CN118240390A - Plasticizer and preparation method thereof - Google Patents

Plasticizer and preparation method thereof Download PDF

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Publication number
CN118240390A
CN118240390A CN202410462792.8A CN202410462792A CN118240390A CN 118240390 A CN118240390 A CN 118240390A CN 202410462792 A CN202410462792 A CN 202410462792A CN 118240390 A CN118240390 A CN 118240390A
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China
Prior art keywords
oil
plasticizer
cardanol
citric acid
rubber
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Pending
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CN202410462792.8A
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Chinese (zh)
Inventor
张靖晨
傅秀成
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Qingdao Fineking New Materials Co ltd
Qingdao Fihonor Chemical Science & Technology Co ltd
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Qingdao Fineking New Materials Co ltd
Qingdao Fihonor Chemical Science & Technology Co ltd
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Priority to CN202410462792.8A priority Critical patent/CN118240390A/en
Publication of CN118240390A publication Critical patent/CN118240390A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515Three-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a plasticizer and a preparation method, wherein the plasticizer comprises paraffin oil and biological base oil, and the structural formula of the biological base oil is as follows: Wherein R 1、R2、R3 is C 5H31‑n or respectively

Description

Plasticizer and preparation method thereof
Technical Field
The invention relates to the technical field of rubber additives, in particular to a plasticizer and a preparation method thereof.
Background
Petroleum-based plasticizers are one of the most used plasticizers in rubber processing, and have the characteristics of good plasticizing effect and low cost, but petroleum-based plasticizers are derived from petroleum refining processes, on one hand, raw material sources are limited, a large amount of energy sources are required for production, and on the other hand, petroleum-based plasticizers have the problem of environmental pollution and potential carcinogenic risks, so that the production and use of petroleum-based plasticizers are correspondingly limited. And bio-based plasticizers are increasingly receiving attention.
The cashew nut oil is a product obtained in the processing process of cashew nuts, has wide sources and simple extraction, the main component of the cashew nut oil is cardanol, and the cardanol can be used as a bio-based plasticizer to be applied to the processing process of rubber, but because the cashew nut oil only contains one benzene ring, the aromatic hydrocarbon content is low, and the affinity with the rubber is poor, further improvement and development are needed.
Disclosure of Invention
Aiming at various defects in the prior art, in order to solve the problems, a plasticizer and a preparation method are provided, and the following technical scheme is provided:
a plasticizer comprising a paraffinic oil and a biobased oil having the structural formula:
Wherein R 1、R2、R3 is C 5H31-n or respectively Where n=0, 2,4 or 6.
Further, R 1、R2 is eachR 3 is C 15H31-n.
Further, the paraffin oil accounts for 30-60% and the biological base oil accounts for 40-70% in percentage by mass.
Further, the paraffin oil is 50% and the biological base oil is 50% in terms of mass percent.
In addition, the invention also provides a preparation method of the plasticizer, which comprises the following steps: mixing paraffin oil and biological base oil under stirring.
Further, the biological base oil is prepared as follows: dissolving citric acid in ethanol or chloroform, adding a catalyst and cardanol into the solution dissolved with the citric acid for esterification reaction to obtain a product between cardanol and citric acid, and reacting the product between cardanol and citric acid with an oxidant in a solvent to obtain the biological base oil.
Further, the molar usage ratio of the citric acid to the cardanol is 1:2-3, and the molar usage ratio of the cardanol to the oxidant is 3:1-3.
Further, the catalyst is copper sulfate, aluminum sulfate or ferric trichloride.
Further, the oxidant is peroxybenzoic acid or hydrogen peroxide.
Further, the reaction temperature of the product between cardanol and citric acid and the oxidant in the solvent is 60-70 ℃, and the reaction time of the product between cardanol and citric acid and the oxidant in the solvent is 2-5h.
By adopting the technical scheme, the invention has the beneficial technical effects that:
1. the novel plasticizer is prepared by combining paraffin oil and bio-based oil, has good compatibility with rubber, and can improve the comprehensive performance of the rubber.
2. The plasticizer provided by the invention contains partial biological base oil, can replace the dosage of partial paraffin oil, and contains three benzene rings, so that the high aromatic hydrocarbon content of the plasticizer is improved, and the compatibility and affinity of the biological base plasticizer and rubber are improved; the biological base oil also contains epoxy groups and alkyl chains containing carbon-carbon double bonds, so that the compatibility of the plasticizer and rubber is further improved, and meanwhile, the processability and mechanical properties are improved, and the biological base oil can replace part of petroleum-based plasticizers to be applied to the rubber processing process.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and based on the embodiments of the present application, other similar embodiments obtained by those skilled in the art without making creative efforts should fall within the protection scope of the present application.
A plasticizer comprising a paraffinic oil and a biobased oil having the structural formula:
Wherein R 1、R2、R3 is C 5H31-n or respectively Where n=0, 2,4 or 6.
The plasticizer disclosed by the invention has paraffin oil and biological base oil, has better compatibility with rubber, and can improve the comprehensive performance of the rubber. The biological base oil has benzene ring, epoxy group and alkyl chain containing carbon-carbon double bond, and the three structures simultaneously have synergistic effect, so that the compatibility of the plasticizer and rubber is improved, the processability and the mechanical property are improved, and the biological base oil can be mixed with paraffin oil to be jointly applied to the rubber processing process.
First, the effect of R 1、R2 and R 3 on plasticizers was investigated
Example 1
The paraffin oil is 50% by mass, and the biological base oil is 50% by mass. Mixing paraffin oil with biological base oil to obtain plasticizer. Wherein R 1 and R 2 of the bio-base oil are eachR 3 is C 15H31-n. The plasticizer is taken as a plasticizer of natural rubber, and the specific formula is as follows: 100 parts of natural rubber, 330 parts of carbon black N, 10 parts of plasticizer, 1.5 parts of antioxidant 4010NA, 5 parts of zinc oxide, 2 parts of stearic acid, 2.2 parts of sulfur and 0.2 part of accelerator TT. The natural rubber sizing material is prepared after mixing and vulcanizing according to the formula.
Example 2
The paraffin oil is 50% by mass, and the biological base oil is 50% by mass. Mixing paraffin oil with biological base oil to obtain plasticizer. Wherein R 1 of the bio-based oil isR 2 and R3 are each C 15H31-n. The plasticizer is taken as a plasticizer of natural rubber, and the specific formula is as follows: 100 parts of natural rubber, 330 parts of carbon black N, 10 parts of plasticizer, 1.5 parts of antioxidant 4010NA, 5 parts of zinc oxide, 2 parts of stearic acid, 2.2 parts of sulfur and 0.2 part of accelerator TT. The natural rubber sizing material is prepared after mixing and vulcanizing according to the formula.
Example 3
The paraffin oil is 50% by mass, and the biological base oil is 50% by mass. Mixing paraffin oil with biological base oil to obtain plasticizer. Wherein R 1、R2 and R 3 of the bio-base oil are eachThe plasticizer is taken as a plasticizer of natural rubber, and the specific formula is as follows: 100 parts of natural rubber, 330 parts of carbon black N, 10 parts of plasticizer, 1.5 parts of antioxidant 4010NA, 5 parts of zinc oxide, 2 parts of stearic acid, 2.2 parts of sulfur and 0.2 part of accelerator TT. The natural rubber sizing material is prepared after mixing and vulcanizing according to the formula.
Comparative example 1
Paraffin oil is used as a plasticizer of natural rubber, and the specific formula is as follows: 100 parts of natural rubber, 330 parts of carbon black N, 10 parts of plasticizer, 4010NA1.5 parts of anti-aging agent, 5 parts of zinc oxide, 2 parts of stearic acid, 2.2 parts of sulfur and 0.2 part of accelerator TT. The natural rubber sizing material is prepared after mixing and vulcanizing according to the formula.
The natural rubber compounds prepared in examples 1 to 3 and comparative example 1 were subjected to various performance tests, and specific test results are shown in tables 1 and 2 below.
TABLE 1 mechanical test results of Natural rubber Compounds prepared in examples 1 to 3 and comparative example 1
TABLE 2 processability and rheology test results of the styrene-butadiene rubber compounds prepared in examples 1 to 3 and comparative example 1
The benzene ring, alkyl chain and epoxy group in the plasticizer are all key factors affecting the processing and performance of rubber, and as can be seen from table 1 above, the difference between R 1、R2 and R 3 makes the obtained rubber material have differences in various performances. In particular, the invention proceeds to the next investigation of the structures of R 1、R2 and R 3 when R 1、R2 is respectivelyR 3 is C 15H31-n, namely, when three benzene rings are provided, the epoxy group and an alkyl chain containing carbon-carbon double bonds are combined to act together, the mechanical property and the wear resistance are optimal, the tensile strength is 25MPa, and the elongation at break is 471 percent as shown in the table 1. When R 1 is/>R 2 and R 3 are C 15H31-n respectively, the epoxy structure is relatively reduced compared with that of the epoxy structure of the example 1, the carbon-carbon double bond is increased, at the moment, the compatibility of the bio-based plasticizer and the rubber is better, but the processability is poor, the scorch time T10 is shortened, and the processability of the rubber is reduced due to the too short scorch time. When R 1、R2 and R 3 are each/>, respectively, of a bio-based oil in a plasticizerAt this time, the bio-base oil does not contain alkyl chain containing carbon-carbon double bond, the compatibility of the plasticizer and the rubber is poor, but the processability is good, therefore, according to the test results of tables 1 and 2, it can be seen that the difference between R 1、R2 and R 3, the prepared bio-base plasticizer has different effects on the processability and mechanical properties of the rubber compound, and when R 1、R2 is respectively/>When R 3 is C 15H31-n, three benzene rings are mutually cooperated with epoxy groups and an alkyl chain containing carbon-carbon double bonds, the processing performance of rubber is improved due to the existence of the benzene ring structure, the influence of the alkyl chain containing carbon-carbon double bonds on the physical and mechanical properties of rubber is better, and the proper epoxy groups further improve the processing performance, so that the scorching time is prolonged.
In addition, in comparative example 1, paraffin oil was used as a plasticizer, and it can be seen from the data of tables 1 and 2 that the combination of paraffin oil and bio-base oil can further improve the compatibility with rubber than the mere paraffin oil, and simultaneously, the processability and mechanical properties can be improved correspondingly.
In particular, the ratio of paraffinic oil to bio-based oil is also an important factor affecting the effectiveness of the plasticizer. The paraffin oil accounts for 30-60% and the biological base oil accounts for 40-70% in percentage by mass. In the proportion range, the biological base oil can supplement the defect of low arene content of paraffin oil and has better compatibility with rubber. Experiments show that when the content of benzene ring is lower than 30%, the advantages of the biological base oil can not be fully exerted, when the content of the biological base oil exceeds 70%, the dosage of paraffin oil is reduced, the biological base oil and the paraffin oil can not be fully cooperated, and the effect of the plasticizer in rubber is lower than that of the biological base oil by 50% and the paraffin oil by 50%.
The invention also provides a preparation method of the plasticizer, which comprises the following steps: mixing paraffin oil and biological base oil under stirring.
Wherein, the preparation flow of the biological base oil is as follows: dissolving citric acid in ethanol or chloroform, adding a catalyst and cardanol into the solution dissolved with the citric acid for esterification reaction to obtain a product between cardanol and citric acid, and reacting the product between cardanol and citric acid with an oxidant in a solvent to obtain the bio-based plasticizer. Specifically, the molar ratio of cardanol to oxidant is 3:1-3, wherein the oxidant is peroxybenzoic acid or hydrogen peroxide.
For example, when the molar amount of the oxidizing agent relative to cardanol is excessive, R 1、R2 and R 3 are eachWhen the molar ratio of the oxidant to the cardanol is 1: at 3, R 1 is/>R 2 and R 3 are each C 15H31-n. When the molar ratio of the oxidant to the cardanol is 2: at 3, R 1 and R 2 are/>R 3 is C 15H31-n.
1.92G of citric acid was dissolved in 100ml of chloroform, and then 0.0192g of iron trichloride and 6.05g of cardanol were added as catalysts, and reacted at 40℃for 8 hours to obtain a product between cardanol and citric acid. The product between cardanol and citric acid and hydrogen peroxide were reacted in methylene chloride at a reaction temperature of 50 c for 5 hours to obtain a bio-based oil as in example 1, with an amount of hydrogen peroxide of 0.45g.
1.92G of citric acid was dissolved in 100ml of chloroform, and then 0.0192g of iron trichloride and 6.05g of cardanol were added as catalysts, and reacted at 40℃for 8 hours to obtain a product between cardanol and citric acid. The product between cardanol and citric acid and hydrogen peroxide were reacted in methylene chloride at a reaction temperature of 50 c for 5 hours to give a biobased oil as in example 2, with hydrogen peroxide in an amount of 0.227g.
1.92G of citric acid was dissolved in 100ml of chloroform, and then 0.0192g of iron trichloride and 6.05g of cardanol were added as catalysts, and reacted at 40℃for 8 hours to obtain a product between cardanol and citric acid. The product between cardanol and citric acid and hydrogen peroxide were reacted in methylene chloride at a reaction temperature of 50 c for 5 hours to give a biobased oil as in example 3, with an amount of hydrogen peroxide of 0.68g.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (10)

1. A plasticizer comprising a paraffinic oil and a biobased oil having the following structural formula:
Wherein R 1、R2、R3 is C 5H31-n or respectively Where n=0, 2,4 or 6.
2. A plasticiser according to claim 1, wherein R 1 and R 2 are eachR 3 is C 15H31-n.
3. A plasticizer according to claim 1, wherein the paraffinic oil is 30-60% and the biobased oil is 40-70% by mass.
4. A plasticizer according to claim 3, wherein the paraffinic oil is 50% and the bio-based oil is 50% by mass.
5. A process for the preparation of a plasticiser according to any one of claims 1 to 4, comprising the steps of: mixing paraffin oil and biological base oil under stirring.
6. The method for producing a plasticizer according to claim 5 wherein the bio-based oil is produced by the following steps: dissolving citric acid in ethanol or chloroform, adding a catalyst and cardanol into the solution dissolved with the citric acid for esterification reaction to obtain a product between cardanol and citric acid, and reacting the product between cardanol and citric acid with an oxidant in a solvent to obtain the biological base oil.
7. The method for preparing the plasticizer according to claim 6, wherein the molar ratio of the citric acid to the cardanol is 1:2-3, and the molar ratio of the cardanol to the oxidant is 3:1-3.
8. The method for preparing a plasticizer according to claim 6, wherein the catalyst is copper sulfate, aluminum sulfate or ferric chloride.
9. The method of claim 6, wherein the oxidizing agent is benzoic acid peroxide or hydrogen peroxide.
10. The method for preparing a plasticizer according to claim 6, wherein the reaction temperature of the product between cardanol and citric acid and the oxidizing agent in the solvent is 60-70 ℃, and the reaction time of the product between cardanol and citric acid and the oxidizing agent in the solvent is 2-5 hours.
CN202410462792.8A 2024-04-17 2024-04-17 Plasticizer and preparation method thereof Pending CN118240390A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410462792.8A CN118240390A (en) 2024-04-17 2024-04-17 Plasticizer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410462792.8A CN118240390A (en) 2024-04-17 2024-04-17 Plasticizer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN118240390A true CN118240390A (en) 2024-06-25

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Application Number Title Priority Date Filing Date
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Country Link
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