CN103387653A - Polyurethane foamed material and preparation method thereof - Google Patents
Polyurethane foamed material and preparation method thereof Download PDFInfo
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- CN103387653A CN103387653A CN2013103635308A CN201310363530A CN103387653A CN 103387653 A CN103387653 A CN 103387653A CN 2013103635308 A CN2013103635308 A CN 2013103635308A CN 201310363530 A CN201310363530 A CN 201310363530A CN 103387653 A CN103387653 A CN 103387653A
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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
Abstract
The invention provides a polyurethane foamed material. The polyurethane foamed material comprises a material A and a material B, wherein the material A comprises an epoxy resin degradation product, a foaming agent, a catalyst and a surfactant; the epoxy resin degradation product is obtained by a solvent decomposition method; the material B is isocyanate; the isocyanate index is 0.8-1.5 by virtue of a mass ratio of the material A to the material B. The epoxy resin degradation product, which is obtained by the polyurethane foamed material through the solvent decomposition method, contains more fatty alcohols and also contains abundant carboxyl and amino functional groups, and therefore, the epoxy resin degradation product is used as polyalcohol to react with isocyanate for preparing the polyurethane foamed material, and a purpose of recycling the epoxy resin is realized. According to the experimental result, the epoxy resin degradation product is adopted as the material, so that the foam density of the prepared polyurethane foamed material is within a range of 22kg/m<3> to 50kg/m<3> and is equivalent to that of the polyurethane foamed material provided in the prior art.
Description
Technical field
The present invention relates to the utilization of epoxy resin degraded product, relate in particular to a kind of polyurethane foamed material and preparation method thereof.
Background technology
The organic high molecular compound that contains two or more epoxide groups in epoxy resin general reference molecule, have excellent adhesive property, resist chemical performance, dielectric properties and higher mechanical property and dimensional stability, therefore epoxy resin is widely used in tackiness agent, corrosion resistant coating, electrical apparatus insulation material and prepare composite, especially as the base mateiral in the fields such as aerospace, automobile, boats and ships, circuit card and sports goods.
Having wide range of applications of epoxy resin, along with the significantly increase of epoxy resin product application, the waste product that contains epoxy resin of generation also increases thereupon, so the recycling of epoxy resin has caused people's concern gradually.At present, the recovery method of epoxy resin and matrix material thereof mainly comprises physics absorption method, energy recovery method and chemical recycling.Physics absorption method and energy recovery method are larger to the infringement of the inorganic materials in epoxy resin composite material, and chemical recycling makes epoxy resin be degraded into small molecule monomer or oligopolymer by chemical reaction, resin and filler are carried out Separation and Recovery, reduced the infringement to inorganic materials in epoxy resin composite material, so chemical recycling is present recovery epoxy resin of greatest concern and the method for matrix material thereof.
Chemical recycling comprises pyrolysis method and solvent decomposition method.Pyrolysis method makes chemical bond rupture crosslinked in epoxy resin by the means of heating, and net macromolecular is resolved into organic molecule, for the fibre property in epoxy resin composite material, certain infringement is arranged also simultaneously; Solvent decomposition method adopts the organic or inorganic solvent, network polymer matrix in epoxy resin is decomposed or be hydrolyzed into low-molecular-weight linear organic compound, do not damage the fiber in epoxy resin composite material, so solvent decomposition method is the effective ways that reclaim epoxy resin composite material.
Application number is that 201010122570,201210009531 Chinese patent, publication number are that Chinese patent that 20090018223 United States Patent (USP) and publication number are 1434838A all discloses solvent decomposition method and reclaims the concrete grammar of epoxy resin, but do not mention the epoxy resin degraded product that how to utilize solvent decomposition method to obtain, to realize the recycling to epoxy resin.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of polyurethane foamed material and preparation method thereof, the epoxy resin degraded product that the present invention obtains solvent decomposition method, as raw material, prepares polyurethane foamed material, has realized the purpose to the epoxy resin recycling.
The invention provides a kind of polyurethane foamed material, comprise A material and B material:
Described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent;
Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains;
Described B material is isocyanic ester;
It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.
Preferably, the hydroxyl value of described epoxy resin degraded product is 50mg KOH/g～800mg KOH/g.
Preferably, described A expects that it is 1.05～1.20 that the mass ratio of with described B, expecting makes isocyanate index.
Preferably, described isocyanic ester is 4, one or more in 4 '-diphenylmethanediisocyanate, tolylene diisocyanate and poly isocyanate.
Preferably, described A material also comprises polyvalent alcohol.
Preferably, the mass ratio of described epoxy resin degraded product, polyvalent alcohol, whipping agent, catalyzer and tensio-active agent is a:b:c:d:e;
0＜a≤100；0≤b＜100；0＜c≤10；0＜d≤5；0＜e≤5。
Preferably, described catalyzer is one or more in amines catalyst and organic tin catalyzer.
Preferably, described tensio-active agent is polysiloxane-based tensio-active agent.
The invention provides a kind of preparation method of polyurethane foamed material, comprise the following steps:
The A material is mixed with the B material, obtain polyurethane foamed material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains, and described B material is isocyanic ester.
Preferably, described solvent decomposition method is specially:
Epoxy resin and alkaline matter are reacted in solvent, obtain the epoxy resin degraded product.
The invention provides a kind of polyurethane foamed material, comprise A material and B material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains; Described B material is isocyanic ester; It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.The present invention adopts solvent decomposition method to obtain the epoxy resin degraded product, contain more fatty alcohol in this epoxy resin degraded product, have simultaneously abundant carboxyl and amido functional group, therefore the present invention with it as polyvalent alcohol and isocyanate reaction, prepare polyurethane foamed material, realized the purpose to the epoxy resin recycling.Experimental result shows, it is raw material that the present invention adopts the epoxy resin degraded product, and the foam density of the polyurethane foamed material of preparation is at 22kg/m
3～50kg/m
3In scope, the foam density of the polyurethane foamed material that provides with prior art is suitable.
Embodiment
The invention provides a kind of polyurethane foamed material, comprise A material and B material:
Described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent;
Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains;
Described B material is isocyanic ester;
It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.
The present invention adopts solvent decomposition method to obtain the epoxy resin degraded product, contain more fatty alcohol in this epoxy resin degraded product, have simultaneously abundant carboxyl and amido functional group, therefore the present invention with it as polyvalent alcohol and isocyanate reaction, prepare polyurethane foamed material, realized the purpose to the epoxy resin recycling.
Polyurethane foamed material provided by the invention, comprise the A material, and described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; In the present invention, described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains.In the present invention, contain more fatty alcohol in described epoxy resin degraded product, have simultaneously abundant carboxyl and amido functional group, thus the present invention with it as polyvalent alcohol and isocyanate reaction, prepare polyurethane foamed material.
In the present invention, described solvent decomposition method is specially:
Epoxy resin and alkaline matter are reacted in solvent, obtain the epoxy resin degraded product.
The present invention preferably joins epoxy resin and alkaline matter in solvent and reacts, obtain the epoxy resin degraded product, after more preferably joining epoxy resin and alkaline matter in solvent, the mixing solutions that obtains is stirred and reacts, most preferably the above-mentioned solution that stirs is placed in reactor and reacts.
Those skilled in the art can be different according to the type of epoxy resin, select consumption, temperature of reaction and the reaction times of suitable alkaline matter, solvent and alkaline matter and solvent, and described epoxy resin is carried out the solvent decomposition method degraded.In the present invention, described epoxy resin is preferably one or more in epoxy-amine resin and bisphenol A type epoxy resin, more preferably one or more in epoxy-amine resin and bisphenol-A diglycidyl ether type epoxy resin.
In the present invention, when described epoxy resin was epoxy-amine resin, described alkaline matter was preferably one or both in sodium hydroxide and potassium hydroxide, more preferably potassium hydroxide; Described solvent is preferably alcoholic solvent, and more preferably the PVOH kind solvent, most preferably be polyoxyethylene glycol; The mass ratio of described epoxy-amine resin, alkaline matter and solvent is preferably 100:(0.5～1.5): (5～15), more preferably 100:(0.8～1.2): (8～12) most preferably are 100:1:10; The temperature of described reaction is preferably 180 ℃～230 ℃, more preferably 190 ℃～210 ℃, most preferably is 200 ℃; The time of described reaction is preferably 50 minutes～and 70 minutes, more preferably 55 minutes～65 minutes, most preferably be 60 minutes.
In the present invention, when described epoxy resin is bisphenol A type epoxy resin, when described bisphenol A type epoxy resin, alkaline matter and solvent, preferably add wherein water.In the present invention, described alkaline matter is preferably one or both in sodium hydroxide and potassium hydroxide, more preferably potassium hydroxide; Described solvent is preferably phenol solvent, more preferably phenol; The mass ratio of described bisphenol A type epoxy resin, alkaline matter, water and solvent is preferably 100:(0.5～1.5): (220～270): (30～50), 100:(0.8～1.2 more preferably): (240～260): (35～45) most preferably are 100:1:250:40; The temperature of described reaction is preferably 270 ℃～320 ℃, more preferably 290 ℃～310 ℃, most preferably is 300 ℃; The time of described reaction is preferably 80 minutes～and 100 minutes, more preferably 85 minutes～95 minutes, most preferably be 90 minutes.
After described epoxy resin and alkali substance reaction are completed, solid product in the reaction soln that the present invention preferably will obtain separates with liquid product, again described liquid product is mixed with pH value conditioning agent, the pH value of described liquid product is transferred to neutrality, then described neutral liquid product is extracted, after extraction is completed, separatory is removed moisture, then organic phase drying, filtration that extraction obtains are obtained the epoxy resin degraded product.In the present invention, the separation method of described solid product and liquid product is preferably filtration.In the present invention, described pH value conditioning agent is preferably acidic cpd, hydrochloric acid more preferably, and the present invention has no particular limits the mass concentration of described hydrochloric acid, and the mass concentration while adopting hydrochloric acid well known to those skilled in the art as pH value conditioning agent gets final product; The present invention does not have special restriction to the method for described extraction, adopts the technical scheme of extraction well known to those skilled in the art to get final product; The present invention does not have special restriction to the method for described drying, adopts the technical scheme of drying well known to those skilled in the art to get final product, and the organic phase that preferably extraction is obtained is mixed with dewatering agent, carries out drying.The present invention does not have special restriction to the method for the filtration described in technique scheme, adopts the technical scheme of filtration well known to those skilled in the art to get final product.
The present invention preferably adopts the pH value of the liquid product that pH value conditioning agent will obtain to transfer to neutrality, makes the epoxy resin degraded product that obtains for neutral.
In the present invention, hydroxyl is to prepare the important reactive group of polyurethane foamed material, and hydroxyl value commonly used characterizes the quantity of reaction hydroxyl groups, and polyvalent alcohol and isocyanate-reactive hydroxyl concentration that it is defined as unit weight, be expressed as mg KOH/g.The present invention adopts epoxy resin degraded product and isocyanate reaction, while preparing polyurethane foamed material, needs to measure the hydroxyl value of epoxy resin degraded product, thereby calculates the consumption of required isocyanic ester.
The present invention adopts GB/T12008 " plastics polyether glycol " the 3rd part: the method for the measurement hydroxyl value of defined in the mensuration of hydroxyl value, measure the hydroxyl value of described epoxy resin degraded product.
The present invention does not have special restriction to the method for calculation of described isocyanic ester consumption, adopts well known to those skilled in the artly while preparing urethane, and the method for calculation of isocyanic ester consumption get final product.
In the present invention, the hydroxyl value of described epoxy resin degraded product is preferably 50mg KOH/g～800mg KOH/g, and more preferably 100mg KOH/g～600mg KOH/g, most preferably be 300mg KOH/g～500mg KOH/g.
In the present invention, described whipping agent is preferably one or more in Chlorofluorocarbons (CFCs) (CFC), Hydrochlorofluorocarbons (HCFC), iso-pentane and pentamethylene, more preferably one or more in CFC, HCFC and iso-pentane.The present invention does not have special restriction to the source of described whipping agent, adopts the whipping agent of mentioned kind well known to those skilled in the art to get final product, as being bought and be obtained by market.
In the present invention, described catalyzer is preferably one or more in amines catalyst and organic tin catalyzer, more preferably one or more in triamine, aromatic amine, quaternary ammonium salt, stannous octoate and dibutyl tin laurate, most preferably be one or more in triethylamine, dimethylcyclohexylamine, triethylenediamine, five methyl diethylentriamine, 2-Hydroxyproyl Trimethyl amine (2-second is for capronate) and 2-Hydroxyproyl Trimethyl amine (manthanoate).In the present invention, catalyzer is used for γ-ray emission reaction and gel reaction, and tertiary amine catalyst can form complex compound, and uncle's nitrogen provides electronics for isocyanate groups, so amines catalyst can accelerate isocyanic ester and water reaction and isocyanic ester and hydroxyl reaction; The organic tin catalyzer is mainly used in accelerating the reaction of isocyanic ester and hydroxyl.The present invention regulates the consumption of catalyzer can realize gel reaction and the aitiogenic balance of gas.In the present invention, owing to containing a certain amount of amido functional group in the epoxy resin degraded product, and in the present invention, the excessive meeting of amines catalyst causes the γ-ray emission excessive velocities, therefore can reduce the consumption of amines catalyst in the process of polyurethane foamed material preparation.In the present invention, the mass ratio of described amines catalyst and organic tin catalyzer is preferably (0～25): 1, more preferably (0.1～10): 1, most preferably be (0.4～2): 1.The present invention does not have special restriction to the source of described catalyzer, adopts the catalyzer of mentioned kind well known to those skilled in the art to get final product, as being bought and be obtained by market.
In the present invention, tensio-active agent can improve the homogeneity of the polyurethane foamed material abscess that obtains.In the present invention, described tensio-active agent is preferably polysiloxane-based tensio-active agent, more preferably one or both in polydimethylsiloxane and poly-cyclohexyl methyl siloxanes.In the present invention, described polysiloxane-based tensio-active agent can change the interface performance of polyurethane foamed material, controls the speed of window thinning of liquid film, prevents that local attenuation from breaking, and helps to control closed-cell foam-cell content in the polyurethane foamed material that obtains.The present invention does not have special restriction to the source of described tensio-active agent, adopts the tensio-active agent of mentioned kind well known to those skilled in the art to get final product, as being bought and be obtained by market.
In the present invention, described A material preferably also comprises polyvalent alcohol.In the present invention, described polyvalent alcohol is preferably one or more in the pure and mild polyether glycol of polyester polyols, more preferably one or more in the pure and mild polyester polyol of polyoxytrimethylene alcohol, propylene oxide end-blocking, most preferably be the glycol of polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene tetrol, propylene oxide end-blocking, the triol of epoxy the third end-blocking, the tetrol of propylene oxide end-blocking and one or more in polyester polyol.The present invention does not have special restriction to the source of described polyvalent alcohol, adopts the polyvalent alcohol of mentioned kind well known to those skilled in the art to get final product, and can be bought and be obtained by market, can prepare voluntarily according to preparation method well known to those skilled in the art yet.In the present invention, described polyester polyol can prepare in accordance with the following methods:
One or more and alcohol compound in Dicarboxylic Acids, organic dibasic acid acid anhydride and organic dibasic ester are reacted, obtain polyester polyol, described reaction is condensation reaction or transesterification reaction.In the present invention, described Dicarboxylic Acids is preferably one or more in phthalic acid, hexanodioic acid and halogeno-benzene dioctyl phthalate; Described organic dibasic acid acid anhydride is preferably phthalate anhydride; Described organic dibasic ester is preferably phthalic acid ester; Described alcohol compound is preferably one or more in glycol, TriMethylolPropane(TMP) and tetrol, more preferably one or more in ethylene glycol, propylene glycol, glycol ether, TriMethylolPropane(TMP) and tetramethylolmethane.The present invention does not have special restriction to the consumption of described Dicarboxylic Acids, organic dibasic acid acid anhydride, organic dibasic ester and alcohol compound, adopts Dicarboxylic Acids well known to those skilled in the art, organic dibasic acid acid anhydride, organic dibasic ester and the consumption of alcohol compound in condensation reaction or transesterification reaction to get final product; The present invention does not have special restriction to the method for described condensation reaction or transesterification reaction, adopts the technical scheme of condensation reaction well known to those skilled in the art or transesterification reaction to get final product.
In the present invention, described polyester polyol also can prepare in accordance with the following methods:
Lactone and alcohol compound are carried out polyreaction, obtain polyester polyol.
The present invention does not have special restriction to the kind of described lactone, adopts lactone well known to those skilled in the art to get final product, and is preferably glucono-lactone; In the present invention, described alcohol compound is consistent with alcohol compound described in technique scheme, does not repeat them here; The present invention does not have special restriction to the consumption of described lactone and alcohol compound, adopts lactone well known to those skilled in the art and the consumption of alcohol compound in polyreaction to get final product; The present invention does not have special restriction to the method for described polyreaction, adopts the technical scheme of polyreaction well known to those skilled in the art to get final product.
The present invention does not have special restriction to the consumption of polyvalent alcohol described in technique scheme, those skilled in the art can regulating ring epoxy resins degraded product and the ratio of polyvalent alcohol, and the equivalents coupling of hydroxyl equivalent number total in described epoxy resin degraded product and polyvalent alcohol and isocyanic ester is got final product; The consumption of described whipping agent has larger impact to the expansion ratio of polyurethane foamed material, and the present invention has obtained the polyurethane foamed material of different foam density; The consumption of described catalyzer has larger impact to the solidification rate of polyurethane foamed material.Therefore in the present invention, the mass ratio of described epoxy resin degraded product, polyvalent alcohol, whipping agent, catalyzer and tensio-active agent is a:b:c:d:e, 0＜a≤100, preferred 10≤a≤90, preferred 20≤a≤80; 0≤b＜100, preferred 20≤b≤80, preferred 40≤b≤60; 0＜c≤10, preferred 3≤c≤8, preferred 4≤c≤6; 0＜d≤5, preferred 0.01≤d≤2, preferred 0.02≤d≤1; 0＜e≤5, preferred 0.1≤e≤3, preferred 1≤e≤2.
In the present invention, described A material preferably also comprises one or more in static inhibitor and fire retardant.
In the present invention, static inhibitor can improve the antistatic property of polyurethane foamed material.In the present invention, described static inhibitor can be cationic antistatic agent, also can be anionic antistatic agents, can also be non-ionic antistatic agent, is preferably ethoxylated fat family alkylamine.The present invention does not have special restriction to the consumption of described static inhibitor and source, adopts static inhibitor well known to those skilled in the art in polyurethane foamed material consumption and the static inhibitor of mentioned kind get final product, as can be by market purchase acquisition.
In the present invention, fire retardant can improve the flame retardant properties of polyurethane foamed material.In the present invention, described fire retardant is preferably one or more in phosphonium flame retardant and halogen-containing flame retardant.The present invention does not have special restriction to the consumption of described fire retardant and source, adopts fire retardant well known to those skilled in the art in polyurethane foamed material consumption and the fire retardant of mentioned kind get final product, as can be by market purchase acquisition.
Polyurethane foamed material provided by the invention, comprise the B material, and described B material is isocyanic ester.In the present invention, isocyanic ester can with any molecular reaction that has active hydrogen, such as hydroxyl, carboxyl and amino, contain abundant hydroxyl, carboxyl and amino active function groups in the epoxy resin degraded product that obtains by solvent decomposition method, these active function groups are easy to react with isocyanic ester.The present invention utilizes the active function groups in the epoxy resin degraded product, and the epoxy resin degraded product that solvent decomposition method is obtained replaces polyvalent alcohol and isocyanate reaction partly or completely, prepares polyurethane foamed material.The isocyanate index that the present invention's needs when preparing polyurethane foamed material are suitable.In the present invention, it is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index, is preferably 1.05～1.20, more preferably 1.08～1.16.In the present invention, described isocyanic ester is preferably 4, one or more in 4 '-diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI) and poly isocyanate, more preferably one or both in tolylene diisocyanate and poly isocyanate, most preferably be poly isocyanate.The present invention does not have special restriction to the source of described isocyanic ester, adopts the isocyanic ester of mentioned kind well known to those skilled in the art to get final product, as being bought and be obtained by market.
Polyurethane foamed material provided by the invention, comprise A material and B material, and the mass ratio of described A material and described B material meets above-mentioned isocyanate index and gets final product.
The invention provides a kind of preparation method of polyurethane foamed material, comprise the following steps:
The A material is mixed with the B material, obtain polyurethane foamed material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains, and described B material is isocyanic ester.
The present invention preferably mixes A material with the B material, obtain polyurethane foamed material, more preferably the B material is joined during A expects, then the mixture that will obtain mixes, and most preferably mixture obtained above is uniformly mixed.In the present invention, the speed of described stirring be preferably 50 turn/min～100 turn/min, more preferably 60 turn/min～90 turn/min, most preferably are 70 to turn/min～80 turn/min.
In the present invention, described solvent decomposition method is consistent with solvent decomposition method described in technique scheme, does not repeat them here; The kind of described A material and B material and mass ratio are consistent with kind and the mass ratio of the material of A described in technique scheme and B material, do not repeat them here.
Polyurethane foamed material provided by the invention can matching while using.While using at the scene, the present invention expects the A material according to putting into container after the accurate weighing of the described mass ratio of technique scheme with B, preferably puts into finally the B material, then the A material is mixed and injects mould or need the space of filling porous plastics to get final product with the B material.
After the present invention obtains polyurethane foamed material, measure its foam density.Experimental result shows, the foam density of polyurethane foamed material provided by the invention is at 22kg/m
3～50kg/m
3In scope, the foam density of the polyurethane foamed material that provides with prior art is suitable.
The invention provides a kind of polyurethane foamed material, comprise A material and B material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains; Described B material is isocyanic ester; It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.The present invention adopts solvent decomposition method to obtain the epoxy resin degraded product, contain more fatty alcohol in this epoxy resin degraded product, have simultaneously abundant carboxyl and amido functional group, the present invention with it as polyvalent alcohol and isocyanate reaction, prepare polyurethane foamed material, realized the purpose to the epoxy resin recycling.Experimental result shows, the present invention adopts the epoxy resin degraded product as raw material, and the foam density of the polyurethane foamed material of preparation is at 22kg/m
3～50kg/m
3In scope, the foam density of the polyurethane foamed material that provides with prior art is suitable.
, in order further to understand the present invention, below in conjunction with embodiment, polyurethane foamed material provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as restriction to protection domain of the present invention.
Embodiment 1
the potassium hydroxide of the waste and old epoxy-amine resin of 100 weight parts and 1 weight part is joined in the polyoxyethylene glycol of 10 weight parts, the mixture that will obtain again stirs, then described mixture is positioned in reactor and reacts, reaction is 60 minutes under 200 ℃, solid product and the liquid product that will obtain pass through filtering separation again, then add water and hydrochloric acid that liquid product is neutralized to neutrality in liquid product, the neutral liquid product separatory that will obtain is again removed moisture, the organic phase that then will obtain adds dewatering agent dry, filter, obtain the epoxy resin degraded product.
The epoxy resin degraded product that the present invention will obtain adopts GB/T12008 " plastics polyether glycol " the 3rd part: the method for the mensuration defined of hydroxyl value is carried out the mensuration of hydroxyl value, and its hydroxyl value is 500mg KOH/g.
Embodiment 2
The potassium hydroxide of the phenol of the water of the bisphenol-A diglycidyl ether type epoxy resin of 20g, 50g, 8g and 0.2g is joined in the autoclave of 100ml and react, reaction is 90 minutes under 300 ℃, solid product and the liquid product that will obtain pass through filtering separation again, then add water and hydrochloric acid that liquid product is neutralized to neutrality in liquid product, the neutral liquid product separatory that will obtain is again removed moisture, the organic phase that then will obtain adds the dewatering agent drying, filters, and obtains the epoxy resin degraded product.
The epoxy resin degraded product that the present invention will obtain carries out the mensuration of hydroxyl value according to the described method of embodiment 1, its hydroxyl value is 300mg KOH/g.
Embodiment 3
The epoxy resin degraded product that the embodiment of 100 weight parts 1 is obtained and the glycol ether (DEG) of 100 weight parts mix, then add the triethylamine of 0.02 weight part, the stannous octoate of 0.02 weight part, the CFC of 1.5 weight parts and the polydimethylsiloxane of 0.1 weight part in the mixture that obtains, obtain the A material;
To the MDI that adds 200 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1, the foam density of the polyurethane foamed material that table 1 provides for the embodiment of the present invention and comparative example.
Embodiment 4
The triol of the epoxy resin degraded product that the embodiment of 1 weight part 1 is obtained and the propylene oxide end-blocking of 100 weight parts mixes, then add the triethylamine of 0.02 weight part, the stannous octoate of 0.02 weight part, the HCFC of 5 weight parts and the poly-cyclohexyl methyl siloxanes of 5 weight parts in the mixture that obtains, obtain the A material;
To the TDI that adds 110 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 5
The epoxy resin degraded product that the embodiment of 100 weight parts 1 is obtained and the polyoxypropyleneglycol of 50 weight parts mix, then add the dimethylcyclohexylamine of 0.02 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 5 weight parts and the polydimethylsiloxane of 3 weight parts in the mixture that obtains, obtain the A material;
To the TDI that adds 180 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 6
The epoxy resin degraded product that the embodiment of 1 weight part 1 is obtained and the polyoxytrimethylene triol of 100 weight parts mix, then add the triethylenediamine of 0.02 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 4 weight parts and the poly-cyclohexyl methyl siloxanes of 2 weight parts in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 110 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 7
The epoxy resin degraded product that the embodiment of 100 weight parts 2 is obtained and the polyoxytrimethylene tetrol of 80 weight parts mix, then add the five methyl diethylentriamine of 0.01 weight part, the stannous octoate of 0.02 weight part, the CFC of 6 weight parts and the polydimethylsiloxane of 1 weight part in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 200 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 8
The glycol of the epoxy resin degraded product that the embodiment of 100 weight parts 2 is obtained and the propylene oxide end-blocking of 50 weight parts mixes, then add the 2-Hydroxyproyl Trimethyl amine (2-second is for capronate) of 0.5 weight part, the stannous octoate of 0.02 weight part, the HCFC of 10 weight parts and the polydimethylsiloxane of 2 weight parts in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 180 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 9
The tetrol of the epoxy resin degraded product that the embodiment of 40 weight parts 1 is obtained and the propylene oxide end-blocking of 80 weight parts mixes, then add the triethylamine of 0.02 weight part, the stannous octoate of 0.02 weight part, the CFC of 1.5 weight parts and the poly-cyclohexyl methyl siloxanes of 1.5 weight parts in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 150 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 10
The epoxy resin degraded product that the embodiment of 100 weight parts 1 is obtained and the polyoxypropyleneglycol of 80 weight parts mix, then add the triethylamine of 0.02 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 6 weight parts and the poly-cyclohexyl methyl siloxanes of 2.5 weight parts in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 200 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 11
The epoxy resin degraded product that the embodiment of 100 weight parts 2 is obtained and the polyoxytrimethylene triol of 80 weight parts mix, then add the dibutyl tin laurate of 0.02 weight part, the CFC of 6 weight parts and the poly-cyclohexyl methyl silica of 3 weight parts in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 220 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 12
The epoxy resin degraded product that the embodiment of 100 weight parts 2 is obtained and the polyoxytrimethylene tetrol of 50 weight parts mix, then add the stannous octoate of 0.02 weight part, the HCFC of 5 weight parts and the methylsiloxane of 0.8 weight part in the mixture that obtains, obtain the A material;
To the poly isocyanate that adds 180 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 13
Epoxy resin degraded product, the stannous octoate of 0.02 weight part, the iso-pentane of 3 weight parts and the polydimethylsiloxane of 2 weight parts that the embodiment of 100 weight parts 2 is obtained mix, and obtain the A material;
To the poly isocyanate that adds 140 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 14
Epoxy resin degraded product, the 2-Hydroxyproyl Trimethyl amine (2-second is for capronate) of 0.01 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 1 weight part and the poly-cyclohexyl methyl siloxanes of 4 weight parts that the embodiment of 100 weight parts 1 is obtained mix, and obtain the A material;
To the poly isocyanate that adds 120 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 15
Epoxy resin degraded product, the 2-Hydroxyproyl Trimethyl amine (manthanoate) of 0.01 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 5 weight parts and the poly-cyclohexyl methyl siloxanes of 3 weight parts that the embodiment of 100 weight parts 2 is obtained mix, and obtain the A material;
To the poly isocyanate that adds 120 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Embodiment 16
Epoxy resin degraded product, the 2-Hydroxyproyl Trimethyl amine (manthanoate) of 0.01 weight part, the polydimethylsiloxane of 2 weight parts, the dibutyl tin laurate of 0.02 weight part and the CFC of 5 weight parts that the embodiment of 100 weight parts 2 is obtained mix, and obtain the A material;
To the poly isocyanate that adds 120 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
Comparative example 1
With the urethane of the YC-4110 model of 100 weight parts expect in vain, the triethylamine of 0.02 weight part, the dibutyl tin laurate of 0.02 weight part, the CFC of 3 weight parts and the poly-cyclohexyl methyl siloxanes of 2 weight parts mix, and obtains the A material;
To the poly isocyanate that adds 100 weight parts in described A material, the mixture that then will obtain mixes, and obtains polyurethane foamed material again.
The present invention measures the foam density of the polyurethane foamed material that obtains, and its foam density is as shown in table 1.
The foam density of the polyurethane foamed material that table 1 embodiment of the present invention and comparative example provide
As can be seen from Table 1, the present invention adopts the epoxy resin degraded product as raw material, and the polyurethane foamed material of preparation and prior art adopt polyvalent alcohol as raw material, and the foam density difference of the polyurethane foamed material of preparation is little, and character is suitable.
As seen from the above embodiment, the invention provides a kind of polyurethane foamed material, comprise A material and B material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains; Described B material is isocyanic ester; It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.The present invention adopts solvent decomposition method to obtain the epoxy resin degraded product, contain more fatty alcohol in this epoxy resin degraded product, have simultaneously abundant carboxyl and amido functional group, the present invention with it as polyvalent alcohol and isocyanate reaction, prepare polyurethane foamed material, realized the purpose to the epoxy resin recycling.Experimental result shows, the present invention adopts the epoxy resin degraded product as raw material, and the foam density of the polyurethane foamed material of preparation is at 22kg/m
3～50kg/m
3In scope, the foam density of the polyurethane foamed material that provides with prior art is suitable.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.To the above-mentioned explanation of the disclosed embodiments, make the special technician in this area can realize or use the present invention, will be apparent concerning the professional and technical personnel of this area to the multiple modification of these embodiment.General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and novel features.
Claims (10)
1. polyurethane foamed material comprises that A material and B expect:
Described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent;
Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains;
Described B material is isocyanic ester;
It is 0.8～1.5 that the mass ratio of described A material and described B material makes isocyanate index.
2. polyurethane foamed material according to claim 1, is characterized in that, the hydroxyl value of described epoxy resin degraded product is 50mg KOH/g～800mg KOH/g.
3. polyurethane foamed material according to claim 2, is characterized in that, it is 1.05～1.20 that the mass ratio of described A material and described B material makes isocyanate index.
4. polyurethane foamed material according to claim 1, is characterized in that, described isocyanic ester is 4, one or more in 4 '-diphenylmethanediisocyanate, tolylene diisocyanate and poly isocyanate.
5. polyurethane foamed material according to claim 1, is characterized in that, described A material also comprises polyvalent alcohol.
6. polyurethane foamed material according to claim 5, is characterized in that, the mass ratio of described epoxy resin degraded product, polyvalent alcohol, whipping agent, catalyzer and tensio-active agent is a:b:c:d:e;
0＜a≤100；0≤b＜100；0＜c≤10；0＜d≤5；0＜e≤5。
7. polyurethane foamed material according to claim 1, is characterized in that, described catalyzer is one or more in amines catalyst and organic tin catalyzer.
8. polyurethane foamed material according to claim 1, is characterized in that, described tensio-active agent is polysiloxane-based tensio-active agent.
9. the preparation method of a polyurethane foamed material comprises the following steps:
The A material is mixed with the B material, obtain polyurethane foamed material, described A material comprises epoxy resin degraded product, whipping agent, catalyzer and tensio-active agent; Described epoxy resin degraded product is the epoxy resin degraded product that solvent decomposition method obtains, and described B material is isocyanic ester.
10. method according to claim 9, described solvent decomposition method is specially:
Epoxy resin and alkaline matter are reacted in solvent, obtain the epoxy resin degraded product.
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| CN105315428A (en) * | 2014-07-18 | 2016-02-10 | 中国人民解放军军械工程学院 | Epoxy-resin-modified polyurethane viscous foaming material |
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| CN101787145A (en) * | 2010-03-12 | 2010-07-28 | 中国科学院长春应用化学研究所 | Method for recovering fiber from epoxy resin/fiber composite material |
| CN101831045A (en) * | 2010-04-30 | 2010-09-15 | 北京化工大学 | High-performance rigid polyurethane foam material containing epoxide group |
| CN102634061A (en) * | 2012-05-04 | 2012-08-15 | 中国科学院长春应用化学研究所 | Decomposition method for epoxy resin or composite materials thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787145A (en) * | 2010-03-12 | 2010-07-28 | 中国科学院长春应用化学研究所 | Method for recovering fiber from epoxy resin/fiber composite material |
| CN101831045A (en) * | 2010-04-30 | 2010-09-15 | 北京化工大学 | High-performance rigid polyurethane foam material containing epoxide group |
| CN102634061A (en) * | 2012-05-04 | 2012-08-15 | 中国科学院长春应用化学研究所 | Decomposition method for epoxy resin or composite materials thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315428A (en) * | 2014-07-18 | 2016-02-10 | 中国人民解放军军械工程学院 | Epoxy-resin-modified polyurethane viscous foaming material |
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