CN102729547B - 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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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, the advantage such as corrosion-resistant, is therefore widely used in the field such as automobile, building.The field such as automobile, building is comparatively paid close attention to the flame-retarding characteristic of glass fiber reinforced plastics composite material.The fire retardant using in glass fiber reinforced plastics composite material is at present generally antimony oxide, and its flame retardant effect is poor.And in antimony oxide product, conventionally also have arsenic oxide arsenoxide, but arsenic oxide arsenoxide is poisonous, so can be to environment, not environmental protection in fiberglass use procedure.
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 is also necessary to provide the method for preparing fireproof glass steel composite material.
Separately, the present invention is also 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 described 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; Described phenolic aldehyde layer is mainly made up of the component of following weight portion: phenol 80-100 part, dimethylbenzene 25-30 part, formaldehyde 100-120 part, triphenyl phosphate 1.5-2 part and glass fibre 25-30 part, the oxygen index (OI) of described glass fiber reinforced plastics composite material is 75-99%, and shore hardness is 98-101D.
Preferably, described epoxy layer is at least two-layer.
Preferably, described phenolic aldehyde layer is arranged between described epoxy layer and epoxy layer.
Preferably, described filler is the mixture of a kind of in fineness 500-550 object iron powder or copper powder or two kinds.
Preferably, described 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, described 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 dimethylbenzene; 112 parts, 114 parts or 118 parts, formaldehyde; 1.5 parts, 1.8 parts or 2 parts of triphenyl phosphates; 25 parts, 28 parts or 30 parts, glass fibre.
A kind of fireproof glass steel composite material, comprise diepoxy layer and a phenolic aldehyde layer, described phenolic aldehyde layer is arranged between described diepoxy layer, and closely compound in aggregates, described epoxy layer is made up of the component of following weight portion: 2 or 3 parts of 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; Described phenolic aldehyde layer is mainly made up of the component of following weight portion: phenol 85-89 part, 96-98 part or 99-100 part; Dimethylbenzene 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 described fireproof glass composite is 75-99%.
Preferably, described filler is nano-calcium carbonate, and the average grain diameter of described nano-calcium carbonate is 350nm.
The preparation method of described nm-class active calcium carbonate, comprise the steps: (1) suspension at calcium hydroxide, pass into the gas that contains carbon dioxide, carbonization to carbonation rate is 33%, add crystal structure adjusting agent, continue carbonization to pH be 8.0, add surface charge and sterically hindered conditioning agent, continue carbonization to pH be 7.0, generate nano level calcite; Said crystal structure adjusting agent is one in phosphate, sulfate, acetate, citrate, monose or polysaccharide and composition thereof, and its addition is slurry weight 3.0%; Said surface charge and sterically hindered conditioning agent are neopelex; The addition of surface charge and sterically hindered conditioning agent is 3.0% of weight of calcium carbonate; (2) by C
16aliphatic acid be mixed with aqueous solution covering; (3) nano-calcium carbonate slurry is heated to 60 DEG C, then add covering, the addition of covering counts 3.5% with the weight of calcium carbonate, the coated processing time is between 2 hours, by slurries filtration, dry, obtain nm-class active calcium carbonate, the average grain diameter of described nano-calcium carbonate is 350nm.
A method of preparing above-mentioned fireproof glass steel composite material, comprises the following steps:
Prepare epoxy layer material: epoxy resin, filler and pigment are dropped into respectively in reactor, the temperature of reactor is controlled between 30-45 DEG C and is stirred, after stirring, add people's magnesium hydroxide, cyclohexanone and cobalt iso-octoate, after continuing to stir, processing prepares epoxy layer materials for later use;
Prepare phenolic aldehyde layer material: phenol, triphenyl phosphate and dimethylbenzene are dropped in reactor, be heated to 90 DEG C of reactions 60 minutes, add formaldehyde, temperature is increased to 110-120 DEG C of reaction 60 minutes; Then be reduced to 50-70 DEG C with regard to temperature, carry out dehydration, after dehydration, add glass fibre to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Prepare glass fiber reinforced plastics composite material: in mould, place epoxy layer material, phenolic aldehyde layer material, then carry out high-temperature pressurizing moulding, make layer material and phenolic aldehyde layer material in aggregates, obtain this glass fiber reinforced plastics composite material.
A kind of fireproof glass steel composite material, described glass fiber reinforced plastics composite material is for the preparation of glass steel tile, and this glass steel tile is applied to building, automotive field.
Use antimony oxide to do fire retardant compared to traditional glass steel composite material, the fire retardant using in glass fiber reinforced plastics composite material provided by the invention is mainly triphenyl phosphate and magnesium hydroxide, and these two kinds of things are not all containing noxious material, environmentally friendly.Magnesium hydroxide also has the effect that suppresses cigarette generation simultaneously, makes the fire resistance of this glass fiber reinforced plastics composite material better.
Detailed description of the invention
Below in conjunction with detailed description of the invention, glass fiber reinforced plastics composite material of the present invention and preparation method thereof is further described.Specific embodiment in detailed description of the invention is for further describing 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, described phenolic aldehyde layer and described epoxy layer are compound in aggregates, and described epoxy layer is composed of the following components: epoxy resin, magnesium hydroxide, cobalt iso-octoate, cyclohexanone, filler and pigment; Described phenolic aldehyde layer is mainly composed of the following components: phenol, dimethylbenzene, formaldehyde, triphenyl phosphate and glass fibre.
Described epoxy resin, phenol, dimethylbenzene, formaldehyde are organism material; Described magnesium hydroxide and triphenyl phosphate are fire retardant; Described cobalt iso-octoate is curing accelerator; Described cyclohexanone is solvent.
The present invention also provides a kind of method of preparing fireproof glass steel composite material, comprises the following steps:
Prepare epoxy layer material: epoxy resin, filler and pigment are dropped into respectively in reactor, the temperature of reactor is controlled between 30-45 DEG C and is stirred, after stirring, add people's magnesium hydroxide, cyclohexanone and cobalt iso-octoate, after continuing to stir, processing prepares epoxy layer materials for later use;
Prepare phenolic aldehyde layer material: phenol, triphenyl phosphate and dimethylbenzene are dropped in reactor, be heated to 90 DEG C of reactions 60 minutes, add formaldehyde, temperature is increased to 110-120 DEG C of reaction 60 minutes; Then be reduced to 50-70 DEG C with regard to temperature, carry out dehydration, after dehydration, add glass fibre to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Prepare glass fiber reinforced plastics composite material: in mould, place epoxy layer material, phenolic aldehyde layer material, then carry out high-temperature pressurizing moulding, make described epoxy layer material and phenolic aldehyde layer material 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 described glass fiber reinforced plastics composite material is for the preparation of glass steel tile, and this glass steel tile is applied to building, automotive field.
Described filler and glass fibre have the mechanical performance that improves this glass fiber reinforced plastics composite material, as shock resistance.
Each performance number in the each embodiment of table 1 in the performance parameter table of product is obtained by following test condition and/or method of testing.According to standard GB/T/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/T/T9341-2008, the impact strength of glass fiber reinforced plastics composite material Izod is tested;
According to standard GB/T/T230.2-2002, the shore hardness of glass fiber reinforced plastics composite material is tested.
According to. according to standard GB/T 5454-85, measure the oxygen index (OI) of glass fiber reinforced plastics composite material with HC-1 type oxygen index measurer.
Constituent and preparation method below in conjunction with specific embodiment to glass fiber reinforced plastics composite material of the present invention are described in detail.
Embodiment 1
First, extracting epoxy resin 80g, fineness are that 500 object iron powder 10g and pigment 2g drop into respectively in reactor, the temperature of reactor is controlled to 45 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 4g, cyclohexanone 2g and cobalt iso-octoate 1g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 80g, triphenyl phosphate 1.5g and dimethylbenzene 25g and drop in reactor, be heated to 90 DEG C of reactions 60 minutes, add formaldehyde 100g, temperature is increased to 118 DEG C of reactions 60 minutes; Then be reduced to 50 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 25g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 15 minutes in the flame of 900 DEG C, and after flame is removed, material surface carbonization, does not burn, indeformable.
Comparative example 1
Magnesium hydroxide in 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 example burns 15 minutes in the flame of 900 DEG C, has flame to burn, and extinguishes after removing 10 seconds of flame, produces strong black smoke when burning.
Embodiment 2
First, extracting epoxy resin 100g, fineness are that 550 object iron powder 15g and pigment 3g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 7g, cyclohexanone 3g and cobalt iso-octoate 3g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 100g, triphenyl phosphate 2g and dimethylbenzene 30g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 120g, and temperature is increased to 120 DEG C of reactions 60 minutes; Then be reduced to 70 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 30g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 10 minutes in the flame of 1000 DEG C, and after flame is removed, material surface carbonization, does not burn, distortion.
Comparative example 2
Magnesium hydroxide in embodiment 2 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 2 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 10 minutes in the flame of 1000 DEG C, has flame to burn, and extinguishes after removing 12 seconds of flame, produces strong black smoke when burning.
Embodiment 3
First, extracting epoxy resin 85g, fineness are that 500 object iron powder 14g and pigment 2.2g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5.8g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 88g, triphenyl phosphate 1.8g and dimethylbenzene 25g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 112g, and temperature is increased to 110 DEG C of reactions 60 minutes; Then be reduced to 60 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 25g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place shellring oxygen layer material, then place two layers of phenolic aldehyde layer material, epoxy layer and phenolic aldehyde layer space, and each phenolic aldehyde layer is arranged between diepoxy layer, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 15 minutes in the flame of 1000 DEG C, and after flame is removed, material surface carbonization, does not burn, indeformable.
Comparative example 3
Magnesium hydroxide in embodiment 3 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 2 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 15 minutes in the flame of 1000 DEG C, has flame to burn, and extinguishes after removing 8 seconds of flame, produces strong black smoke when burning.
Embodiment 4
First, extracting epoxy resin 88g, fineness are that 500 object iron powder 12g and pigment 2.5g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 89g, triphenyl phosphate 1.5g and dimethylbenzene 27g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 114g, and temperature is increased to 110 DEG C of reactions 60 minutes; Then be reduced to 60 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 28g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place shellring oxygen layer material, then place two layers of phenolic aldehyde layer material, epoxy layer and phenolic aldehyde layer space, and each phenolic aldehyde layer is arranged between diepoxy layer, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
Fire-retardant this glass fiber reinforced plastics composite material of the present embodiment burnt after 15 minutes in the flame of 1200 DEG C, and after flame is removed, material surface carbonization, does not burn, distortion.
Comparative example 4
Magnesium hydroxide in embodiment 4 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 4 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 15 minutes in the flame of 1200 DEG C, has flame to burn, and extinguishes after removing 9 seconds of flame, produces strong black smoke when burning.
Embodiment 5
First, extracting epoxy resin 92g, fineness are that 500 object iron powder 14g and pigment 2.5g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 2.5g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 96g, triphenyl phosphate 1.5g and dimethylbenzene 29g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 118g, and temperature is increased to 120 DEG C of reactions 60 minutes; Then be reduced to 55 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 30g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place five layers of epoxy layer material, then place three layers of phenolic aldehyde layer material, epoxy layer and phenolic aldehyde layer space, and each phenolic aldehyde layer is arranged between diepoxy layer, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 30 minutes in the flame of 1000 DEG C, and after flame is removed, material surface carbonization, does not burn, distortion.
Comparative example 5
Magnesium hydroxide in embodiment 5 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 5 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 30 minutes in the flame of 1000 DEG C, has flame to burn, and extinguishes after removing 10 seconds of flame, produces strong black smoke when burning.
Embodiment 6
First, extracting epoxy resin 95g, fineness are that 550 object iron powder 6g and copper powder 6g and pigment 2g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 2g and cobalt iso-octoate 1g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 85g, triphenyl phosphate 1.5g and dimethylbenzene 28g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 112g, and temperature is increased to 120 DEG C of reactions 60 minutes; Then be reduced to 55 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 27g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 45 minutes in the flame of 900 DEG C, and after flame is removed, material surface carbonization, does not burn, indeformable.
Comparative example 6
Magnesium hydroxide in embodiment 6 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 6 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 10 minutes in the flame of 900 DEG C, has flame to burn, and extinguishes after removing 12 seconds of flame, produces strong black smoke when burning.
Embodiment 7
First, extracting epoxy resin 98g, fineness are that 500 object copper powder 15g and pigment 3g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 3g and cobalt iso-octoate 3g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 98g, triphenyl phosphate 2g and dimethylbenzene 28.5g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 116g, and temperature is increased to 120 DEG C of reactions 60 minutes; Then be reduced to 55 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 27.5g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
This glass fiber reinforced plastics composite material of this enforcement burnt after 60 minutes in the flame of 900 DEG C, and after flame is removed, material surface carbonization, does not burn, indeformable.
Comparative example 7
Magnesium hydroxide in embodiment 7 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 7 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 60 minutes in the flame of 900 DEG C, has flame to burn, and extinguishes after removing 12 seconds of flame, produces strong black smoke when burning.
Embodiment 8
First, extracting epoxy resin 99g, nano-calcium carbonate 15g and pigment 3g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 2g and cobalt iso-octoate 2g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 99g, triphenyl phosphate 2g and dimethylbenzene 29g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 118g, and temperature is increased to 115 DEG C of reactions 60 minutes; Then be reduced to 55 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 29g to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, can be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burnt after 10 minutes in the flame of 1000 DEG C, and after flame is removed, material surface carbonization, does not burn, indeformable.
Comparative example 8
Magnesium hydroxide in embodiment 8 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 8 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 10 minutes in the flame of 1000 DEG C, has flame to burn, and extinguishes after removing 8 seconds of flame, produces strong black smoke when burning.
Embodiment 9
First, extracting epoxy resin 99g, fineness are that 500 object copper powder 15g and pigment 3g drop into respectively in reactor, the temperature of reactor is controlled to 30 DEG C of left and right to be stirred, after stirring, add people's magnesium hydroxide 5g, cyclohexanone 2.5g and cobalt iso-octoate 3g, after continuing to stir, processing prepares epoxy layer materials for later use;
Then, get phenol 100g, triphenyl phosphate 2g and dimethylbenzene 29.5g drop in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde 119g, and temperature is increased to 115 DEG C of reactions 60 minutes; Then be reduced to 55 DEG C of left and right with regard to temperature, carry out dehydration, after dehydration, add glass fibre 30g to carry out preimpregnation; Can prepare phenolic aldehyde layer material;
Again, in mould, place one deck epoxy layer material, then place one deck phenolic aldehyde layer material, adding one deck epoxy layer material, then carry out high-temperature pressurizing moulding, make this trilaminate material in aggregates, obtain this fireproof glass steel composite material, and be processed into glass steel tile.
The glass fiber reinforced plastics composite material of the present embodiment burns after 30 minutes in the flame of 1500 DEG C, takes fire, and produce a small amount of cigarette while having fire burning.
Comparative example 9
Magnesium hydroxide in embodiment 9 and triphenyl phosphate are all replaced with antimony oxide, and other components are all identical with embodiment 9 with manufacturing process.
The glass fiber reinforced plastics composite material of this comparative example burns after 50 minutes in the flame of 1500 DEG C, has flame to burn, and extinguishes after removing 13 seconds of flame, produces strong black smoke when burning.
The fire retardant using in fireproof glass steel composite material provided by the invention is mainly triphenyl phosphate and magnesium hydroxide, and these two kinds of things are not all containing noxious material, environmentally friendly.Magnesium hydroxide also has the generation of the cigarette of inhibition and anlistatig effect simultaneously, makes the fire resistance of this glass fiber reinforced plastics composite material better.Can be learnt by combustion test in above-described embodiment, 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 three-decker, can strengthen the heat-insulating property of this flame retardant glass fiber reinforced plastic.Referring to table 1 is described in detail each performance of each embodiment glass fiber reinforced plastics composite material.
The performance parameter table of product in the 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, illustrates that the effect of heat insulation of this flame retardant glass fiber reinforced plastic is better.Oxygen index (OI), more than 70%, belongs to and does not fire product.Shore hardness and impact strength are large, illustrate 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 good anti-flammability, because fire retardant is 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 and obtains magnesia, environmentally safe under the condition of high temperature.The present invention is by adding some metal packings and glass fibre can also strengthen this glass fiber reinforced plastics composite material mechanical strength in addition.
Fireproof glass steel composite material of the present invention can be used to manufacture glass fiber reinforced plastic door and window or glass steel tile, can be applicable to building trade, can also be used to manufacture door and window or other parts of automobile.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (9)
1. a fireproof glass steel composite material, it is characterized in that: comprise epoxy layer and phenolic aldehyde layer, described epoxy layer comprises two-layer, described phenolic aldehyde layer is arranged between described epoxy layer and epoxy layer, described epoxy layer and phenolic aldehyde layer are compound in aggregates, and described epoxy layer is made up of the component of following weight portion: 3 parts of 100 parts of epoxy resin 80 ?, 7 parts of magnesium hydroxide 4 ?, 3 parts of cobalt iso-octoate 1 ?, 3 parts of cyclohexanone 2 ?, 15 parts of filler 10 ?and pigment 2 ?; Described phenolic aldehyde layer is mainly made up of the component of following weight portion: phenol 80 ?100 parts, dimethylbenzene 25 ?30 parts, formaldehyde 100 ?120 parts, triphenyl phosphate 1.5 ?2 parts and glass fibre 25 ?30 parts, the oxygen index (OI) of described glass fiber reinforced plastics composite material be 79 ?99%, shore hardness be 98 ?101D;
Described filler is iron powder, copper powder or nano-calcium carbonate;
The shore hardness of glass fiber reinforced plastics composite material according to standard GB/T/T230.2 ?2002 test;
The oxygen index (OI) of glass fiber reinforced plastics composite material is according to standard GB/T 5454-85, with HC ?1 type oxygen index measurer measure.
2. fireproof glass steel composite material according to claim 1, is characterized in that: described filler is the mixture of a kind of in iron powder or copper powder or two kinds, and the fineness of described filler is 500 ?550 orders.
3. fireproof glass steel composite material according to claim 2, is characterized in that: described 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.
4. fireproof glass steel composite material according to claim 3, is characterized in that: described 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 dimethylbenzene; 112 parts, 114 parts or 118 parts, formaldehyde; 1.5 parts, 1.8 parts or 2 parts of triphenyl phosphates; 25 parts, 28 parts or 30 parts, glass fibre.
5. a fireproof glass steel composite material, it is characterized in that: comprise two epoxy layers and a phenolic aldehyde layer, described phenolic aldehyde layer is arranged between described diepoxy layer, and compound in aggregates, described epoxy layer is made up of the component of following weight portion: 2 or 3 parts of 92 parts of epoxy resin 88 ?, 98 parts of 95 ?or 100 parts of 99 ?, 5 parts of magnesium hydroxides, 3 parts of cobalt iso-octoate 1 ?, 3 parts of cyclohexanone 2 ?, 13 parts of filler 12 ?, 15 parts of 13 ?and pigment; Described phenolic aldehyde layer is made up of the component of following weight portion: phenol 85 ?89 parts, 96 ?98 parts or 99 ?100 parts; Dimethylbenzene 25 ?28 parts or 28.5 ?30 parts; Formaldehyde 112 ?114 parts, 116 ?118 parts or 119 ?120 parts; Triphenyl phosphate 1.5 ?2 parts and glass fibre 25 ?27 parts, 27.5 ?28 parts, 29 ?30 parts, the oxygen index (OI) of described fireproof glass composite be 79 ?99%;
The oxygen index (OI) of glass fiber reinforced plastics composite material is according to standard GB/T 5454-85, with HC ?1 type oxygen index measurer measure.
6. fireproof glass steel composite material according to claim 5, is characterized in that: described filler is nano-calcium carbonate, and the average grain diameter of described nano-calcium carbonate is 350nm.
7. a fireproof glass steel composite material, it is characterized in that: comprise two epoxy layers and a phenolic aldehyde layer, described phenolic aldehyde layer is arranged between described diepoxy layer, and closely compound in aggregates, described 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; Described phenolic aldehyde layer is mainly made up of the component of following weight portion: 25 parts, 80 parts of phenol, 25 parts of dimethylbenzene, 100 parts, formaldehyde, 1.5 parts of triphenyl phosphates and glass fibre; The oxygen index (OI) of described fireproof glass composite is 82%;
The oxygen index (OI) of glass fiber reinforced plastics composite material is according to standard GB/T 5454-85, with HC ?1 type oxygen index measurer measure.
8. a method of preparing the fireproof glass steel composite material as described in claim 1 ?7 any one, comprises the following steps:
Prepare epoxy layer material: epoxy resin, filler and pigment are dropped in reactor, by the temperature of reactor be controlled at 30 ?stir between 45 DEG C, after stirring, add magnesium hydroxide, cyclohexanone and cobalt iso-octoate, after continuing to stir, processing prepares epoxy layer materials for later use;
Prepare phenolic aldehyde layer material: phenol, triphenyl phosphate and dimethylbenzene are dropped in reactor, are heated to 90 DEG C of reactions 60 minutes, add formaldehyde, by temperature be increased to 110 ?120 DEG C of reactions 60 minutes; Then temperature is reduced to 50 ?70 DEG C, carry out dehydration, after dehydration, add glass fibre to carry out preimpregnation; Processing prepares phenolic aldehyde layer material;
Prepare glass fiber reinforced plastics composite material: in mould, place described epoxy layer material, described phenolic aldehyde layer material, then carry out high-temperature pressurizing moulding, make described epoxy layer material and phenolic aldehyde layer material in aggregates, obtain glass fiber reinforced plastics composite material.
9. the fireproof glass steel composite material as described in claim 1 ?7 any one, is characterized in that: described glass fiber reinforced plastics composite material is for the preparation of glass steel tile, and this glass steel tile is applied to building, automotive field.
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| CN103013036B (en) * | 2012-12-14 | 2015-03-18 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN104120835B (en) * | 2014-07-07 | 2016-08-24 | 国家电网公司 | A kind of manufacture method of resin base flashing board |
| 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 |
| 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 |
| 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 |
| 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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