CN113583206A - Thermal insulation material prepared by degrading waste polyurethane and preparation method thereof - Google Patents

Thermal insulation material prepared by degrading waste polyurethane and preparation method thereof Download PDF

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CN113583206A
CN113583206A CN202110771198.3A CN202110771198A CN113583206A CN 113583206 A CN113583206 A CN 113583206A CN 202110771198 A CN202110771198 A CN 202110771198A CN 113583206 A CN113583206 A CN 113583206A
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lignin
polyurethane
degrading
thermal insulation
waste polyurethane
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赵朝阳
顾晓华
齐文斌
董雨磊
刘思雯
吕士伟
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Shanghai Hecheng Polymer Technology Co ltd
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Shanghai Hecheng Polymer Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • 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
    • C08G18/48—Polyethers
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
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    • C08G2101/00—Manufacture of cellular products
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    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W30/50—Reuse, recycling or recovery technologies
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  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The invention relates to a thermal insulation material prepared by degrading lignin and waste polyurethane and a preparation method thereof. The prepared rigid polyurethane heat-insulation product has excellent performance, high compression strength, good elasticity, good thermal stability, good heat insulation and other properties. The recovery rate of the elasticity of the waste polyurethane is close to 100 percent, the cost of the polyurethane rigid foam product is greatly reduced, a new practical way is opened up for the application of the waste polyurethane elastomer in the recovery and preparation of the polyol, and meanwhile, the invention opens up a new way for the utilization of the lignin extracted from the papermaking waste liquid by utilizing the excellent performance of the structure-modified polyurethane reclaimed material of the lignin.

Description

Thermal insulation material prepared by degrading waste polyurethane and preparation method thereof
Technical Field
The invention belongs to the field of chemical material recovery and reuse, and particularly relates to a thermal insulation material prepared by degrading lignin and waste polyurethane and a preparation method thereof.
Background
Since the discovery by professor Bayer 1937 that polyurethanes can be prepared by polyaddition of polyisocyanates with polyols and the industrial application of the polyurethanes on the basis of the discovery, the polyurethane products have received increasing attention. With the progress of science and technology, polyurethane products have been more and more deeply inserted into the lives of people. Because of its excellent physical and chemical properties, polyurethane is widely used in many fields such as automobile manufacturing, transportation, civil engineering and construction, light industry, textile, electromechanical, petrochemical, aerospace, water conservancy and the like. But also many new polyurethane products have been developed.
The polyurethane industry has developed very rapidly and the consumption of polyurethane in the world has essentially doubled every decade. In recent years, with the rapid increase in demand for polyurethane in the asia-pacific region, the global polyurethane production center has shifted to the asia-pacific region, particularly china. The polyurethane market in China shows a stable growth situation in 2018, and the future development condition of the industry is optimistic.
Polyurethane materials are a kind of multipurpose synthetic resin with various forms, and products of the polyurethane materials have various forms, including foamed plastics, elastomers, coatings, adhesives, fibers, synthetic leather waterproof materials and the like. Among them, polyurethane foam is the largest variety of polyurethane synthetic products, and the total production amount thereof is about 60% of the polyurethane products. Is one of the fastest-developing varieties in the modern plastic industry. Polyurethane foams can be classified into three types, namely, soft polyurethane foams, hard polyurethane foams and semi-hard polyurethane foams, according to the hardness of the polyurethane foams. The plastic polyurethane flexible foam is mainly used for filling furniture, automobiles and the like. The polyurethane rigid foam is mainly used in the fields of heat preservation and heat insulation of household appliances, walls, pipelines and the like. The semi-rigid foam is mainly used for manufacturing products such as instrument boards.
Polyurethane products have various types and wide application range, but because the polyurethane belongs to organic compounds, the polyurethane is easy to be oxidized and denatured at higher temperature, for example, the service life of an insulating layer of a petroleum gas transmission pipe can be greatly shortened under the high-temperature condition. Furthermore, the machine parts assembled with the polyurethane elastomer gear are not suitable for long-time and high-power work. The poor heat resistance of polyurethanes limits their use. This has forced the search for a substance that can replace polyurethane under high temperature conditions or improve the heat resistance of polyurethane by means of modification.
The large volume production and widespread use of polyurethane elastomers has led to a large volume of polyurethane waste (including scrap in production and use of aged polyurethane materials of various types). The recyclable polyurethane elastomer waste in China can reach more than 300 million tons every year, but due to the defects of a polyurethane elastomer waste recycling method and a polyurethane elastomer waste recycling technology, the economic benefit in the aspect of polyurethane elastomer recycling is poor, and in addition, the awareness of people to environmental protection is low, so that the recycling amount of polyurethane elastomer waste materials is very small, a large amount of solid polyurethane elastomer waste materials are simply treated and discarded, and the environment is seriously damaged.
Lignin is an abundant and renewable biological material widely present in plants. The second largest amount of natural organic matter, second only to cellulose, is found in nature in total.
The lignin has a carbon chain and a benzene ring in the structure, the carbon chain has hydroxyl, aldehyde group, ketone group, carboxyl or olefinic bond, the benzene ring has hydroxyl, methoxyl and the like, and the lignin is a resource with great usefulness.
Industrial lignin is a by-product of the paper industry, which is present in paper mill effluents from the pulp and paper industry. The amount of waste water from paper making in China is large, accounting for 30% of the amount of waste water from industrial industry in China. The pulping and papermaking waste liquid contains a large amount of lignin which is rarely and effectively utilized till now, and is a blank in the application field of polyurethane degradation, if the waste liquid is not recycled, the waste liquid is directly discharged into sewage bodies along with black liquid, so that resources are wasted, and serious environmental pollution harm is caused. Therefore, from the viewpoint of environmental protection and resource utilization, the development and utilization of lignin must be regarded as important.
The society is a human and natural society, the pursuit is sustainable development, and attention is paid to environmental protection and reasonable utilization of resources while pursuing high-grade and new.
The lignin has a large number of benzene rings in the structure, the benzene rings contain active groups such as phenolic hydroxyl, alcoholic hydroxyl, carboxyl and the like, the structure is complex, other active groups are also contained, if lignin degradation products are used for replacing polyhydric alcohols, the lignin is connected into the obtained regenerated polyurethane polyol, and the foam structure of the polyurethane can be optimized to a great extent and the mechanical property of the polyurethane can be enhanced in a foam system after the lignin is reused.
The polyurethane elastomer is a high molecular polymer and has great social value and economic value, although the treatment methods of polyurethane wastes are various at present, including an energy method, a physical method and a chemical method. However, no literature and patent reports an effective method for effectively utilizing the waste resources of polyurethane elastomers in an economic and environment-friendly manner. Under the environmental pressure and the current shortage of natural resources, the development of a method and a channel for reasonably and effectively recycling polyurethane elastomer waste is urgent.
The polyurethane elastomer is a crosslinked network structure generated by the reaction of hydroxyl on polyol and isocyanate group on diphenylmethane diisocyanate, belongs to chemical reaction, all the chemical reactions cannot be completed, and reversible and dynamic equilibrium of the reaction exists. Thus, an environment can be found in which the polyurethane elastomer can be reversibly reacted to form reactive species or additional products formed from the reactants or products, and the products can then be reused to prepare polyurethane elastomer products or used as otherwise.
In order to embody the economic and environmental value of the polyurethane elastomer waste as much as possible, the waste is preferably processed and then prepared into polyurethane elastomer products again, and the polyurethane elastomer waste is crushed and then used as filler by a physical recycling method. However, only low-grade polyurethane elastomer products can be prepared by adopting the method, and the value of polyurethane waste materials cannot be fully exerted.
Patent document (CN 101469050A) mentions that waste rigid polyurethane foam is degraded into liquid oligomer under the condition of completely using polyether polyol as alcoholysis agent after being crushed, and the degradation product is not degraded by polyurethane elastomer, and the degradation product can be used for preparing polyurethane rigid foam by foaming. Patent document (CN 102924747A) proposes that a novel functionalized alcoholysis agent is used to perform alcohol exchange on a urethane bond through hydroxyl in an alcoholysis agent molecule under the conditions of high temperature and a catalyst to cause polyurethane degradation to generate a polyurethane acrylate resin with smaller molecular weight, and the resin is applied to a photocuring coating. The patent adds more auxiliaries during operation, and the operation is relatively complicated. The waste degradation products are not all converted to useful products. But also the polyurethane waste material is treated primarily, which pollutes the environment. Patent literature (CN 103627024A) also proposes a method for recovering small molecule acids, alcohols, oligomers and other products by degrading waste polyurethane with steam of small molecule alcohol and high heat under ultra-high temperature conditions. The method proposed in this patent needs to be carried out at very high temperatures, the reaction time is relatively long, and a large amount of energy is consumed in the whole process. And is not completely decomposed. Although the final product can obtain small molecular substances, the application of the waste materials is required to be carried out by subsequent separation and purification processes, and the degradation products cannot be directly utilized, so that the recovery cost of the degradation products is increased, and the environment is polluted by the separation and purification waste liquid. In the patent (CN 103374145A), it is proposed to recover polyurethane elastomer by using small molecular alcohol as degradation agent, adding catalyst, and degrading under the protection of inert gas. This patent has added salt material at the degradation in-process and has done the catalyst, and this leads to still need to carry out follow-up loaded down with trivial details desalination processing work to it when using the degradation material, has increased waste material processing procedure, and the polluted environment has increaseed manufacturing cost, and the degradation material of this patent has the layering phenomenon moreover, and degradation material utilization ratio is not high, and this economic value that restricts polyurethane recovery to a great extent. In patent literature (CN 101696261A), there is mentioned a lignin polyurethane and a preparation method thereof, in which modified lignin is dissolved in polyol and reacted with isocyanate to prepare polyurethane foam, which belongs to the physical modification of polyurethane foaming process, and does not relate to the polyurethane degradation category, and there is no report on the application of lignin fiber in the polyurethane degradation system. The defects of the heat insulation material prepared from the polyurethane elastomer degradation material are low foaming strength, limited use and low product recycling rate. In a patent (CN 104672414A), a method for preparing a polyurethane thermal insulation material by using a waste polyurethane elastomer is mentioned, wherein the utilization rate of the waste polyurethane elastomer is not up to 100%, and resource waste is caused.
Disclosure of Invention
In order to overcome the defects, the invention provides the method for improving the strength of the foam pores of the foaming material by utilizing the aromatic heterocyclic structure of the lignin, and improving the compressive strength of the polyurethane elastomer degradation foam material, thereby improving the heat conductivity coefficient. The method has simple processing technology, is easy to operate, has safe and pollution-free whole production flow, has great potential of actual production, and the prepared rigid polyurethane foam product has good heat insulation performance, the heat conductivity coefficient reaches 0.02W/m.K, and the apparent density, the water absorption rate, the compression strength and the like of the rigid polyurethane foam product accord with the national standard.
The invention provides a thermal insulation material prepared by degrading lignin and waste polyurethane, which is prepared by extracting lignin, polyether-based waste polyurethane elastomer and other auxiliary agents in papermaking night.
The invention also provides a preparation method of the thermal insulation material prepared by degrading lignin and waste polyurethane, which comprises the following steps:
step 1: extracting lignin in papermaking black night;
step 2: improving the lignin liquid to obtain lignin modified liquid;
and step 3: mixing polyether-based waste polyurethane elastomer, the lignin modification solution and a chain extension crosslinking agent, continuously stirring under a closed condition of 100-200 ℃, and reacting to prepare polyether polyol degradation solution A;
and 4, step 4: mixing the polyester-based waste polyurethane elastomer, the lignin modification liquid and the chain extension crosslinking agent, and continuously stirring under a closed condition of 120-200 ℃ to react to prepare a polyester polyol degradation liquid B;
and 5: uniformly mixing the polyol degradation liquid A, the polyol degradation liquid B, a physical foaming agent, a catalyst, a foam stabilizer and water according to a certain proportion to obtain a component A;
step 6: isocyanate and the like are taken as the B component material, and the A component material and the B component material are stirred in a certain proportion to be uniformly mixed;
and 7: and (3) injecting the A, B component mixture into a mould to be cured and formed to obtain the hard polyurethane insulation product.
Further, in step 1, the extracting of lignin specifically comprises: taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
Further, in the step 2, adding polyalcohol, an alkaline catalyst and a lignin modifier into the lignin liquid, and reacting for 1-5 hours at 100-;
wherein the lignin is 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts; the polyol is 100 parts; 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts of basic catalyst; 0.5 part, 1 part, 1.5 parts or 2 parts of lignin modifier; wherein, the content of one part is 1 g. Further, the polyalcohol is one or more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, ethylene glycol, 1, 3-propanediol, diethylene glycol, triethylene glycol, tripropylene glycol, 1, 2-propanediol, pentanediol, GR-635C, GR-4110A, GR-4110G, GR-450A, GR-649, PBA-1000, PEG-200, GR-8340A, GR-835G, GRA-6360 and PEDA-1500.
Further, the alkaline catalyst is one or more of lithium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide and cesium hydroxide.
Further, the lignin modifier is one or more of maleic anhydride, ethylene oxide, propylene oxide and epichlorohydrin.
Further, the chain-extending cross-linking agent in the step 3 is one or more of trimethylolpropane, diethyltoluenediamine (DET-DA), dimethylthiotoluenediamine, diethylene glycol (DEG), triethylene glycol, sucrose, glucose, Diethylaminoethanol (DEAE) glycerol, and iso-further, and the chain-extending cross-linking agent in the step 4 is one or more of glycerol, isosorbide, 1, 6-hexanediol, MOCA, trimethylolpropane, diethyltoluenediamine (DET-DA), dimethylthiotoluenediamine, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sucrose, glucose, and Diethylaminoethanol (DEAE).
Further, the physical blowing agent in step 5 is one or more of monofluorodichloroethane (HCFC-141b), HCFC-142b (dichlorofluoroethane), HCFC-123(1,1, 1-trifluorodichloroethane), HCFC-22 (chlorodifluoromethane) cyclopentane, pentane, fluorotrichloromethane (CFC-11), HFC-245fa, HFC-365mfc (1,1,1,3, 3-pentafluorobutane), HFC-334a (1,1,1, 2-tetrafluoroethane), N-azobisisobutyronitrile (N-butane), antimony trioxide, AZ, 1, 1-dichloro-1-fluoroethane, propane butane, dimethyl ether and water.
Further, the catalyst in step 5 is tris (dimethylaminopropyl) hexahydrotriazine (PC-41), dimethylethanolamine, N, N, N ' -pentamethyldiethylenetriamine, triethylenediamine, cyclohexylamine, N, N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2 ' -dimorpholinodiethylether (DMDEE), N, N-dimethylbenzylamine (BDMA), N, N ' -tetramethyl-1, 6-hexanediamine (TMHDA), methyldiethanolamine, N, N, N ' -trimethylaminoethylethanolamine, triethylamine, 1, 2-dimethylimidazole, tetramethylethylenediamine, N, N-Dimethylethanolamine (DMEA), N, N-diethylethanolamine, dimethylaminoethoxyethanol, N, N ' -dimethylethoxyethanol, N, N ' -dimethylethanolamine, N-diethylethanolamine, N, N-dimethylethoxyethanol, N, N ' -dimethylethoxyethanol, N, N, N ' -dimethyldiethanolamine, N, N ' -dimethyldiethanediylethanolamine, N, N, N, one or more of N, N, N ', N' -tetramethyl-1, 3-propylamine (TMPDA), 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine and organotin.
Further, the foam stabilizer in the step 5 is one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, dodecyl/tetradecyl dimethyl tertiary amine and dimethyl siloxane.
Further, the component B in the step 6 is one or more of diphenylmethane diisocyanate (MDI) (MDI-100LL, MDI-100HL, MR-200, M200, 44V20, M20S, 5005), Toluene Diisocyanate (TDI) (TDI80/20, TDI100), polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27, PAPI-135C) and Hexamethylene Diisocyanate (HDI)
Further, in the step 6, the ratio of the group a material to the group B material is: 1:0.8, 1: 0.9, 1:1, 1:1.1, 1:1.2, 1.1.3, 1:1.4 or 1: 1.5.
Further, the stirring time in step 6 is set to be until milky white appears.
The invention has the beneficial effects that:
the method for degrading and recovering the polyurethane elastomer changes the types and the proportion of different alcoholysis agents and alcoholysis assistant agents, optimizes the degradation scheme to obtain a degradation product which is a homogeneous product compared with the existing degradation process and has good fluidity. The elastomer degradation rate is increased by approximately 100%. The degradation material can completely directly replace polyol to prepare the polyurethane thermal insulation material. Meanwhile, the regenerated polyether polyol obtained after the polyurethane elastomer is degraded has a large number of benzene ring rigid structures caused by benzene ring structures in the degradation material, can be called as modified polyether polyol, has structural properties superior to those of the polyether polyol sold in the market, can bring a natural self-reinforcing function when the degradation product is reused, and improves the strength of a product when the degradation material is reused. Therefore, the combination of the rigid structure of the degradation material and the lignin of the papermaking waste liquid is more beneficial to the dispersion effect of the dispersed lignin in the polyurethane matrix and better enhances the strength of the polyurethane product.
Compared with the degradation product prepared by the existing industry, the degradation product related in the invention does not need to be processed again, no additional product is generated, the degradation product can be directly used, and the utilization rate reaches 100%. The production process has no three-waste discharge and is green and environment-friendly.
The invention relates to a method for preparing polyurethane foam by degrading polyurethane elastomer, which comprises adding lignin modifying solution and chain-extending cross-linking agent to be mixed and chemically degraded in the process of degrading polyether-based and polyester-based waste polyurethane elastomer, then preparing polyether-type and polyester-type polyol degrading solution, because lignin is added in the degradation process, the lignin has a multi-benzene ring multi-branch structure and can be grafted on the molecular chain of the regenerated polyol in a chemical bonding way, which is different from the lignin blending modified foaming polyurethane composite material, the chemical modification mode enables lignin to be connected with the regenerated polyol in a chemical bonding mode to be superior to blending modification, greatly and firmly improves the network crosslinking degree of polyurethane, improves the compression strength of the lignin/waste polyurethane composite material, and simultaneously prolongs the service life of the material.
The lignin is derived from papermaking waste liquor. Can consume a large amount of papermaking waste liquid, fully utilizes the potential value of the papermaking waste liquid, and is economic and environment-friendly. The mutually embedded structure of the polyurethane material and the lignin plays a role in isolating oxygen to a certain extent on one hand, and the lignin can play a role in supporting a framework on the other hand. The structure of mutually embedding polyurethane lignin improves the heat resistance and stability of polyurethane foam, enlarges the application range of polyurethane products to a certain extent, and simultaneously greatly improves the mechanical property of polyurethane rigid foam.
The polyol recovered and prepared from the polyurethane elastomer can be directly applied to the industry of producing and preparing polyurethane rigid foam after being researched by a echelon amplification experiment. The heat preservation performance is excellent, the heat conductivity coefficient can reach 0.03/m.K, the compressive strength is 0.26Mpa, the closed pore rate is more than 96 percent, and other performance indexes also reach the national standard.
In the invention, the lignin is added in the alcoholysis process and belongs to chemical addition, and compared with physical blending addition in the foaming process, the prepared regenerated polyurethane elastomer has higher compression strength. This is because the physically added lignin is not uniformly dispersed and easily agglomerated, which affects the skeleton structure of the polyurethane elastomer.
Therefore, the invention has strong practicability for the comprehensive utilization of the wastes in the whole Polyurethane (PU) industry and the wastes in the papermaking industry, and has higher economic and environmental protection values and good social comprehensive benefits.
Drawings
FIG. 1 is a FT-IR curve of a lignin-modified recycled polyurethane rigid foam according to an embodiment of the present invention; (the left side is the wavelength range 4000--1The right diagram is the wavelength range 1800-1000 cm-1Enlargement area)
FIG. 2 is a scanning electron microscope image of a lignin-modified polyurethane rigid foam prepared by adding lignin in the embodiment of the present invention;
FIG. 3 is a thermogravimetric curve of lignin modified regenerated rigid polyurethane foam when 15% and 0% of lignin is added in the embodiment of the invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
Adding 20g of polyol PEDA-1500, 50g of 1, 3-propylene glycol, 2g of potassium hydroxide, 2g of maleic anhydride and 1g of ethylene oxide into 2g of lignin, and reacting in a closed reaction kettle at 150 ℃ for 3 hours to obtain lignin modified liquid.
80g of polyether-based waste polyurethane elastomer is added into a reaction kettle, 3g of cane sugar and 1g of glucose are added, and the mixture is stirred for 5 hours under the sealed condition of 175 ℃ to prepare polyether polyol degradation liquid A.
Adding 75g of polyester-based waste polyurethane elastomer into a reaction kettle, adding 5g of triethylene glycol, and stirring for 6 hours at 150 ℃ under a closed condition to prepare the polyester polyol degradation liquid B.
11g of polyether polyol degradation liquid A, 12g of polyester polyol degradation liquid B, 8g of HFC-245fa, 0.5g of silicone oil L-600, 0.1g of PC-41 and 0.1g of water are uniformly stirred to be used as a component A, and then the mixture is added into the mixture, wherein the total mass ratio of the component A to the component A is 1:1.1, stirring the TDI for 15S to foam, cooling and curing for 24h to obtain the rigid polyurethane foam material.
Example 2
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
Adding 50g of polyol GR-4110A, 30g of polyol GR-649, 30g of 1, 9-nonanediol, 3g of potassium hydroxide and 1g of maleic anhydride into 3g of lignin, and reacting at 175 ℃ in a closed reaction kettle for 3 hours to obtain lignin modified liquid.
100g of polyether-based waste polyurethane elastomer is added into a reaction kettle, 5g of Diethylaminoethanol (DEAE) and 1g of glucose are added, and the mixture is stirred for 2 hours at 185 ℃ under a closed condition to prepare polyether polyol degradation liquid A.
Adding 90g of polyester-based waste polyurethane elastomer into a reaction kettle, adding 3g of glycerol and 2g of isosorbide, and stirring for 3 hours at 130 ℃ under a closed condition to prepare the polyester polyol degradation liquid B.
Taking 10g of polyether polyol degradation liquid A, 9g of polyester polyol degradation liquid B, 7g of HCFC-22, 0.3g of silicone oil CGY-5, 0.3g of triethylene diamine and 0.3g of water, uniformly stirring the mixture to be used as a component A, and then adding a mixture of the component A and the component A in a total mass ratio of 1:1.4, stirring for 15S to foam, cooling and curing for 24h to obtain the rigid polyurethane foam material.
Example 3
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
Taking 3g of lignin, adding 50g of diethylene glycol, 30g of 1, 5-pentanediol, 30g of PEDA-1500, 1.5g of magnesium hydroxide and 2g of propylene oxide, and reacting for 4.5 hours in a closed reaction kettle at 180 ℃ to obtain lignin modified liquid.
Adding 110g of polyether-based waste polyurethane elastomer into a reaction kettle, adding 3g of cane sugar and 1g of glycerol, and stirring for 2 hours at 190 ℃ under a sealed condition to prepare polyether polyol degradation liquid A.
130g of polyester-based waste polyurethane elastomer is added into a reaction kettle, 3g of triethylene glycol and 2g of phthalic anhydride are added, and the mixture is stirred for 4 hours under a closed condition at 150 ℃ to prepare the polyester polyol degradation liquid B.
9g of polyether polyol degradation liquid A, 10g of polyester polyol degradation liquid B, 5g of HCFC-11, 0.4g of silicone oil DC-193, 0.5g of IPDI and 0.1g of water are uniformly stirred to be used as component A, and then the mixture is added into the mixture, wherein the mass ratio of the component A to the component A is 1:0.8 of MDI, stirring for 15S to foam, cooling and curing for 24h to obtain the rigid polyurethane foam material.
Example 4
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
Adding 50g of polyalcohol GR-649, 30g of pentanediol, 30g of 1, 9-nonanediol, 1g of magnesium hydroxide and 2g of ethylene oxide into 2g of lignin, and reacting in a closed reaction kettle at 200 ℃ for 5 hours to obtain lignin modified liquid.
Adding 50g of polyether-based waste polyurethane elastomer into a reaction kettle, adding 4g of MOCA, 3g of neopentyl glycol (NPG), 3g of sucrose and 1g of glucose, and stirring for 5 hours at 130 ℃ under a closed condition to prepare polyether polyol degradation liquid A.
50g of polyester-based waste polyurethane elastomer is added into a reaction kettle, 3g of cane sugar and 5g of phthalic anhydride are added, and the mixture is stirred for 3 hours under the closed condition of 120 ℃ to prepare the polyester polyol degradation liquid B.
Uniformly stirring 10g of polyether polyol degradation liquid A, 11g of polyester polyol degradation liquid B, 10g of dimethyl ether, 0.2g of silicone oil SD-601, 0.3g of DMDEE and 0.3g of water to obtain a component A, and adding the components A and B in a mass ratio of 1:1.2, stirring for 15S to foam, cooling and curing for 24h to obtain the rigid polyurethane foam material.
Example 5
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
1g of lignin is taken, added with 50g of ethylene glycol A, 30g of diethylene glycol, 30g of 1, 8-octanediol, 0.5g of lithium hydroxide and 0.5g of epichlorohydrin, and reacted in a closed reaction kettle at 130 ℃ for 3.5 hours to prepare lignin modified liquid.
Adding 90g of polyether-based waste polyurethane elastomer into a reaction kettle, adding 3g of cane sugar, 1g of glucose and 1g of MOCA, and stirring for 2 hours at 155 ℃ under a sealed condition to prepare polyether polyol degradation liquid A.
90g of polyester-based waste polyurethane elastomer is added into a reaction kettle, 1g of diethyl toluene diamine (DET-DA) and 5g of glucose are added, and the mixture is stirred for 2 hours at 155 ℃ under a sealed condition to prepare the polyester polyol degradation liquid B.
10g of polyether polyol degradation liquid A, 12g of polyester polyol degradation liquid B, 8g of n-butane, 0.1g of silicone oil 5C-154, 0.4g of cyclohexylamine and 0.3g of water are uniformly stirred to be used as component A, and then the mixture is added into the component A according to the total mass ratio of 1:1 TMDI, stirring for 15S to foam, cooling and curing for 24h to obtain the polyurethane rigid foam material.
Example 6
Taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
50g of ethylene glycol A, 30g of diethylene glycol, 30g of 1, 8-octanediol, 0.5g of lithium hydroxide and 0.5g of epichlorohydrin are added into a reaction kettle to prepare a modified solution.
Adding 90g of polyether-based waste polyurethane elastomer into a reaction kettle, adding 3g of cane sugar, 1g of glucose and 1g of MOCA, and stirring for 2 hours at 155 ℃ under a sealed condition to prepare polyether polyol degradation liquid A.
90g of polyester-based waste polyurethane elastomer is added into a reaction kettle, 1g of diethyl toluene diamine (DET-DA) and 5g of glucose are added, and the mixture is stirred for 2 hours at 155 ℃ under a sealed condition to prepare the polyester polyol degradation liquid B.
1g of lignin, 10g of polyether polyol degradation liquid A, 12g of polyester polyol degradation liquid B, 8g of n-butane, 0.1g of silicone oil 5C-154, 0.4g of cyclohexylamine and 0.3g of water are uniformly stirred to be used as a component A, and then the mixture is added into the mixture, wherein the mass ratio of the component A to the component A is 1:1 TMDI, stirring for 15S to foam, cooling and curing for 24h to obtain the blending type polyurethane rigid foam material.
The following table shows examples and comparative examples
Figure BDA0003153473480000071
FIG. 1 is a FT-IR curve of a lignin-modified recycled polyurethane rigid foam in an embodiment of the present invention; (the left side is the wavelength range 4000--1The right diagram is the wavelength range 1800-1000 cm-1Enlargement area)
FIG. 2 is a graph showing the appearance of the lignin-modified recycled polyurethane rigid foam, which is prepared by cutting the lignin-modified recycled polyurethane rigid foam prepared by adding lignin into a thin sample, and observing the thin sample by selecting a region with clear visual field and intact and regular foam pores through a scanning electron microscope, wherein the observation result is shown in FIG. 2.
FIG. 3 is a thermogravimetric curve of lignin modified regenerated rigid polyurethane foam when 15% and 0% of lignin is added in the embodiment of the invention.

Claims (15)

1. The thermal insulation material prepared by degrading lignin and waste polyurethane is characterized by being prepared by extracting lignin, polyether-based waste polyurethane elastomer and other auxiliary agents in papermaking night.
2. A method for preparing the thermal insulation material prepared by degrading the lignin and the waste polyurethane, which is disclosed by the claim 1, is characterized by comprising the following steps of:
step 1: extracting lignin in papermaking black night;
step 2: improving the lignin liquid to obtain lignin modified liquid;
and step 3: mixing polyether-based waste polyurethane elastomer, the lignin modification solution and a chain extension crosslinking agent, continuously stirring under a closed condition of 100-200 ℃, and reacting to prepare polyether polyol degradation solution A;
and 4, step 4: mixing the polyester-based waste polyurethane elastomer, the lignin modification liquid and the chain extension crosslinking agent, and continuously stirring under a closed condition of 120-200 ℃ to react to prepare a polyester polyol degradation liquid B;
and 5: uniformly mixing the polyol degradation liquid A, the polyol degradation liquid B, a physical foaming agent, a catalyst, a foam stabilizer and water according to a certain proportion to obtain a component A;
step 6: isocyanate and the like are taken as the B component material, and the A component material and the B component material are stirred in a certain proportion to be uniformly mixed;
and 7: and (3) injecting the A, B component mixture into a mould to be cured and formed to obtain the hard polyurethane insulation product.
3. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, wherein in the step 1, the extraction of the lignin specifically comprises: taking appropriate papermaking black liquor, acidifying, separating out lignin, filtering, washing, drying and crushing.
4. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane as claimed in claim 2, wherein in the step 2, the polyol, the alkaline catalyst and the lignin modifier are added into the lignin liquid, and the lignin modification liquid is prepared by reacting the mixture for 1 to 5 hours under the sealed condition of 100 ℃ and 200 ℃;
wherein the lignin is 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts; the polyol is 100 parts; 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts of basic catalyst; 0.5 part, 1 part, 1.5 parts or 2 parts of lignin modifier; wherein, the content of one part is 1 g.
5. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 4, wherein the method comprises the following steps: the polyalcohol is one or more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, ethylene glycol, 1, 3-propanediol, diethylene glycol, triethylene glycol, tripropylene glycol, 1, 2-propanediol, pentanediol, GR-635C, GR-4110A, GR-4110G, GR-450A, GR-649, PBA-1000, PEG-200, GR-8340A, GR-835G, GRA-6360 and PEDA-1500.
6. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 4, wherein the alkaline catalyst is one or more of lithium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide and cesium hydroxide.
7. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 4, wherein the method comprises the following steps: the lignin modifier is one or more of maleic anhydride, ethylene oxide, propylene oxide and epichlorohydrin.
8. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, which is characterized in that: and in the step 3, the chain extension crosslinking agent is one or more of trimethylolpropane, diethyltoluenediamine (DET-DA), dimethylthiotoluenediamine, diethylene glycol (DEG), triethylene glycol, sucrose, glucose, Diethylaminoethanol (DEAE) glycerol, isosorbide, glucose, MOCA, neopentyl glycol (NPG), sucrose and acid anhydride.
9. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, wherein the chain-extending cross-linking agent in the step 4 is one or more selected from glycerol, isosorbide, 1, 6-hexanediol, MOCA, trimethylolpropane, diethyltoluenediamine (DET-DA), dimethylthiotoluenediamine, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sucrose, glucose and Diethylaminoethanol (DEAE).
10. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, the method is characterized in that the physical foaming agent in the step 5 is one or more of monofluorodichloroethane (HCFC-141b), HCFC-142b (dichlorofluoroethane), HCFC-123(1,1, 1-trifluorodichloroethane), HCFC-22 (chlorodifluoromethane) cyclopentane, pentane, fluorotrichloromethane (CFC-11), HFC-245fa, HFC-365mfc (1,1,1,3, 3-pentafluorobutane), HFC-334a (1,1,1, 2-tetrafluoroethane), N-azodiisobutyronitrile (N-butane DN), antimonous oxide, AZ, 1, 1-dichloro-1-fluoroethane, propane butane, dimethyl ether and water.
11. The method for preparing thermal insulation material by degrading lignin and waste polyurethane according to claim 2, wherein the catalyst in step 5 is tris (dimethylaminopropyl) hexahydrotriazine (PC-41), dimethylethanolamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, triethylenediamine, cyclohexylamine, N, N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2' -dimorpholinodiethylether (DMDEE), N, N-dimethylbenzylamine (BDMA), N, N ', N "-tetramethyl-1, 6-hexanediamine (TMHDA), methyldiethanolamine, N, N, N' -trimethylaminoethylethanolamine, triethylamine, 1, 2-dimethylimidazole, tetramethylethylenediamine, One or more of N, N-Dimethylethanolamine (DMEA), N, N-diethylethanolamine, dimethylaminoethoxyethanol, N, N, N ', N' -tetramethyl-1, 3-propylamine (TMPDA), 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine and organotin.
12. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, wherein the foam stabilizer in the step 5 is one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, dodecyl/tetradecyl dimethyl tertiary amine and dimethyl siloxane.
13. The method for preparing thermal insulation materials by degrading lignin and waste polyurethane according to claim 2, wherein the component B in the step 6 is one or more of diphenylmethane diisocyanate (MDI) (MDI-100LL, MDI-100HL, MR-200, M200, 44V20, M20S, 5005), Toluene Diisocyanate (TDI) (TDI80/20, TDI100), polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27, PAPI-135C) and Hexamethylene Diisocyanate (HDI).
14. The method for preparing the thermal insulation material by degrading the lignin and the waste polyurethane according to claim 2, wherein the ratio of the group A material to the group B material in the step 6 is as follows: 1:0.8, 1: 0.9, 1:1, 1:1.1, 1:1.2, 1.1.3, 1:1.4 or 1: 1.5.
15. The method for preparing thermal insulation materials by degrading lignin and waste polyurethane according to claim 2, wherein the stirring time in step 6 is set to be milky white.
CN202110771198.3A 2021-07-08 2021-07-08 Thermal insulation material prepared by degrading waste polyurethane and preparation method thereof Pending CN113583206A (en)

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