CN111171264A - Preparation method of lignin polyurethane - Google Patents
Preparation method of lignin polyurethane Download PDFInfo
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2375/08—Polyurethanes from polyethers
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Abstract
The application discloses a preparation method of lignin polyurethane. The method comprises the following steps: mixing the polyalcohol, glycerol and acid catalyst uniformly according to a formula ratio, and preheating to 40-55 ℃; adding lignin while stirring, heating to 100-180 deg.C, reacting for 1.0-4.0 hr under the protection of inert gas, and stopping; adding an alkali regulator to adjust the pH value of the solution to 7.0-7.5, dialyzing, distilling under reduced pressure to obtain lignin polyol, preparing combined ether, and finally compounding with raw materials such as isocyanate and the like to obtain the polyurethane material. The liquid polyol is prepared from the renewable biological resource lignin, so that the defects that the lignin is poor in solubility and not easy to serve as a modifier for polyurethane and alkyd resin are overcome, part of petrochemical raw materials can be replaced, and the production cost of the polyol is reduced; the lignin-based polyol has good use effect, and the process is simple and easy to implement; volatile organic solvent is not used in the polyurethane synthesis link, so that the production process does not pollute the environment, and the cost of the polyurethane product is reduced.
Description
Technical Field
The application relates to the field of preparation of high polymer materials, in particular to a preparation method of lignin polyurethane.
Background
Polyurethane (Polyurethane) PU is a polymer having a repeating structural unit of urethane generally prepared by the reaction of di-or poly-organic isocyanate and a polyol compound (polyether polyol or polyether polyol), and is one of the widely used polymer materials. The polyether polyol and the polyether vinegar are important chemical intermediates for producing polyurethane materials. At present, raw materials for producing the polyvinyl acetate and the polyether polyol are from petrochemical products with strong toxicity and corrosivity, such as benzene alcohol, phthalic acid and the like. However, the polyurethane industry has been greatly impacted as the depletion of petroleum resources has progressed. In addition, the use of petrochemical resources in large quantities also causes serious environmental problems. Therefore, the development of new alternative resources for the development of the polyurethane industry has become a major issue that the human society must solve in the new century.
Disclosure of Invention
The present application is provided to solve the above-mentioned technical problems.
The technical scheme adopted by the application is as follows: the preparation method of the lignin polyurethane is characterized by comprising the following steps:
(1) preparation of lignin polyol: weighing 50-90 parts of polyol, 5-25 parts of glycerol and 1-7 parts of acid catalyst in parts by weight, adding the materials into a reaction device, uniformly mixing, and preheating to 40-55 ℃; adding 8-60 parts of lignin while stirring, heating to 100-180 ℃, reacting for 1.0-4.0h under the protection of inert gas, and then stopping; and adding an alkali regulator to regulate the pH value of the solution to 7.0-7.5, dialyzing, and distilling under reduced pressure to obtain the lignin modified polyol.
(2) Preparing the combined polyether: mixing and stirring uniformly 100-150 parts of lignin polyol, 50-100 parts of polyether polyol, 1-3 parts of amine catalyst, 0.05-0.2 part of organic tin catalyst and 10-30 parts of flame retardant to obtain composite polyether;
(3) synthesis of lignin polyurethane: mixing the combined polyether obtained in the step (2) with isocyanate according to the mass ratio of 0.6: 1-1.5: 1, uniformly mixing, spreading in a container, heating to 50-70 ℃, and curing to obtain lignin polyurethane;
or adding 0.5-2 parts by mass of foam stabilizer and 10-30 parts by mass of foaming agent into the combined polyether obtained in the step (3); adding isocyanate, and mixing the combined polyether and the isocyanate according to the mass ratio of 0.6: 1-1.5: 1; stirring foaming or spraying foaming is adopted to obtain the polyurethane foam.
Further, the lignin in the step (1) is one or more of acetic acid lignin, 1, 4-butanediol lignin, ethylene glycol lignin, alkali extraction lignin and enzymatic hydrolysis lignin.
Further, the polyester polyol is polyether polyol or polyester polyol; the polyol is a polyol with weight average molecular weight less than 2000 and is liquid at normal temperature.
Further, the glycerol is used as an auxiliary liquefaction agent of the lignin polyol.
Further, the acid catalyst is one or a mixture of sulfuric acid, acetic acid, nitric acid or phosphoric acid.
Further, the alkali regulator is one or a mixture of more of sodium hydroxide, ammonia water and potassium hydroxide.
Further, the amine catalyst in the step (2) is one or more of triethylene diamine, triethylamine, tetramethyl diethylene diamine, dimethyl cyclohexylamine, diethanolamine, triethanolamine, diethylene glycol amine and isopropanolamine; the organic tin catalyst is one or more of stannous octoate, dibutyltin dilaurate, monobutyltin oxide and dibutyltin oxide; the phosphorus-containing flame retardant is tris (2-chloropropane) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate or dimethyl methyl phosphate.
Further, the foam stabilizer in the step (3) is an organosilicon surfactant or a nonionic surfactant; the foaming agent is an inert hydrocarbon compound with a low boiling point; the isocyanate is aromatic isocyanate.
Further, the organosilicon surfactant is dimethyl siloxane; the nonionic surfactant is polyoxyethylene sorbitan mono fatty acid ester; the inert hydrocarbon compound with low boiling point is monofluorodichloroethane, 1, 3, 3-pentafluoropropane or 1, 1, 3, 3-pentafluorobutane; the aromatic isocyanate is toluene diisocyanate, xylene diisocyanate or diphenylmethane diisocyanate.
The application has the advantages and positive effects that: according to the preparation method of the lignin polyurethane, the renewable biological resource lignin is prepared into the liquid polyol, so that the defects that the lignin is poor in solubility and not easy to serve as a modifier for polyurethane and alkyd resin are overcome, part of petrochemical raw materials can be replaced, and the production cost of the polyol is reduced; the lignin-based polyol has good use effect, and the process is simple and easy to implement; volatile organic solvent is not used in the polyurethane synthesis link, so that the production process does not pollute the environment, and the cost of the polyurethane product is reduced.
In addition to the technical problems addressed by the present application, the technical features constituting the technical solutions, and the advantages brought by the technical features of the technical solutions described above, other technical problems solved by the present application, other technical features included in the technical solutions, and advantages brought by the technical features will be described in further detail below.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
Example 1
(1) Preparation of lignin polyol: taking 80g of polyethylene glycol-400, 25g of glycerol and 2.5g of concentrated sulfuric acid, uniformly mixing the three components, putting the mixture into a reaction device, preheating the mixture to 45 ℃, adding 25g of enzymatic lignin under stirring, heating the mixture to 170 ℃, stopping the reaction for about 1 hour under the protection of nitrogen, regulating the mixture to be neutral by using a 5% sodium hydroxide solution, cooling the mixture, and removing inorganic salt from the product through a dialysis membrane to obtain about 126g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: uniformly mixing and stirring the lignin polyalcohol solution obtained in the step (1) with 35g of polyether polyol 4110, 1.5g of triethylene diamine, 0.1g of stannous octoate and 8g of tris (2-chloropropyl) phosphate (TCPP) to obtain composite polyether;
(3) adding 0.5g of dimethyl siloxane and 15g of monofluoro dichloroethane into the combined polyether obtained in the step (2); and adding 35g of toluene diisocyanate, stirring and reacting at the rotating speed of 2500 rpm to synthesize polyurethane foam, and curing for 24 hours at room temperature.
Example 2
(1) Preparation of lignin polyol: taking 80g of polyethylene glycol-600, 20g of glycerol, 1.2g of concentrated sulfuric acid and 1.8g of glacial acetic acid, uniformly mixing the three components, placing the three components in a three-neck flask, preheating to 45 ℃, adding 20g of enzymatic lignin under stirring, heating to 130 ℃, reacting for about 1 hour under the protection of nitrogen, stopping the reaction, adjusting to be neutral by using 5% sodium hydroxide solution, cooling, and removing inorganic salt from the product through a dialysis membrane to obtain about 118g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: uniformly mixing and stirring the lignin polyalcohol solution obtained in the step (3) with 30g of polyether polyol 4110, 25g of polyether polyol 403 (purchased from Nanjing Jelara polyurethane Co., Ltd.), 2g of triethylene diamine, 0.07g of stannous octoate and 15g of tris (2-chloropropyl) phosphate (TCPP) to obtain combined polyether;
(3) adding 0.8g of dimethyl siloxane and 10g of monofluoro dichloroethane into the combined polyether obtained in the step (4); then 50g of toluene diisocyanate is added, the mixture is stirred and reacted at the rotating speed of 2500 rpm to synthesize polyurethane foam, and the polyurethane foam is cured for 24 hours at room temperature.
Example 3
(1) Preparation of lignin polyol: taking 45g of polyethylene glycol-400, 45g of polypropylene glycol-400, 6g of glycerol, 2.0g of glacial acetic acid and 0.5g of concentrated nitric acid, uniformly mixing the five components, placing the mixture in a three-neck flask, preheating to 45 ℃, adding 15g of enzymatic lignin under stirring, heating to 150 ℃, reacting for 1h under the protection of nitrogen, stopping the reaction, adjusting the reaction to be neutral by using an ammonia water solution with the concentration of 28%, cooling, and removing inorganic salt from the product through a dialysis membrane to obtain 114g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: uniformly mixing and stirring the lignin polyalcohol solution obtained in the step (1) with 15g of polyether 4110, 5g of polyether polyol 403 (purchased from Nanjing Jera-Hua polyurethane Co., Ltd.), 1g of triethylamine, 0.03g of dibutyltin dilaurate and 4g of tris (2-chloroethyl) phosphate (TCEP) to obtain combined polyether;
(3) adding 0.3g of dimethyl siloxane and 8g of 1, 1, 3, 3-pentafluoropropane into the combined polyether obtained in the step (2); then 30g of toluene diisocyanate is added, the mixture is stirred and reacts at the rotating speed of 2500 rpm to synthesize polyurethane foam, and the polyurethane foam is cured for 24 hours at room temperature.
Example 4
(1) Preparation of lignin polyol: taking 80g of polyethylene glycol-400, 25g of glycerol and 2.5g of concentrated sulfuric acid, uniformly mixing the three components, putting the mixture into a reaction device, preheating the mixture to 45 ℃, adding 25g of enzymatic lignin under stirring, heating the mixture to 170 ℃, stopping the reaction for about 1 hour under the protection of nitrogen, regulating the mixture to be neutral by using a 5% sodium hydroxide solution, cooling the mixture, and removing inorganic salt from the product through a dialysis membrane to obtain about 126g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: uniformly mixing and stirring the lignin polyalcohol solution obtained in the step (1) with 30g of polyether polyol 4110 (purchased from Nanjing Jelara polyurethane Co., Ltd.), 20g of polyether polyol 635, 1.5g of diethanolamine, 0.1g of dibutyltin dilaurate and 20g of tris (2, 3-dichloropropyl) phosphate (TDCP) to obtain combined polyether;
(3) adding 1g of tween-20 and 20g of 1, 1, 3, 3-pentafluoropropane into the combined polyether obtained in the step (2); then adding 120g of toluene diisocyanate, stirring and reacting at the rotating speed of 2500 rpm to synthesize polyurethane foam, and curing for 24 hours at room temperature.
Example 5
(1) Preparation of lignin polyol: taking 80g of polyethylene glycol-600, 20g of glycerol, 1.2g of concentrated sulfuric acid and 1.8g of glacial acetic acid, uniformly mixing the three components, placing the three components in a three-neck flask, preheating to 45 ℃, adding 20g of enzymatic lignin under stirring, heating to 130 ℃, reacting for about 1 hour under the protection of nitrogen, stopping the reaction, adjusting to be neutral by using 5% sodium hydroxide solution, cooling, and removing inorganic salt from the product through a dialysis membrane to obtain about 118g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: uniformly mixing and stirring the lignin polyalcohol solution obtained in the step (1) with 50g of polyether polyol 4110, 20g of polyether polyol 403 (purchased from Nanjing Jera-Hua polyurethane Co., Ltd.), 3g of tetramethylethylenediamine, 0.05g of butyltin dilaurate and 25g of dimethyl methyl phosphate (DMMP) to obtain combined polyether;
(3) adding 2g of Tween-80 and 20g of 1, 1, 3, 3-pentafluorobutane into the combined polyether obtained in the step (2); then adding 110g of xylene diisocyanate, stirring and reacting at the rotating speed of 2500 rpm to synthesize polyurethane foam, and curing for 24 hours at room temperature.
Example 6
(1) Preparation of lignin polyol: taking 45g of polyethylene glycol-400, 45g of polypropylene glycol-400, 6g of glycerol, 2.0g of glacial acetic acid and 0.5g of concentrated nitric acid, uniformly mixing the five components, placing the mixture in a three-neck flask, preheating to 45 ℃, adding 15g of enzymatic lignin under stirring, heating to 150 ℃, reacting for 1h under the protection of nitrogen, stopping the reaction, adjusting the reaction to be neutral by using an ammonia water solution with the concentration of 28%, cooling, and removing inorganic salt from the product through a dialysis membrane to obtain 114g of dark red liquid enzymatic lignin modified polyol.
(2) Preparing the combined polyether: mixing and uniformly stirring the lignin polyalcohol solution obtained in the step (1) with 50g of polyether polyol 635, 1g of tetramethylethylenediamine, 0.1g of dibutyltin dilaurate and 10g of dimethyl methyl phosphate (DMMP) to obtain combined polyether;
(3) and (3) adding 110g of xylene diisocyanate into the combined polyether obtained in the step (2), uniformly stirring, spreading on a tetrafluoroethylene sheet, and curing at 70 ℃ to form a polyurethane film.
The embodiments of the present application have been described in detail, but the description is only for the preferred embodiments of the present application and should not be construed as limiting the scope of the application. All equivalent changes, modifications and the like made within the scope of the present application shall be covered by the claims of the present application.
Claims (9)
1. The preparation method of the lignin polyurethane is characterized by comprising the following steps:
(1) preparation of lignin polyol: weighing 50-90 parts of polyol, 5-25 parts of glycerol and 1-7 parts of acid catalyst in parts by weight, adding the materials into a reaction device, uniformly mixing, and preheating to 40-55 ℃; adding 8-60 parts of lignin while stirring, heating to 100-180 ℃, reacting for 1.0-4.0h under the protection of inert gas, and then stopping; and adding an alkali regulator to regulate the pH value of the solution to 7.0-7.5, dialyzing, and distilling under reduced pressure to obtain the lignin modified polyol.
(2) Preparing the combined polyether: mixing and stirring uniformly 100-150 parts of lignin polyol, 50-100 parts of polyether polyol, 1-3 parts of amine catalyst, 0.05-0.2 part of organic tin catalyst and 10-30 parts of flame retardant to obtain composite polyether;
(3) synthesis of lignin polyurethane: mixing the combined polyether obtained in the step (2) with isocyanate according to the mass ratio of 0.6: 1-1.5: 1, uniformly mixing, spreading in a container, heating to 50-70 ℃, and curing to obtain lignin polyurethane;
or adding 0.5-2 parts by mass of foam stabilizer and 10-30 parts by mass of foaming agent into the combined polyether obtained in the step (3); adding isocyanate, and mixing the combined polyether and the isocyanate according to the mass ratio of 0.6: 1-1.5: 1; stirring foaming or spraying foaming is adopted to obtain the polyurethane foam.
2. The method for preparing lignin polyurethane according to claim 1, wherein the lignin in step (1) is one or more of acetic acid lignin, 1, 4-butanediol lignin, ethylene glycol lignin, alkali-extracted lignin and enzymatic hydrolysis lignin.
3. The method for preparing lignin polyurethane according to claim 1, wherein: the polyester polyol is polyether polyol or polyester polyol; the polyol is a polyol with weight average molecular weight less than 2000 and is liquid at normal temperature.
4. The method for preparing lignin polyurethane according to claim 1, wherein: the glycerol is used as an auxiliary liquefaction agent of the lignin polyol.
5. The method for preparing lignin polyurethane according to claim 1, wherein: the acid catalyst is one or a mixture of sulfuric acid, acetic acid, nitric acid or phosphoric acid.
6. The method for preparing lignin polyurethane according to claim 1, wherein: the alkali regulator is one or a mixture of more of sodium hydroxide, ammonia water or potassium hydroxide.
7. The method for preparing lignin polyurethane according to claim 1, wherein the amine catalyst in step (2) is one or more of triethylene diamine, triethylamine, tetramethyl divinyl diamine, dimethyl cyclohexylamine, diethanolamine, triethanolamine, divinyl glycol amine and isopropanolamine; the organic tin catalyst is one or more of stannous octoate, dibutyltin dilaurate, monobutyltin oxide and dibutyltin oxide; the phosphorus-containing flame retardant is tris (2-chloropropane) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate or dimethyl methyl phosphate.
8. The method for preparing lignin polyurethane according to claim 1, wherein: the foam stabilizer in the step (3) is an organic silicon surfactant or a nonionic surfactant; the foaming agent is an inert hydrocarbon compound with a low boiling point; the isocyanate is aromatic isocyanate.
9. The method for preparing lignin polyurethane according to claim 8, wherein: the organic silicon surfactant is dimethyl siloxane; the nonionic surfactant is polyoxyethylene sorbitan mono fatty acid ester; the inert hydrocarbon compound with low boiling point is monofluorodichloroethane, 1, 3, 3-pentafluoropropane or 1, 1, 3, 3-pentafluorobutane; the aromatic isocyanate is toluene diisocyanate, xylene diisocyanate or diphenylmethane diisocyanate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811334960.6A CN111171264A (en) | 2018-11-12 | 2018-11-12 | Preparation method of lignin polyurethane |
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| CN201811334960.6A CN111171264A (en) | 2018-11-12 | 2018-11-12 | Preparation method of lignin polyurethane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607062A (en) * | 2020-05-29 | 2020-09-01 | 叶正芬 | Biomass polyurethane foam material and preparation method thereof |
| CN112266463A (en) * | 2020-11-09 | 2021-01-26 | 张家港优全汽配有限公司 | Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof |
| CN116554497A (en) * | 2023-06-08 | 2023-08-08 | 齐鲁工业大学(山东省科学院) | Method for preparing polyalcohol and bio-based polymer material by using lignin |
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2018
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607062A (en) * | 2020-05-29 | 2020-09-01 | 叶正芬 | Biomass polyurethane foam material and preparation method thereof |
| CN112266463A (en) * | 2020-11-09 | 2021-01-26 | 张家港优全汽配有限公司 | Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof |
| CN112266463B (en) * | 2020-11-09 | 2022-02-15 | 张家港优全汽配有限公司 | Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof |
| CN116554497A (en) * | 2023-06-08 | 2023-08-08 | 齐鲁工业大学(山东省科学院) | Method for preparing polyalcohol and bio-based polymer material by using lignin |
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Application publication date: 20200519 |