CN110105621A - A kind of orientation biodegrading process of waste polyurethane material - Google Patents
A kind of orientation biodegrading process of waste polyurethane material Download PDFInfo
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- CN110105621A CN110105621A CN201910346481.4A CN201910346481A CN110105621A CN 110105621 A CN110105621 A CN 110105621A CN 201910346481 A CN201910346481 A CN 201910346481A CN 110105621 A CN110105621 A CN 110105621A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- 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
- C08J11/28—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention belongs to organic solid wastes recycling process fields, and in particular to a kind of orientation biodegrading process of waste polyurethane material.The technical issues of present invention mainly solves catalytic efficiency is low, selective scission of link is difficult, and after the reaction was completed, product is not readily separated, and cannot recycle high valuable chemicals.Waste polyurethane material and organic amine or amides catalyst, reaction dissolvent are mixed to form degradation system after reaction degradation is completed and cooled down and add water by the present invention, are filtered, Washing of Filter Cake is simultaneously dried to obtain aromatic multi-amine substance；Filtrate through organic solvent extracting and demixing, mutually dry to obtain long-chain polyether polyols substance by the organic solvent being layered；It is layered the degradation that obtained water phase can be recycled and reused for polyurethane.It can efficiently be activated by this method and urethane bond and urea bond in molecule of degrading, and to the carbon-carbon bond structure in the ehter bond and molecule of polyether polyols alcohol part without obvious catalytic activity, and the aromatic multi-amine substance and polyether polyols alcohols material of high added value are obtained by simple process is separable.
Description
Technical field
The invention belongs to organic solid wastes recycling process fields, and in particular to a kind of orientation degradation of waste polyurethane material
Method.
Technical background
Polyurethane is a kind of huge high molecular material of yield, since it has excellent performance, be widely used in we live and
The every field of production, simultaneously because its waste production is huge, therefore the innoxious and recycling treatment of Methods for Polyurethane Wastes
It is extremely important.For example, refrigerator thermal insulation material is a kind of rigid polyurethane foam, China has entered waste refrigerators and has scrapped peak
Phase scraps up to ten million, refrigerator every year.Hard polyurethane foams quality accounts for the 9% of refrigerator gross mass, and the overwhelming majority is useless
Gurry is landfilled or burns, and not only wastes a large amount of recycling resources in this way, but also will cause waste and the atmosphere in soil
Pollution.Therefore polyurethane recycling and reusing has become polyurethane industrial one of significant problem in the urgent need to address, to waste and old
Polyurethane carries out recycling and reusing, reduces environmental pollution, while reducing the production cost of new product, has realistic meaning.
Polyether polyol polyurethane is one of polyurethane material, is mainly used in refrigerator thermal insulation material, fibre
It is the molecule fragment combined by polyether polyol and polyisocyanates (such as TDI or MDI), by chain extension in sealing material
Crosslinking net macromolecular can be formed, crosslinking degree is bigger, and required condition of degrading is harsher.With the increasing of its crosslinking degree
Greatly, steric hindrance is also gradually increased, and solvent molecule is difficult to enter into ontology, so degradation agent cannot be brought into friendship by solvent molecule
Join intramolecular, degradation is also difficult to carry out.The product that existing degradation mode obtains is not single, and separation is more difficult, industry
Change degree, availability be not high.
There are mainly three types of methods for the recycling of current polyurethane: physical method, chemical method, energy law.Physical method has perhaps
The product properties of more reports and practical technique, the PU production of this method recycling is poor, is only applicable to low-grade product.Energy recovery is
By the way that waste incineration to be recycled to heat, this method will cause secondary pollution, not use substantially.Chemical method mainly has alcohol
Solution, Hydrolyze method, amine-decomposing method, alkaline hydrolysiss, wherein the most commonly used is ethylene glycol decomposition method and amine decomposition method.The deficiency of the method
Be in: in polyurethane resin there are the chemical bonds such as urethane bond, ehter bond, ester bond, urea bond, glycol or amine compounds compared with
It is easy cutting urethane bond, liquid is formed by exchange reaction.At this moment, two alkohol and amines used as distintegrant generate new
Urethane bond and urea bond, entered in liquid decomposition product as carbamate and urea derivative, product cannot decompose
The starting material polyethers of polyurethane resin or the intermediate aromatic polyamine compound of the pure and mild polyisocyanates of polyester polyols are obtained, weight
It is multiple to utilize difficulty, therefore the application of the relevant technologies is restricted.For example, Publication No. CN108623784A, CN105801904A,
The national inventing patent of CN107245162A, which is disclosed, does degradation agent with small molecule dihydric alcohol, and acetate makees catalyst, in 180-230
1-5h is reacted at DEG C, simple process obtains polyurethane degraded product, some confined goods are done with the product, such as: polyurethane shoe
Bottom stoste, electroplate primer, plastic cement race track.The reaction temperature of these methods is higher, and the product after degradation is not readily separated, only
It can directly utilize, do some low grade products.
It is formed containing the soft chain that polyether polyol is formed with fragrant based isocyanate in the molecule of polyether polyol polyurethane
Hard chain, there are ehter bond, urethane bond and urea bonds for intramolecular, if can under certain catalyst action, selectivity beat
The urethane bond and urea bond in molecule are opened, recycles the pure and mild aromatic diamines class compound of polyether polyols of high added value, undoubtedly
With important value.The national inventing patent of Publication No. CN106519292A, CN106565238A discloses a kind of utilization
Urethane bond and urea bond are selectively opened to recycle high added value in unsatuated metal ligand ionic catalysis polyurethane
The method of product, this method need to use a large amount of metal salt, and easily cause part of compounds carbon-carbon bond structure and pair occurs
Reaction.
Summary of the invention
The object of the present invention is to provide urethane bond in a kind of catalysis polyether polyol polyurethane of economical and efficient and
The selectively opened method to recycle high valuable chemicals of urea bond, does not need to use metal salt as catalyst, can return
The catabolites such as pinching ethoxylated polyhydric alcohol, aromatic polyamine compound.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of orientation biodegrading process of waste polyurethane material, include the following steps: by waste polyurethane material with it is organic
Amine or amides catalyst, reaction dissolvent are mixed to form degradation system and add water after reaction degradation is completed and cooled down, and filter, filter
Cake washs and is dried to obtain aromatic multi-amine substance；Through organic solvent extracting and demixing, the organic solvent being layered mutually dries filtrate
It is dry to obtain long-chain polyether polyols substance；It is layered the degradation that obtained water phase can be recycled and reused for polyurethane.Pass through this method
It can efficiently activate and urethane bond and urea bond in molecule of degrading, and in the ehter bond and molecule of polyether polyols alcohol part
Carbon-carbon bond structure obtain the aromatic multi-amine substance of high added value without obvious catalytic activity, and by simple process is separable
With polyether polyols alcohols material.
Further, the organic amine or amides catalyst are small molecule organic amine compound, including urea, sulphur
Urea, ethylenediamine, hexamethylene diamine, 1,2- propane diamine, Putriscine, formamide, acetamide, propionamide, n,N-Dimethylformamide,
Any one in succimide, piperazine or Isosorbide-5-Nitrae-lupetazin.These organic amines or amides catalyst volume compared with
It is small, it is very easy to enter in polyurethane body, and can efficiently open urethane bond and urea bond, selectivity is good, generates
Product structure it is clear.
Further, the reaction dissolvent is polar solvent or its aqueous solution, can be the alcohols or ketone of low molecular weight
The aqueous solution of the alcohols or ketone of class and low molecular weight, comprising: methanol, ethyl alcohol, propyl alcohol, ethylene glycol, 1,2-PD, 1,3-
Propylene glycol, glycerol, acetone, methyl ethyl ketone one or more and their aqueous solution.Above-mentioned solvent can guarantee organic amine or
The dissolution of person's amides catalyst, and realize its free diffusing in polyurethane material, with organic amine or amides catalyst
In addition the activation and degradation of concerted catalysis urethane bond and urea bond also help subsequent product separation and degradation system
Removal process.
Further, the mass fraction of the aqueous solution of the reaction dissolvent is 20% -100%.Due to aromatic multi-amine class
Conjunction object is not soluble in water, and the ratio by adjusting polar solvent and water can be such that polyamine compounds are directly precipitated, to directly obtain
The products such as aromatic multi-amine class compound and long-chain polyether polyols.
Further, the mass ratio of the waste polyurethane material, organic amine or amides catalyst and reaction dissolvent
For 1:0.01-2:1-50.Catalytic amount has a large amount of catalyst residuals after the reaction was completed when being higher than this proportion, cause unnecessary
Waste.In addition, the catalyst of organic diamine class, can form hydrogen bond with water, alcohol, so that being mixed with more urge in the polyalcohol after separation
Agent is unfavorable for its separation；And catalytic amount lower than this proportion when will lead to catalysis not exclusively, catalytic effect is decreased obviously.
Further, the temperature of the reaction degradation is 100-250 DEG C, and the time for reacting degradation is 1-12h.Reaction temperature
When lower than 100 DEG C, reactivity is lower, and reaction carries out needing long time, low efficiency；And when being higher than 250 DEG C, have other
Side reaction occurs, and also has certain destruction to the soft chain of polyether polyol, makes the reduction of its yield.And at such a temperature, both may be used
Degradation completely, and can retain the soft chain of polyether polyol.
Further, the separation of the aromatic multi-amine substance is to be dried at room temperature for；The long-chain polyether polyols class
The separation of substance is dried at being 80-100 DEG C in temperature.Since the presence of amino can be with water and alcohol with hydrogen in aromatic multi-amine substance
The form of key combines, and as the temperature rises, interaction can enhance, to obtain more pure aromatic multi-amine class chemical combination
Object then selects to be dried at room temperature.And the polyether polyols alcohols of long-chain is present in the organic solvent phase after extraction,
At this temperature, organic solvent evaporation can be removed, is higher than 100 DEG C, part long-chain alcohol can be lost, and be lower than 80 DEG C, organic solvent
Evaporation rate it is very slow, obtain more pure long-chain alcohol and take a long time.
Further, the amount that water is added into reaction system is 2-10 times of degradation system, when addition should slowly,
Stand to be precipitated be precipitated completely.Aromatic multi-amine substance is not soluble in water, and after adding water, aromatic multi-amine substance is precipitated, and adds the mistake of water
Cheng Zhongying is slow, and too fast will lead in precipitate contains many other impurity such as: urea, various alcohols cannot be purer
Aromatic multi-amine substance.
Further, the extractant when extraction is organic solvent, including chloroform, ethyl acetate, toluene, petroleum ether.
The extractant and reaction system are immiscible, easily remove, and extraction yield is high.Since solubility of the long-chain alcohol in the extractant is more anti-
Answer system big, so the extractant can effectively extract polyether polyol from reaction system.
Further, the partial size of the waste polyurethane material is 0.01-1cm.Itself and degradation can be increased by adequately crushing
The contact area of agent, so that degradation is easier to carry out.
Compared with prior art, the present invention has the advantage that
1, since the solvent cost of the invention used is low, the separable recycling of low boiling point；
2, since degradation agent used in the present invention is conventional catalyst, source is wide, and price is low, can further decrease recycling
Cost；
3, it is optionally broken urea bond, urethane bond, efficiently and directionally degradable polyurethane retains polyether polyol
Soft chain.Aromatic multi-amine class compound and long-chain polyether polyols substance can be obtained by simple separation.
Detailed description of the invention
Fig. 1 is the catabolite of 1-12 of the embodiment of the present invention --- the nuclear-magnetism of aromatic multi-amine substance characterizes map；
Fig. 2 is the catabolite of 1-4 of the embodiment of the present invention --- polyether polyols alcohols material nuclear-magnetism characterizes map；
Fig. 3 is the catabolite of 5-8 of the embodiment of the present invention --- polyether polyols alcohols material nuclear-magnetism characterizes map；
Fig. 4 is the catabolite of 9-12 of the embodiment of the present invention --- polyether polyols alcohols material nuclear-magnetism characterizes map；
As shown in Figure 1, resulting aromatic multi-amine substance is that (MDI) structure is as follows after degradation:
As shown in Figure 2, resulting polyether polyols alcohols material is poly- 1,2-PD polyether polyol after degradation, and structure is such as
Under:
From the figure 3, it may be seen that resulting polyether polyols alcohols material is polyethylene glycol polyether polyol after degradation, structure is as follows:
As shown in Figure 4, resulting polyether polyols alcohols material is polytetrahydrofuran polyether polyol after degradation, and structure is such as
Under:
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment waste polyurethane material to be degraded is poly- 1,2-PD polyether-polyurethane, and specific structure is as follows:
It is with 0.004g urea, 0.4g mass fraction by the waste polyurethane material that the smashed partial size of 0.4g is 0.01cm
100% ethyl alcohol is mixed to form the degradation system of 0.804g, and in water heating kettle, 12h, reaction degradation are reacted under conditions of 100 DEG C
After completing and cooling down, 8g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dried to obtain
0.13g aromatic multi-amine substance；For filtrate through chloroform extracting and demixing, 80 DEG C of chloroform phase drying being layered obtain 0.25g long-chain
Polyether polyols alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 2
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 1
By the smashed partial size of 0.4g be 0.05cm waste polyurethane material and 0.2g piperazine, 4g mass fraction be 60%
Acetone is mixed to form the degradation system of 4.6g, in water heating kettle, 8h is reacted under conditions of 140 DEG C, reaction degradation completion is simultaneously cold
But after, into the reaction system be added 20g water stand, it is to be precipitated completely after, filtering, Washing of Filter Cake simultaneously be dried to obtain 0.11g virtue
Fragrant polyamines；For filtrate through toluene extracting and demixing, it is more that 100 DEG C of toluene phase drying being layered obtain 0.29g long-chain polyether
First alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 3
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 1
The waste polyurethane material and 0.8g Isosorbide-5-Nitrae-lupetazin, 20g mass for being 1cm by the smashed partial size of 0.4g
Score is the degradation system that 20% methanol is mixed to form 21.2g, and in water heating kettle, 1h, reaction drop are reacted under conditions of 250 DEG C
Solution is completed and after cooling down, and 42.4g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake and drying
Obtain 0.16g aromatic multi-amine substance；Filtrate is layered through petroleum ether extraction, and 85 DEG C of drying of the petroleum ether phase being layered obtain
0.23g long-chain polyether polyols substance；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 4
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 1
The waste polyurethane material and 0.5g Isosorbide-5-Nitrae-lupetazin, embodiment 3 that partial size is 0.2cm after 0.4g is crushed
The water phase of middle recycling is mixed to form the degradation system of 45g, in water heating kettle, 2h is reacted under conditions of 180 DEG C, reaction has been degraded
At and after cooling down, 100g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dried to obtain
0.16g aromatic multi-amine substance；Through ethyl acetate extracting and demixing, the 80 DEG C of drying of ethyl acetate phase being layered obtain filtrate
0.23g long-chain polyether polyols substance；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 5
The present embodiment waste polyurethane material to be degraded is polyethylene glycol polyether-polyurethane, and specific structure is as follows:
The waste polyurethane material and 0.3g thiocarbamide, 10g mass fraction that partial size is 0.6cm after 0.4g is crushed are 70% second
Glycol is mixed to form the degradation system of 10.7g, in water heating kettle, 5h is reacted under conditions of 160 DEG C, reaction degradation completion is simultaneously cold
But after, into the reaction system be added 30g water stand, it is to be precipitated completely after, filtering, Washing of Filter Cake simultaneously be dried to obtain 0.18g virtue
Fragrant polyamines；For filtrate through chloroform extracting and demixing, it is polynary that 80 DEG C of chloroform phase drying being layered obtain 0.21g long-chain polyether
Alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 6
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 5
The waste polyurethane material that partial size is 0.09cm after 0.4g is crushed is 80% with 0.2g ethylenediamine, 5g mass fraction
Methyl ethyl ketone is mixed to form the degradation system of 5.6g, in water heating kettle, 7h is reacted under conditions of 150 DEG C, reaction degradation is completed simultaneously
After cooling, 15g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dried to obtain 0.11g
Aromatic multi-amine substance；For filtrate through toluene extracting and demixing, 100 DEG C of toluene phase drying being layered obtain 0.27g long-chain polyether
Polyols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 7
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 5
The waste polyurethane material that partial size is 0.3cm after 0.4g is crushed is 70% with 0.7g formamide, 16g mass fraction
Propyl alcohol is mixed to form the degradation system of 18.1g, in water heating kettle, 1h is reacted under conditions of 200 DEG C, reaction degradation completion is simultaneously cold
But after, into the reaction system be added 50g water stand, it is to be precipitated completely after, filtering, Washing of Filter Cake simultaneously be dried to obtain 0.16g virtue
Fragrant polyamines；Filtrate is layered through petroleum ether extraction, and 80 DEG C of drying of the petroleum ether phase being layered obtain 0.23g long-chain polyether
Polyols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 8
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 5
The water recycled in the waste polyurethane material and 0.5g formamide, embodiment 7 that partial size is 0.3cm after 0.4g is crushed
The degradation system to form 53g is mixed, in water heating kettle, 2h is reacted under conditions of 190 DEG C, reaction degradation is completed and cooling
Afterwards, into the reaction system be added 130g water stand, it is to be precipitated completely after, filtering, Washing of Filter Cake simultaneously be dried to obtain 0.2g fragrance
Polyamines；For filtrate through ethyl acetate extracting and demixing, it is poly- that 80 DEG C of ethyl acetate phase drying being layered obtain 0.23g long-chain
Ethoxylated polyhydric alcohol substance；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 9
The present embodiment waste polyurethane material to be degraded is polytetrahydrofuran polyether-polyurethane, and specific structure is as follows:
The waste polyurethane material that partial size is 0.7cm after 0.4g is crushed is with 0.3g adipamide, 10g mass fraction
70%1,2- propyl alcohol are mixed to form the degradation system of 10.7g, and in water heating kettle, 5h, reaction degradation are reacted under conditions of 170 DEG C
After completing and cooling down, 30g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dried to obtain
0.16g aromatic multi-amine substance；For filtrate through chloroform extracting and demixing, 80 DEG C of chloroform phase drying being layered obtain 0.23g long-chain
Polyether polyols alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 10
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 9
The waste polyurethane material that partial size is 0.4cm after 0.4g is crushed is 90% with 0.7g propionamide, 16g mass fraction
Glycerol is mixed to form the degradation system of 18.1g, in water heating kettle, 3h is reacted under conditions of 180 DEG C, reaction degradation completion is simultaneously cold
But after, into the reaction system be added 40g water stand, it is to be precipitated completely after, filtering, Washing of Filter Cake simultaneously be dried to obtain 0.11g virtue
Fragrant polyamines；Filtrate is layered through petroleum ether extraction, and 80 DEG C of drying of the petroleum ether phase being layered obtain 0.23g long-chain polyether
Polyols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 11
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 9
The waste polyurethane material that partial size is 1cm after 0.4g is crushed is with 0.2g succimide, 5g mass fraction
80%1,3-propanediol is mixed to form the degradation system of 5.6g, and in water heating kettle, 2h, reaction drop are reacted under conditions of 180 DEG C
Solution is completed and after cooling down, and 20g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dry
To 0.10g aromatic multi-amine substance；For filtrate through toluene extracting and demixing, the 100 DEG C of drying of toluene phase being layered obtain 0.27g long
Chain polyether polyols alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Embodiment 12
The present embodiment waste polyurethane material structure to be degraded is the same as embodiment 9
It is recycled in the waste polyurethane material and 0.5g succimide, embodiment 11 that partial size is 1cm after 0.4g is crushed
Water phase be mixed to form the degradation system of 22g, in water heating kettle, 10h is reacted under conditions of 130 DEG C, reaction degradation is completed simultaneously
After cooling, 70g water is added into the reaction system and stands, it is to be precipitated completely after, filtering, Washing of Filter Cake is simultaneously dried to obtain 0.23g
Aromatic multi-amine substance；For filtrate through ethyl acetate extracting and demixing, the 80 DEG C of drying of ethyl acetate phase being layered obtain 0.30g long
Chain polyether polyols alcohols material；It is layered the degradation that obtained water phase recycling is recycled and reused for polyurethane.
Catalyst in above embodiments can be with are as follows: 1,2- propane diamine, Putriscine, acetamide, N, N- dimethyl
Formamide.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of orientation biodegrading process of waste polyurethane material, characterized by the following steps: by waste polyurethane material
Material is mixed to form degradation system after reaction degradation is completed and cooled down with organic amine or amides catalyst, reaction dissolvent and adds
Water, filtering, Washing of Filter Cake are simultaneously dried to obtain aromatic multi-amine substance；Through organic solvent extracting and demixing, what is be layered has filtrate
Solvent mutually dries to obtain long-chain polyether polyols substance；It is layered the degradation that obtained water phase can be recycled and reused for polyurethane.
2. the orientation biodegrading process of waste polyurethane material according to claim 1, it is characterised in that: the organic amine or
Person's amides catalyst be small molecule organic amine compound, including urea, thiocarbamide, ethylenediamine, hexamethylene diamine, 1,2- propane diamine,
Putriscine, formamide, acetamide, propionamide, n,N-Dimethylformamide, succimide, piperazine or Isosorbide-5-Nitrae-dimethyl
Any one in piperazine.
3. the orientation biodegrading process of waste polyurethane material according to claim 2, it is characterised in that: the reaction dissolvent
For polar solvent or its aqueous solution, the water of the alcohols of low molecular weight or the alcohols or ketone of ketone and low molecular weight can be
Solution, comprising: methanol, ethyl alcohol, propyl alcohol, ethylene glycol, 1,2-PD, 1,3-PD, glycerol, acetone, methyl ethyl ketone one kind
Or a variety of and their aqueous solution.
4. the orientation biodegrading process of waste polyurethane material according to claim 3, it is characterised in that: the reaction dissolvent
Aqueous solution mass fraction be 20% -100%.
5. the orientation biodegrading process of waste polyurethane material according to claim 4, it is characterised in that: the waste and old poly- ammonia
The mass ratio of ester material, organic amine or amides catalyst and reaction dissolvent is 1:0.01-2:1-50.
6. the orientation biodegrading process of waste polyurethane according to claim 5, it is characterised in that: the temperature of the reaction degradation
Degree is 100-250 DEG C, and the time for reacting degradation is 1-12h.
7. the orientation biodegrading process of waste polyurethane according to claim 6, it is characterised in that: the aromatic multi-amine class object
The separation of matter is to be dried at room temperature for；The separation of the long-chain polyether polyols substance is dried at being 80-100 DEG C in temperature.
8. the orientation biodegrading process of waste polyurethane according to claim 7, it is characterised in that: described into reaction system
The amount that water is added is 2-10 times of degradation system, when addition should slowly, stand it is to be precipitated be precipitated it is complete.
9. the orientation biodegrading process of waste polyurethane according to claim 8, it is characterised in that: the extraction when extraction
Agent is organic solvent, including chloroform, ethyl acetate, toluene, petroleum ether.
10. the orientation biodegrading process of -9 described in any item waste polyurethane materials according to claim 1, it is characterised in that: institute
The partial size for stating waste polyurethane material is 0.01-1cm.
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