CN115895139A - High-toughness high-fluidity PVC composite material and preparation method and application thereof - Google Patents
High-toughness high-fluidity PVC composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-toughness high-fluidity PVC composite material, and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The high-toughness high-fluidity PVC composite material comprises the following components in parts by weight: 100 parts of PVC resin, 1.5-5.0 parts of heat stabilizer, 0.8-1.2 parts of lubricant, 3-6 parts of processing aid and 2-4 parts of pigment. The high-toughness high-fluidity PVC composite material provided by the invention adopts specific PVC resin as matrix resin, and specific processing aid multilevel hollow silica nanoparticles are added, so that no toughening modifier is required to be added in the processing process, the problems of dispersion of the toughening modifier and compatibility between the toughening modifier and the matrix PVC resin are solved, the multilevel hollow silica nanoparticles can be efficiently adsorbed, the problem of uneven dispersion of each component in a mixture is solved, and the toughness and fluidity of the PVC composite material are effectively improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-toughness high-fluidity PVC composite material and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) resin is one of the most commonly used general resins at present, has the outstanding advantages of high mechanical strength, good flame retardant property, excellent chemical resistance, good electrical insulation property and the like, and has the advantages of wide raw material sources, low product price and wide application field. In 2020, the apparent consumption of PVC resin in China exceeds 2000 million tons, and the PVC resin is widely applied to building materials, industrial products, agricultural films, family decorations, daily necessities, floor leathers (bricks), artificial leathers, pipes, pipe fittings, wires and cables, packaging films, foaming materials, heat-insulating materials and the like. However, PVC resins also have some inherent disadvantages, mainly manifested by poor heat stability, low toughness, difficult processing, etc.
The prior art provides high-fluidity high-toughness PVC valve injection molding granules aiming at the problem of low toughness of PVC resin, and the high-fluidity high-toughness PVC valve injection molding granules comprise 90-100 parts by weight of general PVC resin, 0-10 parts by weight of toughening agent, 2-4 parts by weight of polyacrylate type or/and composite ester type processing aid, 1.5-4.0 parts by weight of heat stabilizer, 1.5-3.0 parts by weight of lubricant, 3-7 parts by weight of filler, 0.1-0.3 part by weight of light stabilizer and 0.30-0.42 part by weight of toner. The notch impact strength of the high-fluidity high-toughness PVC valve injection molding granules can only be improved to 12KJ/m 2 The requirements of high toughness and high fluidity in the application of PVC composite materials cannot be met, and the PVC composite material cannot be directly used for manufacturing injection molding products such as pipe fittings and the like.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect and the defect that the toughness and the fluidity of the existing PVC composite material cannot meet the use requirement, and provides a high-toughness high-fluidity PVC composite material.
The invention also aims to provide a preparation method of the high-toughness high-fluidity PVC composite material.
The invention further aims to provide application of the high-toughness high-fluidity PVC composite material in preparation of injection molding processing pipe fittings.
It is a further object of the present invention to provide an injection molded pipe.
The above purpose of the invention is realized by the following technical scheme:
a high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 1.5 to 5.0 parts of heat stabilizer, 0.8 to 1.2 parts of lubricant, 3 to 6 parts of processing aid and 0 to 4 parts of pigment,
wherein the polyacrylate rubber mass content of the PVC composite resin is 4-8%, the polymerization degree is 470-800,
the processing aid is a multi-stage hollow silica nanoparticle and comprises a hollow inner core and a raspberry-shaped hollow shell.
Wherein, it needs to be explained that:
the mass content of polyacrylate rubber of the special PVC composite resin in the PVC composite material is 4-8%, and the polymerization degree is 470-800. Wherein, the polyacrylate rubber plays a toughening role and can greatly improve the toughness of the PVC matrix. However, when the content of the polyacrylate rubber is too high, the toughness of the composite material is not greatly improved or even reduced due to the agglomeration of rubber particles, and the fluidity of the composite material is also reduced. Meanwhile, the mechanical property of the material is greatly reduced, and the cost is obviously increased. The content of polyacrylate rubber is too low, and the toughening effect is not obvious. Meanwhile, the mechanical strength of the material is obviously reduced due to the excessively low polymerization degree of the PVC resin, the mechanical property of the product is unqualified, and the fluidity of the PVC resin is too poor due to the excessively high polymerization degree of the PVC resin, so that the requirement on the fluidity of the injection processing technology cannot be met. Therefore, the invention needs to adopt the PVC composite resin with polyacrylate rubber mass content of 4-8% and polymerization degree of 470-800, so as to improve toughness and ensure fluidity.
In addition, the PVC composite material does not need to be added with a toughening modifier, and simultaneously solves the problems of dispersion of the toughening modifier and compatibility between the toughening modifier and matrix PVC resin.
The PVC composite material is also added with special processing aid multilevel hollow Silica (SiO) 2 ) Nanoparticles, multilevel hollow bodies of the inventionSilicon oxide (SiO) 2 ) The nano particles comprise hollow cores and raspberry-shaped hollow shells, the particle appearance is shown in figure 2, and the nano particles can play a role in enhancing the mechanical strength of PVC materials on one hand; on the other hand, the particles are in a multistage form and a porous structure, so that the particles can play a role in uniformly adsorbing and dispersing the auxiliaries, the compatibility of the special PVC composite resin and various auxiliaries is enhanced, and the wear resistance of the product is improved.
Meanwhile, the multi-stage hollow Silica (SiO) of the present invention 2 ) The nanoparticle processing aid can also improve the melt fluidity of the PVC composite material in the processing process, thereby reducing the processing time and reducing the energy consumed in the production process.
The heat stabilizer in the PVC composite material has the functions of preventing or inhibiting the degradation of PVC resin in the processing process of the PVC composite material to remove hydrogen chloride, and simultaneously can keep enough heat stability in the effective service life of a PVC composite material product and slow down the degradation caused by the photo-thermal effect, thereby prolonging the service life of the product.
The lubricant in the PVC composite material has the functions of preventing adhesion between a plastic melt and metal, improving the flow rate of the melt, and reducing the viscous resistance of the material melt in the processing process, thereby promoting the flow of the blend melt.
The PVC composite material can be added with pigment according to the requirement, so that the product is attractive, the commodity value is improved, the weather resistance of the product is improved, and the optical performance of the product is improved.
In particular embodiments, the pigment may be the white inorganic pigment titanium dioxide (TiO) 2 )。
Preferably, the water contact angle of the multi-stage hollow silica nanoparticles is 153-157 degrees.
Wherein, it needs to be explained that:
the multi-stage hollow silica nanoparticles have a water contact angle of 153-157 degrees, are super-hydrophobic materials, and are used as processing aids, so that the multi-stage hollow silica nanoparticles have excellent hydrophobicity, and can play a role in moisture prevention, thereby improving the water resistance and the service life of products in outdoor environments.
The water contact angle of the multi-stage hollow silica nanoparticles is determined according to the following method:
and (3) dripping the centrifugally washed multistage hollow silica nanoparticle dispersion liquid on a glass sheet, and drying in an oven at 50 ℃ for 8 hours to obtain a particle membrane. A contact angle tester with the model of DSA30S of German Kruss company is adopted to test the contact angles of water drops on different positions of the surface of the particle film, an average value is taken, and the hydrophobicity difference of particles with different forms is further compared.
Preferably, the diameter of the multistage hollow silica nanoparticle is 450-600 nm, and the diameter of the hollow core is 200-300 nm.
Among them, it should be noted that:
the particle size control and hollow core inner diameter control of the multi-stage hollow silica nano particles can further control the protrusion size of the hollow raspberry-shaped shell, the protrusion size of the multi-stage hollow silica nano particles is uniform and appropriate, the constructed micro/nano hierarchical structure is more reasonable, the surface with certain roughness can be formed more favorably, and further a better hydrophobic effect can be obtained.
Preferably, the mass content of the polyacrylate rubber of the PVC composite resin is 6-8%, and the polymerization degree is 470-600.
In a particular embodiment, the heat stabilizers of the present invention are calcium zinc stabilizers and/or organotin stabilizers. Preferably, the mass ratio of the calcium-zinc composite stabilizer to the organic tin stabilizer is 4-5.
In a particular embodiment, the lubricant of the present invention is a blend of calcium stearate and stearyl alcohol,
the invention also specifically provides a preparation method of the high-toughness high-fluidity PVC composite material, which comprises the following steps:
s1, uniformly mixing the components at 95-105 ℃, and cooling to below 50 ℃ to obtain a cold mixed material;
and S2, adding the cold mixed material into a conical double-screw extruder, controlling the temperature of a screw heating zone to be 170-185 ℃, performing melt extrusion, and granulating to obtain the high-toughness high-fluidity PVC composite material.
Wherein, it needs to be explained that:
in the preparation method of the high-toughness high-fluidity PVC composite material, the mixing temperature in S1 and the melting temperature in S2 are crucial, and if the mixing temperature is too low, the plasticization of the mixed material is not uniform, the effect of mixing and dispersing is poor, and if the melting temperature is too high, the melt flow is unstable, and the decomposition of the polymer is generated. The invention provides a specific preparation process for a specific PVC composite material, reduces the melting temperature of the PVC composite material, and reduces the energy consumption in the processing process.
The invention also specifically protects the application of the high-toughness high-fluidity PVC composite material in the preparation of injection molding processing pipe fittings.
The invention also specifically protects an injection molding processing pipe fitting which is prepared from the high-toughness high-fluidity PVC composite material.
In a specific embodiment, the specific process for preparing the injection-molded pipe fitting by using the high-toughness high-fluidity PVC composite material can preferably refer to the following method:
and (3) feeding the high-toughness high-fluidity PVC composite material into a screw injection molding machine, controlling the temperature of a heating section of an injection screw to be 178-188 ℃, and controlling the temperature of a nozzle to be 188-192 ℃ for processing and molding to obtain the injection molding pipe fitting.
Among them, it should be noted that: in the injection molding process for manufacturing the pipe fitting by processing and molding the PVC composite material, the key control parameters are the processing temperatures of the charging barrel and the nozzle, and if the temperature is too low, the compound is not uniformly plasticized, the flowability is poor, the molding effect is poor, and the mechanical property of the material is reduced; if the temperature is too high, the composite melt is decomposed, and the mechanical properties of the material are reduced.
Compared with the prior art, the invention has the beneficial effects that:
the high-toughness high-fluidity PVC composite material adopts PVC resin with polyacrylate rubber mass content of 4-8% and polymerization degree of 470-800 as raw materialAdding specific processing aid multilevel hollow silicon dioxide (SiO) into matrix resin 2 ) The nano particles do not need to be added with a toughening modifier in the processing process, so that the problems of dispersion of the toughening modifier and compatibility between the toughening modifier and matrix PVC resin are solved, the multi-stage hollow silica nano particles can be efficiently adsorbed, the problem of uneven dispersion of all components in a mixture is solved, and the toughness and the flowability of the PVC composite material are effectively improved.
Drawings
FIG. 1 is a GPC curve of PVC molecular weight of PVC resin of example 1.
FIG. 2 is a scanning electron microscope image of the morphology of the multi-stage hollow silica nanoparticles of example 1.
Fig. 3 is a photograph of a water droplet static contact angle test of the multi-stage hollow silica nanoparticles of example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments in any way. The starting reagents used in the examples of the present invention are those conventionally purchased, unless otherwise specified.
Example 1
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment. Wherein the heat stabilizer is calcium zinc stabilizer, and is purchased from Xinxin chemical group Limited company in Hebei province.
The lubricant is calcium stearate and stearyl alcohol, and is available from Shanghai Yi En chemical technology, inc.
The pigment is white TiO pigment 2 Purchased from Feng boat chemical reagent science and technology, inc., tianjin.
The processing aid is multi-stage hollow SiO 2 The particle comprises a hollow inner core and a raspberry-shaped hollow shell, the appearance of the particle is shown in figure 2, and the preparation method comprises the following steps:
firstly, methyl triethoxysilane is prehydrolyzed under acidic conditions to obtain amphiphilic silaneThe oligomer is then emulsified with styrene (St) monomer droplets and hydrolyzed and condensed on the surface of the St monomer droplets to form a shell layer with mesopores. Subsequently, the St monomer located inside the cavity of the shell is polymerized by the initiation of the initiator added in advance, and the polymerized product is dried to obtain a powder sample. The powder sample is placed in a muffle furnace to be calcined for 5 hours at 500 ℃ to obtain the multi-stage hollow SiO 2 And (3) particles.
Through measurement, the water contact angle of the multi-stage hollow silica nanoparticles is 157 degrees, as shown in fig. 3, the diameter of the multi-stage hollow silica nanoparticles is 550nm, and the diameter of the hollow core is 250nm.
The polymerization degree of the PVC composite resin is 470, the rubber content of 6 percent, and the specific preparation method comprises the following steps:
800g of deionized water, dispersant, initiator and 87g of polyacrylate latex are added into a 1500mL beaker, and the pH value of the dispersion is adjusted to about 8. The dispersion liquid is evenly mixed and poured into a high-pressure reaction kettle, stirred for 20min at room temperature, then the reaction kettle is sealed, and nitrogen is repeatedly filled and discharged for 3 times. Subsequently, 400g of vinyl chloride monomer is added into the system by a charging tank, stirred for 10min, and then heated and polymerized by introducing hot water into the jacket of the reaction kettle, wherein the polymerization temperature is controlled at 66 +/-0.5 ℃. When the pressure in the kettle is reduced by 0.3MPa, the temperature is reduced and the reaction is stopped. Discharging after removing the unreacted vinyl chloride monomer, washing with deionized water, filtering, and fully drying in a 50 ℃ blast oven to obtain the PVC composite resin dry powder.
The polyacrylate rubber mass content was determined to be about 6%.
The molecular weight GPC curve of PVC composite resin is shown in FIG. 1, and the polymerization degree of PVC resin is 470 calculated from FIG. 1.
The preparation method of the high-toughness high-fluidity PVC composite material comprises the following specific operations:
s1, weighing: according to the manufacturing formula of the special PVC composite resin injection molding pipe fitting, the raw materials are weighed according to the mass parts, and the scheme is as follows: 100 parts (by mass) of special PVC composite resin (the polymerization degree is 470, and the rubber content is 6 percent); 5 parts by mass of a calcium zinc stabilizer; 1 part by mass of a lubricant; multi-stage hollow SiO 2 Particles4 parts by mass; white pigment TiO 2 3 parts by mass;
thermal mixing: the raw materials weighed in the S1 are mixed according to special PVC composite resin, heat stabilizer, lubricant and multi-stage hollow SiO 2 The charging sequence of the particles and the pigment is sequentially added into a mixer for high-speed mixing, and when the temperature of the materials reaches 95 ℃, the materials are discharged into a cold mixer for cooling and mixing;
cold mixing: mixing and cooling at low rotation speed, and discharging into a pre-feeder of an extruder when the temperature of the material in the cold mixer is reduced to below 50 ℃;
s2, extruding and granulating: and adding the cold mixed material into a conical double-screw extruder, controlling the temperature of a screw heating section at 180 ℃, carrying out melt extrusion, and granulating to obtain uniformly plasticized granules and a high-toughness high-fluidity PVC composite material.
An injection molding pipe fitting is obtained by injection molding of the high-toughness high-fluidity PVC composite material, and the specific method is as follows:
and (3) feeding the granules into a screw injection molding machine, controlling the temperature of a screw heating section at 185 ℃, and controlling the temperature of a nozzle at 192 ℃ for processing and molding, and finally obtaining an injection molding processing product of the high-toughness high-fluidity special PVC composite resin.
And (4) performance testing:
(A) The sample is prepared by adopting the processes of mixing, open milling, tabletting and sample preparation, the mechanical property of the sample in the example 1 is tested, and the plasticizing property and the thermal stability of the blended material are tested by adopting a Haake rheometer. The sample preparation steps were as follows:
mixing materials: weighing materials according to the raw material ratio, adding the materials into a high-speed mixer for mixing until the mixing temperature is 105 ℃, putting the materials into a low-speed mixer for mixing, and discharging when the temperature of the materials is cooled to 45 ℃;
open smelting: plasticizing the material by a double-roller open mill, wherein the plasticizing temperature is controlled at 180 ℃, and the plasticizing time is 4min;
tabletting: the plasticized sample is preheated for 8min by a flat vulcanizing machine (or a press), and then is pressed into tablets. The temperature of the press is controlled at 183 ℃, and the pressing time is 8min;
preparing a sample: and (4) manufacturing the pressed sample into a standard sample strip meeting the test requirement.
And (3) detecting the plasticizing performance and stability: a haake plasticizing rheometer is adopted for testing, the testing temperature is 180 ℃, the rotating speed is 60rpm, and the feeding amount is 57g.
(B) The special PVC composite resin pipe fitting is injection-molded according to the method, and the performance of the pipe fitting in the example 1 is detected according to the industry standard of CJ/T272-2008 impact-resistant modified polyvinyl chloride (PVC-M) pipe fitting and pipe fitting for water supply.
Example 2
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of special PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 3 parts of processing aid and 3 parts of pigment.
The components are the same as in example 1, and the water contact angle of the multi-stage hollow silica nanoparticles is 145 degrees, the diameter of the multi-stage hollow silica nanoparticles is 450nm, and the diameter of the hollow core is 200nm.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of the example 1.
The injection molding pipe fitting is obtained by injection molding of the high-toughness high-fluidity PVC composite material obtained in the embodiment 2, and the specific method is the same as the embodiment 1.
The relevant performance test method is the same as that of example 1.
Example 3
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5 parts of heat stabilizer, 1 part of lubricant, 5 parts of processing aid and 3 parts of pigment.
The components are the same as those in example 1, and the water contact angle of the multi-stage hollow silica nanoparticles is 157 degrees, the diameter of the multi-stage hollow silica nanoparticles is 600nm, and the diameter of the hollow core is 300nm.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of the example 1.
An injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 3, and the specific method is the same as the embodiment 1.
The relevant performance test method was the same as in example 1.
Example 4
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment
Wherein the components are the same as in example 1 except that,
the polymerization degree of the PVC composite resin is 800, the rubber content is 6 percent, and the preparation method comprises the following steps: the polymerization temperature in example 1 was changed to 58 ℃ and the other conditions were kept unchanged.
Through measurement, the polymerization degree of the PVC resin is 800, and the mass content of the polyacrylate rubber is 6%.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of example 1.
An injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 4, and the specific method is the same as the embodiment 1.
The relevant performance test method is the same as that of example 1.
Example 5
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment, wherein the components are the same as those in example 1, except that,
the polymerization degree of the PVC composite resin is 600, the rubber content is 6 percent, and the preparation method comprises the following steps: the polymerization temperature in example 1 was changed to 61 ℃ and the other conditions were kept unchanged.
The polymerization degree of the PVC composite resin is about 600, and the mass content of the polyacrylate rubber is 6%.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of example 1.
The injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 5, and the specific method is the same as the embodiment 1.
The relevant performance test method is the same as that of example 1.
Example 6
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment. Wherein each component was the same as in example 1 except that,
the polymerization degree of the PVC composite resin is 470, the rubber content is 4%, and the preparation method comprises the following steps: the polyacrylate emulsion in example 1 was changed from 87g to 58g, with the other conditions being maintained.
Through measurement, the polymerization degree of the PVC composite resin is 470, and the mass content of the polyacrylate rubber is 4%.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of the example 1.
The injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 6, and the specific method is the same as the embodiment 1.
The relevant performance test method is the same as that of example 1.
Example 7
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment. Wherein each component was the same as in example 1 except that,
the polymerization degree of the PVC composite resin is 470, the rubber content is 8%, and the preparation method comprises the following steps: the polyacrylate emulsion of example 1 was changed from 87g to 116g, with the other conditions remaining unchanged.
Through measurement, the polymerization degree of the PVC resin is 470, and the mass content of the polyacrylate rubber is 8%.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of example 1.
An injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 7, and the specific method is the same as the embodiment 1.
The relevant performance test method was the same as in example 1.
Example 8
A high-toughness high-fluidity PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 1.5 parts of heat stabilizer, 1 part of lubricant, 4 parts of processing aid and 3 parts of pigment. The components were the same as in example 1 except that the heat stabilizer was 1.5 parts by mass of an organotin 8831 stabilizer, which was purchased from beijing chemical industry co.
The preparation method of the high-toughness high-fluidity PVC composite material is also the same as that of example 1.
The injection molding pipe fitting is obtained by injection molding the high-toughness high-fluidity PVC composite material obtained in the embodiment 8, and the specific method is the same as the embodiment 1.
The relevant performance test method was the same as in example 1.
Example 9
An injection-molded pipe fitting is obtained by injection-molding the high-toughness high-fluidity PVC composite material of the embodiment 1, and the specific method is as follows:
and (3) feeding the granules into a screw injection molding machine, controlling the temperature of a screw heating section at 178 ℃, and controlling the temperature of a nozzle at 192 ℃ for processing and molding, and finally obtaining an injection molding processing part of the high-toughness high-fluidity special PVC composite resin.
Example 10
An injection-molded pipe fitting is obtained by injection-molding the high-toughness high-fluidity PVC composite material of the embodiment 1, and the specific method is as follows:
and (3) feeding the granules into a screw injection molding machine, controlling the temperature of a screw heating section at 185 ℃, and controlling the temperature of a nozzle at 188 ℃ for processing and molding, and finally obtaining the injection molding processing product of the high-toughness high-fluidity special PVC composite resin.
Comparative example 1:
a PVC composite, substantially the same as example 1, except that the PVC composite resin in example 1 was replaced with an injection type general PVC resin (degree of polymerization of 800) having a rubber content of 0, and the other formulation and manufacturing process were the same as example 1.
The preparation of the PVC composite was also the same as in example 1.
An injection-molded pipe fitting is obtained by injection-molding the PVC composite material of the comparative example 1, and the specific method is the same as that of example 1.
The relevant performance test method was the same as in example 1.
Comparative example 2:
a PVC composite substantially the same as example 6 except that the multi-stage hollow SiO of example 6 was used 2 Replacement of particles with ordinary solid SiO 2 The particles, other formulations and manufacturing processes were identical to those of example 6.
The preparation of the PVC composite was also as in example 6.
An injection-molded pipe fitting is obtained by injection-molding the PVC composite material of comparative example 2, and the specific method is the same as in example 6.
The relevant performance test method was the same as in example 6.
Comparative example 3
The PVC composite material comprises the following components in parts by weight:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 1 part of processing aid and 3 parts of pigment. Wherein, each component is the same as in example 6.
The preparation of the PVC composite was also as in example 6.
The injection-molded pipe fitting is obtained by injection-molding the PVC composite material of the comparative example 3, and the specific method is the same as that in example 6.
The relevant performance test method was the same as in example 6.
Comparative example 4
The PVC composite material comprises the following components in parts by mass:
100 parts of PVC composite resin, 5.0 parts of heat stabilizer, 1 part of lubricant, 8 parts of processing aid and 3 parts of pigment. Wherein, each component is the same as in example 6.
The preparation of the PVC composite was also as in example 6.
An injection-molded pipe fitting is obtained by injection-molding the PVC composite material of comparative example 4, and the specific method is the same as example 6.
The relevant performance test method was the same as in example 6.
Results and analysis
The results of the tests of the above specific examples and comparative examples are shown in Table 1 below.
TABLE 1 comparison table of mechanical property and plasticizing property test results of examples and comparative examples
Table 1 shows the mechanical properties and plasticizing properties of the samples prepared in examples 1-10 and comparative examples 1-4 provided by the present invention. As can be seen from Table 1, compared with comparative example 1, examples 1-5 have shorter plasticizing time, smaller plasticizing equilibrium torque, better fluidity of the mixed material in the processing process and better processing performance, and the notch impact strength of examples 1-5 is remarkably improved, which shows that the formula and the processing technology of the invention achieve excellent effects on impact resistance and processing performance.
Comparing example 1, example 4 and example 5, the notch impact strength shows smaller reduction with the reduction of polymerization degree, but the plasticizing time is shortened, the equilibrium torque is reduced, and the processing fluidity of the mixed material is obviously improved.
As can be seen from examples 1, 6 and 7, the notched impact strength of the special PVC composite resin is obviously improved along with the increase of the rubber content of the special PVC composite resin. Particularly, the impact strength is greatly improved at the stage of rubber content of 4-6%, and then the improvement amplitude is reduced. The special PVC composite resin with the rubber content of about 6 percent is most suitable by combining all aspects of performances and economic cost.
Compared with the comparative example 2, the notch impact strength of the example 1 is higher, the plasticizing time is shorter, and the plasticizing equilibrium torque is smaller, which shows that the multistage hollow silica nanoparticles not only can play a role in enhancing the wear resistance, but also can improve the fluidity of the system. However, it can be seen from the experimental data of comparative examples 3 and 4 that the addition of too much or too little of the multi-stage hollow silica nanoparticles is disadvantageous in terms of both impact strength and flowability.
It can be seen from examples 9 and 10 that the mechanical properties and the flow properties of the special PVC composite resin blend material begin to decrease after the temperature of the nozzle or the screw is reduced. This is probably because the viscosity becomes large and the fluidity becomes poor because the plasticizing temperature of the blended system is low. Meanwhile, the temperature distribution in the system is uneven, and the structure of the composite material is affected in the molding process of the injection molding product, so that the mechanical property is reduced.
From the test results of examples 1-10, it can be found that the processing fluidity of the blend and the toughness of the composite material can be regulated and controlled by changing the polymerization degree (470-800) of the PVC matrix of the special PVC composite resin. So far, the production and application of special PVC composite resin with adjustable polymerization degree range similar to the above-mentioned formula have not been found.
The test results of the performance of the high-toughness high-fluidity special PVC composite resin injection pipe fitting under different formulas and processing conditions are shown in Table 2:
TABLE 2 Performance test results of special PVC composite resin injection-molded pipe fittings under different formulations and processing conditions
As can be seen from table 2: examples 1 to 10 can all be injection molded, and the pipe made of the special high-toughness high-fluidity PVC composite resin blend can completely meet the requirements of the industry standard CJ/T272-2008 "impact-resistant modified polyvinyl chloride (PVC-M) pipe and pipe for water supply", which also reflects the improvement of the processing fluidity of the PVC composite material of the present invention. The improvement of the processing fluidity also enables the special PVC composite resin to smoothly realize injection molding, thus developing the processing technology of the special PVC composite resin molding and expanding the application field of the PVC resin.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The high-toughness high-fluidity PVC composite material is characterized by comprising the following components in parts by mass:
100 parts of PVC composite resin, 1.5 to 5.0 parts of heat stabilizer, 0.8 to 1.2 parts of lubricant, 3 to 6 parts of processing aid and 2 to 4 parts of pigment,
the mass content of polyacrylate rubber of the PVC composite resin is 4-8%, the polymerization degree is 470-800, and the processing aid is a multi-stage hollow silica nanoparticle and comprises a hollow core and a hollow raspberry-shaped shell.
2. The high-toughness high-fluidity PVC composite material according to claim 1, wherein the water contact angle of the multistage hollow silica nanoparticles is 145 to 157 °.
3. The high-toughness high-fluidity PVC composite material according to claim 2, wherein the multistage hollow silica nanoparticles have a diameter of 450 to 600nm and a hollow core diameter of 200 to 300nm.
4. The high-toughness high-fluidity PVC composite material according to claim 1, wherein the PVC composite resin has a polyacrylate rubber content of 6 to 8% by mass and a degree of polymerization of 470 to 600.
5. The high toughness, high flow PVC composite of claim 1, wherein the thermal stabilizer is a calcium zinc stabilizer and/or an organotin stabilizer.
6. The high toughness, high flow PVC composite of claim 1, wherein the lubricant is a blend of calcium stearate and stearyl alcohol.
7. A preparation method of the high-toughness high-fluidity PVC composite material according to any one of claims 1 to 6, characterized by comprising the following steps:
s1, uniformly mixing all the components at 95-105 ℃, and cooling to below 50 ℃ to obtain a cold mixed material;
and S2, adding the cold mixed material into a conical double-screw extruder, controlling the temperature of a screw heating zone to be 170-185 ℃, carrying out melt extrusion, and carrying out grain cutting to obtain the high-toughness high-fluidity PVC composite material.
8. Use of the high-toughness high-flow PVC composite material according to any one of claims 1 to 6 for the production of injection-moulded pipes.
9. An injection-molded pipe prepared from the PVC composite material with high toughness and high fluidity as claimed in any one of claims 1 to 6.
10. An injection moulded pipe as claimed in claim 9, wherein the method of manufacture is as follows:
and (3) feeding the high-toughness high-fluidity PVC composite material into a screw injection molding machine, controlling the temperature of a heating section of an injection screw to be 178-188 ℃, and controlling the temperature of a nozzle to be 188-192 ℃ for processing and molding to obtain the injection molding processing pipe fitting.
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