CN102775585B - Polyester polyol and preparation method thereof - Google Patents
Polyester polyol and preparation method thereof Download PDFInfo
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- CN102775585B CN102775585B CN201210293315.0A CN201210293315A CN102775585B CN 102775585 B CN102775585 B CN 102775585B CN 201210293315 A CN201210293315 A CN 201210293315A CN 102775585 B CN102775585 B CN 102775585B
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Abstract
The invention relates to polyester polyol and a preparation method thereof, and in particular relates to polyester polyol which is prepared by using biomass colophony and crude glycerine serving as a productive biodiesel byproduct as raw materials, belonging to the technical fields of new techniques of organic polymer and comprehensive resource utilization as well as environment friendliness. The preparation method comprises the following steps of: simply purifying dihydric alcohol and the biodiesel byproduct to prepare refined glycerine and colophony; and performing catalytic esterification and etherification reaction on the refined glycerine and colophony under the heating condition to prepare polyester polyol, wherein the hydroxyl value of polyester polyol is 250-330mgKOH/g, and the acid value of polyester polyol is 3-10mgKOH/g.
Description
Technical field
The present invention relates to a kind of polyester polyol and preparation method thereof, be specifically related to a kind ofly with biomass rosin with to produce biological diesel oil byproduct raw glycerine be a kind of polyester polyol of preparing of raw material and preparation method thereof, belong to organic polymer, comprehensive utilization of resources and environmental friendliness novel technique field.
Background technology
Rosin is the important product of China's forest chemical industry, and more than 70 ten thousand tons of annual production, rank first in the world.It has the greasiness of condensing ring rigid structure, and thermotolerance is strong, and this structure is incorporated in polyvalent alcohol, certainly will exert an influence to performances such as its rigidity, gloss, thermotolerances, and then improve the performance by its synthetic material such as urethane resin.
The mixture that rosin is comprised of various kinds of resin acid and a small amount of neutral substance, wherein resinous acid is its main component, accounts for the more than 90% of its total amount.Resinous acid has ternary phenanthrene ring frame structure, and contains two two keys and a carboxyl, and its isomers can be divided into conjugated double bond type resinous acid, unconjugated double bond type resinous acid, dehydrogenation and hydrogenated resin acid.
The raw material of polyvalent alcohol Chang Zuowei urethane foam, conventionally requiring the polyvalent alcohol molecule of this purposes is polyfunctionality, and has viscosity and the molecular weight of certain limit.
China has abundant rosin resource, but its processing and utilization rate only reaches 40% left and right, and added value of product is lower, with the outlet of primary raw materials form, occupies larger proportion.
The patent CN1621429A of Bayer (China) Co., Ltd. application, prepares polyester polyol with aromatic anhydride, single by aliphatics, two or polyamines be basic polyethylene oxide/propylene oxide polyether glycol, for the preparation of rigid urethane foam; The patent CN1247656C of Yantai Wanhua Polyurethane Co., Ltd's application, prepares polyester polyol by dicarboxylic acid derivatives.The raw material of above utilization, is petrochemical complex resource, and well-known, oil is Nonrenewable resources, uses biomass resource petroleum replacing Chemicals, significant.
The present invention is by the by product raw glycerine of cheap rosin and production biofuel, for the preparation of a kind of polyester polyol, by chemical reaction, improve its technology content, value-added content of product is increased, its industrialization to the Sustainable development that promotes rosin process deeply industry and Biodiesel with and technical progress, have great importance.
Summary of the invention
One of object of the present invention is in order to make up the deficiencies in the prior art, and a kind of polyester polyol is provided, and the preparation of this polyester polyol adopts biomass rosin and produces biological diesel oil byproduct raw glycerine is raw material, and production cost is low;
Two of object of the present invention is to provide a kind of preparation method of polyester polyol, its technology of preparing mature and reliable.
Technical scheme of the present invention is as follows:
1. a polyester polyol
Polyester polyol of the present invention, is made by the raw material through chemical reaction of following mass parts:
Further preferred, polyester polyol is made by the raw material through chemical reaction of following mass parts:
Described refining glycerine is obtained by the by product refining crude glycerin of production biofuel;
Described catalyzer is the mixture of tosic acid and titanic acid ester, and the mass ratio of tosic acid and titanic acid ester is 1: 0.5-1.5, and it is one of following that titanic acid ester is selected from: tetra-n-butyl titanate, titanium isopropylate, metatitanic acid four n-propyls, tetraethyl titanate; The use of composite catalyst, causes speed of response to be accelerated, and the reaction times shortens;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
It is one of following that described dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
2. above-described polyester polyol, preparation process is as follows:
(1) raw glycerine is refining
In the raw glycerine of 100 mass parts, add the low boiling point organic solvent of 10-15 mass parts, then with acid, neutralize centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent obtaining recycles, temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine;
Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process;
Described biofuel transesterify, it is one of following that raw material is selected from: wild plant grease, engineering microalgae waterplant grease, animal grease, food garbage oil;
Described polar organic solvent, is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ethyl acetate; Low boiling point organic solvent, not only plays diluting effect, also has the glutinous effect of falling;
Described acid is hydrochloric acid or sulfuric acid; Acid makes to be coated on biofuel and the glycerine desorption in glycerine on the one hand, in addition, reacts generate lipid acid with soap, destroys the emulsifying effect of soap, and the rate of recovery of glycerine is increased.
(2) polyester polyol is synthetic
In reactor, add dibasic alcohol, refining glycerine, rosin, catalyzer, be heated to 180-200 ℃, reaction 1.5-2h, adds dicarboxylic anhydride, is warming up to 210-230 ℃, and reaction 4-6h is to anhydrous distillating, cooling, obtains polyester polyol;
Described hydroxyl value of polyester polyol 250-330mgKOH/g, acid number 3-10mgKOH/g.
Compared with prior art, polyester polyol of the present invention, its outstanding feature is:
(1) rosin and the by product refining glycerine that comes from production biofuel is common as the raw material of preparing polyester polyol.
In this technique, when 180-200 ℃ also catalyzer exists,, first there is intermolecular esterification reaction in dibasic alcohol, refining glycerine and rosin, generates low-molecular-weight hydroxyl telechelic polyester; Add dicarboxylic anhydride, then be warming up to 210-230 ℃, intermolecular by alcoholysis, esterification, molecular chain is further increased, generate macromole polyester polyol; The kind of two sections of heating methods and described raw material and ratio are this technology and the significant difference of other technologies.
(2) rosin is a kind of important natural product, also be a kind of renewable resources, the present invention is using rosin as one of synthetic raw material of polyester polyol, its ternary phenanthrene ring structure is introduced in polyvalent alcohol, rigidity, gloss, the thermotolerance of polyvalent alcohol have been increased, polyvalent alcohol raw materials cost is reduced, and added value of product increases; In addition, the present invention, by the by product raw glycerine of production biofuel, as the synthetic a kind of raw material of polyester polyol, can save and part petroleum replacing chemical resource; The use of rosin and raw glycerine, is rosin and raw glycerine resource, and new application approach and field is provided, and therefore, the Sustainable development of the industrialization of this polyvalent alcohol to ecotope and polyvalent alcohol, has great importance.
(3) this preparation technology is simple, easy to operate, and raw materials cost is low, and its industrialization has significant economic and social benefit.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment, and the change that this field professional does technical solution of the present invention, all should belong in protection scope of the present invention.
Embodiment 1
(1) raw glycerine is refining
In 100g raw glycerine, add the methyl alcohol of 10g, then with hydrochloric acid neutralization, centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, the methanol loop obtaining is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine, is by product raw glycerin phase separated in biofuel Exchange Ester Process, biofuel transesterify, and raw material is selected from food garbage oil;
(2) polyester polyol is synthetic
In reactor, add ethylene glycol 100g, refining glycerine 20g, rosin 40g, catalyzer 0.1g, be heated to 180 ℃, reaction 2h, adds Succinic anhydried 15g, is warming up to 210 ℃, and reaction 6h is to anhydrous distillating, cooling, obtains polyester polyol;
Described hydroxyl value of polyester polyol 253mgKOH/g, acid number 3.4mgKOH/g;
Described catalyzer is the mixture of tosic acid and tetra-n-butyl titanate, and the mass ratio of tosic acid and titanic acid ester is 1: 0.5.
Embodiment 2
(1) raw glycerine is refining
In the raw glycerine of 100g, add the acetone of 15g, then with sulfuric acid neutralization, centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, the acetone recycle obtaining is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process; Biofuel transesterify, raw material Viscotrol C;
(2) polyester polyol is synthetic
In reactor, add butyleneglycol 100g, refining glycerine 50g, rosin 60g, catalyzer 1.0g, be heated to 200 ℃, reaction 1.5h, adds Pyroglutaric acid 30g, is warming up to 230 ℃, and reaction 4h is to anhydrous distillating, cooling, obtains polyester polyol;
Described catalyzer is the mixture of tosic acid and titanium isopropylate, and the mass ratio of tosic acid and titanium isopropylate is 1: 1.3;
Described hydroxyl value of polyester polyol 304mgKOH/g, acid number 6.3mgKOH/g.
Embodiment 3
(1) raw glycerine is refining
In the raw glycerine of 100g, adding mass percent is the methyl acetate of 13g, then with hydrochloric acid, neutralizes centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, and the methyl acetate recycle obtaining is used, temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process; The raw material of biofuel transesterify is for reclaiming animal grease;
(2) polyester polyol is synthetic
In reactor, add neopentyl glycol 100g, refining glycerine 35g, rosin 50g, catalyzer 0.5g, be heated to 190 ℃, reaction 1.5h, adds adipic anhydride 20g, is warming up to 220 ℃, and reaction 5h is to anhydrous distillating, cooling, obtains polyester polyol;
Described catalyzer is the mixture of tosic acid and tetraethyl titanate, and the mass ratio of tosic acid and tetraethyl titanate is 1: 1.2;
Described hydroxyl value of polyester polyol 286mgKOH/g, acid number 3.3mgKOH/g.
Claims (2)
1. a polyester polyol, is characterized in that, by the raw material through chemical reaction of following mass parts, is made:
Described refining glycerine is obtained by the by product refining crude glycerin of production biofuel; Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process;
Described catalyzer is the mixture of tosic acid and titanic acid ester, and the mass ratio of tosic acid and titanic acid ester is 1:0.5-1.5, and it is one of following that titanic acid ester is selected from: tetra-n-butyl titanate, titanium isopropylate, metatitanic acid four n-propyls, tetraethyl titanate;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
It is one of following that described dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride;
Described polyester polyol, preparation process is as follows:
(1) raw glycerine is refining
In the raw glycerine of 100 mass parts, add the low boiling point organic solvent of 10-15 mass parts, then with acid, neutralize centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent obtaining recycles, temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine;
Described acid is hydrochloric acid or sulfuric acid;
Described organic solvent, is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ethyl acetate;
(2) polyester polyol is synthetic
In reactor, add dibasic alcohol, refining glycerine, rosin, catalyzer, be heated to 180-200 ℃, reaction 1.5-2h, adds dicarboxylic anhydride, is warming up to 210-230 ℃, and reaction 4-6h is to anhydrous distillating, cooling, obtains polyester polyol;
Described polyester polyol, hydroxyl value 250-330mgKOH/g, acid number 3-10mgKOH/g.
2. polyester polyol as claimed in claim 1, is characterized in that, by the raw material through chemical reaction of following mass parts, is made:
Described refining glycerine is obtained by the by product refining crude glycerin of production biofuel;
Described catalyzer is the mixture of tosic acid and titanic acid ester, and the mass ratio of tosic acid and titanic acid ester is 1:0.5-1.5, and it is one of following that titanic acid ester is selected from: tetra-n-butyl titanate, titanium isopropylate, metatitanic acid four n-propyls, tetraethyl titanate;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
It is one of following that described dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210293315.0A CN102775585B (en) | 2012-08-17 | 2012-08-17 | Polyester polyol and preparation method thereof |
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| CN201210293315.0A CN102775585B (en) | 2012-08-17 | 2012-08-17 | Polyester polyol and preparation method thereof |
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| CN102775585A CN102775585A (en) | 2012-11-14 |
| CN102775585B true CN102775585B (en) | 2014-04-02 |
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| CN107522832B (en) * | 2017-08-10 | 2020-05-19 | 郑州大学 | Bio-based polyester polyol, preparation method thereof, polyurethane rigid foam prepared from bio-based polyester polyol and preparation method of polyurethane rigid foam |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443899A (en) * | 2002-03-12 | 2003-09-24 | 牛华 | Preparation method of rosen polyester sizing agent |
| CN1683425A (en) * | 2005-02-24 | 2005-10-19 | 烟台万华聚氨酯股份有限公司 | Polymer polyester polyol, its producing process and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443899A (en) * | 2002-03-12 | 2003-09-24 | 牛华 | Preparation method of rosen polyester sizing agent |
| CN1683425A (en) * | 2005-02-24 | 2005-10-19 | 烟台万华聚氨酯股份有限公司 | Polymer polyester polyol, its producing process and its use |
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