CN114456129A - Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same - Google Patents
Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same Download PDFInfo
- Publication number
- CN114456129A CN114456129A CN202011236497.9A CN202011236497A CN114456129A CN 114456129 A CN114456129 A CN 114456129A CN 202011236497 A CN202011236497 A CN 202011236497A CN 114456129 A CN114456129 A CN 114456129A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl chloride
- epoxy
- acid
- ester
- rosin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/18—Plasticising macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Abstract
The invention belongs to the technical field of rosin esters and application thereof, and particularly relates to an epoxy rosin ester and a method for preparing modified polyvinyl chloride by applying the epoxy rosin ester. Dispersing the plasticizer, adding polyvinyl chloride, heating and stirring to obtain modified polyvinyl chloride; the plasticizer comprises epoxy rosin ester and epoxy soybean oil, or comprises one or more of tetrahydroxyalkyl urea, polyhydroxybutyrate and poly (L-lactide-co-glycolide); the molecules of the epoxy rosin ester which is a full-bio-based green product and is obtained by deep processing rosin can be inserted among polyvinyl chloride molecular chains and used for plasticizing and modifying polyvinyl chloride, so that the plasticity and flexibility of the polyvinyl chloride are improved, the mechanical property is enhanced, the elongation at break is as high as 400% or even higher, the performance of the polyvinyl chloride product is improved, and the application field of the epoxy rosin ester is expanded.
Description
Technical Field
The invention belongs to the technical field of rosin esters and application thereof, and particularly relates to an epoxy rosin ester and a method for preparing modified polyvinyl chloride by applying the epoxy rosin ester.
Background
Polyvinyl chloride (PVC) is a general-purpose plastic with wide global applicability and large yield. The material can be widely applied to building materials, food packaging, aerospace, leather, children toys and the like. The common plasticizer is phthalate plasticizer which is a petrochemical product and has toxicity. A bio-based green and environment-friendly plasticizer is urgently needed to be found and used for replacing the traditional plasticizer.
Rosin is a renewable resource with rich yield, and the ternary phenanthrene ring structure of the rosin has characteristic active functional groups, so that the rosin is beneficial to deep processing and utilization.
Therefore, the invention prepares the green and environment-friendly epoxy rosin ester by taking the rosin as the raw material and uses the epoxy rosin ester to replace the traditional toxic phthalate plasticizer to obtain the modified polyvinyl chloride, thereby not only expanding the application field and the application range of natural products, but also improving the performance of the polyvinyl chloride industry.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an epoxy rosin ester and a method for preparing modified polyvinyl chloride by using the same, wherein rosin is processed and utilized to obtain a green product, and the green product is applied to plasticization of modified polyvinyl chloride to obtain a polyvinyl chloride product with excellent mechanical properties.
The technical content of the invention is as follows:
the invention provides a preparation method of epoxy rosin ester, which comprises the following steps: respectively reacting hydrogenated rosin, acrylpimaric acid, fumaropimaric acid with epoxy chloropropane and a catalyst at the temperature of 100-120 ℃ for 2-3 hours, then cooling to perform dechlorination, adding sodium hydroxide and calcium oxide (hydrogen chloride and sodium hydroxide obtained by dechlorination are neutralized, and generated water is absorbed by calcium oxide) to continue to react, then filtering and removing a solvent in vacuum to finally prepare epoxy rosin ester which is respectively hydrogenated rosin glycidyl ester, acrylpimaric acid diglycidyl ester and fumaropimaric acid triglycidyl ester;
the catalyst comprises one of benzyltriethylammonium chloride, N-dimethylaniline, diisopropylethylamine, hexamethylphosphoramide and triethylamine;
the reaction condition of the dechlorination reaction is that the dechlorination reaction is carried out for 3-4 hours at 50-70 ℃;
the preparation method of the acrylpimaric acid comprises the following steps: adding acrylic acid into rosin heated to 180-200 ℃ for addition reaction, heating to 200-210 ℃, reacting for 3-5 hours, and purifying the obtained product by a potassium salt method to obtain purified acrylic pimaric acid;
the preparation method of the fumaropimaric acid comprises the following steps: adding fumaric acid into rosin for addition reaction, heating to 180-210 ℃, reacting for 3-5 h, and purifying the obtained product by a potassium salt method to obtain purified fumaropimaric acid;
dissolving acrylic pimaric acid or fumaropimaric acid in ethanol, heating to dissolve a potassium hydroxide ethanol solution, pouring the solution into an acrylic pimaric acid or fumaropimaric acid solution in batches, continuously stirring to generate acrylic pimaric acid potassium salt or fumaropimaric acid potassium salt, putting filter residue obtained by filtering potassium salt into ethanol for washing, taking out potassium salt, adding potassium hydroxide and deionized water, heating and stirring in a water bath until the potassium salt of the filter residue is completely dissolved, determining the pH of the solution to be more than 10, then adding a hydrochloric acid aqueous solution, adding excessive deionized water when the solution is turbid, determining the pH to be 2, indicating that the acrylic pimaric acid salt or the fumaropimaric acid salt has completely reacted to generate the acrylic pimaric acid or the fumaropimaric acid, and then washing and drying to obtain the purified acrylic pimaric acid or the fumaronic acid.
The invention also provides a method for applying the epoxy rosin ester to the preparation of modified polyvinyl chloride, which comprises the following steps: dispersing the plasticizer, adding polyvinyl chloride, heating and stirring to obtain modified polyvinyl chloride;
the plasticizer comprises epoxy rosin ester and epoxy soybean oil, or comprises one or more of tetrahydroxyalkyl urea, polyhydroxybutyrate and poly (L-lactide-co-glycolide);
the epoxy rosin ester comprises one or more of hydrogenated rosin glycidyl ester, propylene pimaric acid diglycidyl ester and fumaric pimaric acid triglycidyl ester;
the use mass ratio of the plasticizer to the polyvinyl chloride is (0.3-0.5): (0.8 to 1.5);
the heating temperature of the heating and stirring is 30-60 ℃, and the heating is carried out for 0.3-1.5 h;
the solvent adopted by the plasticizer dispersion treatment comprises one of tetrahydrofuran, cyclohexanone, dichloroethane, acetone and benzene.
The invention also provides application of the prepared epoxy rosin ester in plasticizing modified plastic films.
The invention has the following beneficial effects:
the epoxy rosin ester is a full-bio-based green product obtained by deep processing rosin, the raw material source is easy to obtain, the synthesis process is simple, the obtained rosin ester products such as hydrogenated rosin glycidyl ester, propylene pimaric acid diglycidyl ester and fumaric pimaric acid triglycidyl ester have stable structures, and the application fields and application ranges of natural products such as rosin products are expanded;
the epoxy rosin ester prepared by the invention can be used for plasticizing and modifying polyvinyl chloride, the epoxy rosin ester serving as a plasticizer molecule can be inserted between polyvinyl chloride molecular chains, the polar part of the plasticizer acts with polyvinyl chloride, the acting force between polyvinyl chloride molecules is weakened, the plasticity and flexibility of polyvinyl chloride are improved, the mechanical property of polyvinyl chloride is enhanced, the elongation at break after plasticizing and modifying is as high as 400% or even higher, the performance of a polyvinyl chloride product is improved, and the application, development and use fields of polyvinyl chloride are expanded.
Drawings
FIG. 1 is an infrared spectrum of an epoxy rosin ester obtained according to the present invention;
FIG. 2 is a flow chart of the preparation of glycidyl ester of hydrogenated rosin;
FIG. 3 is a flow chart of the preparation of glycidylester of acrylpimaric acid;
FIG. 4 is a flow chart of the preparation of triglycidyl fumaropimarate.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of hydrogenated rosin glycidyl ester: adding 50g of hydrogenated rosin, 170g of epoxy chloropropane and 0.38g of benzyltriethylammonium chloride serving as a catalyst into a flask, reacting for 2 hours at 100 ℃ under the protection of nitrogen, then cooling to 50 ℃ for reacting for 3 hours for dechlorination, adding 6.6g of sodium hydroxide and 9.3g of calcium oxide, continuing to react for 3 hours, filtering by using diatomite, and removing a solvent in vacuum to obtain reddish brown viscous liquid-hydrogenated rosin glycidyl ester with the epoxy equivalent of 380 g/mol-1(theoretical value of 358 g. mol)-1) As shown in fig. 2, it is a process route for preparing hydrogenated rosin glycidyl ester by using hydrogenated rosin;
detecting characteristic peaks of the sample by using a Fourier transform infrared spectrometer, wherein the measurement range is as follows: 500-4000 cm-1The obtained infrared spectrum is shown in figure 1, and the curve a is 1726cm-1And 910cm-1The newly generated ester group C ═ O stretching vibration characteristic peak and epoxy group skeleton stretching vibration absorption peak indicate that hydrogenated rosin glycidyl ester is synthesized;
2) preparing modified polyvinyl chloride: dissolving 0.8g of hydrogenated rosin glycidyl ester and 0.4g of epoxy soybean oil in 50mL of tetrahydrofuran, adding 3g of polyvinyl chloride powder, heating in a water bath to 40 ℃, heating for 0.3h, stirring while heating, pouring the solution in a beaker into a watch glass, drying in a drying oven at 41 ℃ for 24h, and obtaining the modified polyvinyl chloride film after the solvent is completely volatilized.
Example 2
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of hydrogenated rosin glycidyl ester: adding 50g of hydrogenated rosin, 170g of epoxy chloropropane and 0.38g of catalyst N, N-dimethylaniline into a flask, reacting for 2 hours at 100 ℃ under the protection of nitrogen, then cooling to 50 ℃ for reaction for 3 hours for dechlorination, adding 6.6g of sodium hydroxide and 9.3g of calcium oxide, continuing to react for 3 hours, filtering with diatomite, and removing the solvent in vacuum to obtain reddish brown viscous liquid-hydrogenated rosin glycidyl ester;
2) preparing modified polyvinyl chloride: dissolving 1.2g of hydrogenated rosin glycidyl ester, 0.5g of epoxidized soybean oil and 0.3g of tetraalkyl urea in 80mL of cyclohexanone, adding 8g of polyvinyl chloride powder into the cyclohexanone, heating the mixture to 50 ℃ in a water bath, heating the mixture for 1h, stirring the mixture while heating, pouring the solution in a beaker into a watch glass, putting the watch glass into a drying oven, drying the watch glass for 24h at the temperature of 41 ℃, and obtaining the modified polyvinyl chloride film after the solvent is completely volatilized.
Example 3
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of acrylpimaric acid: adding 150mL of acrylic acid into 500g of rosin heated to 180 ℃ for addition reaction, heating to 200 ℃ under the protection of nitrogen, and reacting for 3 hours to obtain a crude product of acrylic pimaric acid, wherein the purity is about 55-60%;
dissolving 200g crude acrylpimaric acid in 700mL of ethanol, pouring a solution of 30g potassium hydroxide in 100mL of ethanol, and stirring under heating in a water bath at 50 ℃ to completely dissolve the crude acrylpimaric acid. And pouring the completely dissolved potassium hydroxide solution into the acrylic pimaric acid ethanol solution cooled to 50 ℃ in several times, and continuously stirring to generate the acrylic pimaric acid potassium salt. Carrying out suction filtration on the potassium acrylpimarate solution, putting the white turbid substance filter residue into an ethanol solution after suction filtration, keeping the temperature of 60 ℃ for heating and washing in a water bath for half an hour, and repeating the operation twice;
adding potassium hydroxide into a beaker filled with potassium acrylpimarate and deionized water, keeping the temperature of the beaker under the water bath heating condition of 50 ℃, and stirring the beaker until the potassium hydroxide is completely dissolved. After the potassium salt of the propylene potassium pimelate is completely dissolved, adding potassium hydroxide into the beaker until the pH value of the measured solution is more than 10;
preparing a hydrochloric acid aqueous solution with the mass fraction of 8%, dropwise adding the hydrochloric acid aqueous solution into a beaker filled with a potassium acrylpimarate solution while stirring, adding excessive deionized water when the solution is cloudy, and when the pH value is measured to be 2, indicating that the acrylpimarate has completely reacted to generate acrylpimaric acid;
carrying out suction filtration on the acrylpimaric acid product, washing filter residues to be neutral by using deionized water to obtain an acrylpimaric acid semi-crude product, and drying the product in a forced air drying oven at 70 ℃ to obtain purified acrylpimaric acid;
2) preparation of acrylpimaric acid diglycidyl ester: adding purified 24g of acrylpimaric acid, 120g of epichlorohydrin and 0.29g of catalyst diisopropylethylamine into a flask, reacting for 2 hours at 100 ℃ under the protection of nitrogen, then cooling to 50 ℃ for reaction for 3 hours for dechlorination, adding 5.2g of sodium hydroxide and 7.1g of calcium oxide, continuing to react for 3 hours, filtering with diatomite, and removing the solvent in vacuum to obtain light yellow viscous liquid-acrylpimaric acid diglycidyl ester with the epoxy equivalent of 270 g.mol-1(theoretical value of 243 g. mol)-1)；
Detecting characteristic peaks of the sample by using a Fourier transform infrared spectrometer, wherein the measurement range is as follows: 500-4000 cm-1The obtained infrared spectrum is shown in figure 1, and the curve b in the graph is 1728cm-1And 910cm-1The newly generated ester group C ═ O stretching vibration characteristic peak and epoxy group skeleton stretching vibration absorption peak are illustrated, and the synthesis of acrylpimaric acid diglycidyl ester is illustrated, as shown in fig. 3, which is a process route for preparing acrylpimaric acid from rosin and then preparing acrylpimaric acid diglycidyl ester;
3) preparing modified polyvinyl chloride: dissolving 0.7g of acrylpimaric acid diglycidyl ester and 0.3g of epoxy soybean oil in 50mL of cyclohexanone, adding 3g of polyvinyl chloride powder, heating in a water bath to 40 ℃, heating for 0.5h, stirring while heating, pouring the solution in a beaker into a watch glass, drying in a drying oven at 41 ℃ for 24h, and obtaining the modified polyvinyl chloride film after the solvent is completely volatilized.
Example 4
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of acrylpimaric acid: adding 150mL of acrylic acid into 500g of rosin heated to 200 ℃ for addition reaction, heating to 210 ℃ under the protection of nitrogen, and reacting for 5 hours to obtain a crude product of acrylic pimaric acid, wherein the purity is about 55-60%;
the purification step of crude acrylpimaric acid is the same as the step 1) of the example 3;
2) preparation of acrylpimaric acid diglycidyl ester: adding 24g of purified acrylpimaric acid, 120g of epichlorohydrin and 0.29g of benzyltriethylammonium chloride serving as a catalyst into a flask, reacting for 3 hours at 110 ℃ under the protection of nitrogen, then cooling to 60 ℃ to react for 3 hours for dechlorination, adding 5.2g of sodium hydroxide and 7.1g of calcium oxide, continuing to react for 3 hours, filtering with diatomite, and removing the solvent in vacuum to obtain light yellow viscous liquid-acrylpimaric acid diglycidyl ester;
3) preparing modified polyvinyl chloride: 0.3g of propylene pimaric acid diglycidyl ester, 0.3g of hydrogenated rosin glycidyl ester, 0.3g of epoxidized soybean oil and 0.1g of polyhydroxybutyrate are dissolved in 50mL of benzene, 3g of polyvinyl chloride powder is added into the solution, the solution is heated to 30 ℃ in a water bath, the heating is carried out for 0.3h, the heating and the stirring are carried out simultaneously, the solution in a beaker is poured into a watch glass, the watch glass is placed into a drying box for drying for 24h at the temperature of 41 ℃, and the modified polyvinyl chloride film is prepared after the solvent is completely volatilized.
Example 5
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of fumaropimaric acid: adding 77g of fumaric acid into 200g of rosin for addition reaction, heating to 210 ℃ under the protection of nitrogen, and reacting for 5 hours to obtain crude fumaropimaric acid with the purity of 50-60%;
200g of crude fumaropimaric acid is dissolved in 700mL of ethanol, and 30g of potassium hydroxide is dissolved in 100mL of ethanol, and the solution is stirred under the heating condition of water bath at 50 ℃ to be completely dissolved. Pouring the completely dissolved potassium hydroxide solution into the fumaropimaric acid ethanol solution cooled to 50 ℃ for several times, and continuously stirring to generate potassium fumaropimaric acid salt;
carrying out suction filtration on the potassium fumaropimelate salt solution, putting the white turbid substance filter residue into an ethanol solution after suction filtration, keeping the temperature of 60 ℃ for heating and washing in a water bath for half an hour, and repeating the operation twice;
adding potassium hydroxide into a beaker filled with potassium fumaropimaric acid salt and deionized water, keeping the temperature of the beaker under the water bath heating condition of 50 ℃, and stirring the beaker until the potassium hydroxide is completely dissolved. After the potassium fumaropimelate salt is completely dissolved, adding potassium hydroxide into the beaker until the pH value of the measured solution is more than 10;
preparing a hydrochloric acid aqueous solution with the mass fraction of 8%, dropwise adding the hydrochloric acid aqueous solution into a beaker filled with a potassium fumaratdirections solution while stirring, adding excessive deionized water when the solution is cloudy, and when the pH value is measured to be 2, indicating that the fumaropimaric acid salt has completely reacted to generate fumaropimaric acid;
carrying out suction filtration on the fumaropimaric acid product, washing filter residues to be neutral by using deionized water to obtain a semi-crude fumaropimaric acid product, and drying the product in a forced air drying oven at 70 ℃ to obtain purified fumaropimaric acid;
2) preparation of triglycidyl fumaropimarate: adding purified 40g of fumaropimaric acid, 270g of epichlorohydrin and 0.65g of catalyst triethylamine into a flask, reacting for 3h at 120 ℃ under the protection of nitrogen, then cooling to 70 ℃ for reacting for 4h for dechlorination, adding 12.0g of sodium hydroxide and 16g of calcium oxide, continuing to react for 3.5h, filtering with diatomite, and removing the solvent in vacuum to obtain light yellow viscous liquid-triglycidyl fumaropimaric acid, wherein the epoxy equivalent is 220 g.mol-1(theoretical value of 195 g. mol)-1)；
Detecting characteristic peaks of the sample by using a Fourier transform infrared spectrometer, wherein the measurement range is as follows: 500-4000 cm-1The obtained infrared spectrum is shown in figure 1, and the curve of c is 1725cm-1And 910cm-1The characteristic peak of the newly generated ester group C ═ O stretching vibration and the absorption peak of the stretching vibration of the epoxy group skeleton are shown, the synthesis of the triglycidyl fumaropimaric acid is illustrated, and as shown in figure 4, the rosin is prepared into fumaropimaric acid and then is processedA process route for preparing the fumaric pimaric acid triglycidyl ester;
3) preparing modified polyvinyl chloride: dissolving 2g of fumaric pimaric acid triglycidyl ester and 1g of epoxy soybean oil in 80mL of acetone, adding 8g of polyvinyl chloride powder into the acetone, heating the mixture to 60 ℃ in a water bath, heating the mixture for 1.5h, stirring the mixture while heating, pouring the solution in a beaker into a watch glass, putting the watch glass into a drying oven, drying the watch glass for 24h at the temperature of 41 ℃, and obtaining the modified polyvinyl chloride film after the solvent is completely volatilized.
Example 6
A method for preparing epoxy rosin ester and modifying polyvinyl chloride comprises the following steps:
1) preparation of fumaropimaric acid: adding 77g of fumaric acid into 200g of rosin for addition reaction, heating to 190 ℃ under the protection of nitrogen, and reacting for 4 hours to obtain crude fumaropimaric acid with the purity of 50-60%;
the purification operation of crude fumaropimaric acid was the same as in step 1) of example 5;
2) preparation of triglycidyl fumaropimarate: adding 40g of purified fumaropimaric acid, 270g of epoxy chloropropane and 0.65g of catalyst hexamethylphosphoramide into a flask, reacting for 2.5h at 110 ℃ under the protection of nitrogen, then cooling to 60 ℃ for reacting for 3.5h for dechlorination, adding 12.0g of sodium hydroxide and 16g of calcium oxide, continuing to react for 3.5h, filtering with diatomite, and removing the solvent in vacuum to obtain light yellow viscous liquid-fumaropimaric acid triglycidyl ester;
3) preparing modified polyvinyl chloride: dissolving 0.6g of fumaric pimaric acid triglycidyl ester, 0.2g of propylene pimaric acid diglycidyl ester, 0.3g of epoxidized soybean oil and 0.1g of poly (L-lactide-co-glycolide) in 50mL of dichloroethane, adding 3g of polyvinyl chloride powder into the dichloroethane, heating the mixture to 50 ℃ for 1.2h, stirring the mixture while heating, pouring the solution in a beaker into a watch glass, drying the beaker in a drying oven for 24h at the temperature of 41 ℃, and obtaining the modified polyvinyl chloride film after the solvent is completely volatilized.
Comparative example 1
Weighing 3.0g of polyvinyl chloride powder, putting the polyvinyl chloride powder into a beaker, dissolving the polyvinyl chloride powder in a constant-temperature magnetic stirring water bath kettle, taking out the beaker, pouring the solution in the beaker into a watch glass, drying the beaker at 40 ℃ for 24 hours in a drying oven, and obtaining the polyvinyl chloride film after the solvent is completely volatilized.
Comparative example 2
Weighing 0.8g of dimethyl phthalate, 0.4g of epoxidized soybean oil and 3.0g of polyvinyl chloride powder, putting the materials into a beaker, dissolving the materials in a constant-temperature magnetic stirring water bath, taking out the materials, pouring the solution in the beaker into a watch glass, drying the solution in a drying oven at 40 ℃ for 24 hours, and obtaining the polyvinyl chloride film after the solvent is completely volatilized.
Comparative example 3
Weighing 1.2g of dimethyl phthalate and 3.0g of polyvinyl chloride powder, putting the dimethyl phthalate and the polyvinyl chloride powder into a beaker, dissolving the dimethyl phthalate and the polyvinyl chloride powder in a constant-temperature magnetic stirring water bath, taking out the beaker, pouring the solution in the beaker into a watch glass, drying the beaker in a drying oven at 40 ℃ for 24 hours, and obtaining the polyvinyl chloride film after the solvent is completely volatilized.
The polyvinyl chloride films prepared in examples 1-6 and comparative example 1 were used for mechanical property detection, and the test results are shown in the following table:
TABLE 1 Properties of epoxy rosin ester plasticized modified polyvinyl chloride
As can be seen from table 1, when the epoxy rosin ester prepared by the present application is used for preparing modified polyvinyl chloride, the mechanical properties of the obtained modified polyvinyl chloride are significantly improved, which indicates that the epoxy rosin ester has a significant plasticizing effect, compared with the toxic plasticizer used in the prior art, the epoxy rosin ester and other bio-based plasticizers used in the present invention are green and environment-friendly products, which is helpful for expanding the application development of rosin and polyvinyl chloride, and the epoxy rosin ester prepared by the present invention has similar plasticizing and modifying effects on other plastic films, and the physical and chemical reactions are the same, which are not repeated herein.
Claims (10)
1. The preparation method of the epoxy rosin ester is characterized by comprising the following steps: respectively reacting hydrogenated rosin, acrylpimaric acid, fumaropimaric acid with epoxy chloropropane and a catalyst at the temperature of 100-120 ℃ for 2-3 h, then cooling for dechlorination, and finally preparing epoxy rosin ester, namely hydrogenated rosin glycidyl ester, acrylpimaric acid diglycidyl ester and fumaropimaric acid triglycidyl ester.
2. The method of claim 1, wherein the catalyst comprises one of benzyltriethylammonium chloride, N-dimethylaniline, diisopropylethylamine, hexamethylphosphoramide, and triethylamine.
3. The method for preparing an epoxy rosin ester according to claim 1, wherein the dechlorination reaction is carried out at 50 to 70 ℃ for 3 to 4 hours.
4. The method for preparing an epoxy rosin ester according to claim 1, wherein the preparation of the acrylpimaric acid is: adding acrylic acid into rosin heated to 180-200 ℃ for addition reaction, heating to 200-210 ℃, reacting for 3-5 hours, and purifying the obtained product by a potassium salt method to obtain purified acrylic pimaric acid.
5. The method for preparing an epoxy rosin ester according to claim 1, wherein the fumaropimaric acid is prepared by: adding fumaric acid into rosin for addition reaction, heating to 180-210 ℃, reacting for 3-5 h, and purifying the obtained product by a potassium salt method to obtain the purified fumaropimaric acid.
6. A method for preparing modified polyvinyl chloride by using the epoxy rosin ester prepared by any one of claims 1 to 5, which is characterized by comprising the following steps: dispersing the plasticizer, adding polyvinyl chloride, heating and stirring to obtain modified polyvinyl chloride;
the plasticizer comprises epoxy rosin ester and epoxy soybean oil;
the epoxy rosin ester comprises one or more of hydrogenated rosin glycidyl ester, propylene pimaric acid diglycidyl ester and fumaric pimaric acid triglycidyl ester.
7. The method for preparing modified polyvinyl chloride according to claim 1, wherein the mass ratio of the plasticizer to the polyvinyl chloride is (0.3-0.5): (0.8 to 1.5).
8. The method for preparing modified polyvinyl chloride according to claim 1, wherein the heating temperature for heating and stirring is 30 to 60 ℃ and the heating time is 0.3 to 1.5 hours.
9. The method for preparing modified polyvinyl chloride according to claim 1, wherein the solvent used for the plasticizer dispersion treatment comprises one of tetrahydrofuran, cyclohexanone, dichloroethane, acetone, and benzene.
10. Use of an epoxy rosin ester prepared according to any one of claims 1 to 5 for plasticising modified plastic films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011236497.9A CN114456129A (en) | 2020-11-09 | 2020-11-09 | Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011236497.9A CN114456129A (en) | 2020-11-09 | 2020-11-09 | Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114456129A true CN114456129A (en) | 2022-05-10 |
Family
ID=81404977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011236497.9A Pending CN114456129A (en) | 2020-11-09 | 2020-11-09 | Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114456129A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024065082A1 (en) * | 2022-09-26 | 2024-04-04 | Sika Technology Ag | Sealing element with improved impact resistance |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201866A (en) * | 1982-05-19 | 1983-11-24 | Arakawa Chem Ind Co Ltd | Method for selectively preparing rosin diglyceride |
| US5770662A (en) * | 1994-03-18 | 1998-06-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Modified resins made from the reaction of epoxidized esters and resin acids |
| CN1204643A (en) * | 1997-07-07 | 1999-01-13 | 中国林业科学研究院林产化学工业研究院 | Method for preparing maleopimaric acid tri-ester plasticizer |
| CN102311544A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN108484396A (en) * | 2018-05-09 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | Maleic rosin tetrahydrogeraniol ester and its preparation method and application |
-
2020
- 2020-11-09 CN CN202011236497.9A patent/CN114456129A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201866A (en) * | 1982-05-19 | 1983-11-24 | Arakawa Chem Ind Co Ltd | Method for selectively preparing rosin diglyceride |
| US5770662A (en) * | 1994-03-18 | 1998-06-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Modified resins made from the reaction of epoxidized esters and resin acids |
| CN1204643A (en) * | 1997-07-07 | 1999-01-13 | 中国林业科学研究院林产化学工业研究院 | Method for preparing maleopimaric acid tri-ester plasticizer |
| CN102311544A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN108484396A (en) * | 2018-05-09 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | Maleic rosin tetrahydrogeraniol ester and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| YINGYING HUANG，等: "Intrinsic kinetics study of rosin hydrogenation on a nickel catalyst supported on spent equilibrium catalyst", RSC ADV., vol. 07, no. 41, pages 25784 * |
| 施英乔，等: "松香合成增塑剂RTP的主成分研究", 林产化学与工业, vol. 12, no. 04, pages 1 - 2 * |
| 李侨光: "松香改性室温硫化硅橡胶的制备及性能研究", 中国博士学位论文全文数据库工程科技Ⅰ辑, no. 01, pages 4 - 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024065082A1 (en) * | 2022-09-26 | 2024-04-04 | Sika Technology Ag | Sealing element with improved impact resistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112409404B (en) | Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) | |
| CN104693024B (en) | Rosin triol ester as well as preparation method and application thereof | |
| CN114456129A (en) | Epoxy rosin ester and method for preparing modified polyvinyl chloride by using same | |
| CN108752506B (en) | Sulfydryl biomass-based monomer internal plasticization PVC material and preparation method thereof | |
| CN114276220A (en) | Preparation method of o-phenylphenoxyethanol | |
| CN110368987B (en) | Preparation method and application of tree-like loofah sponge supported ionic liquid catalyst | |
| CN110713439A (en) | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer | |
| CN113683508B (en) | Vanillin ester environment-friendly plasticizer and preparation method thereof | |
| CN108503732B (en) | Dehydroabietyl amide internal plasticization PVC material and preparation method thereof | |
| CN107200691B (en) | Preparation method of substituted p-phenylenediamine hydrochloride | |
| CN112920394B (en) | Preparation method and application of lactic acid-based environment-friendly plasticizer | |
| CN114456128A (en) | Application of novel isovanillin epoxy resin monomer in preparation of silicon-containing polymer | |
| CN110698376B (en) | Preparation method of antioxidant | |
| CN114702613A (en) | Grease source triazine compound modified internal plasticization PVC material and preparation method thereof | |
| CN109942426B (en) | Treatment method for recycling S- (-) -lipoic acid | |
| CN110028453B (en) | Preparation method of N-nitroiminoimidazolidine | |
| CN113292425A (en) | Production method of bis (2-propyl) heptyl terephthalate | |
| CN115746011B (en) | Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof | |
| CN107245052A (en) | A kind of atazanavir preparation method | |
| WO2001049248A2 (en) | Method of crystallizing and purifying alkyl gallates | |
| CN110903210A (en) | Preparation method of organic intermediate N, N-bis (β -hydroxyethyl) benzamide | |
| CN117050011B (en) | Method for synthesizing 2-methylquinoline by using vinyl acetate as raw material | |
| CN111875577B (en) | Preparation method of R-propylene carbonate | |
| CN109134927B (en) | Antibacterial plasticizing auxiliary agent for PVC and preparation method thereof | |
| CN116332920A (en) | Epoxy levulinate ketal ester plasticizer and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |