CN106750510A - The processing method and polyurethane elastomer of urethane oligomer waste liquid - Google Patents
The processing method and polyurethane elastomer of urethane oligomer waste liquid Download PDFInfo
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- CN106750510A CN106750510A CN201710025725.XA CN201710025725A CN106750510A CN 106750510 A CN106750510 A CN 106750510A CN 201710025725 A CN201710025725 A CN 201710025725A CN 106750510 A CN106750510 A CN 106750510A
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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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application is related to a kind of processing method of urethane oligomer waste liquid and a kind of product containing the processing method as the polyurethane elastomer of filler.The processing method includes：1) to precipitating reagent powder is added in urethane oligomer waste liquid, stir, obtain mixture A；2) to polyisocyanate crosslinker is added in mixture A, mixture B is obtained；3) to water is added dropwise in mixture B, stir, until when there is granular precipitate, being rapidly added water, obtain mixture C；And 4) filtered mixture C, obtain filtrate D and solid component E is reclaimed.By the processing method, can simultaneously reclaim urethane oligomer and solvent and be recycled.
Description
Technical field
The present invention relates to polyurethane industrial field, and in particular to a kind of processing method of urethane oligomer waste liquid and contain
A kind of product of the processing method as filler polyurethane elastomer.
Background technology
As the environmental problems such as greenhouse effects and depletion of the ozone layer are increasingly highlighted, Waste Disposal Technology is ground in recent years
Study carefully exploitation rapidly to develop.From from the viewpoint of resource circulation utilization, the chemistry reused as raw material by the use of chemical treatment
Circulation is useful.
Polyurethane material is widely used in upholstery, household electrical appliances industry, construction industry, transportation industry, shoemaking curriery, physical culture industry
Deng field, global polyurethane demand reaches more than 20,000,000 tons/year within 2016.Polyurethane industrial is same what is brought benefit to the mankind
When, substantial amounts of discarded object is also generated, bring the environmental problem of correlation.
So far, substantial amounts of polyurethane industrial discarded object is not recycled effectively, main processing method
It is landfill method and burning method.Wherein, burial method is difficult to make polyurethane industrial discarded object degrade, and land occupation, consumption money
Source；And burning disposal produces toxic gas due to burning insufficient, secondary pollution is caused.
In order to improve the predicament that substantial amounts of polyurethane industrial discarded object does not obtain effective recycling, many research works
Person has taken action.Patent (TOHKEMY 2000-239961A) describes what a kind of foamed polyurethane scrap concrete was recycled
Method, using containing methylene dianiline, toluenediamine, diethylene glycol (DEG) decomposed solution, in 220~280 DEG C, the bar of 0.5~10MPa
Under part, polyurethane is decomposed, be then used to analyte.Patent (examined patent publication 53-029359 publications) is by making to give up
Abandon polyurethane and mixing is heated in excess diol, thus decompose, generate polyalcohol and the method for reclaiming.Patent (Unexamined Patent 7-
No. 309816 publications, Unexamined Patent 7-224141 publications) disclose the decomposition of the mixture for making to obtain by glycol breakdown method
Primary amine and alkylene oxide reaction, are converted to polyalcohol.In addition to above-mentioned various methods, also patent (JP 2002-212336 public affairs
Report, JP 2002-241538 publications) method introduced, the product after waste polyurethane is decomposed makes as urethane raw
Used time, reactivity is low, it is necessary to add substantial amounts of catalyst.Patent (CN1037851C) is introduced, and is deposited in lewis acid catalyst
Under, polyester is obtained by the intercalation reaction of polyethers and cyclic anhydride.The invention is to be converted into the PPG that polyurethane is reclaimed
A kind of practical approach of curable unsaturated polyester resin.Patent (CN104694064) is related to a kind of using imvite modified
The method that waste polyurethane recovery product prepares polyurethane binder.
Above patented technology is the method on polyurethane industrial end product scrap concrete, and this is clearly inadequate
's.Polyurethane is more long for process route, and various discarded objects can be produced in the process, same urgently to be resolved hurrily.Patent
(CN102251316A) mention after a kind of utilization polyurethane elastomeric fiber waste silk is reclaimed and be re-used for the method for spinning, but be related to
To the problem of waste silk degreaser, secondary pollution is equally caused.Patent (201010249001.1) discloses a kind of from discarded poly- ammonia
The method that DMA is reclaimed in ester urea solution, N, N- dimethyl are extracted using the method soaked in deionized water
Acetamide, the new Methods for Polyurethane Wastes of not only inefficiency, and generation.Patent (CN103409846B) provides a kind of utilization
The method that polyurethane urea solutions produce delustring spandex thread, but obtained spandex thread property is unstable, while serious curtailment sets
Standby usage cycles, influence the stability of production.
Problem to be solved by this invention is different from what above patent was previously mentioned, it is preferred that emphasis is solve urethane oligomer
The technical barrier of DMA devil liquor recovery, while effectively realizing the target of zero-emission using the product after reclaiming.
The content of the invention
The application embodiment provides a kind of processing method of urethane oligomer waste liquid, that the processing method is obtained
Kind of solid product and comprising the solid product as filler polyurethane elastomer.
In a first aspect, the application embodiment provides a kind of processing method of urethane oligomer waste liquid, can include
Following steps：
1) to precipitating reagent powder is added in urethane oligomer waste liquid, stir, obtain mixture A；
2) to polyisocyanate crosslinker is added in mixture A, mixture B is obtained；
3) to water is added dropwise in mixture B, stir, until when there is granular precipitate, being rapidly added water, mixed
Thing C；And
4) mixture C is filtered, obtains filtrate D and solid component E is reclaimed.
In one embodiment, precipitating reagent powder can be the inorganic salts that can form crystalline hydrate, be selected from nothing
Brochanite, calcium oxide, the hydrotalcite of low crystal water content, sodium carbonate, ferrous sulfate, zinc sulfate, alum, calcium sulfate,
One or more in sodium sulphate etc..Preferably, step 1) described in the addition of precipitating reagent powder can be polyurethane oligomeric
The 10%~50% of amount of substance.
In another embodiment, polyisocyanate crosslinker can be selected from triisocyanate or tetraisocyanate, for example
Selected from poly methylene poly phenyl poly isocyanate, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanates),
2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanate, LTI, triisocyanate base nonane,
One or more in the addition product of biuret triisocyanate, toluene di-isocyanate(TDI) and trimethylolpropane.Preferably, walk
It is rapid 2) described in polyisocyanate crosslinker addition can be urethane oligomer quality 1%~20%.
In yet another embodiment, step 1) at 45~60 DEG C stir 3~15 hours, mixing speed can be 1400
~2800 revs/min.
In yet another embodiment, step 2) at 45~60 DEG C or 70~100 DEG C stir 30~180 minutes, stirring
Speed can be 1000~2000 revs/min.
In yet another embodiment, step 3) in be added dropwise water while be stirred, mixing speed can be 100~500
Rev/min, reaction temperature can be 70~100 DEG C.
In yet another embodiment, step 3) in the amount of water that is rapidly added can be urethane oligomer waste liquid quality
10~50%.
In one embodiment, Gu the recovery of component E can include：By it, dry baking 24~48 is small at 80~120 DEG C
When, then crushed, obtain the solid component E of powdery.For doing the steam obtained by drying, condensing reflux can be carried out and essence is made it into
Device processed is reclaimed.
Second aspect, the application embodiment provides a kind of solid product, and it includes precipitating reagent powder and is coated on institute
The cross-linked polymer that the polyisocyanates of precipitating reagent powder surface is formed with water is stated, wherein the space structure of the cross-linked polymer
In swept along urethane oligomer.The solid product is the solid component E that treatment in accordance with the present invention method is obtained.Therefore, with
Description of the upper first aspect on precipitating reagent powder and polyisocyanates is equally applicable to the solid product of second aspect.
The third aspect, the application embodiments further provides a kind of polyurethane elastomer, and it includes solid of the invention and produces
Thing is used as filler, wherein the solid product is in powdery.
Specific embodiment
As described above, prior art is in the treatment to urethane oligomer, it is impossible to which it is molten with DMA
Agent is separated, but uses burning disposal more, and this obviously easily causes the problem of secondary pollution.Polyurethane provided by the present invention is low
The processing method of polymers waste liquid, can efficiently separate urethane oligomer and DMA solvent, and can be real
The existing recycling of the two.
Specifically, urethane oligomer method for treating waste liquid of the invention may include steps of：
1) to precipitating reagent powder is added in urethane oligomer waste liquid, stir, obtain mixture A；
2) to polyisocyanate crosslinker is added in mixture A, mixture B is obtained；
3) to water is added dropwise in mixture B, stir, until when there is granular precipitate, being rapidly added water, mixed
Thing C；And
4) mixture C is filtered, obtains filtrate D and solid component E is reclaimed.
Urethane oligomer is present in various polyurethane industrial discarded objects.For example, when two isocyanic acids in polyurethane synthesis
After ester carries out a period of time with the reaction of polyester or polyether Glycols in pre-polymerization reactor, pre-polymerization reactor is generally required
Cleaning, and will now produce substantial amounts of urethane oligomer waste liquid.For polyurethane, more using such as N, N- dimethylacetamides
Amine (DMAC) solvent is cleaned, therefore urethane oligomer waste liquid is generally the solution of DMAC and urethane oligomer.But,
Processing method of the invention is applied to the urethane oligomer in any source, as long as its number-average molecular weight is 2000~10000.This
The processing method of invention is also applied for any solution comprising the urethane oligomer, and wherein solvent applies to polyurethane production
In common solvent；When using DMAC as solvent, the mass concentration of urethane oligomer waste liquid can be 10%~30%.
Inventors have surprisingly discovered that, for this urethane oligomer waste liquid, when using polyisocyanates to catch
When catching agent, urethane oligomer can be caught by the method being chemically crosslinked, and also precipitated by using precipitating reagent and give birth to
Into cross-linked polymer, so as to realize being completely separated for urethane oligomer and solvent.
Therefore, the polyisocyanates that degree of functionality is 3 or 4 can be selected as agent for capturing, to ensure preferable cross-linking effect.
As agent for capturing or the example of crosslinking agent, poly methylene poly phenyl poly isocyanate, the isocyanic acid of triphenyl methane three can be mentioned
Ester, tri o cresyl thiophosphate (4- phenyl isocyanates), 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanate, bad ammonia
Sour triisocyanate, triisocyanate base nonane, biuret triisocyanate, toluene di-isocyanate(TDI) and trimethylolpropane
Addition product etc..They can be used alone or in combination.It is preferred that poly methylene poly phenyl poly isocyanate (PAPI), it is by 50%
The mixture that polyisocyanates of the methyl diphenylene diisocyanate (MDI) with 50% degree of functionality more than more than 2 is constituted.
Precipitating reagent used by the inventive method is not only required to precipitate generated cross-linked polymer, Er Qieyao
Ask and possess certain water removal effect in initial reaction stage, while facilitation can be played to cross-linking reaction.The present inventor's research hair
It is existing, the precipitating reagent that the inorganic salts of crystalline hydrate are especially suitable for use as in the inventive method, such as anhydrous cupric sulfate, oxygen can be formed
Change calcium, the hydrotalcite of low crystal water content, sodium carbonate, ferrous sulfate, zinc sulfate, alum, calcium sulfate, sodium sulphate etc..When
So, these inorganic salts can be used alone or in combination as precipitating reagent.If further contemplating the compatibility of price and polyurethane material
Etc. factor, anhydrous cupric sulfate, calcium oxide, the hydrotalcite of low crystal water content or its combination, more preferably calcium oxide are preferably used.Such as
Used herein, " low crystal water content " in " hydrotalcite of low crystal water content " refers to its crystal water content less than under normal temperature and pressure
The crystal water content of corresponding hydrotalcite crystal；For example it is set to slough partially crystallizable water by heating hydrotalcite crystal, you can to obtain
" hydrotalcite of low crystal water content ".The hydrotalcite of low crystal water content is more convenient to grind to form powder.
In step 1) in, preferably it is in powder shaped to the precipitating reagent added in urethane oligomer waste liquid；If precipitating reagent is normal
Rule form is not powder, can be processed into powder by grinding, pulverizing etc..Its addition can be urethane oligomer matter
The 10%~50% of amount.It is quick to stir so that it is well mixed while precipitating reagent powder is added and afterwards.For example, can be with
Stirred 3~15 hours at 45~60 DEG C, mixing speed can be 1400~2800 revs/min, be made by this high speed shear
Whole waste liquid emulsification.At the same time, precipitating reagent powder can sponge water that may be present in urethane oligomer waste liquid.
In step 2) in, to step 1) add in the mixture A of the urethane oligomer waste liquid that obtains and precipitating reagent powder
Polyisocyanate crosslinker, quickly stirs.The addition of polyisocyanates can be urethane oligomer quality 1%~
20%.Mixing speed can be 1000~2000 revs/min, be stirred 30~180 minutes at 45~60 DEG C.If polyurethane is low
Polymers waste liquid by not depositing for a long time, it is also possible to the temperature of the process is increased into 70~100 DEG C, so that what is added is more
Isocyanates can generate biuret with the reaction of the urea groups of urethane oligomer, so as to reach catching portion urethane oligomer
Purpose.
In step 3) in, to step 2) obtain comprising urethane oligomer waste liquid and precipitating reagent powder and polyisocyanates
Water is added dropwise in the mixture B of crosslinking agent (in some cases, may also include a small amount of biuret) first, rate of addition can be 5
~15 seconds/drop, and quick stirring simultaneously, mixing speed can be 100~500 revs/min, and reaction temperature can be 70~100
℃.The process will as far as possible control the rate of addition of water, and ensure that the stirring of whole reaction system is homogeneous, with avoid polyisocyanates with
The cross-linking reaction of water is excessively violent, or even gelation is blocking, causes the solid bad crushing of component E for finally giving.With react into
OK, when there is granular precipitate, it is rapidly added water and is proceeded with terminating cross-linking reaction, wherein the water for adding can be
The 10~50% of urethane oligomer waste liquid quality.
By step 3), most urethane oligomer in urethane oligomer waste liquid, and contracting that may be present
Two ureas are all swept along in the space structure of the cross-linked polymer for being generated, and the cross-linked polymeric that polyisocyanates is formed with water
Thing is then coated on precipitating reagent powder surface, is integrally precipitated out eventually as solid component E.
Therefore, in step 4) in, mixture C is filtered, obtain filtrate D and solid component E is reclaimed.Filtrate D master
If the solvent of urethane oligomer waste liquid such as DMA solvent, therefore the inventive method can realize that cleaning is molten
The recycling of agent.Gu the recovery of component E can include：It is done at 80~120 DEG C and is dried 24~48 hours, then carry out powder
It is broken, obtain the solid component E of powdery；For doing the steam (primary aqueous and solvent such as DMA) obtained by drying, can be with
Carry out condensing reflux and make it into refining plant, with further recycling design.
Be can see with reference to the embodiment of the inventive method：It is higher that the present invention generates molecular weight by chemical crosslink reaction
Cross-linked polymer, thus catch urethane oligomer, effectively realize the fixation of urethane oligomer；Sunk using common simultaneously
Shallow lake technology, easily makes urethane oligomer be separated from waste liquid.More importantly, the inventive method is not only solved
The difficult separate technical barrier of urethane oligomer, while realizing the effective recycling of product after separation, reaches zero-emission
Environmentally friendly high standard.
The application embodiments further provides a kind of solid product, namely solid group that treatment in accordance with the present invention method is obtained
Divide E.As described above, Gu component E is its Surface coating the precipitating reagent powder of polyisocyanates and the cross-linked polymer of water formation, its
Described in cross-linked polymer space structure in swept along urethane oligomer and biuret that may be present.
Therefore, the application embodiments further provides a kind of polyurethane elastomer, and it includes solid product of the invention and makees
It is filler, wherein the solid product is in powdery.
Embodiment
Illustrate in greater detail the present invention by the following examples.
Embodiment 1
1) to calcium oxide powder is added in urethane oligomer waste liquid, quickly stir, wherein urethane oligomer gives up
The mass percent concentration of liquid is 10%, and solvent is DMAC, and the number-average molecular weight of urethane oligomer is 5000, calcium oxide plus
It is the 30% of polyurethane oligomeric amount of substance to enter amount.In 45 DEG C of stirring reactions 3 hours, mixing speed was 1800 revs/min, is mixed
Compound A.
2) to poly methylene poly phenyl poly isocyanate (PAPI) is added in mixture A, quickly stir, wherein PAPI
Addition for polyurethane oligomeric amount of substance 5%.Stirring reaction 50 minutes at 45 DEG C, mixing speed is 1000 revs/min,
Obtain mixture B.
3) to water is added dropwise in mixture B, rate of addition is 9 seconds/drop, is quickly stirred, and wherein reaction temperature is 90 DEG C,
Mixing speed is 500 revs/min, until when there is white granular precipitation, substantial amounts of water is rapidly added, wherein be rapidly added
The amount of water is the 30% of urethane oligomer waste liquid quality, obtains mixture C.
4) mixture C is filtered, is obtained filtrate D and solid component E.D feeding refining plants are reclaimed.E is at 90 DEG C
After lower dry baking 24 hours, the filler as polyurethane elastomer is crushed；By gained steam condensing reflux and refining plant is sent into, entered
One step reclaims DMAC.
Embodiment 2
1) to anhydrous cupric sulfate powder is added in urethane oligomer waste liquid, quickly stir, wherein polyurethane oligomeric
The mass percent concentration of thing waste liquid is 15%, and solvent is DMAC, and the number-average molecular weight of urethane oligomer is 10000, anhydrous
The addition of copper sulphate is the 20% of polyurethane oligomeric amount of substance.In 45 DEG C of stirring reactions 4 hours, mixing speed is 1400 turns/
Minute, obtain mixture A.
2) to poly methylene poly phenyl poly isocyanate (PAPI) is added in mixture A, quickly stir, wherein PAPI
Addition for polyurethane oligomeric amount of substance 10%.Stirring reaction 90 minutes at 100 DEG C, mixing speed is 1000 revs/min
Clock, obtains mixture B.
3) to water is added dropwise in mixture B, rate of addition is 12 seconds/drop, is quickly stirred, and wherein reaction temperature is 90
DEG C, mixing speed is 300 revs/min, until when there is blue particle shape precipitation, substantial amounts of water is rapidly added, wherein rapid add
The amount of the water for entering is the 25% of urethane oligomer waste liquid quality, obtains mixture C.
4) mixture C is filtered, is obtained the solid component E of filtrate D and blueness.D feeding refining plants are reclaimed.E
Done at 80 DEG C after drying 36 hours, crush the filler as polyurethane elastomer；By gained steam condensing reflux and send into refined
Device, further reclaims DMAC.
Embodiment 3
1) to addition calcium oxide and low crystal water content hydrotalcite (Mg in urethane oligomer waste liquid4Al(OH)9CO3·
H2O mixed powder), quickly stirs, and wherein the mass percent concentration of urethane oligomer waste liquid is 20%, and solvent is
DMAC, the number-average molecular weight of urethane oligomer is 3000, and the addition of mixed powder is the 30% of polyurethane oligomeric amount of substance,
And calcium oxide and the mass ratio of low crystal water content hydrotalcite are 5 in mixed powder:5.In 60 DEG C of stirring reactions 3 hours, stir
Speed is mixed for 2000 revs/min, mixture A is obtained.
2) to the addition product and the isocyanic acid of biuret three that toluene di-isocyanate(TDI) and trimethylolpropane are added in mixture A
The mixture of ester, quickly stirs, and wherein the addition of the polyisocyanate mixtures is polyurethane oligomeric amount of substance
10%, and the addition product of toluene di-isocyanate(TDI) and trimethylolpropane and the mass ratio of biuret triisocyanate are 5:5.
Stirring reaction 45 minutes at 45 DEG C, mixing speed is 1000 revs/min, obtains mixture B.
3) to water is added dropwise in mixture B, rate of addition is 15 seconds/drop, is quickly stirred, and wherein reaction temperature is 90
DEG C, mixing speed is 400 revs/min, until when there is white granular precipitation, substantial amounts of water is rapidly added, wherein rapid add
The amount of the water for entering is the 15% of urethane oligomer waste liquid quality, obtains mixture C.
4) mixture C is filtered, is obtained filtrate D and solid component E.D feeding refining plants are reclaimed.E is at 80 DEG C
After lower dry baking 48 hours, the filler as polyurethane elastomer is crushed；By gained steam condensing reflux and refining plant is sent into, entered
One step reclaims DMAC.
Embodiment 4
1) 2000 weight portions are added to the Toluene-2,4-diisocyanate of 1000 weight portions under stirring, in 4- diisocyanate (TDI) gathers oneself
Lactone (hydroxyl value is 56), the reaction temperature for keeping system is 75 DEG C, when NCO content reaches 4%, temperature is reduced into 45 DEG C；
2) 100 weight portion steps 1 are taken) product, be added thereto to the solid component E powders that 15 parts by weight of example 3 are obtained,
Stirred 60 minutes at 45 DEG C；
3) to step 2) the chloro- 4,4'- diaminodiphenyl-methanes of 10 weight portion 3,3'- bis- are added in the material that obtains
(MOCA), reacted 60 minutes at 45 DEG C, you can obtain polyurethane elastomer.By detection, the performance parameter of the elastomer is such as
Under：Tensile strength 9.2MPa, Graves tear strength 48.8kN/m, elongation at break 750%.
Relative to method same as Example 4 prepare but without solid component E powders polyurethane elastomer (its performance join
Number is as follows：Tensile strength 8.8MPa, Graves tear strength 49.3kN/m, elongation at break 790%), it is poly- that the embodiment is obtained
The performance of urethane elastomer is not changed in substantially, and solid component E powders save polyurethane elastomer as the use of filler
Preparation cost, while also completing the recycling of waste.Moreover, by selective precipitation agent powder, polyurethane bullet can be made
Gonosome is presented different colors.For example, using anhydrous cupric sulfate as precipitating reagent, final polyurethane elastomer is in blueness.
Claims (10)
1. a kind of processing method of urethane oligomer waste liquid, comprises the following steps：
1) to precipitating reagent powder is added in urethane oligomer waste liquid, stir, obtain mixture A；
2) to polyisocyanate crosslinker is added in mixture A, mixture B is obtained；
3) to water is added dropwise in mixture B, stir, until when there is granular precipitate, being rapidly added water, obtain mixture C；
And
4) mixture C is filtered, obtains filtrate D and solid component E is reclaimed.
2. processing method according to claim 1, it is characterised in that the precipitating reagent powder is to form crystalline hydrate
Inorganic salts, be selected from anhydrous cupric sulfate, calcium oxide, the hydrotalcite of low crystal water content, sodium carbonate, ferrous sulfate, sulfuric acid
One or more in zinc, alum, calcium sulfate, sodium sulphate, preferred steps 1) described in the addition of precipitating reagent powder be
The 10%~50% of polyurethane oligomeric amount of substance.
3. processing method according to claim 1 and 2, it is characterised in that the polyisocyanate crosslinker is selected from three isocyanides
Acid esters or tetraisocyanate, are selected from poly methylene poly phenyl poly isocyanate, triphenylmethane triisocyanate, thio phosphorus
Sour three (4- phenyl isocyanates), 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanate, the isocyanide of lysine three
In the addition product of acid esters, triisocyanate base nonane, biuret triisocyanate, toluene di-isocyanate(TDI) and trimethylolpropane
One or more, preferred steps 2) described in polyisocyanate crosslinker addition for polyurethane oligomeric amount of substance 1%
~20%.
4. processing method according to any one of claim 1 to 3, it is characterised in that step 1) in stirred at 45~60 DEG C
Mix 3~15 hours, mixing speed is 1400~2800 revs/min.
5. processing method according to any one of claim 1 to 4, it is characterised in that step 2) at 45~60 DEG C or
Stirred 30~180 minutes at 70~100 DEG C, mixing speed is 1000~2000 revs/min.
6. processing method according to any one of claim 1 to 5, it is characterised in that step 3) in enter while water is added dropwise
Row stirring, mixing speed is 100~500 revs/min, and reaction temperature is 70~100 DEG C.
7. processing method according to any one of claim 1 to 6, it is characterised in that step 3) in the water that is rapidly added
Measure is the 10~50% of urethane oligomer waste liquid quality.
8. processing method according to any one of claim 1 to 7, it is characterised in that Gu the recovery of component E includes：By its
Done at 80~120 DEG C and dried 24~48 hours, then crushed, obtain the solid component E of powdery.
9. a kind of solid product, its polyisocyanates and water for including precipitating reagent powder and being coated on the precipitating reagent powder surface
The cross-linked polymer of formation, wherein having swept along urethane oligomer in the space structure of the cross-linked polymer.
10. a kind of polyurethane elastomer, it includes solid product according to claim 9 as filler, wherein the solid is produced
Thing is in powdery.
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| CN110628302A (en) * | 2019-09-16 | 2019-12-31 | 罗洪财 | Double-component coating based on modified epoxy resin and preparation method thereof |
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| CN1180689A (en) * | 1996-10-08 | 1998-05-06 | 三星电子株式会社 | Method for preparation of recycled polyols and method for manufacturing polyurethane foams therefrom |
| US20080255353A1 (en) * | 2007-04-13 | 2008-10-16 | Chang Chun Plastics Co., Ltd. | Method for preparing melamine salt of bis(pentaerythritol phosphate) phosphoric acid |
| CN102627750A (en) * | 2012-04-10 | 2012-08-08 | 上海大学 | Method for re-synthesizing rigid polyurethane by using polyurethane wastes of waste refrigerators |
| CN103788335A (en) * | 2014-01-08 | 2014-05-14 | 上海翌能化工科技有限公司 | Method for preparing polyurethane elastomer through solid-phase alcoholysis recovery of polyurethane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180689A (en) * | 1996-10-08 | 1998-05-06 | 三星电子株式会社 | Method for preparation of recycled polyols and method for manufacturing polyurethane foams therefrom |
| US20080255353A1 (en) * | 2007-04-13 | 2008-10-16 | Chang Chun Plastics Co., Ltd. | Method for preparing melamine salt of bis(pentaerythritol phosphate) phosphoric acid |
| CN102627750A (en) * | 2012-04-10 | 2012-08-08 | 上海大学 | Method for re-synthesizing rigid polyurethane by using polyurethane wastes of waste refrigerators |
| CN103788335A (en) * | 2014-01-08 | 2014-05-14 | 上海翌能化工科技有限公司 | Method for preparing polyurethane elastomer through solid-phase alcoholysis recovery of polyurethane |
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| CN110628302A (en) * | 2019-09-16 | 2019-12-31 | 罗洪财 | Double-component coating based on modified epoxy resin and preparation method thereof |
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