Preparation method of hyperbranched cardanol-based self-plasticizing polyvinyl chloride

Abstract

The invention relates to the technical field of plastic processing, in particular to a preparation method of hyperbranched cardanol-based self-plasticizing polyvinyl chloride. Cardanol, polyvinyl chloride, glycidol, organic anhydride and aminothiophenol are used as main raw materials, the cardanol and the glycidol are subjected to a hyperbranched reaction to obtain cardanol polyglycerol with a hyperbranched structure, and then the cardanol polyglycerol and the organic anhydride are subjected to an esterification reaction to obtain ester-terminated cardanol polyglycerol. Then double bonds on a branch chain of the anacardol are epoxidized by using a peroxide source to obtain a hyperbranched anacardol plasticizer, amino thiophenol is adopted as a grafting agent, and the hyperbranched anacardol-based self-plasticizing polyvinyl chloride is obtained by grafting the hyperbranched anacardol plasticizer to polyvinyl chloride by using a click reaction. The main raw materials are renewable and do not depend on petroleum; the preparation process is simple and reasonable and low in energy consumption; the product has good thermal stability and has no hidden danger that the plasticizer seeps to the environment. The self-plasticized polyvinyl chloride prepared by the invention has good toughness and processability.

Description

Technical Field

[0001] The invention relates to the technical field of plastic processing, in particular to a method for preparing hyperbranched cardanol-based self-plasticizing polyvinyl chloride. Background Art

[0002] Polyvinyl chloride is one of the most widely used plastics due to its low cost and excellent mechanical strength. It is used in many fields, including building materials, medical devices, toys, clothing, and automotive parts. However, the limited plasticity and poor processing ability of polyvinyl chloride hinder its application. Therefore, during the use of polyvinyl chloride, plasticizers need to be added to reduce its glass transition temperature and increase its toughness, thereby improving processing performance. Phthalate esters are the most commonly used plasticizers due to their excellent plasticizing properties, but phthalate-based plasticizers have inherent limitations. These plasticizers work by physically blending with polyvinyl chloride and gradually migrate to the surface of plastic components during use, resulting in a decrease in mechanical and thermal properties. In addition, they can also pose a hazard to the environment and human health. With the improvement of environmental awareness in countries around the world, some developed countries have introduced restrictions or even directly banned their use.

[0003] Taking advantage of the non-toxic and renewable properties of biomass materials, researchers have developed a variety of green and non-toxic bio-based plasticizers. However, the functionality of these plasticizers still relies on physical blending. Therefore, the problem of plasticizer migration has not been solved. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride to overcome the shortcomings of traditional plasticizers.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention is a method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride, comprising the following steps:

[0007] Step 1, subjecting cardanol and glycidol to a hyperbranching reaction to obtain cardanol polyglycerol;

[0008] Step 2, esterifying the cardanol polyglycerol with an organic acid anhydride to obtain ester-terminated cardanol polyglycerol;

[0009] Step 3, subjecting the terminal ester cardanol polyglycerol to epoxidation reaction with a peroxygen source to obtain a hyperbranched cardanol plasticizer;

[0010] Step 4, using aminothiophenol as a grafting agent, and utilizing a click reaction to graft the hyperbranched cardanol plasticizer onto polyvinyl chloride to obtain the hyperbranched cardanol-based self-plasticizing polyvinyl chloride.

[0011] The second technical solution of the present invention is a hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared according to the above-mentioned preparation method.

[0012] The third technical solution of the present invention is the use of the above-mentioned hyperbranched cardanol-based self-plasticizing polyvinyl chloride in the preparation of building materials, medical devices, toys, clothing or automobile parts.

[0013] The present invention utilizes biomass materials to synthesize green plasticizers, and covalently bonds with polyvinyl chloride, thereby achieving plasticization and non-migration effects, also known as self-plasticization. The plasticization mechanism of the internal plasticizer is similar to that of the external plasticizer. The plasticizer is grafted onto polyvinyl chloride, which increases the interchain distance, weakens the intermolecular force of polyvinyl chloride, increases the free volume of the polymer, and thus improves the processing properties of polyvinyl chloride. In addition, the present invention also utilizes hyperbranching reaction and esterification reaction to introduce a large number of side chains and ester groups into the internal plasticizer, which can further improve the plasticization efficiency. The present invention utilizes biomass materials to achieve internal plasticization of polyvinyl chloride, which is of great significance.

[0014] The present invention discloses the following technical effects:

[0015] (1) The present invention uses bio-based cardanol as the main raw material, has a competitive production cost, avoids dependence on petrochemical raw materials, reduces the pollution of the chemical synthesis process to the environment, and greatly improves the bio-based content and environmental protection of the plasticizer.

[0016] (2) The present invention adopts click reaction to synthesize self-plasticized polyvinyl chloride, the reaction process is simple, no side reaction and by-product generation, the reaction conditions are mild, the product purity is high and the quality is stable.

[0017] (3) The hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared by the present invention has good plasticizing effect and no exudation. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0019] Figure 1 The infrared analysis spectra of cardanol, cardanol polyglycerol, terminal ester cardanol polyglycerol and hyperbranched cardanol plasticizer in Example 1 of the present invention;

[0020] Figure 2 This is the infrared analysis spectrum of the hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared in Example 1 of the present invention;

[0021] Figure 3 The dynamic thermomechanical analysis of the hyperbranched cardanol-based self-plasticized polyvinyl chloride (i.e., cardanol-based self-plasticized polyvinyl chloride) prepared in Example 1 of the present invention, the temperature corresponding to the peak of the curve is the glass transition temperature of the polyvinyl chloride;

[0022] Figure 4 The migration losses of the hyperbranched cardanol-based self-plasticized polyvinyl chloride prepared in Example 1 of the present invention and the polyvinyl chloride / dioctyl phthalate prepared in Comparative Example 1 in petroleum ether, 30% acetic acid, and 10% ethanol solutions. DETAILED DESCRIPTION

[0023] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0024] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0025] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0026] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0027] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0028] The "parts" described in the present invention, unless otherwise specified, all represent parts by mass.

[0029] The present invention uses biomass materials, and provides a method for synthesizing self-plasticizing polyvinyl chloride based on internal plasticization modification through hyperbranching reaction, esterification, epoxidation reaction and click reaction. The present invention uses cardanol, polyvinyl chloride, glycidol, organic acid anhydride and aminothiophenol as main raw materials, and causes cardanol and glycidol to undergo hyperbranching reaction to obtain cardanol polyglycerol with a hyperbranched structure, and then undergoes esterification reaction with organic acid anhydride to obtain terminal ester cardanol polyglycerol, and then uses a peroxygen source to epoxidize the double bonds on the cardanol side chain to obtain a hyperbranched cardanol plasticizer, and uses aminothiophenol as a grafting agent, and uses a click reaction to graft the hyperbranched cardanol plasticizer onto polyvinyl chloride to obtain a hyperbranched cardanol-based self-plasticizing polyvinyl chloride.

[0030] The main raw materials of the present invention are renewable and do not rely on petroleum; the preparation process is simple and reasonable, and the energy consumption is low; the product has good thermal stability and no hidden danger of plasticizer leakage into the environment. Test results show that the self-plasticizing polyvinyl chloride prepared by the present invention has good toughness and processing performance.

[0031] The first aspect of the present invention provides a method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride, comprising the following steps:

[0032] Step 1, subjecting cardanol and glycidol to a hyperbranching reaction to obtain cardanol polyglycerol;

[0033] Step 2, esterifying the cardanol polyglycerol with an organic acid anhydride to obtain ester-terminated cardanol polyglycerol;

[0034] Step 3, subjecting the terminal ester cardanol polyglycerol to epoxidation reaction with a peroxygen source to obtain a hyperbranched cardanol plasticizer;

[0035] Step 4, using aminothiophenol as a grafting agent, and utilizing a click reaction to graft the hyperbranched cardanol plasticizer onto polyvinyl chloride to obtain the hyperbranched cardanol-based self-plasticizing polyvinyl chloride.

[0036] In a preferred embodiment of the present invention, the molar ratio of the cardanol to the glycidol is 1:(3-9); the hyperbranching reaction is specifically as follows: under an inert atmosphere, first react at 70-90°C for 2h, then heat to 90-110°C for 4h, and then heat to 110-130°C for 2h.

[0037] If the reaction is continued at a temperature within the range of 80-120°C for 8 hours without gradient, the hyperbranched structure will be disordered, forming a variety of hyperbranched structures with different branching degrees, which will affect the performance of the material.

[0038] After the hyperbranching reaction is completed, a filtering step is also included.

[0039] In a preferred embodiment of the present invention, the molar ratio of the cardanol polyglycerol to the organic acid anhydride is 1:(4-12); and the organic acid anhydride is caproic anhydride or acetic anhydride.

[0040] The present invention also attempts to use other organic anhydrides, such as maleic anhydride and itaconic anhydride, but the results often lead to incomplete experiments or difficulty in removing them in subsequent treatments of the experiments.

[0041] In a preferred embodiment of the present invention, the esterification reaction is specifically: reacting at 100-140° C. for 4 hours under an inert atmosphere.

[0042] If the temperature during the esterification reaction is too high, it will lead to more side reactions, and if the temperature is too low, the reaction will be incomplete.

[0043] After the esterification reaction is completed, the steps of dissolving the product with a solution, repeatedly washing with a sodium hydroxide solution (to remove excess organic anhydride), and then distilling under reduced pressure are also included.

[0044] In a preferred embodiment of the present invention, the molar ratio of the terminal ester cardanol polyglycerol to the peroxygen source is 1:3; and the peroxygen source is hydrogen peroxide, m-chloroperbenzoic acid or tert-butyl hydroperoxide.

[0045] In a preferred embodiment of the present invention, the epoxidation reaction is carried out at a temperature of 25-40° C. and for a time of 4 hours.

[0046] After the epoxidation reaction is completed, the product is refrigerated and filtered, washed with a sodium sulfite solution until neutral, and then dried.

[0047] In a preferred embodiment of the present invention, step 4 comprises the step of preparing the hyperbranched cardanol-based self-plasticizing polyvinyl chloride by click reaction, comprising: dissolving polyvinyl chloride and aminothiophenol in tetrahydrofuran under an inert atmosphere, adding potassium carbonate, reacting at 40-80° C. for 4 hours, and then adding a hyperbranched cardanol plasticizer and continuing to react at 40-80° C. for 4 hours; after the reaction, adding a methanol / water mixed solution (v / v=1:1-3) to precipitate the desired product, and obtaining the hyperbranched cardanol-based self-plasticizing polyvinyl chloride after drying.

[0048] In a preferred embodiment of the present invention, the mass ratio of the polyvinyl chloride to the aminothiophenol is 75:(18-24); the molar ratio of the aminothiophenol to the hyperbranched cardanol plasticizer is 1:1; and the molar ratio of the aminothiophenol to the potassium carbonate is 1:1.

[0049] The inert atmosphere described in the present invention, unless otherwise specified, refers to at least one of nitrogen, helium or argon atmosphere.

[0050] The second aspect of the present invention provides a hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared according to the above-mentioned preparation method.

[0051] The self-plasticizing characteristic of the hyperbranched cardanol-based self-plasticizing polyvinyl chloride of the present invention is that the glass transition temperature of the polyvinyl chloride can be permanently reduced without adding an external plasticizer.

[0052] The third aspect of the present invention provides a use of the above-mentioned hyperbranched cardanol-based self-plasticizing polyvinyl chloride in the preparation of building materials, medical devices, toys, clothing or automobile parts.

[0053] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or have been disclosed.

[0054] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0055] Example 1

[0056] A method for preparing hyperbranched cardanol-based self-plasticizing polyvinyl chloride, comprising the following steps:

[0057] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0058] 2) Cardanol polyglycerol and caproic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess caproic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0059] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0060] 4) Dissolve 75 parts of polyvinyl chloride and 24 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0061] Example 2

[0062] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0063] 2) Cardanol polyglycerol and acetic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess acetic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0064] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0065] 4) Dissolve 75 parts of polyvinyl chloride and 24 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0066] Example 3

[0067] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0068] 2) Cardanol polyglycerol and caproic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess caproic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0069] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0070] 4) Dissolve 75 parts of polyvinyl chloride and 22 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0071] Example 4

[0072] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0073] 2) Cardanol polyglycerol and acetic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess acetic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0074] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0075] 4) Dissolve 75 parts of polyvinyl chloride and 22 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0076] Example 5

[0077] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0078] 2) Cardanol polyglycerol and caproic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess caproic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0079] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0080] 4) Dissolve 75 parts of polyvinyl chloride and 20 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0081] Example 6

[0082] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0083] 2) Cardanol polyglycerol and acetic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess acetic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0084] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0085] 4) Dissolve 75 parts of polyvinyl chloride and 20 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain a hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0086] Example 7

[0087] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0088] 2) Cardanol polyglycerol and caproic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess caproic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0089] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0090] 4) Dissolve 75 parts of polyvinyl chloride and 18 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0091] Example 8

[0092] 1) Under nitrogen, cardanol and glycidol are uniformly mixed in a molar ratio of 1:7, the temperature is raised to 80° C., the reaction is continued for 2 hours, then the temperature is raised to 100° C., the reaction is continued for 4 hours, then the temperature is raised to 120° C., the reaction is continued for 2 hours, and after the reaction is completed, the reaction product is filtered to obtain cardanol polyglycerol.

[0093] 2) Cardanol polyglycerol and acetic anhydride are uniformly mixed in a molar ratio of 1:8 under nitrogen, heated to 120° C., and reacted for 4 hours. After the reaction, the product is dissolved in ethyl acetate solution, and repeatedly washed with 50% sodium hydroxide solution to remove excess acetic anhydride, and then the solvent is removed by reduced pressure distillation to obtain terminal ester cardanol polyglycerol.

[0094] 3) 16.7 g of terminal ester cardanol polyglycerol was added to the reactor, 6.9 g of m-chloroperbenzoic acid was dissolved in 250 mL of dichloromethane, and slowly added to the reactor containing terminal ester cardanol polyglycerol, and reacted at 30° C. for 4 h. After the reaction, the product was refrigerated at -4° C. for 3 h and filtered, washed with a saturated sodium sulfite solution until neutral, and then the excess dichloromethane was removed by reduced pressure distillation to obtain a hyperbranched cardanol plasticizer.

[0095] 4) Dissolve 75 parts of polyvinyl chloride and 18 parts of aminothiophenol in tetrahydrofuran under nitrogen (the amount of tetrahydrofuran is sufficient to fully dissolve polyvinyl chloride and aminothiophenol), add potassium carbonate in an amount equal to the molar amount of aminothiophenol, heat to 60°C, react for 4 hours, then add a hyperbranched cardanol plasticizer in an amount equal to the molar amount of aminothiophenol, and continue to react at 60°C for 4 hours. After the reaction is completed, add a methanol / water mixed solution with a volume ratio of 1:1 to precipitate the desired product, and dry at 50°C for 12 hours to obtain hyperbranched cardanol-based self-plasticized polyvinyl chloride.

[0096] Comparative Example 1

[0097] Add dioctyl phthalate (4 g) and polyvinyl chloride (10 g) to 120 mL of tetrahydrofuran, stir at 55°C for 1 hour to mix the solution evenly, and place the product in a petri dish. Dry at room temperature for two days, then move to a constant temperature oven at 60°C and dry for two days to remove tetrahydrofuran, thereby preparing polyvinyl chloride / dioctyl phthalate.

[0098] Figure 1 is the infrared analysis spectrum of cardanol, cardanol polyglycerol, terminal ester cardanol polyglycerol and hyperbranched cardanol plasticizer in Example 1 of the present invention; Figure 1 It can be seen that the hydroxyl peak corresponding to cardanol polyglycerol is enhanced, indicating that the hyperbranched structure is successfully connected to cardanol, while the double bond peak corresponding to the hyperbranched cardanol plasticizer disappears and the epoxy peak appears, indicating that the double bond of the cardanol side chain is successfully epoxidized.

[0099] Figure 2 is the infrared analysis spectrum of the hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared in Example 1 of the present invention; Figure 2 It can be seen that at 3300-3500cm -1 The peaks in the range are the stretching vibration peaks of -OH and -NH, indicating that hyperbranched cardanol was successfully grafted onto polyvinyl chloride.

[0100] Figure 3 The dynamic thermomechanical analysis of the hyperbranched cardanol-based self-plasticized polyvinyl chloride (i.e., cardanol-based self-plasticized polyvinyl chloride) prepared in Example 1 of the present invention, the temperature corresponding to the peak of the curve is the glass transition temperature of the polyvinyl chloride; Figure 3It can be seen that the glass transition temperature of cardanol-based self-plasticizing polyvinyl chloride is significantly lower than that of polyvinyl chloride, which proves that cardanol-based self-plasticizing polyvinyl chloride has good processing properties.

[0101] The products prepared in Example 1 and Comparative Example 1 were subjected to a migration loss test. The test conditions were as follows: the PVC test piece was immersed in 30% acetic acid, 10% ethanol solution or petroleum ether, placed at 30°C for 24 hours, taken out, washed with running water, placed in an oven at 40°C for 12 hours, moved into a dryer to cool to room temperature, and weighed. The mass loss of the PVC test piece before and after the experiment was calculated. The results are shown in Figure 4 As shown. Figure 4 It can be seen that the cardanol-based self-plasticized polyvinyl chloride has no migration loss and has good durability.

[0102] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride, characterized in that: The following steps are involved: Step 1, subjecting cardanol and glycidol to a hyperbranching reaction to obtain cardanol polyglycerol; Step 2, esterifying the cardanol polyglycerol with an organic acid anhydride to obtain ester-terminated cardanol polyglycerol; Step 3, subjecting the terminal ester cardanol polyglycerol to epoxidation reaction with a peroxygen source to obtain a hyperbranched cardanol plasticizer; Step 4, using aminothiophenol as a grafting agent, and utilizing a click reaction to graft the hyperbranched cardanol plasticizer onto polyvinyl chloride to obtain the hyperbranched cardanol-based self-plasticizing polyvinyl chloride.

2. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, wherein The molar ratio of the cardanol to the glycidol is 1:(3-9); the hyperbranching reaction is specifically as follows: under an inert atmosphere, first react at 70-90° C. for 2 hours, then heat to 90-110° C. for 4 hours, and then heat to 110-130° C. for 2 hours.

3. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, characterized in that: The molar ratio of the cardanol polyglycerol to the organic acid anhydride is 1:(4-12); the organic acid anhydride is caproic anhydride or acetic anhydride.

4. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, wherein: The esterification reaction is specifically: reacting at 100-140° C. for 4 hours under an inert atmosphere.

5. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, wherein The molar ratio of the terminal ester cardanol polyglycerol to the peroxygen source is 1:3; the peroxygen source is hydrogen peroxide, meta-chloroperbenzoic acid or tert-butyl hydroperoxide.

6. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, characterized in that: The epoxidation reaction is carried out at a temperature of 25-40° C. and for a time of 4 hours.

7. The method for preparing a hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 1, characterized in that: Step 4: The step of preparing the hyperbranched cardanol-based self-plasticizing polyvinyl chloride by click reaction comprises: dissolving polyvinyl chloride and aminothiophenol in tetrahydrofuran under an inert atmosphere, adding potassium carbonate, reacting at 40-80° C. for 4 hours, and then adding a hyperbranched cardanol plasticizer and reacting at 40-80° C. for 4 hours; after the reaction is completed, adding a methanol / water mixed solution to precipitate the desired product, and obtaining the hyperbranched cardanol-based self-plasticizing polyvinyl chloride after drying.

8. The method for preparing the hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 7, characterized in that: The mass ratio of the polyvinyl chloride to the aminothiophenol is 75:(18-24); the molar ratio of the aminothiophenol to the hyperbranched cardanol plasticizer is 1:1; and the molar ratio of the aminothiophenol to the potassium carbonate is 1:

1.

9. The hyperbranched cardanol-based self-plasticizing polyvinyl chloride prepared according to the preparation method according to any one of claims 1 to 8.

10. Use of the hyperbranched cardanol-based self-plasticizing polyvinyl chloride according to claim 9 in the preparation of building materials, medical devices, toys, clothing or automobile parts.

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