CN102775585A - Polyester polyol and preparation method thereof - Google Patents
Polyester polyol and preparation method thereof Download PDFInfo
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- CN102775585A CN102775585A CN2012102933150A CN201210293315A CN102775585A CN 102775585 A CN102775585 A CN 102775585A CN 2012102933150 A CN2012102933150 A CN 2012102933150A CN 201210293315 A CN201210293315 A CN 201210293315A CN 102775585 A CN102775585 A CN 102775585A
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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 use biomass rosin and produce the biological diesel oil byproduct raw glycerine, belong to organic polymer, comprehensive utilization of resources and environmental friendliness novel technique field as a kind of polyester polyol of feedstock production and preparation method thereof.
Background technology
Rosin is the important product of China's forest chemical industry, and more than 70 ten thousand tons of YO rank first in the world.It has the greasiness of condensing ring rigid structure, and thermotolerance is strong, and this structure is incorporated in the polyvalent alcohol, certainly will exert an influence to performances such as its rigidity, gloss, thermotolerances, and then improve the performance by materials such as its synthetic urethane resins.
The mixture that rosin is made up of various kinds of resin acid and a small amount of neutral substance, wherein resinous acid is its staple, accounts for more than 90% of its total amount.Resinous acid has the 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, requiring the polyvalent alcohol molecule of this purposes usually is polyfunctionality, and has the viscosity and the molecular weight of certain limit.
China has abundant rosin resource, but its processing and utilization rate only reaches about 40%, and added value of product is lower, occupies bigger proportion with the outlet of primary raw materials form.
The patent CN1621429A of Bayer (China) Co., Ltd. application prepares polyester polyol with aromatic anhydride, use aliphatics single, two or polyamines as the polyethylene oxide/propylene oxide polyether glycol on basis, be used to prepare rigid urethane foam; The patent CN1247656C of Yantai Wanhua Polyurethane Co., Ltd's application prepares polyester polyol with dicarboxylic acid derivatives.The raw material that above technology is used is the petrochemical complex resource, and well-known, oil is Nonrenewable resources, uses biomass resource to substitute petrochemicals, and is significant.
The present invention is with the by product raw glycerine of cheap rosin and production biofuel; Be used to prepare a kind of polyester polyol; Improve its technology content through chemical reaction; Value-added content of product is increased, its industrialization to the Sustainable development that promotes rosin deep processing industry and biofuel industry with and technical progress, have great importance.
Summary of the invention
One of the object of the invention is in order to remedy the deficiency of prior art, a kind of polyester polyol to be provided, and it is raw material with producing the biological diesel oil byproduct raw glycerine that biomass rosin is adopted in the preparation of this polyester polyol, and production cost is low;
Two of the object of the invention provides a kind of preparation method of polyester polyol, its technology of preparing mature and reliable.
Technical scheme of the present invention is following:
1. 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:
Said refining glycerine is made with extra care and is got by the by product raw glycerine of production biofuel;
Said 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 said divalent alcohol is selected from: terepthaloyl moietie, Ucar 35, butyleneglycol, NSC 6366, tirethylene glycol, triethylene Glycol;
It is one of following that said 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 following:
(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, again with acid neutralization, spinning; Lower floor is used to prepare soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent that obtains recycles; Temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine;
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process;
It is one of following that said biofuel transesterify, raw material are selected from: wild plant grease, engineering microalgae waterplant grease, animal oil and fat, food garbage oil;
Said polar organic solvent is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ETHYLE ACETATE; Low boiling point organic solvent not only plays diluting effect, also has the glutinous effect of falling;
Said acid is hydrochloric acid or sulfuric acid; Acid makes biofuel and the glycerine desorption that is coated in the glycerine on the one hand, in addition, generates lipid acid with the soap reaction, destroys the emulsifying effect of soap, and the recovery of glycerine is increased.
(2) polyester polyol is synthetic
In reaction kettle, add divalent alcohol, refining glycerine, rosin, catalyzer, be heated to 180-200 ℃, reaction 1.5-2h adds dicarboxylic anhydride, is warming up to 210-230 ℃, reaction 4-6h, and to anhydrous distillating, cooling promptly gets polyester polyol;
Said 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 characteristics are:
(1) with the common raw material of rosin and the by product refining glycerine that comes from the production biofuel as the preparation polyester polyol.
In this technology, when 180-200 ℃ also catalyzer existed, intermolecular esterification reaction took place earlier in divalent alcohol, refining glycerine and rosin, generates low-molecular-weight hydroxyl telechelic polyester; Add dicarboxylic anhydride, be warming up to 210-230 ℃ again, intermolecular through alcoholysis, esterification, molecular chain is further increased, generate the macromole polyester polyol; The kind of two sections heating methods and said raw material and ratio are the significant difference of present technique and other technologies.
(2) rosin is a kind of important natural product; It also is a kind of renewable resources; The present invention as one of polyester polyol synthetic raw material, introduces rosin in the polyvalent alcohol with its ternary phenanthrene ring structure, has increased rigidity, gloss, the thermotolerance of polyvalent alcohol; The polyvalent alcohol raw materials cost is reduced, and added value of product increases; In addition, the present invention as a kind of raw material of polyester polyol synthetic, can practice thrift the by product raw glycerine of production biofuel with part and substitute the petrochemical complex 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 industrialization of this polyvalent alcohol has great importance to the Sustainable development of ecotope and polyvalent alcohol.
(3) this preparation technology is simple, and is easy to operate, and raw materials cost is low, and its industrialization has remarkable economical and social benefit.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention not only is confined to embodiment, the change that this field professional does technical scheme of the present invention all should belong in protection scope of the present invention.
Embodiment 1
(1) raw glycerine is refining
In the 100g raw glycerine, add the methyl alcohol of 10g, again with the hydrochloric acid neutralization, spinning, lower floor is used to prepare soap, upper strata liquid underpressure distillation, the methanol loop that obtains is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process, the biofuel transesterify, and raw material is selected from food garbage oil;
(2) polyester polyol is synthetic
In reaction kettle, add terepthaloyl moietie 100g, refining glycerine 20g, rosin 40g, catalyzer 0.1g, be heated to 180 ℃, reaction 2h adds Succinic anhydried 15g, is warming up to 210 ℃, reaction 6h, and to anhydrous distillating, cooling promptly gets polyester polyol;
Said hydroxyl value of polyester polyol 253mgKOH/g, acid number 3.4mgKOH/g;
Said 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, again with the sulfuric acid neutralization, spinning, lower floor is used to prepare soap, upper strata liquid underpressure distillation, the acetone recycle that obtains is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process; The biofuel transesterify, the raw material Viscotrol C;
(2) polyester polyol is synthetic
In reaction kettle, 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 ℃, reaction 4h, and to anhydrous distillating, cooling promptly gets polyester polyol;
Said catalyzer is the mixture of tosic acid and titanium isopropylate, and the mass ratio of tosic acid and titanium isopropylate is 1: 1.3;
Said 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, again with hydrochloric acid neutralization, spinning; Lower floor is used to prepare soap, upper strata liquid underpressure distillation, and the methyl acetate recycle that obtains is used; Temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process; The raw material of biofuel transesterify is for reclaiming animal oil and fat;
(2) polyester polyol is synthetic
In reaction kettle, add NSC 6366 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 ℃, reaction 5h, and to anhydrous distillating, cooling promptly gets polyester polyol;
Said catalyzer is the mixture of tosic acid and tetraethyl titanate, and the mass ratio of tosic acid and tetraethyl titanate is 1: 1.2;
Said hydroxyl value of polyester polyol 286mgKOH/g, acid number 3.3mgKOH/g.
Claims (7)
1. a polyester polyol is characterized in that, is made by the raw material through chemical reaction of following mass parts:
Said refining glycerine is made with extra care and is got by the by product raw glycerine of production biofuel;
Said 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 said divalent alcohol is selected from: terepthaloyl moietie, Ucar 35, butyleneglycol, NSC 6366, tirethylene glycol, triethylene Glycol;
It is one of following that said dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
2. new polyester polyvalent alcohol as claimed in claim 1 is characterized in that, is made by the raw material through chemical reaction of following mass parts:
Said refining glycerine is made with extra care and is got by the by product raw glycerine of production biofuel;
Said 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 said divalent alcohol is selected from: terepthaloyl moietie, Ucar 35, butyleneglycol, NSC 6366, tirethylene glycol, triethylene Glycol;
It is one of following that said dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
3. according to claim 1 or claim 2 new polyester polyvalent alcohol is characterized in that said polyester polyol preparation process is following:
(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, again with acid neutralization, spinning; Lower floor is used to prepare soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent that obtains recycles; Temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine;
(2) polyester polyol is synthetic
In reaction kettle, add divalent alcohol, refining glycerine, rosin, catalyzer, be heated to 180-200 ℃, reaction 1.5-2h adds dicarboxylic anhydride, is warming up to 210-230 ℃, reaction 4-6h, and to anhydrous distillating, cooling promptly gets polyester polyol.
4. like the described new polyester polyvalent alcohol of claim 1-3, it is characterized in that said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process.
5. new polyester polyvalent alcohol as claimed in claim 3 is characterized in that, the organic solvent in the said step (1) is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ETHYLE ACETATE.
6. new polyester polyvalent alcohol as claimed in claim 3 is characterized in that, the acid in the said step (1) is hydrochloric acid or sulfuric acid.
7. like the described new polyester polyvalent alcohol of claim 1-6, hydroxyl value 250-330mgKOH/g, acid number 3-10mgKOH/g.
Priority Applications (1)
| 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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| 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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| CN102775585A true CN102775585A (en) | 2012-11-14 |
| CN102775585B CN102775585B (en) | 2014-04-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522832A (en) * | 2017-08-10 | 2017-12-29 | 郑州大学 | A kind of bio-based polyurethane polyalcohol and preparation method thereof and the hard polyurethane foam and the method for preparation using its preparation |
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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- 2012-08-17 CN CN201210293315.0A patent/CN102775585B/en not_active Expired - Fee Related
Patent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522832A (en) * | 2017-08-10 | 2017-12-29 | 郑州大学 | A kind of bio-based polyurethane polyalcohol and preparation method thereof and the hard polyurethane foam and the method for preparation using its preparation |
| 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 |
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| CN102775585B (en) | 2014-04-02 |
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