CN109517297B - Polyvinyl chloride profile composite material, self-cleaning polyvinyl chloride door and window profile and preparation method thereof - Google Patents

Polyvinyl chloride profile composite material, self-cleaning polyvinyl chloride door and window profile and preparation method thereof Download PDF

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CN109517297B
CN109517297B CN201811317744.0A CN201811317744A CN109517297B CN 109517297 B CN109517297 B CN 109517297B CN 201811317744 A CN201811317744 A CN 201811317744A CN 109517297 B CN109517297 B CN 109517297B
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CN109517297A (en
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赵东日
刘孝阳
代文健
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Shandong Rike Chemical 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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Abstract

The invention belongs to the technical field of plastic profiles for building doors and windows, and particularly relates to a polyvinyl chloride profile composite material, a self-cleaning polyvinyl chloride door and window profile and a preparation method thereof; the polyvinyl chloride profile composite material comprises the following components in parts by weight: 100 parts by weight of polyvinyl chloride resin, 0.8-5 parts by weight of heat stabilizer, 0.3-2 parts by weight of high-viscosity acrylate processing aid and 4-12 parts by weight of impact modifier; wherein the impact modifier is selected from a chlorinated polyethylene impact modifier or a copolymer of chlorinated polyethylene and acrylate; the elongation at break of the chlorinated polyethylene is 1000-1800%. The defects on the surface of the polyvinyl chloride door and window profile product obtained by the invention can be obviously reduced, and the glossiness can be greatly improved.

Description

Polyvinyl chloride profile composite material, self-cleaning polyvinyl chloride door and window profile and preparation method thereof
Technical Field
The invention belongs to the technical field of plastic profiles for building doors and windows, and particularly relates to a polyvinyl chloride profile composite material, a self-cleaning polyvinyl chloride door and window profile and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is a general thermoplastic with excellent performance and is one of the plastic varieties with the largest output in China. The polyvinyl chloride has the advantages of good flame retardance, corrosion resistance, high mechanical strength, good electrical insulation, good heat preservation and heat insulation, low cost and the like. The application of polyvinyl chloride is in the field of plastic profiles for building doors and windows, and is used for manufacturing plastic-steel doors and windows. Compared with other doors and windows, the polyvinyl chloride plastic-steel door and window has more superior technical characteristics in the aspects of saving energy and improving indoor thermal environmentAnd (4) sex. According to the test of physical institute of institute, the heat transfer coefficient of the single glass fiber reinforced plastic aluminum window is 64W/m2K, heat transfer coefficient of 47W/m for single glass plastic-steel window2K around, the heat transfer coefficient of the common double-layer glass fiber reinforced plastic aluminum window is 3.7W/m2K, whereas the heat transfer coefficient of a conventional double glazing plastic-steel window is about 2.5W/m2K. Therefore, compared with a steel aluminum door window, the plastic-steel door window has better heat preservation and insulation effects and saves more energy in daily use.
The investigation shows that the door and window in China accounts for 30% of the area of the outer enclosure structure of the building, and the heat dissipation capacity of the door and window accounts for 49%. In the main energy consumption of our society, the building energy consumption accounts for more than 20% of the total social energy consumption in 2000, along with the wild development of real estate in recent years, the building energy consumption accounts for more than 40% of the total social energy consumption, and the energy consumption lost through doors and windows accounts for about 50% of the building energy consumption, in other words, the energy consumption lost through doors and windows accounts for about 20% of the total social energy consumption. The low popularization rate of the energy-saving plastic-steel doors and windows causes the energy consumption of the buildings in China to be more than 3 times that of the developed countries. According to the measurement and calculation of related departments, if the energy-saving level of the doors and windows in the existing building area of 430 hundred million square meters in China can reach the current European standard (namely all doors and windows are replaced by energy-saving plastic steel doors and windows), the standard coal is saved by 4.2 million tons every year, which is equivalent to 20 percent of the total annual coal yield in China. The electricity consumption for producing one ton of plastic section is 600KWH, and the electricity consumption for producing one ton of aluminum section is 4880 KWH. Calculated according to the demand of 1000 ten thousand tons of door and window products every year, the production energy consumption saved by using the plastic section is 428 hundred million KWH compared with the aluminum section. In addition, the plastic-steel section bar is cleaned in the whole production process, no waste water, waste gas or dust is generated, the plastic-steel door and window and the waste window can be recycled after aging, and the plastic-steel door and window can be reused after reprocessing, so that the environmental pollution is avoided.
According to the statistics of 2015-2016 reports in the plastic-steel section industry in China, the demand of plastic-steel sections in China is 500 ten thousand tons every year, and with the continuous high-speed development of the real estate market and the acceleration of the urbanization and urbanization processes, the demand of the plastic-steel sections is further expanded in the next 5-10 years, and the annual demand is expected to reach 1000 ten thousand tons. Therefore, the future plastic-steel doors and windows in China have very wide prospects.
However, in the processing process of plastic profile products, the surface of the products can be subjected to melt fracture under the traction action, the surface of the plastic profile products has many small defects, dust can be attached to and accumulated on the rough plastic profile defects and is difficult to clean by wind or rainwater under the influence of weather conditions such as strong wind, haze and the like, the dust is thicker along with the prolonging of time, the appearance of the products is seriously affected, and certain cost and certain risk are required to be spent when doors and windows are cleaned.
Aiming at the defect of the plastic profile product, the research and the improvement of the surface gloss of the plastic profile product are very important.
Disclosure of Invention
The invention aims to provide a polyvinyl chloride profile composite material aiming at the problems of plastic profiles serving as doors and windows in the prior art, the surface defects of door and window products prepared from the polyvinyl chloride profile composite material can be obviously reduced, the surface glossiness of the products can be greatly improved, and the deposition of dust on the surfaces of the profiles is obviously reduced; even if there is some deposited dust, it can be disposed of by the self-cleaning function.
In order to achieve the purpose, the invention provides a polyvinyl chloride profile composite material which comprises the following components in parts by weight:
(a)100 parts by weight of a polyvinyl chloride resin,
(b)0.8 to 5 parts by weight of a heat stabilizer,
(c) 0.3-2 parts by weight of a high-viscosity acrylate processing aid with an intrinsic viscosity of 9-17,
(d)4 to 12 parts by weight of an impact modifier;
wherein the elongation at break of the impact modifier is 1000-1800%; the impact modifier is selected from chlorinated polyethylene impact modifiers or copolymers of chlorinated polyethylene and acrylate polymers.
When the polyvinyl chloride profile is processed in an extruder, materials can be changed into a melt state, and the melt can rub a metal wall of a die when passing through the die, so that the flow rate of the surface layer of the melt is slower than that of the inside of the melt, the stretching amplitude of the surface layer of the melt is larger than that of the inside of the melt at the same drawing speed, the melt of the surface layer can be cracked, defects are formed, conditions are provided for dust adhesion, and the glossiness of the surface is reduced.
The factors influencing the self-cleaning effect of the polyvinyl chloride door and window profile have three points: the surface gloss of the product, the electrostatic size of the profile and the surface tension of the profile surface. The static electricity of the section bar can be solved by adding an antistatic agent; the surface tension of the profile can be improved by using an impact modifier or a filler containing a silicon-based material. The invention mainly solves the problem of surface glossiness of the polyvinyl chloride door and window profile. In the prior art, the mode of improving the glossiness is to change and adjust the use parts of the lubricant and the low-viscosity processing aid, and the final effects are that the glossiness improving range of the section is limited, the cost is increased, and the mechanical property of the polyvinyl chloride door and window section is seriously influenced.
Aiming at the problem, the invention researches the influence of different factors on the surface gloss of the profile by deeply researching the mechanism in the profile extrusion process, and finds out that the mode of thoroughly changing the gloss problem is to endow the product with certain melt strength and high elongation at break, so that the melt does not break when the surface layer is stretched, the defects on the surface are reduced, and the gloss is improved.
The applicant of the invention finds that chlorinated polyethylene with a chain structure is dispersed in polyvinyl chloride matrix in a net structure, so that the melt fracture elongation of the polyvinyl chloride product can be obviously improved, and the melt fracture elongation of the modified polyvinyl chloride product is increased along with the increase of the elongation of the added impact modifier, so that the fusing phenomenon can be effectively reduced. Therefore, the chlorinated polyethylene with high elongation at break (1000-. However, for chlorinated polyethylene with high elongation at break or a copolymer of chlorinated polyethylene and an acrylate polymer, molecules are intertwined with each other, and a processing aid with high melt viscosity needs to be added to increase the shearing of a melt and help the chlorinated polyethylene to be uniformly dispersed in a polyvinyl chloride matrix to form an ideal network structure, so that the gloss of a profile product can be finally improved. Meanwhile, the addition of the high-viscosity processing aid can also improve the melt strength of the product and further reduce melt fracture.
In addition, the use amount of the high-viscosity processing aid has great influence on the improvement of the glossiness of the profile product, when the use amount is too large, the melt strength is further improved, the fluidity of the melt is deteriorated, the shearing is too high, and the polyvinyl chloride product is over-plasticized, so that the glossiness of the product is reduced; when the amount is too small, the effect of promoting the melt strength is not significant.
And other types of impact modifiers are added into the polyvinyl chloride matrix, such as the acrylate impact modifier, because the acrylate impact modifier is in a core-shell structure, after the acrylate impact modifier is independently added into the polyvinyl chloride matrix, the matrix is dispersed in a 'sea-island' structure, and the elongation at break of the melt is not obviously improved.
According to the polyvinyl chloride profile composite provided by the invention, preferably, the weight percentage of chlorine in the impact modifier is 33-40 wt% based on the total weight of the chlorinated polyethylene being 100 wt%. In the chlorinated polyethylene related by the invention, when the content of chlorine is high, the toughness of the chlorinated polyethylene is poor, and the improvement of the glossiness of a plastic profile product is influenced due to the reduction of the elongation at break of the chlorinated polyethylene; when the chlorine content is small, the chlorinated polyethylene becomes sticky and is not easy to disperse, and the compatibility with PVC also becomes poor. Therefore, the chlorine content of the impact modifier (based on the total weight of the chlorinated polyethylene being 100 wt%) is controlled to be 33-40 wt%, which may affect the properties of the obtained profile to some extent.
The impact modifier is preferably a chlorinated polyethylene-based impact modifier. The chlorinated polyethylene is in a chain structure, can be uniformly dispersed in a polyvinyl chloride matrix in a net structure, and can obviously improve the elongation at break of a melt of a product. And with the increase of the elongation of the chlorinated polyethylene, the elongation at break of the melt of the modified polyvinyl chloride product is increased, so that the fusing phenomenon can be effectively reduced, and the glossiness of the prepared plastic profile product is improved.
Preferably, in the copolymer of chlorinated polyethylene and an acrylate polymer, the content of the chlorinated polyethylene chain segment is 50-99 wt% and the content of the acrylate polymer chain segment is 1-50 wt%, based on 100 wt% of the total weight of the copolymer;
preferably, the copolymer of chlorinated polyethylene and acrylate polymer is a copolymer of chlorinated polyethylene-alkyl methacrylate-butyl acrylate.
In some examples of the present invention, the chlorinated polyethylene-based impact modifier as described above is prepared by the following method:
adding 0.1-0.50 part by weight of methyl methacrylate-acrylic acid copolymer dissolved in water as a dispersing agent and 0.12-0.50 part by weight of polyethylene oxide dodecyl ether as an emulsifier into a reactor (a metal kettle) provided with a stirring paddle, then adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials (dispersing agent and emulsifier) is 220-270 parts by weight, and then adding 25-36 parts by weight of high-density polyethylene; after the temperature of a reaction material is raised to 75-80 ℃ under stirring at 85-150 rpm, starting to introduce 8-20 parts by weight of chlorine, keeping the speed of introducing the chlorine at 8-20 parts by weight/hour, then heating to 132-145 ℃ while introducing the chlorine, wherein the heating time is 1.2-2 hours, simultaneously heating and introducing the chlorine, keeping the temperature at 132-145 ℃ after the reaction temperature reaches 132-145 ℃, and introducing the rest 12-22 parts by weight of chlorine at the speed of 12-22 parts by weight/hour. And then keeping the temperature between 132 and 148 ℃ for reaction for 2 to 3 hours, cooling to below 40 ℃, centrifuging and drying to obtain the chlorinated polyethylene rubber powder with the elongation at break of 1000 to 1800%, the hardness of 50 to 60 and the tensile strength of 8 to 12.
In some examples of the invention, copolymers of chlorinated polyethylene and acrylic polymers as described above are prepared by:
adding 0.05-0.2 part by weight of water-soluble polymethyl methacrylate-acrylic acid copolymer serving as a dispersing agent and 0.03-0.1 part by weight of initiator dibenzoyl peroxide into a reactor (metal kettle) provided with a stirring paddle, then adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials (dispersing agent and initiator) is 220-280 parts by weight, then adding 30-40 parts by weight of prepared chlorinated polyethylene rubber powder, raising the temperature of a reaction material to 70-85 ℃ under the stirring of 75-95 rpm, then adding 1-12 parts by weight of n-butyl acrylate and 1-29 parts by weight of methyl methacrylate, keeping the temperature at 80-85 ℃, cooling to below 40 ℃ after reacting for 3 hours, centrifuging, and drying to obtain rubber powder with the breaking elongation of 1800-60%, the hardness of 50-60 and the tensile strength of 8-12.
Of course, any commercially available impact modifier satisfying the limitations of the present invention may be used.
According to the polyvinyl chloride profile composite material provided by the invention, preferably, the polyvinyl chloride resin is selected from polyvinyl chloride homopolymer and/or polyvinyl chloride copolymer;
more preferably, the polyvinyl chloride copolymer comprises 80 to 99.99 wt% of vinyl chloride units and 0.01 to 20 wt% of units consisting of other monomers, based on 100 wt% of the total weight of the polyvinyl chloride copolymer; wherein the other monomer is selected from one or more of vinyl acetate, propylene, styrene, alkyl methacrylate and alkyl acrylate. For example, the polyvinyl chloride resin of the present invention may be selected from the group consisting of polyvinyl chloride resin SG-5 of Qilu petrochemical and Shandong east Yue.
In the present invention, the alkyl group present may be a straight-chain alkyl group or a branched-chain alkyl group. Preferably, the "alkyl" is selected from the group consisting of C1-C12 straight chain alkyl groups or C1-C12 branched chain alkyl groups, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, decyl.
According to the polyvinyl chloride profile composite material provided by the invention, after the impact modifier with high elongation at break (for example, chlorinated polyethylene) is added, a processing aid with high melt viscosity is added to increase the shearing of a melt, so that the chlorinated polyethylene is uniformly dispersed in a polyvinyl chloride matrix to form an ideal network structure; meanwhile, the high-viscosity processing aid can also improve the melt strength of the product and further reduce melt fracture. However, the high viscosity processing aid can also affect the fluidity of the melt while improving the melt strength, and therefore, the composition and the amounts of the components thereof need to be optimized for better effects. Preferably, the high viscosity acrylate-based processing aid is selected from alkyl acrylate copolymers, alkyl acrylate-styrene-acrylonitrile copolymers, or mixtures of alkyl acrylate copolymers and styrene-acrylonitrile copolymers. The alkyl acrylate copolymer described herein may be a copolymer obtained by copolymerization of at least two monomers among methyl methacrylate, n-butyl acrylate and isooctyl acrylate. In some examples of the invention, each of the monomers involved in the high viscosity acrylate-based processing aid comprises 5ppm to 10ppm of a polymerization inhibitor; the polymerization inhibitor contained in each monomer is selected from p-tert-butyl catechol and/or p-hydroxyanisole.
In the invention, the intrinsic viscosity measuring method of the high-viscosity acrylate processing aid comprises the following steps: firstly, putting the to-be-measured acrylate processing aid into a 65 ℃ constant temperature box, keeping the to-be-measured acrylate processing aid for 10 hours, accurately weighing 0.072g by a ten-thousandth balance after cooling, putting the to-be-measured acrylate processing aid into a 25ml volumetric flask, then adding about 20ml of trichloromethane to dissolve the trichloromethane, standing the solution for 24 hours, putting the solution into a constant temperature water tank at 25 +/-0.1 ℃ after all the trichloromethane is dissolved, keeping the temperature for 15 minutes, diluting the solution to 25ml of scale by the trichloromethane, filtering the solution by a No. 3 sand core funnel to be measured, measuring the viscosity of the solution by an Ubbelohde viscometer, and measuring. The intrinsic viscosity is calculated as follows:
ηr＝t/t0；ηsp＝ηr-1；
Figure BDA0001856744630000071
where t is the time for the plasticizing modifier solution to flow through the capillary, t0Is a solvent IIIThe time during which the methyl chloride was passed through the same capillary, and c is the concentration of the solution (g/100 ml).
More preferably, the alkyl acrylate copolymer is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts by weight of the total monomers: 60 to 99 parts by weight of an alkyl methacrylate, and 1 to 40 parts by weight of an alkyl acrylate.
More preferably, the alkyl acrylate-styrene-acrylonitrile copolymer is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts by weight of the total monomers: 35-80 parts by weight of alkyl methacrylate, 0-40 parts by weight of alkyl acrylate, 1-64 parts by weight of styrene monomer and 1-25 parts by weight of acrylonitrile monomer.
More preferably, the mixture of the alkyl acrylate copolymer and the styrene-acrylonitrile copolymer comprises the following components in parts by weight, based on 100 parts by weight of the total mixture: 40-99 parts by weight of an alkyl acrylate copolymer, and 1-60 parts by weight of a styrene-acrylonitrile copolymer;
the styrene-acrylonitrile copolymer is prepared by copolymerizing the following monomers in parts by weight, wherein the total parts by weight of the monomers is 100: 65-99 parts of styrene monomer and 1-35 parts of acrylonitrile monomer.
In some examples of the invention, the alkyl acrylate copolymer as described above is prepared by:
injecting 80-140 parts by weight of water into a reactor, putting 60-99 parts by weight of methyl methacrylate, 1-40 parts by weight of n-butyl acrylate, 0.8-2.0 parts by weight of sodium dodecyl sulfate and 0.004-0.1 part by weight of potassium persulfate into the reactor at one time, heating to 40-60 ℃ at the rotating speed of 180-250 rpm, and controlling the reaction temperature within 40-60 ℃ for reaction to obtain an emulsion of a copolymer; and drying to obtain the acrylic acid alkyl ester copolymer.
In some examples of the invention, the alkyl acrylate-styrene-acrylonitrile copolymer as described above is prepared by the following method:
injecting 80-140 parts by weight of water into a reactor, putting 35-80 parts by weight of methyl methacrylate, 0-40 parts by weight of n-butyl acrylate, 1-64 parts by weight of styrene, 1-25 parts by weight of acrylonitrile, 0.8-2.0 parts by weight of sodium dodecyl sulfate and 0.004-0.1 part by weight of potassium persulfate into the reactor at one time, heating to 40-60 ℃ at the rotating speed of 180-250 rpm, and controlling the reaction temperature within 40-60 ℃ for reaction to obtain a copolymer emulsion; and drying to obtain the copolymer of acrylic acid alkyl ester-styrene-acrylonitrile.
In some examples of the invention, the mixture of alkyl acrylate copolymer and styrene-acrylonitrile copolymer as described above is prepared by:
injecting 80-140 parts by weight of water into a reactor, putting 65-99 parts by weight of styrene, 1-55 parts by weight of acrylonitrile, 0.8-2.0 parts by weight of sodium dodecyl sulfate and 0.004-0.1 part by weight of potassium persulfate into the reactor at one time, heating to 40-60 ℃ at the rotating speed of 180-250 rpm, and controlling the reaction temperature within 40-60 ℃ for reaction to obtain copolymer emulsion; and drying to obtain the styrene-acrylonitrile copolymer. And mixing the obtained styrene-acrylonitrile copolymer with the obtained acrylate copolymer, wherein the mixture comprises 40-99 parts by weight of alkyl acrylate copolymer and 1-60 parts by weight of styrene-acrylonitrile copolymer.
Of course, any commercially available high viscosity acrylate-based processing aid satisfying the limitations of the present invention may be used.
According to the polyvinyl chloride section material composite material provided by the invention, preferably, the heat stabilizer is selected from one or more of an organic tin stabilizer, a calcium zinc stabilizer and a lead salt stabilizer.
According to the polyvinyl chloride profile composite material provided by the invention, preferably, the polyvinyl chloride profile composite material further comprises the following components in parts by weight:
(e)0 to 5 parts by weight of an antistatic agent,
(f)5 to 35 parts by weight of a filler,
(g)0 to 4 parts by weight of a lubricant,
(h)0.5 to 10 parts by weight of a pigment.
More preferably, the antistatic agent is selected from one or more of alkyl phosphates, ethoxylated alcohols, alkyl sulfonates and fatty acid esters.
More preferably, the filler is selected from one or more of calcium carbonate, talc and white carbon black; wherein the average particle diameter (D50) of the filler is preferably 0.5 μm or less; those skilled in the art will appreciate that D50, also known as the mean or median diameter, represents the cumulative 50% point diameter (or 50% pass particle diameter). The particle size of the filler also has a certain influence on the fracture of the melt, and the larger the particle size of the filler is, the larger the formed defect is, the more easily the melt is broken; therefore, it is necessary to select an appropriate filler particle size in the composite.
More preferably, the lubricant is selected from one or more of oxidized polyethylene wax, paraffin wax, stearic acid, monoglycerides of stearic acid, pentaerythritol stearate, pentaerythritol adipate and calcium stearate.
More preferably, the pigment is selected from one or more of titanium dioxide, carbon black, ultramarine pigments and fluorescent whitening agents.
Another objective of the present invention is to provide a self-cleaning pvc door and window profile, which is manufactured by processing the pvc profile composite material; for example, by processing through a twin-screw extruder (parallel twin-screw extruder or conical twin-screw extruder).
The glossiness (test angle is 60 degrees) of the self-cleaning polyvinyl chloride door and window profile is more than 50.
The invention also provides a preparation method of the self-cleaning polyvinyl chloride door and window profile, which comprises the following steps:
(1) mixing the components of the polyvinyl chloride profile composite material according to parts by weight to obtain the polyvinyl chloride profile composite material;
(2) and extruding and molding the polyvinyl chloride profile composite material in a double-screw extruder, and then shaping, cooling, drawing and cutting to obtain the self-cleaning polyvinyl chloride door and window profile (such as polyvinyl chloride door and window profiles with different section structures).
According to the preparation method provided by the invention, preferably, the temperature for mixing the components of the polyvinyl chloride profile composite material in the step (1) is 110-125 ℃, and the mixed material is cooled to be below 45 ℃. When the materials of the components are weighed, the weighing error is controlled within 2 per thousand. It will be appreciated by those skilled in the art that mixing can be carried out using material mixing equipment commonly used in the art.
In the step (1), when the components of the polyvinyl chloride profile composite material are mixed, the components can be added and mixed at one time or sequentially. For example, the component materials can be sequentially placed into a high-speed mixer in the following feeding sequence: adding polyvinyl chloride resin powder and a stabilizer at 50-60 ℃; adding a lubricant at the temperature of 60-70 ℃; adding a high-viscosity acrylate processing aid and an impact modifier at the temperature of 70-80 ℃; adding a filling agent, a pigment and an antistatic agent at the temperature of 80-90 ℃.
Preferably, in the extrusion molding process of the step (2), the processing temperature of the cylinder area of the double-screw extruder is 170-185 ℃, and the temperature of the die area is 175-190 ℃. It will be understood by those skilled in the art that the extrusion of the compounded composition may be accomplished by using a screw extruder commonly used in the art.
The invention provides a polyvinyl chloride profile composite material for improving the surface glossiness of profile products, which reduces the dust adsorption on the surface of the profile to the maximum extent by reducing the defects on the surface of the profile. Tests show that compared with the common plastic section, the plastic section produced by the polyvinyl chloride section composite material has the advantages that the defects on the surface of the section product are obviously reduced, the glossiness is greatly improved, and the deposition of dust on the surface of the section is obviously reduced; even if partial deposited dust exists, the dust is easily cleaned through wind or rainwater in the natural environment, and a novel domestic self-cleaning and maintenance-free energy-saving door and window is created.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) the surface glossiness of the self-cleaning polyvinyl chloride door and window profile can reach more than 50, so that the adhesion and adsorption of dust on the surface of the profile are reduced, and the self-cleaning effect of the polyvinyl chloride door and window profile is achieved;
(2) in a preferred embodiment, the chlorinated polyethylene is added as an impact modifier, so that the elongation at break of the melt of the polyvinyl chloride product can be increased, the fusing phenomenon can be effectively reduced, and finally the glossiness of the surface of the profile product can be improved;
(3) meanwhile, the high-viscosity processing aid is added into the polyvinyl chloride profile composite material, so that the dispersion of the impact modifier can be promoted, the melt strength of the product can be improved, the melt fracture is further reduced, and the improvement of the glossiness of the surface of the profile product can be promoted finally.
Drawings
FIG. 1 is an SEM photograph of the surface of the polyvinyl chloride door/window profile prepared in example 13;
FIG. 2 is an SEM photograph of the surface of the polyvinyl chloride door/window profile prepared in comparative example 6.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
In one example of the invention, a polyvinyl chloride profile composite material comprises the following components in parts by weight:
(a)100 parts by weight of a polyvinyl chloride resin,
(b)0.8 to 5 parts by weight of a heat stabilizer,
for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight,
(c)0.3 to 2 parts by weight of a high viscosity acrylate processing aid,
for example, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, and an intrinsic viscosity of 9 to 17,
(d)4 to 12 parts by weight of an impact modifier,
for example, 5 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, the elongation at break is 1000-1800%;
wherein the impact modifier is selected from chlorinated polyethylene impact modifiers or copolymers of chlorinated polyethylene and acrylic polymers, and preferably is the chlorinated polyethylene impact modifier.
In some preferred embodiments, the impact modifier contains 33 to 40 wt% of chlorine, based on 100 wt% of the total weight of the chlorinated polyethylene. The content of chlorine in the impact modifier is defined as 33 to 40 wt% of chlorine in the chlorinated polyethylene impact modifier, based on 100 wt% of the total weight of the chlorinated polyethylene; or in the copolymer of the re-chlorinated polyethylene and the acrylate polymer, the weight percentage of chlorine contained in the copolymer is 33-40 wt% based on 100 wt% of the total weight of the chlorinated polyethylene.
In some examples, the copolymer of chlorinated polyethylene and an acrylate polymer has a content of chlorinated polyethylene chain segments of 50 to 99 wt%, for example, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 90 wt%, and a content of acrylate polymer chain segments of 1 to 50 wt%, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, based on 100 wt% of the total weight of the copolymer; in a preferred embodiment, the copolymer of chlorinated polyethylene and an acrylate polymer is a chlorinated polyethylene-alkyl methacrylate-butyl acrylate copolymer.
In some examples, the polyvinyl chloride resin is selected from polyvinyl chloride homopolymers and/or polyvinyl chloride copolymers; preferably, the polyvinyl chloride copolymer comprises 80 to 99.99 wt% of vinyl chloride units and 0.01 to 20 wt% of units consisting of other monomers, based on 100 wt% of the total weight of the polyvinyl chloride copolymer; wherein the other monomer is selected from one or more of vinyl acetate, propylene, styrene, alkyl methacrylate and alkyl acrylate.
In some examples, the high viscosity acrylate-based processing aid is selected from an alkyl acrylate copolymer, an alkyl acrylate-styrene-acrylonitrile copolymer, or a mixture of an alkyl acrylate copolymer and a styrene-acrylonitrile copolymer.
The alkyl acrylate copolymer is prepared by copolymerizing the following monomers in parts by weight, wherein the total parts by weight of the monomers is 100: 60 to 99 parts by weight (e.g., 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight) of an alkyl methacrylate, and 1 to 40 parts by weight (e.g., 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight) of an alkyl acrylate.
The copolymer of alkyl acrylate-styrene-acrylonitrile is prepared by copolymerizing the following monomers in parts by weight, wherein the total parts by weight of the monomers is 100: 35 to 80 parts by weight (e.g., 40 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 75 parts by weight) of an alkyl methacrylate, 0 to 40 parts by weight (e.g., 2 parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight) of an alkyl acrylate, 1 to 64 parts by weight (e.g., 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight) of a styrene-based monomer and 1 to 25 parts by weight (e.g., 2 parts by weight, 4 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight) of an acrylonitrile monomer.
The mixture formed by the alkyl acrylate copolymer and the styrene-acrylonitrile copolymer comprises the following components in parts by weight, based on the total weight of the mixture as 100: 40 to 99 parts by weight (e.g., 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight) of an alkyl acrylate copolymer, 1 to 60 parts by weight (e.g., 2 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight) of a styrene-acrylonitrile copolymer;
the styrene-acrylonitrile copolymer is prepared by copolymerizing the following monomers in parts by weight, wherein the total parts by weight of the monomers is 100: 65 to 99 parts by weight (e.g., 70 parts by weight, 80 parts by weight, 90 parts by weight) of a styrene-based monomer and 1 to 35 parts by weight (e.g., 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight) of an acrylonitrile monomer.
The heat stabilizer is selected from one or more of organic tin stabilizer, calcium zinc stabilizer and lead salt stabilizer.
In some examples, the polyvinyl chloride profile composite further comprises the following components in parts by weight:
(e)0 to 5 parts by weight of an antistatic agent, for example 2 parts by weight or 3 parts by weight,
(f)5 to 35 parts by weight of a filler, for example, 10 parts by weight, 20 parts by weight or 30 parts by weight,
(g)0 to 4 parts by weight of a lubricant, for example, 1 part by weight, 2 parts by weight, or 3 parts by weight,
(h)0.5 to 10 parts by weight of a pigment, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, or 8 parts by weight.
The antistatic agent is selected from one or more of alkyl phosphate, ethoxylated alcohol, alkyl sulfonate and fatty acid ester;
the filler is selected from one or more of calcium carbonate, talcum powder and white carbon black; preferably, the average particle size of the filler is below 0.5 micron;
the lubricant is selected from one or more of oxidized polyethylene wax, paraffin wax, stearic acid monoglyceride, pentaerythritol stearate, pentaerythritol adipate and calcium stearate;
the pigment is selected from one or more of titanium dioxide, carbon black, ultramarine pigment and fluorescent whitening agent.
In some examples, the self-cleaning polyvinyl chloride door and window profile is made using a polyvinyl chloride profile composite as described above processed through a twin screw extruder (e.g., a parallel twin screw extruder or a tapered twin screw extruder); and the glossiness of the prepared self-cleaning polyvinyl chloride door and window profile is more than 50.
In some examples, the preparation method of the self-cleaning polyvinyl chloride door and window profile comprises the following steps:
(1) weighing and mixing the components of the polyvinyl chloride profile composite material according to parts by weight to obtain the polyvinyl chloride profile composite material; in some examples, the mixing temperature of the components of the polyvinyl chloride profile composite material in the mixing process in the step (1) is 110-125 ℃; when the temperature of the materials rises to the range of 110-125 ℃, the polyvinyl chloride mixed material is put into a low-speed cold mixer, so that the polyvinyl chloride section material composite material is cooled to the temperature below 45 ℃, and the polyvinyl chloride section material composite material is stored and kept stand for later use.
(2) And extruding and molding the polyvinyl chloride profile composite material in a screw extruder, and then shaping, cooling, drawing, cutting and packaging to obtain the self-cleaning polyvinyl chloride door and window profile (for example, the self-cleaning polyvinyl chloride door and window profile with different section structures). In some examples, the extrusion molding process of step (2) has a barrel zone processing temperature of 170 ℃ to 185 ℃ and a die zone temperature of 175 ℃ to 190 ℃. The extrusion processing of the section bar can adopt a parallel twin-screw extruder or a conical twin-screw extruder.
< sources of raw materials >
Polyvinyl chloride resin, Qilu petrochemical SG-5;
calcium zinc stabilizer, Shandong Jinchang tree JCS-602Z;
organotin stabilizers, starry plastics additives (zhouhing) limited;
lead salt stabilizers, inner mongolia, Haohai chemical Limited liability company;
high viscosity acrylate processing aids, available from Shandong Nikko Chemicals Co., Ltd. (see preparation examples 1 to 4 and comparative preparation example 1);
acrylate impact modifier HL-50, Hippon Nichico chemical Co., Ltd;
impact modifiers with high elongation at break, available from Shandong Nikko Chemie GmbH, prepared by itself (see preparation examples 5-8 and comparative preparation example 2);
light calcium carbonate, yuxin ltd, qingzhou;
titanium dioxide, derby Yuxing chemical Co., Jinan;
antistatic agent GMS, Technological technologies, Inc. of Jiangshan;
methyl methacrylate, cellulote international (china) chemical company, ltd;
n-butyl acrylate, Shandongtai petrochemical acrylic acid, Inc.;
styrene, north China division, petrochemical industries, sales, Inc.;
acrylonitrile, Zibo Quanxing chemical Co., Ltd;
sodium lauryl sulfate, Jiangsu qingting washings, Inc.;
potassium persulfate, Jiangsu qingting washings Co., Ltd;
polyethylene oxide dodecyl ether, south Tongde Rick chemical Co., Ltd;
high density polyethylene, Qingdao Sainuo chemical Co., Ltd;
dibenzoyl peroxide, Shanghai Hua Runzi chemical Co., Ltd.
< test methods >
1. Melt strength: and connecting an electronic tension meter to the extrusion material, stopping the rotating speed of the main machine after the traction is stable, keeping the traction speed unchanged until the polyvinyl chloride melt is broken, and recording the maximum value displayed by the tension meter during the period. Melt strength is the tensile value per cross-sectional area of the profile.
2. Melt elongation at break: and connecting an electronic tension meter to the extrusion material, stopping the rotating speed of the main machine after the traction is stable, keeping the traction speed unchanged, marking a position 2cm away from the neck mold, breaking the melt of the sample to be detected, and recording the distance L of the pulled melt of 2 cm. The melt elongation at break was (L-2)/2.
3. Gloss: the gloss data at an angle of 60 ℃ on the visible side of the profile were determined with a gloss meter (Jinan DeRux instruments Ltd., model: DRK 118B).
4. Self-cleaning effect: uniformly spreading a layer of carbon dust on the visible surface of the extruded profile, then dripping 0.5ml of distilled water on the surface of the profile by using a sample injector, inclining the profile at an angle of 30 degrees to ensure that water drops roll downwards, and comparing the surface state of the rolled profile.
Taking the calcium zinc stabilizer system as an example, a profile formulation with a loading of 20 parts was selected for data collection and verification. The polyvinyl chloride section bar composite material is mixed according to a certain proportion, the mixture is extruded by a conical double-screw extruder, the melt strength, the melt elongation at break, the electron microscope structure and the glossiness of the surface of a product in the extrusion process are tested, and factors influencing the glossiness in contrast are observed.
1. Preparation of the low viscosity acrylate processing aid used in the comparative examples and the high viscosity (intrinsic viscosity 9-17) acrylate processing aid used in the examples:
preparation example 1:
the preparation method of the acrylate processing aid with the intrinsic viscosity of 9.0 comprises the following steps: injecting 120 parts by weight of water into a reactor, putting 85 parts by weight of methyl methacrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 20ppm), 15 parts by weight of n-butyl acrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 20ppm), 1.2 parts by weight of sodium dodecyl sulfate and 0.04 part by weight of potassium persulfate into the reactor at one time, heating to 55 ℃ at the rotating speed of 225 revolutions per minute, and controlling the reaction temperature within 55-58 ℃ for reacting for 16 hours to obtain copolymer emulsion; and drying to obtain the acrylate processing aid product with the intrinsic viscosity of 9.0, wherein the conversion rate is 98.63%.
Preparation example 2
The preparation method of the acrylate processing aid with the intrinsic viscosity of 17 comprises the following steps: injecting 120 parts by weight of water into a reactor, putting 90 parts by weight of methyl methacrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 8ppm), 10 parts by weight of n-butyl acrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 8ppm), 1.5 parts by weight of sodium dodecyl sulfate and 0.007 part by weight of potassium persulfate into the reactor at one time, heating to 50 ℃ at the rotating speed of 250 revolutions per minute, and controlling the reaction temperature within 52-56 ℃ for reacting for 17 hours to obtain copolymer emulsion; and drying to obtain the acrylate processing aid product with the intrinsic viscosity of 17, wherein the conversion rate is 98.34%.
Preparation example 3:
the preparation method of the acrylate processing aid with the intrinsic viscosity of 13.4 comprises the following steps: injecting 140 parts by weight of water into a reactor, placing 75 parts by weight of methyl methacrylate (the content of p-hydroxyanisole serving as a polymerization inhibitor is 10ppm), 20 parts by weight of styrene (the content of p-tert-butylcatechol serving as the polymerization inhibitor is 10ppm), 5 parts by weight of acrylonitrile (the content of p-hydroxyanisole serving as the polymerization inhibitor is 10ppm), 1.2 parts by weight of sodium dodecyl sulfate and 0.018 part by weight of potassium persulfate into the reactor at one time, heating to 50 ℃ at the rotating speed of 300 revolutions per minute, and controlling the reaction temperature within 50-54 ℃ for reacting for 17 hours to obtain an emulsion of a copolymer; and drying to obtain the acrylate processing aid product with the intrinsic viscosity of 13.4, wherein the conversion rate is 98.89%.
Preparation example 4:
the mixture of alkyl acrylate copolymer with intrinsic viscosity of 15.2 and styrene-acrylonitrile copolymer was prepared as follows: injecting 120 parts by weight of water into a reactor, putting 85 parts by weight of methyl methacrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 10ppm), 15 parts by weight of n-butyl acrylate (wherein the content of p-hydroxyanisole serving as a polymerization inhibitor is 10ppm), 1.6 parts by weight of sodium dodecyl sulfate and 0.01 part by weight of potassium persulfate into the reactor at one time, heating to 50 ℃ at the rotating speed of 270 revolutions per minute, controlling the reaction temperature within 50-54 ℃ for reacting for 18 hours, and drying to obtain a methyl methacrylate-n-butyl acrylate copolymer; injecting 140 parts by weight of water into a reactor, placing 75 parts by weight of styrene (the content of polymerization inhibitor p-tert-butylcatechol is 10ppm), 25 parts by weight of acrylonitrile (the content of polymerization inhibitor p-tert-butylcatechol is 10ppm), 1.5 parts by weight of sodium dodecyl sulfate and 0.008 part by weight of potassium persulfate into the reactor at one time, rapidly heating to 55 ℃ at the rotating speed of 275 rpm, controlling the reaction temperature within 55-58 ℃ for reaction for 15 hours, drying to obtain a styrene-acrylonitrile copolymer, and mixing the methyl methacrylate-n-butyl acrylate copolymer and the styrene-acrylonitrile copolymer according to the weight ratio of 60:40 to obtain a mixture formed by an alkyl acrylate copolymer with the intrinsic viscosity of 15.2 and the styrene-acrylonitrile copolymer.
Comparative preparation example 1:
the preparation method of the processing aid with the intrinsic viscosity of 5 comprises the following steps: injecting 120 parts by weight of water into a reactor, putting 78 parts by weight of methyl methacrylate, 10 parts by weight of n-butyl acrylate, 12 parts by weight of styrene, 2.0 parts by weight of sodium dodecyl sulfate and 0.12 part by weight of potassium persulfate into the reactor at one time, heating to 65 ℃ at the rotating speed of 300 revolutions per minute, and controlling the reaction temperature within 65-75 ℃ for reaction for 14 hours to obtain copolymer emulsion; and drying to obtain the processing aid product with the intrinsic viscosity of 5, wherein the conversion rate is 98.99 percent.
2. Preparation of the low elongation at break impact modifier used in the comparative example and the high elongation at break impact modifier used in the examples (1000-:
preparation example 5
Adding 0.25 part by weight of water-soluble methyl methacrylate-acrylic acid copolymer serving as a dispersing agent and 0.24 part by weight of polyethylene oxide dodecyl ether serving as an emulsifier into a 24-cubic-meter reactor provided with a stirring paddle, then adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials is 250 parts by weight, adding 30 parts by weight of high-density polyethylene, raising the temperature of a reaction material to 80 ℃ under the stirring of 125 revolutions per minute, starting to introduce 20 parts by weight of chlorine gas, keeping the chlorine gas introduction speed at 18 parts by weight per hour, raising the temperature to 138 ℃ while introducing the chlorine gas, keeping the temperature at 138 ℃ after the reaction temperature reaches 138 ℃, and introducing the rest 16 parts by weight of chlorine gas at the speed of 16 parts by weight per hour. Then, the temperature was maintained at 138 to 140 ℃ for reaction for 3 hours, and then, the reaction mixture was cooled to 40 ℃ or less, centrifuged, and dried to obtain chlorinated polyethylene rubber powder (sample 1) having a breaking elongation of 1000%, a hardness of 55, and a tensile strength of 9.8. The conversion of the product obtained in the reaction was 99.4%.
Preparation example 6
Adding water into a 24-cubic-meter reactor provided with a stirring paddle, adding 0.1 part by weight of polymethyl methacrylate-acrylic acid copolymer serving as a dispersing agent and 0.05 part by weight of dibenzoyl peroxide, then adding water until the total water consumption and the sum of the auxiliary raw material consumption is 250 parts by weight, adding 36 parts by weight of sample 1 prepared in preparation example 5, raising the temperature of the reaction material to 80 ℃ under stirring at 85 revolutions per minute, then adding 3 parts by weight of n-butyl acrylate and 5 parts by weight of methyl methacrylate, keeping the temperature at 80-85 ℃, cooling to below 40 ℃ after reacting for 3 hours, centrifuging, and drying to obtain rubber powder (sample 2) with the breaking elongation of 1320%, the hardness of 53 and the tensile strength of 9.0. The conversion of the product obtained in the reaction was 99.3%.
Preparation example 7
Adding 0.28 weight part of water-soluble methyl methacrylate-acrylic acid copolymer serving as a dispersing agent and 0.27 weight part of polyethylene oxide dodecyl ether serving as an emulsifier into a 24 cubic meter reactor provided with a stirring paddle, then adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials is 250 weight parts, then adding 34 weight parts of high-density polyethylene, raising the temperature of a reaction material to 80 ℃ under the stirring of 140 revolutions per minute, starting to introduce 15 weight parts of chlorine gas, keeping the chlorine gas introduction speed at 15 weight parts per hour, raising the temperature to 135 ℃ while introducing the chlorine gas, keeping the temperature at 135 ℃ after the reaction temperature reaches 135 ℃, and introducing the rest 22 weight parts of chlorine gas at the speed of 22 weight parts per hour. Then, the temperature was maintained at 138 to 142 ℃ for reaction for 3 hours, and then, the reaction mixture was cooled to 40 ℃ or less, centrifuged, and dried to obtain chlorinated polyethylene rubber powder having an elongation at break of 1800% and a hardness of 50 and a tensile strength of 8.1 (sample 3). The conversion of the product obtained in the reaction was 99.0%.
Preparation example 8
Adding 0.24 weight part of water-soluble methyl methacrylate-acrylic acid copolymer serving as a dispersing agent into a 24 cubic meter reactor provided with a stirring paddle, adding 0.24 weight part of polyethylene oxide dodecyl ether serving as an emulsifier, then adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials is 250 weight parts, adding 32 weight parts of high-density polyethylene, raising the temperature of a reaction material to 78 ℃ under the stirring of 132 revolutions per minute, starting to introduce 12 weight parts of chlorine gas, keeping the chlorine gas introduction speed at 12 weight parts per hour, raising the temperature to 138 ℃ while introducing the chlorine gas, keeping the temperature at 138 ℃ after the reaction temperature reaches 138 ℃, and introducing the rest 20 weight parts of chlorine gas at the speed of 18 weight parts per hour. Then, the temperature was maintained at 140 to 143 ℃ for reaction for 3 hours, and then, the reaction mixture was cooled to 40 ℃ or less, centrifuged, and dried to obtain chlorinated polyethylene rubber powder (sample 4) having an elongation at break of 1560% and a hardness of 50 and a tensile strength of 8.7. The conversion of the product obtained in the reaction was 99.2%.
Comparative preparation example 2
Adding 0.26 part by weight of water-soluble methyl methacrylate-acrylic acid copolymer serving as a dispersing agent into a 24-cubic-meter reactor provided with a stirring paddle, adding 0.30 part by weight of polyethylene oxide dodecyl ether serving as an emulsifier, adding water until the sum of the total water consumption and the use amount of all auxiliary raw materials is 250 parts by weight, adding 30 parts by weight of high-density polyethylene, raising the temperature of a reaction material to 85 ℃ under 75 r/m stirring, starting to introduce 20 parts by weight of chlorine gas, keeping the chlorine gas introduction speed at 20 parts by weight/h, raising the temperature to 132 ℃ while introducing the chlorine gas, keeping the temperature at 132 ℃ after the reaction temperature reaches 132 ℃, and introducing the rest 12 parts by weight of chlorine gas at the speed of 12 parts by weight/h. Then, the temperature was maintained at 132 to 135 ℃ for reaction for 3 hours, and then, the reaction mixture was cooled to 40 ℃ or less, centrifuged, and dried to obtain a chlorinated polyethylene rubber powder (sample 5) having an elongation at break of 880% and a hardness of 56 and a tensile strength of 10.2. The conversion of the product obtained in the reaction was 99.2%.
3. The preparation method and the process conditions of the self-cleaning polyvinyl chloride door and window section bar are as follows:
3.1 preparation method
(1) Weighing the components of the polyvinyl chloride profile composite material according to parts by weight and mixing the components by using mixing equipment to obtain the polyvinyl chloride profile composite material;
mixing equipment: high speed mixer SHR-Z800 equipment volume: 800L;
putting polyvinyl chloride resin and a calcium-zinc stabilizer into a high-speed mixer at 50 ℃, and starting a high-stirring device to be switched on and off; putting the high-viscosity acrylate processing aid and the impact modifier into a high-speed mixer at 75 ℃; the filler, pigment and antistatic agent were put into a high-speed mixer at 85 ℃. When the temperature of the materials reaches 118 ℃, putting the materials into a low-speed cold mixer, cooling the materials to below 45 ℃, sieving the materials with a 40-mesh sieve, and standing for storage;
(2) and (2) extruding the polyvinyl chloride profile composite material mixed in the step (1) according to the process shown in the following table 1.
3.2 Process conditions
The type of the extrusion equipment: 45/100 conical twin-screw extruder, the technical process conditions are shown in Table 1.
Table 1: extrusion process for polyvinyl chloride profile composite material
Process for the preparation of a coating Parameter(s)
Barrel 1 (. degree. C.) 180
Barrel 2 (. degree. C.) 178
Barrel 3 (. degree. C.) 175
Confluence core (. degree. C.) 172
Die 1 (. degree. C.) 185
Die 2 (. degree.C.)) 183
Die 3 (. degree. C.) 185
Die 4 (. degree. C.) 185
Feed rotation speed (rpm) 15.8
Main unit rotating speed (rpm) 17.5
Traction (m/min) 1.0
4. Preparation and performance test of self-cleaning polyvinyl chloride door and window profile
4.1, mixing the materials according to the compounding ratio of the polyvinyl chloride profile materials in the table 2, wherein the mixing process is described in the section 3.1 above; and self-cleaning polyvinyl chloride door and window profiles were prepared according to the extrusion process of table 1, and the extruded self-cleaning polyvinyl chloride door and window profiles were tested.
Table 2: polyvinyl chloride profile composite material proportioning for examples 1-6 and comparative examples 1-2
Figure BDA0001856744630000201
Figure BDA0001856744630000211
In table 2, the process for preparing the acrylate-based processing aid with η ═ 9.0, 17, 13.4, and 5.0 is described in preparation example 1, preparation example 2, preparation example 3, and comparative preparation example 1; see preparation example 5 for the preparation of sample 1 with an elongation at break of 1000%.
The extruded self-cleaning polyvinyl chloride door and window profiles were tested according to the test methods of melt elongation at break, melt strength, gloss and self-cleaning effect, and the test data of examples 1-6 and comparative examples 1-2 are shown in Table 3.
Table 3: test data of self-cleaning polyvinyl chloride door and window profile
Figure BDA0001856744630000212
Figure BDA0001856744630000221
As can be seen from the analysis of the results in Table 3, the melt strength and gloss gradually improved with the increase in the amount of the high viscosity (same intrinsic viscosity) processing aid used in examples 1-3; from the analysis of the results of examples 1 and 5, it is found that the higher the intrinsic viscosity of the processing aid, the higher the gloss of the profile, at the same amount. When the low-viscosity processing aid is used in comparative example 1, the gloss of the profile does not have a good effect even though a large amount of the processing aid is added; when the amount of the high-viscosity processing aid used in comparative example 2 was too low, a high melt strength could not be formed, and the product had low gloss and poor self-cleaning effect.
4.2 impact of impact modifiers of different elongation at Break on gloss of articles
After adding impact modifiers with different elongations, the materials were mixed according to the compounding ratio of polyvinyl chloride profile materials in table 4, and the mixing process is described in part 3.1; and self-cleaning polyvinyl chloride door and window profiles were prepared according to the extrusion process of table 1, as in examples 7-12 and comparative examples 3-5.
Table 4: polyvinyl chloride section material composite material proportion added with impact modifiers with different elongations
Figure BDA0001856744630000222
Figure BDA0001856744630000231
In table 4, the procedures for preparing samples 1, 3 and 4 were as described in preparation examples 5, 7 and 8, and the procedure for preparing sample 5 was as described in comparative preparation example 2; see preparation example 3 for the preparation of acrylate-based processing aids η 13.4.
The extruded self-cleaning polyvinyl chloride door and window profiles were tested according to the test methods of melt elongation at break, melt strength, gloss and self-cleaning effect, and the test data of examples 7-12 and comparative examples 3-5 are shown in Table 5.
Table 5: test data for polyvinyl chloride profiles obtained in examples 7 to 12 and comparative examples 3 to 5
Figure BDA0001856744630000232
Figure BDA0001856744630000241
Analysis of the detection data in table 5 shows that in examples 7-9, with the increase of the amount of the impact modifier used at the same elongation at break, the elongation at break of the melt of the obtained product is increased, the gloss is improved, and the self-cleaning effect of the product is improved; in example 7 and examples 11 to 12, the elongation at break of the impact modifier was increased under the same amount of the impact modifier, and the melt elongation at break and the gloss of the article were also improved. When the modifier with low elongation at break in comparative example 3 or the impact modifier with high elongation at break in comparative example 4 is used in a low amount, the gloss of the profile cannot be effectively improved, and both are lower than 50; in contrast, in comparative example 5, the addition of the acrylate impact modifier did not effectively increase the elongation at break of the melt, and the gloss of the profile product was not more than 50.
4.3 comparison of the Effect of fillers (calcium carbonate) of different particle sizes on the gloss of articles
After adding fillers (calcium carbonate) with different particle sizes, mixing the materials according to the compounding ratio of the polyvinyl chloride profile materials in the table 6, wherein the mixing process is described in the section 3.1; and self-cleaning polyvinyl chloride door and window profiles were prepared according to the extrusion process of table 1, as in comparative examples 6-7 and examples 13-15. The glossiness and the self-cleaning effect of the product are tested, and the test results are shown in table 6.
Table 6: proportioning of polyvinyl chloride profile composite material and profile gloss test result
Figure BDA0001856744630000242
Figure BDA0001856744630000251
See preparation example 3 for the acrylate-based processing aid used in table 6 with η ═ 13.4; the preparation of sample 2 used as an impact modifier participated in preparation example 6.
From the gloss data and the self-cleaning effect of comparative examples 6 to 7 and examples 13 to 15, it is evident that: as the particle size of the filler decreases, the gloss of the article may also increase. Because calcium carbonate is poor in compatibility with organic polyvinyl chloride, the position of the calcium carbonate is equivalent to a defect, and when the defect is larger, the strength and the elongation of a melt in a micro area around the calcium carbonate are obviously reduced, so that the position of the calcium carbonate is easy to break the melt, larger defects are caused, and the surface gloss of a product is influenced. As can be seen from FIG. 1, the filler is uniformly dispersed in the polyvinyl chloride melt on the surface of the profile obtained in example 13 of the present application, and a large amount of calcium carbonate is also dispersed on the surface of the melt. As can be seen from FIG. 2, the surface of the profile obtained in comparative example 6 has a significantly increased number of defects caused by the filler in the polyvinyl chloride melt, which affects the surface gloss of the product. In conclusion, the filler with the average particle size (D50) of less than 0.5 micron is added into the polyvinyl chloride melt, so that the fracture of the polyvinyl chloride melt is improved, and the glossiness of the profile is improved.
4.4 influence of different Filler contents and different stabilizer systems on the gloss of polyvinyl chloride door and window profiles
Simultaneously, the contents of different fillers and different stabilizer systems are changed, and the materials are mixed according to the compounding ratio and the process of the polyvinyl chloride profile material in the table 7, wherein the mixing process refers to the description in the 3.1 part; extruded and tested through a conical twin-screw extruder under the respective process conditions, as in examples 16 to 22. The melt strength, melt elongation at break and gloss of the resulting profile were obtained and the profile test data are shown in table 8.
Table 7: example 16-22 formulation (parts by weight) and extrusion Process of polyvinyl chloride composite Material
Figure BDA0001856744630000261
Figure BDA0001856744630000271
Figure BDA0001856744630000281
See preparation example 4 for the acrylate-based processing aid used in table 7 with η ═ 15.2; the preparation of sample 2 used as an impact modifier participated in preparation example 6.
Table 8: test data for polyvinyl chloride profiles obtained in examples 16 to 22
Figure BDA0001856744630000282
In summary, when a high-viscosity acrylate processing aid with an intrinsic viscosity of 9-17 and an impact modifier with an elongation at break of 1000-1800% are selected for use, the melt elongation at break and the melt strength of the profile product can be obviously improved, so that the occurrence of melt fracture is reduced, and the profile product is endowed with a good surface structure and gloss. In addition, the filler with the particle size D50 of less than 0.5 micron is added into the polyvinyl chloride matrix, has certain effect on improving the melt breaking elongation and the melt strength of the profile product, and can endow the profile product with good surface structure and glossiness.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (18)

1. The polyvinyl chloride profile composite material is characterized by comprising the following components in parts by weight:
(a)100 parts by weight of a polyvinyl chloride resin,
(b)0.8 to 5 parts by weight of a heat stabilizer,
(c)0.3 to 2 parts by weight of a high-viscosity acrylate processing aid having an intrinsic viscosity of 17,
(d)4 to 12 parts by weight of an impact modifier;
wherein the elongation at break of the impact modifier is 1000-1800%; the impact modifier is selected from chlorinated polyethylene impact modifiers.
2. The polyvinyl chloride profile composite according to claim 1, wherein the chlorinated polyethylene-based impact modifier is a copolymer of a chlorinated polyethylene and an acrylate-based polymer.
3. The polyvinyl chloride profile composite according to claim 1, wherein the chlorinated polyethylene-based impact modifier is chlorinated polyethylene.
4. The polyvinyl chloride profile composite according to claim 2, wherein the impact modifier contains 33 to 40 wt% of chlorine, based on 100 wt% of the total weight of the chlorinated polyethylene; and/or
In the copolymer of the chlorinated polyethylene and the acrylate polymer, the content of a chlorinated polyethylene chain segment is 50-99 wt% and the content of an acrylate polymer chain segment is 1-50 wt%, wherein the total weight of the copolymer is 100 wt%; and/or
The copolymer of the chlorinated polyethylene and the acrylate polymer is a copolymer of the chlorinated polyethylene, alkyl methacrylate and butyl acrylate.
5. The polyvinyl chloride profile composite according to claim 1, wherein the polyvinyl chloride resin is selected from polyvinyl chloride homopolymers and/or polyvinyl chloride copolymers.
6. The polyvinyl chloride profile composite according to claim 5, wherein the polyvinyl chloride copolymer comprises 80 to 99.99 wt% of vinyl chloride units and 0.01 to 20 wt% of units consisting of other monomers, based on 100 wt% of the total weight of the polyvinyl chloride copolymer; wherein the other monomer is selected from one or more of vinyl acetate, propylene, styrene, alkyl methacrylate and alkyl acrylate.
7. The polyvinyl chloride profile composite according to claim 1, wherein the high viscosity acrylate-based processing aid is selected from an alkyl acrylate copolymer or a mixture of an alkyl acrylate copolymer and a styrene-acrylonitrile copolymer.
8. The polyvinyl chloride profile composite according to claim 7, wherein the alkyl acrylate copolymer is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts by weight of the total monomers: 60 to 99 parts by weight of an alkyl methacrylate, and 1 to 40 parts by weight of an alkyl acrylate.
9. The polyvinyl chloride profile composite according to claim 7, wherein the alkyl acrylate copolymer is an alkyl acrylate-styrene-acrylonitrile copolymer.
10. The polyvinyl chloride profile composite according to claim 9, wherein the alkyl acrylate-styrene-acrylonitrile copolymer is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts by weight of the total monomers: 35-80 parts by weight of alkyl methacrylate, 0-40 parts by weight of alkyl acrylate, 1-64 parts by weight of styrene monomer and 1-25 parts by weight of acrylonitrile monomer.
11. The polyvinyl chloride profile composite material as claimed in claim 7, wherein the mixture of the alkyl acrylate copolymer and the styrene-acrylonitrile copolymer comprises the following components in parts by weight, based on the total parts by weight of the mixture as 100: 40-99 parts by weight of an alkyl acrylate copolymer, and 1-60 parts by weight of a styrene-acrylonitrile copolymer;
the styrene-acrylonitrile copolymer is prepared by copolymerizing the following monomers in parts by weight, wherein the total parts by weight of the monomers is 100: 65-99 parts of styrene monomer and 1-35 parts of acrylonitrile monomer.
12. The polyvinyl chloride profile composite according to claim 1, wherein the heat stabilizer is selected from one or more of an organotin stabilizer, a calcium zinc stabilizer and a lead salt stabilizer.
13. The polyvinyl chloride profile composite according to any one of claims 1 to 12, further comprising the following components in parts by weight:
(e)0 to 5 parts by weight of an antistatic agent,
(f)5 to 35 parts by weight of a filler,
(g)0 to 4 parts by weight of a lubricant,
(h)0.5 to 10 parts by weight of a pigment.
14. The polyvinyl chloride profile composite according to claim 13, wherein the antistatic agent is selected from one or more of alkyl phosphate, ethoxylated alcohol, alkyl sulfonate and fatty acid ester; and/or
The filler is selected from one or more of calcium carbonate, talcum powder and white carbon black; and/or
The lubricant is selected from one or more of oxidized polyethylene wax, paraffin wax, stearic acid monoglyceride, pentaerythritol stearate, pentaerythritol adipate and calcium stearate; and/or
The pigment is selected from one or more of titanium dioxide, carbon black, ultramarine pigment and fluorescent whitening agent.
15. The polyvinyl chloride profile composite according to claim 14, wherein the filler has an average particle diameter of 0.5 μm or less.
16. A self-cleaning polyvinyl chloride door and window profile, which is characterized by being processed and manufactured by the polyvinyl chloride profile composite material as defined in any one of claims 1 to 15;
the glossiness of the self-cleaning polyvinyl chloride door and window profile is more than 50.
17. The method for preparing a self-cleaning polyvinyl chloride door and window profile as claimed in claim 16, comprising the steps of:
(1) mixing the components of the polyvinyl chloride profile composite material according to parts by weight to obtain the polyvinyl chloride profile composite material;
(2) and extruding and molding the polyvinyl chloride profile composite material in a double-screw extruder, and then shaping, cooling, drawing and cutting to obtain the self-cleaning polyvinyl chloride door and window profile.
18. The preparation method as claimed in claim 17, wherein the temperature for mixing the components of the polyvinyl chloride profile composite material in the step (1) is 110-125 ℃, and the mixed material is cooled to below 45 ℃;
in the extrusion molding process of the step (2), the processing temperature of a machine barrel area of the double-screw extruder is 170-185 ℃, and the temperature of a die area is 175-190 ℃.
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