CN113817223A - Aconitate polyvinyl chloride plasticizer and preparation method and application thereof - Google Patents
Aconitate polyvinyl chloride plasticizer and preparation method and application thereof Download PDFInfo
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- CN113817223A CN113817223A CN202111002979.2A CN202111002979A CN113817223A CN 113817223 A CN113817223 A CN 113817223A CN 202111002979 A CN202111002979 A CN 202111002979A CN 113817223 A CN113817223 A CN 113817223A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/604—Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
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Abstract
An aconitate polyvinyl chloride plasticizer and its preparation method and application are provided. The invention belongs to the field of polyvinyl chloride plasticizers and preparation thereof. The invention aims to solve the technical problem that the plasticizing effect of the existing environment-friendly plasticizer is limited. The invention takes trans-aconitic acid and the like as raw materials to prepare the aconitate polyvinyl chloride plasticizer by a one-step method. The aconitate and the polyvinyl chloride have good compatibility, can effectively reduce the strong interaction between PVC polar molecular chains, greatly reduce the tensile modulus and the glass transition temperature, improve the elongation at break of the PVC, and have good volatility and solvent extraction resistance.
Description
Technical Field
The invention belongs to the field of polyvinyl chloride plasticizers and preparation thereof, and particularly relates to an aconitate polyvinyl chloride plasticizer and a preparation method and application thereof.
Background
The plasticizer is an important modification auxiliary agent widely applied to rubber and plastic products such as polyvinyl chloride (PVC) resin and the like, and can reduce Van der Waals force among polymer molecules, increase mobility and plasticity of molecular chains, and reduce crystallinity, so that mechanical properties and processing properties of the plastic are enhanced. The functional difference of the product can be achieved by controlling the kind and added amount of the plasticizer, so that the desired material having a specific functionality, usually the added amount of the plasticizer is in the range of 10-70%.
The phthalate of petrochemical source is the most common plasticizer at present, and accounts for more than 85 percent of the market. However, with long-term use, the serious environmental and health hazards of phthalate plasticizers have been continuously proven, which has led to significant safety challenges for the PVC industry, and has received widespread government, industry and academia. Strict regulatory restrictions on the use of phthalate plasticizers have been made in countries around the world, and development of green and environmentally friendly plasticizers has received much attention from research and industry.
Several bio-based environment-friendly plasticizers such as citrate esters and epoxy vegetable oil esters are developed successively, but compared with the traditional plasticizer with excellent plasticizing effect and low production cost, the bio-based environment-friendly plasticizer still lacks competitiveness, can be used only in a few special fields limited by the admittance of the traditional plasticizer, and cannot be widely replaced.
Therefore, the development of a novel bio-based plasticizer which has excellent performance, is safe and environment-friendly and can be widely replaced is worthy of attention, and the novel bio-based plasticizer has important economic value and social benefit for solving the safety problem of the plasticizer facing PVC and other rubber and plastic industries.
Disclosure of Invention
The invention aims to solve the technical problem that the plasticizing effect of the existing environment-friendly plasticizer is limited, and provides an aconitate polyvinyl chloride plasticizer and a preparation method and application thereof.
The general structural formula of the aconitate polyvinyl chloride plasticizer is shown in the specification
Wherein R is alkyl, cycloalkyl or cycloalkylalkyl with the carbon atom number more than or equal to 1.
Further defined, the cycloalkyl group is an unsubstituted cycloalkyl group or an alkyl-substituted cycloalkyl group.
Further defined, the cycloalkylalkyl is unsubstituted cycloalkylalkyl or alkyl-substituted cycloalkylalkyl.
Further defined, the alkyl substituent in said alkyl-substituted cycloalkylalkyl is ring-substituted or linear-substituted.
The preparation method of the aconitate polyvinyl chloride plasticizer comprises the following steps:
step 1: adding trans-aconitic acid into an alcohol solvent, stirring for dissolving, adding an acid catalyst after the trans-aconitic acid is completely dissolved, and stirring for reacting at high temperature to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing the aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and then performing vacuum pumping under a heating state to obtain the aconitate polyvinyl chloride plasticizer.
Further, in the step 1, the alcohol solvent is an alkyl alcohol.
Further defined, the alkyl alcohol is methanol, ethanol, propanol, n-butanol, pentanol, hexanol, heptanol, octanol, nonanol, isobutanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-ethoxyethanol, 4-phenylbutanol, 2-butoxyethanol, cyclohexanol, cyclohexylmethanol, 2-ethylhexanol, or benzyl alcohol.
Further, in the step 1, the acidic catalyst is an inorganic acid, an organic acid or an inorganic acid salt.
Further limited, the inorganic acid is sulfuric acid, phosphoric acid, boric acid.
Further defined, the organic acid is p-toluenesulfonic acid.
Further limited, the inorganic acid salt is ferric chloride, ferric sulfate, ferrous sulfate, zinc sulfate or cerium sulfate.
Further limiting, the ratio of the amount of trans-aconitic acid to alcoholic solvent in step 1 is 1: (3-9).
Further limiting, the ratio of the amounts of the acidic catalyst and the trans-aconitic acid in step 1 is 1: (2-100).
Further limiting, the dissolution is carried out by stirring at 100 ℃ in step 1.
Further limiting, the temperature of the stirring reaction at the high temperature in the step 1 is 100-210 ℃.
Further, the step 2 of vacuumizing under a heating state means vacuumizing to 0.03mbar to 0.1mbar at a temperature of 40 ℃ to 60 ℃.
The aconitate polyvinyl chloride plasticizer is used for plasticizing polyvinyl chloride.
The cycloalkylalkyl group in the present invention means a cycloalkyl-substituted alkyl group.
The reaction equation of the preparation method of the invention is as follows:
compared with the prior art, the invention has the following remarkable effects:
1) the aconitate of the invention has good compatibility with polyvinyl chloride, can effectively reduce the strong interaction between PVC polar molecular chains, greatly reduces the tensile modulus and the glass transition temperature, improves the elongation at break of PVC, and has good volatility and solvent extraction resistance.
2) The substituent in the aconitate provided by the invention can be effectively inserted between PVC molecular chains, the interaction of the molecular chains is reduced, the plasticity and the extraction resistance of the material are increased, wherein the insertion effect is more obvious and the plasticity and the extraction resistance of the material are higher along with the increase of a straight chain; meanwhile, the naphthenic base and the naphthenic alkyl with similar carbon number have more obvious insertion effect due to larger steric hindrance, and the material has better plasticity.
3) The polyvinyl chloride plasticizer provided by the invention has the characteristics of simple and convenient preparation method, simple production, environmental protection and convenient construction.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a plasticized PVC tensile rupture specimen using the plasticizer of example 1; FIG. 2 is an enlarged view of FIG. 1 at area A; FIG. 3 is an enlarged view of FIG. 1 at area B;
FIG. 4 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fractured sample using the plasticizer of example 2; FIG. 5 is an enlarged view of FIG. 4 at area A; FIG. 6 is an enlarged view of FIG. 4 at area B;
FIG. 7 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fractured sample using the plasticizer of example 3; FIG. 8 is an enlarged view of FIG. 7 at area A; FIG. 9 is an enlarged view of FIG. 7 at area B;
FIG. 10 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fractured sample using the plasticizer of example 4; FIG. 11 is an enlarged view of FIG. 10 at area A; FIG. 12 is an enlarged view of FIG. 10 at area B;
FIG. 13 is a scanning electron micrograph of a cross-section of a plasticized PVC tensile fractured sample using the plasticizer of example 5; FIG. 14 is an enlarged view of FIG. 13 at area A; FIG. 15 is an enlarged view of FIG. 13 at area B;
FIG. 16 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fractured sample using the plasticizer of example 6; FIG. 17 is an enlarged view of FIG. 16 at area A; FIG. 18 is an enlarged view of FIG. 16 at area B;
FIG. 19 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fractured sample using the plasticizer of example 7;
FIG. 20 is a scanning electron microscope picture of a cross section of a plasticized PVC tensile fracture sample using epoxidized soybean oil; FIG. 21 is an enlarged view of FIG. 20 at area A; FIG. 22 is an enlarged view of FIG. 20 at area B;
FIG. 23 is a scanning electron micrograph of a cross section of a plasticized PVC tensile fracture sample using acetyl tributyl citrate; FIG. 24 is an enlarged view of FIG. 23 at area A; FIG. 25 is an enlarged view of FIG. 23 at area B;
FIG. 26 is a scanning electron micrograph of a cross-section of a plasticized PVC tensile fracture sample using DOP; FIG. 27 is an enlarged view of FIG. 26 at area A; fig. 28 is an enlarged view of fig. 26 at region B.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The raw material aconitate-removing plasticizers used in the following examples are all commercially available products.
Example 1: the structural formula of an aconitate polyvinyl chloride plasticizer (triethyl aconitate) in the example is shown in the specification
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 1 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 28.6g of ethanol, stirring and dissolving at 100 ℃, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.1mbar at 40 deg.C to obtain triethyl aconitate, i.e. the aconitate polyvinyl chloride plasticizer.
Example 2: the structural formula of an aconitate polyvinyl chloride plasticizer (tributyl aconitate) in this example is
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 2 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 45.8g of n-butanol, stirring and dissolving at 100 ℃, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.1mbar at 40 deg.C to obtain tributyl aconitate, i.e. the aconitate polyvinyl chloride plasticizer.
Example 3: the structural formula of an aconitate polyvinyl chloride plasticizer (triamyl aconitate) in the example is shown in the specification
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 3 was carried out as follows:
step 1: adding 5g trans-aconitic acid into 54.6g pentanol, stirring and dissolving at 100 ℃, adding 3.24g concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.07mbar at 50 deg.C to obtain tripentyl aconitate, i.e. aconitate polyvinyl chloride plasticizer.
Example 4: the structural formula of an aconitate polyvinyl chloride plasticizer (aconitate trihexyl) of this example is
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 4 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 63.2g of hexanol, stirring and dissolving at 100 ℃, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.05mbar at 60 deg.C to obtain trihexyl aconitate, i.e. the aconitate polyvinyl chloride plasticizer.
Example 5: the structural formula of an aconitate polyvinyl chloride plasticizer (trioctyl aconitate) in this example is
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 5 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 80.5g of n-octanol, stirring at 100 ℃ to dissolve, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, stirring at 140 ℃ to react, and obtaining a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.05mbar at 60 ℃ to obtain trioctyl aconitate, namely the aconitate polyvinyl chloride plasticizer.
Example 6: the structural formula of an aconitate polychloroethylene plasticizer (aconitic acid tricyclohexyl) in this example is
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 6 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 61.9g of cyclohexanol, stirring and dissolving at 100 ℃, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.05mbar at 60 deg.C to obtain tricyclohexyl aconitate, i.e. aconitate polyvinyl chloride plasticizer.
Example 7: the structural formula of an aconitate polyvinyl chloride plasticizer (tricyclohexylmethyl aconitate) in this example is
The method of preparing the aconitate-based polyvinyl chloride plasticizer of example 7 was carried out as follows:
step 1: adding 5g of trans-aconitic acid into 70.6g of cyclohexylmethanol, stirring and dissolving at 100 ℃, adding 3.24g of concentrated sulfuric acid after the trans-aconitic acid is completely dissolved, and stirring and reacting at 140 ℃ to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and vacuumizing to 0.05mbar at 60 deg.C to obtain tricyclohexylmethyl aconitate, i.e. the aconitate polyvinyl chloride plasticizer.
Example 8: 100 parts of PVC-1300 powder, 3 parts of stabilizer (methyl tin mercaptide) and 30 parts of aconitate polyvinyl chloride plasticizer of examples 1-7 are uniformly mixed and then added into an open mill for mixing, the roll temperature of the open mill is not more than 165 ℃, the rotating speed of a front roll is 19.5rpm, the rotating speed of a rear roll is 16.0rpm, the initial roll moment is 0.5mm, the roll moment is increased to 1.0mm after the roll is wrapped, the sheet is discharged through air, the whole mixing process is not more than 3.0min, and the plasticized PVC is obtained after mixing.
Comparative example 1: this example differs from example 8 in that: the plasticizer was replaced with epoxidized soybean oil.
Comparative example 2: this example differs from example 8 in that: the plasticizer was replaced with acetyl tributyl citrate.
Comparative example 3: this example differs from example 8 in that: the plasticizer was replaced with dioctyl phthalate DOP.
Test one: the following performance tests were performed on the plasticized PVC obtained in example 8 and comparative examples 1-3, and a test sample was prepared before the tests, and the specific procedures were as follows: the method comprises the steps of manufacturing a test sample by adopting a mould pressing method, folding and placing a mixed plasticized PVC sample in a mould of 200 x 2.0mm, paving aluminum foil paper on the upper part and the lower part of the mould to facilitate demoulding, setting the temperature of a flat vulcanizing instrument to be 165 ℃, setting the pressure to be 6.0MPa, preheating for 5.0min, hot-pressing for 5.0min (exhausting for five times), and demoulding after cold pressing for 5.0min to obtain the test sample.
The tensile property test: firstly, a test sample is made into dumbbell type standard sample bars by a rotary cutting machine, then all the sample bars are tested for tensile property according to GB/T1040.1-2006 test standard, a zwick roll electronic tensile tester of American Instron company is adopted to test the tensile property (tensile modulus and breaking elongation) of the sample bars, and the test speed of the tensile modulus is 1 mm.min-1.5 bars were measured for each sample and the measurements averaged as detailed in Table 1.
(II) detecting the glass transition temperature: a Differential Scanning Calorimeter (DSC) is used for representing the glass transition temperature of plasticized PVC, and a sample is firstly processed from 0 ℃ to min-1Heating to 200 deg.C at a heating rate of 10 deg.C/min-1Then keeping the temperature at 200 ℃ for 5min to eliminate the thermal history, then cooling the sample to 0 ℃, and finally cooling the sample at 10 ℃ for min-1The temperature rise rate of (2) was increased to 200 ℃ twice, and the detection results are shown in Table 1.
(III) PVC fracture cross-section morphology: a tensile fracture sample of plasticized PVC is directly adhered to a conductive adhesive, the section is exposed outside, after gold spraying is carried out in a vacuum environment, the appearance of the fracture cross section of the PVC is observed by using a scanning electron microscope, the accelerating voltage is 5.0kv, scanning electron microscope pictures of the tensile fracture sample section shown in figures 1-28 are obtained, as can be seen from figures 1-28, the brittle fracture area of the plasticized PVC obtained by using the plasticizer of examples 1-7 of the invention is obviously less than that of comparative examples 1-3, which shows that the plasticizer of examples 1-7 of the invention has better plasticizing effect on PVC and is more environment-friendly than dioctyl phthalate DOP of comparative example 3, in addition, as can be seen from the figures, the plasticizing effect is better and the ductile fracture area is more because the steric hindrance is larger by using the naphthenic base and naphthenic base alkyl substituted aconitate plasticizer, the insertion effect is more obvious, and the material has better plasticity.
And (IV) volatility testing: performing volatility test by referring to GB/T3830-2008, placing a PVC sample in a dryer for 4 hours, accurately weighing the mass, hanging the PVC sample in a 70 ℃ oven for 24 hours, taking out the PVC sample, cooling the PVC sample to room temperature in the dryer, weighing the mass, calculating mass loss, measuring three groups of samples, and averaging the measurement results, wherein the results are shown in Table 1.
And (V) cutting the plasticized PVC sample into small pieces, accurately weighing the mass, respectively soaking the sample pieces in 200mL of petroleum ether, standing at room temperature for 96h, taking out, placing in an oven, drying by air blowing at 30 ℃ for 48h, accurately weighing the mass again, calculating the mass loss, measuring three groups of samples, and averaging the measurement results, wherein the results are shown in Table 1.
TABLE 1 results for plasticized PVC Properties obtained in example 8 and comparative examples 1-3
The aconitate serving as a PVC plasticizer is non-toxic and harmless, has good environmental friendliness, has higher plasticizing performance which is not possessed by epoxidized soybean oil and acetyl tributyl citrate plasticizers, can still keep higher mechanical performance of the plasticized PVC material, and is superior to DOP in volatilization resistance and solvent extraction resistance on the basis of health and environmental protection compared with DOP. In conclusion, the tributyl aconitate as a safe and efficient PVC plasticizer has a wide application prospect in PVC products with higher plasticizing performance and safety performance requirements such as biological medicine and the like.
Claims (10)
1. An aconitate polyvinyl chloride plasticizer is characterized in that the structural general formula of the aconitate polyvinyl chloride plasticizer is shown as
Wherein R is alkyl, cycloalkyl or cycloalkylalkyl with the carbon atom number more than or equal to 1.
2. An aconitate-based polyvinyl chloride plasticizer according to claim 1, wherein said cycloalkyl is unsubstituted cycloalkyl or alkyl-substituted cycloalkyl.
3. An aconitate-based polyvinyl chloride plasticizer according to claim 1, wherein the cycloalkylalkyl group is an unsubstituted cycloalkylalkyl group or an alkyl-substituted cycloalkylalkyl group, and the alkyl substituent in the alkyl-substituted cycloalkylalkyl group is ring-substituted or linear-substituted.
4. A process for the preparation of an aconitate-type polyvinyl chloride plasticizer according to any of claims 1 to 3, which comprises the steps of:
step 1: adding trans-aconitic acid into an alcohol solvent, stirring for dissolving, adding an acid catalyst after the trans-aconitic acid is completely dissolved, and stirring for reacting at high temperature to obtain a mixed solution containing aconitate;
step 2: adding sodium bicarbonate into the mixed solution containing the aconitate to quench reaction, extracting with ethyl acetate, performing rotary evaporation concentration after extraction, and then performing vacuum pumping under a heating state to obtain the aconitate polyvinyl chloride plasticizer.
5. The method of claim 4, wherein the alcohol solvent in step 1 is an alkyl alcohol, and the acidic catalyst in step 1 is an inorganic acid, an organic acid or an inorganic acid salt.
6. The method of claim 5, wherein the alkyl alcohol is methanol, ethanol, propanol, n-butanol, pentanol, hexanol, heptanol, octanol, nonanol, isobutanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-ethoxyethanol, 4-phenylbutanol, 2-butoxyethanol, cyclohexanol, cyclohexylmethanol, 2-ethylhexanol, or benzyl alcohol, the inorganic acid is sulfuric acid, phosphoric acid, boric acid, the organic acid is p-toluenesulfonic acid, and the inorganic acid salt is ferric chloride, ferric sulfate, ferrous sulfate, zinc sulfate, or cerium sulfate.
7. The method for preparing an aconitate-based polyvinyl chloride plasticizer according to claim 4, wherein the amount ratio of trans-aconitic acid to alcoholic solvent in step 1 is 1: (3-9), wherein the mass ratio of the acidic catalyst to the trans-aconitic acid in the step 1 is 1: (2-100).
8. The method for preparing an aconitate-based polyvinyl chloride plasticizer according to claim 4, wherein the stirring dissolution is performed at 100 ℃ in step 1, and the temperature of the stirring reaction at high temperature in step 1 is 100 to 210 ℃.
9. The method for preparing an aconitate-based polyvinyl chloride plasticizer according to claim 4, wherein the evacuation in the heated state in the step 2 is performed at a temperature of 40 to 60 ℃ to 0.03 to 0.1 mbar.
10. Use of an aconitate-based polyvinyl chloride plasticizer according to any of claims 1 to 3 for polyvinyl chloride plasticization.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114315576A (en) * | 2022-01-05 | 2022-04-12 | 山东万图高分子材料股份有限公司 | Preparation method of bio-based degradable plasticizer |
| CN114773748A (en) * | 2022-04-20 | 2022-07-22 | 山东万图高分子材料股份有限公司 | Composition containing tributyl aconitate and application thereof |
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| GB827388A (en) * | 1956-07-09 | 1960-02-03 | Allied Chem | Plasticised vinyl resin composition containing vinylcyclohexanol esters |
| US20070072988A1 (en) * | 2005-09-26 | 2007-03-29 | Vertellus Performance Materials, Inc. | Tricarboxylic acid ester plasticizers and methods of making |
| CN102336665A (en) * | 2011-07-15 | 2012-02-01 | 苏州大学 | Unsaturated ester containing perfluoroalkyl and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB632758A (en) * | 1947-09-08 | 1949-12-05 | Hugh Gavin Reid | New plastic compositions |
| GB707235A (en) * | 1950-12-22 | 1954-04-14 | Ici Ltd | Plasticised compositions |
| GB827388A (en) * | 1956-07-09 | 1960-02-03 | Allied Chem | Plasticised vinyl resin composition containing vinylcyclohexanol esters |
| US20070072988A1 (en) * | 2005-09-26 | 2007-03-29 | Vertellus Performance Materials, Inc. | Tricarboxylic acid ester plasticizers and methods of making |
| CN102336665A (en) * | 2011-07-15 | 2012-02-01 | 苏州大学 | Unsaturated ester containing perfluoroalkyl and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114315576A (en) * | 2022-01-05 | 2022-04-12 | 山东万图高分子材料股份有限公司 | Preparation method of bio-based degradable plasticizer |
| CN114773748A (en) * | 2022-04-20 | 2022-07-22 | 山东万图高分子材料股份有限公司 | Composition containing tributyl aconitate and application thereof |
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