CN103342830A - Inorganic composite phenol modified urea formaldehyde resin foam and preparation method thereof - Google Patents
Inorganic composite phenol modified urea formaldehyde resin foam and preparation method thereof Download PDFInfo
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Abstract
The invention provides inorganic composite phenol modified urea formaldehyde resin foam and a preparation method thereof. The preparation method of the inorganic composite phenol modified urea formaldehyde resin foam comprises the following steps of: foaming and forming inorganic filler and phenol modified urea formaldehyde resin to obtain the inorganic composite phenol modified urea formaldehyde resin foam, wherein the weight-part ratio of the inorganic filler to the phenol modified urea formaldehyde resin is (0.1-0.5):1. According to the inorganic composite phenol modified urea formaldehyde resin foam material provided by the invention, the flame retardance is remarkably improved to the A2 level while guaranteeing the light weight and low heat conduction of the urea formaldehyde foam, and the material can be applied to external wall insulation and architectural decoration.
Description
Technical field
The present invention relates to a kind of inorganic compounding phenol modified urea-formaldehyde resins foam and preparation method thereof.
Background technology
Energy consumption increases day by day, and building energy conservation comes into one's own day by day, and doing heat insulation work to building external envelope structure is energy-conservation effective measure.No matter to public building, or covil construction, glass, door and window and external wall reconstruction all are energy-conservation keys.For covil construction, mainly realize energy-conservation with the lagging material coating layer.But in recent years a lot of Highrise buildings wildfire accident reviews of Fa Shenging we, the flame retardant properties of building thermal insulation material can not be ignored.
Lagging material for building divides organic and inorganic two kinds: organic class lagging material, commonly used has advantage in light weight, good effect of heat insulation as styrofoam (PS), urethane (SPU), phenolic aldehyde (PF) etc., but shortcoming be not ageing-resistant, deformation coefficient greatly, easy firing etc.; Wherein inflammableness forms very big threat to building safety, organic insulation material is through flame-retardant modified, and its flame retardant properties also can only be the B level, and in case burning will produce hypertoxic gas, serious threat personnel life when the buildings presence of fire is the important arch-criminal who causes great loss of life and personal injury.Inorganic heat insulation material; poor as heat insulating efficient such as glass bead, pearlstone, closed perlite, rock wools; but the fire protection flame retarding excellence, deformation coefficient is little, anti-aging, stable performance, be combined better with plinth course and float coat, safety and firmness is good, thermal insulation layer intensity and weather resistance be than organic insulation material height.
Summary of the invention
An object of the present invention is to provide a kind of inorganic compounding phenol modified urea-formaldehyde resins foam and preparation method thereof.
The method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam provided by the present invention comprises the steps: mineral filler and phenol modified urea-formaldehyde resins foaming are prepared the phenol-modified urea-formaldehyde foam of inorganic compounding; Wherein, the ratio of weight and number of described mineral filler and described phenol modified urea-formaldehyde resins is 0.1～0.5:1.
Described method with mineral filler and phenol modified urea-formaldehyde resins foaming can comprise the steps:
(1) inorganic filler surface is handled:
Mineral filler and coupling agent are mixed, obtain the mineral filler after the surface treatment;
(2) mixture of preparation mineral filler and phenol modified urea-formaldehyde resins:
With the mineral filler after the described surface treatment and phenol modified urea-formaldehyde resins mixing, obtain the mixture of mineral filler and phenol modified urea-formaldehyde resins;
(3) preparation foam
Mixture, foaming liquid with described mineral filler and phenol modified urea-formaldehyde resins are raw material, utilize the technology of preparation urea-formaldehyde resin foam, prepare inorganic compounding phenol modified urea-formaldehyde resins foam.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described mineral filler is selected from as follows: flyash, hollow glass micropearl, aluminium hydroxide, perlite, nano-calcium carbonate, calcium stearate, white portland cement and talcum powder;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described coupling agent is selected from as follows: γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan and N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, the ratio of quality and the number of copies of described coupling agent and described mineral filler is (0.001-0.01): 1, be specially (0.008-0.01): 1, be specially 0.003:1,0.008:1,0.006:1,0.01:1,0.004:1 or 0.001:1 again.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, the ratio of quality and the number of copies of described mineral filler and described phenol modified urea-formaldehyde resins is specially 0.1:1,0.43:1,0.5:1,0.31:1,0.38:1 or 0.4:1 again for being specially 0.31-0.43:1.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described foaming liquid is made up of tensio-active agent, resin curing agent and water; The massfraction of tensio-active agent, resin curing agent and water is than being 1:(2-6.7): (50-173), be specially 1:6.6-6.7:(85-120), be specially 1:2.4:100,1:6.7:85,1:6:173,1:6.6:120,1:2:50 or 1:3.2:64.6 again;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described tensio-active agent is selected from following at least a: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate and lauric acid sodium sulfate;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described resin curing agent is acid as curing agent;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described acid as curing agent is selected from following at least a: phosphoric acid, sulfuric acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid;
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, the ratio of quality and the number of copies of described foaming liquid and described phenol modified urea-formaldehyde resins is (0.5-1.5): 1, be specially (0.85-0.93): 1, be specially 1.45:1,0.93:1,1.5:1,0.85:1,0.5:1 or 0.75:1 again.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, described phenol modified urea-formaldehyde resins is prepared as follows and obtains: be raw material with formaldehyde, phenol and urea, prepare urea-formaldehyde resin; The molar ratio of described urea, phenol and formaldehyde is 1:0.2～1.0:2.0～3.0.
Among the preparation method of above-mentioned phenol modified urea-formaldehyde resins, the described preparation for preparing in the urea-formaldehyde resin comprises the steps:
With regulating pH value to 7～9 behind formaldehyde and the phenol mixing, be warmed up to 70～80 ℃ of insulation reaction 1～2 hour again, add first urea, be warmed up to 85～100 ℃ of insulation reaction again after 15～30 minutes; Cool to 60-80 ℃ and add second batch of urea, be warmed up to 90～100 ℃ of insulation reaction 15～30 minutes again, regulate pH value to 5～7 then, react present the white opacity shape to reaction system after; Regulate pH value to 7～9, add the 3rd batch of urea, cool to 50-65 ℃, insulation reaction 30～60 minutes and getting;
Wherein, first, the mass ratio of second batch and the 3rd batch urea is 50-70:20-40:5-15, is specially 55:35:10.
Among the preparation method of above-mentioned phenol modified urea-formaldehyde resins, can regulate with following all ingredients when regulating the pH value for 7-9: sodium hydroxide, hexamethylenetetramine, ammoniacal liquor, trolamine, S-WAT or Sodium Tetraborate;
Among the preparation method of above-mentioned phenol modified urea-formaldehyde resins, can regulate with following all ingredients when regulating the pH value for 5-7: as ammonium chloride, ammonium sulfate, formic acid, acetic acid or zinc chloride;
Among the preparation method of above-mentioned phenol modified urea-formaldehyde resins, 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;
Among the preparation method of above-mentioned phenol modified urea-formaldehyde resins, described formaldehyde is to add 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%.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, in the step (1), in the described blending process, temperature is 40 ℃, and the time of mixing is 50min.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, in the step (1), described mixing is to use the high speed kneader, and mixing speed is 1000r/min-2000r/min.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, in the step (2), described mixing is 30 ℃-50 ℃ and stirs 45min-90min down.
In the above-mentioned method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam, in the step (3), the technology of preparation urea-formaldehyde resin foam comprises the steps: to stir foaming liquid with stirrer under the room temperature, blast 0.2～0.9MPa(by air compressor simultaneously and be specially 0.4～0.8MPa, be specially 0.4MPa or 0.8MPa again) pressurized air, be pressed into air filled cavity, when treating that foam volume reaches the highest, continue to stir, the mixture that adds described mineral filler and phenol modified urea-formaldehyde resins simultaneously, stirring and evenly mixing, it is stable to treat that material becomes, behind the foam, move in the mould uniformly, (being specially 45～55 ℃ solidified 30 hours to solidify 24-48 hour at 35～50 ℃, be specially again 45 ℃ solidify solidified 30 hours in 30 hours or 55 ℃), obtain inorganic compounding phenol modified urea-formaldehyde resins foam.
The inorganic compounding phenol modified urea-formaldehyde resins foam that is prepared by above-mentioned arbitrary described method also belongs to protection scope of the present invention.
The character of described inorganic compounding phenol modified urea-formaldehyde resins foam is at least a in following: foam density is 62-85Kg/m
3, be specially 82-85Kg/m
3, be specially again, 62Kg/m
3, 82Kg/m
3, 75Kg/m
3, 85Kg/m
3, 64Kg/m
3, 73Kg/m
3Compressive strength 0.16-0.26MPa is specially 0.25MPa-0.26MPa, is specially 0.16MPa, 0.25MPa, 0.23MPa, 0.26MPa, 0.19MPa, 0.23MPa again; Tensile strength 0.13-0.17MPa is specially 0.14MPa-0.16MPa, is specially 0.13MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.15MPa, 0.17MPa again; Thermal conductivity 0.034-0.035W/KM is specially 0.034W/KM; Calorific value≤3.0KJ/kg is specially 2.35-2.99KJ/kg, is specially 2.35KJ/kg-2.5KJ/kg, is specially 2.9KJ/kg, 2.35KJ/kg, 2.99KJ/kg, 2.5KJ/kg, 3.45KJ/kg again.
The invention still further relates to the phenol-modified urea-formaldehyde foam of above-mentioned inorganic compounding as the application of lagging material.
The phenol-modified urea-formaldehyde foam of inorganic compounding provided by the invention is different from the compound foam of organic-inorganic that the outside inorganic materials of general employing coats inner organic foam core, the common foaming of realization is prepared from the phenol-modified urea-formaldehyde foam organic materials but a large amount of inorganic materials are dosed in employing, wherein organic composition is mainly the urea-formaldehyde foam after phenol-modified, inorganic components adopts multiple low heat value powder, the material of preparing is homogeneous, has organic materials low thermal conductivity, low density and inorganic materials excellent flame retardancy energy concurrently.
The preparation method of the compound phenol-modified urea-formaldehyde foam lagging material of a kind of novel inorganic that the present invention proposes, wherein organic composition is based on urea-formaldehyde resin, and adds a large amount of inorganic powder fillers, and product cost is low; The present invention can be near foaming under the room temperature, and the preparation process thermal discharge is little, and energy consumption is low, and is simple to operate, and can realize that industrialization produces continuously.
The phenol-modified urea-formaldehyde foam of the inorganic compounding for preparing is when guaranteeing urea-formaldehyde foam lightweight, low heat conduction, and its flame retardant properties is improved largely, and reaches the A2 level, can be used for exterior-wall heat insulation, building decoration etc.
Inorganic compounding phenol modified urea-formaldehyde resins foam materials of the present invention is when guaranteeing urea-formaldehyde foam lightweight, low heat conduction, and its flame retardant properties is improved largely, and reaches the A2 level, can be used for exterior-wall heat insulation, building decoration.
The preparation method of the phenol-modified urea-formaldehyde foam lagging material of inorganic compounding of the present invention, wherein organic composition is based on urea-formaldehyde resin, and adds a large amount of inorganic powder fillers, and product cost is low; The present invention can be near foaming under the room temperature, and the preparation process thermal discharge is little, and energy consumption is low, and is simple to operate, and can realize that industrialization produces continuously.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The umber of used material is mass parts among the following embodiment.
The preparation method of the phenol modified urea-formaldehyde resins that uses among following each embodiment is as follows:
Free phenol is tested according to GB/T14074-2006 wood adhesive and the resin method of inspection thereof in the phenol modified urea-formaldehyde resins;
The method of free aldehyde is for to test according to GB/T14074-2006 wood adhesive and the resin method of inspection thereof;
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;
Thermal conductivity is tested according to GB/T10294-2008;
Density is tested according to GB/T6343-2009.
Embodiment 1,
One, preparation phenol modified urea-formaldehyde resins
Be formalin and 10 parts of phenol mixings of 37% with 65 parts of mass percentage concentration, pH value to 8 with 2mol/L aqueous sodium hydroxide solution regulation system, be warmed up to 75 ℃ of insulation reaction after 1.5 hours, add 11 parts in first urea (55%), be warmed up to 85 ℃ of insulation reaction 30 minutes; Cool to 70 ℃ then and add 7 parts in second batch of urea (35%), and then be warmed up to 98 ℃ of insulation reaction 30 minutes, add mass percentage concentration then and be 15% aqueous formic acid the pH value is transferred to 6, react when presenting the white opacity shape to system, namely reach terminal point; Regulate pH value to 8 with the 2mol/L aqueous sodium hydroxide solution rapidly afterwards, and then add the 3rd batch of 2 parts in urea (10%), be cooled to 65 ℃ rapidly, insulation reaction 50 minutes obtains phenol-modified urea aldehyde provided by the invention (PUF) resin.
The viscosity of this phenol modified urea-formaldehyde resins under 25 ℃ is 20cp, and the quality percentage composition of water is 48.3%, and solid content is 49.2%, and the quality percentage composition of free phenol is 1.90%, and the quality percentage composition of free aldehyde is that 0.96%, pH value is 7.5; % all refers to the quality percentage composition.
Two, preparation foam
With under 40 ℃ of 5 parts in flyash and the 0.015 part of γ-An Bingjisanyiyangjiguiwans in the high speed kneader with the rotating speed mixing 50min of 1000r/min, mix; Temperature of charge is 40 ℃;
Add 50 parts of phenol modified urea-formaldehyde resins that method one makes, 40 ℃ are continued to stir 60min, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 70 parts of 0.7 part of sodium lauryl sulphate, phosphatase 11 .7 part, water, be mixed with foaming liquid.
Stir 72.4 parts of foaming liquids with homogenizer with the speed that per minute 1000 changes under the room temperature, blast the pressurized air of 0.2MPa simultaneously by air compressor, be pressed into air filled cavity, when treating that foam volume reaches the highest, continue to stir, add phenol-modified urea aldehyde (PUF) resin and mineral filler mixture simultaneously, stirring and evenly mixing is behind the stirring 50s, after treating that material becomes stable, uniform foam, move into rapidly in the mould, solidified 48 hours at 35 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 61.6Kg/m
3, compressive strength 0.1632MPa, tensile strength 0.1306MPa, thermal conductivity 0.035W/KM, calorific value 2.9036KJ/kg.
Embodiment 2,
One, preparation phenol modified urea-formaldehyde resins: identical among method and the embodiment 1.
Two, preparation foam
Take by weighing 26 parts of hollow glass micropearls and 0.2 part of γ-glycidyl ether oxygen propyl trimethoxy silicane rotating speed mixing 50min with 1500r/min in the high speed kneader, mix; Temperature of charge is 40 ℃;
Add 60 parts of phenol modified urea-formaldehyde resins that method one makes, stir 90min at 30 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.6 part of Sodium dodecylbenzene sulfonate, 2.2 parts in sulfuric acid, phosphatase 11 .8 part, 51 parts in water is mixed with foaming liquid.With homogenizer 55.6 parts of frothed liquids are stirred rapidly, blast the pressurized air of 0.4MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 50s and the mixture of mineral filler continue to stir 30s, move in the mould rapidly, solidified 30 hours at 45 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 81.6Kg/m
3, compressive strength 0.2541MPa, tensile strength 0.1412MPa, thermal conductivity 0.034W/KM, calorific value 2.3452KJ/kg.
Embodiment 3,
One, preparation phenol modified urea-formaldehyde resins: identical among method and the embodiment 1.
Two, preparation foam
Take by weighing 30 parts in aluminium hydroxide and 0.19 part of γ-(methacryloxypropyl) propyl trimethoxy silicane rotating speed mixing 50min with 2000r/min in the high speed kneader, mix; Temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 60 parts of methods one make and stir 45min at 50 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.5 part of dioctyl sodium sulfosuccinate, 3.0 parts of phthalic acids, 86.5 parts in water, be mixed with foaming liquid.With homogenizer 90 parts of frothed liquids are stirred rapidly, blast the pressurized air of 0.4MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 60s and the mixture of mineral filler continue to stir 20s, move in the mould rapidly, solidified 36 hours at 50 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 75.25Kg/m
3, compressive strength 0.2312MPa, tensile strength 0.1513MPa, thermal conductivity 0.034W/KM, calorific value 2.9914KJ/kg.
Embodiment 4,
One, preparation phenol modified urea-formaldehyde resins: identical among method and the embodiment 1.
Two, preparation foam
Take by weighing 23 parts of perlites and 0.23 part of γ-An Bingjisanyiyangjiguiwan rotating speed mixing 50min with 1800r/min in the high speed kneader, mix; Temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 75 parts of methods one make and stir 60min at 40 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.50 part in lauric acid sodium sulfate, 3.3 parts in phenylformic acid, 60 parts in water, be mixed with foaming liquid.With homogenizer 63.8 parts of frothed liquids are stirred rapidly, blast the pressurized air of 0.8MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 55s and the mixture of mineral filler continue to stir 60s, move in the mould rapidly, solidified 30 hours at 55 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 85.31Kg/m
3, compressive strength 0.2572MPa, tensile strength 0.1615MPa, thermal conductivity 0.034W/KM, calorific value 2.496KJ/kg.
Embodiment 5,
One, preparation phenol modified urea-formaldehyde resins: identical among method and the embodiment 1.
Two, preparation foam
Take by weighing 5 parts of nano-calcium carbonates, 15 parts of hollow glass micropearls and 0.08 part of γ-glycidyl ether oxygen propyl trimethoxy silicane rotating speed mixing 50min with 1400r/min in the high speed kneader mix; Temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 53 parts of methods one make and stir 90min at 30 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.5 part of Sodium dodecylbenzene sulfonate, 1.0 parts in phenylformic acid, 25 parts in water, be mixed with foaming liquid.With homogenizer 26.5 parts of frothed liquids are stirred rapidly, blast the pressurized air of 0.6MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 60s and the mixture of mineral filler continue to stir 45s, move in the mould rapidly, solidified 24 hours at 45 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 64.35Kg/m
3, compressive strength 0.1912MPa, tensile strength 0.1501MPa, thermal conductivity 0.034W/KM, calorific value 2.893KJ/kg.
Embodiment 6,
One, preparation phenol modified urea-formaldehyde resins: identical among method and the embodiment 1.
Two, preparation foam
Take by weighing calcium stearate 24 and 0.024 part of γ-glycidyl ether oxygen propyl trimethoxy silicane rotating speed mixing 50min with 1600r/min in the high speed kneader, mix; Wherein, temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 60 parts of methods one make and stir 80min at 50 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.65 part in lauric acid sodium sulfate, 1.5 parts in sulfuric acid, 0.6 part of Monochloro Acetic Acid, 42 parts in water, be mixed with foaming liquid.With homogenizer 44.75 parts of frothed liquids are stirred rapidly, blast the pressurized air of 0.9MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 50s and the mixture of mineral filler continue to stir 60s, move in the mould rapidly, solidified 30 hours at 44 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
Recording the PUF foam density for preparing is 73.35Kg/m
3, compressive strength 0.2269MPa, tensile strength 0.1653MPa, thermal conductivity 0.035W/KM, calorific value 3.451KJ/kg.
Comparative Examples 1,
Take by weighing 60 parts of 0.52 part of sodium lauryl sulphate, phosphatase 11 .7 part, water, be mixed with foaming liquid.
With homogenizer frothed liquid is stirred rapidly, blast the pressurized air of 0.4MPa simultaneously by air compressor, add the phenol modified urea-formaldehyde resins continuation stirring 60s that 50 parts of methods one make after stirring 60s, move in the mould rapidly, solidified 24 hours at 35 ℃, obtain phenol-modified urea aldehyde (PUF) foam.
This Comparative Examples does not add mineral filler.Recording the PUF foam density of preparing is 51.6Kg/m
3, compressive strength 0.1232MPa, tensile strength 0.1106MPa, thermal conductivity 0.032W/KM, calorific value 17.12KJ/kg.
Comparative Examples 2,
Take by weighing 2.5 parts in flyash and 0.013 part of γ-glycidyl ether oxygen propyl trimethoxy silicane rotating speed mixing 50min with 2000r/min in the high speed kneader; Wherein, temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 50 parts of methods one make and stir 60min at 40 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.45 part of Sodium dodecylbenzene sulfonate, phenylformic acid: 45 parts of 2.8 parts, water are mixed with foaming liquid.
With homogenizer frothed liquid is stirred rapidly, blast the pressurized air of 0.4MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 60s and the mixture of mineral filler continue to stir 60s, move in the mould rapidly, solidified 24 hours at 50 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
This Comparative Examples mineral filler add-on is less.Recording the PUF foam density of preparing is 64.35Kg/m
3, compressive strength 0.1312MPa, tensile strength 0.1120MPa, thermal conductivity 0.034W/KM, calorific value 15.11KJ/kg.
Comparative Examples 3,
Take by weighing 30 parts in aluminium hydroxide and in the high speed kneader, mix 50min with 0.15 part of γ-An Bingjisanyiyangjiguiwan; Wherein, temperature of charge is 40 ℃;
Add the phenol modified urea-formaldehyde resins that 50 parts of methods one make and stir 60min at 40 ℃, make phenol-modified urea aldehyde (PUF) resin and mineral filler mixture;
Take by weighing 0.65 part of Sodium dodecylbenzene sulfonate, phosphoric acid: 45 parts of 2.5 parts, water are mixed with foaming liquid.
With homogenizer frothed liquid is stirred rapidly, blast the pressurized air of 1.0MPa simultaneously by air compressor, the phenol modified urea-formaldehyde resins that adding prepares behind the stirring 60s and the mixture of mineral filler continue to stir 60s, move in the mould rapidly, solidified 24 hours at 40 ℃, obtain the phenol-modified urea aldehyde of inorganic compounding (PUF) foam.
This Comparative Examples mineral filler add-on height.Recording the PUF foam density of preparing is 93.14Kg/m
3, foam is crisp, and efflorescence is serious, intensity difference.
Two, three, four phenol modified urea-formaldehyde resins that prepare are with the following method carried out the experiment of above-described embodiment 1-6, the result all with embodiment 1-6 in the result do not have significant difference.
Method two:
According to the step of step 1 among the embodiment 1, only be that the mass parts of 37% formalin replaces with 55 parts with mass percentage concentration, obtain phenol modified urea-formaldehyde resins provided by the invention.
The viscosity of this phenol modified urea-formaldehyde resins under 25 ℃ 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 that 0.63%, pH value is 6.8.
Method three:
Be formalin and 10 parts of phenol mixings of 37% with 55 parts of mass percentage concentration, pH value to 7 with 2mol/L aqueous sodium hydroxide solution regulation system, be warmed up to 70 ℃ of insulation reaction after 2 hours, add 11 parts in first urea (55%), be warmed up to 100 ℃ of insulation reaction 15 minutes; Cool to 60 ℃ then and add 7 parts in second batch of urea (35%), and then be warmed up to 100 ℃ of insulation reaction 15 minutes, add mass percentage concentration then and be 15% aqueous formic acid the pH value is transferred to 5, react when presenting the white opacity shape to system, namely reach terminal point; Regulate pH value to 7 with the 2mol/L aqueous sodium hydroxide solution rapidly afterwards, and then add the 3rd batch of 2 parts in urea (10%), be cooled to 50 ℃ rapidly, insulation reaction 60 minutes obtains phenol-modified urea aldehyde provided by the invention (PUF) resin.
The content of the content of the viscosity of this phenol modified urea-formaldehyde resins under 25 ℃, water-content, solid content, free phenol, free aldehyde and pH value and method two do not have substantive difference.
Method four:
Be formalin and 10 parts of phenol mixings of 37% with 55 parts of mass percentage concentration, pH value to 9 with 2mol/L aqueous sodium hydroxide solution regulation system, be warmed up to 80 ℃ of insulation reaction after 1 hour, add 11 parts in first urea (55%), be warmed up to 90 ℃ of insulation reaction 30 minutes; Cool to 80 ℃ then and add 7 parts in second batch of urea (35%), and then be warmed up to 90 ℃ of insulation reaction 30 minutes, add mass percentage concentration then and be 15% aqueous formic acid the pH value is transferred to 5, react when presenting the white opacity shape to system, namely reach terminal point; Regulate pH value to 7 with the 2mol/L aqueous sodium hydroxide solution rapidly afterwards, and then add the 3rd batch of 2 parts in urea (10%), be cooled to 55 ℃ rapidly, insulation reaction 55 minutes obtains phenol-modified urea aldehyde provided by the invention (PUF) resin.
The content of the content of the viscosity of this phenol modified urea-formaldehyde resins under 25 ℃, water-content, solid content, free phenol, free aldehyde and pH value and method two do not have substantive difference.
Claims (10)
1. a method for preparing inorganic compounding phenol modified urea-formaldehyde resins foam may further comprise the steps: with mineral filler and phenol modified urea-formaldehyde resins foaming, prepare the phenol-modified urea-formaldehyde foam of inorganic compounding; Wherein, the ratio of weight and number of described mineral filler and described phenol modified urea-formaldehyde resins is 0.1～0.5:1.
2. method according to claim 1, it is characterized in that: described method with mineral filler and phenol modified urea-formaldehyde resins foaming comprises the steps:
(1) inorganic filler surface is handled:
Mineral filler and coupling agent are mixed, obtain the mineral filler after the surface treatment;
(2) mixture of preparation mineral filler and phenol modified urea-formaldehyde resins:
With the mineral filler after the described surface treatment and phenol modified urea-formaldehyde resins mixing, obtain the mixture of mineral filler and phenol modified urea-formaldehyde resins;
(3) preparation foam
Mixture, foaming liquid with described mineral filler and phenol modified urea-formaldehyde resins are raw material, utilize the technology of preparation urea-formaldehyde resin foam, prepare inorganic compounding phenol modified urea-formaldehyde resins foam.
3. method according to claim 1 and 2, it is characterized in that: described mineral filler is selected from as follows: flyash, hollow glass micropearl, aluminium hydroxide, perlite, nano-calcium carbonate, calcium stearate, white portland cement and talcum powder;
And/or described coupling agent is selected from as follows: γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan and N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane;
And/or the ratio of quality and the number of copies of described coupling agent and described mineral filler is (0.001-0.01): 1, be specially (0.008-0.01): 1.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: the ratio of quality and the number of copies of described mineral filler and described phenol modified urea-formaldehyde resins is 0.31-0.43:1.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: described foaming liquid is made up of tensio-active agent, resin curing agent and water; The massfraction of tensio-active agent, resin curing agent and water is than being 1:(2-6.7): (50-173), be specially 1:6.6-6.7:(85-120);
And/or described tensio-active agent is selected from following at least a: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate and lauric acid sodium sulfate;
And/or described resin curing agent is acid as curing agent;
And/or described acid as curing agent is selected from following at least a: phosphoric acid, sulfuric acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid;
And/or the ratio of quality and the number of copies of described foaming liquid and described phenol modified urea-formaldehyde resins is (0.5-1.5): 1, be specially (0.85-0.93): 1.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described phenol modified urea-formaldehyde resins is prepared as follows and obtains:
Be raw material with formaldehyde, phenol and urea, prepare urea-formaldehyde resin; The molar ratio of described urea, phenol and formaldehyde is 1:0.2～1.0:2.0～3.0.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: the described preparation for preparing in the urea-formaldehyde resin comprises the steps:
With regulating pH value to 7～9 behind formaldehyde and the phenol mixing, be warmed up to 70～80 ℃ of insulation reaction 1～2 hour again, add first urea, be warmed up to 85～100 ℃ of insulation reaction again after 15～30 minutes;
Cool to 60-80 ℃ and add second batch of urea, be warmed up to 90～100 ℃ of insulation reaction 15～30 minutes again, regulate pH value to 5～7 then, react present the white opacity shape to reaction system after;
Regulate pH value to 7～9, add the 3rd batch of urea, cool to 50-65 ℃, insulation reaction 30～60 minutes and getting;
Wherein, first, the mass ratio of second batch and the 3rd batch urea is 50-70:20-40:5-15, is specially 55:35:10.
8. according to the arbitrary described method of claim 1-7, it is characterized in that: in the step (1), in the described blending process, temperature is 40 ℃, and the time of mixing is 50min.
9. according to the arbitrary described method of claim 1-8, it is characterized in that: in the step (3), the technology of preparation urea-formaldehyde resin foam comprises the steps: to stir foaming liquid with stirrer under the room temperature, blast the pressurized air of 0.2～0.9MPa simultaneously by air compressor, be pressed into air filled cavity, when treating that foam volume reaches the highest, continue to stir, the mixture that adds described mineral filler and phenol modified urea-formaldehyde resins simultaneously, stirring and evenly mixing, it is stable to treat that material becomes, behind the foam, move in the mould uniformly, solidified 24-48 hour at 35～50 ℃, obtain inorganic compounding phenol modified urea-formaldehyde resins foam.
10. the inorganic compounding phenol modified urea-formaldehyde resins foam that is prepared by the arbitrary described method of claim 1-9;
And/or the character of described inorganic compounding phenol modified urea-formaldehyde resins foam is at least a in following: foam density is 62-85Kg/m
3, be specially 82-85Kg/m
3Compressive strength 0.16-0.26MPa is specially 0.25MPa-0.26MPa; Tensile strength 0.13-0.17MPa is specially 0.14MPa-0.16MPa; Thermal conductivity 0.034-0.035W/KM is specially 0.034W/KM; Calorific value≤3.0KJ/kg is specially 2.35-2.99KJ/kg, is specially 2.35KJ/kg-2.5KJ/kg again.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105131513A (en) * | 2015-09-27 | 2015-12-09 | 常州市奥普泰科光电有限公司 | Preparation method of heat preservation foaming plate doped with modified urea-formaldehyde resin |
| CN105566846A (en) * | 2014-10-17 | 2016-05-11 | 王长志 | Modified amino foam insulation board and preparation method thereof |
| CN107556698A (en) * | 2017-10-12 | 2018-01-09 | 溧阳市乔森塑料有限公司 | A kind of high temperature resistant urea moulding material and preparation method thereof |
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| CN101029164A (en) * | 2007-03-09 | 2007-09-05 | 刘兴国 | Urea-resin foaming thermal-insulating composite powder, the synthetic board therewith and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101029164A (en) * | 2007-03-09 | 2007-09-05 | 刘兴国 | Urea-resin foaming thermal-insulating composite powder, the synthetic board therewith and method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566846A (en) * | 2014-10-17 | 2016-05-11 | 王长志 | Modified amino foam insulation board and preparation method thereof |
| CN105131513A (en) * | 2015-09-27 | 2015-12-09 | 常州市奥普泰科光电有限公司 | Preparation method of heat preservation foaming plate doped with modified urea-formaldehyde resin |
| CN107556698A (en) * | 2017-10-12 | 2018-01-09 | 溧阳市乔森塑料有限公司 | A kind of high temperature resistant urea moulding material and preparation method thereof |
| CN107556698B (en) * | 2017-10-12 | 2019-08-09 | 溧阳市乔森塑料有限公司 | A kind of high temperature resistant urea moulding material and preparation method thereof |
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