CN111978525A - Method for preparing polyester polyol containing nitrogen heterocycle - Google Patents
Method for preparing polyester polyol containing nitrogen heterocycle Download PDFInfo
- Publication number
- CN111978525A CN111978525A CN202010967990.1A CN202010967990A CN111978525A CN 111978525 A CN111978525 A CN 111978525A CN 202010967990 A CN202010967990 A CN 202010967990A CN 111978525 A CN111978525 A CN 111978525A
- Authority
- CN
- China
- Prior art keywords
- polyester polyol
- glycol
- nitrogen
- hydroxyethyl
- isocyanurate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the field of polyols, in particular to a method for preparing polyols containing nitrogen heterocyclic ring, which comprises the following steps of synthesizing polyester polyol by using combined dihydric alcohol, trihydric alcohol, acid anhydride and dibasic acid, introducing tris (2-hydroxyethyl) isocyanurate, esterifying in a one-step synthesis mode, and removing micromolecules after complete reaction under the action of a catalyst to obtain a final product. The invention has the beneficial effects that the scheme of synthesizing the polyester polyol by introducing the nitrogen-containing heterocycle and then using the polyester polyol in polyurethane can obviously improve the oxygen index of the final liquid, can be used in a polyurethane system with higher flame-retardant requirement, has obvious flame-retardant effect and thus has strong practicability.
Description
Technical Field
The invention relates to the field of polyols, in particular to a method for preparing polyester polyol containing nitrogen heterocycles.
Background
The polyurethane rigid foam is widely applied to heat insulation materials, a large amount of flame retardant is often needed in application scenes needing high flame retardance, and even if the flame retardant is used, a high oxygen index is still difficult to obtain; while the Oxygen Index (OI) is the minimum oxygen concentration required for the material to undergo flaming combustion in a mixed gas stream of oxygen and nitrogen under specified conditions, a high oxygen index indicates that the material is not readily combustible, a low oxygen index indicates that the material is readily combustible, and the minimum oxygen concentration at which the material just maintains flaming combustion in a mixed gas of O2 and N2 at room temperature under specified test conditions is expressed as a percentage by volume, with a higher oxygen index indicating better flame retardancy.
Disclosure of Invention
The invention aims to solve the problems and invents a method for preparing polyester polyol with nitrogen heterocyclic ring, which is used for a polyurethane rigid foam system and can obviously improve the flame retardant property and increase the oxygen index.
The technical scheme of the invention is that the method for preparing the polyol containing the azacyclo is characterized in that the combined dihydric alcohol, trihydric alcohol, anhydride and dibasic acid are selected to synthesize polyester polyol, tris (2-hydroxyethyl) isocyanurate is introduced, and esterification is carried out in a one-step synthesis mode, and after complete reaction under the action of a catalyst, micromolecules are removed to obtain a final product.
As a further illustration of the invention, the dihydric alcohol is one or more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, neopentyl glycol.
As a further illustration of the invention, the triol is one or both of glycerol or trimethylolpropane.
As a further illustration of the invention, the dibasic acid is one or more of terephthalic acid, phthalic anhydride and adipic acid.
As a further illustration of the invention, the tris (2-hydroxyethyl) isocyanurate comprises 15-45% of the final liquid content.
As a further illustration of the invention, the esterification catalyst is one of T9, T12, T120, titanate, and the like.
As a further illustration of the present invention, the final product is a light yellow transparent liquid, i.e., a polyester polyol having a nitrogen-containing heterocycle, and the hydroxyl value of the polyester polyol is 150-350 mgKOH/g.
As a further illustration of the invention, the esterification catalyst is preferably present in an amount of from 0.01% to 0.2% of the substrate proportion.
The method for preparing the polyester polyol containing the nitrogen heterocycles has the advantages that the scheme that the polyester polyol is synthesized by introducing the nitrogen heterocycles and then used for polyurethane is adopted, so that the oxygen index of final liquid can be obviously improved, the method can be used for a polyurethane system with higher flame-retardant requirement, and the flame-retardant effect is obvious, so that the method has strong practicability.
Detailed Description
The invention provides a scheme for synthesizing polyester polyol by introducing nitrogen-containing heterocycles and then applying the polyester polyol to polyurethane, which can obviously improve the oxygen index of final liquid, in particular to a method for preparing the polyester polyol with the nitrogen-containing heterocycles.
The invention relates to a manufacturing process for preparing polyester polyol containing nitrogen heterocycles, which is realized by introducing nitrogen heterocycles, taking tris (2-hydroxyethyl) isocyanurate as a raw material and preparing the polyester polyol through one-time feeding esterification, specifically, the polyester polyol is synthesized by selecting combined dihydric alcohol, trihydric alcohol, anhydride and dibasic acid, introducing tris (2-hydroxyethyl) isocyanurate, and the esterification is completed in a one-time synthesis mode under the action of a catalyst, and then a final product is obtained after small molecules are removed, wherein the obtained final product is a light yellow transparent liquid which is the needed polyester polyol containing nitrogen heterocycles; wherein the materials are added, nitrogen replacement is carried out, the temperature is raised, esterification reaction is carried out under the action of a catalyst, the reaction temperature required by esterification catalysis is 90-170 ℃, the time is 3-8 hours, and after the temperature is reduced, the vacuum pumping is carried out to remove small molecules, the temperature is reduced, and the material is discharged to obtain the final product.
In the reaction, one of T9, T12, T120, titanate and the like is selected as an esterification catalyst, and the mentioned dihydric alcohol is one or more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexanediol and neopentyl glycol; the trihydric alcohol is one or two of glycerol or trimethylolpropane; the dibasic acid is one or more of terephthalic acid, phthalic anhydride and adipic acid; the content of the tris (2-hydroxyethyl) isocyanurate in the final liquid is 15-45%, while the esterification catalyst is preferably 0.01-0.2% of the substrate proportion, and the final product has a hydroxyl value of 150-350mgKOH/g by adjusting the ratio of the alcohol to the acid.
In order to better understand the invention, the invention will now be further illustrated by the following examples:
example 1: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 250g of tris (2-hydroxyethyl) isocyanurate, 250g of diethylene glycol, 50g of glycerol, 450g of phthalic anhydride and 0.2g T9 are added, nitrogen is replaced, then the temperature is raised to 150 ℃ for esterification reaction, the temperature is reduced to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is reduced and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 180mgKOH/g, and the viscosity is 27000cps (25 ℃).
Example 2: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 250g of tri (2-hydroxyethyl) isocyanurate, 350g of dipropylene glycol, 50g of glycerol, 450g of phthalic anhydride and 0.2g T9 of titanate are added, nitrogen is replaced, then the temperature is raised to 150 ℃ for esterification reaction, the temperature is lowered to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is lowered and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 230mgKOH/g, and the viscosity is 20000cps (25 ℃).
Example 3: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 350g of tris (2-hydroxyethyl) isocyanurate, 250g of diethylene glycol, 50g of glycerol, 450g of terephthalic acid and 0.2g T9 are added, nitrogen is replaced, then the temperature is raised to 150 ℃ for esterification reaction, the temperature is reduced to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is reduced and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 250mgKOH/g, and the viscosity is 21000cps (25 ℃).
Example 4: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 450g of tris (2-hydroxyethyl) isocyanurate, 250g of diethylene glycol, 50g of glycerol, 450g of phthalic anhydride and 0.2g T9 are added, nitrogen is replaced, the temperature is raised to 150 ℃ for esterification reaction, the temperature is reduced to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is reduced and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 290mgKOH/g, and the viscosity is 31000cps (25 ℃).
Example 5: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 350g of tris (2-hydroxyethyl) isocyanurate, 150g of diethylene glycol, 100g of ethylene glycol, 400g of adipic acid and 0.2g of titanate are added, nitrogen is replaced, then the temperature is raised to 150 ℃ for esterification reaction, the temperature is reduced to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is reduced and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 260mgKOH/g, and the viscosity is 20000cps (25 ℃).
Example 6: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 350g of tri (2-hydroxyethyl) isocyanurate, 200g of dipropylene glycol, 100g of glycerol, 400g of adipic acid and 0.2g T9 are added, nitrogen is replaced, then the temperature is raised to 150 ℃ for esterification reaction, the temperature is lowered to 130 ℃ after 5 hours, vacuum pumping is carried out for 3 hours, the temperature is lowered, discharging is carried out, and a light yellow transparent liquid is obtained, wherein the hydroxyl value test result is 260mgKOH/g, and the viscosity is 23000cps (25 ℃).
Example 7: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 250g of tri (2-hydroxyethyl) isocyanurate, 250g of ethylene glycol, 100g of trimethylolpropane, 560g of phthalic anhydride and 0.2g T12 are added, after nitrogen replacement, the temperature is raised to 150 ℃ for esterification reaction, after 5 hours, the temperature is lowered to 130 ℃, vacuum pumping is carried out for 3 hours, the temperature is lowered and discharging is carried out, thus obtaining light yellow transparent liquid, the hydroxyl value test result is 280mgKOH/g, and the viscosity is 27000cps (25 ℃).
Example 8: a water separator, a stirrer, a condenser, a thermometer and an electric heater are connected to a 1.5L 4-mouth flask, 450g of tris (2-hydroxyethyl) isocyanurate, 300g of dipropylene glycol, 200g of adipic acid, 200g of phthalic anhydride and 0.2g T9 are added, after nitrogen replacement, the temperature is raised to 150 ℃ for esterification reaction, after 5 hours, the temperature is lowered to 130 ℃, vacuum pumping is carried out for 3 hours, the temperature is lowered and discharging is carried out, thus obtaining a light yellow transparent liquid, the hydroxyl value test result is 200mgKOH/g, and the viscosity is 21000cps (25 ℃).
The light yellow liquid obtained in the above examples is polyester polyol having nitrogen-containing heterocycle, and table 1 shows that the oxygen index is measured after foaming based on the polyester polyol in examples 1, 2, 3, and 4 and the comparative commonly used phthalic anhydride polyester polyol.
TABLE 1
From the comparison of the data in the table 1, it can be easily found that under the condition of the same flame retardant dosage and the same black-white material ratio, the oxygen index is obviously improved and is generally improved by more than 2 percent compared with the traditionally used phthalic anhydride polyester polyol.
The technical solutions described above only represent the preferred technical solutions of the present invention, and some possible modifications to some parts of the technical solutions by those skilled in the art all represent the principles of the present invention, and fall within the protection scope of the present invention.
Claims (8)
1. A method for preparing polyatomic alcohol containing nitrogen heterocyclic ring is characterized in that dihydric alcohol, trihydric alcohol, acid anhydride and dibasic acid which are combined are selected to synthesize polyester polyol, tris (2-hydroxyethyl) isocyanurate is introduced, esterification is carried out in a one-step synthesis mode, and a final product is obtained after micromolecules are removed after complete reaction under the action of a catalyst.
2. The method of claim 1, wherein the diol is one or more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, and neopentyl glycol.
3. The method of claim 1, wherein the triol is one or both of glycerol and trimethylolpropane.
4. The method of claim 1, wherein the dibasic acid is one or more of terephthalic acid, phthalic anhydride, and adipic acid.
5. The method of claim 1, wherein the tris (2-hydroxyethyl) isocyanurate comprises 15-45% of the final liquid content.
6. The process of claim 1, wherein the esterification catalyst is one of T9, T12, T120, titanate, and the like.
7. The method as claimed in claim 1, wherein the final product is a light yellow transparent liquid, that is, a polyester polyol having a nitrogen-containing heterocyclic ring, and the hydroxyl value of the polyester polyol is 150-350 mgKOH/g.
8. The process of claim 1, wherein the esterification catalyst is preferably present in an amount of 0.01% to 0.2% based on the weight of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010967990.1A CN111978525A (en) | 2020-09-15 | 2020-09-15 | Method for preparing polyester polyol containing nitrogen heterocycle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010967990.1A CN111978525A (en) | 2020-09-15 | 2020-09-15 | Method for preparing polyester polyol containing nitrogen heterocycle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111978525A true CN111978525A (en) | 2020-11-24 |
Family
ID=73450510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010967990.1A Pending CN111978525A (en) | 2020-09-15 | 2020-09-15 | Method for preparing polyester polyol containing nitrogen heterocycle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111978525A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN109232849A (en) * | 2018-06-08 | 2019-01-18 | 青岛海尔股份有限公司 | Flame-proof polyol composition and preparation method thereof, application |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
-
2020
- 2020-09-15 CN CN202010967990.1A patent/CN111978525A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN109232849A (en) * | 2018-06-08 | 2019-01-18 | 青岛海尔股份有限公司 | Flame-proof polyol composition and preparation method thereof, application |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6133329A (en) | Aromatic polyester polyols made from a natural oil | |
| EP0835901A2 (en) | A method for preparation of recycled polyols and a method for manufacturing polyurethane foams | |
| WO2007072893A1 (en) | Catalyst for producing polyester and method for producing polyester | |
| CN105153410A (en) | Preparation method of flame retardant polyester ether polyol | |
| EP1178062B1 (en) | Method and apparatus for producing polyester polyol | |
| CN112831040A (en) | Method for synthesizing polyester ether polyol | |
| KR20200032669A (en) | Polyester resin composition and method for manufacturing the same | |
| CN111978525A (en) | Method for preparing polyester polyol containing nitrogen heterocycle | |
| CN107857896B (en) | A kind of ester composition and preparation method thereof from PTA substandard goods | |
| KR102054675B1 (en) | flame-retardant ester polyol, the manufacturing method thereof and polyisocyanurates including the anti-flame ester polyol | |
| CN105237752B (en) | A method of preparing polyalcohol using waste and old polyester bottle | |
| CN114805775B (en) | Regenerated PET polyester, regenerated flame-retardant PET foaming material and preparation method thereof | |
| JP3153875B2 (en) | Flame retardant polyester polyol composition | |
| KR100627209B1 (en) | Recycled Polyol Removed Aromatic Amine and Remained Glycol and Polyurethane Using the Same | |
| JP2000191756A (en) | Production of aromatic polyesterpolyol | |
| JP2001040075A (en) | Aromatic polyester polyol, its production and rigid polyurethane foam obtained from aromatic polyester polyol | |
| JP3197513B2 (en) | Flame retardant polyester polyol composition | |
| CN111995742A (en) | Method for preparing nitrogenous heterocyclic polyester polyol with good pentane compatibility | |
| US6323305B1 (en) | Process for preparing polyethylene naphthalate based polymers by using NDCA or its derivates | |
| KR102682807B1 (en) | Manufacturing method flame retardant polyol and flame retardant polyurethane by depolymerization | |
| CN102757554A (en) | Halogen-containing aromatic polycarbonate polyol as well as preparation method and application thereof | |
| RU2236422C1 (en) | Method for production of polyester-polyols and rigid foamed plastics based thereon | |
| JP4512491B2 (en) | Polyester polyol, polyurethane and rigid polyurethane foam using the same | |
| KR101269949B1 (en) | Fire retardancy recycled polyester using waste polyester and method thereof | |
| CN115785418B (en) | Polyester polyol, preparation method thereof and polyurethane flexible foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 213000 No. 28 ChuangSheng Road, Qiaonan village, Yaoguan Town, Wujin District, Changzhou City, Jiangsu Province Applicant after: Jiangsu Delida New Material Co.,Ltd. Address before: 213000 No. 28 ChuangSheng Road, Qiaonan village, Yaoguan Town, Wujin District, Changzhou City, Jiangsu Province Applicant before: Jiangsu Delida New Material Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201124 |
|
| WD01 | Invention patent application deemed withdrawn after publication |