High-toughness synthetic resin and preparation method thereof

Abstract

The invention discloses high-toughness synthetic resin and a preparation method thereof, and relates to the field of resin materials for synthetic resin tiles. The high-toughness synthetic resin is prepared from 100 parts by weight of PVC (Polyvinyl Chloride) resin, 5.5 to 6.8 parts by weight of ethylene-alkyl acrylate-glycidyl acrylate copolymer, 3.3 to 4.2 parts by weight of maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, 4.2 to 5.6 parts by weight of modified inorganic toughening particles and 0.5 to 1 part by weight of heat stabilizer; wherein the modified inorganic toughening particles are obtained by grafting inorganic toughening particles with long-chain monounsaturated fatty acid and an amino silane coupling agent and then polymerizing with alkyl acrylate. In the high-toughness synthetic resin disclosed by the invention, the ethylene-alkyl acrylate-glycidyl acrylate copolymer and the maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer are not easy to separate out along with time, and the durability of the high-toughness synthetic resin is good.

Description

Technical Field

[0001] The present application relates to the field of resin materials for synthetic resin tiles, and in particular to a high-toughness synthetic resin and a preparation method thereof. Background Art

[0002] In the field of materials science, polyvinyl chloride (PVC) resin is widely used in many industries, including construction, packaging, and electronics, due to its excellent mechanical properties, chemical resistance, and processing performance. However, PVC resin itself has the problem of insufficient toughness, which greatly limits its application in some scenarios that require high material toughness. For example, when used in the construction field to manufacture synthetic resin tiles, if the PVC resin has poor toughness, the resin tiles are prone to cracking and brittleness when subjected to external impact or temperature changes, seriously affecting their service life and performance.

[0003] To improve the toughness of PVC resin, elastomers are often added for impact modification. While elastomers can enhance the toughness of PVC resin to a certain extent, their compatibility with the resin is limited, making it difficult to evenly disperse the two when mixed, which in turn affects the stability of the material's overall performance. Furthermore, over time, elastomers tend to leach out of the PVC resin, significantly reducing the material's durability and making it unsuitable for long-term use. Summary of the Invention

[0004] In order to improve the problem of poor durability of PVC synthetic resin, the present application provides a high-toughness synthetic resin and a preparation method thereof.

[0005] In the first aspect, the present application provides a high-toughness synthetic resin using the following technical solutions: A high-toughness synthetic resin comprises 100 parts by weight of PVC resin, 5.5-6.8 parts by weight of ethylene-alkyl acrylate-glycidyl acrylate copolymer, 3.3-4.2 parts by weight of maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, 4.2-5.6 parts by weight of modified inorganic toughening particles, and 0.5-1 part by weight of a heat stabilizer. The modified inorganic toughening particles are obtained by grafting long-chain monounsaturated fatty acids and aminosilane coupling agents onto inorganic toughening particles, followed by polymerization with alkyl acrylate.

[0006] The high-toughness synthetic resin of this application is based on PVC resin and incorporates ethylene-alkyl acrylate-glycidyl acrylate copolymer and modified inorganic toughening particles. The ethylene-alkyl acrylate-glycidyl acrylate copolymer and modified inorganic toughening particles serve as impact modifiers to enhance the toughness of the PVC resin. To improve the compatibility of the ethylene-alkyl acrylate-glycidyl acrylate copolymer with the PVC resin, a portion of maleic anhydride-grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer is added. In addition, the modified inorganic toughening particles of the present application are obtained by grafting an aminosilane coupling agent and a long-chain monounsaturated fatty acid onto inorganic toughening particles and then polymerizing them with an alkyl acrylate. The modified inorganic toughening particles have good dispersibility in PVC resin. At the same time, through the interaction between the amino groups on the modified inorganic toughening particles and the epoxy groups in the ethylene-alkyl acrylate-glycidyl acrylate copolymer and the maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, the problem of the ethylene-alkyl acrylate-glycidyl acrylate copolymer and the maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin being easily precipitated over time can be improved to a certain extent, which is beneficial to improving the durability of the high-toughness synthetic resin.

[0007] In some specific embodiments, in the modified inorganic toughening particles, the weight ratio of the inorganic toughening particles, the aminosilane coupling agent, the long-chain monounsaturated fatty acid and the alkyl acrylate is 10:(2-3):(1-2):(0.2-0.4).

[0008] In the modified inorganic toughening particles of the present application, the weight ratio of the inorganic toughening particles, aminosilane coupling agent, long-chain monounsaturated fatty acid and alkyl acrylate is preferably 10:(2-3):(1-2):(0.2-0.4), which can further improve the problem of ethylene-alkyl acrylate-glycidyl acrylate copolymer in high-toughness synthetic resin easily precipitating over time, and is beneficial to further improve the durability of the high-toughness synthetic resin.

[0009] In some specific embodiments, the long-chain monounsaturated fatty acid is a monounsaturated fatty acid with 16-18 carbon atoms.

[0010] In the present application, the long-chain monounsaturated fatty acid is preferably a monounsaturated fatty acid with 16-18 carbon atoms, which is beneficial to reducing the polarity difference between the inorganic toughening particles and the PVC resin, increasing the steric hindrance, reducing the agglomeration tendency of the modified inorganic toughening particles, and promoting the uniform dispersion of the modified inorganic toughening particles, which is beneficial to improving toughness. At the same time, it can also promote the improvement of the durability of the high-toughness synthetic resin.

[0011] In some specific embodiments, the alkyl acrylate is at least one of ethyl acrylate and butyl acrylate.

[0012] When preparing modified inorganic toughening particles in the present application, the alkyl acrylate is preferably ethyl acrylate or butyl acrylate, which can further improve the problem of ethylene-alkyl acrylate-glycidyl acrylate copolymer in high-toughness synthetic resin easily precipitating over time, and is beneficial to further improve the durability of high-toughness synthetic resin.

[0013] In some specific embodiments, the method for preparing the modified inorganic toughening particles comprises the following steps: After the inorganic toughening particles are dried at 100-120°C, they are added to a dispersion solution of toluene and acetone, and after being uniformly dispersed by ultrasonication, long-chain monounsaturated fatty acids are added, and the mixture is stirred and reacted at 75-85°C, followed by centrifugal separation, washing, and drying to obtain a preliminary product; The preliminary product is added to a mixed solution of an aminosilane coupling agent and an ethanol aqueous solution, the pH is adjusted to 4-5, the temperature is raised to 55-65° C., stirred for reaction, and then centrifuged, washed, and vacuum-dried to obtain an intermediate product; The intermediate product is added to alkyl acrylate, an initiator is added, and the mixture is stirred and reacted at 70-80° C., followed by centrifugal separation, washing, and drying to obtain modified inorganic toughened particles.

[0014] In the present application, the modified inorganic toughening particles are prepared by the above method, which can prevent the problem of the amino group in the aminosilane coupling agent reacting with the carboxyl group in the long-chain monounsaturated fatty acid, thereby improving the problem of the ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin being easily precipitated over time, which is beneficial to improving the durability of the high-toughness synthetic resin.

[0015] In some specific embodiments, the ethylene-alkyl acrylate-glycidyl acrylate copolymer is at least one of ethylene-ethyl acrylate-glycidyl acrylate, ethylene-butyl acrylate-glycidyl acrylate copolymer, and ethylene-octyl acrylate-glycidyl acrylate.

[0016] In some specific embodiments, the heat stabilizer is at least one of calcium stearate, zinc stearate, and an organotin heat stabilizer.

[0017] In a second aspect, the present application provides a method for preparing a high-toughness synthetic resin using the following technical solution: A method for preparing a high-toughness synthetic resin comprises the following steps: PVC resin, ethylene-alkyl acrylate-glycidyl acrylate copolymer, maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, modified inorganic toughening particles and heat stabilizer are uniformly mixed according to the proportion, put into an extruder, melt-extruded at 190-220°C, and then cooled and granulated to obtain a high-toughness synthetic resin.

[0018] In the present application, the above-mentioned method is used to prepare high-toughness synthetic resin, which is conducive to the uniform mixing of various raw materials and can improve the uniformity of the product.

[0019] In summary, this application has at least the following beneficial effects: (1) The high-toughness synthetic resin of the present application is based on PVC resin and is added with ethylene-alkyl acrylate-glycidyl acrylate copolymer and modified inorganic toughening particles. The ethylene-alkyl acrylate-glycidyl acrylate copolymer and modified inorganic toughening particles serve as impact modifiers to enhance the toughness of the PVC resin. Specifically, in order to improve the compatibility of the ethylene-alkyl acrylate-glycidyl acrylate copolymer with the PVC resin, a portion of maleic anhydride-grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer is added. In addition, the modified inorganic toughening particles of the present application are obtained by grafting an aminosilane coupling agent and a long-chain monounsaturated fatty acid onto inorganic toughening particles and then polymerizing them with an alkyl acrylate. The modified inorganic toughening particles have good dispersibility in PVC resin. At the same time, through the interaction between the amino groups on the modified inorganic toughening particles and the epoxy groups in the ethylene-alkyl acrylate-glycidyl acrylate copolymer and the maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, the problem of the ethylene-alkyl acrylate-glycidyl acrylate copolymer and the maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin being easily precipitated over time can be improved to a certain extent, which is beneficial to improving the durability of the high-toughness synthetic resin.

[0020] (2) In the modified inorganic toughening particles of the present application, the weight ratio of the inorganic toughening particles, aminosilane coupling agent, long-chain monounsaturated fatty acid and alkyl acrylate is preferably 10:(2-3):(1-2):(0.2-0.4), which can further improve the problem that the ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin is easily precipitated over time, and is beneficial to further improve the durability of the high-toughness synthetic resin. DETAILED DESCRIPTION

[0021] The present application is further described below in conjunction with specific experiments. Example

[0022] [Example 1] A high-toughness synthetic resin comprises 100 kg of Qilu Petrochemical SG5 PVC resin, 5.5 kg of ethylene-butyl acrylate-glycidyl acrylate copolymer, 3.3 kg of maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer, 5.6 kg of modified inorganic toughening particles, and 0.5 kg of a heat stabilizer. The ethylene-butyl acrylate-glycidyl acrylate copolymer is Arkema model AX8700; the maleic anhydride-grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer has a grafting amount of 0.8% maleic anhydride; the heat stabilizer is specifically calcium stearate; and the modified inorganic toughening particles are specifically modified nano-calcium carbonate. The raw materials for preparing the modified nano-calcium carbonate include 10 kg of nano-calcium carbonate, 2 kg of aminosilane coupling agent KH550, 2 kg of oleic acid, and 0.4 kg of butyl acrylate. The specific preparation method comprises the following steps: After drying at 100°C, nano-calcium carbonate was added to a dispersion solution of toluene and acetone in a weight ratio of 1:3. After ultrasonic dispersion, oleic acid was added and stirred at 75°C for reaction. The product was then centrifuged, washed with ethanol, and dried to obtain a preliminary product. The preliminary product is added to a mixed solution of aminosilane coupling agent KH550 and 1+1 ethanol aqueous solution, wherein the weight ratio of aminosilane coupling agent KH550 to 1+1 ethanol aqueous solution is 1:9, after adjusting the pH to 4-5, the mixture is heated to 55° C. and stirred for reaction, followed by centrifugation, ethanol washing, and vacuum drying to obtain an intermediate product; The intermediate product is added to butyl acrylate, and azobisisobutyronitrile is added, and the mixture is stirred and reacted at 70° C., followed by centrifugal separation, ethanol washing, and drying to obtain modified nano-calcium carbonate, wherein the amount of azobisisobutyronitrile added is 0.1% by weight of the butyl acrylate.

[0023] In this embodiment, the preparation method of the high-toughness synthetic resin is as follows: PVC resin, ethylene-butyl acrylate-glycidyl acrylate copolymer, maleic anhydride grafted ethylene-butyl acrylate-glycidyl acrylate copolymer, modified inorganic toughening particles and heat stabilizer are uniformly mixed according to the proportion, put into an extruder, melt-extruded at 190-220°C, and then cooled and granulated to obtain a high-toughness synthetic resin.

[0024] [Example 2] A high-toughness synthetic resin comprises 100 kg of Qilu Petrochemical SG5 PVC resin, 6.8 kg of ethylene-butyl acrylate-glycidyl acrylate copolymer, 4.2 kg of maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer, 4.2 kg of modified inorganic toughening particles, and 1 kg of heat stabilizer. The ethylene-butyl acrylate-glycidyl acrylate copolymer is Arkema model AX8700; the maleic anhydride-grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer has a grafting amount of 0.8% maleic anhydride; zinc stearate is used as the heat stabilizer; and the modified inorganic toughening particles are made of modified nano-calcium carbonate, prepared from raw materials including 10 kg of nano-calcium carbonate, 3 kg of aminosilane coupling agent KH550, 1 kg of oleic acid, and 0.2 kg of butyl acrylate. The specific preparation method comprises the following steps: After drying at 100°C, nano-calcium carbonate was added to a dispersion solution of toluene and acetone in a weight ratio of 1:3. After ultrasonic dispersion, oleic acid was added and stirred at 85°C for reaction. The product was then centrifuged, washed with ethanol, and dried to obtain a preliminary product. The preliminary product is added to a mixed solution of aminosilane coupling agent KH550 and 1+1 ethanol aqueous solution, wherein the weight ratio of aminosilane coupling agent KH550 to 1+1 ethanol aqueous solution is 1:9, after adjusting the pH to 4-5, the mixture is heated to 65° C. and stirred for reaction, followed by centrifugation, ethanol washing, and vacuum drying to obtain an intermediate product; The intermediate product is added to butyl acrylate, and azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80° C., followed by centrifugal separation, ethanol washing, and drying to obtain modified nano-calcium carbonate, wherein the amount of azobisisobutyronitrile added is 0.1% by weight of the butyl acrylate.

[0025] In this embodiment, the preparation method of the high-toughness synthetic resin is as follows: PVC resin, ethylene-butyl acrylate-glycidyl acrylate copolymer, maleic anhydride grafted ethylene-butyl acrylate-glycidyl acrylate copolymer, modified inorganic toughening particles and heat stabilizer are uniformly mixed according to the proportion, put into an extruder, melt-extruded at 190-220°C, and then cooled and granulated to obtain a high-toughness synthetic resin.

[0026] [Example 3] A high-toughness synthetic resin differs from Example 1 in that the raw material ratio of the modified nano-calcium carbonate is different. In this example, the raw materials for preparing the modified nano-calcium carbonate include 10 kg of nano-calcium carbonate, 0.5 kg of aminosilane coupling agent KH550, 0.5 kg of oleic acid, and 0.05 kg of butyl acrylate.

[0027] [Example 4] A high-toughness synthetic resin, which differs from [Example 1] in that: When preparing modified nano-calcium carbonate, butyl acrylate is replaced by heptyl acrylate of equal mass.

[0028] Comparative Example [Comparative Example 1] A synthetic resin, which differs from [Example 1] in that: When preparing modified nano-calcium carbonate, oleic acid is replaced by linoleic acid of equal mass.

[0029] [Example 2] A synthetic resin, which differs from [Example 1] in that: When preparing modified nano-calcium carbonate, butyl acrylate is replaced by styrene of equal mass.

[0030] Performance testing Izod impact strength: Referring to the provisions of GB / T1843-2008 "Determination of Izod Impact Strength of Plastics" for unnotched Izod impact strength, the performance of samples placed at room temperature (25°C) for 7 days and 168 days was tested, and the results are recorded in Table 1 below.

[0031] Table 1 The difference between Comparative Example 1 and Example 1 is that when preparing modified nano-calcium carbonate, oleic acid is replaced by linoleic acid of equal mass. In combination with the data recorded in Table 1 above, it can be seen that after oleic acid is replaced by linoleic acid of equal mass, the downward trend of the Izod impact strength of the synthetic resin after being placed for a long time increases. The reason is that when linoleic acid is used, the reaction of the amino group in the modified nano-calcium carbonate with the epoxy group in the ethylene-butyl acrylate-glycidyl acrylate copolymer or the maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer is hindered, resulting in the ethylene-butyl acrylate-glycidyl acrylate copolymer or the maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer in the synthetic resin being easily precipitated during storage in the later stage, causing the impact durability of the synthetic resin to decline.

[0032] The difference between Comparative Example 2 and Example 1 is that when preparing modified nano-calcium carbonate, butyl acrylate is replaced by styrene of equal mass. In conjunction with the data recorded in Table 1, it can be seen that after butyl acrylate is replaced by styrene of equal mass, the Izod impact strength of the synthetic resin after long-term storage also decreases rapidly. The main reason is that the introduction of styrene also hinders the reaction of the amino group in the modified nano-calcium carbonate with the epoxy group in the ethylene-butyl acrylate-glycidyl acrylate copolymer or the maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer, causing the ethylene-butyl acrylate-glycidyl acrylate copolymer or the maleic anhydride-grafted ethylene-butyl acrylate-glycidyl acrylate copolymer in the synthetic resin to separate out easily, causing the impact durability of the synthetic resin to decline.

[0033] The difference between Example 3 and Example 1 is that the ratio of the raw materials is different when preparing the modified nano-calcium carbonate. Combined with the data recorded in Table 1 above, it can be seen that the weight ratio of the inorganic toughening particles, aminosilane coupling agent, long-chain monounsaturated fatty acid and alkyl acrylate is preferably 10: (2-3): (1-2): (0.2-0.4), which can further improve the problem that the ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin is easily precipitated over time, which is beneficial to further improve the durability of the high-toughness synthetic resin.

[0034] The difference between Example 4 and Example 1 is that, when preparing the modified nano-calcium carbonate, the alkyl acrylate in Example 1 is butyl acrylate, while the alkyl acrylate in Example 4 is heptyl acrylate. Combined with the data in Table 1, it can be seen that the alkyl acrylate is preferably butyl acrylate, which can further improve the problem of ethylene-alkyl acrylate-glycidyl acrylate copolymer in the high-toughness synthetic resin being easily precipitated over time, thereby further improving the durability of the high-toughness synthetic resin.

[0035] This specific implementation manner is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the specific implementation manner as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high-toughness synthetic resin, characterized by: The invention comprises 100 parts by weight of PVC resin, 5.5-6.8 parts by weight of ethylene-alkyl acrylate-glycidyl acrylate copolymer, 3.3-4.2 parts by weight of maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, 4.2-5.6 parts by weight of modified inorganic toughening particles and 0.5-1 part by weight of heat stabilizer, wherein the modified inorganic toughening particles are obtained by grafting long-chain monounsaturated fatty acid and aminosilane coupling agent onto inorganic toughening particles, and then polymerizing with alkyl acrylate.

2. The high-toughness synthetic resin according to claim 1, characterized in that: In the modified inorganic toughening particles, the weight ratio of the inorganic toughening particles, the aminosilane coupling agent, the long-chain monounsaturated fatty acid and the alkyl acrylate is 10:(2-3):(1-2):(0.2-0.4).

3. The high-toughness synthetic resin according to claim 1, characterized in that: The long-chain monounsaturated fatty acid is a monounsaturated fatty acid with 16 to 18 carbon atoms.

4. The high-toughness synthetic resin according to claim 1, characterized in that: The alkyl acrylate is at least one of ethyl acrylate and butyl acrylate.

5. The high-toughness synthetic resin according to claim 1, characterized in that: The inorganic toughening particles are at least one of nano calcium carbonate, nano silicon dioxide and nano aluminum oxide.

6. A high-toughness synthetic resin according to any one of claims 1 to 5, characterized in that: The preparation method of the modified inorganic toughening particles comprises the following steps: After the inorganic toughening particles are dried at 100-120°C, they are added to a dispersion solution of toluene and acetone, and after being uniformly dispersed by ultrasonication, long-chain monounsaturated fatty acids are added, and the mixture is stirred and reacted at 75-85°C, followed by centrifugal separation, washing, and drying to obtain a preliminary product; The preliminary product is added to a mixed solution of an aminosilane coupling agent and an ethanol aqueous solution, the pH is adjusted to 4-5, the temperature is raised to 55-65° C., stirred for reaction, and then centrifuged, washed, and vacuum-dried to obtain an intermediate product; The intermediate product is added to alkyl acrylate, an initiator is added, and the mixture is stirred and reacted at 70-80° C., followed by centrifugal separation, washing, and drying to obtain modified inorganic toughened particles.

7. The high-toughness synthetic resin according to claim 1, characterized in that: In the ethylene-alkyl acrylate-glycidyl acrylate copolymer, the mass fraction of alkyl acrylate is 23-28%, and the mass fraction of glycidyl acrylate is 6-9%.

8. The high-toughness synthetic resin according to claim 7, characterized in that: The ethylene-alkyl acrylate-glycidyl acrylate copolymer is at least one of ethylene-ethyl acrylate-glycidyl acrylate, ethylene-butyl acrylate-glycidyl acrylate copolymer, and ethylene-octyl acrylate-glycidyl acrylate.

9. The high-toughness synthetic resin according to claim 1, characterized in that: The heat stabilizer is at least one of calcium stearate, zinc stearate, and an organic tin heat stabilizer.

10. A method for preparing a high-toughness synthetic resin according to any one of claims 1 to 9, characterized in that: The following steps are involved: PVC resin, ethylene-alkyl acrylate-glycidyl acrylate copolymer, maleic anhydride grafted ethylene-alkyl acrylate-glycidyl acrylate copolymer, modified inorganic toughening particles and heat stabilizer are uniformly mixed according to the proportion, put into an extruder, melt-extruded at 190-220°C, and then cooled and granulated to obtain a high-toughness synthetic resin.

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