Plasticizer based on AI sensor and preparation method thereof

Abstract

The invention discloses a plasticizer based on an AI sensor and a preparation method of the plasticizer, and belongs to the technical field of plasticizers. Comprising the following steps: mixing a citrate derivative and diketene, and preparing a material A under the catalytic action of a catalyst I; ricinoleic acid and the material A are mixed for reaction, and a material B is prepared; mixing the material B with a cyclohexane alcohol derivative, and preparing a material C under the catalytic action of a catalyst II; mixing the material C with 2-mercaptoethanol, adding a photoinitiator, and preparing a material D under an ultraviolet radiation condition; and mixing the material D, epoxy chloropropane and tetrabutylammonium bromide, heating, refluxing, stirring, cooling, adding a sodium hydroxide solution, continuously stirring, centrifugally separating, and taking a liquid phase, thereby obtaining the plasticizer. By applying the prepared plasticizer with good performance to PVC resin, the flexibility and processability of the material are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of plasticizers, and in particular relates to a plasticizer for an AI sensor and a preparation method thereof. Background Art

[0002] Artificial intelligence (AI) sensors are intelligent sensing systems that tightly integrate advanced AI algorithms with traditional sensor hardware. By applying cutting-edge technologies such as machine learning and deep learning, these systems significantly enhance data acquisition, processing, and decision-making capabilities. Their core principle lies in leveraging AI to empower sensors with self-learning, self-adaptation, and self-decision-making capabilities, thus surpassing the single, simple data acquisition and processing capabilities of traditional sensors. At the hardware level, AI sensors achieve comprehensive multi-dimensional data acquisition by integrating sensor arrays with multiple sensor types, such as image, temperature, pressure, and spectral sensors. These sensors typically consist of a flexible substrate, electrodes, a liquid metal film, and a flexible encapsulation layer. For example, the sensor described in patent application number CN201910395010.2 uses materials such as PVC as a flexible encapsulation layer; while patent application number CN201310688406.9 utilizes PVC and plasticizers to create a flexible film. Plasticizers are additives added to polymers to enhance their plasticity, flexibility, and flowability during processing. As one of the five most common resin materials, polyvinyl chloride (PVC) is widely used in numerous production fields due to its low price, excellent mechanical properties, and good chemical resistance. However, due to its relatively poor flexibility and plasticity, PVC cannot meet the material requirements of soft products such as sensor films. Therefore, plasticizers are needed to improve its processability and stretchability. Currently, dioctyl phthalate (DOP) is one of the most widely used PVC plasticizers. However, DOP has poor migration resistance and easily migrates out of PVC products, which can lead to performance degradation of PVC products. More seriously, DOP is reproductive toxic and may pose a threat to both human health and the environment. In view of this, the development of a green, low-toxic, and environmentally friendly plasticizer to replace DOP has become extremely urgent. Summary of the Invention

[0003] The purpose of the present invention is to provide a plasticizer for AI sensors and a preparation method thereof, to provide a green, low-toxic, environmentally friendly plasticizer with good plasticizing effect to replace the toxic dioctyl phthalate plasticizer, while improving the migration resistance of the plasticizer in PVC materials.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a plasticizer for an AI sensor comprises the following steps: S1. Mixing a citrate derivative and diketene under the catalytic action of catalyst I to obtain material A; S2, taking ricinoleic acid and material A and mixing them to obtain material B; S3, taking the material B and the cyclohexanol derivative and mixing them under the catalytic action of catalyst II to obtain material C; S4, mixing the material C and 2-mercaptoethanol, adding a photoinitiator, and preparing the material D under ultraviolet irradiation conditions; S5. Mix the material D, epichlorohydrin and tetrabutylammonium bromide, heat under reflux with stirring, cool, add sodium hydroxide solution, continue stirring, centrifuge and separate the liquid phase to obtain the plasticizer.

[0005] As a preferred technical solution of the present invention, in step S1, the catalyst I includes any one of concentrated sulfuric acid, triethylamine and sodium methoxide.

[0006] As a preferred technical solution of the present invention, in step S1, the citrate derivative includes any one of trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, and tripentyl citrate.

[0007] As a preferred technical solution of the present invention, in step S3, the cyclohexanol derivative includes any one of 1,4-cyclohexanediol, cis-cyclohexylcyclohexanol, 3-(cyclohexyloxy)propan-1-ol, and 2-(4-propylcyclohexyl)-1,3-propanediol.

[0008] As a preferred technical solution of the present invention, in step S3, the catalyst II is at least one of a sulfonic acid functionalized ionic liquid catalyst and p-toluenesulfonic acid.

[0009] As a preferred technical solution of the present invention, in step S4, the photoinitiator includes any one of azobisisobutyronitrile, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, azobisisoheptanenitrile, dimethylphenylphosphine, benzoin dimethyl ether, and benzoyl peroxide.

[0010] As a preferred technical solution of the present invention, in step S4, the ultraviolet irradiation condition is to apply 150-200W / m 2 , ultraviolet irradiation with a wavelength of 250-420nm for 40-60min.

[0011] The plasticizer for AI sensor is prepared by the above preparation method.

[0012] Beneficial effects of the present invention: The present invention introduces a multi-branched structure during the preparation of the plasticizer to obtain a branched plasticizer material, which is applied to PVC resin to improve the flexibility and processing performance of the material. Furthermore, the introduction of the cyclic rigid structure can better act on the polar structure of the molecular chain during the plasticization of PVC, thereby improving the stability of the plasticizer while maintaining good flexibility of the material. Furthermore, by performing epoxidation modification during the preparation of the plasticizer, the compatibility between the plasticizer and the PVC resin is improved. DETAILED DESCRIPTION

[0013] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0014] Example 1 A method for preparing a plasticizer for an AI sensor comprises the following steps: S1. Mix 1 mol of triethyl citrate and 1 mol of diethylene ketone, add 0.27 g of triethylamine, stir at 50° C. for 1 hour, filter with suction, extract the product by column chromatography using a dichloromethane and ethyl acetate eluent with a volume ratio of 30:1, and then purify the resulting liquid by rotary evaporation to obtain material A; diethylene ketone reacts with the active hydrogen of the hydroxyl group of the citrate derivative with a branched structure to generate material A containing an acetyl functional group; S2. 1 mol of ricinoleic acid and 1 mol of material A were mixed, heated and stirred at 130° C. for 2 h in a nitrogen atmosphere to obtain a crude product. The crude product was thoroughly washed with a 5% by mass NaHCO3 solution and deionized water until neutral. The upper layer of the oily crude product was then separated and subjected to reduced pressure distillation on a rotary evaporator at -0.1 MPa and 80° C. for 10 h to obtain material B. Material A with an introduced acetyl functional group underwent a nucleophilic substitution reaction with the hydroxyl group in ricinoleic acid to obtain a modified ricinoleic acid material B, thereby introducing a branched structure into material B. S3. 1.6 mol of material B, 0.9 mol of 2-(4-propylcyclohexyl)-1,3-propanediol, 2.45 g of 1-propyl-3-methylimidazole p-toluenesulfonate, and 10 mL of toluene were mixed, and the mixture was stirred at 120° C. under condensation reflux for 5 h in a nitrogen atmosphere. After the product was cooled to room temperature, the product was washed three times with a 5% by mass NaHCO3 solution until the pH was neutral, and then washed three times with deionized water. The product was purified by liquid separation and vacuum distillation to obtain material C; the carboxyl group contained in ricinoleic acid was esterified with the hydroxyl group of 2-(4-propylcyclohexyl)-1,3-propanediol, thereby introducing material C containing a cyclic structure; S4. In a nitrogen atmosphere, take 10 g of material C into a quartz flask, add 68 g of 2-mercaptoethanol and 5 mg of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and apply 150 W / m 2 , irradiating with ultraviolet light of 300 nm for 40 min to obtain material D through a click reaction between thiol and carbon-carbon double bond; S5. Take 10 g of material D, 22 g of epichlorohydrin and 0.3 g of tetrabutylammonium bromide, mix them, reflux and stir at 65 ° C for 4 h, cool to 50 ° C, add 40 mL of 50% sodium hydroxide solution, continue stirring for 3 h, carry out epoxidation reaction, centrifuge, wash the liquid phase to neutrality, and distill the organic phase under reduced pressure to obtain the plasticizer.

[0015] Example 2 A method for preparing a plasticizer for an AI sensor comprises the following steps: S1. Mix 1 mol of tributyl citrate and 1 mol of diketene, add 0.36 g of triethylamine, stir at 55°C for 1.5 h, filter, and extract the product by column chromatography using a dichloromethane and ethyl acetate eluent with a volume ratio of 30:1. Then, purify the obtained liquid by rotary evaporation to obtain material A; S2. Mix 1 mol of ricinoleic acid and 1 mol of material A, heat and stir at 135°C in a nitrogen atmosphere for 3 h to obtain a crude product. The crude product was thoroughly washed with a 5% by mass NaHCO3 solution and deionized water until neutral. The upper layer of the oily crude product was separated and vacuum distilled on a rotary evaporator at -0.1 MPa and 80°C for 11 h to obtain material B. S3. Take 1.6 mol of material B, 0.9 mol of 2-(4-propylcyclohexyl)-1,3-propanediol, 2.45 g of 1-propyl-3-methylimidazole p-toluenesulfonate, and 10 mL of toluene, mix them, reflux under condensation at 120°C in a nitrogen atmosphere, and stir for 6 h. After the product is cooled to room temperature, wash the product with a 5% by mass NaHCO3 solution 5 times until the pH is neutral, then wash it with deionized water 5 times, and purify it by separation and vacuum distillation to obtain material C; S4. In a nitrogen atmosphere, take 10 g of material C into a quartz flask, add 68 g of 2-mercaptoethanol and 5 mg of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and apply 180 W / m 2 , ultraviolet irradiation with a wavelength of 400 nm for 60 min to obtain material D; S5. Take 10 g of material D, 22 g of epichlorohydrin and 0.3 g of tetrabutylammonium bromide, mix them, reflux and stir at 70 ° C for 5 h, cool to 50 ° C, add 40 mL of 50% sodium hydroxide solution, continue stirring for 3.5 h, centrifuge and separate, take the liquid phase and wash it until neutral, and distill the organic phase under reduced pressure to obtain the plasticizer.

[0016] Example 3 A method for preparing a plasticizer for an AI sensor comprises the following steps: S1. Mix 1 mol of tripropyl citrate and 1 mol of diketene, add 0.31 g of triethylamine, stir at 60°C for 2 h, filter, and extract the product by column chromatography using a dichloromethane and ethyl acetate eluent with a volume ratio of 30:1. Then, purify the obtained liquid by rotary evaporation to obtain material A. S2. Mix 1 mol of ricinoleic acid and 1 mol of material A, heat and stir at 140°C in a nitrogen atmosphere for 4 h to obtain a crude product. The crude product was thoroughly washed with a 5% by mass NaHCO3 solution and deionized water until neutral. The upper layer of the oily crude product was separated and vacuum distilled on a rotary evaporator at -0.1 MPa and 80°C for 12 h to obtain material B. S3. Take 1.6 mol of material B, 0.9 mol of 2-(4-propylcyclohexyl)-1,3-propanediol, 2.45 g of 1-propyl-3-methylimidazole p-toluenesulfonate, and 10 mL of toluene, mix them, reflux under condensation at 120°C in a nitrogen atmosphere, and stir for 7 h. After the product is cooled to room temperature, wash the product with 5% by mass NaHCO3 solution 5 times until the pH is neutral, then wash it with deionized water 5 times, and purify it by separation and vacuum distillation to obtain material C; S4. In a nitrogen atmosphere, take 10 g of material C into a quartz flask, add 68 g of 2-mercaptoethanol and 5 mg of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and apply 200 W / m 2 , ultraviolet irradiation with a wavelength of 420 nm for 50 min to obtain material D; S5. Take 10 g of material D, 22 g of epichlorohydrin and 0.3 g of tetrabutylammonium bromide, mix them, reflux and stir at 75 ° C for 6 h, cool to 50 ° C, add 40 mL of 50% sodium hydroxide solution, continue stirring for 4 h, centrifuge and separate, take the liquid phase and wash it until neutral, and distill the organic phase under reduced pressure to obtain the plasticizer.

[0017] Comparative Example 1 The difference from Example 2 is that the preparation process of step S1 is cancelled and acetic anhydride is used instead of material A.

[0018] Comparative Example 2 The difference from Example 2 is that in the preparation process of step S3, 1,4-dihydroxybutane is used instead of 2-(4-propylcyclohexyl)-1,3-propanediol.

[0019] Comparative Example 3 The difference from Example 2 is that the preparation process of steps S4 and S5 is eliminated, and the material C obtained in step S3 is used as a plasticizer.

[0020] Comparative Example 4 The difference from Example 2 is that in the preparation process of step S3, benzyl alcohol is used instead of 2-(4-propylcyclohexyl)-1,3-propanediol.

[0021] Performance Testing 5 parts by weight of the plasticizers prepared in Examples 1-3 and Comparative Examples 1-3, 90 parts by weight of PVC resin, and 8 parts by weight of calcium stearate were added to a high-speed mixer. After uniform mixing, the mixture was melt-blended in a twin-screw extruder and extruded into pellets. The resulting pellets were dried at 80°C for 10 hours and then injection-molded into standard bars. Performance testing was performed. The test results are shown in Table 1 below.

[0022] Table 1

[0023] As can be seen from Table 1, the plasticizers prepared in Examples 1 to 3 of the present application are used for PVC resin processing to obtain materials with good flexibility and processability, low mobility, and excellent durability; in Comparative Example 1, no branched structure is introduced, resulting in a decrease in the flexibility of the prepared PVC material and an increase in the mobility of the plasticizer; in Comparative Example 2, a flexible carbon chain is used to replace 2-(4-propylcyclohexyl)-1,3-propanediol, which increases the flexibility of the prepared PVC material, but significantly increases the mobility of the plasticizer; in Comparative Example 3, no epoxidation modification is performed, resulting in a deterioration in the compatibility between the prepared plasticizer and PVC, resulting in a decrease in the performance of the prepared PVC material; in Comparative Example 4, a rigid benzene ring is used to replace 2-(4-propylcyclohexyl)-1,3-propanediol, which reduces the mobility of the prepared plasticizer, but causes the flexibility of the prepared PVC material to deteriorate.

[0024] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a plasticizer for AI sensor, characterized in that: The following steps are involved: S1. Mixing a citrate derivative and diketene under the catalytic action of catalyst I to obtain material A; S2, taking ricinoleic acid and material A and mixing them to obtain material B; S3, taking the material B and the cyclohexanol derivative and mixing them under the catalytic action of catalyst II to obtain material C; S4, mixing the material C and 2-mercaptoethanol, adding a photoinitiator, and preparing the material D under ultraviolet irradiation conditions; S5. Mix the material D, epichlorohydrin and tetrabutylammonium bromide, heat under reflux with stirring, cool, add sodium hydroxide solution, continue stirring, centrifuge and separate the liquid phase to obtain the plasticizer.

2. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S1, the catalyst I includes any one of concentrated sulfuric acid, triethylamine and sodium methoxide.

3. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S1, the citrate derivative includes any one of trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, and tripentyl citrate.

4. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S3, the cyclohexanol derivative includes any one of 1,4-cyclohexanediol, cis-cyclohexylcyclohexanol, 3-(cyclohexyloxy)propan-1-ol, and 2-(4-propylcyclohexyl)-1,3-propanediol.

5. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S3, the catalyst II is at least one of a sulfonic acid functionalized ionic liquid catalyst and p-toluenesulfonic acid.

6. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S4, the photoinitiator includes any one of azobisisobutyronitrile, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, azobisisoheptanenitrile, dimethylphenylphosphine, benzoin dimethyl ether, and benzoyl peroxide.

7. The method for preparing a plasticizer for an AI sensor according to claim 1, characterized in that: In step S4, the ultraviolet irradiation condition is to apply 150-200W / m 2 , ultraviolet irradiation with a wavelength of 250-420nm for 40-60min.

8. A plasticizer for AI-based sensors prepared by the preparation method according to any one of claims 1 to 7.

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