CN104250386B - Preparation method of flame-retardant melamine hard foam - Google Patents
Preparation method of flame-retardant melamine hard foam Download PDFInfo
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- CN104250386B CN104250386B CN201410494905.9A CN201410494905A CN104250386B CN 104250386 B CN104250386 B CN 104250386B CN 201410494905 A CN201410494905 A CN 201410494905A CN 104250386 B CN104250386 B CN 104250386B
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Abstract
The invention belongs to the technical field of macromolecular foam materials, and in particular relates to a preparation method of flame-retardant melamine hard foam. The method comprises the steps of performing reaction on melamine and paraformaldehyde according to a mole ratio of 1:(1.5 to 3.5), melamine and a modifier I according to a mass ratio of 1:(0.1 to 0.6) and alcohol serving as a solvent under a water bath of 75 DEG C till the materials are clarified and transparent, adding a modifier II and melamine into resin according to a mass ratio of (0.05 to 0.2):1, continuously performing reaction for 0.5-2 hours, removing the solvent, and adjusting the solid content by water to 85-92 percent to obtain a foam prepolymer. The flame-retardant melamine hard foam prepared by the preparation method disclosed by the invention has the advantages of high compressive strength, high closing rate, excellent flame retardancy and the like, cannot enable powder to fall off and can be applied to the air conditioner air pipe, laminboard and external wall heat preservation material markets.
Description
Technical field
The invention belongs to polymeric foamed material technical field, specially a kind of preparation of flame melamine rigid foam
Method.
Background technology
In recent years, domestic construction field fire takes place frequently, and the fire of particularly skyscraper causes great property loss
And casualties, one of its reason is exactly that inflammable external-wall heat-insulation material result in spreading rapidly and expanding for the intensity of a fire.For this purpose, public
Peace portion, house and town and country construction portion successively issued No. 46 it is literary, No. 65 are literary, No. 350 a series of files and the notices such as literary, External Wall
The fire resistance of insulation material has made clear and definite regulation, and requires various places strict implement.But it is constrained to external-wall heat-insulation material
The property of itself, conventional inorganic external wall thermal-insulation material, although the such as fire resistance such as rock wool, glass, foam cement meets country
Standard, but heat conductivity is higher, is unsatisfactory for the related request to newly-built house energy-saving heat preserving.And existing organic heat-insulating material
The heat conductivitys such as material, such as EPS, XPS, polyurethane are relatively low, but are all combustible materials, and can discharge in combustion a large amount of
Toxic smog, fire occur when can cause secondary injury to personnel.Although their fire retardancy is all after addition fire retardant
Increase, but As time goes on, fire retardant gradually can lose causes its fire resistance substantially to reduce.In addition, it
Also there is respective limitation, such as EPS, XPS are thermoplastic, can be shunk under high temperature, and dimensional stability is not good；It is big absolutely
Some polyurethanes are extremely difficult to the requirement of GB8624-2012B1 levels, and seldom partly reach the polyurethane material price of requirement very
Height, cost pressure is excessive and is difficult to large-scale application.And there is intensity in the phenolic foam material that can meet fire resistance requirement
It is low, the higher defect of water absorption rate.Therefore, a kind of fire-retardant and excellent thermal insulation performance, and affordable, physical property are needed on market badly
The external-wall heat-insulation material for requiring can be met again.
Tripolycyanamide is often added into due to its excellent fire resistance in various materials to be used to improve the fire-retardant of product
Ability, the melamine resin foam prepared by tripolycyanamide and formaldehyde inherit this advantage, need not add any resistance
Combustion agent can show excellent fire resistance.But the defect existed due to melamine resin foam and technically still
An open question, for a long time, more energy are put into melamine resin open celled foam by researcher
In research and development, and cleaning, insulation and acoustics adjustment field are applied it to, achieve immense success.But this foam is due to which
Percent opening is high to cause its water absorption rate excessive, and its intensity can not meet the requirement of external-wall heat-insulation material in addition, thus it is difficult to will
Melamine resin open celled foam is applied to exterior-wall heat insulation field.In comparison, tripolycyanamide closed-cell foam can be well
Meet the requirement of external-wall heat-insulation material.The document published such as, a kind of tripolycyanamide first disclosed in CN201210328428
The preparation method of urea formaldehyde closed-cell foam, foam obtained by this method have higher rate of closed hole and oxygen index (OI), heat conductivity
It is relatively low, but foam prepolymer resin obtained in which is solid-state, needs to use Jing after the dissolving of adjusting adhesive, is particularly which
Adjusting adhesive is inflammable organic solvent, reduces the fire resistance of its foam to a certain extent.Additionally, its performed polymer is in solid-state
Increased its industrialized difficulty.CN201310646482 employs the method drop of etherified melamine polyimide resin in acid condition
The viscosity of low resin, and improve the toughness of resin using Polyethylene Glycol etc., also achieve beneficial effect.
The content of the invention
In order to solve above technical problem, the invention provides a kind of side for preparing melamine formaldehyde resin closed-cell foam
Method, is not pulverized easily using melamine formaldehyde resin closed-cell foam obtained in the method, and comprcssive strength is high, with base material cementitiousness
By force, while foam prepolymer resin viscosity is suitable, facilitate implementation industrialization and continuously produce.
The technical scheme is that：
1）The synthesis of modified melamine-formaldehyde resin
Flame melamine rigid foam disclosed in this invention, the building-up process of its foaming prepolymer resin include：Will
During tripolycyanamide, paraformaldehyde, modifying agent I and solvent add the reaction vessel with stirring, stirring is opened, with triethanolamine or hydrogen
Oxide adjusts material pH value to 9-11, reacts to material clear, adds modifying agent II, continue reaction under 75 DEG C of water-baths
After 0.5-2h, solvent removed by vacuum being opened, and material solid content being adjusted between 85%-92% with water, cooling obtains transparent pre-polymerization
Body resin.Its main component includes：Tripolycyanamide and paraformaldehyde mol ratio 1:1.5-3.5, preferably 1:2.5-3.Tripolycyanamide
With I mass ratio 1 of modifying agent:0.1-0.8, preferably 1:0.2-0.6, tripolycyanamide and II mass ratio 1 of modifying agent：0.05-0.2.Institute
Modifying agent I is stated selected from methyl tripolycyanamide, benzoguanamine, hydroxyl ethoxyethyl tripolycyanamide, three (2- ethoxys) isocyanide urine
Any one or a few mixture in acid esters, carbamide, dicyandiamide, carbonic acid of the modifying agent II in ester type compound
Ester and oxalic acid ester compound, it is even furthermore preferable that dimethyl carbonate, diethyl carbonate, dimethyl oxalate., oxalic acid diethyl
Any one or a few mixture in ester, ethylene carbonate, Allyl carbonate.The solvent is selected from alcohols material, preferably
Methanol, ethanol, propanol or isopropanol.
2）The preparation of flame melamine rigid foam
Measure 100 mass parts steps 1）In the modified melamine-formaldehyde resin performed polymer that obtains, by itself and surface activity
Agent, firming agent, foaming agent, auxiliary agent after mix homogeneously, are poured in pre-prepd mould under high velocity agitation, are put into baking oven or micro-
In ripple chemical reactor, foam at 60-80 DEG C 15-30min, obtains fire-retardant three at transferring to 80-120 DEG C after ripening 2-3h
Poly cyanamid rigid foam.The surfactant is selected from dodecylbenzene sodium sulfonate, sodium lauryl sulphate, polyoxyethylene nonyl phenyl second
Any one or a few mixture in alkene ether sodium sulfate.The firming agent selected from formic acid, acetic acid, oxalic acid, p-methyl benzenesulfonic acid,
Any one or a few mixture in sulphuric acid, phosphoric acid, hydrochloric acid.The foaming agent selected from pentane, Pentamethylene., normal hexane,
Any one or a few mixture in hexamethylene, a fluorine dichloroethanes.The auxiliary agent is in silicone oil, silane coupler
Any one or a few mixture.
In view of the easy efflorescence shown in preparing by melamine formaldehyde resin closed-cell foam, low intensity, prepolymer resin
The big shortcoming of viscosity, the basic ideas of the present invention are, in melamine resin synthesis phase, to add the modified of low degree of functionality
Agent, reduces the crosslink density of melamine resin, so as to improve the fragility of melamine formaldehyde resin closed-cell foam, improves
The intensity of foam.React under conditions of with water as solvent, the melamine resin viscosity of high solids content rises comparatively fast, no
The viscosity of resin easy to control.And it was found that exchanging instead with alcohol as solvent and with carbonates or oxalic acid ester compound
Ying Houneng substantially reduces the viscosity of resin, and its reason is probably that in the basic conditions, Ester is tied with the methylol in resin
Structure there occurs exchange reaction, and react the low mass molecule alcohol for producing and subsequently slough under vacuum, promote reaction balance to hydroxyl
There is change of direction movement in methyl structural, improve the conversion ratio of exchange reaction, and pass through the modified trimerization that exchange reaction is obtained
Cyanamide formaldehyde resin not only introduces partially modified segment, while its crosslink density is also reduce further, so as to improve tree
The fragility of the viscosity and foam of fat.Water is met in the basic conditions due to Ester hydrolysis easily occurs, thus reaction adopts alcohols
Generation of the material as solvent to avoid hydrolyzing.
Compared with prior art, beneficial effects of the present invention are：
Flame melamine rigid foam obtained in of the invention, by the modified of melamine resin and the work that foams
The improvement of skill, reduces the crosslink density of melamine resin, so as to improve melamine formaldehyde resin closed-cell foam
Fragility, improve the intensity of melamino-formaldehyde foam.Obtained foam not dry linting is made, caking property is strong, can be with metal, nonwoven
The various Material claddings such as cloth, cement are used.High rate of closed hole can effectively reduce the water absorption rate and heat conductivity of foam, so that its
Can apply to air conditioning wind pipe, battenboard and building exterior wall heat preserving market.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.These embodiments are to the present invention
It is expanded on further, the present invention is not limited to this or is limited.Technical staff in the field can be according in the invention
Appearance is made some nonessential modifications and adaptations and is implemented, but the scope that this should not be interpreted as above-mentioned theme of the invention is only
It is limited to following embodiments.
Embodiment 1：
By 252g tripolycyanamide, 75.6g benzoguanamines, 205g paraformaldehydes, 40g hydroxyl ethoxyethyl tripolycyanamide and
During 150g deionized waters add the glass flask of 1L band stirrings, open and stir material mix homogeneously, using potassium hydroxide by thing
Material PH is adjusted to 9.0 or so, reacts to material clear, add 25g dimethyl carbonate under 75 DEG C of water-baths, continues reaction 1h
After open vacuum removal deionized water, obtain 110g distillations, material normally cannot be stirred, add 85.5g deionized waters set
Fat solid content is adjusted to 88%, resin viscosity 380000cps（25℃）, cool down standby.
Take resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, firming agent p-methyl benzenesulfonic acid 5g, foaming
Agent pentane 5g, auxiliary agent silane coupler Z6011（Dow corning chemical company）3g Forced Mixings under 1200rpm are uniform,
Pour in preprepared mould, be transferred at 120 DEG C after the 15min that foams in being put into 70 DEG C of baking ovens and solidify 2h, obtain foam
MF1。
Embodiment 2：
By 252g tripolycyanamide, 75.6g benzoguanamines, 205g paraformaldehydes, 40g hydroxyl ethoxyethyl tripolycyanamide and
During 150g ethanol adds the glass flask of 1L band stirrings, open and stir material mix homogeneously, using potassium hydroxide by material PH
Adjust to 9.0 or so, react under 75 DEG C of water-baths to material clear, add 25g dimethyl carbonate, open after continuing reaction 1h
Vacuum removal ethanol, obtains 132g distillations, adds 63.5g deionized waters resin solid content to be adjusted to 88%, resin viscosity
80000cps（25℃）, cool down standby.
Take resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, firming agent p-methyl benzenesulfonic acid 5g, foaming
Agent pentane 5g, auxiliary agent silane coupler Z6011（Dow corning chemical company）3g Forced Mixings under 1200rpm are uniform,
Pour in preprepared mould, be transferred at 120 DEG C after the 15min that foams in being put into 70 DEG C of baking ovens and solidify 2h, obtain foam
MF2。
Embodiment 3：
By 252g tripolycyanamide, 50.4g methyl tripolycyanamide, 213g paraformaldehydes, 50g hydroxyl ethoxyethyl tripolycyanamide and
During 150g ethanol adds the glass flask of 1L band stirrings, open and stir material mix homogeneously, using triethanolamine by material PH
Adjust to 9.0 or so, react under 75 DEG C of water-baths to material clear, add 35g ethylene carbonates, open after continuing reaction 1h
Vacuum removal ethanol, obtains 140g distillations, adds 60.4g deionized waters resin solid content to be adjusted to 89.5%, resin viscosity
150000cps（25℃）, cool down standby.
Take resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, firming agent phosphoric acid（85%）5g, foaming agent
Pentane 5g, auxiliary agent phenol formaldehyde foam silicone oil FQ-5502（Jiangsu Maysta Chemical Co., Ltd.）3g is forced under 1200rpm
Mix homogeneously, pours in preprepared mould, is transferred at 120 DEG C and solidifies 2h in being put into 70 DEG C of baking ovens after the 15min that foams,
Obtain foam MF3.
Embodiment 4：
By 252g tripolycyanamide, 78.6g tri- (2- ethoxys) chlorinated isocyanurates, 205g paraformaldehydes, 40g hydroxyl ethoxyethyls
During tripolycyanamide and 150g isopropanols add glass flasks of the 1L with stirring, stirring is opened by material mix homogeneously, using three second
Hydramine adjusts material PH to 9.0 or so, reacts to material clear, add 30g Allyl carbonaties under 75 DEG C of water-baths, after
Vacuum removal isopropanol is opened after continuous reaction 1h, 134g distillations are obtained, add 74.5g deionized waters by resin solid content adjust to
87%, resin viscosity 50000cps（25℃）, cool down standby.
Take resin 100g and surfactant nonylphenol polyoxyethylene ether sulfate 1.5g, formic acid（87%）3g, foaming agent
Normal hexane 5g, auxiliary agent silane coupler SH6030（Dow corning chemical company）3g Forced Mixings under 1200rpm are uniform,
Enter in preprepared mould, be transferred at 120 DEG C after the 15min that foams in being put into 75 DEG C of baking ovens and solidify 2h, obtain foam
MF4。
Embodiment 5：
By 252g tripolycyanamide, 42g dicyandiamides, 200g paraformaldehydes, 50g hydroxyl ethoxyethyl tripolycyanamide and 150g methanol
In adding glass flasks of the 1L with stirring, stirring is opened by material mix homogeneously, material PH is adjusted to 9.0 using sodium hydroxide
Left and right, reacts under 75 DEG C of water-baths to material clear, adds 35g dimethyl carbonate, opens vacuum removal after continuing reaction 1h
Methanol, obtains 142g distillations, adds 94.2g deionized waters resin solid content to be adjusted to 85%, resin viscosity 15000cps
（25℃）, cool down standby.
Take resin 100g and surfactant nonylphenol polyoxyethylene ether sulfate 1.5g, sulphuric acid（85%）5g, foaming agent
Pentamethylene. 5g, auxiliary agent FQ-5503（Jiangsu Maysta Chemical Co., Ltd.）3g Forced Mixings under 1200rpm are uniform,
Enter in preprepared mould, be transferred at 120 DEG C after the 15min that foams in being put into 70 DEG C of baking ovens and solidify 2h, obtain foam
MF5。
Embodiment 6：
By 252g tripolycyanamide, 25.2g carbamide, 205g paraformaldehydes, 35g hydroxyl ethoxyethyl tripolycyanamide and 150g propanol
In adding glass flasks of the 1L with stirring, stirring is opened by material mix homogeneously, material PH is adjusted to 9.0 using diethanolamine
Left and right, reacts under 75 DEG C of water-baths to material clear, adds 40g dimethyl oxalate .s, opens vacuum removal after continuing reaction 1h
Propanol, obtains 138g distillations, adds 67.6g deionized waters resin solid content to be adjusted to 87.5%, resin viscosity 65000cps
（25℃）, cool down standby.
Take resin 100g and surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.5g, firming agent phosphoric acid（85%）5g, foaming agent
One fluorine dichloroethanes 5g, auxiliary agent Z6020（Dow corning chemical company）3g Forced Mixings under 1200rpm are uniform, pour into pre-
First in ready mould, it is transferred at 120 DEG C after the 15min that foams in being put into 70 DEG C of baking ovens and solidifies 2h, obtain foam MF6.
Then foam resulting in embodiment 1 to embodiment 6 is tested, every test is carried out according to GB.
Test result such as following table：
| Project | Unit | MF1 | MF2 | MF3 | MF4 | MF5 | MF6 |
| Density | kg/m³ | 95 | 62 | 65 | 60 | 60 | 60 |
| Heat conductivity | w/m·k | 0.045 | 0.030 | 0.031 | 0.028 | 0.026 | 0.030 |
| Compression performance | kpa | Rupture | 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 |
By obtained in embodiment one resin due to viscosity greatly, cannot normally bubble in foaming stages, cause its density mistake
Height, foam is excessively crisp cannot to be deformed upon, thus rupture occurs when being compressed performance test.
Density is tested according to GB/T6343-2009；
Heat 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 tests method；
Volume water absorption rate is according to GB/T8810-2005 rigid foam water absorption rate tests；
Rate of closed hole is tested using ultrafoam true density instrument；
Dimensional stability GB/T8811-2008 rigid foam dimensional stability test method is tested.
The resin by obtained in the present invention has relatively low viscosity, is more easy to realize industrialization, and the foam by obtained in the resin is closed
Porosity is high, excellent thermal insulation performance, it is adaptable to as insulation material.
Claims (5)
1. a kind of preparation method of flame melamine rigid foam, it is characterised in that the method is comprised the following steps：
1）The synthesis technique of tripolycyanamide rigid foam performed polymer
By tripolycyanamide and paraformaldehyde in molar ratio 1:1.5-3.5, tripolycyanamide and modifying agent I in mass ratio 1:0.1-0.6,
With alcohol as solvent, react under 75 DEG C of water-baths to material clear, by modifying agent II by with tripolycyanamide mass ratio be 0.05-
0.2:During 1 adds resin, after continuing reaction 0.5-2h, desolvation is simultaneously adjusted solid content to 85-92% with water and obtains foam
Performed polymer；The modifying agent I is selected from methyl tripolycyanamide, benzoguanamine, hydroxyl ethoxyethyl tripolycyanamide, three (2- hydroxyl second
Base) chlorinated isocyanurates, carbamide, any one or a few the mixture in dicyandiamide；The modifying agent II is selected from esters chemical combination
Any one or a few mixture of carbonic ester and oxalate in thing；
2）The preparation technology of tripolycyanamide rigid foam
By step 1）The performed polymer for obtaining by weight, with 100 parts with surfactant 1-10 parts, firming agent 2-6 parts, foaming agent
1-8 parts, pour in mould after auxiliary agent 1-10 part mix homogeneously, continue at 80-120 DEG C after the 15-30min that foams at 60-80 DEG C
Flame melamine rigid foam is obtained after lower ripening 2-3h.
2. the preparation method of the flame melamine rigid foam described in claim 1, it is characterised in that：The surfactant
Any one or a few in dodecylbenzene sodium sulfonate, sodium lauryl sulphate, nonylphenol polyoxyethylene ether sulfate
Mixture.
3. the preparation method of the flame melamine rigid foam described in claim 1, it is characterised in that：The firming agent is selected from
Any one or a few mixture in formic acid, acetic acid, oxalic acid, p-methyl benzenesulfonic acid, sulphuric acid, phosphoric acid, hydrochloric acid.
4. the preparation method of the flame melamine rigid foam described in claim 1, it is characterised in that：The foaming agent is selected from
Any one or a few mixture in pentane, Pentamethylene., normal hexane, hexamethylene, a fluorine dichloroethanes.
5. the preparation method of the flame melamine rigid foam described in claim 1, it is characterised in that：The auxiliary agent is selected from silicon
Any one or a few mixture in oil, silane coupler.
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