CN103342830B - 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 PDF

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CN103342830B
CN103342830B CN201310259503.6A CN201310259503A CN103342830B CN 103342830 B CN103342830 B CN 103342830B CN 201310259503 A CN201310259503 A CN 201310259503A CN 103342830 B CN103342830 B CN 103342830B
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modified urea
foam
formaldehyde resins
phenol modified
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CN103342830A (en
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赵彤
王娟
李�昊
翁启赛
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Institute of Chemistry of CAS
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Institute of Chemistry of CAS
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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

A kind of inorganic compounding phenol modified urea-formaldehyde resins foam and preparation method thereof
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 are all energy-conservation keys.For covil construction, mainly realize energy-conservation with lagging material coating layer.But a lot of Highrise buildings wildfire accident reviews occurred in recent years 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 lagging material, conventional have advantage that is lightweight, good effect of heat insulation as styrofoam (PS), urethane (SPU), phenolic aldehyde (PF) etc., but shortcoming be not ageing-resistant, deformation coefficient large, easy firing etc.; Wherein inflammableness forms very large threat to building safety, organic insulation material is through flame-retardant modified, and its flame retardant properties also can only be B level, and once burning will produce hypertoxic gas, the serious threat human life when buildings presence of fire is the important arch-criminal causing great loss of life and personal injury.Inorganic heat insulation material; as thermal insulation separation poor thermal efficiency such as glass bead, pearlstone, closed perlite, rock wools; but fire protection flame retarding is excellent, 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 higher than organic insulation material.
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 preparing inorganic compounding phenol modified urea-formaldehyde resins foam provided by the present invention, comprises the steps:, by mineral filler and phenol modified urea-formaldehyde resins foaming, to 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.
The described method by mineral filler and phenol modified urea-formaldehyde resins foaming can comprise the steps:
(1) inorganic filler surface process:
Mineral filler is mixed with coupling agent, obtains the mineral filler after surface treatment;
(2) mixture of mineral filler and phenol modified urea-formaldehyde resins is prepared:
Mineral filler after described surface treatment and phenol modified urea-formaldehyde resins are mixed, obtains the mixture of mineral filler and phenol modified urea-formaldehyde resins;
(3) foam is prepared
With the mixture of described mineral filler and phenol modified urea-formaldehyde resins, foaming liquid for raw material, utilize the technique preparing urea formaldehyde resin foam, prepare inorganic compounding phenol modified urea-formaldehyde resins foam.
Above-mentionedly prepare in the method for 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;
Above-mentionedly prepare in the method for 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-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane and N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane;
Above-mentionedly prepare in the method for 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, then be specially 0.003:1,0.008:1,0.006:1,0.01:1,0.004:1 or 0.001:1.
Above-mentionedly prepare in the method for 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 for being specially 0.31-0.43:1, then is specially 0.1:1,0.43:1,0.5:1,0.31:1,0.38:1 or 0.4:1.
Above-mentionedly prepare in the method for 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), then 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;
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, described tensio-active agent is selected from following at least one: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl succinate disulfonate acid and lauric acid sodium sulfate;
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, described resin curing agent is acid as curing agent;
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, described acid as curing agent is selected from following at least one: phosphoric acid, sulfuric acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid;
Above-mentionedly prepare in the method for 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, then be specially 1.45:1,0.93:1,1.5:1,0.85:1,0.5:1 or 0.75:1.
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, described phenol modified urea-formaldehyde resins is prepared as follows and obtains: with formaldehyde, phenol and urea for raw material, prepare urea-formaldehyde resin; The molar ratio of described urea, phenol and formaldehyde is 1:0.2 ~ 1.0:2.0 ~ 3.0.
In the preparation method of above-mentioned phenol modified urea-formaldehyde resins, described in the preparation prepared in urea-formaldehyde resin comprise 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, is specially 55:35:10.
In the preparation method of above-mentioned phenol modified urea-formaldehyde resins, can regulate with following all ingredients when adjust ph is 7-9: sodium hydroxide, hexamethylenetetramine, ammoniacal liquor, trolamine, S-WAT or Sodium Tetraborate;
In the preparation method of above-mentioned phenol modified urea-formaldehyde resins, can regulate with following all ingredients when adjust ph is 5-7: as ammonium chloride, ammonium sulfate, formic acid, acetic acid or zinc chloride;
In 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;
In the preparation method of above-mentioned phenol modified urea-formaldehyde resins, 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%.
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, in step (1), in described blending process, temperature is 40 DEG C, and the time of mixing is 50min.
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, in step (1), described mixing uses high-speed kneading machine, and mixing speed is 1000r/min-2000r/min.
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, in step (2), described mixing stirs 45min-90min at being 30 DEG C-50 DEG C.
Above-mentionedly prepare in the method for inorganic compounding phenol modified urea-formaldehyde resins foam, in step (3), foaming liquid is stirred with stirrer under the technique preparing urea formaldehyde resin foam comprises the steps: 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, press-in air filled cavity, when foam volume reaches the highest, continue to stir, add the mixture of described mineral filler and phenol modified urea-formaldehyde resins simultaneously, stirring and evenly mixing, treat that material becomes stable, after uniform foam, move in mould, (45 ~ 55 DEG C of solidifications 30 hours are specially 35 ~ 50 DEG C of solidifications 24-48 hour, be specially again 45 DEG C solidification 30 hours or 55 DEG C solidification 30 hours), obtain inorganic compounding phenol modified urea-formaldehyde resins foam.
The inorganic compounding phenol modified urea-formaldehyde resins foam 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 be following at least one: foam density is 62-85Kg/m 3, be specially 82-85Kg/m 3, then be specially, 62Kg/m 3, 82Kg/m 3, 75Kg/m 3, 85Kg/m 3, 64Kg/m 3, 73Kg/m 3; Compressive strength 0.16-0.26MPa, is specially 0.25MPa-0.26MPa, then is specially 0.16MPa, 0.25MPa, 0.23MPa, 0.26MPa, 0.19MPa, 0.23MPa; Tensile strength 0.13-0.17MPa, is specially 0.14MPa-0.16MPa, then is specially 0.13MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.15MPa, 0.17MPa; 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, then is specially 2.9KJ/kg, 2.35KJ/kg, 2.99KJ/kg, 2.5KJ/kg, 3.45KJ/kg.
The invention still further relates to the application of the phenol-modified urea-formaldehyde foam of above-mentioned inorganic compounding as lagging material.
The phenol-modified urea-formaldehyde foam of inorganic compounding provided by the invention is different from the organo-mineral complexing foam of the inner organic foam core of the outside inorganic material coating of general employing, but a large amount of inorganic materials is dosed in phenol-modified urea-formaldehyde foam organic materials by employing, and realizing foams jointly is prepared from, wherein organic composition is mainly the urea-formaldehyde foam after phenol-modified, inorganic components adopts multiple low heat value powder, the material prepared is homogeneous, has organic materials low thermal conductivity, low density and inorganic materials excellent flame retardant performance concurrently.
The preparation method of the phenol-modified urea-formaldehyde foam lagging material of a kind of novel inorganic compound that the present invention proposes, wherein organic composition is based on urea-formaldehyde resin, and adds a large amount of inorganic powder filler, and product cost is low; The present invention can foaming at approximately room temperature, and preparation process thermal discharge is little, and energy consumption is low, simple to operate, and can realize industrialization continuous seepage.
The phenol-modified urea-formaldehyde foam of the inorganic compounding prepared is while guarantee urea-formaldehyde foam lightweight, low heat conduction, and its flame retardant properties is improved largely, and reaches 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 while guarantee urea-formaldehyde foam lightweight, low heat conduction, and its flame retardant properties is improved largely, and reaches 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 filler, and product cost is low; The present invention can foaming at approximately room temperature, and preparation process thermal discharge is little, and energy consumption is low, simple to operate, and can realize industrialization continuous seepage.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The number of material used in following embodiment is mass parts.
The preparation method of the phenol modified urea-formaldehyde resins used in each embodiment following is as follows:
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;
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, phenol modified urea-formaldehyde resins is prepared
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.
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; % all refers to mass percentage.
Two, foam is prepared
By 5 parts, flyash with at 0.015 part of γ-aminopropyl triethoxysilane 40 DEG C in high-speed kneading machine with the rotating speed mixing 50min of 1000r/min, mix; Temperature of charge is 40 DEG C;
Add the phenol modified urea-formaldehyde resins that 50 parts of methods one are obtained, 40 DEG C are continued to stir 60min, make phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take sodium lauryl sulphate 0.7 part, phosphatase 11 .7 part, 70 parts, water, be mixed with foaming liquid.
72.4 parts of foaming liquids are stirred with homogenizer with the speed of per minute 1000 turns under room temperature, blasted the pressurized air of 0.2MPa by air compressor simultaneously, press-in air filled cavity, when foam volume reaches the highest, continue to stir, add phenol-modified urea aldehyde (PUF) resin and inorganic filler compound simultaneously, stirring and evenly mixing, after stirring 50s, become after stable, uniform foam until material, in rapid immigration mould, 35 DEG C of solidifications 48 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared 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, phenol modified urea-formaldehyde resins is prepared: method is in the same manner as in Example 1.
Two, foam is prepared
Take hollow glass micropearl 26 parts and 0.2 part of γ-glycidyl ether oxygen propyl trimethoxy silicane in high-speed kneading machine with the rotating speed mixing 50min of 1500r/min, mix; Temperature of charge is 40 DEG C;
Add the phenol modified urea-formaldehyde resins that 60 parts of methods one are obtained, stir 90min at 30 DEG C, make phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take Sodium dodecylbenzene sulfonate 0.6 part, 2.2 parts, sulfuric acid, phosphatase 11 .8 part, 51 parts, water, is mixed with foaming liquid.With homogenizer, 55.6 parts of frothed liquids are stirred rapidly, blasted the pressurized air of 0.4MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 50s continues to stir 30s, in rapid immigration mould, 45 DEG C of solidifications 30 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared 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, phenol modified urea-formaldehyde resins is prepared: method is in the same manner as in Example 1.
Two, foam is prepared
Take 30 parts, aluminium hydroxide and 0.19 part of γ-(methacryloxypropyl) propyl trimethoxy silicane in high-speed kneading machine with the rotating speed mixing 50min of 2000r/min, mix; Temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 60 parts of methods one obtained stirs 45min at 50 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take dioctyl succinate disulfonate acid 0.5 part, phthalic acid 3.0 parts, 86.5 parts, water, be mixed with foaming liquid.With homogenizer, 90 parts of frothed liquids are stirred rapidly, blasted the pressurized air of 0.4MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 60s continues to stir 20s, in rapid immigration mould, 50 DEG C of solidifications 36 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared 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, phenol modified urea-formaldehyde resins is prepared: method is in the same manner as in Example 1.
Two, foam is prepared
Take perlite 23 parts and 0.23 part of γ-aminopropyl triethoxysilane in high-speed kneading machine with the rotating speed mixing 50min of 1800r/min, mix; Temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 75 parts of methods one obtained stirs 60min at 40 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take 0.50 part, lauric acid sodium sulfate, 3.3 parts, phenylformic acid, 60 parts, water, be mixed with foaming liquid.With homogenizer, 63.8 parts of frothed liquids are stirred rapidly, blasted the pressurized air of 0.8MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 55s continues to stir 60s, in rapid immigration mould, 55 DEG C of solidifications 30 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared 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, phenol modified urea-formaldehyde resins is prepared: method is in the same manner as in Example 1.
Two, foam is prepared
Take nano-calcium carbonate 5 parts, hollow glass micropearl 15 parts and 0.08 part of γ-glycidyl ether oxygen propyl trimethoxy silicane with the rotating speed mixing 50min of 1400r/min, mix in high-speed kneading machine; Temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 53 parts of methods one obtained stirs 90min at 30 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take Sodium dodecylbenzene sulfonate 0.5 part, 1.0 parts, phenylformic acid, 25 parts, water, be mixed with foaming liquid.With homogenizer, 26.5 parts of frothed liquids are stirred rapidly, blasted the pressurized air of 0.6MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 60s continues to stir 45s, in rapid immigration mould, 45 DEG C of solidifications 24 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared 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, phenol modified urea-formaldehyde resins is prepared: method is in the same manner as in Example 1.
Two, foam is prepared
Take calcium stearate 24 and 0.024 part of γ-glycidyl ether oxygen propyl trimethoxy silicane in high-speed kneading machine with the rotating speed mixing 50min of 1600r/min, mix; Wherein, temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 60 parts of methods one obtained stirs 80min at 50 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take 0.65 part, lauric acid sodium sulfate, 1.5 parts, sulfuric acid, Monochloro Acetic Acid 0.6 part, 42 parts, water, be mixed with foaming liquid.With homogenizer, 44.75 parts of frothed liquids are stirred rapidly, blasted the pressurized air of 0.9MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 50s continues to stir 60s, in rapid immigration mould, 44 DEG C of solidifications 30 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
Recording the PUF foam density prepared is 73.35Kg/m 3, compressive strength 0.2269MPa, tensile strength 0.1653MPa, thermal conductivity 0.035W/KM, calorific value 3.451KJ/kg.
Comparative example 1,
Take sodium lauryl sulphate 0.52 part, phosphatase 11 .7 part, 60 parts, water, be mixed with foaming liquid.
With homogenizer, frothed liquid is stirred rapidly, blasted the pressurized air of 0.4MPa by air compressor simultaneously, add the obtained phenol modified urea-formaldehyde resins of 50 parts of methods one after stirring 60s to continue to stir 60s, in rapid immigration mould, 35 DEG C of solidifications 24 hours, obtain phenol-modified urea aldehyde (PUF) foam.
This comparative example does not add mineral filler.Recording the PUF foam density prepared is 51.6Kg/m 3, compressive strength 0.1232MPa, tensile strength 0.1106MPa, thermal conductivity 0.032W/KM, calorific value 17.12KJ/kg.
Comparative example 2,
Take 2.5 parts, flyash and 0.013 part of γ-glycidyl ether oxygen propyl trimethoxy silicane in high-speed kneading machine with the rotating speed mixing 50min of 2000r/min; Wherein, temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 50 parts of methods one obtained stirs 60min at 40 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take Sodium dodecylbenzene sulfonate 0.45 part, phenylformic acid: 2.8 parts, 45 parts, water, be mixed with foaming liquid.
With homogenizer, frothed liquid is stirred rapidly, blasted the pressurized air of 0.4MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 60s continues to stir 60s, in rapid immigration mould, 50 DEG C of solidifications 24 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
This comparative example mineral filler add-on is less.Recording the PUF foam density prepared is 64.35Kg/m 3, compressive strength 0.1312MPa, tensile strength 0.1120MPa, thermal conductivity 0.034W/KM, calorific value 15.11KJ/kg.
Comparative example 3,
Take 30 parts, aluminium hydroxide and in high-speed kneading machine, mix 50min with 0.15 part of γ-aminopropyl triethoxysilane; Wherein, temperature of charge is 40 DEG C;
The phenol modified urea-formaldehyde resins adding 50 parts of methods one obtained stirs 60min at 40 DEG C, makes phenol-modified urea aldehyde (PUF) resin and inorganic filler compound;
Take Sodium dodecylbenzene sulfonate 0.65 part, phosphoric acid: 2.5 parts, 45 parts, water, be mixed with foaming liquid.
With homogenizer, frothed liquid is stirred rapidly, blasted the pressurized air of 1.0MPa by air compressor simultaneously, the mixture adding phenol modified urea-formaldehyde resins and the mineral filler prepared after stirring 60s continues to stir 60s, in rapid immigration mould, 40 DEG C of solidifications 24 hours, obtain inorganic compounding phenol-modified urea aldehyde (PUF) foam.
This comparative example mineral filler add-on is high.Recording the PUF foam density prepared is 93.14Kg/m 3, foam is crisp, and efflorescence is serious, intensity difference.
Two, three, four phenol modified urea-formaldehyde resins prepared with the following method are carried out the experiment of above-described embodiment 1-6, result all with result in embodiment 1-6 without significant difference.
Method two:
According to the step of step one in 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.
Method three:
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 method two are without substantive difference.
Method four:
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 method two are without substantive difference.

Claims (17)

1. prepare a method for inorganic compounding phenol modified urea-formaldehyde resins foam, comprise the following steps:
(1) inorganic filler surface process:
Mineral filler is mixed with coupling agent, obtains the mineral filler after surface treatment;
(2) mixture of mineral filler and phenol modified urea-formaldehyde resins is prepared:
Mineral filler after described surface treatment and phenol modified urea-formaldehyde resins are mixed, obtains the mixture of mineral filler and phenol modified urea-formaldehyde resins;
(3) foam is prepared
With the mixture of described mineral filler and phenol modified urea-formaldehyde resins, foaming liquid for raw material, utilize the technique preparing urea formaldehyde resin foam, prepare inorganic compounding phenol modified urea-formaldehyde resins foam;
The ratio of weight and number of described mineral filler and described phenol modified urea-formaldehyde resins is 0.1 ~ 0.5:1;
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;
Described coupling agent is selected from as follows: γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane and N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane;
The ratio of quality and the number of copies of described coupling agent and described mineral filler is (0.001-0.01): 1;
Described phenol modified urea-formaldehyde resins is prepared as follows and obtains:
With formaldehyde, phenol and urea for raw material, 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.
2. method according to claim 1, is characterized in that: the ratio of quality and the number of copies of described coupling agent and described mineral filler is (0.008-0.01): 1.
3. method according to claim 1 and 2, 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.
4. method according to claim 1, is characterized in that: described foaming liquid is made up of tensio-active agent, resin curing agent and water; The ratio of quality and the number of copies of tensio-active agent, resin curing agent and water is 1:(2-6.7): (50-173).
5. method according to claim 4, is characterized in that: the ratio of quality and the number of copies of described tensio-active agent, resin curing agent and water is 1:(6.6-6.7): (85-120).
6. method according to claim 4, is characterized in that: described tensio-active agent is selected from following at least one: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl succinate disulfonate acid and lauric acid sodium sulfate.
7. method according to claim 5, is characterized in that: described resin curing agent is acid as curing agent.
8. method according to claim 7, is characterized in that: described acid as curing agent is selected from following at least one: phosphoric acid, sulfuric acid, phthalic acid, phenylformic acid and Monochloro Acetic Acid.
9. method according to claim 8, is characterized in that: 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.
10. method according to claim 9, is characterized in that: the ratio of quality and the number of copies of described foaming liquid and described phenol modified urea-formaldehyde resins is (0.85-0.93): 1.
11. methods according to claim 1 and 2, is characterized in that: described in prepare in urea-formaldehyde resin first, the mass ratio of second batch and the 3rd batch of urea is 55:35:10.
12. according to the arbitrary described method of claim 1 or 2, and it is characterized in that: in step (1), in described blending process, temperature is 40 DEG C, and the time of mixing is 50min.
13. methods according to claim 1 and 2, it is characterized in that: in step (3), foaming liquid is stirred with stirrer under the technique preparing urea formaldehyde resin foam comprises the steps: room temperature, blasted the pressurized air of 0.2 ~ 0.9MPa by air compressor simultaneously, press-in air filled cavity, when foam volume reaches the highest, continue to stir, add the mixture of described mineral filler and phenol modified urea-formaldehyde resins simultaneously, stirring and evenly mixing, treat that material becomes stable, after uniform foam, move in mould, at 35 ~ 50 DEG C of solidification 24-48 hour, obtain inorganic compounding phenol modified urea-formaldehyde resins foam.
14. the inorganic compounding phenol modified urea-formaldehyde resins foam prepared by the arbitrary described method of claim 1-13.
15. methods according to claim 13, is characterized in that: the character of described inorganic compounding phenol modified urea-formaldehyde resins foam be following at least one: foam density is 62-85Kg/m 3; Compressive strength 0.16-0.26MPa; Tensile strength 0.13-0.17MPa; Thermal conductivity 0.034-0.035W/KM; Calorific value≤3.0KJ/kg.
16. methods according to claim 15, is characterized in that: the character of described inorganic compounding phenol modified urea-formaldehyde resins foam be following at least one: foam density is 82-85K g/m 3; Compressive strength is 0.25MPa-0.26MPa; Tensile strength is 0.14MPa-0.16MPa; Thermal conductivity 0.034W/KM; Calorific value is 2.35-2.99KJ/kg.
17. methods according to claim 15 or 16, is characterized in that: described calorific value is 2.35KJ/kg-2.5KJ/kg.
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