CN104326929A - Bio-based polyol prepared by utilizing tung oil and preparation method thereof - Google Patents
Bio-based polyol prepared by utilizing tung oil and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of chemical synthesis, and concretely relates to a method for preparing bio-based polyol by utilizing tung oil. The to-be solved technical problem is to provide a method for preparing bio-based polyol by utilizing tung oil. The method comprises the following steps: performing saponification reaction on the tung oil in a mixed solvent, so as to generate eleostearic acid; performing esterification on glycerin and boric acid to generate boric diglyceride, then performing esterification reaction on boric diglyceride and eleostearic acid to generate eleostearic-acid boroglyceride, and then performing hydrolysis to generate eleostearic-acid monoglyceride; then adding an epoxidizing agent to perform epoxidization reaction, so as to generate epoxy eleostearate; and finally reacting epoxy eleostearate with a ring-opening agent. The employed raw material tung oil is biological renewable resources, the cost is relatively low, and the obtained bio-based polyol can replace petrochemical polyether polyol to prepare polyurethane foam, and dependence on petrochemical products is reduced.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of biopolyol utilizing tung oil to prepare and preparation method thereof.
Background technology
Two large main raw material polyvalent alcohols of synthesis of polyurethane and isocyanic ester are all the derived product of the Nonrenewable resources such as oil, coal, petroleum base urethane is as a kind of important plastics, there is extremely strong stability, degraded is difficult under physical environment, can exist on tens century-old, become the main source of white garbage.Along with petroleum resources day by day exhausted and environmental requirement improves day by day, seek oil substitutes, reduce from source the dependence of Nonrenewable resources and reduce or eliminate the pollution of environment is seemed particularly important.Bio-based polyurethane material due to degradation speed fast, on environment and ecological impact then much smaller, therefore, development biopolyol is imperative in order to the technology preparing bio-based polyurethane material.
At present, more existing technology adopting vegetables oil to prepare polyvalent alcohol are reported, as adopted the polyols such as glycerine and vegetables oil to carry out alcoholysis reaction, rear and epoxide carries out addition reaction, prepares urethane vegetable oil polyol; Or vegetables oil prepares urethane vegetable oil polyol by carrying out the reactions such as epoxidation, open loop, alcoholysis.Patent literature was all adopt soybean oil, rapeseed oil, linseed oil, Oleum Gossypii semen, palm wet goods to prepare urethane biopolyol as raw material mostly in the past.Though China is rapeseed oil, soybean oil big producing country, this is the main edible oil of China, considers that China has a large population and a few land, and adopts the material industry of soybean oil, vegetable seed wet goods development bio-based polyurethane, faces the contradiction of striving ground with the people.
Adopt tung oil to prepare biopolyol and only have a small amount of report, patent CN101139252B discloses a kind of method adopting the reactions such as alcoholysis, epoxidation, open loop to prepare biopolyol, patent CN101125912B discloses the biopolyol adopting epoxidation, open loop, alcoholysis and addition reaction to prepare, and Material synthesis urethane foam based on this.
Summary of the invention
The technical problem to be solved in the present invention be exactly existing employing vegetables oil to prepare raw materials cost existing for biopolyol method higher, with the people strive etc. problem, in conjunction with China's present status of biological resources, there is provided a kind of tung oil that adopts as raw material, adopt the techniques such as saponification, esterification, epoxidation, open loop to prepare the method for biopolyol.By above-mentioned reaction, finally can obtain the oxy-compound of higher functionality, we, by oxy-compound obtained for aforesaid method, are referred to as biopolyol.
First technical problem to be solved by this invention is the method utilizing tung oil to prepare biopolyol.The method comprises the following steps:
A, saponification reaction: tung oil is carried out saponification reaction with mixed solvent in the presence of a catalyst, generate eleostearic acid; Saponification reaction temperature is 50 ~ 95 DEG C, and the reaction times is 1 ~ 3h; Described catalyzer is any one in alkali metal hydroxide or alkali metal alkoxide; Described mixed solvent is alcohol water mixed solvent, counts ， Chun ︰ water=1.5 ~ 4 ︰ 1 by volume;
B, esterification: glycerine and boric acid, under protection of inert gas, esterification is occurred, generate boric acid double glyceride; Then eleostearic acid generation esterification boric acid double glyceride and step a obtained in the presence of a catalyst, generates eleostearic acid boroglyceride; The first step esterification reaction temperature is 160 ~ 280 DEG C, and the reaction times is 2 ~ 6h; Second step esterification reaction temperature is 180 ~ 260 DEG C, and the reaction times is 1 ~ 4h; Described catalyzer be acid or anhydrous acid salt in any one;
C, hydrolysis reaction: the eleostearic acid boric acid glycerin Ester hydrolysis obtained by step b again, generate eleostearic acid mono-glycerides;
D, epoxidation reaction: the eleostearic acid mono-glycerides obtained by step c adds epoxidizing agent in the presence of a catalyst and carries out epoxidation reaction, generate epoxy eleostearate; Epoxidation reaction temperature is 40 ~ 90 DEG C, reaction times 2 ~ 9h; Described catalyzer is any one in sulfuric acid or phosphoric acid; Described epoxidizing agent is peroxide organic acid;
E, ring-opening reaction: the epoxy eleostearate that steps d is obtained in the presence of a catalyst with ring opening agent generation ring-opening reaction, generate poly-hydroxy eleostearic acid fat, be biopolyol; Ring-opening reaction temperature is 90 ~ 175 DEG C, and the reaction times is 1 ~ 8h; Described ring opening agent is any one in alcohol or hydramine, and ratio, adds the amount of ring opening agent for opening epoxy bond number=0.6 ~ 1.8 ︰ 1 in ring agent ︰ epoxy eleostearate; Described catalyzer is any one in alkali metal hydroxide, alkali metal alkoxide or organic bases.
Preferably, in above-mentioned reactions steps a, the alcohol in described alcohol water mixed solvent is any one in methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, phenylcarbinol, sorbyl alcohol, Xylitol or hexalin.
Preferably, in above-mentioned reactions steps a, described alkali metal hydroxide is any one in sodium hydroxide, lithium hydroxide or potassium hydroxide.
Preferably, in above-mentioned reactions steps a, described alkali metal alkoxide is any one in sodium methylate, sodium ethylate or potassium methylate.
Further, in above-mentioned reactions steps a, ratio, the amount adding catalyzer is Cuiization Ji ︰ tung oil=1 ~ 6.5 ︰ 1.
Preferably, in above-mentioned reactions steps b, the amount adding catalyzer is 0.1 ~ 5% of boric acid double glyceride and eleostearic acid gross weight.
Preferably, in above-mentioned reactions steps b, described acid is any one in the vitriol oil, hydrochloric acid, phosphoric acid or tosic acid.
Preferably, in above-mentioned reactions steps b, described anhydrous acid salt is any one in sal enixum, sodium-acetate, iron(ic) chloride or aluminum chloride.
Preferably, in above-mentioned reactions steps d, described peroxide organic acid is obtained by hydrogen peroxide oxidation organic acid.
Preferably, in above-mentioned reactions steps d, described organic acid is any one in formic acid, acetic acid, phenylformic acid or alkyl para Toluic Acid.
Further, in above-mentioned reactions steps d, described organic acid mole number is 0.5 ~ 2 times of unsaturated double-bond value in eleostearic acid mono-glycerides.
Further, in above-mentioned reactions steps d, the mole number of described hydrogen peroxide is 1.0 ~ 2.5 times of unsaturated double-bond value in eleostearic acid mono-glycerides.
Preferably, in above-mentioned reactions steps d, the add-on of described catalyzer accounts for 0.1 ~ 5% of eleostearic acid mono-glycerides weight.
Preferably, in above-mentioned reactions steps e, described hydramine is any one in monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine or trolamine.
Preferably, in above-mentioned reactions steps e, described alcohol is any one in methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, TriMethylolPropane(TMP), glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol or sorbyl alcohol.
Preferably, in above-mentioned reactions steps e, described alkali metal hydroxide be in sodium hydroxide, potassium hydroxide or lithium hydroxide any one.
Preferably, in above-mentioned reactions steps e, described alkali metal alkoxide be in sodium methylate, sodium ethylate or potassium methylate any one.
Preferably, in above-mentioned reactions steps e, described organic bases is any one in dimethylamine, Trimethylamine 99, triethylamine, N, N-dimethylcyclohexylamine or pentamethyl-diethylenetriamine.
Further, in above-mentioned reactions steps e, the add-on of described catalyzer is 0.5 ~ 2.5% of epoxy eleostearate and ring opening agent gross weight.
Second Problem to be solved by this invention is to provide the biopolyol that aforesaid method prepares.
3rd technical problem to be solved by this invention is the method utilizing above-mentioned biopolyol to prepare urethane foam.The method comprises the following steps: biopolyol and polyether glycol, auxiliary agent are mixed with premixed systems, then premixed systems and isocyanic ester is mixed, after foaming, curing molding; Described auxiliary agent comprises catalyzer, suds-stabilizing agent, fire retardant, whipping agent.
Preferably, in aforesaid method, described premixed systems is counted by weight ratio: biopolyol 20 ~ 50 parts, polyether glycol 50 ~ 80 parts, catalyzer 0.1 ~ 5 part, suds-stabilizing agent 0.1 ~ 5 part, whipping agent 0.5 ~ 5 part, fire retardant 0.5 ~ 20 part.
Concrete, in aforesaid method, described auxiliary agent also comprises at least one in linking agent, chainextender, tensio-active agent, tinting material, pore-creating agent, anti-aging agent, antifogging agent, releasing agent, antioxidant or softening agent.
Preferably, in aforesaid method, described catalyzer is at least one in organic amine or organotin.
Further, in aforesaid method, described organic amine is at least one in triethylamine, tripropyl amine, Tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethyl cyclohexyl amine, dimethylin sulfuric ether, triethylenediamine, trolamine, α-amino isopropyl alcohol, pentamethyl-diethylenetriamine or quaternary amine.
Further, in aforesaid method, the addition of described organic amine is 2 ~ 5% of biopolyol weight.
Further, in aforesaid method, described organotin is at least one in stannous octoate, dibutyl tin laurate or dibutyltin diacetate.
Further, in aforesaid method, the addition of described organotin is 0.1 ~ 0.5% of biopolyol weight.
Concrete, in aforesaid method, described suds-stabilizing agent is organic silicon surfactant.
Further, in aforesaid method, described organic silicon surfactant is any one in dimethyl silicone oil or ethyl silicon oil.
Further, in aforesaid method, the addition of described suds-stabilizing agent is 2 ~ 4% of biopolyol weight.
Concrete, in aforesaid method, described fire retardant is trichloroethyl phosphate, three (2,3-dibromopropyl) trimeric cyanamide fat, methyl-phosphoric acid dimethyl ester, halo acid anhydrides, TDE, many bromos phenyl ether, poly-dibromobenzene aether, three (2,3-dibromopropyl) poly-isocyanurates or pentabromochlorocyclohexane any one.
Concrete, in aforesaid method, described whipping agent is at least one in water, pentamethylene, iso-pentane, Skellysolve A, butane, hexane, hexanaphthene, a fluorine ethylene dichloride, 3-pentafluorobutane, Tetrafluoroethane, pentafluoropropane, difluorochloromethane, tetrafluoro ethyl-methyl ether or tetrafluoro methyl ethyl ether.
Concrete, in aforesaid method, described isocyanic ester is tolylene diisocyanate, diphenyl diisocyanate, xylylene diisocyanate, isophorone diisocyanate, nitro diphenyl diisocyanate, 1, hexamethylene-diisocyanate, 1, any one in the sub-how group diisocyanate of 5-, Isosorbide-5-Nitrae-Ya Nai group diisocyanate or their prepolymer type modification body, isocyanurate-modified body, urea modification body or carbodiimide modified body.
Further, in aforesaid method, the NCO in isocyanic ester is 0.8 ~ 1.5 with the ratio of the equivalent of the OH in premixed systems.
The present invention is the method that biopolyol prepared by raw material with tung oil, has that level of response is high, operating procedure wide ranges, controls functionality comparatively advantages of higher that is convenient, product; Simultaneously raw material have cost lower, do not strive with the people ground, not by petroleum resources impact, belong to the feature of bio-renewables; Production technique collectivity of the present invention is strong simultaneously, and conversion rate of products is high.
Embodiment
Chemical reaction principal reaction formula of the present invention is as follows:
Step a: saponification reaction (for methanol-water solvent, R'OH nail alcohol in formula):
Step b and c: esterification and hydrolysis reaction:
Steps d: epoxidation reaction (for formic acid):
Step e: ring-opening reaction (ring opening agent is for diisopropanolamine (DIPA)):
Alkali metal alkoxide described in the present invention is the product after alcohol and alkali metal hydroxide dewater, such as sodium methylate, sodium ethylate etc.
Anhydrous acid salt described in the present invention refers to that crystalline hydrate loses whole crystal water and the material formed, and just refers to the acid salt compound of general nodeless mesh water.
Embodiment 1
Step a: saponification reaction: in 250mL there-necked flask, add 6.7gKOH, 60mL methyl alcohol and 30mL water, be heated with stirring to 70 DEG C, adds 29.9g tung oil fast, reaction 2h, then after refining, obtain weak yellow liquid eleostearic acid 28.6g, acid number is 195.8mg/g;
Step b: esterification: 13.8g glycerine and 6.2g boric acid are joined in there-necked flask, under protection of inert gas, temperature controls at 200 DEG C, reaction 1.5h, then refine and obtain boroglyceride, add 28.7g eleostearic acid and 0.3g tosic acid again, temperature controls at 220 DEG C, obtains eleostearic acid boroglyceride after reaction 2h;
Step c: hydrolysis reaction: under room temperature, with the hydrochloric acid soln hydrolysis eleostearic acid boroglyceride of 2mol/L, then obtains eleostearic acid mono-glycerides product 35.2g through refining;
Steps d: epoxidation reaction: get eleostearic acid mono-glycerides 20g in step c and 1.48g formic acid (85%), the phosphoric acid of 0.1mL adds in the there-necked flask of 250mL, stir, drip 10.2g hydrogen peroxide (30%), 6h is reacted under the condition of 60 DEG C, again after refining, obtain epoxy eleostearate, oxirane value is 3.58%;
Step e: ring-opening reaction: by the product epoxy eleostearate 20g in steps d; diisopropanolamine (DIPA) 6.8g; potassium hydroxide 0.1g; control temperature of reaction 145 DEG C; under protection of inert gas, reaction 7h, then carries out refining to obtain product biopolyol 24.5g; hydroxyl value 435mgKOH/g, moisture≤0.10%.
Prepare urethane foam: get above-mentioned biopolyol 12g, polyether glycol 24.6g, dibutyl tin laurate 0.03g, trolamine 0.15g, three (2, 3 ?dibromopropyl) trimeric cyanamide fat 3.4g, silicone oil 1.05g and deionized water 0.35g adds in there-necked flask, after abundant stirring 20min, regulate blowing temperature to 25 DEG C, add 52.7g tolylene diisocyanate again, after abundant mixing, 10s is stirred under high speed agitator, pour into immediately in chunk, die temperature remains on 45 DEG C, then put into 50 DEG C of baking ovens to solidify 2h and can obtain urethane foam.
Embodiment 2
Step a: saponification reaction: in 250mL there-necked flask, add 7.8gNaOH, 70mL ethanol and 35mL water, be heated with stirring to 60 DEG C, adds 34.9g tung oil fast, reaction 1.5h, then after refining, obtain weak yellow liquid eleostearic acid 32.8g, acid number is 199.5mg/g;
Step b: esterification: 16.5g glycerine and 9.3g boric acid are joined in there-necked flask, under protection of inert gas, temperature controls at 180 DEG C, reaction 2h, then refine and obtain boroglyceride, add 34.8g eleostearic acid and 0.4g phosphoric acid again, temperature controls at 230 DEG C, obtains eleostearic acid boroglyceride after reaction 1.5h;
Step c: under room temperature, with the hydrochloric acid soln hydrolysis eleostearic acid boroglyceride of 2mol/L, then obtains eleostearic acid mono-glycerides product 39.4g through refining;
Steps d: epoxidation reaction: get eleostearic acid mono-glycerides 25g in step c and 1.85g formic acid (85%), the phosphoric acid of 0.1mL adds in the there-necked flask of 250mL, stir, drip 12.7g hydrogen peroxide (30%), 5h is reacted under the condition of 65 DEG C, again after refining, obtain epoxy eleostearate, oxirane value is 3.64%;
Step e: ring-opening reaction: by the product epoxy eleostearate 25g in steps d; trolamine 9.5g; potassium hydroxide 0.1g; control temperature of reaction 170 DEG C; under protection of inert gas, reaction 6h, then carries out refining to obtain product biopolyol 31.5g; hydroxyl value 410mgKOH/g, moisture≤0.10%.
Prepare urethane foam: get above-mentioned biopolyol 12.9g, polyether glycol 19.4g, dibutyl tin laurate 0.09g, trolamine 0.16g, three (2, 3-dibromopropyl) trimeric cyanamide fat 3.1g, silicone oil 0.97g and pentamethylene 4.86g adds in there-necked flask, after abundant stirring 20min, regulate blowing temperature to 22 DEG C, add 11.3g tolylene diisocyanate again, after abundant mixing, 8s is stirred under high speed agitator, pour into immediately in chunk, die temperature remains on 45 DEG C, then put into 90 DEG C of baking ovens to solidify 3h and can obtain urethane foam.
Claims (9)
1. utilize tung oil to prepare the method for biopolyol, it is characterized in that: comprise the following steps:
A, saponification reaction: tung oil is carried out saponification reaction with mixed solvent in the presence of a catalyst, generate eleostearic acid; Saponification reaction temperature is 50 ~ 95 DEG C, and the reaction times is 1 ~ 3h; Described catalyzer is any one in alkali metal hydroxide or alkali metal alkoxide; Described mixed solvent is alcohol water mixed solvent, counts ， Chun ︰ water=1.5 ~ 4 ︰ 1 by volume;
B, esterification: glycerine and boric acid, under protection of inert gas, esterification is occurred, generate boric acid double glyceride; Then eleostearic acid generation esterification boric acid double glyceride and step a obtained in the presence of a catalyst, generates eleostearic acid boroglyceride; The first step esterification reaction temperature is 160 ~ 280 DEG C, and the reaction times is 2 ~ 6h; Second step esterification reaction temperature is 180 ~ 260 DEG C, and the reaction times is 1 ~ 4h; Described catalyzer be acid or anhydrous acid salt in any one;
C, hydrolysis reaction: the eleostearic acid boric acid glycerin Ester hydrolysis obtained by step b again, generate eleostearic acid mono-glycerides;
D, epoxidation reaction: the eleostearic acid mono-glycerides obtained by step c adds epoxidizing agent in the presence of a catalyst and carries out epoxidation reaction, generate epoxy eleostearate; Epoxidation reaction temperature is 40 ~ 90 DEG C, reaction times 2 ~ 9h; Described catalyzer is any one in sulfuric acid or phosphoric acid; Described epoxidizing agent is peroxide organic acid;
E, ring-opening reaction: the epoxy eleostearate that steps d is obtained in the presence of a catalyst with ring opening agent generation ring-opening reaction, generate poly-hydroxy eleostearic acid fat, be biopolyol; Ring-opening reaction temperature is 90 ~ 175 DEG C, and the reaction times is 1 ~ 8h; Described ring opening agent is any one in alcohol or hydramine, and ratio, adds the amount of ring opening agent for opening epoxy bond number=0.6 ~ 1.8 ︰ 1 in ring agent ︰ epoxy eleostearate; Described catalyzer is any one in alkali metal hydroxide, alkali metal alkoxide or organic bases.
2. method according to claim 1, is characterized in that: in described step a, ratio, and the amount adding catalyzer is Cuiization Ji ︰ tung oil=1 ~ 6.5 ︰ 1.
3. method according to claim 1, is characterized in that: in described step b, and the amount adding catalyzer is 0.1 ~ 5% of boric acid double glyceride and eleostearic acid gross weight.
4. method according to claim 1, is characterized in that: in described steps d, and described catalyzer accounts for 0.1 ~ 5% of eleostearic acid mono-glycerides weight.
5. method according to claim 1, is characterized in that: in described step e, and the amount adding catalyzer is 0.5 ~ 2.5% of epoxy eleostearate and ring opening agent gross weight.
6. the biopolyol prepared by method described in Claims 1 to 5.
7. utilize the biopolyol described in claim 6 to prepare the method for urethane foam, it is characterized in that: comprise the following steps: biopolyol described in claim 6 and polyether glycol, auxiliary agent are mixed with premixed systems, again premixed systems and isocyanic ester are mixed, after foaming, curing molding; Wherein, described auxiliary agent comprises catalyzer, suds-stabilizing agent, fire retardant, whipping agent.
8. method according to claim 7, is characterized in that: described premixed systems is counted by weight ratio: biopolyol 20 ~ 50 parts, polyether glycol 50 ~ 80 parts, catalyzer 0.1 ~ 5 part, suds-stabilizing agent 0.1 ~ 5 part, whipping agent 0.5 ~ 5 part, fire retardant 0.5 ~ 20 part.
9. the method according to claim 7 or 8, is characterized in that: described auxiliary agent also comprises: at least one in linking agent, chainextender, tensio-active agent, tinting material, pore-creating agent, anti-aging agent, antifogging agent, releasing agent, antioxidant or softening agent.
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| CN105131237A (en) * | 2015-08-20 | 2015-12-09 | 盐城工学院 | Preparation method for plant oil-based rigid polyurethane foam plastics by all-water foaming |
| CN105712881A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Tung oil polyol with high hydroxyl value and preparation method thereof |
| CN106957227A (en) * | 2016-01-11 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of method for producing tung oil polyalcohol and by-product glycerol |
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN109111561A (en) * | 2018-08-24 | 2019-01-01 | 吉林大学 | A kind of eleostearic acid based polyurethanes sound-absorbing material and preparation method thereof |
| CN110951029A (en) * | 2019-11-27 | 2020-04-03 | 中国林业科学研究院林产化学工业研究所 | Organic silicon modified vegetable oil-based polyol and preparation method and application thereof |
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| CN105712881A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Tung oil polyol with high hydroxyl value and preparation method thereof |
| CN105712881B (en) * | 2014-12-05 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof |
| CN105131237A (en) * | 2015-08-20 | 2015-12-09 | 盐城工学院 | Preparation method for plant oil-based rigid polyurethane foam plastics by all-water foaming |
| CN105131237B (en) * | 2015-08-20 | 2017-12-22 | 盐城工学院 | The preparation method of full water foamed plant oil base RPUF |
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| CN106957227B (en) * | 2016-01-11 | 2020-01-10 | 中国石油化工股份有限公司 | Method for producing tung oil polyalcohol and byproduct glycerol |
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN109111561A (en) * | 2018-08-24 | 2019-01-01 | 吉林大学 | A kind of eleostearic acid based polyurethanes sound-absorbing material and preparation method thereof |
| CN110951029A (en) * | 2019-11-27 | 2020-04-03 | 中国林业科学研究院林产化学工业研究所 | Organic silicon modified vegetable oil-based polyol and preparation method and application thereof |
| CN111253549A (en) * | 2020-03-25 | 2020-06-09 | 上海应用技术大学 | Phosphorus-containing palm oil-based pure water polyurethane nano-emulsion and preparation method thereof |
| CN112521697A (en) * | 2020-11-23 | 2021-03-19 | 中国林业科学研究院林产化学工业研究所 | Tung oil hyperbranched polyester plasticizer and preparation method and application thereof |
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