CN102627750A - Method for re-synthesizing rigid polyurethane by using polyurethane wastes of waste refrigerators - Google Patents
Method for re-synthesizing rigid polyurethane by using polyurethane wastes of waste refrigerators Download PDFInfo
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- CN102627750A CN102627750A CN2012101022066A CN201210102206A CN102627750A CN 102627750 A CN102627750 A CN 102627750A CN 2012101022066 A CN2012101022066 A CN 2012101022066A CN 201210102206 A CN201210102206 A CN 201210102206A CN 102627750 A CN102627750 A CN 102627750A
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Abstract
The invention discloses a method for re-synthesizing rigid polyurethane by using polyurethane wastes of waste refrigerators. The raw material comes from the polyurethane material in waste refrigerators of recovered electric appliances. The method comprises the following steps of: crushing the polyurethane wastes of the waste refrigerators into polyurethane fragments; mixing an alcoholysis agent, a catalyst and the polyurethane fragments in a reaction container according to a mass ratio of (80-200):(0.5-5):100 and continuously heating at the temperature of 150-240 DEG C; continuously reacting for 0-5 hours, wherein an obtained resultant after the reaction is a mixture; fractionating the excess alcoholysis agent in the mixture produced by the reaction at the constant temperature of 150-250 DEG C; only reserving polybasic alcohol mixture in the reaction container; and mixing the polybasic alcohol mixture and combined polyether glycol according to a mass ratio of (5-50):100 to form a comprehensive reactant and reacting with an equal amount of isocyanate to synthesize the rigid polyurethane. Thus, the effect of recycling the polyurethane of the recovered waste refrigerator is finally achieved.
Description
Technical field
The present invention relates to a kind of urethane compound method, particularly a kind of polyurethane waste gurry material resourcesization prepares the method for hard polyaminoester, belongs to waste treatment technique and changing rejected material to useful resource technical field.
Background technology
China is behind the high speed development that has experienced more than 30 year; Living standards of the people generally are improved, and are that the household electrical appliance of representative get into family in a large number with the electricrefrigerator, according to State Statistics Bureau's data presentation; The social recoverable amount of China's refrigerator is about 1.5 hundred million at present; If calculated in 10 ~ 15 years by its serviceable bife, discarded refrigerator quantity is up to annual 4000000, and the continual renovation of new and high technology is used in addition; The update cycle of refrigerator product will shorten greatly, most underground terminal market circulations through informal channel.If so a large amount of discarded refrigerators can not in time be recycled; A large amount of electronic wastes of its generation will cause serious destruction to ecotope, and ecotope such as the atmosphere that we are depended on for existence, soil, river has constituted serious potential ecology and health risk.Wherein account for the maximum thermofin hard-foam polyurethane of discarded refrigerator volume owing to stable in properties, difficult degraded are particularly great to the pressure of environment.Therefore, the recovery of refrigerator polyurethane waste material has caused governments at all levels and scientific and technical personnel's attention with utilizing research again, becomes the important topic that needs to be resolved hurrily.Discarded refrigerator urethane is carried out the resource utilization recovery can not only alleviate resource scarcity, can also avoid exploiting the energy consumption that fossil feedstock is brought, to setting up conservation-minded society, it is significant to walk sustainable development path.
Urethane as the electricrefrigerator thermal insulation material is thermosetting resin, and sclerosis back molecule is the ternary network structure, is difficult to dissolving or thawing, so be difficult for utilizing, its waste product can only burn and bury processing usually again.The burning disposal process causes secondary pollution, thereby should not adopt if incomplete combustion will produce toxic gas.If the employing landfill disposal, with occupying a large amount of land resources, and the urethane stable in properties is difficult to degraded, will cause lasting pollution to environment.And adopt the foam article degradation after the physical method regeneration, and only being suitable for low-grade parts, application surface is narrow, and technology is loaded down with trivial details, labor capacity is big.In the processing to discarded refrigerator, the effective utilization that accounts for the urethane of maximum volume becomes the difficult problem of recovery.
Summary of the invention
In order to solve the prior art problem; The object of the present invention is to provide a kind of discarded refrigerator polyurethane waste material method of synthetic hard polyaminoester again of utilizing; Method through the discarded refrigerator urethane of alcoholysis obtains polyvalent alcohol; Use the polyol blends that reclaims to mix with fresh combined polyether glycol again and synthesize hard-foam polyurethane, finally reach the effect of the discarded refrigerator urethane recycling of recovery with isocyanate reaction.
For reaching the foregoing invention purpose, the present invention adopts following technical proposals:
A kind of discarded refrigerator polyurethane waste material method of synthetic hard polyaminoester again of utilizing, the polyurethane material of raw material sources in the waste refrigerators that reclaims household electrical appliances comprises the steps:
1) will discard the refrigerator polyurethane waste material and be ground into the urethane fragment;
2) in reaction vessel, the urethane fragment that alcoholysis agent, catalyzer and step 1) are obtained is with mass ratio (80～200): (0.5～5): continue heating after 100 the mixed, Heating temperature is 150 ℃ ~ 240 ℃, and concrete steps are:
A. at first with being heated to dissolving in alcoholysis agent and the catalyzer adding reaction vessel;
B. the urethane fragment that then step 1) is obtained adopts the mode of continuous charging slowly to join in the reaction vessel, and the urethane fragment of promptly waiting until adding adds follow-up urethane fragment again when having dissolved soon;
C., whole urethane fragments picks up counting when just all dissolving, reaction melt successive reaction 0～5h that alcoholysis agent and urethane are formed, and the resultant that reaction obtains after accomplishing is a mixture;
3) under 150 ℃～250 ℃ of constant temperature, make the reaction in the step c generate unnecessary alcoholysis agent fractionation in the mixture, in reaction vessel, only stay polyol blends;
4) polyol blends that step 3) is obtained and combined polyether glycol are by mass ratio (5～50): 100 mixed forms the combined reaction thing, make again the combined reaction thing with etc. the synthetic hard-foam polyurethane of isocyanate reaction of quality.
In above-mentioned steps 1) in the gravel size decision 1mm～20mm of the urethane fragment that obtains, be easy to add reaction vessel, and be easy to fusion.
In above-mentioned steps 1) in the reaction vessel that uses adopt there-necked flask, wherein two bottlenecks of there-necked flask are mounting temperature meter and reflux condensing tube respectively, another of there-necked flask mouthful is the reactant charging opening, there-necked flask is simple in structure, and is easy to use.
The type of heating of above-mentioned there-necked flask adopts in the constant temperature oil bath and heats, and flask internal reaction melt is heated evenly.
Above-mentioned alcoholysis agent is a divalent alcohol.
Above-mentioned divalent alcohol preferably adopts terepthaloyl moietie, glycol ether, polyoxyethylene glycol, 1,2-Ucar 35,1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol and 1, any one divalent alcohol in the 4-butyleneglycol or any several kinds of diol mixture will; Above-mentioned divalent alcohol is preferably terepthaloyl moietie.
Above-mentioned catalyzer preferably adopts inorganic acetate, an alkali metal salt or alcamine compound; Above-mentioned inorganic acetate preferably adopts any one inorganic acetate or any several kinds of inorganic acetate saline admixtures in sodium acetate, potassium acetate and the zinc acetate; Above-mentioned an alkali metal salt preferably adopts any one an alkali metal salt or any several kinds of alkaline metal salt mixtures in sodium hydroxide, Pottasium Hydroxide and the yellow soda ash, and above-mentioned hydramine preferably adopts any one hydramine or the alcamines mixture of its two formation in trolamine and the diethylolamine; Above-mentioned catalyzer is preferably the mixture of any one or its two formation in sodium hydroxide and the sodium acetate.
The present invention has following conspicuous outstanding substantive distinguishing features and remarkable advantage compared with prior art:
1. the present invention does not need protection of inert gas such as nitrogen in alcoholysis process;
2. the present invention's disposal and recycling that will reclaim the discarded refrigerator urethane of household electrical appliances organically combines; Not only solved effective handling problems of the urethane that accounts for discarded refrigerator maximum volume; And obtained the hard polyaminoester that can utilize again, reduced the production cost of refrigerator hard polyaminoester;
3. the present invention carries out under normal pressure, and equipment is simple, easy handling.
Description of drawings
Fig. 1 is the compressive strength graphic representation that the embodiment of the invention one is utilized discarded refrigerator urethane synthetic hard polyaminoester.
Fig. 2 is the stereoscan photograph that the embodiment of the invention one is utilized discarded refrigerator urethane synthetic hard polyaminoester.
Embodiment
In conjunction with accompanying drawing, details are as follows to the preferred embodiments of the present invention:
A kind of discarded refrigerator polyurethane waste material method of synthetic hard polyaminoester again of utilizing, the polyurethane material of raw material sources in the waste refrigerators that reclaims household electrical appliances comprises the steps:
1. will discard refrigerator urethane and pulverize, obtain the fragment of 10mm size;
2. installation reaction unit: getting there-necked flask is reaction vessel, wherein two mouthfuls of mounting temperature meter, reflux condensing tubes respectively, and another mouthful is charging opening, there-necked flask put into constant temperature oil bath heat, Heating temperature is 196 ℃;
3. get 100 parts of quality of glycol umbers; 1 part of sodium hydroxide mass fraction; 100 parts of discarded refrigerator urethane fragment mass fractions are heated to dissolving with in terepthaloyl moietie and the sodium hydroxide adding there-necked flask, because of the urethane volume bigger; The urethane fragment adopts the mode of continuous charging slowly to join in the there-necked flask, and the urethane of promptly waiting until adding adds follow-up urethane again when having dissolved soon.Urethane successive reaction 2h picks up counting when whole urethane just all dissolves.
4. the mixture that will react after accomplishing is following to unnecessary alcoholysis agent fractionation 240 ℃ of constant temperature, stays polyol blends.
5. polyol blends is mixed by mass ratio 10% with fresh combined polyether glycol, again with etc. the synthetic hard-foam polyurethane of isocyanate reaction of quality.
The hydroxyl value that above-mentioned steps 4 stays polyol blends is that 856.8 mgKOH/g, viscosity are that 41000cps, acid number are that 0.059 mgKOH/g, pH are 8.5.
The compressive strength of step 5 synthetic hard polyaminoester is as shown in Figure 1, the prescribed value of accord with Q B/T 2081-1995.Fig. 2 is the stereoscan photograph of step 5 synthetic hard polyaminoester, and as can be seen from the figure synthetic urethane is polynuclear plane, the hole size homogeneous.The present invention adopts alcoholysis method that discarded refrigerator urethane is carried out raw material and reclaims, thereby the recycling household electrical appliances reclaim the urethane in the discarded refrigerator in back.
Combine accompanying drawing that the embodiment of the invention is illustrated above; But the invention is not restricted to the foregoing description; Can also make multiple variation according to the purpose of innovation and creation of the present invention; Change, the modification of making under all spirit and principles according to technical scheme of the present invention, substitute, combination, simplify, all should be the substitute mode of equivalence, as long as goal of the invention according to the invention; Only otherwise deviate from the present invention and utilize discarded refrigerator the polyurethane waste material know-why and the inventive concept of the method for synthetic hard polyaminoester again, all belong to protection scope of the present invention.
Claims (8)
1. one kind is utilized the discarded refrigerator polyurethane waste material method of synthetic hard polyaminoester again, and the polyurethane material of raw material sources in the waste refrigerators that reclaims household electrical appliances is characterized in that, comprises the steps:
1) will discard the refrigerator polyurethane waste material and be ground into the urethane fragment;
2) in reaction vessel, the urethane fragment that alcoholysis agent, catalyzer and said step 1) are obtained is with mass ratio (80～200): (0.5～5): continue heating after 100 the mixed, Heating temperature is 150 ℃ ~ 240 ℃, and concrete steps are:
A. at first with being heated to dissolving in alcoholysis agent and the catalyzer adding reaction vessel;
B. the urethane fragment that then said step 1) is obtained adopts the mode of continuous charging slowly to join in the reaction vessel, and the urethane fragment of promptly waiting until adding adds follow-up urethane fragment again when having dissolved soon;
C., whole urethane fragments picks up counting when just all dissolving, reaction melt successive reaction 0～5h that alcoholysis agent and urethane are formed, and the resultant that reaction obtains after accomplishing is a mixture;
3) under 150 ℃～250 ℃ of constant temperature, make the reaction in the said step c generate unnecessary alcoholysis agent fractionation in the mixture, in reaction vessel, only stay polyol blends;
4) polyol blends that said step 3) is obtained and combined polyether glycol are by mass ratio (5～50): 100 mixed forms the combined reaction thing, make again said combined reaction thing with etc. the synthetic hard-foam polyurethane of isocyanate reaction of quality.
2. the discarded refrigerator polyurethane waste material of utilization according to claim 1 is the method for synthetic hard polyaminoester again, and it is characterized in that: the urethane fragment that said step 1) obtains is of a size of 1mm～20mm.
3. the discarded refrigerator polyurethane waste material of utilization according to claim 1 is the method for synthetic hard polyaminoester again; It is characterized in that: the reaction vessel that in said step 1), uses adopts there-necked flask; Wherein two bottlenecks of said there-necked flask are distinguished mounting temperature meter and reflux condensing tube, and another mouth of said there-necked flask is the reactant charging opening.
4. the discarded refrigerator polyurethane waste material of utilization according to claim 3 is the method for synthetic hard polyaminoester again, it is characterized in that: the type of heating of said there-necked flask adopts in the constant temperature oil bath and heats.
5. according to the discarded refrigerator polyurethane waste material of any described utilization in the claim 1～4 method of synthetic hard polyaminoester again, it is characterized in that: said alcoholysis agent is a divalent alcohol.
6. the discarded refrigerator polyurethane waste material of utilization according to claim 5 is the method for synthetic hard polyaminoester again; It is characterized in that: said divalent alcohol is terepthaloyl moietie, glycol ether, polyoxyethylene glycol, 1; 2-Ucar 35,1, ammediol, 1,2-butyleneglycol, 1; 3-butyleneglycol and 1, any one divalent alcohol in the 4-butyleneglycol or any several kinds of diol mixture will.
7. according to the discarded refrigerator polyurethane waste material of any described utilization in the claim 1～4 method of synthetic hard polyaminoester again, it is characterized in that: said catalyzer is inorganic acetate, an alkali metal salt or alcamine compound.
8. the discarded refrigerator polyurethane waste material of utilization according to claim 7 is the method for synthetic hard polyaminoester again; It is characterized in that: said inorganic acetate is any one inorganic acetate or any several kinds of inorganic acetate saline admixtures in sodium acetate, potassium acetate and the zinc acetate; Said an alkali metal salt is any one an alkali metal salt or any several kinds of alkaline metal salt mixtures in sodium hydroxide, Pottasium Hydroxide and the yellow soda ash, and said hydramine is any one hydramine or the alcamines mixture of its two formation in trolamine and the diethylolamine.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756285A (en) * | 2014-01-08 | 2014-04-30 | 上海应用技术学院 | Preparation method of polyurethane (PU) elastomer with high wear resistance |
| CN105001390A (en) * | 2015-07-29 | 2015-10-28 | 龙江神华节能墙材有限公司 | Method for preparing all-water polyurethane rigid foam |
| CN106397725A (en) * | 2016-08-30 | 2017-02-15 | 天津军星管业集团有限公司 | Heat preservation tube material prepared by recycling waste hard polyurethane foaming plastic, heat preservation tube and manufacturing method |
| CN106750510A (en) * | 2017-01-13 | 2017-05-31 | 郑州中远氨纶工程技术有限公司 | The processing method and polyurethane elastomer of urethane oligomer waste liquid |
| CN106832204A (en) * | 2017-01-05 | 2017-06-13 | 广州特种承压设备检测研究院 | A kind of modified polyurethane roofing heat insulating material and preparation method thereof |
| CN107446345A (en) * | 2017-08-29 | 2017-12-08 | 河北科技大学 | A kind of filled-type flexible polyurethane foams based on vamp leftover pieces and preparation method thereof |
| CN107602911A (en) * | 2017-10-18 | 2018-01-19 | 上海第二工业大学 | A kind of method of microwave radiation technology alcoholysis waste refrigerators polyurethane |
| CN107955206A (en) * | 2017-11-28 | 2018-04-24 | 山东诺威新材料有限公司 | The method of waste polyurethane foam degraded recycling polyether polyol |
| CN113999429A (en) * | 2021-12-21 | 2022-02-01 | 浙江工业大学 | Method for efficiently degrading polyurethane coating solid waste |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469050A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院过程工程研究所 | Regenerative utilizing method for waste hard polyurethane foam plastic |
| CN102061009A (en) * | 2010-12-21 | 2011-05-18 | 浙江华峰新材料股份有限公司 | Method for producing polyol by using polyurethane waste |
| CN102108116A (en) * | 2011-01-12 | 2011-06-29 | 江南大学 | Method for producing polyurethane foaming material by using waste polyester fibers |
-
2012
- 2012-04-10 CN CN2012101022066A patent/CN102627750A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469050A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院过程工程研究所 | Regenerative utilizing method for waste hard polyurethane foam plastic |
| CN102061009A (en) * | 2010-12-21 | 2011-05-18 | 浙江华峰新材料股份有限公司 | Method for producing polyol by using polyurethane waste |
| CN102108116A (en) * | 2011-01-12 | 2011-06-29 | 江南大学 | Method for producing polyurethane foaming material by using waste polyester fibers |
Non-Patent Citations (2)
| Title |
|---|
| 付新建 等: "利用硬质PU泡沫醇解回收料制备PU防水涂料的研究", 《塑料工业》 * |
| 胡朝辉 等: "醇解废旧聚氨酯回收多元醇研究进展", 《聚氨酯工业》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756285A (en) * | 2014-01-08 | 2014-04-30 | 上海应用技术学院 | Preparation method of polyurethane (PU) elastomer with high wear resistance |
| CN103756285B (en) * | 2014-01-08 | 2016-06-08 | 上海应用技术学院 | A kind of method for preparing polyurethane elastic body with high-wearing feature |
| CN105001390A (en) * | 2015-07-29 | 2015-10-28 | 龙江神华节能墙材有限公司 | Method for preparing all-water polyurethane rigid foam |
| CN106397725A (en) * | 2016-08-30 | 2017-02-15 | 天津军星管业集团有限公司 | Heat preservation tube material prepared by recycling waste hard polyurethane foaming plastic, heat preservation tube and manufacturing method |
| CN106397725B (en) * | 2016-08-30 | 2019-05-07 | 天津军星管业集团有限公司 | Utilize recycling waste hard polyurethane foam production insulating tube material, insulating tube and production method |
| CN106832204A (en) * | 2017-01-05 | 2017-06-13 | 广州特种承压设备检测研究院 | A kind of modified polyurethane roofing heat insulating material and preparation method thereof |
| CN106750510A (en) * | 2017-01-13 | 2017-05-31 | 郑州中远氨纶工程技术有限公司 | The processing method and polyurethane elastomer of urethane oligomer waste liquid |
| CN106750510B (en) * | 2017-01-13 | 2020-04-03 | 郑州中远氨纶工程技术有限公司 | Method for treating polyurethane oligomer waste liquid and polyurethane elastomer |
| CN107446345A (en) * | 2017-08-29 | 2017-12-08 | 河北科技大学 | A kind of filled-type flexible polyurethane foams based on vamp leftover pieces and preparation method thereof |
| CN107602911A (en) * | 2017-10-18 | 2018-01-19 | 上海第二工业大学 | A kind of method of microwave radiation technology alcoholysis waste refrigerators polyurethane |
| CN107955206A (en) * | 2017-11-28 | 2018-04-24 | 山东诺威新材料有限公司 | The method of waste polyurethane foam degraded recycling polyether polyol |
| CN113999429A (en) * | 2021-12-21 | 2022-02-01 | 浙江工业大学 | Method for efficiently degrading polyurethane coating solid waste |
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Application publication date: 20120808 |