CN110922570A - Bio-based hyperbranched polyester plasticizer prepared by one-step method and application thereof in PVC cable material - Google Patents
Bio-based hyperbranched polyester plasticizer prepared by one-step method and application thereof in PVC cable material Download PDFInfo
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- CN110922570A CN110922570A CN201911231534.4A CN201911231534A CN110922570A CN 110922570 A CN110922570 A CN 110922570A CN 201911231534 A CN201911231534 A CN 201911231534A CN 110922570 A CN110922570 A CN 110922570A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a one-step method for preparing a bio-based hyperbranched polyester plasticizer and application of the bio-based hyperbranched polyester plasticizer in PVC cable materials. Succinic acid diglycidyl ether, trimethylolpropane and anhydride are used as main raw materials, and a one-step polycondensation method is adopted to synthesize the bio-based hyperbranched polyester plasticizer. The main raw materials of the invention have wide sources, are renewable and do not depend on petroleum; the preparation process is simple and reasonable, the energy consumption is low, and the product quality is stable; the product has large molecular weight, has smaller viscosity and good thermal stability compared with polyester plasticizers with the same molecular weight, is used for PVC cable materials by being compounded with other plasticizers, has excellent plasticizing effect, has extremely low emigration in cyclohexane and soybean oil mimics, and meets the requirements of oil resistance, heat resistance, solvent resistance and environmental protection of cable material products.
Description
Technical Field
The invention relates to a development and preparation technology of a durable environment-friendly bio-based plasticizer, in particular to a one-step method for preparing a bio-based hyperbranched polyester plasticizer and application of the bio-based hyperbranched polyester plasticizer in PVC cable materials, and belongs to the technical field of polymer synthesis and functionalized application.
Background
The plasticizer is the most important additive used in the plastic processing industry, and the required amount of the plasticizer accounts for about 60 percent of the total production amount of the plastic additives. The plasticizer for PVC is one of the fine chemicals which are used by more than million tons in China at present, and is still increased by 7-10% per year. Dioctyl phthalate (DOP) plasticizer is a plastic additive which is consumed in the largest amount in the world, but in the use process of PVC products, DOP is easy to migrate to an external medium, so that the performance of the products is reduced, meanwhile, the products cause harm to human health and environment, and the use range is increasingly limited. The PVC cable material is particles prepared by taking polyvinyl chloride as basic resin, adding a stabilizer, a plasticizer such as DOP, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dioctyl terephthalate (DOTP), trioctyl trimellitate (TOTM) and the like, an inorganic filler such as calcium carbonate and the like, an additive such as an auxiliary agent, a lubricant and the like, and mixing, kneading and extruding. In the cable industry, although there is no regulation for plasticizers, the use of DINP, DIDP, etc. in the PVC cable industry is also affected, and some enterprises have proposed the concept of environmentally friendly cable materials in which the use of conventional o-benzene plasticizers is limited.
The migration resistance and the heat resistance of the plasticizer are closely related to the molecular weight and the molecular structure of the plasticizer, and the target plasticizer can be endowed with better migration resistance and thermal stability by improving the molecular weight of the plasticizer and carrying out structural design on the plasticizer. Compared with linear polyester with the same molecular weight, the hyperbranched polyester has higher end group density and relatively larger free volume, and can obviously increase the movement performance of molecules in a plasticizing system. Meanwhile, the hyperbranched polyester plasticizer reserves the advantages of low diffusivity, low volatility, strong polarity and the like of the original high molecular weight polyester plasticizer, and has the function of fixing other plasticizers from migrating to the surface when being compounded with other plasticizers for use. The characteristics show that the hyperbranched polyester plasticizer can be applied to PVC cable materials with higher requirements on heat resistance, durability and environmental protection. At present, the plasticizer is rarely reported to be used for the research of cable materials.
Disclosure of Invention
The invention aims to provide a one-step method for preparing a bio-based hyperbranched polyester plasticizer, application of the bio-based hyperbranched polyester plasticizer in PVC cable materials and a preparation method of the bio-based hyperbranched polyester plasticizer, and provides a plasticizer which is good in durability, non-toxic and environment-friendly and a preparation method of the plasticizer aiming at the defects of small molecular weight, poor compatibility, high toxicity, single performance and the like of the traditional plasticizer.
The technical scheme of the invention is as follows: the method for preparing the bio-based hyperbranched polyester plasticizer by the one-step method takes a bio-based platform compound succinic acid as a main raw material, and adopts a one-step polycondensation method to synthesize a bio-based hyperbranched polyester plasticizer product, which specifically comprises the following steps: mixing succinic acid diglycidyl ether and trimethylolpropane, heating, adding a catalyst for reaction for a period of time, carrying out reduced pressure reflux reaction for a period of time, cooling, adding anhydride, keeping the reaction under the nitrogen atmosphere of 100-140 ℃, washing the reaction product to be neutral, and carrying out reduced pressure distillation and dehydration to obtain the bio-based hyperbranched polyester plasticizer product.
The catalyst is any one of tetrabutylammonium chloride, benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate.
The acid anhydride comprises any one of acetic anhydride, butyric anhydride or lauric anhydride.
The method for preparing the bio-based hyperbranched polyester plasticizer by the one-step method takes a bio-based platform compound succinic acid as a main raw material, and adopts a one-step polycondensation method to synthesize a bio-based hyperbranched polyester plasticizer product, which specifically comprises the following steps: mixing succinic acid diglycidyl ether and trimethylolpropane, heating, adding a catalyst for reaction for a period of time, carrying out reduced pressure reflux reaction for a period of time, cooling, adding anhydride, keeping the reaction under the nitrogen atmosphere of 100-140 ℃, washing the reaction product to be neutral, and carrying out reduced pressure distillation and dehydration to obtain the bio-based hyperbranched polyester plasticizer product.
The succinic acid diglycidyl ether is prepared by the following method: heating succinic acid, epoxy chloropropane and a catalyst for reaction, cooling reactants, adding sodium hydroxide, reacting the mixture, filtering, and distilling the filtrate under reduced pressure to recover excessive epoxy chloropropane to obtain succinic acid diglycidyl ether.
The catalyst is benzyltriethylammonium chloride or triphenylphosphine.
The pressure is 0.01-0.05MPa during reduced pressure distillation.
The mol ratio of the succinic acid diglycidyl ether to the trimethylolpropane is as follows: 1.3-1.8:1.
Heating to 100-150 ℃.
The one-step method is used for preparing the bio-based hyperbranched polyester plasticizer and is applied to PVC cable materials.
Has the advantages that:
(1) the bio-based hyperbranched polyester plasticizer product prepared by the invention has good durability and excellent plasticizing effect, and meets the requirements of cable material products on oil resistance, heat resistance, solvent resistance, environmental protection and the like.
(2) The invention takes succinic acid which is a renewable resource as a main raw material, has competitive production cost, avoids the dependence on petrochemical raw materials, reduces the pollution of a chemical synthesis process to the environment, and greatly improves the bio-based content and the environmental protection of a target plasticizer.
(3) The invention adopts a one-step method to synthesize the bio-based hyperbranched polyester plasticizer product, and has the advantages of simple reaction process, less three wastes, mild reaction conditions, low energy consumption, stable product quality and economic and environment-friendly production process.
Drawings
FIG. 1 is an infrared analysis spectrum of a bio-based hyperbranched polyester plasticizer prepared by the present invention;
FIG. 2 is a thermogram of thermo-gravimetric analysis of bio-based hyperbranched polyester plasticizer prepared according to the present invention and DOP plasticized PVC products. The result shows that the hyperbranched polyester plasticizer can obviously improve the thermal stability of the PVC product;
FIG. 3 shows the migration loss of the bio-based hyperbranched polyester plasticizer prepared by the present invention in cyclohexane and soybean oil under the following test conditions: immersing the PVC test piece into cyclohexane or soybean oil, standing at the temperature of 30 ℃ for 24h, taking out, washing with ethanol, drying in an oven at the temperature of 40 ℃ for 12h, transferring into a drier, cooling to room temperature, weighing, and calculating the mass loss of the PVC test piece before and after the experiment.
FIG. 4 is an infrared analysis spectrum of the diglycidyl succinate ether prepared according to the present invention.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The bio-based hyperbranched polyester plasticizer prepared by a one-step method and the application thereof in PVC cable materials are prepared by taking a bio-based platform compound succinic acid as a main raw material and adopting a one-step polycondensation method to synthesize a bio-based hyperbranched polyester plasticizer product: adding succinic acid diglycidyl ether and trimethylolpropane with a certain molar ratio into a four-neck flask, heating to 100-150 ℃, adding a catalyst, wherein the amount of the catalyst is 1-5 mol% of the epoxy material, reacting for 1-2h, converting into a reduced pressure distillation device, continuing to react for 1-2h at 80-120 ℃, cooling to 60 ℃, adding anhydride, continuing to react for 2-5h under the nitrogen atmosphere at 140 ℃ and 100 ℃, washing the reaction product to be neutral by 2-5% sodium bicarbonate solution and deionized water, and performing reduced pressure distillation and dehydration at 80-100 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
The preparation method of the succinic acid diglycidyl ether comprises the following steps: 1mol of succinic acid, 5 to 10mol of epichlorohydrin and 0.01 to 0.05mol of catalyst are added into a three-neck flask which is provided with a reflux condenser, a magnetic stirring device and a thermometer. The reaction temperature is raised to 90-120 ℃ and kept for 1-5 h. And cooling the reactant, adding 2mol of sodium hydroxide, stirring the mixture at 50-100 ℃ for 1-5h, filtering, and distilling the filtrate under reduced pressure to recover excessive epichlorohydrin to obtain succinic acid diglycidyl ether. The catalyst can be selected from benzyltriethylammonium chloride or triphenylphosphine.
The mol ratio of the succinic acid diglycidyl ether to the trimethylolpropane is as follows: 1.3:1-1.8:1.
The catalyst is any one of tetrabutylammonium chloride, benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate.
The pressure of the reduced pressure distillation device is 0.01-0.05 MPa.
The acid anhydride comprises any one of acetic anhydride, butyric anhydride or lauric anhydride.
The application of the hyperbranched polyester plasticizer in PVC cable materials comprises the following components in percentage by mass: 100 parts of polyvinyl chloride resin, 30-50 parts of dioctyl phthalate plasticizer, 30-50 parts of hyperbranched polyester plasticizer, 1 part of chlorinated paraffin and 3 parts of calcium-zinc stabilizer.
Example 1
Adding 1mol of succinic acid, 10mol of epichlorohydrin and 0.01mol of benzyltriethylammonium chloride catalyst into a three-neck flask provided with a reflux condenser tube, magnetic stirring and a thermometer, uniformly stirring, heating to 100 ℃, keeping for 4 hours, stopping heating, continuously adding 2mol of sodium hydroxide particles after reactants are cooled, heating the mixture to 80 ℃, reacting for 2 hours, cooling and filtering, and recovering excessive epichlorohydrin from the filtrate through reduced pressure distillation to obtain the succinic acid diglycidyl ether.
Example 2
Mixing a mixture of 1: 1.3, adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 100 ℃, adding tetrabutyl ammonium chloride catalyst with the amount of 2 mol% of epoxy, continuously reacting for 2h, converting into a reduced pressure distillation device, continuously reacting for 2h at 80 ℃, cooling to 60 ℃, adding acetic anhydride, continuously reacting for 3h under the nitrogen atmosphere at 120 ℃, washing the reaction product to be neutral by 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 80 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 3
Mixing a mixture of 1: 1.4 adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 120 ℃, adding tetrabutyl ammonium chloride catalyst with the amount of 1 mol% of epoxy, continuously reacting for 1h, converting into a reduced pressure distillation device, continuously reacting for 1h at 120 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 3h under the nitrogen atmosphere at 120 ℃, washing the reaction product to be neutral by 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 4
Mixing a mixture of 1: adding 1.5 parts of succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 120 ℃, adding a benzyl triethyl ammonium chloride catalyst with the amount of 1 mol% of the epoxy material, continuously reacting for 1h, converting into a reduced pressure distillation device, continuously reacting for 2h at 100 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 4h under the nitrogen atmosphere at 140 ℃, washing the reaction product to be neutral by 2% of sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 5
Mixing a mixture of 1: 1.6 adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 120 ℃, adding tetrabutylammonium hydrogen sulfate catalyst with the amount of 3 mol% of epoxy, continuously reacting for 1h, converting into a reduced pressure distillation device with the pressure of 0.05MPa, continuously reacting for 2h at 100 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 4h under the nitrogen atmosphere at 130 ℃, washing the reaction product to be neutral by 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 6
Mixing a mixture of 1: 1.8 adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 150 ℃, adding tetrabutyl ammonium chloride, adding a catalyst in an amount of 1 mol% of the epoxy compound, continuously reacting for 1h, converting into a reduced pressure distillation device, continuously reacting for 1h at 120 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 2h under the nitrogen atmosphere at 140 ℃, washing the reaction product to be neutral by a 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 7
Mixing a mixture of 1: 1.3, adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 100 ℃, adding tetrabutylammonium hydrogen sulfate catalyst with the amount of 2 mol% of epoxy, continuously reacting for 2h, converting into a reduced pressure distillation device with the pressure of 0.01MPa, continuously reacting for 1-2h at 80-120 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 2-5h under the nitrogen atmosphere of 100 ℃ and 140 ℃, washing the reaction product to be neutral by 2-5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 80-110 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 8
Mixing a mixture of 1: 1.3, adding succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 100 ℃, adding tetrabutyl ammonium chloride, adding a catalyst in an amount of 3 mol% of the epoxy compound, continuously reacting for 2 hours, converting into a reduced pressure distillation device, continuously reacting for 1-2 hours at 120 ℃ under the pressure of the reduced pressure distillation device of 0.01MPa, cooling to 60 ℃, adding anhydride, continuously reacting for 4 hours under the nitrogen atmosphere at 120 ℃, washing the reaction product to be neutral by a 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
Example 9
Mixing a mixture of 1: adding 1.5 parts of succinic acid diglycidyl ether and trimethylolpropane into a four-neck flask, uniformly stirring, heating to 120 ℃, adding tetrabutyl ammonium chloride catalyst with the amount of 1.5 mol% of epoxy, continuously reacting for 1h, converting into a reduced pressure distillation device, continuously reacting for 2h at 120 ℃, cooling to 60 ℃, adding anhydride, continuously reacting for 3h under the nitrogen atmosphere at 140 ℃, washing the reaction product to be neutral by 5% sodium bicarbonate solution and deionized water, and then performing reduced pressure distillation and dehydration at 90 ℃ to obtain the bio-based hyperbranched polyester plasticizer product.
The plasticizer and the dioctyl phthalate prepared by the invention are respectively used as plasticizers to be applied to PVC for comparative experiments, and the mass percentages are as follows: 100 parts of polyvinyl chloride resin, 30-50 parts of plasticizer, 1 part of chlorinated paraffin and 3 parts of calcium-zinc stabilizer are taken, the mixture is stirred for 5min in a high-speed mixer, and then a PVC sheet with a certain thickness is prepared by a double-roller open mill for performance test. As can be seen from FIGS. 2 and 3, the heat resistance, oil resistance and solvent resistance of the bio-based hyperbranched polyester plasticizer are superior to those of DOP, and the bio-based hyperbranched polyester plasticizer can be used in PVC cable materials at 70 ℃ or below instead of DOP.
Claims (10)
1. The one-step method for preparing the bio-based hyperbranched polyester plasticizer is characterized in that a bio-based platform compound succinic acid is used as a main raw material, and a one-step polycondensation method is adopted to synthesize a bio-based hyperbranched polyester plasticizer product, which specifically comprises the following steps: mixing succinic acid diglycidyl ether and trimethylolpropane, heating, adding a catalyst for reaction for a period of time, carrying out reduced pressure reflux reaction for a period of time, cooling, adding anhydride, keeping the reaction under the nitrogen atmosphere of 100-140 ℃, washing the reaction product to be neutral, and carrying out reduced pressure distillation and dehydration to obtain the bio-based hyperbranched polyester plasticizer product.
2. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 1, wherein the catalyst is any one of tetrabutylammonium chloride, benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate.
3. The one-step method for preparing the bio-based hyperbranched polyester plasticizer according to claim 1, wherein the acid anhydride comprises any one of acetic anhydride, butyric anhydride or lauric anhydride.
4. The one-step method for preparing the bio-based hyperbranched polyester plasticizer according to any one of claims 1 to 3 is characterized in that a bio-based platform compound succinic acid is used as a main raw material, and a one-step polycondensation method is adopted to synthesize a bio-based hyperbranched polyester plasticizer product, and specifically comprises the following steps: mixing succinic acid diglycidyl ether and trimethylolpropane, heating, adding a catalyst for reaction for a period of time, carrying out reduced pressure reflux reaction for a period of time, cooling, adding anhydride, keeping the reaction under the nitrogen atmosphere of 100-140 ℃, washing the reaction product to be neutral, and carrying out reduced pressure distillation and dehydration to obtain the bio-based hyperbranched polyester plasticizer product.
5. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 4, wherein the succinic acid diglycidyl ether is prepared by the following method: heating succinic acid, epoxy chloropropane and a catalyst for reaction, cooling reactants, adding sodium hydroxide, reacting the mixture, filtering, and distilling the filtrate under reduced pressure to recover excessive epoxy chloropropane to obtain succinic acid diglycidyl ether.
6. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 5, wherein the catalyst is benzyltriethylammonium chloride or triphenylphosphine.
7. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 4, wherein the pressure of the reduced pressure distillation is 0.01-0.05 MPa.
8. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 4, wherein the molar ratio of the succinic acid diglycidyl ether to the trimethylolpropane is as follows: 1.3-1.8:1.
9. The one-step method for preparing bio-based hyperbranched polyester plasticizer according to claim 4, wherein: heating to 100-150 ℃.
10. The use of the one-step method of preparing bio-based hyperbranched polyester plasticizer according to claim 1 in PVC cable materials.
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| CN113088543A (en) * | 2021-04-09 | 2021-07-09 | 江南大学 | Environment-friendly hyperbranched polyester plasticizer and preparation method thereof |
| CN113121805A (en) * | 2021-03-09 | 2021-07-16 | 武汉科技大学 | Preparation and application of sulfur-containing copolyester based on 2, 5-thiophenedicarboxylic acid |
| CN116041282A (en) * | 2022-12-15 | 2023-05-02 | 上海树脂厂有限公司 | Preparation method of aliphatic epoxy diluent |
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| CN116041282A (en) * | 2022-12-15 | 2023-05-02 | 上海树脂厂有限公司 | Preparation method of aliphatic epoxy diluent |
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