CN101475728B - Phenolic foam for exterior wall heat preservation and preparation thereof - Google Patents
Phenolic foam for exterior wall heat preservation and preparation thereof Download PDFInfo
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- CN101475728B CN101475728B CN2009100284375A CN200910028437A CN101475728B CN 101475728 B CN101475728 B CN 101475728B CN 2009100284375 A CN2009100284375 A CN 2009100284375A CN 200910028437 A CN200910028437 A CN 200910028437A CN 101475728 B CN101475728 B CN 101475728B
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Abstract
The invention relates to phenolic foam for external wall insulation and a preparation method thereof, which belong to the technical field of building material. The phenolic foam comprises the following raw materials in portion by weight: 100 portions of myrica extract modified phenol-formaldehyde resin, 1 to 8 portions of a foam homogenizing agent, 5 to 20 portions of a foaming agent, and 10 to 20 portions of a firming agent, wherein the myrica extract modified phenol-formaldehyde resin is prepared from the following compositions in portion by weight: 100 portions of phenol, 200 to 300 portions of a formaldehyde solution, 12 to 25 portions of a myrica extract solution, 0.5 to 8 portions of metal oxide, 4 to 30 portions of a modifying addition agent, and 1 to 20 portions of a mixed catalyst. The phenolic foam has the advantages that the phenolic foam has fine foaming pores, high porosity by closed pore, low coefficient of heat conductivity, low water absorption, high strength and good dimension stability, can be used as an external wall insulating material, has the advantages of simple manufacture, easily obtained raw materials and low cost, and is applicable to mass production.
Description
Technical field
The present invention relates to phenolic foam for exterior wall heat preservation, also relate to its preparation method simultaneously, belong to building material technical field.
Background technology
Phenol formaldehyde foam is a kind of thermal insulation material of hard closed pore, characteristics such as low smokiness, dimensional stability when having good thermal insulation, flame retardant resistance, burning, and easily processing, and production cost is low, is extensive use of as various material of construction in recent years.But existing phenol formaldehyde foam also exists various shortcomings, and for example rate of closed hole is low, the easy perforate of foam, and fragility is big, long-time uses easily aging becoming fragile even efflorescence etc., and phenol formaldehyde foam is met water and met also degraded, weightlessness easily of the time of tide.These shortcomings of existing phenol formaldehyde foam have greatly limited it and had comparatively ideal thermal conductivity, intensity and anti-aging stability in long-time, therefore be difficult to be applied to the exterior-wall heat insulation field, the warming plate that present domestic phenol formaldehyde foam is made can only be used for the insulation of central air-conditioning airduct.In recent years, the derived product of petrochemical complex class is subjected to resource limit, needs a kind of renewable resources of alternative petrochemical complex series products to prepare phenol formaldehyde foam.
Summary of the invention
The objective of the invention is: at the problem of prior art existence, provide a kind of when skin is possessed excellent heat insulation function, the phenolic foam for exterior wall heat preservation that also has good durability, crushing resistance, closed pore and heat insulating ability provides its preparation method simultaneously.
For achieving the above object, a technical scheme of the present invention provides phenolic foam for exterior wall heat preservation, and this phenol formaldehyde foam is made by following weight part proportioning raw material: 100 parts of myrica extract modified phenolic resinss, 1～8 part of foam stabilizer, 5～20 parts of whipping agents, 10～20 parts in solidifying agent; Described myrica extract modified phenolic resins is formulated by each component of following weight part: 100 parts of phenol, 200～300 parts of formaldehyde solutions, 12～25 parts of myrica extract solution, 0.5～8 part of metal oxide, 4～30 parts of modified additives, 1～20 part of mixed catalyst.
Mixed catalyst described in the technique scheme is made up of ammoniacal liquor and metal oxide, and the mass ratio of described ammoniacal liquor and metal oxide is 0.3: 1～5: 1; Described modified additive is an organic amine compound, at least a in preferred hexanediamine, tetradecy lamine, cetylamine, the stearylamine.
At least a in the preferred calcium oxide of metal oxide described in the technique scheme, magnesium oxide, cupric oxide, the ferric oxide.
Foam stabilizer described in the technique scheme is a Tween-60, tween-80, at least a among the organosilicon DC193; Described whipping agent is the non-halogenated compound of alkanes, at least a in preferred normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, the hexanaphthene; Described solidifying agent is at least a in hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, tosic acid, the xylene monosulfonic acid.
For achieving the above object, the invention provides the preparation method of phenolic foam for exterior wall heat preservation, its method may further comprise the steps:
1) by weight ratio 1/4th to 1/2nd (i.e. 50～150 parts of formaldehyde solutions), the metal oxide of 12～25 parts, 200～300 parts formaldehyde solutions of myrica extract solution joined in the reactor for 0.5～8 part, stir, be cooled to below 40 ℃ after 15～60 minutes in reaction under 50～85 ℃;
2) adding 100 parts of phenol, 4～30 parts of modified additives, mixed catalyst by weight ratio in reactor mixes for 1～20 part, be incubated 25～50 minutes and divide remaining formaldehyde solution (promptly 1/2nd of 200～300 parts of formaldehyde solutions to 3/4ths) 3～5 times and add, be warming up to 95～120 ℃, react and be cooled to below 40 ℃ after 20～40 minutes, add acid again and regulate pH value to neutral;
3) at vacuum tightness 10～15KPa, underpressure distillation dehydration gets promptly that water content is 3～15%, viscosity is the myrica extract modified phenolic resins of 1000～30000mPas under 60～80 ℃ of conditions of temperature;
4) by weight ratio with 100 parts of myrica extract modified phenolic resinss, 1～8 part of foam stabilizer, 5～20 parts of mixing of whipping agent, add 10～20 parts in solidifying agent again, vigorous stirring makes it to mix, pour mixture into mould, under 50～95 ℃ of conditions, solidified 5～120 minutes, obtain rate of closed hole at the phenol formaldehyde foam more than 95%.
Add mass ratio described in the technique scheme in the reactor and be 0.3: 1～5: 1 ammoniacal liquor and metal oxide as mixed catalyst; Add at least a in hexanediamine, tetradecy lamine, cetylamine, the stearylamine in the described reactor as modified additive.
At least a in the preferred calcium oxide of metal oxide described in the technique scheme, magnesium oxide, cupric oxide, the ferric oxide.
The solution of myrica extract described in the technique scheme is that 30%～75% Cortex Myricae Rubrae extract makes by tannin content.
Used for building exterior wall phenolic resin foam provided by the invention has the following advantages:
1, excellent performance.Adopt the myrica extract modified phenolic resins as main component, and the macromole tannin structure in the myrica extract can be improved foamy fragility, improve its fire line, therefore the over-all propertieies such as water tolerance, crushing resistance and closed pore of phenol formaldehyde foam are improved, are suitable for the outer insulation of external wall.
2, reaction efficiency height.Adopt mixed catalyst to add in batches, make entire reaction course steadily controlled, avoided the reactor local temperature instability that causes because of exothermic heat of reaction, improved the quality and the reaction efficiency of reactant.
3, safety and environmental protection.Adopt myrica extract to replace the petroleum-type product as raw material; Select for use alkane derivative as whipping agent simultaneously, avoid producing carbonic acid gas, no Greenhouse effect coefficient; And by organic amine compound in conjunction with free formaldehyde, reduced the content of formaldehyde in the foam.
In a word, phenol formaldehyde foam abscess exquisiteness of the present invention, the rate of closed hole height, thermal conductivity is low, and water-intake rate is low, the intensity height, dimensional stability is good, is suitable for to make architecture exterior wall insulating materials; Make simply, raw material is easy to get, and cost is low, is fit to mass production.
Embodiment
Below by specific embodiment the present invention further is illustrated.
Embodiment 1
Cortex Myricae Rubrae through water logging, concentrate, drying makes the myrica extract of tannin content between 30%～75%, is 20%～50% myrica extract solution with the water-soluble mass ratio that obtains of myrica extract again.Add 64.1kg myrica extract solution in 1 ton of reactor, the 200kg mass ratio is 37% formaldehyde solution, and 10kg magnesium oxide stirs, and 50 ℃ of following addition reactions 60 minutes, generates the lower molecular weight adduct that contains the methylol active group.Be cooled to below 40 ℃, add 400kg phenol, 4kg tetradecy lamine, 5kg ammoniacal liquor (density 0.92g/cm
3), 10kg magnesium oxide stirs, and be incubated 25 minutes, and divides and add remaining 423kg formaldehyde solution for 3 times, is warming up to 95 ℃ of polycondensations 40 minutes, generates polycondensation product, is cooled to then below 40 ℃, adds acetic acid accent pH value to 7 again.In reaction process, tetradecy lamine utilizes amino and self snappiness group to insert in the phenolic aldehyde molecule on the one hand, increases its flexibility and rate of closed hole, combines with free formaldehyde on the other hand, has reduced the content of formaldehyde in the myrica extract modified phenolic resins.60 ℃ of temperature, underpressure distillation is 2 hours under the 10KPa condition, and obtaining viscosity is 4000mPas, and water content is 15% myrica extract modified phenolic resins.
Get myrica extract modified phenolic resins 100kg, tween-80 3kg, Skellysolve A 25kg mixes, add tosic acid 12kg again, xylene monosulfonic acid 2kg, vigorous stirring is 2 minutes under the room temperature, pour mixture into mould, solidified 95 minutes at 50 ℃, obtaining density is 34kg/m
3Phenol formaldehyde foam A, it is carried out The performance test results sees Table 1.
Embodiment 2
Adding the 80kg mass ratio in 1 ton of reactor is 20%～50% myrica extract solution (method of making myrica extract solution is with embodiment 1), the 400kg mass ratio is 37% formaldehyde solution, the 2kg calcium oxide, stir, reacted 50 minutes down at 60 ℃, be cooled to below 40 ℃, add 400kg phenol, the 4kg hexanediamine, 5kg ammoniacal liquor (density 0.92g/cm
3), the 8kg calcium oxide stirs, and be incubated 30 minutes, and divides and add remaining 410kg formaldehyde solution for 4 times, is warming up to 95 ℃ of reactions 30 minutes, is cooled to then below 40 ℃, adds acetic acid accent pH value to 7 again.70 ℃ of temperature, underpressure distillation is 2 hours under the 12KPa condition, and obtaining viscosity is 9000mPas, and water content is 10% myrica extract modified phenolic resins.
Get myrica extract modified phenolic resins 100kg, organosilicon DC193 3kg, normal butane 15kg mixes, add tosic acid 8kg again, phosphatase 24 kg, vigorous stirring is 5 minutes under the room temperature, pour mixture into mould, solidified 75 minutes at 65 ℃, obtaining density is 32kg/m
3Phenol formaldehyde foam B, it is carried out The performance test results sees Table 1.
Embodiment 3
Adding the 50kg mass ratio in 1 ton of reactor is 20%～50% myrica extract solution (method of making myrica extract solution is with embodiment 1), the 300kg mass ratio is 37% formaldehyde solution, 2kg calcium oxide, 2kg magnesium oxide, stir, reacted 35 minutes down at 75 ℃, be cooled to below 40 ℃, add 400kg phenol, the 4kg cetylamine, 5kg ammoniacal liquor (density 0.92g/cm
3), the 5kg calcium oxide stirs, and be incubated 40 minutes, and divides and add remaining 389kg formaldehyde solution for 5 times, is warming up to 110 ℃ of reactions 25 minutes, is cooled to then below 40 ℃, adds acetic acid accent pH value to 7 again.75 ℃ of temperature, underpressure distillation is 2 hours under the 14KPa condition, and obtaining viscosity is 12000mPas, and water content is 6% myrica extract modified phenolic resins.
Get myrica extract modified phenolic resins 100kg, Tween-60 4kg, normal hexane 20kg mixes, and adds xylene monosulfonic acid 6kg again, hydrochloric acid 2kg, vigorous stirring is 8 minutes under the room temperature, pours mixture into mould, solidifies 45 minutes at 80 ℃, and obtaining density is 34kg/m
3Phenol formaldehyde foam ℃, it is carried out The performance test results sees Table 1.
Embodiment 4
Adding the 100kg mass ratio in 1 ton of reactor is 20%～50% myrica extract solution (method of making myrica extract solution is with embodiment 1), the 350kg mass ratio is 37% formaldehyde solution, 5kg calcium oxide, 1kg magnesium oxide, stir, reacted 15 minutes down at 85 ℃, be cooled to below 40 ℃, add 400kg phenol, the 5kg stearylamine, 5kg ammoniacal liquor (density 0.92g/cm
3), 5kg magnesium oxide stirs, and be incubated 50 minutes, and divides and add remaining 350kg formaldehyde solution for 3 times, is warming up to 120 ℃ of reactions 20 minutes, is cooled to then below 40 ℃, adds acetic acid accent pH value to 7 again.80 ℃ of temperature, underpressure distillation is 2 hours under the 15KPa condition, and obtaining viscosity is 15000mPas, and water content is 3% myrica extract modified phenolic resins.
Get myrica extract modified phenolic resins 100kg, tween-80 2kg, organosilicon DC193 2kg, normal hexane 25kg, mix, add tosic acid 8kg again, phosphoric acid 8kg, vigorous stirring is 5 minutes under the room temperature, pour mixture into mould, solidified 30 minutes at 95 ℃, obtaining density is 36kg/m
3Phenol formaldehyde foam D, it is carried out The performance test results sees Table 1.
Get common phenol formaldehyde foam E and carry out performance test, the results are shown in Table 1.
Table 1
| Numbering | Rate of closed hole (%) | Water-intake rate (%) | Ultimate compression strength (kPa) | Thermal conductivity (W/mk) | Oxygen index |
| A | 96 | 4.4 | 139 | 0.024 | 51 |
| B | 97 | 4.1 | 142 | 0.023 | 53 |
| C | 95 | 4.4 | 140 | 0.023 | 51 |
| D | 95 | 4.5 | 140 | 0.025 | 52 |
| E | 76 | 9.8 | 97 | 0.107 | 35 |
This shows that phenolic foam for exterior wall heat preservation of the present invention all has clear improvement than original common phenol formaldehyde foam various aspects of performance index.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (9)
1. phenolic foam for exterior wall heat preservation, it is characterized in that: described phenol formaldehyde foam is made by following weight part proportioning raw material: 100 parts of myrica extract modified phenolic resinss, 1～8 part of foam stabilizer, 5～20 parts of whipping agents, 10～20 parts in solidifying agent; Described myrica extract modified phenolic resins is formulated by each component of following weight part: 100 parts of phenol, 200～300 parts of formaldehyde solutions, 12～25 parts of myrica extract solution, 0.5～8 part of metal oxide, 4～30 parts of modified additives, 1～20 part of mixed catalyst; Described modified additive is at least a in organic amine compound hexanediamine, tetradecy lamine, cetylamine, the stearylamine, and described mixed catalyst is made up of ammoniacal liquor and metal oxide.
2. phenolic foam for exterior wall heat preservation according to claim 1 is characterized in that: the mass ratio of described ammoniacal liquor and metal oxide is 0.3: 1～5: 1.
3. phenolic foam for exterior wall heat preservation according to claim 1 and 2 is characterized in that: described metal oxide is at least a in calcium oxide, magnesium oxide, cupric oxide, the ferric oxide.
4. phenolic foam for exterior wall heat preservation according to claim 1 is characterized in that: described foam stabilizer is at least a among Tween-60, tween-80, the organosilicon DC193.
5. phenolic foam for exterior wall heat preservation according to claim 1 is characterized in that: described whipping agent is at least a in the non-halogenated compound normal butane of alkanes, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, the hexanaphthene.
6. phenolic foam for exterior wall heat preservation according to claim 1 is characterized in that: described solidifying agent is at least a in hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, tosic acid, the xylene monosulfonic acid.
7. the preparation method of phenolic foam for exterior wall heat preservation is characterized in that: may further comprise the steps:
1) by weight ratio 1/4th to 1/2nd and metal oxide of 12～25 parts, 200～300 parts formaldehyde solutions of myrica extract solution joined in the reactor for 0.5～8 part, stir, be cooled to below 40 ℃ after 15～60 minutes in reaction under 50～85 ℃;
2) adding 100 parts of phenol, 4～30 parts of modified additives, mixed catalyst by weight ratio in reactor mixes for 1～20 part, wherein modified additive is at least a in organic amine compound hexanediamine, tetradecy lamine, cetylamine, the stearylamine, mixed catalyst is that mass ratio is 0.3: 1～5: 1 ammoniacal liquor and a metal oxide, be incubated 25～50 minutes and divide 3～5 addings remaining formaldehyde solution, be warming up to 95～120 ℃, react and be cooled to below 40 ℃ after 20～40 minutes, add acid for adjusting pH value again to neutral;
3) at vacuum tightness 10～15KPa, underpressure distillation dehydration gets promptly that water content is 3～15%, viscosity is the myrica extract modified phenolic resins of 1000～30000mPas under 60～80 ℃ of conditions of temperature;
4) by weight ratio with 100 parts of myrica extract modified phenolic resinss, 1～8 part of foam stabilizer, 5～20 parts of mixing of whipping agent, add 10～20 parts in solidifying agent again, vigorous stirring makes it to mix, pour mixture into mould, under 50～95 ℃ of conditions, solidified 5～120 minutes, obtain rate of closed hole at the phenol formaldehyde foam more than 95%.
8. the preparation method of phenolic foam for exterior wall heat preservation according to claim 7 is characterized in that: described metal oxide is at least a in calcium oxide, magnesium oxide, cupric oxide, the ferric oxide.
9. the preparation method of phenolic foam for exterior wall heat preservation according to claim 7 is characterized in that: described myrica extract solution is that 30%～75% Cortex Myricae Rubrae extract makes by tannin content.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100284375A CN101475728B (en) | 2009-01-20 | 2009-01-20 | Phenolic foam for exterior wall heat preservation and preparation thereof |
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| CN2009100284375A CN101475728B (en) | 2009-01-20 | 2009-01-20 | Phenolic foam for exterior wall heat preservation and preparation thereof |
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| CN101475728B true CN101475728B (en) | 2010-10-06 |
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| US9975311B2 (en) | 2010-03-26 | 2018-05-22 | Asahi Kasei Construction Materials Corporation | Phenolic resin foam laminated sheet and method for manufacturing the same |
| WO2012162681A2 (en) * | 2011-05-25 | 2012-11-29 | E. I. Du Pont De Nemours And Company | Mixed tannin-phenolic foams |
| CN102558758B (en) * | 2012-01-04 | 2013-12-25 | 上海柯瑞冶金炉料有限公司 | Phenolic resin foam material and preparing method thereof |
| CN103613904B (en) * | 2013-11-27 | 2016-03-02 | 山东圣泉新材料股份有限公司 | A kind of Low-density low-acidicity phenol formaldehyde foam board and preparation technology thereof |
| CN107446305A (en) * | 2017-07-18 | 2017-12-08 | 合肥广能新材料科技有限公司 | Phenolic resin warming plate and preparation method thereof |
| CN107312292A (en) * | 2017-07-18 | 2017-11-03 | 合肥广能新材料科技有限公司 | Toughening modifying phenolic foam heat insulation plate and preparation method thereof |
| CN107418324A (en) * | 2017-08-03 | 2017-12-01 | 合肥泓定科技有限公司 | Fire resistance high resistant damping paint and preparation method thereof |
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