CN103709593A - Polystyrene/phosphatized phenolic resin syntactic foam, and preparation method thereof - Google Patents
Polystyrene/phosphatized phenolic resin syntactic foam, and preparation method thereof Download PDFInfo
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- CN103709593A CN103709593A CN201310665326.1A CN201310665326A CN103709593A CN 103709593 A CN103709593 A CN 103709593A CN 201310665326 A CN201310665326 A CN 201310665326A CN 103709593 A CN103709593 A CN 103709593A
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Abstract
The invention relates to polystyrene/phosphatized phenolic resin syntactic foam, and a preparation method thereof, and belongs to the field of flame retardant materials. A formula for the syntactic foam comprises polystyrene foam particles, a thermoset phosphatized phenolic resin prepolymer and a curing agent. The preparation method of the syntactic foam comprises the steps of coating the thermoset phosphatized phenolic resin prepolymer on surfaces of preset polystyrene foam particles; and then preparing the polystyrene/phosphatized phenolic resin syntactic foam under proper temperature and pressure. The syntactic foam has the characteristics of high flame retardant property, low smoke production amount, low cost and excellent performances. Fire melting drip of polystyrene is solved fundamentally; and novel selection is provided for exterior wall thermal insulation materials.
Description
Technical field
The present invention relates to a kind of polystyrene/phosphatization resol syntactic foam and preparation method thereof, belong to fire retardant material field.
Background technology
Polystyrene foamed plastics is the external-wall heat-insulation material of current global usage quantity maximum.But polystyrene foamed plastics very easily burns, burning produces a large amount of dense smoke, and easy molten drop during burning, accelerates fire spread, to security against fire, brings very big hidden danger.Therefore, improve the combustibility of polystyrene foamed plastics, improve the security of polystyrene foamed plastics, become study hotspot and emphasis in the industry.
At present, the flame resistant method of polystyrene foamed plastics mainly adopts the way of adding fire retardant to realize, and the method is comparatively simple and practical.As first proposed to prepare the method for the polystyrene foamed plastics (EPS) that contains graphite granule in patent US6130265, US6340713, described EPS has self-extinguishing, can pass through the B2 level of DIN4102 combustion test.In addition, in US Patent No. 6420442, point out, the composite use of 1%～12% expanded graphite and phosphorus flame retardant (red phosphorus or triphenylphosphate) can obtain the fire-retardant EPS of self-extinguishing type.The combustibility of the equal p-poly-phenyl vinylic foam of aforesaid method has larger improvement, has improved fire safety performance, but is all difficult to solve the molten drop problem of polystyrene foamed plastics.Recently, Pekinese's external wall energy-saving lagging material forecloses polystyrene foamed plastics, and reason can produce molten drop while burning because of it exactly, and polystyrene foamed plastics industrial chain faces industry crisis.
Summary of the invention
Drippage problem while burning for solving polystyrene foamed plastics, and effectively improve its flame retardant properties, the object of the present invention is to provide a kind of polystyrene/phosphatization resol syntactic foam and preparation method thereof.
For achieving the above object, technical scheme of the present invention is as follows:
Polystyrene/phosphatization resol syntactic foam, the formula of described porous plastics is as follows:
Thermoset phosphatization resol prepolymer 100 weight parts;
Polystyrene foam particles 40～167 weight parts;
Solidifying agent 5～15 weight parts;
Described thermoset phosphatization resol prepolymer is the resole prepolymer of phosphorus chemistry modification.
Described polystyrene foam particles is the Expandable Polystyrene (EPS) plastic grain of sending out through pre-, and density is at 14g/L～16g/L.
Described solidifying agent is one or more of sulfuric acid, toluene sulfonic acide, phenol sulfonic acid, phosphoric acid, boric acid.
The consumption of described polystyrene foam particles is preferably:
Polystyrene foam particles 50～100 weight parts.
Described thermoset phosphatization resol prepolymer can obtain by following preparation method: by phenol and phosphoric acid dehydration esterification Depressor response again, with sodium hydroxide solution adjust pH to 10～11, add formaldehyde solution and zinc acetate to be warming up to 90-100 ℃ of reaction, be cooled to again 65 ℃ of vacuum and steam except moisture content, obtain thermoset phosphatization resol prepolymer.
A preparation method for polystyrene/phosphatization resol syntactic foam of the present invention, described method steps is as follows:
(1) the even overlay film of polystyrene foam particles
In polystyrene foam particles, add thermoset phosphatization resol prepolymer, after stirring, add solidifying agent, continue to be stirred to the polystyrene foam particles that obtains being uniformly coated with thermoset phosphatization resol prepolymer;
(2) compression molding: the polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer obtaining in step (1) is placed in to steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.03～0.07MPa, after pressurize 30～50s, release, cooling, die sinking obtain described polystyrene/phosphatization resol resin compounded porous plastics.
Beneficial effect of the present invention is
1. the invention provides a kind of polystyrene/phosphatization resol syntactic foam, difficulty is fired to phosphatization phenolic resin heat and be fixed in granules of polystyrene surface, when can make material in burning or receiving flame bombardment, do not produce molten drop.Described syntactic foam has the features such as high, the raw cigarette amount of flame retardant properties is low, with low cost, excellent performance, has fundamentally solved the burning molten drop problem of polystyrene.
2. the present invention also provides the preparation method of described polystyrene/phosphatization resol syntactic foam, be specially and adopt cheap thermoset phosphatization resol prepolymer, evenly be coated on the granules of polystyrene of having sent out in advance surperficial, then under suitable temperature and pressure, prepare high flame retardant, low cigarette and without polystyrene/phosphatization resol syntactic foam of molten drop.
Embodiment
Below, by embodiment, the invention will be further described.In embodiment 1～7, sulfuric acid and phosphoric acid are commercially available industrial sulphuric acid (concentration is about 98wt%) and phosphoric acid (concentration is about 85wt%), and " part " is weight part, and polystyrene foam particles is Dalian petrochemical iy produced.Limiting oxygen index(LOI) obtains according to GB GB/T2046.2 test.
Embodiment 1
The preparation of thermoset phosphatization resol prepolymer: take phenol 100g, phosphoric acid 58g, is placed in the middle of 500ml there-necked flask, is warming up to (vacuum tightness-0.08MPa) reaction 2h that reduces pressure again after 135 ℃ of dehydration esterification 5h, be cooled to 70 ℃, sodium hydroxide solution with 30% regulates pH value to 10～11, adds the formaldehyde solution 130g of 38wt%, zinc acetate 1.2g, be warming up to 95 ℃ of reaction 3.5h, be cooled to subsequently 65 ℃, with pump vacuum, steam except moisture content, obtain thermoset phosphatization resol prepolymer.
The allotment of solidifying agent: get phenol sulfonic acid 30wt%, sulfuric acid 20wt%, phosphoric acid 20wt%, water 30wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (density is 14g/L), add above-mentioned thermoset phosphatization resol prepolymer 84g, after stirring, add above-mentioned solidifying agent 7g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.05MPa, and after pressurize 40s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 24.9%.
Embodiment 2
The allotment of solidifying agent: get tosic acid 20wt%, boric acid 15wt%, phosphatase 11 5wt%, sulfuric acid 20wt%, water 30wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (16g/L), thermoset phosphatization resol prepolymer (prepared by the embodiment 1) 400g that adds foregoing curable, after stirring, add above-mentioned solidifying agent 24g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.03MPa, and after pressurize 50s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 34.7%.
Embodiment 3
The allotment of solidifying agent: get phenol sulfonic acid 10wt%, boric acid 20wt%, phosphoric acid 20wt%, tosic acid 10wt%, sulfuric acid 20wt%, water 20wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (16g/L), add above-mentioned thermoset phosphatization resol prepolymer (prepared by embodiment 1) 200g, after stirring, add above-mentioned solidifying agent 16g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.07MPa, and after pressurize 30s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 30.5%.
Embodiment 4
The allotment of solidifying agent: get phenol sulfonic acid 10wt%, boric acid 20wt%, phosphoric acid 20wt%, tosic acid 10wt%, sulfuric acid 20wt%, water 20wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (16g/L), add above-mentioned thermoset phosphatization resol prepolymer (prepared by embodiment 1) 100g, after stirring, add above-mentioned solidifying agent 5g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.06MPa, and after pressurize 38s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 27.9%.
Embodiment 5
The allotment of solidifying agent: get phenol sulfonic acid 10wt%, boric acid 20wt%, phosphoric acid 20wt%, tosic acid 10wt%, sulfuric acid 20wt%, water 20wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (16g/L), add above-mentioned thermoset phosphatization resol prepolymer (prepared by embodiment 1) 160g, after stirring, add above-mentioned solidifying agent 12g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.05MPa, and after pressurize 40s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 29.5%.
Embodiment 6
The allotment of solidifying agent: get phenol sulfonic acid 10wt%, boric acid 20wt%, phosphoric acid 20wt%, tosic acid 10wt%, sulfuric acid 20wt%, water 20wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (16g/L), add above-mentioned thermoset phosphatization resol prepolymer (prepared by embodiment 1) 100g, after stirring, add above-mentioned solidifying agent 15g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.04MPa, and after pressurize 45s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 28.5%.
Embodiment 7
The allotment of solidifying agent: get phenol sulfonic acid 10wt%, boric acid 20wt%, phosphoric acid 20wt%, tosic acid 10wt%, sulfuric acid 20wt%, water 20wt% stirring and dissolving is stand-by;
The even overlay film of polystyrene foam particles: get 10L polystyrene foam particles base-material (14g/L), add above-mentioned thermoset phosphatization resol prepolymer (prepared by embodiment 1) 280g, after stirring, add above-mentioned solidifying agent 42g, continue to be stirred to and obtain evenly coated polystyrene foam particles;
Compression molding: the above-mentioned polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer is added in steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.04MPa, and after pressurize 45s, release, cooling, die sinking, obtain polystyrene/phosphatization resol syntactic foam, the limiting oxygen index(LOI) of described porous plastics is 32.8%.
When burning, produce dense black smoke with traditional polystyrene foamed plastics and compare, polystyrene/phosphatization phenolic aldehyde syntactic foam that embodiment 1～7 obtains produces light few when burning, and without drippage.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. polystyrene/phosphatization resol syntactic foam, is characterized in that, the formula of described porous plastics is as follows:
Thermoset phosphatization resol prepolymer 100 weight parts;
Polystyrene foam particles 40～167 weight parts;
Solidifying agent 5～15 weight parts;
Described thermoset phosphatization resol prepolymer is the resole prepolymer of phosphorus chemistry modification;
Described polystyrene foam particles is the Expandable Polystyrene (EPS) plastic grain of sending out through pre-, and density is at 14g/L～16g/L;
Described solidifying agent is one or more of sulfuric acid, toluene sulfonic acide, phenol sulfonic acid, phosphoric acid, boric acid.
2. a kind of polystyrene/phosphatization resol syntactic foam according to claim 1, is characterized in that, the consumption of described polystyrene foam particles is:
Polystyrene foam particles 50～100 weight parts.
3. a kind of polystyrene/phosphatization resol syntactic foam according to claim 1, it is characterized in that, described thermoset phosphatization resol prepolymer obtains by following preparation method: by phenol and phosphoric acid dehydration esterification Depressor response again, with sodium hydroxide solution adjust pH to 10～11, add formaldehyde solution and zinc acetate to be warming up to 90-100 ℃ of reaction, be cooled to again 65 ℃ of vacuum and steam except moisture content, obtain thermoset phosphatization resol prepolymer.
4. the preparation method of a kind of polystyrene/phosphatization resol syntactic foam as described in claim 1～3 any one, is characterized in that, described method steps is as follows:
(1) the even overlay film of polystyrene foam particles
In polystyrene foam particles, add thermoset phosphatization resol prepolymer, after stirring, add solidifying agent, continue to be stirred to the polystyrene foam particles that obtains being uniformly coated with thermoset phosphatization resol prepolymer;
(2) compression molding: the polystyrene foam particles that is uniformly coated with thermoset phosphatization resol prepolymer obtaining in step (1) is placed in to steam heat compression mould, closing molding, pass into the high-pressure steam that pressure is 0.03～0.07MPa, after pressurize 30～50s, release, cooling, die sinking obtain described polystyrene/phosphatization resol resin compounded porous plastics.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754239A (en) * | 2016-03-24 | 2016-07-13 | 潍坊学院 | Preparation method of ceramic composite modified resin coated EPS foam flame-retardant thermal-insulation material |
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| CN101020735A (en) * | 2006-12-28 | 2007-08-22 | 李超 | Synthesis process of phosphoric phenolic resin |
| CN102391588A (en) * | 2011-05-26 | 2012-03-28 | 中国科学院过程工程研究所 | High-flame-retardant low-smoke-density polystyrene foam compound heat insulating material and preparation method thereof |
| CN102807683A (en) * | 2011-06-03 | 2012-12-05 | 北京艾迪泰克技术咨询有限公司 | Method for preparing flame-retardant moulded anti-dripping EPS (expandable polystyrene) foam material |
| CN102863706A (en) * | 2012-08-28 | 2013-01-09 | 赵毅 | Polystyrene/thermosetting resin syntactic foam and method for preparing same |
| CN103172970A (en) * | 2013-04-15 | 2013-06-26 | 山东圣泉化工股份有限公司 | Modified polystyrene foam and preparation method thereof |
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- 2013-12-10 CN CN201310665326.1A patent/CN103709593A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020735A (en) * | 2006-12-28 | 2007-08-22 | 李超 | Synthesis process of phosphoric phenolic resin |
| CN102391588A (en) * | 2011-05-26 | 2012-03-28 | 中国科学院过程工程研究所 | High-flame-retardant low-smoke-density polystyrene foam compound heat insulating material and preparation method thereof |
| CN102807683A (en) * | 2011-06-03 | 2012-12-05 | 北京艾迪泰克技术咨询有限公司 | Method for preparing flame-retardant moulded anti-dripping EPS (expandable polystyrene) foam material |
| CN102863706A (en) * | 2012-08-28 | 2013-01-09 | 赵毅 | Polystyrene/thermosetting resin syntactic foam and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105754239A (en) * | 2016-03-24 | 2016-07-13 | 潍坊学院 | Preparation method of ceramic composite modified resin coated EPS foam flame-retardant thermal-insulation material |
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Application publication date: 20140409 |