A kind of preparation method of flame melamine rigid foamTechnical field
The invention belongs to polymeric foamed material technical field, be specially a kind of preparation method of flame melamine rigid foam.
background technology
In recent years, domestic construction field fire takes place frequently, and particularly the fire of Highrise buildings causes great property damage and loss of life and personal injury, and one of its reason is exactly rapid spread and the expansion that inflammable external-wall heat-insulation material result in the intensity of a fire.For this reason, the Ministry of Public Security, house and town and country construction portion have successively issued No. 46 literary compositions, and No. 65 literary compositions, a series of file and the notices such as No. 350 literary compositions, the flame retardant properties of External Wall lagging material has made clear and definite regulation, and requires various places strict implement.But be limited to the character of external-wall heat-insulation material itself, conventional inorganic external wall thermal-insulation material, although meet national standard as flame retardant propertiess such as rock wool, glass, foam cements, thermal conductivity is higher, do not meet the related request to newly-built house energy-saving heat preserving.And existing organic insulation material, as lower in thermal conductivitys such as EPS, XPS, urethane, but be all inflammable material, and a large amount of toxic smogs can be discharged in combustion, secondary injury can be caused to personnel when fire occurs.Although their fire retardancy all increases after adding fire retardant, As time goes on, fire retardant can lose gradually and cause its flame retardant properties obviously to reduce.In addition, also there is respective limitation in them, and if EPS, XPS are thermoplastic material, can shrink under high temperature, dimensional stability is not good; Overwhelming majority urethane is difficult to the requirement reaching GB8624-2012B1 level, and it is very high seldom partly to meet the requirements of polyurethane material price, and cost pressure is excessive and be difficult to large-scale application.And there is low strength, the defect that water-intake rate is higher in the phenolic foam material that can meet flame retardant properties requirement.Therefore, market is needed a kind of fire-retardant and excellent thermal insulation performance badly, and affordable, the external-wall heat-insulation material that physicals can meet the demands again.
Trimeric cyanamide is often added into due to the flame retardant properties of its excellence in various material for improving the fire retardancy of goods, the terpolycyantoamino-formaldehyde resin foam prepared by trimeric cyanamide and formaldehyde inherits this advantage, can show excellent flame retardant properties without the need to adding any fire retardant.But the defect existed due to terpolycyantoamino-formaldehyde resin foam and technical still open question, for a long time, more energy is put in the research and development of terpolycyantoamino-formaldehyde resin open celled foam by researcher, and apply it to clean, insulation and acoustics adjustment field, achieve immense success.But this foam causes its water-intake rate excessive because its percentage of open area is high, its intensity can not meet the requirement of external-wall heat-insulation material in addition, is thus difficult to terpolycyantoamino-formaldehyde resin open celled foam to be applied to exterior-wall heat insulation field.In comparison, trimeric cyanamide closed-cell foam is well positioned to meet the requirement of external-wall heat-insulation material.The document published as, the preparation method of a kind of melamine formaldehyde resin closed-cell foam disclosed in CN201210328428, foam obtained by this method has higher rate of closed hole and oxygen index, thermal conductivity is also lower, but its obtained foam prepolymer resin is solid-state, need could use after the dissolving of adjusting adhesive, particularly its adjusting adhesive is inflammable organic solvent, reduces the flame retardant properties of its foam to a certain extent.In addition, its performed polymer is solid-stately too increase its industrialized difficulty.CN201310646482 have employed the viscosity of the method reduction resin of etherify melamine resin in acid condition, and uses polyoxyethylene glycol etc. to improve the toughness of resin, also achieves useful effect.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of method preparing melamine formaldehyde resin closed-cell foam, adopt the melamine formaldehyde resin closed-cell foam not easily efflorescence that this method is obtained, ultimate compression strength is high, strong with base material viscosifying power, foam prepolymer resin viscosity is suitable for simultaneously, is convenient to realize industrialization continuous seepage.
Technical scheme of the present invention is:
1) synthesis of modified melamine-formaldehyde resin
Flame melamine rigid foam disclosed in this invention, the building-up process of its foaming prepolymer resin comprises: trimeric cyanamide, paraformaldehyde, properties-correcting agent I and solvent are added in the reaction vessel of band stirring, open and stir, material pH value is adjusted to 9-11 with trolamine or oxyhydroxide, react under 75 DEG C of water-baths to material clear, add properties-correcting agent II, after continuing reaction 0.5-2h, open solvent removed by vacuum, and with between water adjustment material solid content to 85%-92%, cooling obtains transparent prepolymer resin.Its main component comprises: trimeric cyanamide and paraformaldehyde mol ratio 1:1.5-3.5, preferred 1:2.5-3.Trimeric cyanamide and properties-correcting agent I mass ratio 1:0.1-0.8, preferred 1:0.2-0.6, trimeric cyanamide and properties-correcting agent II mass ratio 1:0.05-0.2.Described properties-correcting agent I is selected from any one or a few the mixture in first band trimeric cyanamide, benzoguanamine, hydroxyl ethoxyethyl trimeric cyanamide, three (2-hydroxyethyl) chlorinated isocyanurates, urea, Dyhard RU 100, described properties-correcting agent II is selected from carbonic ether in ester compound and oxalic acid ester compound, any one or a few the mixture further preferably in methylcarbonate, diethyl carbonate, dimethyl oxalate, oxalic acid diethyl ester, NSC 11801, propylene carbonate.Described solvent is selected from alcohols material, particular methanol, ethanol, propyl alcohol or Virahol.
2) preparation of flame melamine rigid foam
Measure the modified melamine-formaldehyde resin performed polymer obtained in 100 mass parts step 1), after it is mixed under high velocity agitation with tensio-active agent, solidifying agent, whipping agent, auxiliary agent, pour in pre-prepd mould, put into baking oven or microwave chemical reactor, foam 15-30min at 60-80 DEG C, obtains flame melamine rigid foam at transferring to 80-120 DEG C after slaking 2-3h.Described tensio-active agent is selected from any one or a few the mixture in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, nonylphenol polyoxyethylene ether sulfate.Described solidifying agent is selected from any one or a few the mixture in formic acid, acetic acid, oxalic acid, tosic acid, sulfuric acid, phosphoric acid, hydrochloric acid.Described whipping agent is selected from any one or a few the mixture in Skellysolve A, pentamethylene, normal hexane, hexanaphthene, a fluorine ethylene dichloride.Described auxiliary agent is selected from any one or a few the mixture in silicone oil, silane coupling agent.
In view of the easy efflorescence shown in melamine formaldehyde resin closed-cell foam preparation, intensity is low, the shortcoming that prepolymer resin viscosity is large, basic ideas of the present invention are at terpolycyantoamino-formaldehyde resin synthesis phase, add the properties-correcting agent of low functionality, reduce the cross-linking density of terpolycyantoamino-formaldehyde resin, thus improve the fragility of melamine formaldehyde resin closed-cell foam, improve the intensity of foam.React under the condition being solvent with water, the terpolycyantoamino-formaldehyde resin viscosity of high solids content rises very fast, the viscosity of wayward resin.And we find, be solvent with alcohol and with carbonates or oxalic acid ester compound generation permutoid reaction after obviously can reduce the viscosity of resin, its reason may be in the basic conditions, methylol structure in Ester and resin there occurs permutoid reaction, and the low mass molecule alcohol that reaction produces is sloughed subsequently under vacuum, molecular balance is impelled to move to methylol structure generation change of direction, improve the transformation efficiency of permutoid reaction, and not only introduce partially modified segment by the modified melamine-formaldehyde resin that permutoid reaction obtains, also reduce further its cross-linking density simultaneously, thus improve the viscosity of resin and the fragility of foam.Meet water in the basic conditions due to Ester to be easily hydrolyzed, thus reaction adopts alcohols material as solvent to avoid the generation be hydrolyzed.
Compared with prior art, beneficial effect of the present invention is:
The flame melamine rigid foam that the present invention obtains, by to the modification of terpolycyantoamino-formaldehyde resin and the improvement of foam process, reduce the cross-linking density of terpolycyantoamino-formaldehyde resin, thus improve the fragility of melamine formaldehyde resin closed-cell foam, improve the intensity of melamino-formaldehyde foam.Make the foam not dry linting obtained, cohesiveness is strong, can use with the various Material cladding such as metal, non-woven fabrics, cement.High rate of closed hole effectively can reduce water-intake rate and the thermal conductivity of foam, thus makes it can be applied to air conditioning wind pipe, sandwich board and building exterior wall heat preserving market.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.These embodiments are that the present invention is not limited to this or is limited to further elaboration of the present invention.These those of skill in the art can make some nonessential improvement according to described summary of the invention and adjustment is implemented, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1:
By 252g trimeric cyanamide, 75.6g benzoguanamine, 205g paraformaldehyde, 40g hydroxyl ethoxyethyl trimeric cyanamide and 150g deionized water add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use potassium hydroxide that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 25g methylcarbonate, vacuum removal deionized water is opened after continuing reaction 1h, obtain 110g overhead product, material cannot normally stir, add 85.5g deionized water and resin solid content is adjusted to 88%, resin viscosity 380000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, solidifying agent tosic acid 5g, whipping agent Skellysolve A 5g, auxiliary agent silane coupling agent Z6011(Dow corning chemical company) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 70 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF1.
Embodiment 2:
By 252g trimeric cyanamide, 75.6g benzoguanamine, 205g paraformaldehyde, 40g hydroxyl ethoxyethyl trimeric cyanamide and 150g ethanol add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use potassium hydroxide that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 25g methylcarbonate, open vacuum removal ethanol after continuing reaction 1h, obtain 132g overhead product, add 63.5g deionized water and resin solid content is adjusted to 88%, resin viscosity 80000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, solidifying agent tosic acid 5g, whipping agent Skellysolve A 5g, auxiliary agent silane coupling agent Z6011(Dow corning chemical company) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 70 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF2.
Embodiment 3:
By 252g trimeric cyanamide, 50.4g first substituted melamine, 213g paraformaldehyde, 50g hydroxyl ethoxyethyl trimeric cyanamide and 150g ethanol add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use trolamine that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 35g NSC 11801, open vacuum removal ethanol after continuing reaction 1h, obtain 140g overhead product, add 60.4g deionized water and resin solid content is adjusted to 89.5%, resin viscosity 150000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, solidifying agent phosphoric acid (85%) 5g, whipping agent Skellysolve A 5g, auxiliary agent phenol formaldehyde foam silicone oil FQ-5502(Jiangsu Maysta Chemical Co., Ltd.) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 70 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF3.
Embodiment 4 "
By 252g trimeric cyanamide, 78.6g tri-(2-hydroxyethyl) chlorinated isocyanurates, 205g paraformaldehyde, 40g hydroxyl ethoxyethyl trimeric cyanamide and 150g Virahol add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use trolamine that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 30g propylene carbonate, vacuum removal Virahol is opened after continuing reaction 1h, obtain 134g overhead product, add 74.5g deionized water and resin solid content is adjusted to 87%, resin viscosity 50000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and tensio-active agent nonylphenol polyoxyethylene ether sulfate 1.5g, formic acid (87%) 3g, whipping agent normal hexane 5g, auxiliary agent silane coupling agent SH6030(Dow corning chemical company) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 75 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF4.
Embodiment 5:
By 252g trimeric cyanamide, 42g Dyhard RU 100,200g paraformaldehyde, 50g hydroxyl ethoxyethyl trimeric cyanamide and 150g methyl alcohol add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use sodium hydroxide that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 35g methylcarbonate, open vacuum removal methyl alcohol after continuing reaction 1h, obtain 142g overhead product, add 94.2g deionized water and resin solid content is adjusted to 85%, resin viscosity 15000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and tensio-active agent nonylphenol polyoxyethylene ether sulfate 1.5g, sulfuric acid (85%) 5g, whipping agent pentamethylene 5g, auxiliary agent FQ-5503(Jiangsu Maysta Chemical Co., Ltd.) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 70 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF5.
Embodiment 6:
By 252g trimeric cyanamide, 25.2g urea, 205g paraformaldehyde, 35g hydroxyl ethoxyethyl trimeric cyanamide and 150g propyl alcohol add in the glass flask of 1L band stirring, open stirring mixing of materials is even, use diethanolamine that material PH is adjusted to about 9.0, react under 75 DEG C of water-baths to material clear, add 40g dimethyl oxalate, open vacuum removal propyl alcohol after continuing reaction 1h, obtain 138g overhead product, add 67.6g deionized water and resin solid content is adjusted to 87.5%, resin viscosity 65000cps(25 DEG C), cool for subsequent use.
Get this resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, solidifying agent phosphoric acid (85%) 5g, whipping agent one fluorine ethylene dichloride 5g, auxiliary agent Z6020(Dow corning chemical company) 3g Forced Mixing under 1200rpm is even, pour in preprepared mould, put into 70 DEG C of baking ovens foam be transferred to 120 DEG C after 15min at solidify 2h, obtain foam MF6.
Then tested by the foam obtained in embodiment 1 to embodiment 6, every test is all carried out according to GB.Test result is as following table:
| Project | Unit | MF1 | MF2 | MF3 | MF4 | MF5 | MF6 |
| Density | kg/m | 95 | 62 | 65 | 60 | 60 | 60 |
| Thermal conductivity | w/m·k | 0.045 | 0.030 | 0.031 | 0.028 | 0.026 | 0.030 |
| Compression performance | kpa | Break | 305 | 350 | 288 | 285 | 275 |
| Volume water absorption rate | % | 1.0 | 3.6 | 3.2 | 3.8 | 3.7 | 4.2 |
| Rate of closed hole | % | 96 | 92 | 93 | 90 | 91 | 87 |
| Dimensional stability | % | 0.2 | 1.2 | 1.0 | 1.4 | 1.4 | 1.6 |
The resin obtained by embodiment one is very big due to viscosity, normally cannot bubble, cause its density too high at foaming stages, and foam is crossed and crisply deformation cannot be occurred, and breaks when thus carrying out compression performance test.
Density is tested according to GB/T6343-2009;
Thermal conductivity is tested according to GB/T10294-2008 Technology of Steady State Thermal Resistance of Thermal Insulating Material;
Compressive strength is tested according to GB/T15048-1994 rigid foam compression creep test method;
Volume water absorption rate is tested according to GB/T8810-2005 rigid foam water-intake rate;
Rate of closed hole uses ultrafoam true density instrument to test;
Dimensional stability GB/T8811-2008 rigid foam dimensional stability test method is tested.
The resin obtained by the present invention has lower viscosity, more easily realizes industrialization, and the foam rate of closed hole obtained by this resin-made is high, and excellent thermal insulation performance, is applicable to as lagging material.