CN102924747A - Method for degrading and recycling waste solid polyurethane - Google Patents
Method for degrading and recycling waste solid polyurethane Download PDFInfo
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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
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Abstract
The invention belongs to the technical field of polymer degrading and recycling. The method for degrading and recycling the waste solid polyurethane comprises the following steps of: firstly, adding a functionalized alcoholysis agent into a reaction kettle with a stirrer, heating the agent till the temperature rises to 180 to 220 DEG C, starting to stir the agent, adding a catalyst and a hindered phenolic antioxidant, gradually adding reclaimed scraps of polyurethane, allowing the reclaimed polyurethane scraps to dissolve completely, continuing the reaction with stirring till the viscosity is constant, cooling the mixture to below 50 to 80 DEG C with stirring, adding a decolorizer, and cooling the mixture to room temperature. The functionalized alcoholysis agent is a compound which has 1 to 2 hydroxys, 1 tertiary amine core and an acrylate group with molecular weight ranging from 500 to 2,000. The formula of the compound is (OH)n (NH) (CH2CHCOOR)m. According to the method, the degradation product of the waste solid polyurethane is polyurethane acrylate resin, which has high photocuring activity and can be widely used in the formula of photocurable paints.
Description
Technical field
The invention belongs to high molecular polymer degraded recycle technical field, be specifically related to a kind of degraded recoverying and utilizing method of waste and old solid polyurethane.
Background technology
Urethane is many fields such as the important macromolecular material of a class, automobile making, refrigerator manufacturing, communications and transportation, civil construction, footwear, synthetic leather, fabric, electromechanics, petrochemical complex, mining machinery, aviation, medical treatment, the agricultural of being widely used because of its remarkable performance.Urethane foam is widely used at present.Flexible foam plastic is mainly used in furniture and the various pad materials of the vehicles, sound-proof material etc.; Rigid foam is mainly used in household electrical appliance thermofin, roof/wall surface thermal-insulating waterproof spray-coating foam, pipe insulation material, building board, refrigerator car and the heat insulation material of freezer etc.; Half rigid foam is used for fascia, bearing circle etc.The porous plastics of existing all size purposes combination material (two-pack Preblend) on the market is mainly used in (cold-curing) high-elastic foam plastic, half rigid foam, casting and spraying rigid foam etc.Polyurethane elastomer can have in wider durometer level wear resistance, oil-proofness, resistance to fatigue and the anti-vibration resistance of higher elasticity and intensity, excellence, has the title of " abrasive rubber ".Though polyurethane elastomer output in polyurethane products is little, polyurethane elastomer has excellent over-all properties, has been widely used in the industrial sectors such as metallurgy, oil, automobile, ore dressing, water conservancy, weaving, printing, medical treatment, physical culture, grain processing, building.PU is urethane, and the PU skin is exactly the epidermis of urethane composition.Clothing factory is commonly called as the imitation leather clothes extensively with this kind material produce clothes now.It is that general its reverse side is the second layer cladding of ox-hide that PU joins skin, is coated with last layer PU resin on the surface, so also claim the pad pasting ox-hide.Its price is more cheap, and utilization ratio is high.It also makes the kind of various class with the variation of technique, such as two layers of ox-hide of import, because of technique unique, steady quality, the characteristics such as kind novelty are present high-grade leather, price and class are all not second to head layer corium.
Global urethane consumption reached 1,870 ten thousand tons in 2010, and China is third place in the world large economy body, also was the second largest consumption market of urethane.At first, domestic product the thermal container in the whole world 95%, 60% shoes and 70% toy; Secondly, the output of the building materials of China, spandex, textiles, synthetic leather and automobile all ranks first in the world; Simultaneously, the urbanization process of China, high-speed railway investment, environmental protection synthetic wood demand etc., the advantage development of these industries all is that urethane has brought the huge market opportunity.The flourish demand growth that is also stimulating the urethane of Science in Future in China of China's industry, its chief motivation be from building thermal-insulation energy-saving, sizing agent coating and four broad aspect such as elastomerics, automobile and composite sheet, and have huge market development space.It is reported that the MDI chemical name of China in 2015 is " diphenylmethanediisocyanate ", a kind of important urethane raw market will reach 1,620,000 tons.Estimate that Europe reaches 1,500,000 tons, 1,200,000 tons in the U.S., India are 160,000 tons.From this, China will become urethane market the biggest in the world.Why the ammonia ester material can access international widespread use, is because its heat-insulating property is best, and excellent mechanical property.
The polyurethane material that is used for building heat preservation accounts for 30% of global total amount.A large amount of test datas international and domestic various research institutions are verified, and no matter from thermal conductivity relatively, or from workability relatively, hard polyurethane foam all is better than other kinds lagging material.Therefore, refrigerator, aerospace engineering, the insulation of LNG transport-ship etc. all is to adopt hard polyurethane foam.Exactly because the advantage aspect insulation, urethane are able to widespread use on international building is energy-conservation.Germany just implements exterior-wall heat insulation with hard polyurethane foam since the sixties, and the hard polyurethane foam of American-European countries 50% is to be used in the building heat preservation field.In Japan, spray coating polyurethane rigid foam is widely used in the interior insulation of high-rise apartment building body of wall, and ratio has surpassed 50%.And in China, hard polyurethane foam is in the application percentage in building heat preservation field less than 10% still, and Application Areas has huge space.In recent years, the polyurethane building power-saving technology develops rapidly at home, domestic multinomial key construction project, such as room wall internal insulation and the vault insulation of waterproof thermal-insulated, the Bird's Nest of the outer wall heat insulating of Ministry of Public Security's office block and roofing, and Shanghai World's Fair Chinese Pavilion, German shop etc. have all adopted the spray coating polyurethane rigid foam material.
In China, the consumption total amount of estimating direct urethane in 2010 is 6,000,000 tons approximately, and whole industrial output value is at more than 1,200 hundred million yuan, family more than 20,000 of the enterprise of whole industry.Over past ten years, although the average growth rate per annum of Chinese urethane is the twice of GDP, the consumption of the equal urethane of Chinese does not reach world average level yet.Calculate by GDP per capita development and urethane growth rate, the rapid growth period that Chinese Polyurethane Industry still being in.The Chinese Polyurethane Industry development " 12 planning " of submitting to according to national polyurethane industrial association, by 2015, China's urethane consumption will reach ten thousand tons of 900-1000, huge urethane application market like this, after a residing application reaches work-ing life, must be accompanied by and produce a large amount of polyurethane waste materials, cause environmental destruction.On the whole, waste polyurethane comprises that mainly the leftover bits of manufacturer, mould overflow material, the polyurethane foam in abandoned car, the refrigerator and elastomerics, apparatus for building pad barrier material, waste and old sole and waste and old PU leather, spandex duds thing etc.Under the pressure of environmental stress be to consider that by the economized of resource U.S. polyurethane TIA (API) and the isocyanic ester production council of European Union (ISOPA) have released waste polyurethane regeneration techniques and regeneration theory very energetically.Comprise Japan; the U.S.; Italy; Germany; France; Russia; Finland; Korea S; New Zealand; Romania; Spain; Australia; Holland; Canada; Korea S etc. just began to enrich the regeneration application technical research of urethane reclaimed materials before year more than ten in interior about more than 40 countries and regions; Bayer; Mobius; Ford Motor; Troy; Arco; BASF; Air Products and Chemicals; Tao Shi; ICI; Hess; the Honda skill is ground; many the well-known chemical enterprises in the whole world such as Korea S Samsung have been carried out this respect research; and obtained corresponding patented technology, and the urethane reclaimed materials of the built legislate modelling of part regeneration enterprise.
The solid polyurethane waste material that China possesses recovering condition every year can reach more than 3,000,000 tons, but be subjected to the restriction of polyurethane waste material recovery and utilization technology, and waste material purchasing price restriction, it is lower for a long time that the urethane solid waste reclaims ratio, and a large amount of discarded solid polyurethane materials cause serious impact to environmental ecology.On the other hand, because polyurethane waste material can not get the regeneration of high-level efficiency and added value, ever-increasing polyurethane material consumption has to increase isocyanic ester virgin material usage quantity, this forces again upstream isocyanic ester manufacturer to strengthen the size of capacity, and dangerous high phosgene processing technology routine is still adopted in the manufacturing of isocyanic ester so far, in case leak, consequence is hardly imaginable; And isocyanate-monomer itself also is the stronger industrial chemicals of toxicity, and chemical materials is made link significantly increases these high murders by poisoning, high risk raw material output and accumulating amount, all is great threat to social environment and physical environment.Polyurethane material is because its excellent outstanding over-all properties, be difficult to again can predict in the future replaced.Therefore, how to make good use of existing urethane and reclaim waste material, recycle with technical approach efficient, energy-saving and environmental protection, regeneration forms urethane raw and the material of high added value, serve society, can excite undoubtedly to attract more urethane to reclaim industry, significantly reduce polyurethane waste material to the impact of ecotope, also can significantly reduce simultaneously polyurethane material industry to the dependence of the manufacturing of high toxicity isocyanic ester and accumulating link, the environmental safety factor is improved.
In addition, also point out about the clauses and subclauses of cleaner production and economized production in the national development strategy planning, various material manufacturings to environment generation harm should realize the internal recycling of manufacturing processed, produce for the flexible polyurethane rigid foam, the processing of a large amount of leftover bits is very thorny, and the leftover bits cyclic regeneration lacks again corresponding technical support.In sum, it is imperative to carry out the subject study of urethane solid waste hi-tech regeneration.
The urethane solid reclaimed materials regenerative use technology of basis and technical study aspect comprises energy method, Physical and chemical method.The energy method is exactly that heat energy is obtained in the solid polyurethane burning of reclaiming, or is used for generating.The method is not the desirable approach that polyurethane material reclaims, and not only causes the poor efficiency of organic carbon resource to use, and combustion processes also will produce great amount of carbon dioxide and harmful nitrogen oxide compound, cause atmospheric environment further to worsen.The physics recoverying and utilizing method mainly is the particle that the solid polyurethane waste material is ground into certain particle diameter, organic elastomer stopping composition as newly-generated type polyurethane material uses, hot-forming, bonding extrusion forming, extrusion moulding are arranged and be used as filler etc., and take bonding extrusion forming as main.The added value that the physics absorption method produces is lower, and acquisition cost is also extremely cheap, and polyurethane foam crushed material market value per kilogram only about 3 yuan, is difficult to form the market buildup effect, and it is fast-developing to be unfavorable for that polyurethane waste material reclaims industry.
Because the polyreaction of urethane is reversible, control certain reaction conditions, polyreaction can counter movement, can is former reactant or other material by depolymerization progressively, and then by equipment such as distillations, can obtain pure starting monomer polyvalent alcohol, isocyanic ester, amine etc.The chemical recycling added value is relatively high, and easily regeneration obtains the starting material of concrete structure and performance, in order to synthesis of polyurethane material again.Process the waste and old material of urethane with chemical process, reclaim polyvalent alcohol etc. and prepare the operational path of urethane as raw material again, existing many covering devices drop into trial run, are one of main striving directions of current recycling waste polyurethane.The chemical recovery technology has been summed up six kinds: alcoholysis method, hydrolysis method, based on alkaline hydrolysis, ammonolysis process, pyrolysis method, hydrocracking process.The degradation production that the whole bag of tricks produces is different.Alcoholysis method generally generates polyol blends; Hydrolysis method generates polyvalent alcohol and polyamine; Based on alkaline hydrolysis generates the carbonate of amine, pure and mild corresponding alkali; Ammonolysis process generates polyvalent alcohol, amine, urea; Pyrolysis method generates the mixture of gaseous state and liquid fraction; And the hydrocracking process primary product is that oil is gentle.
The technology of main flow remains alcoholysis method in the chemical recycling, catalytic alcohol permutoid reaction occurs and degrades in urethane under small molecular weight dibasic alcohol environment, main regeneration obtains all kinds of polyether Glycols, aliphatic dihydric alcohol and part low molecular weight polyurethane dibasic alcohol, and for example publication number is the patent of CN 202432915, CN 101845152, CN 102061009.But these methods are often followed gradually phase-splitting of reaction system, and lower floor contains in a large number that the ammonia ester is strong, urea strong, amino rich nitrogen degradation product is not had use value and is taken as refuse and abandons, and causes secondary pollution.Although the degradation of polyurethane technology under raw material alcoholysis agent effect can obtain the dibasic alcohol raw materials such as more valuable polyether Glycols, realize easily extensive industrialization running, but its energy consumption is higher, and produce the dibasic alcohol reclaimed materials of acquisition when reusing, must consume the isocyanic ester of considerable scale, this is undoubtedly again in the isocyanic ester industry expanding production and the accumulating that further stimulate high toxicity, high risk, environment and safety are caused larger pressure, that is to say that current main flow alcoholysis is reclaimed the urethane method and had the aspect pressure such as technology and environment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of waste polyurethane degraded recoverying and utilizing method is provided, the method adopts novel functionalized alcoholysis agent, under catalysis, hot conditions, by the hydroxyl in the alcoholysis agent molecule ammonia ester bond is carried out the alcohol exchange, cause degradation of polyurethane, generate the less polyurethane acrylate resin of molecular weight.It is active that this degraded product has good photocuring, can be widely applied among the photo-cured coating prescription.Therefore the method has strengthened the recycle value of waste polyurethane recovery hydrolysis products.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of degraded recoverying and utilizing method of waste and old solid polyurethane is: at first, functionalized alcoholysis agent is joined in the reactor with agitator, be heated to 180～220 ℃, start and stir, add catalyzer, hindered phenol antioxygen adds the chip that reclaims urethane by amount, behind the urethane chip dissolve complete to be recycled again, continue insulated and stirred and react constant to viscosity, during whipped state borehole cooling to 50 ℃～below 80 ℃, add discoloring agent, be cooled to room temperature;
Described functionalized alcoholysis agent is the compound of molecular weight between 500～2000 with one to two hydroxyl, a tertiary amine centers and some acrylate groups, and molecular formula is (OH)
n(NH) (CH
2CHCOOR)
m
As preferred version, described n is preferably 1～2, m and is preferably 50～80.Alcoholysis agent molecule amount is too little, can make reaction product small molecular quantity of material too much, is unfavorable for stable performance.Molecular weight is crossed conference makes speed of response excessively slow, and reaction product viscosity is excessive, is unfavorable for using.
As preferred version, the consumption of described functionalized alcoholysis agent is for reclaiming 80～200% of weight polyurethane.
Very important of catalyzer and the alcohol exchange DeR that reclaims urethane, catalyzer commonly used is the carboxylate salt, carbonate, muriate of potassium, sodium metal ion etc. in traditional urethane alcoholysis technology.As preferred version, catalyzer of the present invention is at least a carboxylate salt in potassium, sodium, calcium, the strontium and the mixture of carbonate.Use the catalyzer of the type can Reaction time shorten, reduce temperature of reaction, also can reduce the color and luster of reaction product simultaneously.
As preferred version, described catalyst levels is for reclaiming 0.1～2% of weight polyurethane.
As preferred version, the add-on of described hindered phenol antioxygen is 0.3 ~ 1% of weight polyurethane, and it is excessively dark that the interpolation hindered phenol antioxygen can suppress the degraded product color.
As preferred version, described type of heating is microwave heating.Temperature of reaction of the present invention is 180～220 ℃, under this temperature, reacts 4 hours, can make product viscosity basicly stable.And the mode of employing microwave heating, the recovery urethane material of 500g, under the microwave reactor effect of 800w, the control temperature of reaction system is at 180～220 ℃, and the microwave-assisted degradation of polyurethane time can foreshorten to 40 minutes, has greatly shortened the reaction times.
As preferred version, the chip of described recovery urethane is that each edge lengths is all less than the recovery urethane chip particle of 3mm.
As preferred version, described discoloring agent is one or both the mixture in red aluminium or the sodium borohydride solution, and add-on is 0.2 ~ 0.5% of urethane gross weight.Discoloring agent can make oneself shoal through the very dark degraded product appropriateness of variable color.
The resulting product of degradation of polyurethane method of the present invention is to have to supply the liquid polyurethane acrylate resin of photo-cured coating modulation, be that degraded product is mainly the urethane oligomer with acrylate end groups or side group, have the good light curing activity, and it is modulated into the photo-cured coating that can supply timber floor, furniture application to be suitable for.
The product the key technical indexes is as follows:
The degraded product molecular-weight average is controlled at (GPC molecular weight) between the 800-6000;
Degraded gained resin normal temperature viscosity controller is between 1000-8000cps, and viscosity test carries out according to GB rotational viscosimeter method;
Colourity: with reference to GB GB 12007.1-89 standard, degraded product resin Gardner colourity is the 4-6 look;
Light-cured performance: simple resin adds 2-5% part by weight light trigger, uv irradiation under medium pressure mercury lamp, light intensity 2.0-6.0 mW/cm2 between control 320-400 nanosection, the final polymerisation conversion of gained resin acrylic double bond reaches more than 50% (for the hard bubble urethane acrylate in source of PU) or transformation efficiency reaches (for the urethane acrylate in the soft bubble of PU source) 70% or more, and the acrylic double bond turnover ratio is measured according to enforcement infrared spectra (RT-IR) technology execution advanced in the row.
The present invention has following beneficial effect:
1) adopts novel functionalized alcoholysis agent, recovery urethane can be degraded into have the liquid polyurethane acrylate resin that can supply photo-cured coating to modulate, be that degraded product is mainly the urethane oligomer with acrylate end groups or side group, have the good light curing activity, and it is modulated into the photo-cured coating that can supply timber floor, furniture application to be suitable for.Increased greatly reclaim urethane utilize scope and added value.
2) adopt microwave assistant degradation, shortened greatly the DeR time, improved efficient, saved the energy.
3) catalyst system therefor of the present invention is at least a carboxylate salt in potassium, sodium, calcium, the strontium and the mixture of carbonate, compared to existing technology, the advantage of using this catalyzer is not only can Reaction time shorten, reduce temperature of reaction, and the color of reaction product also can be shallow a lot.
Embodiment
The present invention will be described in detail below in conjunction with embodiment, and embodiment only is preferred implementation of the present invention, is not limitation of the invention.
The detection method of indices is as follows among the embodiment:
Degradation of polyurethane reaction system and degraded product viscosity adopt Brookfield Model DV-II+ type rotational viscosimeter 30 ℃ of lower mensuration.
Polyurethane degraded product molecule measuring pilot production gel chromatography is reflected mutter (THF) as moving phase, polystyrene are standard specimen take tetrahydrochysene, uses Waters 150C gel permeation chromatograph each product to be carried out the mensuration of molecular weight and molecualr weight distribution.
Polyurethane degraded product colourity adopts iron one to bore the reference liquid colorimetry with reference to GB GB 12007.1-89 standard, and comparison is confirmed from 1 ~ 18 grade of colourity.
Polyurethane degraded product light-cured performance measuring method: the DeR product adds 2-5% part by weight light trigger, uv irradiation under medium pressure mercury lamp, the final polymerisation conversion of light intensity 2.0-6.0 mW/cm2 gained resin acrylic double bond is as the evaluation method of reaction product light-cured performance between control 320-400 nanosection, and the acrylic double bond turnover ratio is measured according to enforcement infrared spectra (RT-IR) technology advanced in the row and carried out.
Solidified coating sticking power carries out with reference to GB GB/T 9286-1998,66 cross-hatchings, and adhesive tape pulls open, and observes the coating shedding situation, is divided into 0 ~ 5 grade by excellent to bad.
The solidified coating water tolerance is with reference to GB GB1733-(79) 88 paint film water tolerance assay methods, 2/3 area of japanning model is put into temperature be the distilled water of (25 scholar 1) ℃, take out after the soak time that reaches the product standard regulation, whether the range estimation evaluation has the phenomenons such as foaming, loss of gloss, variable color.The solidified coating determination of pencil hardness carries out with reference to GB GB6739-86.
Embodiment one
At first, with the novel functionalized alcoholysis agent (n=2 in the molecular formula of 500g, m=50) join in the three neck reactors that 2L has agitator, be heated to 180 ℃, start and stir, add 0.4g yellow soda ash and 0.8g strontium acetate, the 2.5g hindered phenol antioxygen adds 500g by amount again and reclaims the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 50 ℃, add the 2.0g sodium borohydride solution, be cooled to room temperature, indices is measured in discharging.The degraded product number-average molecular weight is 5179, and viscosity is 6189cps, and it is No. 5 looks that moral is received colourity.The acrylic double bond turnover ratio is 78% in the light-cured performance test.
Embodiment two
At first, with the novel functionalized alcoholysis agent (n=2 in the molecular formula of 400g, m=60) join in the three neck reactors that 2L has agitator, be heated to 210 ℃, start and stir, add 0.4g yellow soda ash and 0.8g strontium acetate, the 2.5g hindered phenol antioxygen adds 500g by amount again and reclaims the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 80 ℃, add the red aluminum solutions of 2.0g, be cooled to room temperature, indices is measured in discharging.Degrade to the basicly stable required time of viscosity be 4 hours, the degraded product number-average molecular weight is 5645, viscosity is 6482cps, it is No. 5 looks that moral is received colourity.The acrylic double bond turnover ratio is 80% in the light-cured performance test.
Embodiment three
At first, with the novel functionalized alcoholysis agent (n=2 in the molecular formula of 500g, m=80) join in the three neck reactors that 2L has agitator, be heated to 180 ℃, start and stir, add 0.4g yellow soda ash and 0.8g strontium acetate, the 2.5g hindered phenol antioxygen adds 500g by amount again and reclaims the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 50 ℃, add the 2.0g sodium borohydride solution, be cooled to room temperature, indices is measured in discharging.Degrading to the basicly stable required time of viscosity is that 3 hours degraded product number-average molecular weights are 5179, and viscosity is 6189cps, and it is No. 6 looks that moral is received colourity.The acrylic double bond turnover ratio is 78% in the light-cured performance test.
Embodiment four
At first, with the novel functionalized alcoholysis agent (n=2 in the molecular formula of 500g, m=80) join in the three neck reactors that 2L has agitator, and three neck reactors are placed the microwave heater of 800w, be heated to 180 ℃, start and stir, add 0.4g yellow soda ash and 0.8g strontium acetate, 2.5g hindered phenol antioxygen, add 500g by amount again and reclaim the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 50 ℃, add the 2.0g sodium borohydride solution, be cooled to room temperature, indices is measured in discharging.Degrade to the basicly stable required time of viscosity be 40 minutes, the degraded product number-average molecular weight is 4851, viscosity is 5791cps, it is No. 5 looks that moral is received colourity.The acrylic double bond turnover ratio is 75% in the light-cured performance test.
Embodiment five
At first, with the novel functionalized alcoholysis agent (n=2 in the molecular formula of 500g, m=80) join in the three neck reactors that 2L has agitator, and three neck reactors are placed the microwave heater of 800w, be heated to 180 ℃, start and stir, add 0.4g yellow soda ash and 0.8g strontium acetate, 2.5g hindered phenol antioxygen, add 500g by amount again and reclaim the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 80 ℃, add the red aluminum solutions of 2.0g, be cooled to room temperature, indices is measured in discharging.Degrade to the basicly stable required time of viscosity be 40 minutes, the degraded product number-average molecular weight is 4800, viscosity is 5631cps, it is No. 4 looks that moral is received colourity.The acrylic double bond turnover ratio is 75% in the light-cured performance test.
Embodiment six
At first, with the novel functionalized alcoholysis agent (n=1 in the molecular formula of 1000g, m=50) join in the three neck reactors that 2L has agitator, and three neck reactors are placed the microwave heater of 800w, be heated to 220 ℃, start and stir, add 0.4g salt of wormwood and 0.8g calcium acetate, 1.5g hindered phenol antioxygen, add 500g by amount again and reclaim the urethane chip, added in 40 minutes, behind urethane chip dissolve complete, continue insulated and stirred and react constant to viscosity, in the time of below the whipped state borehole cooling to 80 ℃, add the mixture of the red aluminum solutions of 0.5g and 0.5g sodium borohydride solution, be cooled to room temperature, indices is measured in discharging.Degrade to the basicly stable required time of viscosity be 40 minutes, the degraded product number-average molecular weight is 4800, viscosity is 5631cps, it is No. 4 looks that moral is received colourity.The acrylic double bond turnover ratio is 75% in the light-cured performance test.
Above-mentioned degraded products therefrom is mixed with urethane acrylate 1:1 with photo-cured coating, theme resin as photo-cured coating, the 2-hydroxy-2-methyl of adding 5%-1-phenyl-1-acetone (HMPT) is as light trigger, glycol diacrylate (HDDA) is as thinner, adjusting viscosity is at 2000cps, roller coating is (the rear about 20 μ m of film thickness are solidified in control) on the tinplate testing plate, coating is uv irradiation under medium pressure mercury lamp, light intensity 2.0-6.0 mW/cm2 between control 320-400 nanosection, solidify, measure solidified coating sticking power, pencil hardness and water tolerance, the results list is shown in table 1:
Table 1
| The embodiment numbering | Sticking power | Hardness | Water tolerance |
| Embodiment 1 | 1 | 2H | Unchanged |
| Embodiment 2 | 1 | 2H | Unchanged |
| Embodiment 3 | 1 | 3H | Unchanged |
| Embodiment 4 | 0 | 3H | Unchanged |
| Embodiment 5 | 0 | 3H | Unchanged |
| Embodiment 6 | 0 | 3H | Unchanged |
As can be seen from the above table, the present invention obtain product be used for photo-cured coating after fresh photo-cured coating mixes with resin 1:1, excellent performance can satisfy the specific requirement of photo-cured coating construction fully.
Claims (9)
1. the degraded recoverying and utilizing method of a waste and old solid polyurethane is characterized in that degradation method is:
At first, functionalized alcoholysis agent is joined in the reactor with agitator, be heated to 180～220 ℃, start and stir, add catalyzer, hindered phenol antioxygen adds the chip that reclaims urethane by amount, behind the urethane chip dissolve complete to be recycled again, continue insulated and stirred and react constant to viscosity, during whipped state borehole cooling to 50 ℃～below 80 ℃, add discoloring agent, be cooled to room temperature;
Described functionalized alcoholysis agent is the compound of molecular weight between 500～2000 with one to two hydroxyl, a tertiary amine centers and some acrylate groups, and molecular formula is (OH)
n(NH) (CH
2CHCOOR)
m
2. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1, it is characterized in that: described n is preferably 1～2, m and is preferably 50～80.
3. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1 is characterized in that: the consumption of described functionalized alcoholysis agent is for reclaiming 80～200% of weight polyurethane.
4. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1 is characterized in that: described catalyzer is at least a carboxylate salt in potassium, sodium, calcium, the strontium and the mixture of carbonate.
5. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 4 is characterized in that: described catalyst levels is for reclaiming 0.1～2% of weight polyurethane.
6. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1, it is characterized in that: the add-on of described hindered phenol antioxygen is 0.3 ~ 1% of weight polyurethane.
7. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1, it is characterized in that: described type of heating is microwave heating.
8. the degraded recoverying and utilizing method of waste and old solid polyurethane according to claim 1 is characterized in that: the chip of described recovery urethane for each edge lengths all less than the recovery urethane chip particle of 3mm.
9. according to the degraded recoverying and utilizing method of waste and old solid polyurethane claimed in claim 1, it is characterized in that: described discoloring agent is one or both the mixture in red aluminium or the sodium borohydride solution, and add-on is 0.2 ~ 0.5% of urethane gross weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210401790.5A CN102924747B (en) | 2012-10-22 | 2012-10-22 | Method for degrading and recycling waste solid polyurethane |
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| CN102924747A true CN102924747A (en) | 2013-02-13 |
| CN102924747B CN102924747B (en) | 2015-05-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159981A (en) * | 2013-03-22 | 2013-06-19 | 天津大学 | Method for recycling polyhydric alcohol by degrading thermal-insulation polyurethane foam materials for buildings |
| CN104327300A (en) * | 2014-11-10 | 2015-02-04 | 镇江中化聚氨酯工业设备有限公司 | Alkaline hydrolysis processing technology of polyurethane wastes |
| CN105860000A (en) * | 2016-04-12 | 2016-08-17 | 广州聚天化工科技有限公司 | Waterproof coating prepolymer prepared based on polyurethane degradation product, and preparation method and application thereof |
| CN111909336A (en) * | 2020-07-15 | 2020-11-10 | 芦娜 | Degradation method of polyurethane solid waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190789A (en) * | 2011-03-23 | 2011-09-21 | 安庆飞凯高分子材料有限公司 | Preparation method of polyurethane acrylate resin |
| CN102504331A (en) * | 2011-11-03 | 2012-06-20 | 中山大学 | Degrading method for recovering polyurethane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190789A (en) * | 2011-03-23 | 2011-09-21 | 安庆飞凯高分子材料有限公司 | Preparation method of polyurethane acrylate resin |
| CN102504331A (en) * | 2011-11-03 | 2012-06-20 | 中山大学 | Degrading method for recovering polyurethane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159981A (en) * | 2013-03-22 | 2013-06-19 | 天津大学 | Method for recycling polyhydric alcohol by degrading thermal-insulation polyurethane foam materials for buildings |
| CN104327300A (en) * | 2014-11-10 | 2015-02-04 | 镇江中化聚氨酯工业设备有限公司 | Alkaline hydrolysis processing technology of polyurethane wastes |
| CN105860000A (en) * | 2016-04-12 | 2016-08-17 | 广州聚天化工科技有限公司 | Waterproof coating prepolymer prepared based on polyurethane degradation product, and preparation method and application thereof |
| CN105860000B (en) * | 2016-04-12 | 2019-03-26 | 广州聚天化工科技有限公司 | A kind of water-repellent paint performed polymer and its preparation method and application based on polyurethane degraded product preparation |
| CN111909336A (en) * | 2020-07-15 | 2020-11-10 | 芦娜 | Degradation method of polyurethane solid waste |
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| CN102924747B (en) | 2015-05-27 |
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