CN104744884B - A kind of resin combination, styrofoam and preparation method thereof - Google Patents
A kind of resin combination, styrofoam and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of resin combination, styrofoam and preparation method thereof, for solving the prior art there are expansion polyphenyl plate combustibility is poor, while the problem of sheet deformation is trickled, and the intensity of a fire is easily spread.The present invention provides a kind of resin combination, styrofoam and preparation method thereof, due to being with the addition of thermosetting resin mixed liquor, curing agent so that the burning behavior class of styrofoam is improved；Meanwhile thermosetting property is presented in plate, during ignition, volume is basically unchanged, and is not trickled, from fiery self-extinguishment.
Description
Technical field
The present invention relates to thermal insulation material technical fields, and in particular, to a kind of resin combination, styrofoam and its preparation side
Method.
Background technology
Expansion polyphenyl plate be by after the heated prefoam of expandable polystyrene particle, in a mold hot briquetting and be made
The polystyrol plastic foam plate material with hole-closing structure, be widely used in building inside and outside wall thermal insulation field, be domestic use
Measure maximum thermal insulation material.
The main raw material(s) of common expansion polyphenyl plate is the combustable organics object such as polystyrene, styrene, pentane, so combustion
It burns performance and can only achieve B2 grades, it is impossible to meet relevant criterion requirement.
Expansion polyphenyl plate generally uses following technological process：Curing → shaping → cutting → packaging is sent out → dried to particle in advance.
The feed particles of expansion polyphenyl plate are expandable polystyrene particle, are styrol copolymers, contain penta in particle
The easy expanding gas such as alkane, when particle is heated by steam, polystyrene softening, pentane gas expansion increases particle volume, close
Degree reduces.Then cured by dry, distribute the vapor inside particle, dry air is enriched inside particle and steady
It is fixed.Particle is pumped into big panel moulding apparatus again, be passed through hot steam make particle epidermis soften, pressurization bonding form big plate, then according to
The size needed is cut.
Common expansion polyphenyl plate has the following disadvantages：
1st, combustibility depend on raw material, fire retardant it is usually used be hexabromo dodecane, hexabromo dodecane can burn
When capture reaction free radical, stop the lasting progress of chain reaction, but due to after heated fire retardant participate in reaction and consume,
So flame retardant effect is bad during sustained combustion, combustibility can only achieve B3 B2 ranks, in addition, hexabromo dodecane is made into
Fire retardant can discharge noxious material when being used in cellular insulant, and while running into fire can generate rapidly poison gas.
2nd, thermoplasticity thermal insulation material is belonged to, during ignition, heat preservation plate material deformation trickling, the intensity of a fire is easily spread.
The content of the invention
Technical solution is a kind of resin combination, styrofoam and preparation method thereof used by solving the above problems.
The present invention provides a kind of resin combination, including：Thermosetting resin mixed liquor, curing agent.
Preferably, the resin combination in terms of mass fraction including：Thermosetting resin mixed liquor 1.5-2 mass parts,
Curing agent 0.1-0.3 mass parts.
Preferably, the thermosetting resin mixed liquor in terms of mass fraction including：Phenolic resin 60-80 mass parts, chaff
Urea formaldehyde 20-40 mass parts, melamine resin 0.1-20 mass parts.
Preferably, the phenolic resin be by phenol and formaldehyde carry out polycondensation generation single order it is solvable can cladding resin,
In, phenol and formaldehyde mole ratio are (0.7-0.9)：1.
Preferably, the furfural resin is the thermosetting resin by furfuryl alcohol and phenolic aldehyde polycondensation generation.
Preferably, the melamine resin is the thermosetting resin by formaldehyde and melamine polycondensation generation,
Wherein, the molar ratio of formaldehyde and melamine is (2-3)：1.
By the way that three kinds of resin compoundings can be reduced to the brittle property of phenolic resin, resistance to compression, tensile strength and water resistance are improved.
Preferably, the curing agent in terms of mass fraction including：Boric acid 5-20 mass parts, benzene sulfonic acid 30-50 mass parts,
P-methyl benzenesulfonic acid 10-30 mass parts, ethyl-sulfate 0-20 mass parts, magnesia 5-10 mass parts, aluminium hydroxide 5-10 mass parts,
Alumina silicate 5-10 mass parts, graphite particle 0-5 mass parts.
Wherein, the effect of boric acid is to promote phenolic resin carbonized in burning, reduces the combustibility of phenolic resin, is formed
The carbon residue skeleton structure of high stability improves volume stability；Benzene sulfonic acid, p-methyl benzenesulfonic acid, ethyl-sulfate, which all have, promotes heat
The cured effect of thermosetting resin, three are compounded with certain proportion, and solidification effect is more preferable；Magnesia, aluminium hydroxide, alumina silicate belong to
Refractory mineral in burning, is filled in the effect that fireproof coating can be played in the skeleton of carbonization.
Preferably, the average particle size range of the graphite particle is 80-120nm.
Graphite particle can play the role of absorption and reflection heat, reduce when burning to the heat of resin matrix internal transmission
Amount.
The present invention also provides a kind of preparation methods of styrofoam, and above-mentioned resin combination is handled according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, is added with stirring thermosetting property tree
Fat mixed liquor, curing agent obtain precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made.
Preferably, the expansion ratio of the polystyrene curing particle is 40-50, loose bulk density 18-25kg/
m3。
Preferably, the mass fraction of water is controlled below 5% in the dry particle.
Preferably, it is described by dry particle carry out curing hot briquetting include：
After dry particle is cured 8-24h at 10-35 DEG C, into forming machine, the hot steam of 0.3-0.5MPa is passed through, is added
Hot 5-10 minutes aftershaping.
The present invention also provides a kind of styrofoam, the styrofoam is prepared using above-mentioned preparation method.
Resin combination provided by the invention, styrofoam and preparation method thereof, due to be with the addition of thermosetting resin mixed liquor,
Curing agent causes the burning behavior class of styrofoam to be improved；Meanwhile thermosetting property, during ignition, volume is presented in plate
It is basically unchanged, does not trickle, from fiery self-extinguishment.
Specific embodiment
For those skilled in the art is made to more fully understand technical scheme, With reference to embodiment to this
Invention is described in further detail.
Embodiment 1：
The present embodiment provides a kind of resin combination, including：Thermosetting resin mixed liquor, curing agent.
Wherein, granules of polystyrene, thermosetting resin mixed liquor, the mass ratio of curing agent are shown in Table 1；Thermosetting resin mixes
Liquid, curing agent subgroup in itself point and content are shown in Table 2.
The present embodiment also provides a kind of preparation method of styrofoam, and above-mentioned resin combination is handled according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, is added with stirring thermosetting property tree
Fat mixed liquor, curing agent obtain precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made.
Specifically,
Expansion ratio will be obtained after the pre- dry curing of hair shaft of granules of polystyrene as 50, loose bulk density 25kg/m3's
Polystyrene cures particle, and for prior art scope, this is no longer going to repeat them for the specific pre- dry curing of hair shaft；
It will be stirred in polystyrene curing particle input mixer, while thermosetting resin added in by the mass ratio in table 1
Mixed liquor and curing agent, stirring to obtain precursor granules；
Precursor granules stirring is passed through to 100 DEG C of hot wind after ten minutes, it is 5 minutes dry, it then drains into fluid bed and continues to do
Dry 5 minutes, the mass fraction of water in dry particle is controlled after drying twice below 5%, water in dry particle in the present embodiment
Mass fraction be 2%；
After dry particle is cured for 24 hours at 35 DEG C, into forming machine, the hot steam of 0.5MPa is passed through, is heated 10 minutes
Aftershaping.
Optionally, the styrofoam after shaping is cut, packaging.
The styrofoam of preparation is tested according to country or professional standard, for example, apparent density is tested by GB/T6343；Pressure
Contracting intensity is tested by GB/T8813；Thermal conductivity factor is tested by GB/T10294；It is tested perpendicular to surface tensile strength by JG149；Ruler
Very little stability is tested by GB/T8811；Oxygen index (OI), burning grade, dropping are tested by GB8624-2012, and test result is shown in Table 3.
Embodiment 2：
The present embodiment provides a kind of resin combination, including：Thermosetting resin mixed liquor, curing agent.
Wherein, granules of polystyrene, thermosetting resin mixed liquor, the mass ratio of curing agent are shown in Table 1；Thermosetting resin mixes
Liquid, curing agent subgroup in itself point and content are shown in Table 2.
The present embodiment also provides a kind of preparation method of styrofoam, and above-mentioned resin combination is handled according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, is added with stirring thermosetting property tree
Fat mixed liquor, curing agent obtain precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made.
Specifically,
Expansion ratio will be obtained after the pre- dry curing of hair shaft of granules of polystyrene as 40, loose bulk density 18kg/m3's
Polystyrene cures particle, and for prior art scope, this is no longer going to repeat them for the specific pre- dry curing of hair shaft；
It will be stirred in polystyrene curing particle input mixer, while thermosetting resin added in by the mass ratio in table 1
Mixed liquor and curing agent, stirring to obtain precursor granules；
Precursor granules stirring is passed through to 80 DEG C of hot wind after five minutes, it is 3 minutes dry, it then drains into fluid bed and continues dry 3
Minute, twice dry after control dry particle in water mass fraction below 5%, in the present embodiment in dry particle water matter
It is 3% to measure fraction；
After dry particle is cured 8h at 10 DEG C, into forming machine, the hot steam of 0.3MPa is passed through, heating is after five minutes
Shaping.
Optionally, the styrofoam after shaping is cut, packaging.
The styrofoam of preparation is tested according to country or professional standard, for example, apparent density is tested by GB/T6343；Pressure
Contracting intensity is tested by GB/T8813；Thermal conductivity factor is tested by GB/T10294；It is tested perpendicular to surface tensile strength by JG149；Ruler
Very little stability is tested by GB/T8811；Oxygen index (OI), burning grade, dropping are tested by GB8624-2012, and test result is shown in Table 3.
Embodiment 3：
The present embodiment provides a kind of resin combination, including：Thermosetting resin mixed liquor, curing agent.
Wherein, granules of polystyrene, thermosetting resin mixed liquor, the mass ratio of curing agent are shown in Table 1；Thermosetting resin mixes
Liquid, curing agent subgroup in itself point and content are shown in Table 2.
The present embodiment also provides a kind of preparation method of styrofoam, and above-mentioned resin combination is handled according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, is added with stirring thermosetting property tree
Fat mixed liquor, curing agent obtain precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made.
Specifically,
Expansion ratio will be obtained after the pre- dry curing of hair shaft of granules of polystyrene as 45, loose bulk density 20kg/m3's
Polystyrene cures particle, and for prior art scope, this is no longer going to repeat them for the specific pre- dry curing of hair shaft；
It will be stirred in polystyrene curing particle input mixer, while thermosetting resin added in by the mass ratio in table 1
Mixed liquor and curing agent, stirring to obtain precursor granules；
90 DEG C of hot wind is passed through after precursor granules are stirred 8 minutes, it is 4 minutes dry, it then drains into fluid bed and continues dry 4
Minute, twice dry after control dry particle in water mass fraction below 5%, in the present embodiment in dry particle water matter
It is 1% to measure fraction；
After dry particle is cured 15h at 20 DEG C, into forming machine, the hot steam of 0.4MPa is passed through, after heating 8 minutes
Shaping.
Optionally, the styrofoam after shaping is cut, packaging.
The styrofoam of preparation is tested according to country or professional standard, for example, apparent density is tested by GB/T6343；Pressure
Contracting intensity is tested by GB/T8813；Thermal conductivity factor is tested by GB/T10294；It is tested perpendicular to surface tensile strength by JG149；Ruler
Very little stability is tested by GB/T8811；Oxygen index (OI), burning grade, dropping are tested by GB8624-2012, and test result is shown in Table 3.
Embodiment 4：
The present embodiment provides a kind of resin combination, including：Thermosetting resin mixed liquor, curing agent.
Wherein, granules of polystyrene, thermosetting resin mixed liquor, the mass ratio of curing agent are shown in Table 1；Thermosetting resin mixes
Liquid, curing agent subgroup in itself point and content are shown in Table 2.
The present embodiment also provides a kind of preparation method of styrofoam, and above-mentioned resin combination is handled according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, is added with stirring thermosetting property tree
Fat mixed liquor, curing agent obtain precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made.
Specifically,
Expansion ratio will be obtained after the pre- dry curing of hair shaft of granules of polystyrene as 46, loose bulk density 23kg/m3's
Polystyrene cures particle, and for prior art scope, this is no longer going to repeat them for the specific pre- dry curing of hair shaft；
It will be stirred in polystyrene curing particle input mixer, while thermosetting resin added in by the mass ratio in table 1
Mixed liquor and curing agent, stirring to obtain precursor granules；
90 DEG C of hot wind is passed through after precursor granules are stirred 7 minutes, it is 4 minutes dry, it then drains into fluid bed and continues dry 5
Minute, twice dry after control dry particle in water mass fraction below 5%, in the present embodiment in dry particle water matter
It is 3.5% to measure fraction；
After dry particle is cured 20h at 30 DEG C, into forming machine, the hot steam of 0.5MPa is passed through, after heating 9 minutes
Shaping.
Optionally, the styrofoam after shaping is cut, packaging.
The styrofoam of preparation is tested according to country or professional standard, for example, apparent density is tested by GB/T6343；Pressure
Contracting intensity is tested by GB/T8813；Thermal conductivity factor is tested by GB/T10294；It is tested perpendicular to surface tensile strength by JG149；Ruler
Very little stability is tested by GB/T8811；Oxygen index (OI), burning grade, dropping are tested by GB8624-2012, and test result is shown in Table 3.
The performance parameter of styrofoam each side of the invention is superior to commercially available styrofoam as seen from Table 3, especially burns
Performance；Meanwhile thermosetting property is presented in plate, during ignition, volume is basically unchanged, and is not trickled, and from fiery self-extinguishment, combustibility is reachable
To B1 grades.
Thermosetting resin mixed liquor can reduce the brittle property of phenolic resin by the way that three kinds of resins are compounded in the present invention, carry
High resistance to compression, tensile strength and water resistance.
The effect of boric acid in the present invention in curing agent is to promote the carbonisation of phenolic resin in burning；Benzene sulfonic acid,
P-methyl benzenesulfonic acid, ethyl-sulfate, which all have, promotes the cured effect of thermosetting resin, and three is compounded with certain proportion, solidification effect
More preferably；Magnesia, aluminium hydroxide, alumina silicate belong to refractory mineral, burning when, be filled in the skeleton of carbonization can play it is anti-
The effect of fiery coating；Graphite particle can play the role of absorption and reflection heat, reduce when burning to resin matrix internal transmission
Heat.
Thermosetting resin and refractory material are in granules of polystyrene surface in the styrofoam of the present invention, by polystyrene
Particle forms isolation cabin of preventing fires one by one, and in ignition, thermosetting resin is carbonized to form skeleton, and refractory material is filled wherein
It plays enhancing skeleton and heat-insulated effect, graphite particle is then further reduced the transmission of heat, play good flame retardant effect.
Meanwhile thermosetting resin is carbonized to form the skeleton of high porosity, and volume is basically unchanged, closed pore air layer therein
It can play the role of reducing heat conduction and convection current, internal unburned granules of polystyrene can be protected not trickle, and have self-extinguishment
Function.
1 resin combination component of table and each component mass parts
| Resin combination component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polystyrene (mass parts) | 1 | 1 | 1 | 1 |
| Thermosetting resin mixed liquor (mass parts) | 1.5 | 1.8 | 2 | 1.9 |
| Curing agent (mass parts) | 0.3 | 0.2 | 0.1 | 0.25 |
2 thermosetting resin mixed liquor of table and the component of curing agent and each component mass parts
3 commercially available expansion polyphenyl plate of table and the performance test results of the styrofoam prepared in various embodiments of the present invention
| Inspection project | Commercially available expansion polyphenyl plate | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Apparent density (kg/m3) | 20 | 38 | 40 | 43 | 42 |
| Compressive strength (Mpa) | 0.095 | 0.25 | 0.28 | 0.29 | 0.29 |
| Perpendicular to the tensile strength (Mpa) of plate face | 0.12 | 0.18 | 0.20 | 0.23 | 0.22 |
| Thermal conductivity factor (w/m.k) | 0.039 | 0.039 | 0.037 | 0.036 | 0.037 |
| Dimensional stability (%) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Burning behavior class | B2 | B1 | B1 | B1 | B1 |
| Oxygen index (OI), % | 26 | 42 | 44 | 45 | 45 |
| Whether dropping is had | Have | Nothing | Nothing | Nothing | Nothing |
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, the essence of the present invention is not being departed from
In the case of refreshing and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of styrofoam, which is characterized in that handle resin combination according to the following steps：
Granules of polystyrene is subjected to the dry curing of pre- hair shaft and obtains polystyrene curing particle, thermosetting resin is added with stirring and mixes
Close liquid, curing agent obtains precursor granules；
Precursor granules are subjected to dry acquisition dry particle twice；
Dry particle is subjected to curing hot briquetting, styrofoam is made；
The resin combination includes：Thermosetting resin mixed liquor, curing agent；
The thermosetting resin mixed liquor in terms of mass fraction including：Phenolic resin 60-80 mass parts, furfural resin 20-40 matter
Measure part, melamine resin 0.1-20 mass parts；
In terms of mass fraction including：Thermosetting resin mixed liquor 1.5-2 mass parts, curing agent 0.1-0.3 mass parts；
The curing agent in terms of mass fraction including：Boric acid 5-20 mass parts, benzene sulfonic acid 30-50 mass parts, p-methyl benzenesulfonic acid 10-
30 mass parts, ethyl-sulfate 0-20 mass parts, magnesia 5-10 mass parts, aluminium hydroxide 5-10 mass parts, alumina silicate 5-10 matter
Measure part, graphite particle 0.2-5 mass parts.
2. the preparation method of styrofoam as described in claim 1, which is characterized in that the phenolic resin is by phenol and formaldehyde
Carry out polycondensation generation single order it is solvable can cladding resin, wherein, phenol and formaldehyde mole ratio are (0.7-0.9): 1.
3. the preparation method of styrofoam as described in claim 1, which is characterized in that the furfural resin is by furfuryl alcohol and phenolic aldehyde
Polycondensation generates thermosetting resin.
4. the preparation method of styrofoam as described in claim 1, which is characterized in that the melamine resin is by first
Aldehyde and the thermosetting resin of melamine polycondensation generation, wherein, the molar ratio of formaldehyde and melamine is (2-3): 1.
5. the preparation method of styrofoam as described in claim 1, which is characterized in that the average particle size range of the graphite particle
For 80-120nm.
6. the preparation method of styrofoam as described in claim 1, which is characterized in that the foaming of the polystyrene curing particle
Multiplying power is 40-50, loose bulk density 18-25kg/m3。
7. the preparation method of styrofoam as described in claim 1, which is characterized in that the mass fraction of water in the dry particle
Control is below 5%.
8. the preparation method of styrofoam as described in claim 1, which is characterized in that
It is described by dry particle carry out curing hot briquetting include：
After dry particle is cured 8-24h at 10-35 DEG C, into forming machine, the hot steam of 0.3-0.5MPa is passed through, heats 5-
It is molded after ten minutes.
9. a kind of styrofoam, which is characterized in that the styrofoam is the system using the styrofoam as described in claim 1-8 is any
What Preparation Method prepared.
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| CN104004282A (en) * | 2014-05-29 | 2014-08-27 | 哈尔滨工业大学空间钢结构幕墙有限公司 | Thermosetting composite resin foam insulation board and preparation method thereof |
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