low density oxidized polyethylene waxes used in examples 1-4 had a density of 0.93g/cm 3 。
Example 1
The preparation method of the composite toughening agent used in the embodiment is as follows:
step (1): 50 parts by weight of PVC resin powder and 50 parts by weight of ABS high-glue powder are respectively weighed and added into a high-speed mixer, and stirred for 2 minutes.
Step (2): and (2) respectively weighing 5 parts by weight of chlorinated polyethylene, 1 part by weight of white oil and 0.1 part by weight of dispersing agent, adding into the high-speed mixer in the step (1), stirring and mixing for 2min, and heating to 60 ℃ in the stirring process, wherein the stirring speed is 1000rpm.
Step (3): and (3) weighing 3 parts by weight of nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing for 5min, heating to 100 ℃ in the stirring process, stirring at 2000rpm, and cooling to 40 ℃ under low-speed stirring at 500-800rpm to obtain the composite toughening agent.
A high-strength impact-resistant polyvinyl chloride injection molding material composition, the preparation method comprises the following steps:
step one: adding 100 parts by weight of PVC resin powder, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester plasticizer into a high-speed mixer for mixing, and heating to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of pentaerythritol stearate, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010, 0.3 part by weight of light stabilizer UV531 and 4 parts by weight of composite toughening agent into a high-speed mixer in the step one for mixing, and controlling the mixing temperature at 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain a high-strength impact-resistant polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
Example 2
The preparation method of the composite toughening agent used in the embodiment is as follows:
step (1): 50 parts by weight of PVC resin powder and 50 parts by weight of ABS high-glue powder are respectively weighed and added into a high-speed mixer, and stirred for 1min.
Step (2): and (2) respectively weighing 6 parts by weight of chlorinated polyethylene, 1.5 parts by weight of white oil and 0.2 part by weight of dispersing agent, adding into the high-speed mixer in the step (1), stirring and mixing for 4min, and heating to 60 ℃ in the stirring process, wherein the stirring speed is 1500rpm.
Step (3): weighing 5 parts by weight of nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing for 8min, heating to 110 ℃ in the stirring process, stirring at the speed of 1000rpm, and cooling to 43 ℃ under low-speed stirring at the speed of 500-800rpm to obtain the composite toughening agent.
A high-strength impact-resistant polyvinyl chloride injection molding material composition, the preparation method comprises the following steps:
step one: adding 100 parts by weight of PVC resin powder, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester plasticizer into a high-speed mixer for mixing, and heating to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of pentaerythritol stearate, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010, 0.3 part by weight of light stabilizer UV531 and 5 parts by weight of composite toughening agent into a high-speed mixer in the step one for mixing, and controlling the mixing temperature at 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain a high-strength impact-resistant polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
Example 3
The preparation method of the composite toughening agent used in the embodiment is as follows:
step (1): 50 parts by weight of PVC resin powder and 50 parts by weight of ABS high-glue powder are respectively weighed and added into a high-speed mixer, and stirred for 1min.
Step (2): 8 parts by weight of chlorinated polyethylene, 2 parts by weight of white oil and 0.3 part by weight of dispersing agent are respectively weighed and added into the high-speed mixer in the step (1) to be stirred and mixed for 5min, and then the temperature is raised to 60 ℃ in the stirring process, and the stirring speed is 2000rpm.
Step (3): and (2) weighing 7 parts by weight of nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing for 10min, heating to 120 ℃ in the stirring process, stirring at 1600rpm, and cooling to 50 ℃ under low-speed stirring at 500-800rpm to obtain the composite toughening agent.
A high-strength impact-resistant polyvinyl chloride injection molding material composition, the preparation method comprises the following steps:
step one: 100 parts by weight of PVC resin powder S700, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester plasticizer are added into a high-speed mixer to be mixed, and the temperature is raised to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of pentaerythritol stearate, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010, 0.3 part by weight of light stabilizer UV531 and 6 parts by weight of composite toughening agent into a high-speed mixer in the step one for mixing, and controlling the mixing temperature at 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain a high-strength impact-resistant polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
Example 4
The preparation method of the composite toughening agent used in the embodiment is as follows:
step (1): 50 parts by weight of PVC resin powder and 50 parts by weight of ABS high-glue powder are respectively weighed and added into a high-speed mixer, and stirred for 2 minutes.
Step (2): and (2) respectively weighing 10 parts by weight of chlorinated polyethylene, 3 parts by weight of white oil and 0.4 part by weight of dispersing agent, adding into the high-speed mixer in the step (1), stirring and mixing for 3min, and heating to 60 ℃ in the stirring process, wherein the stirring speed is 1800rpm.
Step (3): weighing 8 parts by weight of nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing for 6min, heating to 118 ℃ in the stirring process, stirring at 2000rpm, and cooling to 46 ℃ under low-speed stirring at 500-800rpm to obtain the composite toughening agent.
A high-strength impact-resistant polyvinyl chloride injection molding material composition, the preparation method comprises the following steps:
step one: adding 100 parts by weight of PVC resin powder, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester plasticizer into a high-speed mixer for mixing, and heating to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of brightening agent, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010, 0.3 part by weight of light stabilizer UV531 and 5 parts by weight of composite toughening agent into a high-speed mixer in the step one for mixing, and controlling the mixing temperature at 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain a high-strength impact-resistant polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
Comparative example 1
The preparation method of the polyvinyl chloride injection molding material composition comprises the following steps:
step one: adding 100 parts by weight of PVC resin powder, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester solid plasticizer into a high-speed mixer for mixing, and heating to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of brightening agent, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010, 0.3 part by weight of light stabilizer UV531 and 4 parts by weight of Ruifeng LB-156 type MBS toughening agent into a high-speed mixer for mixing, and controlling the mixing temperature at 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain the polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
Comparative example 2
The preparation method of the polyvinyl chloride injection molding material composition comprises the following steps:
step one: adding 100 parts by weight of PVC resin powder, 2.5 parts by weight of isooctyl dimercaptoacetate di-n-octyl tin, 1.5 parts by weight of glycerin fatty acid ester, 0.5 part by weight of calcium stearate and 1.5 parts by weight of sebacic acid polyester plasticizer into a high-speed mixer for mixing, and heating to 60 ℃ in the mixing process;
step two: adding 1 part by weight of polyethylene wax, 0.5 part by weight of oxidized polyethylene wax, 0.3 part by weight of brightener pentaerythritol stearate, 2 parts by weight of acrylic ester processing aid, 0.2 part by weight of antioxidant 1010 and 0.3 part by weight of light stabilizer UV531 into a high-speed mixer in the step one for mixing, and controlling the mixing temperature to 90 ℃;
step three: adding 10 parts by weight of nano active calcium carbonate into a high-speed mixer for mixing, controlling the rotating speed to be 1000-1500rpm, and heating to 120 ℃ in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling, and discharging when the temperature of the mixture is reduced to 45 ℃;
step five: adding the mixture obtained in the step four into a conical double-screw extruder to extrude, granulate and hot-cut granules, and cooling the granules to obtain the polyvinyl chloride injection molding material composition, wherein the extrusion temperature of the conical double-screw extruder is 178 ℃ in one area; the temperature of the second area is 175 ℃; the temperature of the third region is 169 ℃, the temperature of the fourth region is 165 ℃, and the temperature of the confluence core is 167 ℃; the temperature of the handpiece was 165 ℃. The rotation speed is 60r/min.
The polyvinyl chloride injection molding material compositions of examples 1 to 4 and comparative examples 1 to 2 were each tested for each property, and the test results are shown in Table 1, wherein the test criteria for each property index are as follows: density: GB/T1033.1; notched Izod impact Strength: GB/T1843; vicat softening temperature: GB/T1633; flexural modulus: GB/T9341; flexural strength: GB/T9341; tensile strength: GB/T1040.
TABLE 1 results of Performance test of polyvinyl chloride injection molding material compositions of examples 1-4 and comparative examples 1-2
The polyvinyl chloride injection molding material compositions in examples 1 to 4 and comparative examples 1 to 2 were injection molded, and the injection molding process parameters were as follows: the injection molding temperature is 178 ℃ in the first area, 185 ℃ in the second area, 188 ℃ in the third area, 197 ℃ in the fourth area, 205 ℃ in the fifth area, 210 ℃ in the nozzle, and the mold temperature is 40-60 ℃; the glue injection pressure is 90-100kg/cm 2 Pressure maintaining of 20-30 kg/cm 2 Back pressure of 5-15kg/cm 2 The obtained injection molded article was subjected to a dynamic punching test at 0.67MPa, and the test results are shown in Table 2.
TABLE 2 dynamic press test results for polyvinyl chloride injection molding material compositions of examples 1-4 and comparative examples 1-2
As shown by the test results in Table 1, the notched Izod impact strength of the polyvinyl chloride injection molding material compositions obtained in examples 1-4 is significantly higher than that of the polyvinyl chloride injection molding material composition obtained in comparative example 2, which indicates that the polyvinyl chloride injection molding material composition provided by the invention has better impact strength. The flexural strength, flexural modulus and tensile strength of the polyvinyl chloride injection molding material compositions obtained in examples 1 to 4 were all higher than those of the polyvinyl chloride injection molding material composition obtained in comparative example 1, indicating that the flexural strength, flexural modulus and tensile strength of the polyvinyl chloride injection molding material composition provided by the invention were superior to those of the polyvinyl chloride injection molding material composition obtained using the existing toughening agent. The polyvinyl chloride injection molding material composition obtained in example 2 and comparative example 1, which use the same parts by weight of the toughening agent, has a Vicat softening temperature of 74.3 ℃ and a higher notched Izod impact strength than the polyvinyl chloride injection molding material composition obtained in comparative example 1, which indicates that the polyvinyl chloride injection molding material composition provided by the invention can reach the Vicat softening temperature of the polyvinyl chloride injection molding material composition obtained by using the conventional toughening agent, but has higher impact strength.
As can be seen from the test results in Table 2, the injection molded articles obtained in examples 1 to 4 were not broken after being subjected to 80000 dynamic punches under the same test pressure, and could be used continuously; after 68000 times of dynamic stamping, the injection molding product obtained in the comparative example 1 has deformation water leakage and cannot be used continuously; after 46000 times of dynamic stamping, the injection molding product obtained in the comparative example 2 has the conditions of bursting and water leakage and cannot be used continuously; the polyvinyl chloride injection molding material composition provided by the invention has good impact resistance, and the impact resistance is superior to that of the polyvinyl chloride injection molding material composition obtained by using the existing toughening agent.
In summary, comparative example 1 is different from comparative example 2 in that the MBS toughening agent is used, and the use of the MBS toughening agent improves the impact resistance of the polyvinyl chloride injection molding material composition to some extent, but sacrifices the flexural strength and flexural modulus of the polyvinyl chloride injection molding material composition, and the impact resistance of the polyvinyl chloride injection molding material composition is not significantly improved due to the difference in young's modulus and poisson's ratio between the nano activated calcium carbonate and the PVC matrix. The technical scheme provided by the invention can not only effectively improve the toughness of the polyvinyl chloride injection molding material composition, but also enable the polyvinyl chloride injection molding material composition to have high bending strength and high bending modulus, realize the balance of the comprehensive performance of the polyvinyl chloride injection molding material composition, and improve the impact resistance of the polyvinyl chloride injection molding material composition.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (10)

1. The high-strength impact-resistant polyvinyl chloride injection molding material composition is characterized by comprising the following components in parts by weight: 100 parts of PVC resin powder, 1.5-4 parts of heat stabilizer, 1-3 parts of solid plasticizer, 1.5-3.5 parts of processing aid, 4-6 parts of composite toughening agent, 6-20 parts of inorganic filler, 0.5-2.5 parts of external lubricant, 1.5-4 parts of internal lubricant, 0.2-0.5 part of light stabilizer, 0.1-0.4 part of antioxidant and 0.1-1 part of brightening agent.
2. The high-strength impact-resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the PVC resin powder is a PVC resin synthesized by a general vinyl method, and the polymerization degree of the PVC resin is 650-750.
3. The high-strength impact-resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the preparation method of the composite toughening agent comprises the following steps:
step (1): respectively weighing PVC resin powder and ABS high-glue powder, and adding the PVC resin powder and the ABS high-glue powder into a high-speed mixer for stirring;
step (2): respectively weighing chlorinated polyethylene, white oil and a dispersing agent, adding the chlorinated polyethylene, the white oil and the dispersing agent into the high-speed mixer in the step (1), stirring and mixing, and heating in the stirring process;
step (3): and (3) weighing nano active calcium carbonate, adding the nano active calcium carbonate into the high-speed mixer in the step (2), stirring and mixing, heating in the stirring process, and then cooling under low-speed stirring to obtain the composite toughening agent.
4. The high strength, impact resistant polyvinyl chloride injection molding material composition of claim 1, wherein the heat stabilizer is at least one of isooctyl dimercaptoacetate di-n-octyl tin, isooctyl dimethyldimercaptoacetate tin, and di-n-octyl beta-mercaptopropionate tin.
5. A high strength, impact resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the processing aid is an acrylic copolymer.
6. A high strength, impact resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the inorganic filler is at least one of nano activated calcium carbonate and nano activated barium sulfate.
7. A high strength, impact resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the external lubricant is a polyethylene wax and a low density oxidized polyethylene wax, the weight ratio of polyethylene wax to low density oxidized polyethylene wax being from 2 to 4:1, the polyethylene wax adopts an ethylene synthesis method with the molecular weight of 1000-1500 g/mol.
8. The high-strength impact-resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the internal lubricant is glycerin fatty acid ester and calcium stearate, and the weight ratio of the glycerin fatty acid ester to the calcium stearate is 3-5:1.
9. the high-strength impact-resistant polyvinyl chloride injection molding material composition as claimed in claim 1, wherein the light stabilizer is UV531, the antioxidant is antioxidant 1010, the dispersing agent is vinyl bis-stearamide, the kinematic viscosity of the white oil is 4-5cst, and the brightening agent is pentaerythritol stearate.
10. A method for preparing a high strength, impact resistant polyvinyl chloride injection molding material composition as claimed in any one of claims 1 to 9, comprising the steps of:
step one: adding PVC resin powder, a heat stabilizer, an internal lubricant and a solid plasticizer into a high-speed mixer for mixing, and heating in the mixing process;
step two: adding an external lubricant, a brightening agent, a processing aid, an antioxidant, a light stabilizer and a composite toughening agent into a high-speed mixer in the first step, and heating and mixing;
step three: adding inorganic filler into the high-speed mixer in the second step, stirring and mixing, and heating in the mixing process to obtain a mixture;
step four: placing the mixture obtained in the third step into a cold mixer for cooling and discharging;
step five: and (3) adding the mixture obtained in the step (IV) into a conical double-screw extruder, extruding, granulating and hot cutting the granules, and cooling the granules to obtain the high-strength impact-resistant polyvinyl chloride injection molding material composition.
CN202311234095.9A 2023-09-23 2023-09-23 High-strength impact-resistant polyvinyl chloride injection molding material composition and preparation method thereof Pending CN117384452A (en)

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