CN104387568A - Synthesis method of biological-based polyester polyol - Google Patents
Synthesis method of biological-based polyester polyol Download PDFInfo
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- CN104387568A CN104387568A CN201410778450.3A CN201410778450A CN104387568A CN 104387568 A CN104387568 A CN 104387568A CN 201410778450 A CN201410778450 A CN 201410778450A CN 104387568 A CN104387568 A CN 104387568A
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Abstract
The invention belongs to the technical field of polyester polyol synthesis, and in particular relates to a synthesis method of biological-based polyester polyol. The synthesis method comprises the steps of adding a mixture of micromolecular acid and micromolecular alcohol into a reaction kettle, generating polymerization reaction under the action of a catalyst, and adding an antioxidant after all indexes are standard for cooling and blanking to obtain biological-based polyester polyol. The polyester polyol synthesized by the synthesis method disclosed by the invention is excellent in mechanical property and usability and can meet the requirement on the use of a polyurethane material; by the adoption of a biological base with 100 percent of butanedioic acid, the environmental footprint is reduced; furthermore, a product is stable in quality and environment-friendly; carbon dioxide is isolated, so that the energy efficiency is high; biological-based micromolecular alcohol replaces conventional micromolecular alcohol, so that a large amount of oxygen does not need to be consumed in a raw material production process, waste gas and wastewater cannot be emitted, required raw materials are renewable and highly available, and the environmental pollution is reduced.
Description
Technical field
The invention belongs to polyester polyol synthesis technical field, be specifically related to a kind of synthetic method of biological poly ester polyol.
Background technology
Polyurethane material, as the increasing macromolecular material of application, is widely used in the numerous areas such as building, traffic, weaving, printing packaging, tackiness agent with the mechanical property of its excellence, high abrasion and the advantage such as resilience, working conditions variation.Just because of this, the process of polyurethane material waste product and its impact of environment is more and more come into one's own.Polyester polyol is as one of important raw material of polyurethane industries among others, and its structures shape performance and the characteristic of prepared material.
Usual polyester polyol synthesizes primarily of hexanodioic acid and small molecular alcohol, and most domestic hexanodioic acid is that cyclohexane oxidation process or the synthesis of hexalin nitric acid oxidation method obtain, and is the derived product of Nonrenewable resources.Along with the enhancing of people's environmental consciousness and the appearance of national a series of policies and regulations, develop and a kind ofly can meet polyurethane material user demand and can reduce again the polyester polyol product of environmental hazard very urgent.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of biological poly ester polyol, the polyester polyol obtained not only has splendid mechanical property, preferably use properties, and Bio-based content is higher, is beneficial to environmental protection.
The synthetic method of biological poly ester polyol of the present invention joins in reactor by small molecules acid with the mixture of small molecular alcohol; under oxygen free condition and nitrogen protection; polymerization reaction take place under the effect of catalyzer, adds oxidation inhibitor cooling blowing, to obtain final product after indices is all up to standard.
With weight parts,
Described small molecules acid is bio-based succinic acid.Bio-based succinic acid is based on yeast-leavened explained hereafter, 100% bio-based materials.
Described small molecules acid also comprises hexanodioic acid or sebacic acid.
Hexanodioic acid or sebacic acid are added or do not added to described small molecules acid, based on bio-based succinic acid, as small molecules acid constituents, addition≤10 part of hexanodioic acid or sebacic acid in right amount.
Described small molecular alcohol is one or more in biological ethyl glycol, bio-based 1,3-PD or bio-based BDO.
Described catalyzer is organic titanate class catalyzer or organic tin catalyzer.
Described organic titanate class catalyzer is the one in metatitanic acid four methyl esters, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate; Organic tin catalyzer is the one in stannous octoate, di-nbutyltin oxide or Mono-n-butyltin; The sub-tin of catalyzer preferably octanoic acid.
Described oxidation inhibitor is the one in Hinered phenols, phosphorous acid esters or complex class oxidation inhibitor, preferred antioxidant 1010.
Described indices is acid number≤1mgKOH/g, and hydroxyl value is 117-55mgKOH/g, and water content is less than 0.05%.
The synthetic method of biological poly ester polyol of the present invention, step is as follows:
(1) get small molecules acid and small molecular alcohol joins in the reactor that thermometer, water-and-oil separator and agitator are housed, nitrogen protection, is heated to 225 DEG C with 20 DEG C/h temperature rise rate, controls top warm lower than 100 DEG C;
(2) when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add catalyzer after 0.8-1.2h and carry out polycondensation, when acid number is less than 1.0mgKOH/g, stopped reaction, be cooled to 140 DEG C to add oxidation inhibitor and mix, obtain product.
The present invention compared with prior art, has following beneficial effect:
(1) the polyester polyol mechanical property of the present invention's synthesis and use properties excellent, the requirement that polyurethane material uses can be met;
(2) succinic acid that the present invention adopts is 100% bio-based, reduces environmental footprint, and constant product quality, more friendly to environment, carbon dioxide sequestration (CO
2), Energy efficiency is high;
(3) the present invention adopts bio-based small molecular alcohol to substitute conventional small molecule alcohol, and do not need to consume a large amount of oxygen in this raw material production process, do not have waste gas, discharge of wastewater, desired raw material belongs to renewable, abundance, reduces environmental pollution;
(4) the present invention finally obtains high, the easy to use and eco-friendly polyester polyol of a kind of Bio-based content.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
By bio-based succinic acid 61 parts; bio-based ethylene glycol 38 parts joins in the reactor that thermometer, water-and-oil separator and agitator are housed; nitrogen protection; 225 DEG C are heated to 20 DEG C/h temperature rise rate; control top temperature lower than 100 DEG C; when aquifer yield reaches 85% of theoretical aquifer yield; start to vacuumize; control vacuum tightness and be less than 0.096MPa; add 0.05 part of tetrabutyl titanate after 1h and carry out polycondensation, when acid number is 0.8mgKOH/g, stopped reaction; be cooled to 140 DEG C to add 0.5 part of antioxidant 1010 and mix, after cooling, obtain product.
Gained polyester polyol index is as follows: be solid under normal temperature, acid number (mgKOH/g): 0.8, hydroxyl value (mgKOH/g): 117, and water content is 0.03%.
Embodiment 2
By bio-based succinic acid 57 parts, bio-based ethylene glycol 17 parts, bio-based 1, 4 butyleneglycols 25 parts join and thermometer are housed, in the reactor of water-and-oil separator and agitator, nitrogen protection, 225 DEG C are heated to 20 DEG C/h temperature rise rate, control top temperature lower than 100 DEG C, when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add 0.1 part of stannous octoate after 0.8h and carry out polycondensation, when acid number is 0.4mgKOH/g, stopped reaction, be cooled to 140 DEG C to add 0.5 part of antioxidant 1010 and mix, product is obtained after cooling.
Gained polyester polyol index is as follows: be solid under normal temperature, acid number (mgKOH/g): 0.4, hydroxyl value (mgKOH/g): 76, and water content is 0.03%.
Embodiment 3
By bio-based succinic acid 55 parts, bio-based 1, ammediol 20 parts, bio-based 1, 4 butyleneglycols 24 parts join and thermometer are housed, in the reactor of water-and-oil separator and agitator, nitrogen protection, 225 DEG C are heated to 20 DEG C/h temperature rise rate, control top temperature lower than 100 DEG C, when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add 0.05 part of stannous octoate after 1.2h and carry out polycondensation, when acid number is 1.0mgKOH/g, stopped reaction, be cooled to 140 DEG C to add 0.8 part of antioxidant 1010 and mix, product is obtained after cooling.
Gained polyester polyol index is as follows: be solid under normal temperature, acid number (mgKOH/g): 1.0, hydroxyl value (mgKOH/g): 63, and water content is 0.03%.
Embodiment 4
By bio-based succinic acid 51 parts, hexanodioic acid 10 parts, bio-based ethylene glycol 17 parts, bio-based 1, ammediol 21 parts joins and thermometer is housed, in the reactor of water-and-oil separator and agitator, nitrogen protection, 225 DEG C are heated to 20 DEG C/h temperature rise rate, control top temperature lower than 100 DEG C, when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add 0.07 part of stannous octoate after 1h and carry out polycondensation, when acid number is 0.5mgKOH/g, stopped reaction, be cooled to 140 DEG C to add 1 part of antioxidant 1010 and mix, product is obtained after cooling.
Gained polyester polyol index is as follows: be wax-like under normal temperature, acid number (mgKOH/g): 0.5, hydroxyl value (mgKOH/g): 55, and water content is 0.03%.
Embodiment 5
By bio-based succinic acid 53 parts, sebacic acid 6 parts, bio-based ethylene glycol 16 parts, bio-based 1, 4-butyleneglycol 24 parts joins and thermometer is housed, in the reactor of water-and-oil separator and agitator, nitrogen protection, 225 DEG C are heated to 20 DEG C/h temperature rise rate, control top temperature lower than 100 DEG C, when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add 0.05 part of stannous octoate after 1h and carry out polycondensation, when acid number is 0.4mgKOH/g, stopped reaction, be cooled to 140 DEG C to add 0.5 part of antioxidant 1010 and mix, product is obtained after cooling
Gained polyester polyol index is as follows: be wax-like under normal temperature, acid number (mgKOH/g): 0.7, hydroxyl value (mgKOH/g): 56, and water content is 0.03%.
Claims (10)
1. the synthetic method of a biological poly ester polyol; small molecules acid is it is characterized in that to join in reactor with the mixture of small molecular alcohol, under oxygen free condition and nitrogen protection, polymerization reaction take place under the effect of catalyzer; add oxidation inhibitor cooling blowing after indices is all up to standard, to obtain final product.
2. the synthetic method of biological poly ester polyol according to claim 1, is characterized in that with weight parts,
3. the synthetic method of biological poly ester polyol according to claim 1, is characterized in that described small molecules acid is bio-based succinic acid.
4. the synthetic method of biological poly ester polyol according to claim 3, is characterized in that described small molecules acid also comprises hexanodioic acid or sebacic acid.
5. the synthetic method of biological poly ester polyol according to claim 1, is characterized in that described small molecular alcohol is one or more in biological ethyl glycol, bio-based 1,3-PD or bio-based BDO.
6. the synthetic method of biological poly ester polyol according to claim 1, is characterized in that described catalyzer is organic titanate class catalyzer or organic tin catalyzer.
7. the synthetic method of biological poly ester polyol according to claim 6, is characterized in that described organic titanate class catalyzer is the one in metatitanic acid four methyl esters, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate; Organic tin catalyzer is the one in stannous octoate, di-nbutyltin oxide or Mono-n-butyltin.
8. the synthetic method of biological poly ester polyol according to claim 1, is characterized in that described oxidation inhibitor is the one in Hinered phenols, phosphorous acid esters or complex class oxidation inhibitor.
9. the synthetic method of biological poly ester polyol according to claim 1, it is characterized in that described indices is acid number≤1mgKOH/g, hydroxyl value is 117-55mgKOH/g, and water content is less than 0.05%.
10., according to the synthetic method of the arbitrary described biological poly ester polyol of claim 1-9, it is characterized in that step is as follows:
(1) get small molecules acid and small molecular alcohol joins in the reactor that thermometer, water-and-oil separator and agitator are housed, nitrogen protection, is heated to 225 DEG C with 20 DEG C/h temperature rise rate, controls top warm lower than 100 DEG C;
(2) when aquifer yield reaches 85% of theoretical aquifer yield, start to vacuumize, control vacuum tightness and be less than 0.096MPa, add catalyzer after 0.8-1.2h and carry out polycondensation, when acid number is less than 1.0mgKOH/g, stopped reaction, be cooled to 140 DEG C to add oxidation inhibitor and mix, obtain product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| CN110105552A (en) * | 2019-04-19 | 2019-08-09 | 广东大盈新材料科技有限公司 | A kind of biomass environment-friendly polyester polyol and preparation method thereof |
| CN113518613A (en) * | 2019-02-27 | 2021-10-19 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN113549199A (en) * | 2021-07-23 | 2021-10-26 | 华大化学集团有限公司 | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof |
| CN116102717A (en) * | 2022-02-25 | 2023-05-12 | 沈阳工业大学 | Preparation method and application of novel biodegradable aliphatic copolyester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130597A (en) * | 2007-09-29 | 2008-02-27 | 山东东大一诺威聚氨酯有限公司 | Synthesis method of solvent resistant solvent type urethane elastomer |
| CN102532460A (en) * | 2011-12-14 | 2012-07-04 | 浙江华峰新材料股份有限公司 | Bio-based polyurethane microporous elastomer, preparation method and application thereof |
| WO2013026809A1 (en) * | 2011-08-23 | 2013-02-28 | Basf Se | Method for producing polyurethanes |
| CN103183816A (en) * | 2013-04-20 | 2013-07-03 | 德州市鑫华润聚胺酯工业有限公司 | Solvent resistance polyester polyol synthesizing method |
-
2014
- 2014-12-16 CN CN201410778450.3A patent/CN104387568A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130597A (en) * | 2007-09-29 | 2008-02-27 | 山东东大一诺威聚氨酯有限公司 | Synthesis method of solvent resistant solvent type urethane elastomer |
| WO2013026809A1 (en) * | 2011-08-23 | 2013-02-28 | Basf Se | Method for producing polyurethanes |
| CN102532460A (en) * | 2011-12-14 | 2012-07-04 | 浙江华峰新材料股份有限公司 | Bio-based polyurethane microporous elastomer, preparation method and application thereof |
| CN103183816A (en) * | 2013-04-20 | 2013-07-03 | 德州市鑫华润聚胺酯工业有限公司 | Solvent resistance polyester polyol synthesizing method |
Non-Patent Citations (3)
| Title |
|---|
| 俞中锋 等: "聚氨酯用丁二酸聚酯二醇的合成", 《聚氨酯工业》 * |
| 杨茹果 等: "丁二酸系聚氨酯弹性体的研制", 《太原理工大学学报》 * |
| 赵兵 等: "丁二酸聚酯二元醇及其在聚氨酯中的应用", 《聚氨酯工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| CN113518613A (en) * | 2019-02-27 | 2021-10-19 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN113518613B (en) * | 2019-02-27 | 2023-12-01 | 巴斯夫欧洲公司 | Bio-based pearlescent wax |
| CN110105552A (en) * | 2019-04-19 | 2019-08-09 | 广东大盈新材料科技有限公司 | A kind of biomass environment-friendly polyester polyol and preparation method thereof |
| CN110105552B (en) * | 2019-04-19 | 2021-09-14 | 广东大盈新材料科技有限公司 | Biomass environment-friendly polyester polyol and preparation method thereof |
| CN113549199A (en) * | 2021-07-23 | 2021-10-26 | 华大化学集团有限公司 | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof |
| CN113549199B (en) * | 2021-07-23 | 2024-01-30 | 华大化学集团有限公司 | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof |
| CN116102717A (en) * | 2022-02-25 | 2023-05-12 | 沈阳工业大学 | Preparation method and application of novel biodegradable aliphatic copolyester |
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Application publication date: 20150304 |