CN1462760A - Method for synthesizing foam material of lignin polyurethane - Google Patents
Method for synthesizing foam material of lignin polyurethane Download PDFInfo
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- CN1462760A CN1462760A CN 03131649 CN03131649A CN1462760A CN 1462760 A CN1462760 A CN 1462760A CN 03131649 CN03131649 CN 03131649 CN 03131649 A CN03131649 A CN 03131649A CN 1462760 A CN1462760 A CN 1462760A
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Abstract
A process for synthesizing the foam lignin-polyurethane material includes drying lignin, sieving, preactivating at 90-170 deg.C for 0.5-3.5 hrs to obtain polyhydroxy lignin compound, copolymerizing with binary acid anhydride and biol at 120-280 deg.C for 5-6 hrs to obtain lignin polyol polyester, mixing with polyether, silica oil and foaming agent, adding organotin and amine, stirring, and high-speed stirring while foaming.
Description
One, technical field
The present invention relates to a kind of synthetic method that multiple lignin raw material is produced the lignin polyurethane foamed material that is adapted to.
Two, background technology
Lignin is a kind of resource of growing, and also is the potential natural organic raw material that is fully utilized on a large scale as yet at present.Hydrolysis, paper industry are just utilized the Mierocrystalline cellulose in the plant material, and with lignin partly as waste discharge, this is not only the resource significant wastage, also environment has been caused severe contamination.Utilizing lignin to prepare the lignin polyurethane foamed material, is one of approach of being fully utilized on a large scale of lignin, and simultaneously, because lignin belongs to natural high moleculer eompound, the material that makes possesses biodegradability, thereby has broad application prospects.At present, the method for utilizing lignin to prepare the lignin polyurethane foamed material has two kinds: the one, with the lignin raw material directly and oxyethane, the condensation reaction of propylene oxide high pressure; The 2nd, with the lignin raw material earlier with the maleic anhydride reaction, again with the epoxy compounds reaction, what two kinds of methods made is polyether-type lignin polyol resin, two kinds of reactions all are solid and gas phase reaction under high pressures, facility investment is big, the aftertreatment complexity is to having relatively high expectations of lignin raw material.So do not have actual popularizing application prospect.
Three, technology contents
Technical problem: the invention provides and to reduce technological equipment investment and can have the wide advantage of selectable range in the method for synthetic lignin polyurethane foamed material under the normal pressure as the lignin of raw material required for the present invention.
Technical scheme: the present invention is a kind of synthetic method of lignin polyurethane foamed material, earlier lignin oven dry back is crossed and be not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, temperature of reaction is to carry out pre-priming reaction under 90 ℃-170 ℃ the condition to obtain the lignin polyol, its reaction times is 0.5 hour-3.5 hours, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins.
Technique effect: 1. owing to each the step reaction in the operational path of the present invention can be carried out under normal pressure, compare with the facility investment that the reaction under high pressure of prior art is required, the present invention has the little advantage of technological equipment investment, the present invention is to the pre-activation of lignin, be that the lignin raw material is made the lignin polyol that can become the homogeneous system with pet reaction, improved lignin raw material activity, make the present invention can select wood saccharification industry, lignin in the paper industry waste is as the raw material of the synthetic lignin polyurethane foam of the present invention, or selection dilute acid hydrolysis lignin, the concentrated acid lignin, kraft lignin, alkali lignin, lignins such as Sulfite lignin are produced the required raw material of lignin polyurethane foam as the present invention, therefore, the present invention has the wide advantage of selectable range of the synthetic required lignin of technology.2. the present invention selects maleic anhydride and glycol ether to support polyol resin as participating in producing lignin, can improve the physicochemical property of foam materials, and its density setting range is big, physics and chemistry intensity height.
Four, specific embodiments
The synthetic method of 1 one kinds of lignin polyurethane foamed materials of embodiment, earlier hydrolytic lignin oven dry back is crossed and be not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, temperature of reaction is to carry out pre-priming reaction under 90 ℃-170 ℃ the condition to obtain the lignin polyol, its reaction times is 1.5 hours-3.5 hours, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins, in the present embodiment, the pre-priming reaction of lignin is lignin and phenol after the oven dry of sieving are carried out 1.5 hours-3.5 hours under 100 ℃-170 ℃ a phenolic hydroxyl group reaction cooling back adding formaldehyde, ℃ of-95 ℃ reactions of reheat to 80 2 hours-3 hours, decompression dehydration; With lignin and the maleic anhydride, glycol ether copolymerization after the activation in advance, get the lignin polyol resin, specifically, present embodiment is that lignin and maleic anhydride, glycol ether after activating in advance are mixed and heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number obtains the lignin polyol resin after restraining less than 5 milligrams of KOH/, the whipping agent of present embodiment adopts F141b, stir, add polyphenyl polyisocyanate or vulcabond again and stir foaming for 100 parts.
The synthetic method of 2 one kinds of lignin polyurethane foamed materials of embodiment, earlier hydrolytic lignin oven dry back is crossed and be not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, carry out pre-priming reaction under the condition that temperature of reaction is 90 ℃-95 ℃ and obtain the lignin polyol, 0.5 hour-3.5 hours its reaction times, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins, in the present embodiment, the pre-priming reaction of lignin is with the lignin after the oven dry of sieving, formaldehyde, caustic soda and water are mixed and heated to 90 ℃-95 ℃, reacted 0.5 hour-3.5 hours, add the phenolic aldehyde performed polymer again and be heated to 80 ℃-90 ℃, react dewater after 2 hours-3 hours to water ratio less than 10%, and the method for making of phenolic aldehyde performed polymer is that phenol and formaldehyde are mixed and heated to 80 ℃-95 ℃ reactions 2 hours-3 hours, after treating its layering, its lower-layer resin is the phenolic aldehyde performed polymer, the copolyreaction that lignin and dibasic acid anhydride and dibasic alcohol carry out is with lignin and maleic anhydride after activating in advance, the glycol ether copolymerization, get the lignin polyol resin, present embodiment is then selected lignin and maleic anhydride after activating in advance, glycol ether is mixed and heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number restrains less than 5 milligrams of KOH/, the whipping agent of present embodiment adopts F141b, stir, add polyphenyl polyisocyanate or vulcabond again and stir foaming for 100 parts.
The synthetic method of 3 one kinds of lignin polyurethane foamed materials of embodiment, earlier alkali lignin oven dry back is crossed and be not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, temperature of reaction is to carry out pre-priming reaction under 90 ℃-170 ℃ the condition to obtain the lignin polyol, its reaction times is 1.5 hours-3.5 hours, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins, in the present embodiment, the pre-priming reaction of lignin is lignin and phenol after the oven dry of sieving are carried out 1.5 hours-3.5 hours under 100 ℃-170 ℃ a phenolic hydroxyl group reaction cooling back adding formaldehyde, ℃ of-95 ℃ reactions of reheat to 80 2 hours-3 hours, decompression dehydration; The acquisition of lignin polyol resin is that lignin and maleic anhydride, mixed with propylene glycol after activating in advance are heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number obtains the lignin polyol resin after restraining less than 5 milligrams of KOH/, the whipping agent of present embodiment adopts F141b, stirs, and adds polyphenyl polyisocyanate or vulcabond again and stirs foaming for 100 parts.
The synthetic method of 4 one kinds of lignin polyurethane foamed materials of embodiment, earlier alkali lignin oven dry back is crossed and be not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, temperature of reaction is to carry out pre-priming reaction under 90 ℃-95 ℃ the condition to obtain the lignin polyol, its reaction times is 0.5 hour-3.5 hours, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins, in the present embodiment, the pre-priming reaction of lignin is with the lignin after the oven dry of sieving, formaldehyde, caustic soda and water are mixed and heated to 80 ℃-95 ℃, reacted 0.5 hour-3 hours, add the phenolic aldehyde performed polymer again and be heated to 80 ℃-95 ℃, react dewater after 2 hours-3 hours to water ratio less than 10%, and the method for making of phenolic aldehyde performed polymer is that phenol and formaldehyde are mixed and heated to 80 ℃-95 ℃ reactions 2 hours-3 hours, after treating its layering, its lower-layer resin is the phenolic aldehyde performed polymer, the copolyreaction that above-mentioned lignin and dibasic acid anhydride and dibasic alcohol carry out is with lignin and phthalic anhydride after activating in advance, the ethylene glycol copolymerization, get the lignin polyol resin, be with lignin and phthalic anhydride after activating in advance specifically, ethylene glycol is mixed and heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number restrains less than 5 milligrams of KOH/, the whipping agent of present embodiment adopts F141b, stir, add polyphenyl polyisocyanate or vulcabond again and stir foaming for 100 parts.
Claims (8)
1. the synthetic method of a lignin polyurethane foamed material, it is characterized in that earlier lignin oven dry back being crossed being not less than 40 mesh sieves, lignin after will sieving again is at normal pressure, temperature of reaction is to carry out pre-priming reaction under 90 ℃-170 ℃ the condition to obtain the lignin polyol, its reaction times is 0.5 hour-3.5 hours, then with preactivated lignin at normal pressure, temperature of reaction is under 120 ℃-280 ℃ the condition, carry out copolyreaction with dibasic acid anhydride and dibasic alcohol, obtain the lignin polyol polyester, its reaction times is 5 hours-6 hours, at last, with weight part is the lignin polyol polyester of 30-70 part, weight part is the polyethers of 70-30 part, weight part is the silicone oil of 0.5-2 part, weight part is that to mix and add weight part as catalyzer be that the organotin and the weight part of 0.05-0.15 part is the amine of 1-3 part to the whipping agent of 10-30 part, stir, the final isocyanic ester that adds, and stir foaming with the rotating speed that is not less than 1000 rev/mins.
2. the synthetic method of lignin polyurethane foamed material according to claim 1, the pre-priming reaction that it is characterized in that lignin is lignin and phenol after the oven dry of sieving are carried out 1.5 hours-3.5 hours under 100 ℃-170 ℃ a phenolic hydroxyl group reaction cooling back adding formaldehyde, ℃ of-95 ℃ reactions of reheat to 80 2 hours-3 hours, decompression dehydration.
3. the synthetic method of lignin polyurethane foamed material according to claim 2 is characterized in that lignin and maleic anhydride, glycol ether copolymerization after the activation in advance, must the lignin polyol resin.
4. the synthetic method of lignin polyurethane foamed material according to claim 3, lignin after it is characterized in that activating in advance and maleic anhydride, glycol ether are mixed and heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number restrains less than 5 milligrams of KOH/.
5. the synthetic method of lignin polyurethane foamed material according to claim 1, the pre-priming reaction that it is characterized in that lignin is that lignin, formaldehyde, caustic soda and water after the oven dry of sieving are mixed and heated to 90 ℃-95 ℃, reacted 0.5 hour-3 hours, add the phenolic aldehyde performed polymer again and be heated to 80 ℃-95 ℃, react dewater after 2 hours-3 hours to water ratio less than 10%.
6, the synthetic method of lignin polyurethane foamed material according to claim 5, the method for making that it is characterized in that the phenolic aldehyde performed polymer is that phenol and formaldehyde are mixed and heated to 80 ℃-95 ℃ reactions 2 hours-3 hours, after treating its layering, its lower-layer resin is the phenolic aldehyde performed polymer.
7, according to the synthetic method of claim 5 or 6 described lignin polyurethane foamed materials, it is characterized in that lignin and maleic anhydride, glycol ether copolymerization after the activation in advance, must the lignin polyol resin.
8. the synthetic method of lignin polyurethane foamed material according to claim 7, lignin after it is characterized in that activating in advance and maleic anhydride, glycol ether are mixed and heated to 180 ℃-200 ℃, reacted 3 hours-5 hours, be heated to 250 ℃-260 ℃ more gradually, continue to react to moisture less than 0.5%, acid number restrains less than 5 milligrams of KOH/.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03131649 CN1226325C (en) | 2003-05-30 | 2003-05-30 | Method for synthesizing foam material of lignin polyurethane |
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| CN 03131649 CN1226325C (en) | 2003-05-30 | 2003-05-30 | Method for synthesizing foam material of lignin polyurethane |
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| CN1462760A true CN1462760A (en) | 2003-12-24 |
| CN1226325C CN1226325C (en) | 2005-11-09 |
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| CN 03131649 Expired - Fee Related CN1226325C (en) | 2003-05-30 | 2003-05-30 | Method for synthesizing foam material of lignin polyurethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012332B (en) * | 2007-02-09 | 2010-10-13 | 李长玉 | Lignin and waste rigid foam powder fluorine-free polyurethane heat insulation material and preparing method |
| CN103665357A (en) * | 2014-01-07 | 2014-03-26 | 东北林业大学 | Polyester polyol containing lignin, preparing method thereof and polyurethane adhesive synthesized by same |
-
2003
- 2003-05-30 CN CN 03131649 patent/CN1226325C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012332B (en) * | 2007-02-09 | 2010-10-13 | 李长玉 | Lignin and waste rigid foam powder fluorine-free polyurethane heat insulation material and preparing method |
| CN103665357A (en) * | 2014-01-07 | 2014-03-26 | 东北林业大学 | Polyester polyol containing lignin, preparing method thereof and polyurethane adhesive synthesized by same |
| CN103665357B (en) * | 2014-01-07 | 2015-12-09 | 东北林业大学 | A kind of polyester polyol containing xylogen and the adhesive for polyurethane utilizing it to prepare |
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| CN1226325C (en) | 2005-11-09 |
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