CN102729547A - Fire-retardant fiber reinforced plastic composite material, preparation method and application thereof - Google Patents
Fire-retardant fiber reinforced plastic composite material, preparation method and application thereof Download PDFInfo
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- CN102729547A CN102729547A CN2012102180457A CN201210218045A CN102729547A CN 102729547 A CN102729547 A CN 102729547A CN 2012102180457 A CN2012102180457 A CN 2012102180457A CN 201210218045 A CN201210218045 A CN 201210218045A CN 102729547 A CN102729547 A CN 102729547A
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Abstract
The present invention discloses a fire-retardant fiber reinforced plastic composite material, a preparation method and an application thereof. The fire-retardant fiber reinforced plastic composite material comprises epoxy layers and a phenol formaldehyde layer, wherein the phenol formaldehyde layer is arranged between the epoxy layers, the epoxy layers and the phenol formaldehyde layer are compounded into the integration, the two epoxy layers comprise an epoxy resin, magnesium hydroxide, cobalt isooctanoate, cyclohexanone, a filler and a pigment, and the phenol formaldehyde layer mainly comprises phenol, xylene, formaldehyde, triphenyl phosphate, and glass fibers. According to the present invention, the fire-retardant agent used in the fire-retardant fiber reinforced plastic composite material of the present invention is mainly triphenyl phosphate or magnesium hydroxide; the environmental-friendliness is provided; the oxygen index of the fire-retardant fiber reinforced plastic composite material is more than 70%; and the fire-retardant fiber reinforced plastic composite material belongs to the incombustible material.
Description
Technical field
The present invention relates to field of compound material, relate in particular to a kind of fireproof glass composite, its preparation method and application thereof.
Background technology
Glass fiber reinforced plastics composite material has light weight, good toughness, advantage such as corrosion-resistant, therefore is widely used in fields such as automobile, building.Field such as automobile, building is comparatively paid close attention to the flame-retarding characteristic of glass fiber reinforced plastics composite material.Employed fire retardant is generally antimony oxide in the glass fiber reinforced plastics composite material at present, and its flame retardant effect is poor.And also have arsenic oxide arsenoxide in the antimony oxide product usually, yet arsenic oxide arsenoxide is poisonous, so in the fiberglass use, not environmental protection can be polluted to environment.
Summary of the invention
In sum, the present invention is necessary to provide a kind of fireproof glass steel composite material with good flame retardant effect and nontoxic environmental protection.
The present invention also is necessary to provide the method for preparing the fireproof glass steel composite material.
In addition, the present invention also is necessary to provide the application of fireproof glass steel composite material.
A kind of fireproof glass steel composite material; Comprise epoxy layer and phenolic aldehyde layer; This epoxy layer and phenolic aldehyde layer are compound in aggregates, and said epoxy layer is made up of the component of following weight portion: epoxy resin 80-100 part, magnesium hydroxide 4-7 part, cobalt iso-octoate 1-3 part, cyclohexanone 2-3 part, filler 10-15 part and pigment 2-3 part; Said phenolic aldehyde layer mainly is made up of the component of following weight portion: phenol 80-100 part, xylenes 25-30 part, formaldehyde 100-120 part, triphenyl phosphate 1.5-2 part and glass fibre 25-30 part; The oxygen index (OI) of said glass fiber reinforced plastics composite material is 75-99%, and shore hardness is 98-101D.
Preferably, said epoxy layer is at least two-layer.
Preferably, said phenolic aldehyde layer is arranged between said epoxy layer and the epoxy layer.
Preferably, said filler is the mixture of a kind of in fineness 500-550 purpose iron powder or the copper powder or two kinds.
Preferably, said epoxy layer is made up of the component of following weight portion: 85 parts, 88 parts or 92 parts of epoxy resin; 5 parts or 7 parts of magnesium hydroxides; 2 parts or 2.5 parts of cobalt iso-octoates; 2.5 parts or 3 parts of cyclohexanone; 2.2 parts 2.5 parts of 12 parts of fillers or 14 parts and pigment.
Preferably, said phenolic aldehyde layer is made up of the component of following weight portion: 88 parts, 89 parts or 96 parts of phenol; 25 parts, 27 parts or 29 parts of xylenes; 112 parts, 114 parts or 118 parts in formaldehyde; 1.5 parts, 1.8 parts or 2 parts of triphenyl phosphates; 25 parts, 28 parts or 30 parts in glass fibre.
A kind of fireproof glass steel composite material; Comprise diepoxy layer and a phenolic aldehyde layer; Said phenolic aldehyde layer is arranged between the said diepoxy layer; And closely compound in aggregates, said epoxy layer is made up of the component of following weight portion: epoxy resin 88-92 part, 95-98 part or 99-100 part, 5 parts of magnesium hydroxides, cobalt iso-octoate 1-3 part, cyclohexanone 2-3 part, filler 12-13 part or 13-15 part and pigment 2 or 3 parts; Said phenolic aldehyde layer mainly is made up of the component of following weight portion: phenol 85-89 part, 96-98 part or 99-100 part; Xylenes 25-28 part or 28.5-30 part; Formaldehyde 112-114 part, 116-118 part or 119-120 part; Triphenyl phosphate 1.5-2 part and glass fibre 25-27 part, 27.5-28 part or 29-30 part, the oxygen index (OI) of said fireproof glass composite is 75-99%.
Preferably, said filler is a nano-calcium carbonate, and the average grain diameter of said nano-calcium carbonate is 350nm.
The preparation method of said nm-class active calcium carbonate comprises the steps: (1) suspension at calcium hydroxide, feeds the gas that contains carbon dioxide; Carbonization to carbonation rate is 33%; Add crystal structure adjusting agent, continuing carbonization is 8.0 to pH, adding surface charge and sterically hindered conditioning agent; Continue carbonization to pH be 7.0, generate nano level cube calcium carbonate; Said crystal structure adjusting agent is a kind of and composition thereof in phosphate, sulfate, acetate, citrate, monose or the polysaccharide, and its addition is 3.0% of a slurry weight; Said surface charge and sterically hindered conditioning agent are neopelex; The addition of surface charge and sterically hindered conditioning agent is 3.0% of a weight of calcium carbonate; (2) with C
16Aliphatic acid be mixed with aqueous solution covering; (3) the nano-calcium carbonate slurry is heated to 60 ℃, adds covering then, the addition of covering counts 3.5% with the weight of calcium carbonate; Coating the processing time is between 2 hours, with slurries filtration, and drying; Promptly obtain nm-class active calcium carbonate, the average grain diameter of said nano-calcium carbonate is 350nm.
A kind of method for preparing above-mentioned fireproof glass steel composite material may further comprise the steps:
Preparation epoxy layer material: drop into epoxy resin, filler and pigment in the agitated reactor respectively; The temperature of agitated reactor is controlled between 30-45 ℃ stirs; Add people's magnesium hydroxide, cyclohexanone and cobalt iso-octoate after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Preparation phenolic aldehyde layer material: phenol, triphenyl phosphate and xylenes are dropped in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde, and temperature is increased to 110-120 ℃ of reaction 60 minutes; Be reduced to 50-70 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Preparation glass fiber reinforced plastics composite material: in mould, place epoxy layer material, phenolic aldehyde layer material, carry out the high-temperature pressurizing moulding then, make that layer material and phenolic aldehyde layer material are in aggregates, obtain this glass fiber reinforced plastics composite material.
A kind of fireproof glass steel composite material, said glass fiber reinforced plastics composite material is used to prepare glass steel tile, and this glass steel tile is applied to building, automotive field.
Use antimony oxide to do fire retardant compared to the traditional glass steel composite material, employed fire retardant is mainly triphenyl phosphate and magnesium hydroxide in the glass fiber reinforced plastics composite material provided by the invention, and these two kinds of things all do not contain Toxic matter, and are environmentally friendly.Magnesium hydroxide also has the effect that suppresses the cigarette generation simultaneously, makes that the fire resistance of this glass fiber reinforced plastics composite material is better.
The specific embodiment
Below in conjunction with the specific embodiment glass fiber reinforced plastics composite material of the present invention and preparation method thereof is done further to describe.Specific embodiment in the specific embodiment is further explain the present invention, non-limiting protection scope of the present invention.
A kind of fireproof glass steel composite material provided by the invention; Comprise epoxy layer and phenolic aldehyde layer; Said phenolic aldehyde layer and said epoxy layer are compound in aggregates, and said epoxy layer is composed of the following components: epoxy resin, magnesium hydroxide, cobalt iso-octoate, cyclohexanone, filler and pigment; Said phenolic aldehyde layer is mainly composed of the following components: phenol, xylenes, formaldehyde, triphenyl phosphate and glass fibre.
Said epoxy resin, phenol, xylenes, formaldehyde are organism material; Said magnesium hydroxide and triphenyl phosphate are fire retardant; Said cobalt iso-octoate is a curing accelerator; Said cyclohexanone is a solvent.
The present invention also provides a kind of method for preparing the fireproof glass steel composite material, may further comprise the steps:
Preparation epoxy layer material: drop into epoxy resin, filler and pigment in the agitated reactor respectively; The temperature of agitated reactor is controlled between 30-45 ℃ stirs; Add people's magnesium hydroxide, cyclohexanone and cobalt iso-octoate after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Preparation phenolic aldehyde layer material: phenol, triphenyl phosphate and xylenes are dropped in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde, and temperature is increased to 110-120 ℃ of reaction 60 minutes; Be reduced to 50-70 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Preparation glass fiber reinforced plastics composite material: in mould, place epoxy layer material, phenolic aldehyde layer material, carry out the high-temperature pressurizing moulding then, make that said epoxy layer material and phenolic aldehyde layer material are in aggregates, obtain this glass fiber reinforced plastics composite material.
The present invention also provides a kind of application of fireproof glass steel composite material: a kind of glass fiber reinforced plastics composite material, and said glass fiber reinforced plastics composite material is used to prepare glass steel tile, and this glass steel tile is applied to building, automotive field.
Said filler and glass fibre have the mechanical performance that improves this glass fiber reinforced plastics composite material, like shock resistance.
Each performance number among each embodiment of table 1 in the performance of products parameter list is obtained by following test condition and/or method of testing.According to standard GB/T3139-1982 Test method for thermal conductivity of glassfiber reinforced plastics the thermal conductivity factor of this glass fiber reinforced plastics composite material is measured;
According to standard GB/T9341-2008 the impact strength of glass fiber reinforced plastics composite material Izod is tested;
According to standard GB/T230.2-2002 the shore hardness of glass fiber reinforced plastics composite material is tested.
According to. according to standard GB 5454-85, measure the oxygen index (OI) of glass fiber reinforced plastics composite material with HC-1 type limiting oxygen index determination appearance.
Constituent and preparation method to glass fiber reinforced plastics composite material of the present invention specifies below in conjunction with specific embodiment.
Embodiment 1
At first; Extracting epoxy resin 80g, fineness are that 500 purpose iron powder 10g and pigment 2g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 45 ℃ stirs; Add people's magnesium hydroxide 4g, cyclohexanone 2g and cobalt iso-octoate 1g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 80g, triphenyl phosphate 1.5g and xylenes 25g and drop in the agitated reactor, heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 100g, and temperature is increased to 118 ℃ of reactions 60 minutes; Be reduced to about 50 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 25g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 15 minutes in 900 ℃ flame, after flame removed, the material surface carbonization is not burnt, and was indeformable.
Comparative Examples 1
Magnesium hydroxide among the embodiment 1 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 1 with manufacturing process.
The glass fiber reinforced plastics composite material of this Comparative Examples burnt in 900 ℃ flame 15 minutes, had flame then to burn, and removed flame and extinguished after 10 seconds, produced strong black smoke during burning.
Embodiment 2
At first; Extracting epoxy resin 100g, fineness are that 550 purpose iron powder 15g and pigment 3g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 7g, cyclohexanone 3g and cobalt iso-octoate 3g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 100g, triphenyl phosphate 2g and xylenes 30g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 120g, and temperature is increased to 120 ℃ of reactions 60 minutes; Be reduced to about 70 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 30g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 10 minutes in 1000 ℃ flame, after flame removed, the material surface carbonization was not burnt, distortion.
Comparative Examples 2
Magnesium hydroxide among the embodiment 2 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 2 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 10 minutes in 1000 ℃ flame, there is flame then to burn, removes flame and extinguish after 12 seconds, produce strong black smoke during burning.
Embodiment 3
At first; Extracting epoxy resin 85g, fineness are that 500 purpose iron powder 14g and pigment 2.2g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5.8g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 88g, triphenyl phosphate 1.8g and xylenes 25g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 112g, and temperature is increased to 110 ℃ of reactions 60 minutes; Be reduced to about 60 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 25g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place shellring oxygen layer material, place two layers of phenolic aldehyde layer material then; Epoxy layer and phenolic aldehyde layer space; And each phenolic aldehyde layer is arranged between the diepoxy layer, carries out the high-temperature pressurizing moulding then, makes that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 15 minutes in 1000 ℃ flame, after flame removed, the material surface carbonization is not burnt, and was indeformable.
Comparative Examples 3
Magnesium hydroxide among the embodiment 3 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 2 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 15 minutes in 1000 ℃ flame, there is flame then to burn, removes flame and extinguish after 8 seconds, produce strong black smoke during burning.
Embodiment 4
At first; Extracting epoxy resin 88g, fineness are that 500 purpose iron powder 12g and pigment 2.5g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 89g, triphenyl phosphate 1.5g and xylenes 27g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 114g, and temperature is increased to 110 ℃ of reactions 60 minutes; Be reduced to about 60 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 28g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place shellring oxygen layer material, place two layers of phenolic aldehyde layer material then; Epoxy layer and phenolic aldehyde layer space; And each phenolic aldehyde layer is arranged between the diepoxy layer, carries out the high-temperature pressurizing moulding then, makes that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After fire-retardant this glass fiber reinforced plastics composite material of present embodiment burnt 15 minutes in 1200 ℃ flame, after flame removed, the material surface carbonization was not burnt, distortion.
Comparative Examples 4
Magnesium hydroxide among the embodiment 4 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 4 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 15 minutes in 1200 ℃ flame, there is flame then to burn, removes flame and extinguish after 9 seconds, produce strong black smoke during burning.
Embodiment 5
At first; Extracting epoxy resin 92g, fineness are that 500 purpose iron powder 14g and pigment 2.5g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 96g, triphenyl phosphate 1.5g and xylenes 29g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 118g, and temperature is increased to 120 ℃ of reactions 60 minutes; Be reduced to about 55 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 30g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place five layers of epoxy layer material, place three layers of phenolic aldehyde layer material then; Epoxy layer and phenolic aldehyde layer space; And each phenolic aldehyde layer is arranged between the diepoxy layer, carries out the high-temperature pressurizing moulding then, makes that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 30 minutes in 1000 ℃ flame, after flame removed, the material surface carbonization was not burnt, distortion.
Comparative Examples 5
Magnesium hydroxide among the embodiment 5 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 5 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 30 minutes in 1000 ℃ flame, there is flame then to burn, removes flame and extinguish after 10 seconds, produce strong black smoke during burning.
Embodiment 6
At first; Extracting epoxy resin 95g, fineness are that 550 purpose iron powder 6g and copper powder 6g and pigment 2g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 2g and cobalt iso-octoate 1g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 85g, triphenyl phosphate 1.5g and xylenes 28g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 112g, and temperature is increased to 120 ℃ of reactions 60 minutes; Be reduced to about 55 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 27g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 45 minutes in 900 ℃ flame, after flame removed, the material surface carbonization is not burnt, and was indeformable.
Comparative Examples 6
Magnesium hydroxide among the embodiment 6 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 6 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 10 minutes in 900 ℃ flame, there is flame then to burn, removes flame and extinguish after 12 seconds, produce strong black smoke during burning.
Embodiment 7
At first; Extracting epoxy resin 98g, fineness are that 500 purpose copper powder 15g and pigment 3g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 3g and cobalt iso-octoate 3g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 98g, triphenyl phosphate 2g and xylenes 28.5g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 116g, and temperature is increased to 120 ℃ of reactions 60 minutes; Be reduced to about 55 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 27.5g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After this glass fiber reinforced plastics composite material of this enforcement burnt 60 minutes in 900 ℃ flame, after flame removed, the material surface carbonization is not burnt, and was indeformable.
Comparative Examples 7
Magnesium hydroxide among the embodiment 7 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 7 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 60 minutes in 900 ℃ flame, there is flame then to burn, removes flame and extinguish after 12 seconds, produce strong black smoke during burning.
Embodiment 8
At first; Extracting epoxy resin 99g, nano-calcium carbonate 15g and pigment 3g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 2g and cobalt iso-octoate 2g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 99g, triphenyl phosphate 2g and xylenes 29g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 118g, and temperature is increased to 115 ℃ of reactions 60 minutes; Be reduced to about 55 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 29g and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, can be processed into glass steel tile.
After the glass fiber reinforced plastics composite material of present embodiment burnt 10 minutes in 1000 ℃ flame, after flame removed, the material surface carbonization is not burnt, and was indeformable.
Comparative Examples 8
Magnesium hydroxide among the embodiment 8 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 8 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 10 minutes in 1000 ℃ flame, there is flame then to burn, removes flame and extinguish after 8 seconds, produce strong black smoke during burning.
Embodiment 9
At first; Extracting epoxy resin 99g, fineness are that 500 purpose copper powder 15g and pigment 3g drop in the agitated reactor respectively; The temperature of agitated reactor is controlled at about 30 ℃ stirs; Add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 3g after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Then, get phenol 100g, triphenyl phosphate 2g and xylenes 29.5g drop in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde 119g, and temperature is increased to 115 ℃ of reactions 60 minutes; Be reduced to about 55 ℃ with regard to temperature then, carry out dehydration, the dehydration back adds glass fibre 30g and carries out preimpregnation; Can prepare the phenolic aldehyde layer material;
Once more, in mould, place one deck epoxy layer material, place one deck phenolic aldehyde layer material then; Adding one deck epoxy layer material, carry out the high-temperature pressurizing moulding then, make that this trilaminate material is in aggregates; Obtain this fireproof glass steel composite material, and be processed into glass steel tile.
The glass fiber reinforced plastics composite material of present embodiment takes fire when fire burns is arranged after in 1500 ℃ flame, burning 30 minutes, and produces a spot of cigarette.
Comparative Examples 9
Magnesium hydroxide among the embodiment 9 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 9 with manufacturing process.
After the glass fiber reinforced plastics composite material of this Comparative Examples burnt 50 minutes in 1500 ℃ flame, there is flame then to burn, removes flame and extinguish after 13 seconds, produce strong black smoke during burning.
Employed fire retardant is mainly triphenyl phosphate and magnesium hydroxide in the fireproof glass steel composite material provided by the invention, and these two kinds of things all do not contain Toxic matter, and are environmentally friendly.Magnesium hydroxide also has generation of the cigarette of inhibition and anlistatig effect simultaneously, makes that the fire resistance of this glass fiber reinforced plastics composite material is better.Can learn that by combustion test in the foregoing description not so glass fiber reinforced plastics composite material provided by the invention is almost.In addition, glass fiber reinforced plastics composite material of the present invention is a three-decker, can strengthen the heat-insulating property of this flame retardant glass fiber reinforced plastic.Each performance that sees also table 1 pair each embodiment glass fiber reinforced plastics composite material is done detailed description.
Performance of products parameter list among each embodiment of table 1
Can be drawn by table 1, fireproof glass steel composite material of the present invention has higher oxygen index (OI), and thermal conductivity factor is also lower, explains that the effect of heat insulation of this flame retardant glass fiber reinforced plastic is preferable.Oxygen index (OI) belongs to and does not fire article more than 70%.Shore hardness and impact strength are big, explain that the mechanical performance of this flame retardant glass fiber reinforced plastic is also higher, are very suitable for building and automotive field.Compared to prior art; Fireproof glass steel composite material of the present invention has excellent flame-retardant performance; Because fire retardant is a magnesium hydroxide, magnesium hydroxide also can effectively improve the corrosion resistance of this glass fiber reinforced plastics composite material, thereby increases the service life of this glass fiber reinforced plastics composite material.And magnesium hydroxide reacts under the condition of high temperature and obtains magnesia, environmentally safe.The present invention can also strengthen this glass fiber reinforced plastics composite material mechanical strength through adding some metal packings and glass fibre in addition.
Fireproof glass steel composite material of the present invention can be used to make glass fiber reinforced plastic door and window or glass steel tile, can be applicable to building trade, can also be used to making door and window or other parts of automobile.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. fireproof glass steel composite material; It is characterized in that: comprise epoxy layer and phenolic aldehyde layer; Said epoxy layer and phenolic aldehyde layer are compound in aggregates, and said epoxy layer is made up of the component of following weight portion: epoxy resin 80-100 part, magnesium hydroxide 4-7 part, cobalt iso-octoate 1-3 part, cyclohexanone 2-3 part, filler 10-15 part and pigment 2-3 part; Said phenolic aldehyde layer mainly is made up of the component of following weight portion: phenol 80-100 part, xylenes 25-30 part, formaldehyde 100-120 part, triphenyl phosphate 1.5-2 part and glass fibre 25-30 part; The oxygen index (OI) of said glass fiber reinforced plastics composite material is 75-99%, and shore hardness is 98-101D.
2. fireproof glass steel composite material according to claim 1 is characterized in that: said epoxy layer comprises two-layer at least, and said phenolic aldehyde layer is arranged between said epoxy layer and the epoxy layer.
3. fireproof glass steel composite material according to claim 1 is characterized in that: said filler is the mixture of a kind of in iron powder or the copper powder or two kinds, and the fineness of said filler is the 500-550 order.
4. fireproof glass steel composite material according to claim 3 is characterized in that: said epoxy layer is made up of the component of following weight portion: 85 parts, 88 parts or 92 parts of epoxy resin; 5 parts or 7 parts of magnesium hydroxides; 2 parts or 2.5 parts of cobalt iso-octoates; 2.5 parts or 3 parts of cyclohexanone; 2.2 parts or 2.5 parts of 12 parts of fillers or 14 parts and pigment.
5. fireproof glass steel composite material according to claim 4 is characterized in that: said phenolic aldehyde layer is made up of the component of following weight portion: 88 parts, 89 parts or 96 parts of phenol; 25 parts, 27 parts or 29 parts of xylenes; 112 parts, 114 parts or 118 parts in formaldehyde; 1.5 parts, 1.8 parts or 2 parts of triphenyl phosphates; 25 parts, 28 parts or 30 parts in glass fibre.
6. fireproof glass steel composite material; It is characterized in that: comprise diepoxy layer and a phenolic aldehyde layer; Said phenolic aldehyde layer is arranged between the said diepoxy layer; And compound in aggregates, said epoxy layer is made up of the component of following weight portion: epoxy resin 88-92 part, 95-98 part or 99-100 part, 5 parts of magnesium hydroxides, cobalt iso-octoate 1-3 part, cyclohexanone 2-3 part, filler 12-13 part, 13-15 part and pigment 2 or 3 parts; Said phenolic aldehyde layer is made up of the component of following weight portion: phenol 85-89 part, 96-98 part or 99-100 part; Xylenes 25-28 part or 28.5-30 part; Formaldehyde 112-114 part, 116-118 part or 119-120 part; Triphenyl phosphate 1.5-2 part and glass fibre 25-27 part, 27.5-28 part, 29-30 part, the oxygen index (OI) of said fireproof glass composite is 75-99%.
7. fireproof glass steel composite material according to claim 6 is characterized in that: said filler is a nano-calcium carbonate, and the average grain diameter of said nano-calcium carbonate is 350nm.
8. fireproof glass steel composite material; It is characterized in that: comprise diepoxy layer and a phenolic aldehyde layer; Said phenolic aldehyde layer is arranged between the said diepoxy layer; And closely compound in aggregates, said epoxy layer is made up of the component of following weight portion: 2 parts of 80 parts of epoxy resin, 4 parts of magnesium hydroxides, 1 part of cobalt iso-octoate, 2 parts of cyclohexanone, 10 parts of fillers and pigment; Said phenolic aldehyde layer mainly is made up of the component of following weight portion: 25 parts in 80 parts of phenol, 25 parts of xylenes, 100 parts in formaldehyde, 1.5 parts of triphenyl phosphates and glass fibre; The oxygen index (OI) of said fireproof glass composite is 82%.
9. method for preparing like each described fireproof glass steel composite material of claim 1-8 may further comprise the steps:
Preparation epoxy layer material: epoxy resin, filler and pigment are dropped in the agitated reactor; The temperature of agitated reactor is controlled between 30-45 ℃ stirs; Add magnesium hydroxide, cyclohexanone and cobalt iso-octoate after stirring, the back processing and preparing that continues to stir obtains the epoxy layer materials for later use;
Preparation phenolic aldehyde layer material: phenol, triphenyl phosphate and xylenes are dropped in the agitated reactor, and heat temperature raising to 90 ℃ reaction 60 minutes adds formaldehyde, and temperature is increased to 110-120 ℃ of reaction 60 minutes; Then temperature is reduced to 50-70 ℃, carries out dehydration, the dehydration back adds glass fibre and carries out preimpregnation; Processing and preparing obtains the phenolic aldehyde layer material;
Preparation glass fiber reinforced plastics composite material: in mould, place said epoxy layer material, said phenolic aldehyde layer material, carry out the high-temperature pressurizing moulding then, make that said epoxy layer material and phenolic aldehyde layer material are in aggregates, obtain glass fiber reinforced plastics composite material.
10. one kind by each described fireproof glass steel composite material of claim 1-8, and it is characterized in that: said glass fiber reinforced plastics composite material is used to prepare glass steel tile, and this glass steel tile is applied to building, automotive field.
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| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN104120835A (en) * | 2014-07-07 | 2014-10-29 | 国家电网公司 | Resin-based rain board and manufacturing method thereof |
| CN105086366A (en) * | 2015-08-10 | 2015-11-25 | 南通德瑞森复合材料有限公司 | Glass fiber reinforced plastic |
| CN106496953A (en) * | 2016-11-30 | 2017-03-15 | 北京天宜上佳新材料股份有限公司 | A kind of glass steel tile back of the body and its production technology |
| CN106751481A (en) * | 2016-11-30 | 2017-05-31 | 北京天宜上佳新材料股份有限公司 | A kind of fiberglass and by its obtained fiberglass dovetail |
| CN107031071A (en) * | 2017-05-02 | 2017-08-11 | 广西北海跃达玻璃钢制品有限公司 | A kind of fiberglass sand inclusion tile makes production method |
| CN109535336A (en) * | 2018-09-12 | 2019-03-29 | 濮阳市盛源石油化工（集团）有限公司 | A kind of halogen-free flameproof unsaturated polyester resin glass fibre reinforced plastics and preparation method thereof |
| CN109836768A (en) * | 2017-11-27 | 2019-06-04 | 宜兴市乐华冶金辅助材料有限公司 | A kind of fireproof glass steel composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN103013036B (en) * | 2012-12-14 | 2015-03-18 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN104120835A (en) * | 2014-07-07 | 2014-10-29 | 国家电网公司 | Resin-based rain board and manufacturing method thereof |
| CN105086366A (en) * | 2015-08-10 | 2015-11-25 | 南通德瑞森复合材料有限公司 | Glass fiber reinforced plastic |
| CN106496953A (en) * | 2016-11-30 | 2017-03-15 | 北京天宜上佳新材料股份有限公司 | A kind of glass steel tile back of the body and its production technology |
| CN106751481A (en) * | 2016-11-30 | 2017-05-31 | 北京天宜上佳新材料股份有限公司 | A kind of fiberglass and by its obtained fiberglass dovetail |
| CN106496953B (en) * | 2016-11-30 | 2018-12-21 | 北京天宜上佳高新材料股份有限公司 | A kind of glass steel tile back and its production technology |
| CN106751481B (en) * | 2016-11-30 | 2018-12-21 | 北京天宜上佳高新材料股份有限公司 | A kind of glass reinforced plastic and glass reinforced plastic dovetail as made from it |
| CN107031071A (en) * | 2017-05-02 | 2017-08-11 | 广西北海跃达玻璃钢制品有限公司 | A kind of fiberglass sand inclusion tile makes production method |
| CN109836768A (en) * | 2017-11-27 | 2019-06-04 | 宜兴市乐华冶金辅助材料有限公司 | A kind of fireproof glass steel composite material |
| CN109535336A (en) * | 2018-09-12 | 2019-03-29 | 濮阳市盛源石油化工（集团）有限公司 | A kind of halogen-free flameproof unsaturated polyester resin glass fibre reinforced plastics and preparation method thereof |
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