CN106565638B - A method of catalytic degradation polyurethane material by different level - Google Patents
A method of catalytic degradation polyurethane material by different level Download PDFInfo
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- CN106565638B CN106565638B CN201610975832.4A CN201610975832A CN106565638B CN 106565638 B CN106565638 B CN 106565638B CN 201610975832 A CN201610975832 A CN 201610975832A CN 106565638 B CN106565638 B CN 106565638B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
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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
Abstract
A kind of method of the polyurethane material of catalytic degradation by different level is to mix the first catalyst, water with polyurethane material to be made into degradation of polyurethane system；Heating carries out degradation reaction, is filtered, washed, is dried later, obtained polyurethane degraded product；Polyurethane degraded product is added the second catalyst and is made into secondary degradation system, heating carries out secondary degradation reaction, gaseous product obtains tetrahydrofuran after distillation, condensation, collection, and remaining solid product after the reaction was completed is washed, filters, is dried to obtain derivative containing phenyl ring.The present invention has at low cost, recycling mild condition, the high advantage of degrading activity.
Description
Technical field
The invention belongs to Degradation of Polymer Materials recycling fields, and in particular to a kind of catalytic degradation polyurethane by different level
The method of material.
Background technique
Polyurethane is a kind of important synthetic resin, and polyether-type and polyester polyurethane can be chemically divided into structure,
Wherein polyether polyurethane is mainly copolymerized by more isocyanide esters with polyether polyol.It is with excellent performance, multiple product
The advantages such as form, easy moulding process are widely used.It can be with foamed plastics, elastomer, coating, adhesive, fiber, anti-
The multiple products form such as water material and pavement material is applied to communications and transportation, building, machinery, electronic equipment, synthetic leather etc.
Numerous areas.Wherein, the other synthesis thermal insulation materials of the thermal conductivity ratio of rigid polyurethane foam and natural insulation be all
It is low, and can be the increasing synthetic resin thermal insulation material of dosage, be widely used in civilian with cast in situs, rapid shaping
The field of household electrical appliances, pipe insulation and industrial heat preservation；Flex foam is widely used as the features such as elasticity is good, good air permeability with it
The mat material of bed accessory, car and boat and furniture seat etc.；And polyurethane elastomer is made then with wear-resisting, low temperature resistant, high-intensitive, oil resistant is famous
It is used to make the various rubber components of mine oilfield machinery for special synthetic rubber.
China is 9,380,000 tons in polyurethane yield in 2014, almost accounts for the half of world's polyurethane yield, but poly-
While urethane industry develops rapidly, the processing of a large amount of leftover pieces and waste product and recycling are then that relevant enterprise is had to face
Pair problem.It is several that the recovery method of spent high molecular material can be divided into mechanical recycling, recuperation of heat, chemical recovery, wherein chemical
Recycling is due to its mild condition, the advantages such as renewable performance is good, is the direction place of Degradation of Polymer Materials recycling.Current poly- ammonia
The chemical degradation of ester material mainly under highly basic effect, opens the urethane bond and urea bond in polyurethane material, reduces
Crosslinking degree in its structure makes it be converted into the thermoplastic macromolecule material that can be dissolved or melt, but in this mistake
Cheng Li generally requires to use alcohols solvent or polyether polyol as reaction dissolvent, and reaction temperature is higher, reaction dissolvent
It participates in reaction process, product is complicated；In addition unstable aniline structure is more easily damaged, and recycling to catabolite and is mentioned
It is pure to bring difficulty.
Summary of the invention
The object of the present invention is to provide a kind of at low cost, recycling mild condition, the high catalytic degradations by different level of degrading activity
The method of polyether polyurethane.
Polyurethane is usually containing by polyether polyol or polyester polyol and polyisocyanates (such as TDI or MDI)
In conjunction with molecule fragment, by chain extension formed crosslinking net macromolecular, do not dissolve in organic solvent or water, for water/acid/
Alkali is quite stable with organic solvent, is recycled to it and generally requires to destroy its three-dimensional molecular structure.In polyurethane structural
Polyether polyol can be polytetrahydrofuran/polyethylene/polypropylene glycol etc., they pass through urethane bond and polyisocyanic acid
Ester combines, and the amino addition of the isocyanate group of polyisocyanates and chain extender production urea bond (typical structure is as follows).
Polyisocyanates and chain extender are in the presence of high temperature and pressure and catalyst, it is possible to by the chemical bond in molecule without
The opening of selectivity, still, the reaction product obtained in this way are often excessively complicated, and contain a large amount of nitrogen and chlorine element, after
Continuous processing is very difficult, so the chemical bond being selectively opened in above-mentioned molecule is the key that polyurethane high efficiente callback.If
By different level and the urea bond in polyurethane molecular, urethane bond can be selectively opened under mild reaction conditions
Or ehter bond, just have the catabolite that can respectively obtain chain extender, aniline category matter and polyethers, realize polyurethane material it is complete at
Divide recycling.Aqueous phase system, which is coordinated unsaturated metal ion, has consumingly complexation propensity, it easily with the original with lone pair electrons
Son forms complexing, induces its electron cloud to shift, to be catalyzed coupled chemical bond rupture.Recognized based on above-mentioned
Know, we are opened the urea bond in polyurethane molecular with being coordinated unsaturated metalloform-selective using aqueous phase system, are generated
The relatively small polyether polyol of molecular weight (end group contains TDI structural unit) and chain extender MOCA.The polyether polyol of generation
It is highly stable in aqueous phase system, but can efficiently degrade under solvent-free acid catalytic systems, generate corresponding small molecule
Object is closed, these small molecule compounds such as tetrahydrofuran/acetaldehyde or propionic aldehyde are easy to volatilize evolution, condensation collection, and polyisocyanic acid
Ester (such as TDI) thaumatropy is phenylenediamine substances.
The present invention provides a kind of method of catalytic degradation polyether polyurethane by different level, and this method is by the disconnected of selectivity
The initial breakdown that urea bond realizes polyurethane is split, benzene derivate and polytetrahydrofuran segment are obtained；Catabolite is carried out two again
Secondary degradation, obtains tetrahydrofuran monomers and benzene derivate.
It is of the invention specific steps are as follows:
(1) the first catalyst and water are made into the reaction solution that catalyst quality concentration is 5~70%；
(2) reaction solution is mixed with polyurethane material by the weight ratio of 100:1~200, is made into degradation of polyurethane system；
(3) the degradation of polyurethane system being made into is heated to 50~250 DEG C, carries out degradation 10min~72h；
(4) after cooling is completed in reaction, degradation system is filtered, washed, is dried, obtained polyurethane degraded product；
(5) the second catalyst is added in polyurethane degraded product, is uniformly mixed by the weight ratio of 100:1~100 and is made into secondary drop
Enzymatic hydrolysis system；
(6) the secondary degradation system being made into is heated to 50~300 DEG C and carries out secondary degradation, react 5min~36h；
(7) gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reacting, and residue after the reaction was completed is solid
Body product is washed, filter, is dried to obtain derivative containing phenyl ring.
In the step (1), the first catalyst is the chlorine that zinc ion, magnesium ion, aluminium ion, iron ion or copper ion are formed
Compound, sulfate, nitrate or acetate.
In the step (5), the second catalyst be the concentrated sulfuric acid, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, iron chloride,
One of aluminium chloride or a variety of mixtures.
The invention has the following advantages over the prior art:
1. since solvent for use of the present invention is low in cost, and boiling point is lower, can separate and recover.
2. it is from a wealth of sources since catalyst used in the present invention is conventional catalyst, it is cheap, it can be further
Reduce cost recovery.
It, can be by polytetrahydrofuran segment into one by secondary degradation 3. selective scission of link, can orient degradable polyurethane
Step is degraded into tetrahydrofuran.
Specific embodiment
Degradable polyurethane material structure in embodiment is as follows:
Embodiment 1
By ZnCl2It is made into the solution 100g that mass concentration is 60% with water, 1g elastic polyurethane is added in reaction solution
Body is heated to 150 DEG C, and degrade 10h.Degradation solution and insoluble solids are filtered after reaction is cooling, catabolite is obtained, with distillation
It is dry after water supersound washing, obtain polyurethane degraded product 0.98g.0.98g phosphorus is added in obtained polyurethane degraded product
Wolframic acid is heated to 180 DEG C and carries out secondary degradation, reacts 30min, gaseous product obtains after distillation, condensation, collection during reaction
Tetrahydrofuran 0.72g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 0.24g of derivative containing phenyl ring.
Embodiment 2
By FeCl2It is made into the solution 30g that mass concentration is 40% with water, 5g elastic polyurethane is added in reaction solution
Body is heated to 230 DEG C, and degradation is for 24 hours.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 4.8g.2.3g silico-tungstic acid is added in obtained polyurethane degraded product, is heated to 100 DEG C
Secondary degradation is carried out, reacts 1h, gaseous product obtains tetrahydrofuran 3.6g after distillation, condensation, collection during reaction, has reacted
Remaining solid product after is washed, filters, is dried to obtain the 1.1g of derivative containing phenyl ring.
Embodiment 3
By MgCl2It is made into the solution 60g that mass concentration is 20% with water, 30g elastic polyurethane is added in reaction solution
Body is heated to 240 DEG C, and degrade 5h.Degradation solution and insoluble solids are filtered after reaction is cooling, catabolite is obtained, with distillation
It is dry after water supersound washing, obtain polyurethane degraded product 28g.0.5g phosphorus molybdenum is added in the polyurethane degraded product 10g obtained
Acid is heated to 300 DEG C and carries out secondary degradation, reacts 5min.Gaseous product obtains four after distillation, condensation, collection during reaction
Hydrogen furans 7.3g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.5g of derivative containing phenyl ring.
Embodiment 4
By ZnSO4It is made into the solution 50g that mass concentration is 30% with water, 50g elastic polyurethane is added in reaction solution
Body is heated to 80 DEG C, and degrade 72h.Degradation solution and insoluble solids are filtered after reaction is cooling, done with after distilled water supersound washing
It is dry, obtain polyurethane degraded product 46g.The 0.1g concentrated sulfuric acid is added in the polyurethane degraded product 10g that obtains, be heated to 50 DEG C into
The secondary degradation of row, reacts 36h.Gaseous product obtains tetrahydrofuran 7.4g after distillation, condensation, collection during reaction, has reacted
Remaining solid product after is washed, filters, is dried to obtain the 2.3g of derivative containing phenyl ring.
Embodiment 5
By ZnCl2It is made into the solution 20g that mass concentration is 50% with water, 30g elastic polyurethane is added in reaction solution
Body is heated to 250 DEG C, and degrade 36h.Degradation solution and insoluble solids are filtered after reaction is cooling, catabolite is obtained, with distillation
It is dry after water supersound washing, obtain polyurethane degraded product 29g.5g phosphotungstic acid is added in the polyurethane degraded product 10g obtained,
It is heated to 180 DEG C and carries out secondary degradation, react 20min.Gaseous product obtains tetrahydro after distillation, condensation, collection during reaction
Furans 7.3g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.3g of derivative containing phenyl ring.
Embodiment 6
By CuCl2It is made into the solution 50g that mass concentration is 35% with water, 20g elastic polyurethane is added in reaction solution
Body is heated to 250 DEG C, and degrade 36h.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 18g.1g silico-tungstic acid is added in the polyurethane degraded product 10g obtained, is heated to 260 DEG C
Secondary degradation is carried out, 30min is reacted.Gaseous product obtains tetrahydrofuran 7.5g after distillation, condensation, collection during reaction, instead
Remaining solid product after the completion of answering is washed, filters, is dried to obtain the 2.4g of derivative containing phenyl ring.
Embodiment 7
By Fe2(SO4)3It is made into the solution 50g that mass concentration is 43% with water, 100g polyurethane is added in reaction solution
Elastomer is heated to 100 DEG C, and degrade 72h.Degradation solution and insoluble solids are filtered after reaction is cooling, washed with distilled water ultrasound
It is dry after washing, obtain polyurethane degraded product 98g.6g iron chloride is added in the polyurethane degraded product 12g obtained, is heated to
260 DEG C carry out secondary degradation, react 10min.Gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reaction
8.6g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 3.1g of derivative containing phenyl ring.
Embodiment 8
By ZnCl2It is made into the solution 10g that mass concentration is 60% with water, 10g elastic polyurethane is added in reaction solution
Body is heated to 240 DEG C, and degrade 5min.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 9.5g.12g phosphotungstic acid is added in the polyurethane degraded product that obtains, be heated to 180 DEG C into
The secondary degradation of row, reacts 3h.Gaseous product obtains tetrahydrofuran 6.8g after distillation, condensation, collection during reaction, and reaction is completed
Remaining solid product afterwards is washed, filter, is dried to obtain the 1.8g of derivative containing phenyl ring.
Embodiment 9
By AlCl3It is made into the solution 50g that mass concentration is 10% with water, 25g elastic polyurethane is added in reaction solution
Body is heated to 160 DEG C, and degrade 18h.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 24g.0.1g phosphotungstic acid is added in the polyurethane degraded product 10g obtained, is heated to 180
DEG C secondary degradation is carried out, reacts 7h.Gaseous product obtains tetrahydrofuran 7.3g after distillation, condensation, collection during reaction, reaction
Remaining solid product after the completion is washed, filter, is dried to obtain the 2.1g of derivative containing phenyl ring.
Embodiment 10
By Al2(SO4)3It is made into the solution 40g that mass concentration is 8% with water, 20g polyurethane bullet is added in reaction solution
Property body, be heated to 120 DEG C, degrade 14h.Degradation solution and insoluble solids are filtered after reaction is cooling, with distilled water supersound washing
After dry, obtain polyurethane degraded product 18g.2.5g aluminium chloride is added in the polyurethane degraded product 10g obtained, is heated to
130 DEG C carry out secondary degradation, react 7h.Gaseous product obtains tetrahydrofuran 7.1g after distillation, condensation, collection during reaction,
Remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.5g of derivative containing phenyl ring.
Embodiment 11
By ZnSO4It is made into the solution 50g that mass concentration is 20% with water, 18g elastic polyurethane is added in reaction solution
Body is heated to 150 DEG C, and degrade 8h.Degradation solution and insoluble solids are filtered after reaction is cooling, done with after distilled water supersound washing
It is dry, obtain polyurethane degraded product 16g.0.8 silico-tungstic acid is added in the polyurethane degraded product 10g that obtains, be heated to 180 DEG C into
The secondary degradation of row, reacts 2.5h.Gaseous product obtains tetrahydrofuran 7.2g after distillation, condensation, collection during reaction, has reacted
Remaining solid product after is washed, filters, is dried to obtain the 2.1g of derivative containing phenyl ring.
Embodiment 12
By CuSO4It is made into the solution 40g that mass concentration is 35% with water, 20g elastic polyurethane is added in reaction solution
Body is heated to 140 DEG C, and degrade 15h.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 16g.The 1g concentrated sulfuric acid and 1g silico-tungstic acid is added in the polyurethane degraded product 10g obtained, adds
Heat carries out secondary degradation to 230 DEG C, reacts 34h.Gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reaction
7.5g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.2g of derivative containing phenyl ring.
Embodiment 13
By Zn (CH3COO)2It is made into the solution 30g that mass concentration is 25% with water, 30g polyurethane is added in reaction solution
Elastomer is heated to 140 DEG C, and degrade 10h.Degradation solution and insoluble solids are filtered after reaction is cooling, washed with distilled water ultrasound
It is dry after washing, obtain polyurethane degraded product 26g.3.5g phosphomolybdic acid is added in the polyurethane degraded product 10g obtained, is heated to
180 DEG C carry out secondary degradation, react 2h.Gaseous product obtains tetrahydrofuran 7.4g after distillation, condensation, collection during reaction,
Remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.3g of derivative containing phenyl ring.
Embodiment 14
By ZnCl2It is made into the solution 25g that mass concentration is 45% with water, 5g elastic polyurethane is added in reaction solution
Body is heated to 200 DEG C, and degrade 10h.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 4.6g.0.5g silico-tungstic acid is added in the polyurethane degraded product 3g obtained, is heated to 180
DEG C secondary degradation is carried out, reacts 3h.Gaseous product obtains tetrahydrofuran 2.1g after distillation, condensation, collection during reaction, reaction
Remaining solid product after the completion is washed, filter, is dried to obtain the 0.8g of derivative containing phenyl ring.
Embodiment 15
By Al (CH3COO)3It is made into the solution 20g that mass concentration is 20% with water, 20g polyurethane is added in reaction solution
Elastomer is heated to 200 DEG C, and degrade 10min.Degradation solution and insoluble solids are filtered after reaction is cooling, with distilled water ultrasound
It is dry after washing, obtain polyurethane degraded product 19g.0.5g phosphotungstic acid, heating is added in the polyurethane degraded product 10g obtained
Secondary degradation is carried out to 180 DEG C, reacts 30min.Gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reaction
7.6g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.1g of derivative containing phenyl ring.
Embodiment 16
By CuCl2It is made into the solution 60g that mass concentration is 32% with water, 20g elastic polyurethane is added in reaction solution
Body is heated to 250 DEG C, and degrade 15h.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 17g.8.5g phosphotungstic acid is added in the polyurethane degraded product 10g obtained, is heated to 180
DEG C secondary degradation is carried out, reacts 2h.Gaseous product obtains tetrahydrofuran 7.6g after distillation, condensation, collection during reaction, reaction
Remaining solid product after the completion is washed, filter, is dried to obtain the 2.0g of derivative containing phenyl ring.
Embodiment 17
By ZnCl2It is made into the solution 50g that mass concentration is 70% with water, 20g elastic polyurethane is added in reaction solution
Body is heated to 150 DEG C, and degrade 5h.Degradation solution and insoluble solids are filtered after reaction is cooling, done with after distilled water supersound washing
It is dry, obtain polyurethane degraded product 19g.The 4.5g concentrated sulfuric acid, 1g silico-tungstic acid, 1g is added in the polyurethane degraded product 10g obtained
Silicomolybdic acid and 1g phosphotungstic acid are heated to 280 DEG C and carry out secondary degradation, react 2h.During reaction gaseous product through distillation, condensation,
Tetrahydrofuran 7.5g is obtained after collection, remaining solid product after the reaction was completed is washed, filters, is dried to obtain containing phenyl ring derivative
Object 2.3g.
Embodiment 18
By Zn (NO3)2It is made into the solution 50g that mass concentration is 5% with water, 20g elastic polyurethane is added in reaction solution
Body is heated to 50 DEG C, and degrade 36h.Degradation solution and insoluble solids are filtered after reaction is cooling, done with after distilled water supersound washing
It is dry, obtain polyurethane degraded product 15g.The 1g concentrated sulfuric acid, 2g silico-tungstic acid, 1g silicon is added in the polyurethane degraded product 10g obtained
Molybdic acid and 1g phosphotungstic acid are heated to 200 DEG C and carry out secondary degradation, react 2h.Gaseous product is through distillation, condensation, receipts during reaction
Tetrahydrofuran 7.3g is obtained after collection, remaining solid product after the reaction was completed is washed, filters, is dried to obtain derivative containing phenyl ring
2.6g。
Embodiment 19
By ZnCl2It is made into the solution 10g that mass concentration is 60% with water, 10g elastic polyurethane is added in reaction solution
Body is heated to 240 DEG C, and degrade 5min.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 9.5g.2g phosphotungstic acid and 2g silico-tungstic acid, heating is added in obtained polyurethane degraded product
Secondary degradation is carried out to 180 DEG C, reacts 3h.Gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reaction
6.8g, remaining solid product after the reaction was completed is washed, filter, is dried to obtain the 2.1g of derivative containing phenyl ring.
Embodiment 20
By ZnCl2It is made into the solution 10g that mass concentration is 60% with water, 10g elastic polyurethane is added in reaction solution
Body is heated to 240 DEG C, and degrade 5min.Degradation solution and insoluble solids are filtered after reaction is cooling, after distilled water supersound washing
It is dry, obtain polyurethane degraded product 9.5g.5g phosphomolybdic acid, 3g iron chloride, 2g chlorine is added in obtained polyurethane degraded product
Change aluminium and 2g silico-tungstic acid, is heated to 180 DEG C and carries out secondary degradation, react 3h.Gaseous product is through distillation, condensation, receipts during reaction
Tetrahydrofuran 6.6g is obtained after collection, remaining solid product after the reaction was completed is washed, filters, is dried to obtain derivative containing phenyl ring
2.2g。
Claims (1)
1. a kind of method of catalytic degradation polyurethane material by different level, characterized by the following steps:
(1) the first catalyst and water are made into the reaction solution that catalyst quality concentration is 5~70%, the first catalyst be zinc from
Chloride, sulfate, nitrate or the acetate that son, magnesium ion, aluminium ion, iron ion or copper ion are formed；
(2) reaction solution is mixed with polyurethane material by the weight ratio of 100:1~200, is made into degradation of polyurethane system；
(3) the degradation of polyurethane system being made into is heated to 50~250 DEG C, carries out degradation 10min~72h；
(4) after cooling is completed in reaction, degradation system is filtered, washed, is dried, and polyurethane degraded product is obtained；
(5) the second catalyst is added in polyurethane degraded product, is uniformly mixed by the weight ratio of 100:1~100 and is made into secondary degradation body
System, the second catalyst is one of phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid or a variety of mixtures；
(6) the secondary degradation system being made into is heated to 50~300 DEG C and carries out secondary degradation, react 5min~36h；
(7) gaseous product obtains tetrahydrofuran after distillation, condensation, collection during reacting, and remaining solid after the reaction was completed produces
Object is washed, filter, is dried to obtain derivative containing phenyl ring.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275587A (en) * | 1999-06-01 | 2000-12-06 | 徐玉良 | Water phase decomposition recovery process for polyurethane waste material |
| CN102504331A (en) * | 2011-11-03 | 2012-06-20 | 中山大学 | Degrading method for recovering polyurethane |
| CN103627024A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Method for recycling waste polyurethane |
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- 2016-11-07 CN CN201610975832.4A patent/CN106565638B/en active Active
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|---|---|---|---|---|
| CN1275587A (en) * | 1999-06-01 | 2000-12-06 | 徐玉良 | Water phase decomposition recovery process for polyurethane waste material |
| CN102504331A (en) * | 2011-11-03 | 2012-06-20 | 中山大学 | Degrading method for recovering polyurethane |
| CN103627024A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Method for recycling waste polyurethane |
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| Title |
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| Degradation of polyurethanes in sea water;M. Rutkowska et al.;《Polymer Degradation and Stability》;20021231;第76卷;第233-239页 * |
| Recovery of polyols from flexible polyurethane foam by ‘‘split-phase’’ glycolysis with new catalysts;C. Molero et al.;《Polymer Degradation and Stability》;20051005;第91卷;第894-901页 * |
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| 废聚氨酯的综合利用;吴自强等;《再生资源研究》;20031231(第4期);第19-23页 * |
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