CN103304758B - Phenol modified urea-formaldehyde foam and preparation method thereof - Google Patents
Phenol modified urea-formaldehyde foam and preparation method thereof Download PDFInfo
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- CN103304758B CN103304758B CN201310258596.0A CN201310258596A CN103304758B CN 103304758 B CN103304758 B CN 103304758B CN 201310258596 A CN201310258596 A CN 201310258596A CN 103304758 B CN103304758 B CN 103304758B
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Abstract
The invention discloses a phenol modified urea-formaldehyde foam and a preparation method thereof as well as application. The method comprises the following steps of: firstly, mixing formaldehyde with phenol for reaction to a certain extent under an alkaline condition, regulating the PH value of the system by using an alkaline liquor to an alkaline value, and then adding urea in batches according to process requirements, and carrying out a temperature-increased reaction, thereby obtaining white, thick phenol modified urea-formaldehyde resin; stirring a foam liquid diluted 5-15 times by a high-speed stirrer at a rate ranging from 1000 to 5000 r/min at a room temperature, and simultaneously, blasting compressed air of 0.1-0.4 MPa through an air compressor, stirring for 30-120 s, adding the prepared phenol modified urea-formaldehyde resin and continuously stirring for 30-60 seconds, and then rapidly transferring the stirred mixture into a die and curing for 24-48 hours at a temperature ranging from 35 to 55 DEG C, thereby obtaining white phenol modified urea-formaldehyde (PUF) foam. The PUF foam is characterized in that while the advantages of low light, high flame resistance, low heat conductivity, low cost and the like of the urea-formaldehyde foam are maintained, the introduction of a benzene ring structure is advantageous for improving the defects of poor waterproofness and the like of the urea-formaldehyde foam; and the product has good heat insulation performance.
Description
Technical field
The present invention relates to a kind of phenol-modified urea-formaldehyde foam and preparation method thereof.
Background technology
Urea-formaldehyde resin is that polycondensation under acid or alkaline condition obtains by urea and formaldehyde, and with low cost, of light color, hardness is high, oil resistant, anti-mildew, has good insulativity and temperature tolerance, is one of thermosetting resin developing comparatively morning.Foam urea-formaldehyde resin is generally prepared in the basic conditions, and the mol ratio of formaldehyde/urea is 1.5 ~ 2.0, ensures resin thermal curable.German a companys in 1933 development research first " urea-formaldehyde foamed plastics ", researched and developed successfully through the researchs of 5 years in 1938, after 1940, " urea-formaldehyde foamed plastics " has been gone into operation by the BASF AG of Germany, due to urea-formaldehyde foam there is poor water resistance, the shortcoming such as stability is low, ageing resistance is weak and Form aldehyde release is high, so its application is restricted.
Summary of the invention
The object of this invention is to provide a kind of phenol-modified urea-formaldehyde foam and preparation method thereof.
The method preparing phenol modified urea-formaldehyde resins provided by the invention, comprise the steps: adjust ph to 7 ~ 9 after formaldehyde and phenol mixing, be warmed up to 70 ~ 80 DEG C of insulation reaction 1 ~ 2 hour again, add first urea, then be warmed up to 85 ~ 100 DEG C of insulation reaction after 15 ~ 30 minutes;
Cool to 60-80 DEG C and add second batch urea, then be warmed up to 90 ~ 100 DEG C of insulation reaction 15 ~ 30 minutes, then adjust ph to 5 ~ 7, react after presenting white opacity shape to reaction system;
Adjust ph to 7 ~ 9, add the 3rd batch of urea, cool to 50-65 DEG C, insulation reaction 30 ~ 60 minutes and obtaining;
Wherein, first, the mass ratio of second batch and the 3rd batch of urea is 50-70: 20-40: 5-15.
In aforesaid method, described first, the mass ratio of second batch and the 3rd batch of urea is 55: 35: 10.
Can regulate with following all ingredients when adjust ph is 7-9: sodium hydroxide, hexamethylenetetramine, ammoniacal liquor, trolamine, S-WAT or Sodium Tetraborate;
Can regulate with following all ingredients when adjust ph is 5-7: as ammonium chloride, ammonium sulfate, formic acid, acetic acid or zinc chloride;
The molar ratio of described urea, phenol and formaldehyde is 1: 0.2 ~ 1.0: 2.0 ~ 3.0, is specially 1: 0.3: 2.4 or 1: 0.3: 2.1 or 1: 0.3: 2.1-2.4;
Described formaldehyde adds with the aqueous solution form of formaldehyde, and the mass percentage concentration of the aqueous solution of formaldehyde is 365-40%, specifically can be 37%.
The phenol modified urea-formaldehyde resins prepared according to the method described above, also belongs to protection scope of the present invention.
The viscosity of described phenol modified urea-formaldehyde resins at 25 DEG C is 15 ~ 30cp, is specially 20-24cp;
The mass percentage of water is 40% ~ 55%, is specially 48.3-45.9%;
Solid content is 45% ~ 55%, is specially 48.6-49.2%;
The mass percentage of free phenol is 1.0 ~ 4.9%, is specially 1.90-4.90%;
The mass percentage of free aldehyde is 0.5 ~ 1.0%, is specially 0.63-0.96%;
PH value is 6 ~ 8, is specially 6.8-7.5.
Present invention also offers a kind of method preparing phenol-modified urea-formaldehyde foam, the method to comprise the steps: with above-mentioned phenol modified urea-formaldehyde resins provided by the invention, for raw material, to utilize foam process, obtain phenol-modified urea-formaldehyde foam.
Described foam process comprises the steps: after foaming liquid dilute with water, under whipped state, blast pressurized air, after stirring 30-120s, add after described phenol modified urea-formaldehyde resins stirs 30-60s again and stop stirring, be transferred in mould and solidify, obtain described phenol-modified urea-formaldehyde foam.
In aforesaid method, described foaming liquid is made up of tensio-active agent, solidifying agent and water;
Described tensio-active agent is specifically selected from least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, dioctyl succinate disulfonate acid and lauric acid sodium sulfate;
Described solidifying agent is commercially available sterling, is specifically selected from least one in sulfuric acid, phosphoric acid, oxalic acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid;
In described foaming liquid, mass ratio 1.0-1.5: 2.0-10: 6-10 of tensio-active agent, solidifying agent and water;
Concrete, the mass parts of tensio-active agent with the timing of 1.0-1.5 part,
The mass parts of solidifying agent is 2.4,2.58,3.6,4.2,4.5,5.1,6.1,9.1 or 2.4-9.1 part;
The mass parts of water is 5.2,5.5,5.8,6.8,7.5,9.3 or 5.2-9.3 part.
Described foaming liquid is specially and is made up of the component of following each mass parts:
The number of water is 2.5 parts, the number of sodium lauryl sulphate is 0.33 part, the number of phosphoric acid is 1.7 parts; Or,
The number of water is 3.0 parts, the number of sodium lauryl sulphate is 0.58 part, the number of phosphoric acid is 1.4 parts; Or,
The number of water is 3.4 parts, the number of sodium lauryl sulphate is 0.50 part, the number of phosphoric acid is 1.8 parts; Or,
The number of water is 3.5 parts, the number of Sodium dodecylbenzene sulfonate is 0.60 part, the number of phenylformic acid 0.8, sulfuric acid is 1.7 parts; Or,
The number of water is 4.6 parts, the number of lauric acid sodium sulfate is 0.55 part, benzoic number is 5.0 parts; Or,
The number of water is 2.5 parts, the number of sodium lauryl sulphate is 0.5 part, the number of phosphoric acid is 1.5 parts; Or,
The number of water is 2.7 parts, the number of dioctyl succinate disulfonate acid is 0.49 part, the number of phthalic acid is 3.0 parts; Or,
The number of water is 3.3 parts, the number of Sodium dodecylbenzene sulfonate is 0.53 part, benzoic number is 1.0 parts.
After described dilution, the weight ratio of foaming liquid and phenol modified urea-formaldehyde resins is 0.5 ~ 1.5: 1, is specially 0.67: 1,0.86: 1,0.84: 1,0.93: 1,1.05: 1,1: 1 or 0.67-1.5: 1;
The weight ratio of described solidifying agent and phenol modified urea-formaldehyde resins is 0.02 ~ 0.10: 1, is specially 0.03: 1,0.034: 1,0.04: 1,0.05: 1,0.06: 1,0.1: 1 or 0.03-0.1: 1.
In described dilution step, the quality multiple of dilution is 5-15 times, is specially 5,6,7,8,9,10,14 or 5-14 or 6-10 or 7-14 or 8-10 or 6-14 times.
Described compressed-air actuated pressure is 0.1-0.4MPa, is specially 0.2MPa;
In described whipping step, rotating speed is 1000-5000r/min, is specially 3500r/min;
In described curing schedule, temperature is 35-55 DEG C, is specially 45 DEG C;
Time is 15-72 hour, is specially 24-48 hour.
The phenol-modified urea-formaldehyde foam prepared according to the method described above, also belongs to protection scope of the present invention.
The density of this phenol-modified urea-formaldehyde foam is 30-80Kg/m
3, be specially 34.0Kg/m
3, 48.20Kg/m
3, 48.20Kg/m
3, 51.6Kg/m
3, 54.1Kg/m
3, 58.3Kg/m
3, 75.6Kg/m
3, 34.0Kg/m
3-75.6Kg/m
3;
Compressive strength is 0.08 ~ 0.15MPa, is specially 0.0876MPa, 0.0951MPa, 0.1196MPa, 0.1232MPa, 0.1256MPa, 0.1265MPa or 0.0876MPa-0.1265MPa;
Tensile strength is 0.09 ~ 0.15MPa, is specially 0.0921MPa, 0.1011MPa, 0.1106MPa, 0.1231Pa, 0.1411MPa or 0.0921MPa-0.1411MPa;
Thermal conductivity is 0.030 ~ 0.035W/KM, is specially 0.032W/KM, 0.034W/KM, 0.035W/KM or 0.032W/KM-0.035W/KM;
Rate of closed hole is 40% ~ 90%, is specially 43%, 45%, 62%, 67%, 86% or 43-86%;
Volume water absorption rate is less than 12%, is specially 6.2%, 7.9%, 8.2%, 9.9%, 10.2%, 10.9% or 6.2%-10.9%;
Aperture is 100 μm ~ 250 μm, is specially 100 μm ~ 120 μm, 120 μm ~ 150 μm, 150 μm ~ 180 μm or 180 μm ~ 250 μm.
The invention provides a kind of phenol-modified urea aldehyde (PUF) foam and preparation method thereof.The method is first by phenol and formaldehyde reaction, form methylolphenol structure, add urea reaction again, make to introduce benzene ring structure in urea-formaldehyde resin, effectively can close the water suction group of resin, before remaining urea-formaldehyde foam lightweight, high flame retardant, low heat conduction, the advantage such as inexpensive under topic, the introducing of benzene ring structure makes the water tolerance of the PUF foam prepared significantly improve, and burst size of methanal is controlled, meet national environmental standard, product has good heat-proof quality, and this foam can be used for exterior-wall heat insulation, building decoration etc.
Accompanying drawing explanation
Fig. 1 is the Field desorption mass spectra figure of embodiment 1 gained phenol modified urea-formaldehyde resins.
Fig. 2 is the stereoscan photograph of the phenol-modified urea-formaldehyde foam of embodiment 5 gained.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.The number of described raw material if no special instructions, is mass parts.Described content if no special instructions, is mass percentage.
In phenol modified urea-formaldehyde resins, free phenol is tested according to GB/T14074-2006 wood adhesive and the resin method of inspection thereof;
The method of free aldehyde is for test according to GB/T14074-2006 wood adhesive and the resin method of inspection thereof;
Phenol-modified urea-formaldehyde foam compressive strength is tested according to GB/T15048-1994 rigid foam compression creep test method;
Tensile strength is tested according to GB/T9641-1988 rigid foam Erichsen test method;
Rate of closed hole adopts AccuPyc1340 true density instrument to test, and test pressure is 3psig, tests 5 times, averages;
Aperture adopts field emission scanning electron microscope scanning samples surface to characterize;
Thermal conductivity is tested according to GB/T10294-2008;
Density is tested according to GB/T6343-2009.
Embodiment 1, prepare phenol-modified urea aldehyde (PUF) resin
Be formalin and 10 parts of phenol mixings of 37% by 65 parts of mass percentage concentration, by the pH value of 2mol/L aqueous sodium hydroxide solution regulation system to 8, be warmed up to 75 DEG C of insulation reaction after 1.5 hours, add 11 parts, first urea (55%), be warmed up to 85 DEG C of insulation reaction 30 minutes;
Then cool to 70 DEG C and add 7 parts, second batch urea (35%), and then be warmed up to 98 DEG C of insulation reaction 30 minutes, then add mass percentage concentration be 15% aqueous formic acid pH value is transferred to 6, react when presenting white opacity shape to system, namely reach terminal;
Use rapidly 2mol/L aqueous sodium hydroxide solution adjust ph to 8 afterwards, and then add the 3rd batch of 2 parts, urea (10%), be cooled to rapidly 65 DEG C, insulation reaction 50 minutes, obtain phenol-modified urea aldehyde (PUF) resin provided by the invention.
Analyze resin structure by Field desorption mass spectra (FD-MS) method, result as shown in Figure 1.
FD-MS spectrogram middle-molecular-weihydroxyethyl 91 (monomethylolurea, NH
2-CO-NHCH
2oH), 121 (dimethylolurea HOCH
2-NH-CO-NHCH
2and 151 (trimethylol urea, HOCH OH)
2-NH-CO-N (CH
2oH) CH
2and a small amount of 181 (tatramethylol urea HOCH OH)
2-N (CH
2oH)-CO-N (CH
2oH)-CH
2oH) urea-formaldehyde resin adduct is in the basic conditions, and 163 (NH
2-CO-NH-CH
2-NH-CO-NH-CH
2oH), 193 (HOCH
2-NH-CO-NH-CH
2-NH-CO-NH-CH
2etc. OH) urea-formaldehyde resin biuret products is respectively; Except above Structure of UF resin, 94 (phenol C in spectrogram
6h
5-OH), 124 (methylol fortified phenol HO-C
6h
4-CH
2oH), 154 (dihydroxymethyl fortified phenol HO-C
6h
3-(CH
2oH)
2) and 184 (trishydroxymethyl fortified phenol HO-C
6h
2-(CH
2oH)
3) be then phenol and formaldehyde addition products, and 230 (methylol replacement dihydroxydiphenyl methane HO-C
6h
3(CH
2oH)-CH
2-C
6h
4-OH) and 260 (dihydroxymethyl replaces dihydroxydiphenyl methane, and possible consists of HO-C
6h
3(CH
2oH)-CH
2-C
6h
3(CH
2oH)-OH) be then resol dimer product; Except above urea-formaldehyde resin and phenolic resin structure product, 196 and 226 that occur in figure is phenol-urea-formaldehyde copolymerization product, and its possible composition is respectively HO-C
6h
4-CH
2-NH-CO-NH-CH
2and HO-C OH)
6h
3(CH
2oH)-CH
2-NH-CO-NH-CH
2oH) etc., can show namely have urea-formaldehyde resin and phenolic resin structure in prepared phenol modified urea-formaldehyde resins by the FD-MS spectrogram of phenol modified urea-formaldehyde resins, also there is phenol-urea-formaldehyde terpolymer structure.
The viscosity of this phenol modified urea-formaldehyde resins at 25 DEG C is 20cp, and the mass percentage of water is 48.3%, and solid content is 49.2%, and the mass percentage of free phenol is 1.90%, and the mass percentage of free aldehyde is 0.96%, and pH value is 7.5.
Embodiment 2, prepare phenol-modified urea aldehyde (PUF) resin
According to the step of embodiment 1, be only that the mass parts of the formalin of 37% replaces with 55 parts by mass percentage concentration, obtain phenol modified urea-formaldehyde resins provided by the invention.
The viscosity of this phenol modified urea-formaldehyde resins at 25 DEG C is 24cp, and water-content is 45.9%, and solid content is 48.6%, and the content of free phenol is 4.90%, and the content of free aldehyde is 0.63%, and pH value is 6.8.
Embodiment 3, prepare phenol-modified urea aldehyde (PUF) resin
Be formalin and 10 parts of phenol mixings of 37% by 55 parts of mass percentage concentration, by the pH value of 2mol/L aqueous sodium hydroxide solution regulation system to 7, be warmed up to 70 DEG C of insulation reaction after 2 hours, add 11 parts, first urea (55%), be warmed up to 100 DEG C of insulation reaction 15 minutes;
Then cool to 60 DEG C and add 7 parts, second batch urea (35%), and then be warmed up to 100 DEG C of insulation reaction 15 minutes, then add mass percentage concentration be 15% aqueous formic acid pH value is transferred to 5, react when presenting white opacity shape to system, namely reach terminal;
Use rapidly 2mol/L aqueous sodium hydroxide solution adjust ph to 7 afterwards, and then add the 3rd batch of 2 parts, urea (10%), be cooled to rapidly 50 DEG C, insulation reaction 60 minutes, obtain phenol-modified urea aldehyde (PUF) resin provided by the invention.
The content of the viscosity of this phenol modified urea-formaldehyde resins at 25 DEG C, water-content, solid content, free phenol, the content of free aldehyde and pH value and embodiment 2 are without substantive difference.
Embodiment 4, prepare phenol-modified urea aldehyde (PUF) resin
Be formalin and 10 parts of phenol mixings of 37% by 55 parts of mass percentage concentration, by the pH value of 2mol/L aqueous sodium hydroxide solution regulation system to 9, be warmed up to 80 DEG C of insulation reaction after 1 hour, add 11 parts, first urea (55%), be warmed up to 90 DEG C of insulation reaction 30 minutes;
Then cool to 80 DEG C and add 7 parts, second batch urea (35%), and then be warmed up to 90 DEG C of insulation reaction 30 minutes, then add mass percentage concentration be 15% aqueous formic acid pH value is transferred to 5, react when presenting white opacity shape to system, namely reach terminal;
Use rapidly 2mol/L aqueous sodium hydroxide solution adjust ph to 7 afterwards, and then add the 3rd batch of 2 parts, urea (10%), be cooled to rapidly 55 DEG C, insulation reaction 55 minutes, obtain phenol-modified urea aldehyde (PUF) resin provided by the invention.
The content of the viscosity of this phenol modified urea-formaldehyde resins at 25 DEG C, water-content, solid content, free phenol, the content of free aldehyde and pH value and embodiment 2 are without substantive difference.
Embodiment 5, prepare phenol-modified urea-formaldehyde foam
Take embodiment 1 and prepare gained phenol modified urea-formaldehyde resins 50 parts, Surfactant SDS 0.33 part, solidifying agent phosphatase 11 .7 part, 40 parts, water.
Wherein be used for that the number of the water preparing foaming liquid is 2.5 parts, the number of sodium lauryl sulphate is 0.33 part, the number of phosphoric acid is 1.7 parts.
After the above-mentioned component preparing foaming liquid is mixed, after being diluted to 9 times of quality with 37.5 parts of water, with homogenizer, frothed liquid is stirred with the rotating speed of per minute 3500 turns, blasted the pressurized air stirring 60s of 0.2MPa by air compressor simultaneously, add the PUF resin agitating 60s prepared, stop immediately stirring, rapidly foam is transferred in ready mould, 45 DEG C of solidifications 24 hours, obtain phenol-modified urea-formaldehyde foam.
The density of this phenol-modified urea-formaldehyde foam is 51.6Kg/m
3, compressive strength is 0.1232MPa, and tensile strength is 0.1106MPa, and thermal conductivity is 0.032W/KM, and volume water absorption rate is that to record foam rate of closed hole be 75% to 7.9%, Accupcy II1340 true density instrument.
The photo of scanning electronic microscope S-4800 shown in Fig. 2 shows, and the aperture of phenol formaldehyde foam is 100 μm ~ 120 μm.Foam is fine and smooth, and intensity is good, does not fall slag.
Embodiment 6, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Embodiment 1 prepares gained phenol modified urea-formaldehyde resins 70 parts, sodium lauryl sulphate 0.58 part, 1.4 parts, sulfuric acid, 70 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 3.0 parts, the number of sodium lauryl sulphate is 0.58 part, the number of phosphoric acid is 1.4 parts.The number wherein diluting the water of foaming liquid is 67 parts, dilutes foaming liquid with these 67 parts of water, and the multiple of dilution is 14 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 75.6Kg/m
3, compressive strength 0.1256MPa, tensile strength 0.1411MPa, thermal conductivity 0.034W/KM, volume water absorption rate 6.2%, Accupcy II1340 true density instrument record foam rate of closed hole be 86%, scanning electronic microscope S-4800 display foam aperture be 100 μm ~ 120 μm.Foam is fine and smooth, and intensity is good, does not fall slag.Owing to adding PUF resin demand, foam density increases.
Embodiment 7, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Embodiment 1 prepares gained phenol modified urea-formaldehyde resins 45 parts, sodium lauryl sulphate 0.50 part, phosphatase 11 .8 part, 45 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 3.4 parts, the number of sodium lauryl sulphate is 0.50 part, the number of phosphoric acid is 1.8 parts.The number wherein diluting the water of foaming liquid is 41.6 parts.Dilute foaming liquid with these 41.6 parts of water, the multiple of dilution is 8 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 34.0Kg/m
3, compressive strength 0.0951MPa, tensile strength 0.0921MPa, thermal conductivity 0.032W/KM, volume water absorption rate be less than 11.8%, Accupcy II1340 true density instrument record foam rate of closed hole be 43%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 150 μm ~ 180 μm.Owing to decreasing PUF resin demand, foam density reduces, and intensity is slightly poor, and rate of closed hole reduces.
Embodiment 8, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Embodiment 1 prepares gained phenol modified urea-formaldehyde resins 50 parts, Sodium dodecylbenzene sulfonate 0.60 part, phenylformic acid 0.8,1.7 parts, sulfuric acid, 40 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 3.5 parts, the number of Sodium dodecylbenzene sulfonate is 0.60 part, the number of phenylformic acid 0.8, sulfuric acid is 1.7 parts.The number wherein diluting the water of foaming liquid is 36.5 parts.Dilute this foaming liquid with these 36.5 parts of water, the multiple of dilution is 7 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 48.20Kg/m
3, compressive strength 0.1196MPa, tensile strength 0.1011MPa, thermal conductivity 0.035W/KM, volume water absorption rate be less than 10.9%, Accupcy II1340 true density instrument record foam rate of closed hole be 45%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 180 μm ~ 250 μm.
Embodiment 9, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Embodiment 1 prepares gained phenol modified urea-formaldehyde resins 50 parts, 0.55 part, lauric acid sodium sulfate, 5.0 parts, phenylformic acid, 68 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 4.6 parts, the number of lauric acid sodium sulfate is 0.55 part, benzoic number is 5.0 parts.The number wherein diluting the water of foaming liquid mother liquor is 63.4 parts.Dilute foaming liquid with these 63.4 parts of water, the multiple of dilution is 7 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 58.3Kg/m
3, compressive strength 0.1265MPa, tensile strength 0.1231Pa, thermal conductivity 0.034W/KM, volume water absorption rate 8.2%, Accupcy II1340 true density instrument record foam rate of closed hole be 67%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 120 μm ~ 150 μm.
Embodiment 10, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Gained phenol modified urea-formaldehyde resins prepared by embodiment 1 to replace with embodiment 2 and prepare gained phenol modified urea-formaldehyde resins 50 parts, sodium lauryl sulphate 0.5 part, phosphatase 11 .5 part, 23 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 2.5 parts, the number of sodium lauryl sulphate is 0.5 part, the number of phosphoric acid is 1.5 parts.The number wherein diluting the water of foaming liquid mother liquor is 20.5 parts.Dilute this foaming liquid with these 20.5 parts of water, the multiple of dilution is 6 times.
The density of the phenol-modified urea-formaldehyde foam of gained is 54.1Kg/m
3, compressive strength 0.0876MPa, tensile strength 0.0921MPa, thermal conductivity 0.032W/KM, volume water absorption rate 9.9%, Accupcy II1340 true density instrument record foam rate of closed hole be 62%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 100 μm ~ 120 μm.Foam is fine and smooth, but reduces due to resin-formaldehyde and urea ratio, and resin free phenol is slightly high, and foamy body is slightly poor.
Embodiment 11, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Gained phenol modified urea-formaldehyde resins prepared by embodiment 1 to replace with embodiment 2 and prepare gained phenol modified urea-formaldehyde resins 50 parts, dioctyl succinate disulfonate acid 0.49 part, phthalic acid 3.0 parts, 30 parts, water.
Wherein be used for that the number of the water preparing foaming liquid is 2.7 parts, the number of dioctyl succinate disulfonate acid is 0.49 part, the number of phthalic acid is 3.0 parts.The number wherein diluting the water of foaming liquid is 27.3 parts.Dilute this foaming liquid with these 27.3 parts of water, the multiple of dilution is 5 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 48.20Kg/m
3, compressive strength 0.1196MPa, tensile strength 0.1011MPa, thermal conductivity 0.035W/KM, volume water absorption rate be less than 10.9%, Accupcy II1340 true density instrument record foam rate of closed hole be 45%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 180 μm ~ 250 μm.
Embodiment 12, prepare phenol-modified urea-formaldehyde foam
According to the step of embodiment 5, only each raw material is replaced with following mass parts, obtains phenol-modified urea-formaldehyde foam provided by the invention:
Gained phenol modified urea-formaldehyde resins prepared by embodiment 1 to replace with embodiment 2 and prepare gained phenol modified urea-formaldehyde resins 50 parts, Sodium dodecylbenzene sulfonate 0.53 part, phenylformic acid: 1.0 parts, 45 parts, water.
Wherein be used for that the number of the water preparing foaming liquid mother liquor is 3.3 parts, the number of Sodium dodecylbenzene sulfonate is 0.53 part, benzoic number is 1.0 parts.The number wherein diluting the water of foaming liquid mother liquor is 41.7 parts.Dilute this foaming liquid with these 41.7 parts of water, the multiple of dilution is 10 times of quality.
The density of the phenol-modified urea-formaldehyde foam of gained is 58.3Kg/m
3, compressive strength 0.1265MPa, tensile strength 0.1231Pa, thermal conductivity 0.034W/KM, volume water absorption rate 10.2%, Accupcy II1340 true density instrument record foam rate of closed hole be 67%, scanning electronic microscope S-4800 display phenol formaldehyde foam aperture be 120 μm ~ 150 μm.Foam is fine and smooth, and intensity is high.
In addition, embodiment 2 used in gained phenol modified urea-formaldehyde resins, embodiment 12 prepared by embodiment 1 used in embodiment 6-11 to prepare gained phenol modified urea-formaldehyde resins and all replace with embodiment 3 or 4 gained urea-formaldehyde resin, the physical property of the phenol-modified urea-formaldehyde foam of gained and embodiment 5-12 are without substantive difference.
Claims (7)
1. prepare a method for phenol-modified urea-formaldehyde foam, comprise the steps: with phenol modified urea-formaldehyde resins to be raw material, utilize foam process, obtain phenol-modified urea-formaldehyde foam;
Prepare the method for described phenol modified urea-formaldehyde resins, to comprise the steps: with formaldehyde, phenol and urea, for raw material, to prepare urea-formaldehyde resin;
The molar ratio of described urea, phenol and formaldehyde is 1:0.2 ~ 1.0:2.0 ~ 3.0; The described preparation prepared in urea-formaldehyde resin comprises the steps:
By adjust ph to 7 ~ 9 after formaldehyde and phenol mixing, then be warmed up to 70 ~ 80 DEG C of insulation reaction 1 ~ 2 hour, add first urea, then be warmed up to 85 ~ 100 DEG C of insulation reaction after 15 ~ 30 minutes;
Cool to 60-80 DEG C and add second batch urea, then be warmed up to 90 ~ 100 DEG C of insulation reaction 15 ~ 30 minutes, then adjust ph to 5 ~ 7, react after presenting white opacity shape to reaction system;
Adjust ph to 7 ~ 9, add the 3rd batch of urea, cool to 50-65 DEG C, insulation reaction 30 ~ 60 minutes and obtaining;
Wherein, first, the mass ratio of second batch and the 3rd batch of urea is 50-70:20-40:5-15;
Described foam process comprises the steps: after foaming liquid dilute with water, under whipped state, blast pressurized air, after stirring 30-120s, add after described phenol modified urea-formaldehyde resins stirs 30-60s again and stop stirring, be transferred in mould and solidify, obtain described phenol-modified urea-formaldehyde foam;
Described foaming liquid is made up of tensio-active agent, solidifying agent and water;
Described tensio-active agent is selected from least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, dioctyl succinate disulfonate acid and lauric acid sodium sulfate;
Described solidifying agent is selected from least one in sulfuric acid, phosphoric acid, oxalic acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid;
In described foaming liquid, the mass ratio 1.0-1.5:2.0-10:6-10 of tensio-active agent, solidifying agent and water;
In described dilution step, the quality multiple of dilution is 5-15 times;
After dilution, described foaming liquid and phenol modified urea-formaldehyde resins weight ratio are 0.5 ~ 1.5:1;
And the weight ratio of described solidifying agent and phenol modified urea-formaldehyde resins is 0.02 ~ 0.10:1;
Described compressed-air actuated pressure is 0.1-0.4MPa;
In described whipping step, rotating speed is 1000-5000r/min;
In described curing schedule, temperature is 35-55 DEG C;
Time is 15-72 hour.
2. method according to claim 1, is characterized in that: described compressed-air actuated pressure is 0.2MPa;
In described whipping step, rotating speed is 3500r/min;
In described curing schedule, temperature is 45 DEG C;
Time is 24-48 hour.
3., according to the method that power requires described in 1, it is characterized in that: first, the mass ratio of second batch and the 3rd batch of urea is 55:35:10.
4., according to the arbitrary described method of claim 1-3, it is characterized in that: the viscosity of described phenol modified urea-formaldehyde resins at 25 DEG C is 15 ~ 30cP;
The mass percentage of water is 40% ~ 55%;
Solid content is 45% ~ 55%;
The mass percentage of free phenol is 1 ~ 4.9%;
The mass percentage of free aldehyde is 0.5 ~ 1.0%;
PH value is 6 ~ 8.
5. method according to claim 4, is characterized in that: the viscosity of described phenol modified urea-formaldehyde resins at 25 DEG C is 20-24cP;
The mass percentage of water is 48.3-45.9%;
Solid content is 48.6-49.2%;
The mass percentage of free phenol is 1.90-4.90%;
The mass percentage of free aldehyde is 0.63-0.96%;
PH value is 6.8-7.5.
6. the phenol-modified urea-formaldehyde foam for preparing of the arbitrary described method of claim 1-5.
7. phenol-modified urea-formaldehyde foam according to claim 6, is characterized in that: the density of described phenol-modified urea-formaldehyde foam is 30-80kg/m3;
Compressive strength is 0.08 ~ 0.15MPa;
Tensile strength is 0.09 ~ 0.15MPa;
Thermal conductivity is 0.030 ~ 0.035 W/ (mK);
Rate of closed hole is 40% ~ 90%;
Volume water absorption rate is less than 12%;
Aperture is 100 μm ~ 250 μm.
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