Composite polyvinyl chloride particles, preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a composite polyvinyl chloride particle, a preparation method and application. The composite polyvinyl chloride particle comprises the following components in parts by weight: 50 parts of waste powder generated in UPVC preparation, 0.01-0.1 parts of a silane coupling agent, 40-70 parts of a high polymer, 30-60 parts of a plasticizer, 1-5 parts of a calcium-zinc stabilizer and 5-25 parts of a filler. The high polymer comprises polyvinyl chloride, a styrene polymer and acrylonitrile-butadiene-styrene / polycarbonate blend in a weight ratio of (1.3-1.5):1:(0.6-0.8). The application can realize the recycling of the waste powder generated in UPVC preparation, and the composite polyvinyl chloride particle has excellent comprehensive performance when used for preparing a sealing strip.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a composite polyvinyl chloride particle, its preparation method, and its application. Background Technology

[0002] PVC sealing strips for plastic doors and windows are an indispensable part of modern construction, primarily used to improve the sealing performance of doors and windows, thereby enhancing the building's sound insulation, waterproofing, dustproofing, and thermal insulation. In some special applications, such as laboratories and other places with high requirements for internal environmental control, door and window sealing strips not only need to provide basic sealing functions but also need to ensure stable performance under various operating conditions. For example, sealing materials with low heat shrinkage rates can better meet these high standards.

[0003] Chinese patent CN116496590B discloses a method for preparing polyvinyl chloride (PVC) sealing strip material using red mud and tire waste. Red mud and tire waste are used as a composite filler to fill a modified PVC resin matrix. Red mud can act as a rigid filler, brown colorant, heat stabilizer, and acid gas neutralizer, while waste tires can act as a toughening filler. The synergistic effect of the two improves the thermal stability, mechanical properties, and aging resistance of the matrix.

[0004] Rigid polyvinyl chloride (UPVC) pipes are widely used in construction, water supply and drainage, chemical and other fields due to their excellent performance. The manufacturing process of rigid PVC pipes requires the addition of various additives to the PVC, such as stabilizers, fillers, titanium dioxide, and processing aids. Simultaneously, stirring is necessary, which easily generates a large amount of dust. PVC resin, as one of the main raw materials, may itself contain a certain proportion of small particles or fine powder. Furthermore, most of the additives added to achieve specific performance requirements are also in powder form. From the initial batching stage to the final product molding, all processing steps may involve material crushing, screening, conveying, and mixing, each of which can become a source of dust generation. How to properly handle these dusty waste materials is a major problem that urgently needs to be solved. Although currently, clean, uniformly colored dust collected by dust collectors can be directly recycled and reused, the performance of the products produced is often still unsatisfactory. Summary of the Invention

[0005] The purpose of this invention is to provide a composite polyvinyl chloride (PVC) granule, its preparation method, and its application. By using the dust waste generated during the PVC production process of rigid PVC pipes and compounding it with various raw materials, the prepared composite PVC granules exhibit excellent mechanical properties and low heating shrinkage, which can meet the market requirements for sealing strips for doors and windows under special usage conditions.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A composite polyvinyl chloride granule comprises the following components in parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.01-0.1 parts of silane coupling agent, 40-70 parts of polymer, 30-60 parts of plasticizer, 1-5 parts of calcium-zinc stabilizer, and 5-25 parts of filler.

[0008] Preferably, the components include the following parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.03-0.05 parts of silane coupling agent, 50-60 parts of polymer, 40-50 parts of plasticizer, 1-3 parts of calcium-zinc stabilizer, and 10-20 parts of filler.

[0009] More preferably, the weight ratio of the polymer to the plasticizer is (50-54):(42-45).

[0010] Preferably, the components include the following parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.04 parts of silane coupling agent, 54 parts of polymer, 43 parts of plasticizer, 2 parts of calcium-zinc stabilizer, and 17 parts of filler.

[0011] Preferably, the polymer comprises polyvinyl chloride, styrene-based polymers, and acrylonitrile-butadiene-styrene / polycarbonate blends in a weight ratio of (1.3-1.5):1:(0.6-0.8).

[0012] Preferably, the average degree of polymerization of the polyvinyl chloride is 970-1050, and the apparent density is 0.4-0.5 g / cm³. 3 .

[0013] Preferably, the polyvinyl chloride has an average degree of polymerization of 970-1050 and an apparent density of 0.45 g / cm³. 3 Model number: TL-1000; Brand: Tianjin LG Bohai Chemical Co., Ltd.

[0014] Preferably, the styrene-based polymer is selected from polystyrene-maleic anhydride copolymer.

[0015] Preferably, the molar ratio of styrene to maleic anhydride in the polystyrene-maleic anhydride copolymer is one or more of 1:1 and 3:1.

[0016] In a preferred embodiment, the polystyrene-maleic anhydride copolymer has a styrene to maleic anhydride molar ratio of 1:1, a Mw of 5500, and is capped with cumene. The polystyrene-maleic anhydride copolymer can be commercially available or homemade; commercially available copolymers can be purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.

[0017] Preferably, the melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend is 5-7 g / 10 min at 250°C and 2.16 kg.

[0018] Preferably, the melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend is 6 g / 10 min at 250°C and 2.16 kg. The acrylonitrile-butadiene-styrene / polycarbonate blend can be commercially available or homemade. Commercially available blends can be purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number A301679.

[0019] Preferably, the plasticizer comprises poly(1,2-propanediol adipate), a bio-based plasticizer, and a high- and low-temperature resistant plasticizer in a weight ratio of 1:(1.2-1.5):(0.6-0.8).

[0020] The high and low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25℃ and a specific gravity of 0.970 at 25 / 25℃. The plasticizer model is W-797-ZHID, manufactured by DISEN Investment Co., Ltd.

[0021] The bio-based plasticizer has a viscosity of 550-850 mPa·s at 25°C and a specific gravity of 1.010 at 25 / 25°C. The bio-based plasticizer is model W-1810-BIO, manufactured by DISEN Investment Co., Ltd.

[0022] Preferably, the filler is calcium carbonate.

[0023] Preferably, the silane coupling agent is selected from one or more of silane coupling agents KH550, KH560, and KH570.

[0024] This invention provides a method for preparing composite polyvinyl chloride granules, comprising the following steps: mixing a silane coupling agent with waste powder generated from UPVC preparation, stirring at 90-95℃ for 15-20 min, sequentially adding a polymer, plasticizer, calcium-zinc stabilizer and filler, stirring at 85-90℃ for 15-20 min, and extruding and granulating using a twin-screw extruder to obtain composite polyvinyl chloride granules.

[0025] A third aspect of the present invention provides the application of the composite polyvinyl chloride particles in the preparation of sealing strips.

[0026] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0027] 1. This invention uses waste powder generated during UPVC production as a raw material, and adds a high-molecular polymer to improve the tensile strength and tensile impact strength of PVC sealing strips. By recycling waste powder from the UPVC production process, this invention reduces industrial waste generation, helps reduce environmental pollution, promotes resource recycling, and aligns with the concepts of green manufacturing and sustainable development. Using waste powder as a partial raw material can also reduce raw material costs.

[0028] 2. By adding a specific proportion of high molecular weight polymers and plasticizers, this invention improves low-temperature performance, extends the service life of the sealing strip, and reduces the replacement frequency, thereby reducing the user's operating costs in the long run. This not only improves the durability and reliability of the sealing strip, but also expands its application range, especially in situations where high material performance is required.

[0029] 3. This invention adds a compounded plasticizer to the system, which can improve the heating shrinkage rate of polyvinyl chloride (PVC) particles. By optimizing the plasticizer formulation, the shrinkage of PVC sealing strips under heating conditions can be effectively reduced. Under high-temperature environments or after a period of use, the sealing strips can maintain more stable dimensions, ensuring that they continue to provide a good sealing effect. This makes PVC sealing strips more suitable for environments with large temperature variations, and can be applied to environments with high requirements for material dimensional stability and weather resistance, thereby improving user satisfaction. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Calcium and zinc stabilizer, Shanghai Huiluo Trading Co., Ltd., Calcium and zinc stabilizer CZ-11.

[0032] Silane coupling agent, silane coupling agent KH550.

[0033] Waste powder generated during UPVC production is collected from dust produced during the mixing of additives in PVC during the manufacturing process of rigid PVC pipes.

[0034] Example 1

[0035] This embodiment provides a composite polyvinyl chloride granule, comprising the following components in parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.04 parts of silane coupling agent, 54 parts of polymer, 43 parts of plasticizer, 2 parts of calcium-zinc stabilizer, and 17 parts of filler.

[0036] The polymers include polyvinyl chloride, styrene-based polymers, and acrylonitrile-butadiene-styrene / polycarbonate blends in a weight ratio of 1.4:1:0.7.

[0037] The average degree of polymerization of polyvinyl chloride is 970-1050, and the apparent density is 0.45 g / cm³. 3 Model number: TL-1000; Brand: Tianjin LG Bohai Chemical Co., Ltd.

[0038] The styrene-based polymer is selected from polystyrene-maleic anhydride copolymer. The polystyrene-maleic anhydride copolymer has a styrene to maleic anhydride molar ratio of 1:1, a Mw of 5500, and is capped with cumene. It was purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.

[0039] The melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend was 6 g / 10 min at 250°C and 2.16 kg. It was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number A301679.

[0040] The plasticizer comprises poly(1,2-propanediol adipate) in a weight ratio of 1:1.4:0.7, a bio-based plasticizer, and a high / low temperature resistant plasticizer. The high / low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25°C and a specific gravity of 0.970 at 25 / 25°C. The high / low temperature resistant plasticizer is model W-797-ZHID, manufactured by DISEN Investment Co., Ltd. The bio-based plasticizer has a viscosity of 550-850 mPa·s at 25°C and a specific gravity of 1.010 at 25 / 25°C. The bio-based plasticizer is model W-1810-BIO, also manufactured by DISEN Investment Co., Ltd.

[0041] The filler is calcium carbonate. Shanghai Liangjiang Titanium Dioxide Chemical Products Co., Ltd., Light Calcium Carbonate (Rubber and Plastic Grade).

[0042] The method for preparing the composite polyvinyl chloride granules includes the following steps: mixing a silane coupling agent with waste powder generated from UPVC preparation, stirring at 92°C for 18 minutes, sequentially adding a polymer, plasticizer, calcium-zinc stabilizer and filler, stirring at 87°C for 18 minutes, and granulating by extrusion using a twin-screw extruder, with the screw zone temperatures being 165°C in zone one, 180°C in zone two, 190°C in zone three, 185°C in zone four and 175°C in zone five, to obtain composite polyvinyl chloride granules.

[0043] Example 2

[0044] The difference between this embodiment and Embodiment 1 is that the amount of plasticizer used is different in the polymer.

[0045] A composite polyvinyl chloride granule is provided, comprising the following components in parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.04 parts of silane coupling agent, 60 parts of polymer, 40 parts of plasticizer, 2 parts of calcium-zinc stabilizer, and 17 parts of filler.

[0046] Example 3

[0047] This embodiment provides a composite polyvinyl chloride granule, comprising the following components in parts by weight: 50 parts of waste powder generated from UPVC preparation, 0.1 parts of silane coupling agent, 70 parts of polymer, 30 parts of plasticizer, 5 parts of calcium-zinc stabilizer, and 5 parts of filler.

[0048] The polymers include polyvinyl chloride, styrene-based polymers, and acrylonitrile-butadiene-styrene / polycarbonate blends in a weight ratio of 1.3:1:0.6.

[0049] The average degree of polymerization of polyvinyl chloride is 970-1050, and the apparent density is 0.45 g / cm³. 3 Model number: TL-1000; Brand: Tianjin LG Bohai Chemical Co., Ltd.

[0050] The styrene-based polymer is selected from polystyrene-maleic anhydride copolymer. The polystyrene-maleic anhydride copolymer has a styrene to maleic anhydride molar ratio of 1:1, a Mw of 5500, and is capped with cumene. It was purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.

[0051] The melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend was 6 g / 10 min at 250°C and 2.16 kg. It was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number A301679.

[0052] The plasticizer comprises poly(1,2-propanediol adipate) in a weight ratio of 1:1.2:0.8, a bio-based plasticizer, and a high / low temperature resistant plasticizer. The high / low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25°C and a specific gravity of 0.970 at 25 / 25°C. The high / low temperature resistant plasticizer is model W-797-ZHID, manufactured by DISEN Investment Co., Ltd. The bio-based plasticizer has a viscosity of 550-850 mPa·s at 25°C and a specific gravity of 1.010 at 25 / 25°C. The bio-based plasticizer is model W-1810-BIO, also manufactured by DISEN Investment Co., Ltd.

[0053] The filler is calcium carbonate. Shanghai Liangjiang Titanium Dioxide Chemical Products Co., Ltd., Light Calcium Carbonate (Rubber and Plastic Grade).

[0054] The method for preparing the composite polyvinyl chloride granules includes the following steps: mixing a silane coupling agent with waste powder generated from UPVC preparation, stirring at 90°C for 20 minutes, sequentially adding a polymer, plasticizer, calcium-zinc stabilizer, and filler, stirring at 85°C for 15-20 minutes, and granulating by extrusion using a twin-screw extruder, with the screw zone temperatures being 165°C in zone one, 180°C in zone two, 190°C in zone three, 185°C in zone four, and 175°C in zone five, to obtain composite polyvinyl chloride granules.

[0055] Comparative Example 1

[0056] The difference between this comparative example and Example 1 is that the polymer used is polyvinyl chloride (PVC), with an average degree of polymerization of 970-1050 and an apparent density of 0.45 g / cm³. 3 Model number: TL-1000; Brand: Tianjin LG Bohai Chemical Co., Ltd.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Example 1 is that the polymer comprises polyvinyl chloride and styrene-based polymers in a weight ratio of 1.4:1:.

[0059] The average degree of polymerization of polyvinyl chloride is 970-1050, and the apparent density is 0.45 g / cm³. 3 Model number: TL-1000; Brand: Tianjin LG Bohai Chemical Co., Ltd.

[0060] The styrene-based polymer is selected from polystyrene-maleic anhydride copolymer. The polystyrene-maleic anhydride copolymer has a styrene to maleic anhydride molar ratio of 1:1, a Mw of 5500, and is capped with cumene. It was purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.

[0061] Comparative Example 3

[0062] The difference between this comparative example and Example 1 is that the polymers include polyvinyl chloride, styrene-based polymers, and acrylonitrile-butadiene-styrene / polycarbonate blends in a weight ratio of 1:1:1.

[0063] The average degree of polymerization of polyvinyl chloride is 970-1050, and the apparent density is 0.45 g / cm3. The model number is TL-1000, and the brand is Tianjin LG Bohai Chemical Co., Ltd.

[0064] The styrene-based polymer is selected from polystyrene-maleic anhydride copolymer. The polystyrene-maleic anhydride copolymer has a styrene to maleic anhydride molar ratio of 1:1, a Mw of 5500, and is capped with cumene. It was purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.

[0065] The melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend was 6 g / 10 min at 250°C and 2.16 kg. It was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number A301679.

[0066] Comparative Example 4

[0067] The difference between this comparative example and Example 1 is that the plasticizer is diisobutyl phthalate.

[0068] Comparative Example 5

[0069] The difference between this comparative example and Example 1 is that the plasticizer is poly(1,2-propanediol adipate).

[0070] Comparative Example 6

[0071] The difference between this comparative example and Example 1 is that the plasticizer comprises poly(1,2-propanediol adipate) and a high / low temperature resistant plasticizer in a weight ratio of 1:0.7. The high / low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25°C and a specific gravity of 0.970 at 25 / 25°C. The high / low temperature resistant plasticizer is model W-797-ZHID, manufactured by DISEN Investment Co., Ltd.

[0072] Comparative Example 7

[0073] The difference between this comparative example and Example 1 is as follows: the plasticizer comprises poly(1,2-propanediol adipate), a bio-based plasticizer, and a high / low temperature resistant plasticizer in a weight ratio of 1:1:1. The high / low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25°C and a specific gravity of 0.970 at 25 / 25°C. The high / low temperature resistant plasticizer is model W-797-ZHID, manufactured by DISEN Investment Co., Ltd. The bio-based plasticizer has a viscosity of 550-850 mPa·s at 25°C and a specific gravity of 1.010 at 25 / 25°C. The bio-based plasticizer is model W-1810-BIO, also manufactured by DISEN Investment Co., Ltd.

[0074] Performance testing

[0075] The composite polyvinyl chloride granules prepared in Examples 1-3 and Comparative Examples 1-7 were re-plasticized and extruded using a single-screw extruder. The extruder body temperature was 165°C, and the die temperature was 180°C. After cooling and cutting, sealing strips were obtained. The sealing strips underwent the following performance tests:

[0076] 1. Low-temperature performance at -40℃ was determined according to GB5470-2008;

[0077] 2. Tensile impact strength shall be determined in accordance with GB / T13525-1992;

[0078] 3. Refer to GB / T1040-2022, and determine the tensile strength at a tensile speed of 250 mm / min;

[0079] 4. The heat shrinkage rate was determined according to GB / T12002-1989 "Sealing Strips for Plastic Doors and Windows". The test results are shown in Table 1.

[0080] Table 1 Performance Test Results

[0081]

[0082] As shown in Table 1, Examples 1-3 exhibit excellent tensile strength, tensile impact strength, and heat shrinkage, with Example 1 showing even better low-temperature performance. In Examples 2 and 3, the altered ratio of polymer and plasticizer resulted in a decrease in the low-temperature performance of the PVC sealing strip, indicating that the polymer and plasticizer used in this invention can work together to improve the low-temperature performance of the sealing strip.

[0083] In Comparative Example 1, only polyvinyl chloride (PVC) was used, and the tensile strength and tensile impact strength of the PVC sealing strip decreased.

[0084] In Comparative Example 2, a styrene-based polymer was added to polyvinyl chloride. Compared with Example 1, the tensile strength and tensile impact strength of the sealing strip decreased. However, compared with Comparative Example 1, which only used polyvinyl chloride, the tensile impact strength increased and the decrease in tensile strength was not significant. The analysis suggests that the use of plasticizer in this invention helps to improve the compatibility between styrene-based polymers and PVC and alleviates the rigidity of styrene-based polymers.

[0085] In Comparative Example 3, the tensile strength and tensile impact strength of the PVC sealing strip decreased to varying degrees when different proportions of polymers were used. The toughening agent of this invention can facilitate the interfacial bonding of polymers within the system.

[0086] In comparative examples 4-7, the different compositions of plasticizers resulted in higher heating shrinkage rates for polyvinyl chloride (PVC) particles. During the experiments, it was found that using poly(1,2-propanediol adipate) as a plasticizer in the system of this invention was more effective than using diisobutyl phthalate (DIP), but this still could not meet market demands. To further reduce the heating shrinkage rate of the sealing strip, two commercially available plasticizers were added in combination. By adjusting the ratio, the heating shrinkage rate of the sealing strip could be significantly reduced.

[0087] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A composite polyvinyl chloride granule, characterized in that, The components include the following parts by weight: 50 parts waste powder generated from UPVC preparation, 0.01-0.1 parts silane coupling agent, 40-70 parts polymer, 30-60 parts plasticizer, 1-5 parts calcium-zinc stabilizer, and 5-25 parts filler. The polymers include polyvinyl chloride, styrene-based polymers, and acrylonitrile-butadiene-styrene / polycarbonate blends in a weight ratio of (1.3-1.5):1:(0.6-0.8). The plasticizer comprises poly(1,2-propanediol adipate), bio-based plasticizer, and high and low temperature resistant plasticizer in a weight ratio of 1:(1.2-1.5):(0.6-0.8). The high and low temperature resistant plasticizer has a viscosity of 95-130 mPa·s at 25℃ and a specific gravity of 0.970 at 25 / 25℃. The model is W-797-ZHID from D.E. Investment Co., Ltd. The bio-based plasticizer has a viscosity of 550-850 mPa·s at 25°C and a specific gravity of 1.010 at 25 / 25°C. The model is W-1810-BIO from D.E. Investment Co., Ltd.

2. The composite polyvinyl chloride granules according to claim 1, characterized in that, The product comprises the following components in parts by weight: 50 parts waste powder generated during UPVC production, 0.03-0.05 parts silane coupling agent, 50-60 parts polymer, 40-50 parts plasticizer, 1-3 parts calcium-zinc stabilizer, and 10-20 parts filler.

3. The composite polyvinyl chloride granules according to claim 1, characterized in that, The average degree of polymerization of polyvinyl chloride is 970-1050, and the apparent density is 0.4-0.5 g / cm³. 3 .

4. The composite polyvinyl chloride granules according to claim 1, characterized in that, The styrene-based polymer is selected from polystyrene-maleic anhydride copolymer.

5. The composite polyvinyl chloride granules according to claim 4, characterized in that, The polystyrene-maleic anhydride copolymer has a molar ratio of styrene to maleic anhydride of 1:1 or 3:1 or more.

6. The composite polyvinyl chloride granules according to claim 1, characterized in that, The melt index of the acrylonitrile-butadiene-styrene / polycarbonate blend is 5-7 g / 10 min at 250 °C and 2.16 kg.

7. A method for preparing composite polyvinyl chloride particles according to any one of claims 1-6, characterized in that, Includes the following steps: The silane coupling agent is mixed with the waste powder generated from the preparation of UPVC and stirred at 90-95℃ for 15-20 minutes. Then, the polymer, plasticizer, calcium-zinc stabilizer and filler are added in sequence and stirred at 85-90℃ for 15-20 minutes. The mixture is then extruded and granulated using a twin screw extruder to obtain composite polyvinyl chloride granules.

8. The application of the composite polyvinyl chloride particles according to any one of claims 1-6 in the preparation of sealing strips.

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