Weather-resistant toughened PVC (polyvinyl chloride) film as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer film materials, and particularly relates to a weather-resistant toughened PVC film as well as a preparation method and application thereof. The PVC film comprises the following components in parts by mass: 100 parts of PVC resin, 1-5 parts of a stabilizer, 2-5 parts of a plasticizer, 2-8 parts of an organic silicon modified composite flexibilizer and 1-3 parts of a lubricant, the organic silicon modified composite toughening agent is a polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network compound, and a preparation method of the organic silicon modified composite toughening agent comprises the following steps: adding liquid polybutadiene, vinyl silicone oil and CPE into an organic solvent, dissolving and mixing, then adding an initiator, carrying out a heating copolymerization reaction, carrying out spray granulation on the mixed reaction liquid, and drying to obtain the organic silicon modified composite toughening agent. The polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network compound is obtained. The obtained PVC film has obviously improved toughness, low temperature resistance and weather resistance, and can be used for preparing PVC label films.

Description

Technical Field

[0001] This invention belongs to the field of polymer film material technology, specifically relating to a weather-resistant and toughened PVC film, its preparation method, and its application. Background Technology

[0002] PVC film is made from polyvinyl chloride (PVC) as the main component of a thermoplastic plastic, with the addition of stabilizers, plasticizers, and other additives. It is widely used in food packaging and other fields. It features high strength, good water resistance, and good corrosion resistance. However, conventional PVC materials have poor high and low temperature resistance and toughness, often requiring modification.

[0003] Modification methods for PVC materials are divided into chemical grafting modification and physical blending. Chemical grafting modification is less commonly used due to its large processing volume, complex processes, and high costs, while physical blending is more widely used due to its simple process and convenient performance adjustment. To enhance the toughness of PVC materials, the main methods currently used are blending with rubber elastomers such as NBR (nitrile rubber), SBS (styrene-butadiene-styrene block copolymer), EPDM (ethylene propylene diene monomer rubber), ABS (acrylonitrile-butadiene-styrene terpolymer), MBS (methyl methacrylate-butadiene-styrene terpolymer), ACR (acrylate copolymer), and EVA (ethylene-vinyl acetate copolymer). However, firstly, the compatibility of these rubber elastomers with PVC materials is poor, and excessive addition can lead to a decrease in material strength; secondly, the improvement effect of these rubber elastomers on the weather resistance and low-temperature resistance of PVC materials is limited.

[0004] Organosilicon materials, due to their good weather resistance and low-temperature flexibility, show promising application prospects in the modification of PVC materials. However, because of the poor compatibility between organosilicon materials and PVC materials, the current main method is chemical grafting modification. For example, relevant literature (Qing Shengbo. Research on Organosilicon Reaction Processing Modification of Polyvinyl Chloride. Master's Thesis. 2001.5.1) discloses the use of hydrogen-containing polysiloxanes (PHMS) to modify PVC through reaction processing, which can improve the impact strength, hardness, tensile strength, and yield strength of PVC materials under plasticizer conditions. However, the effect of organosilicon modification on improving the weather resistance and low-temperature resistance of PVC materials has not been studied. Summary of the Invention

[0005] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a weather-resistant and toughened PVC film.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned weather-resistant and toughened PVC film.

[0007] Another object of the present invention is to provide the application of the above-mentioned weather-resistant and toughened PVC film in the preparation of PVC label film.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A weather-resistant and toughened PVC film, comprising the following components in parts by weight:

[0010] 100 parts PVC resin, 1-5 parts stabilizer, 2-5 parts plasticizer, 2-8 parts silicone-modified composite toughening agent, and 1-3 parts lubricant;

[0011] The organosilicon-modified composite toughening agent is a polybutadiene-vinyl polysiloxane copolymer / chlorinated polyethylene (CPE) interpenetrating network composite, and its preparation method is as follows:

[0012] Liquid polybutadiene, vinyl silicone oil, and chlorinated polyethylene (CPE) were dissolved and mixed in an organic solvent, and then an initiator was added and heated for copolymerization. The mixed reaction solution was then spray-granulated to obtain a polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0013] Furthermore, the liquid polybutadiene contains >20 mol% 1,2-vinyl structure and has a viscosity of 500-5000 mPa·s (25°C). The liquid polybutadiene is a commercially available raw material with the following structural formula:

[0014] .

[0015] Furthermore, the vinyl silicone oil used is a vinyl-terminated silicone oil with a viscosity of 500-5000 mPa·s (25°C). The vinyl-terminated silicone oil is a commercially available raw material, and its structural formula is as follows:

[0016] .

[0017] Furthermore, the chlorine content of the CPE is 30%~40% (by mass). CPE with the above-mentioned chlorine content exhibits good compatibility with PVC, thereby significantly improving the compatibility of polybutadiene-vinyl polysiloxane copolymer with PVC.

[0018] Furthermore, the mass ratio of the liquid polybutadiene, vinyl silicone oil, and CPE is 1~2:1~2:1~4.

[0019] Furthermore, the organic solvent is toluene or xylene.

[0020] Furthermore, the initiator is azobisisobutyronitrile (AIBN); the temperature of the heating copolymerization reaction is 50~75℃, and the time is 2~8h.

[0021] Furthermore, the stabilizer is an organotin heat stabilizer, such as butyltin mercaptan or methyltin mercaptan.

[0022] Furthermore, the plasticizer is dioctyl terephthalate or diisooctyl cyclohexane-1,2-dicarboxylic acid.

[0023] Furthermore, the lubricant is calcium stearate or glyceryl stearate.

[0024] The preparation method of the above-mentioned weather-resistant and toughened PVC film includes the following steps:

[0025] PVC resin, stabilizer, plasticizer, silicone-modified composite toughening agent and lubricant are added to a mixer for mixing. The mixed material is then fed into a calender for calendering and winding to obtain a weather-resistant toughened PVC film.

[0026] The above-mentioned weather-resistant and toughened PVC film is used in the preparation of PVC label film.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] (1) This invention uses a polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite as a toughening modifier for PVC resin. The polybutadiene-vinyl polysiloxane copolymer elastomer can significantly improve the toughness, low-temperature resistance and weather resistance of PVC. CPE itself has a certain toughening effect, and at the same time, as a compatibilizer for polybutadiene-vinyl polysiloxane copolymer elastomer, it can significantly improve the compatibility between polybutadiene-vinyl polysiloxane copolymer elastomer and PVC resin, thereby synergistically improving the toughness, low-temperature resistance and weather resistance of PVC.

[0029] (2) The polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite prepared by the specific method of the present invention has a significantly improved compatibilization and synergistic effect compared with simple physical mixing. Detailed Implementation

[0030] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0031] Example 1

[0032] (1) Preparation of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite:

[0033] Liquid polybutadiene (1,2-vinyl content 30 mol%, viscosity 2000 mPa·s), vinyl-terminated silicone oil (viscosity 2000 mPa·s), and CPE (chlorine content 35%) were dissolved and mixed in toluene solvent at a mass ratio of 1:1:2. Then, AIBN initiator was added and the mixture was heated to copolymerize at 60–70 °C for 5 hours. After the reaction was complete, the mixed reaction solution was spray-granulated to obtain a toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0034] (2) Preparation of weather-resistant and toughened PVC film:

[0035] Weigh out 100 parts by weight of PVC resin, 3 parts by weight of stabilizer butyltin mercaptan, 4 parts by weight of plasticizer dioctyl terephthalate, 6 parts by weight of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and 2 parts by weight of lubricant calcium stearate. Add the above raw materials to a high-speed mixer and mix them at a temperature of 90~100℃. Add the mixed material to a calender and calender it at 160~190℃. After winding, obtain a weather-resistant toughened PVC film.

[0036] The performance test results of the PVC film obtained in this embodiment are shown in Table 1 below.

[0037] Table 1 Performance Test Results

[0038] The tensile strength and elongation at break tests were conducted in accordance with GB / T1040.3-2006 standard; the low-temperature resistance test was conducted in accordance with ISO 180-2019, which tested the low-temperature impact strength of the specimen after treatment at -30℃ for 4 hours; the weathering resistance test method was to place the specimen in a QUV aging chamber (UVA-340 lamp) for 2000 hours, test the mechanical properties according to GB / T1040.3-2006, and calculate the retention rate of tensile strength and elongation at break.

[0039] Example 2

[0040] (1) Preparation of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite:

[0041] Liquid polybutadiene (40 mol% 1,2-vinyl content, 1500 mPa·s viscosity), vinyl-terminated silicone oil (3000 mPa·s viscosity), and CPE (35% chlorine content) were dissolved and mixed in toluene solvent at a mass ratio of 1:1.5:2. Then, AIBN initiator was added and the mixture was heated to copolymerize at 60–70 °C for 5 hours. After the reaction was complete, the mixture was spray-granulated to obtain a toughening agent for the polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0042] (2) Preparation of weather-resistant and toughened PVC film:

[0043] Weigh out 100 parts by weight of PVC resin, 2 parts by weight of stabilizer butyltin mercaptan, 5 parts by weight of plasticizer dioctyl terephthalate, 4 parts by weight of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and 3 parts by weight of lubricant calcium stearate. Add the above raw materials to a high-speed mixer and mix them at a temperature of 90~100℃. Add the mixed material to a calender and calender it at 160~190℃. After winding, obtain a weather-resistant toughened PVC film.

[0044] The performance test results of the PVC film obtained in this embodiment are shown in Table 2 below.

[0045] Table 2 Performance Test Results

[0046] Example 3

[0047] (1) Preparation of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite:

[0048] Liquid polybutadiene (1,2-vinyl content 50 mol%, viscosity 1200 mPa·s), vinyl-terminated silicone oil (viscosity 4000 mPa·s), and CPE (chlorine content 35%) were dissolved and mixed in toluene solvent at a mass ratio of 1:2:3. Then, AIBN initiator was added and the mixture was heated to copolymerize at 60-70℃ for 6 hours. After the reaction was completed, the mixed reaction solution was spray-granulated to obtain a toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0049] (2) Preparation of weather-resistant and toughened PVC film:

[0050] Weigh out 100 parts by weight of PVC resin, 1 part by weight of butyltin mercaptan stabilizer, 5 parts by weight of dioctyl terephthalate plasticizer, 2 parts by weight of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and 1 part by weight of lubricant calcium stearate. Add the above raw materials to a high-speed mixer and mix them at a temperature of 90-100℃. Add the mixed material to a calender and calender it at 160-190℃. After calendering, the mixture is wound up to obtain a weather-resistant toughened PVC film.

[0051] The performance test results of the PVC film obtained in this embodiment are shown in Table 3 below.

[0052] Table 3 Performance Test Results

[0053] Example 4

[0054] (1) Preparation of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite:

[0055] Liquid polybutadiene (20 mol% 1,2-vinyl content, 3000 mPa·s viscosity), vinyl-terminated silicone oil (1000 mPa·s viscosity), and CPE (35% chlorine content) were dissolved and mixed in toluene solvent at a mass ratio of 1.5:1:2. Then, AIBN initiator was added and the mixture was heated to copolymerize at 60-70°C for 4 hours. After the reaction was complete, the mixture was spray-granulated to obtain a toughening agent for the polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0056] (2) Preparation of weather-resistant and toughened PVC film:

[0057] Weigh out 100 parts by weight of PVC resin, 4 parts by weight of butyltin mercaptan stabilizer, 3 parts by weight of dioctyl terephthalate plasticizer, 5 parts by weight of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and 2 parts by weight of lubricant calcium stearate. Add the above raw materials to a high-speed mixer and mix them at a temperature of 90-100℃. Add the mixed material to a calender and calender it at 160-190℃. After calendering, the mixture is wound up to obtain a weather-resistant toughened PVC film.

[0058] The performance test results of the PVC film obtained in this embodiment are shown in Table 4 below.

[0059] Table 4 Performance Test Results

[0060] Example 5

[0061] (1) Preparation of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite:

[0062] Liquid polybutadiene (20 mol% 1,2-vinyl content, 3000 mPa·s viscosity), vinyl-terminated silicone oil (2000 mPa·s viscosity), and CPE (35% chlorine content) were dissolved and mixed in xylene solvent at a mass ratio of 2:1:4. Then, AIBN initiator was added, and the mixture was heated to copolymerize at 60-70°C for 5 hours. After the reaction was complete, the mixture was spray-granulated to obtain a toughening agent for the polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

[0063] (2) Preparation of weather-resistant and toughened PVC film:

[0064] Weigh out 100 parts by weight of PVC resin, 5 parts by weight of stabilizer methyl tin mercaptan, 5 parts by weight of plasticizer cyclohexane-1,2-dicarboxylic acid diisooctyl ester, 8 parts by weight of toughening agent for polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and 2 parts by weight of lubricant glyceryl stearate. Add the above raw materials to a high-speed mixer and mix them at a mixing temperature of 90~100℃. Add the mixed material to a calender and calender it at 160~190℃, then wind it up to obtain a weather-resistant toughened PVC film.

[0065] The performance test results of the PVC film obtained in this embodiment are shown in Table 5 below.

[0066] Table 5 Performance Test Results

[0067] Comparative Example 1

[0068] Weigh out 100 parts by weight of PVC resin, 3 parts by weight of stabilizer butyltin mercaptan, 4 parts by weight of plasticizer dioctyl terephthalate, 6 parts by weight of CPE (chlorine content 35%) toughening agent, and 2 parts by weight of lubricant calcium stearate. Add the above raw materials to a high-speed mixer for mixing, controlling the mixing temperature at 90~100℃. Add the mixed material to a calender and calender at 160~190℃ to form the film, then wind it up to obtain a weather-resistant toughened PVC film.

[0069] The performance test results of the PVC film obtained in this comparative example are shown in Table 6 below.

[0070] Table 6 Performance Test Results

[0071] The comparison results between this comparative example and Example 1 show that the PVC film obtained by simply toughening and modifying it with CPE exhibits a significant decrease in elongation at break, low-temperature impact strength, and weather resistance. This indicates that the polybutadiene-vinyl polysiloxane copolymer elastomer of the present invention can significantly improve the elasticity, low-temperature toughness, and weather resistance of PVC.

[0072] Comparative Example 2

[0073] (1) Preparation of toughening agent of polybutadiene-vinyl polysiloxane copolymer:

[0074] Liquid polybutadiene (1,2-vinyl content 30 mol%, viscosity 2000 mPa·s) and vinyl-terminated silicone oil (viscosity 2000 mPa·s) were dissolved and mixed in toluene solvent at a mass ratio of 1:1. Then, AIBN initiator was added and the mixture was heated to copolymerize at 60-70℃ for 5 hours. After the reaction was completed, the mixture was spray-granulated to obtain a polybutadiene-vinyl polysiloxane copolymer toughening agent.

[0075] (2) Preparation of weather-resistant and toughened PVC film:

[0076] Weigh out 100 parts by weight of PVC resin, 3 parts by weight of butyltin mercaptan stabilizer, 4 parts by weight of dioctyl terephthalate plasticizer, 3 parts by weight of polybutadiene-vinyl polysiloxane copolymer toughening agent, 3 parts by weight of CPE (chlorine content 35%) toughening agent, and 2 parts by weight of calcium stearate lubricant. Add the above raw materials to a high-speed mixer for mixing, controlling the mixing temperature at 90~100℃. Add the mixed material to a calender and calender at 160~190℃ to form the film, then wind it up to obtain a weather-resistant toughened PVC film.

[0077] The performance test results of the PVC film obtained in this comparative example are shown in Table 7 below.

[0078] Table 7 Performance Test Results

[0079] The comparison between Comparative Example 2 and Comparative Example 1 shows that while the toughening effect of the PVC film obtained by mixing and toughening with polybutadiene-vinyl polysiloxane copolymer elastomer and CPE is improved to some extent, the tensile strength is significantly reduced. This is because the polybutadiene-vinyl polysiloxane copolymer elastomer has poor compatibility with PVC material. The comparison between Examples 1-5 of this invention and Comparative Example 2 shows that the polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite prepared by the specific method of this invention has a significantly improved compatibility-enhancing synergistic effect compared to simple physical mixing.

[0080] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A weather-resistant and toughened PVC film, characterized in that... The components include the following parts by mass: 100 parts PVC resin, 1-5 parts stabilizer, 2-5 parts plasticizer, 2-8 parts silicone-modified composite toughening agent, and 1-3 parts lubricant; The organosilicon-modified composite toughening agent is a polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite, and its preparation method is as follows: Liquid polybutadiene, vinyl silicone oil, and CPE are dissolved and mixed in an organic solvent, then an initiator is added and heated for copolymerization. The mixed reaction solution is then spray-granulated to obtain a polybutadiene-vinyl polysiloxane copolymer / CPE interpenetrating network composite.

2. The weather-resistant toughened PVC film according to claim 1, characterized in that: The liquid polybutadiene contains >20 mol% 1,2 vinyl structure and has a viscosity of 500-5000 mPa·s; the vinyl silicone oil used is an end-vinyl silicone oil with a viscosity of 500-5000 mPa·s.

3. The weather-resistant toughened PVC film according to claim 1, characterized in that: The chlorine content of the CPE is 30%~40%.

4. The weather-resistant toughened PVC film according to claim 1, characterized in that: The mass ratio of the liquid polybutadiene, vinyl silicone oil and CPE is 1~2:1~2:1~4.

5. The weather-resistant toughened PVC film according to claim 1, characterized in that: The organic solvent is toluene or xylene; the initiator is AIBN; the temperature of the heating copolymerization reaction is 50~75℃, and the time is 2~8h.

6. The weather-resistant toughened PVC film according to claim 1, characterized in that: The stabilizer is an organotin heat stabilizer.

7. The weather-resistant toughened PVC film according to claim 1, characterized in that: The plasticizer is dioctyl terephthalate or diisooctyl cyclohexane-1,2-dicarboxylic acid.

8. The weather-resistant and toughened PVC film according to claim 1, characterized in that: The lubricant is calcium stearate or glyceryl stearate.

9. A method for preparing a weather-resistant and toughened PVC film according to any one of claims 1 to 8, characterized in that... Includes the following steps: PVC resin, stabilizer, plasticizer, silicone-modified composite toughening agent and lubricant are added to a mixer for mixing. The mixed material is then fed into a calender for calendering and winding to obtain a weather-resistant toughened PVC film.

10. The application of the weather-resistant and toughened PVC film according to any one of claims 1 to 8 in the preparation of PVC label film.

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