CN102391513A - Silicon-resin flame retardant agent and synthesis method thereof - Google Patents
Silicon-resin flame retardant agent and synthesis method thereof Download PDFInfo
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- CN102391513A CN102391513A CN201110248459XA CN201110248459A CN102391513A CN 102391513 A CN102391513 A CN 102391513A CN 201110248459X A CN201110248459X A CN 201110248459XA CN 201110248459 A CN201110248459 A CN 201110248459A CN 102391513 A CN102391513 A CN 102391513A
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Abstract
The invention discloses a silicon-resin flame retardant agent and a synthesis method thereof, and relates to a silicon-resin flame retardant agent made of bisphenol A cross-linked hydrogen-containing silicon oil and a synthesis method thereof. The obtained silicon-resin flame retardant agent made of bisphenol A cross-linked hydrogen-containing silicon oil has the advantages that the flame retardant effect is good, the variety of the silicon-containing flame retardant agent is increased, the application of the silicon-containing flame retardant agent is expanded, the synthesis method is simple, and the cost is low. The silicon-resin flame retardant agent is obtained by reaction of bisphenol A, hydrogen-containing silicon oil, catalysts and methylbenzene. The synthesis method comprises the following steps of: adding the bisphenol A, the hydrogen-containing silicon oil, the catalysts and the methylbenzene into a reaction container in sequence, putting the reaction container in a constant-temperature oil bath for reaction, rotatably evaporating a system after reaction, then cleaning with diethyl ether, drying and obtaining the silicon-resin flame retardant agent. If the silicon-containing flame retardant agent is added into a polycarbonate system, and the obtained flame retardant material is environmentally-friendly, and is excellent in mechanical property and high in flame retardant efficiency. According to the mass percentage, 97% pure polycarbonate and 3% flame retardant agent are mixed uniformly and formed to obtain the flame retardant material, the oxygen index is higher than 35.6%, and the vertical burning test passes V0 grade.
Description
Technical field
The present invention relates to a kind of silicone resin fire retardant and compound method thereof, be specifically related to silicone resin fire retardant of the crosslinked containing hydrogen silicone oil of a kind of dihydroxyphenyl propane and preparation method thereof.
Background technology
Silicon be flame-retarded technology be a kind of novel enjoy that people pay close attention to be used for one of fire-retardant new technology of engineering plastics.Up to the present its fire-retardant research mainly comprises two aspects: 1. ZGK 5 fire retardant; It has the oxygen index that improves material, the ability that reduces heat release and press down cigarette; This fire retardant mainly comprises: polymethyl siloxane, phenyl silicone and side chain ZGK 5, and the side chain ZGK 5 has better flame retardant effect.People such as Lji M. study and have synthesized the side chain PSI, and discover that it has the good flame effect to polycarbonate (PC), add 6%, and oxygen index can reach 40.6.With polymethyl siloxane and polycarbonate-copolymerized high oxygen index (LOI=37) material that obtains.The fire retardant mechanism of ZGK 5 in polycarbonate is considered to the surface that ZGK 5 can be moved to polycarbonate, forms resist heat insulation, oxygen barrier.Zhou Wenjun, people such as Yang Hui study the pyrolysis behavior of straight chain and side chain, have confirmed that the side chain ZGK 5 has higher thermostability than straight chain ZGK 5.2. cage modle siloxanes oligopolymer (POSS) is used for the polymer nanocomposite strongthener; POSS is used to Vestolen PP 7052 (PP), polybutyl terapthalate (PBT), the urethane fire-retardant researchs of polymkeric substance such as (PU) as fire retardant; POSS can effectively reduce the HRR of material; But the contribution to oxygen index is limited, and the fire-retardant requirement that satisfy the engineering macromolecular material also needs further research.By the GE company of the U.S., the productions such as NEC Corporation of Japan, it is mainly used in the fire-retardant of polycarbonate to silicon-series five-retardant (ZGK 5) at present.
Yet also more single to the research of silicon-series five-retardant both at home and abroad at present, what practical application was arranged mainly is polymethyl siloxane, phenyl silicone and side chain ZGK 5 etc., and is mainly used in the polycarbonate.Add sulphonate and can effectively improve the effect of silicon-series five-retardant, can cause environmental pollution but introduce sulfonic group.Present in addition silica-based fire retardant price is very expensive, and general application probably is difficult to accept.
Summary of the invention
A kind of silicone resin fire retardant and compound method thereof have been the purpose of this invention is to provide; Obtain the silicone resin fire retardant of the crosslinked containing hydrogen silicone oil of dihydroxyphenyl propane, have the good flame effect, increased the kind of resinous silicon fire retardant; Expanded the application of siliceous fire retardant, compound method is simple, cost is low.
Silicone resin fire retardant of the present invention is to be obtained by 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene prepared in reaction by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride, iron trichloride.
The compound method of silicone resin fire retardant of the present invention realizes through following steps: one, take by weighing 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride, iron trichloride; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, catalyzer and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 30～70 ℃ constant temperature oil bath; Reacted 2～5 hours; Then oil bath is warming up to 70～120 ℃, isothermal reaction is 3～10 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
It is a kind of web-like silicon resin structure of the crosslinked containing hydrogen silicone oil of bridge that siliceous resin fire retardant of the present invention adopts dihydroxyphenyl propane and side chain containing hydrogen silicone oil generation condensation reaction to generate with the dihydroxyphenyl propane.The compound method of siliceous resin fire retardant of the present invention is simple, cost is low.
Siliceous resin fire retardant of the present invention is evenly sneaked in the polycarbonate based polyalcohol (PC based polyalcohol); The polycarbonate fire retardant material that both can have high flame resistance, this polycarbonate fire retardant material good flame resistance, oxygen index reaches 35.6%; The test of UL94 vertical combustion is through the V0 level; And the polycarbonate fire retardant material is pollution-free, and siliceous resin fire retardant addition is low, and mechanical property is excellent.
Description of drawings
Fig. 1 is the structural representation of the silicone resin fire retardant of embodiment one; Wherein
representes containing hydrogen silicone oil, and
representes dihydroxyphenyl propane;
Fig. 2 is Fourier's infrared spectrum; Curve a is the infrared spectrum of the dihydroxyphenyl propane in the step 1 of embodiment 15 among the figure; Curve b is the infrared spectrum of the containing hydrogen silicone oil in the step 1 of embodiment 15, and curve c is the infrared spectrum of embodiment 15 synthetic silicone resin fire retardants;
Fig. 3 is embodiment 15 synthetic silicone resin fire retardants
13The C-NMR wave spectrogram;
Fig. 4 is embodiment 15 synthetic silicone resin fire retardants
29The Si-NMR wave spectrogram;
Fig. 5 is Fourier's infrared spectrum of embodiment 16, and curve a is the infrared spectrum of the dihydroxyphenyl propane in the step 1 among the figure, and curve b is the infrared spectrum of the containing hydrogen silicone oil in the step 1, and curve c is the infrared spectrum of synthetic silicone resin fire retardant;
Fig. 6 is Fourier's infrared spectrum of embodiment 17, and curve a is the infrared spectrum of the dihydroxyphenyl propane in the step 1 among the figure, and curve b is the infrared spectrum of the containing hydrogen silicone oil in the step 1, and curve c is the infrared spectrum of synthetic silicone resin fire retardant;
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment is the silicone resin fire retardant; It is to be obtained by 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene prepared in reaction by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride, iron trichloride.
The silicone resin fire retardant of this embodiment adopts dihydroxyphenyl propane and side chain containing hydrogen silicone oil generation condensation reaction to generate, and is a kind of web-like silicon resin structure of the crosslinked containing hydrogen silicone oil of bridge with the dihydroxyphenyl propane.This crosslinked reticulated structure improves the thermostability of fire retardant own greatly, and the dihydroxyphenyl propane that adds simultaneously makes polymkeric substance such as fire retardant and PC that good consistency arranged.Its structural representation is as shown in Figure 1; Wherein
representes containing hydrogen silicone oil, and
representes dihydroxyphenyl propane.
The siliceous resin fire retardant of this embodiment is evenly sneaked in the polycarbonate, and the polycarbonate fire retardant material that both can have high flame resistance (wherein, is pressed mass percent content; Siliceous resin fire retardant is 3%, and polycarbonate is 97%), this polycarbonate fire retardant material good flame resistance; Oxygen index reaches 35.6%, and the test of UL-94 vertical combustion is through the V0 level, and the polycarbonate fire retardant material is pollution-free; Siliceous resin fire retardant addition is low, and mechanical property is excellent.
Embodiment two: what this embodiment and embodiment one were different is that the silicone resin fire retardant is to be obtained by 2.5～10 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1.5 part catalyzer and 72～80 parts toluene prepared in reaction by weight.Other parameter is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is that the silicone resin fire retardant is to be obtained by 3～6 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1 part catalyzer and 72～80 parts toluene prepared in reaction by weight.Other parameter is identical with embodiment one.
More preferably be that the silicone resin fire retardant is to be obtained by 3.38 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part catalyzer and 72 parts toluene prepared in reaction by weight in this embodiment.
Embodiment four: this embodiment and embodiment one are different is that the quality percentage composition of active hydrogen in the containing hydrogen silicone oil is 0.12%～5%.Other parameter is identical with embodiment one.
The quality percentage composition of active hydrogen preferably 0.15%～2% in the containing hydrogen silicone oil in this embodiment, better is 0.18%.
Embodiment five: this embodiment is that the compound method of silicone resin fire retardant realizes through following steps: one, take by weighing 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride, iron trichloride; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, catalyzer and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 30～70 ℃ constant temperature oil bath; Reacted 2～5 hours; Then oil bath is warming up to 70～120 ℃, isothermal reaction is 3～10 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
This embodiment adopts dihydroxyphenyl propane and side chain containing hydrogen silicone oil generation condensation reaction to generate the silicone resin structure of the crosslinked containing hydrogen silicone oil of dihydroxyphenyl propane, and the preparation method of siliceous resin fire retardant is simple, cost is low.
The synthetic white solid silicone resin fire retardant product that obtains of this embodiment is the silicone resin fire retardant described in the embodiment one.
Embodiment six: what this embodiment and embodiment five were different is to take by weighing 2.5～10 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1.5 part catalyzer and 72～80 parts toluene in the step 1 by weight.Other step and parameter are identical with embodiment five.
Embodiment seven: what this embodiment and embodiment five were different is to take by weighing 3～6 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1 part catalyzer and 72～80 parts toluene in the step 1 by weight.Other step and parameter are identical with embodiment five.
Embodiment eight: what this embodiment and embodiment five were different is to take by weighing 3.38 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part catalyzer and 72 parts toluene in the step 1 by weight.Other step and parameter are identical with embodiment five.
Embodiment nine: this embodiment is different with one of embodiment five to eight be in the step 1 in the containing hydrogen silicone oil quality percentage composition of active hydrogen be 0.12%～5%.Other step and parameter are identical with one of embodiment five to eight.
Embodiment ten: this embodiment is different with one of embodiment five to eight be in the step 1 in the containing hydrogen silicone oil quality percentage composition of active hydrogen be 0.15%～2%.Other step and parameter are identical with one of embodiment five to eight.
Embodiment nine: this embodiment is different with one of embodiment five to eight be in the step 1 in the containing hydrogen silicone oil quality percentage composition of active hydrogen be 0.18%.Other step and parameter are identical with one of embodiment five to eight.
Embodiment ten: this embodiment is different with one of embodiment five to nine is in the step 2 reaction vessel to be put into 50～68 ℃ constant temperature oil bath, reacts 2.5～4 hours.Other step and parameter are identical with one of embodiment five to nine.
Embodiment 11: this embodiment is different with one of embodiment five to nine is in the step 2 reaction vessel to be put into 65 ℃ constant temperature oil bath, reacts 3 hours.Other step and parameter are identical with one of embodiment five to nine.
Embodiment 12: what this embodiment was different with one of embodiment five to 11 is then oil bath to be warming up to 75～100 ℃ in the step 2, and isothermal reaction is 3～8 hours again.Other step and parameter are identical with one of embodiment five to 11.
Embodiment 13: what this embodiment was different with one of embodiment five to 11 is then oil bath to be warming up to 80～90 ℃ in the step 2, and isothermal reaction is 3～5 hours again.Other step and parameter are identical with one of embodiment five to 11.
Embodiment 14: what this embodiment was different with one of embodiment five to 11 is then oil bath to be warming up to 85 ℃ in the step 2, and isothermal reaction is 3 hours again.Other step and parameter are identical with one of embodiment five to 11.
Embodiment 15: this embodiment is the compound method of silicone resin fire retardant; It is realized through following steps: one, take by weighing 2.5 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part stannous octoate catalyst and 72 parts toluene by weight, wherein the quality percentage composition of active hydrogen is 0.18% in the containing hydrogen silicone oil; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, stannous octoate catalyst and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 65 ℃ constant temperature oil bath; Reacted 3 hours; Then oil bath is warming up to 85 ℃, isothermal reaction is 3 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
This embodiment synthetic silicone resin fire retardant is to be obtained by 2.5 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part catalyzer and 72 parts toluene prepared in reaction by weight.
Fourier's infrared spectrum of this embodiment synthetic silicone resin fire retardant as a comparison, is also painted the infrared spectrum of dihydroxyphenyl propane in the step 1 and containing hydrogen silicone oil to Fig. 2 shown in the curve c among Fig. 2, respectively shown in curve a and curve b.Visible by Fig. 2, curve a goes up 3360cm
-1Corresponding is the phenolic group in the dihydroxyphenyl propane; Curve b goes up 2164cm
-1The strong peak at place is corresponding to the charateristic avsorption band of si-h bond in the containing hydrogen silicone oil; Yet in curve c, these two absorption peaks have all disappeared, and dehydrogenation reaction has taken place for this explanation dihydroxyphenyl propane and containing hydrogen silicone oil.Simultaneously in institute's sintetics, the charateristic avsorption band 1607and3074cm of phenyl ring
-1There is obvious absorption to explain that also institute's sintetics is the reticulated structure of the crosslinked containing hydrogen silicone oil of dihydroxyphenyl propane.。
This embodiment synthetic silicone resin fire retardant
13The C-NMR wave spectrogram is as shown in Figure 3, can be known by Fig. 3, and-2.54ppm peak is corresponding to-Si (CH
3)
3C on the group.Near 31ppm be-Si (CH
3)
3The characteristic peak of methyl C in the group, the multiplet at 118.99-127.92ppm place is the absorption peak of C on the phenyl in the spectrogram.
This embodiment synthetic silicone resin fire retardant
29The Si-NMR wave spectrogram is as shown in Figure 4, and is visible, from
29In the Si-NMR wave spectrogram-absorption peak of 20.00ppm belongs to-Si (CH
3)
2Si atom in the-group, and-36.72 belong to-the Si-H group with-37.23ppm place absorption peak at-64.95ppm place is-SiO
1.5The absorption peak of group.
Evenly sneak into this embodiment synthetic silicone resin fire retardant in the polycarbonate; The polycarbonate fire retardant material that both can have high flame resistance, this polycarbonate fire retardant material good flame resistance, oxygen index reaches 35.6%; The test of UL-94 vertical combustion is through the V0 level; And the polycarbonate fire retardant material is pollution-free, and siliceous resin fire retardant addition is low, and mechanical property is excellent.Wherein, Concrete preparation method with polycarbonate fire retardant material of high flame resistance is: press mass percent; Take by weighing 3% siliceous resin fire retardant of this embodiment synthetic and 97% polycarbonate, then with polycarbonate at 240 ℃ of following heating and meltings, more siliceous resin fire retardant is added in the polycarbonate of molten state; Through melt blending 10min, reshaping promptly obtains the polycarbonate fire retardant material of high flame resistance.
Oxygen index is pressed the GB/T2408-1996 test in this embodiment, and the GB/T2406-1994 test is pressed in the UL94 test.
Embodiment 16: this embodiment is the compound method of silicone resin fire retardant; It is realized through following steps: one, take by weighing 3.38 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part stannous octoate catalyst and 72 parts toluene by weight, wherein the quality percentage composition of active hydrogen is 0.18% in the containing hydrogen silicone oil; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, stannous octoate catalyst and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 65 ℃ constant temperature oil bath; Reacted 3 hours; Then oil bath is warming up to 85 ℃, isothermal reaction is 3 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
This embodiment synthetic silicone resin fire retardant is to be obtained by 3.38 parts dihydroxyphenyl propane, 20 parts containing hydrogen silicone oil, 0.1 part catalyzer and 72 parts toluene prepared in reaction by weight.
Fourier's infrared spectrum of this embodiment synthetic silicone resin fire retardant as a comparison, is also painted the infrared spectrum of dihydroxyphenyl propane in the step 1 and containing hydrogen silicone oil to Fig. 5 shown in the curve c among Fig. 5, respectively shown in curve a and curve b.Visible by Fig. 5, curve a goes up 3360cm
-1Corresponding is the phenolic group in the dihydroxyphenyl propane; Curve b goes up 2164cm
-1The strong peak at place is corresponding to the charateristic avsorption band of si-h bond in the containing hydrogen silicone oil; Yet in curve c, 2164cm
-1The strong peak completely dissolve at place, and 3360cm
-1Corresponding phenolic group still exists, just intensity relatively a little less than.Dehydrogenation reaction has taken place in this explanation dihydroxyphenyl propane and containing hydrogen silicone oil, but that the phenolic group in the dihydroxyphenyl propane has is remaining.In institute's sintetics, the charateristic avsorption band 1607and3074cm of phenyl ring
-1There is obvious absorption to explain that also institute's sintetics is the reticulated structure of the crosslinked containing hydrogen silicone oil of dihydroxyphenyl propane.
Evenly sneak into this embodiment synthetic silicone resin fire retardant in the polycarbonate; The polycarbonate fire retardant material that both can have high flame resistance, this polycarbonate fire retardant material good flame resistance, oxygen index reaches 34.8%; The test of UL-94 vertical combustion is through the V0 level; And the polycarbonate fire retardant material is pollution-free, and siliceous resin fire retardant addition is low, and mechanical property is excellent.Wherein, Concrete preparation method with polycarbonate fire retardant material of high flame resistance is: press mass percent; Take by weighing 3.5% siliceous resin fire retardant of this embodiment synthetic and 96.5% polycarbonate, then with polycarbonate at 240 ℃ of following heating and meltings, more siliceous resin fire retardant is added in the polycarbonate of molten state; Through melt blending 10min, reshaping promptly obtains the polycarbonate fire retardant material of high flame resistance.
Oxygen index is pressed the GB/T2408-1996 test in this embodiment, and the GB/T2406-1994 test is pressed in the UL94 test.
Embodiment 17: this embodiment is the compound method of silicone resin fire retardant; It is realized through following steps: one, take by weighing 3.38 parts dihydroxyphenyl propane, 30 parts containing hydrogen silicone oil, 0.1 part stannous octoate catalyst and 72 parts toluene by weight, wherein the quality percentage composition of active hydrogen is 0.18% in the containing hydrogen silicone oil; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, stannous octoate catalyst and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 65 ℃ constant temperature oil bath; Reacted 3 hours; Then oil bath is warming up to 85 ℃, isothermal reaction is 3 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
This embodiment synthetic silicone resin fire retardant is to be obtained by 3.38 parts dihydroxyphenyl propane, 30 parts containing hydrogen silicone oil, 0.1 part catalyzer and 72 parts toluene prepared in reaction by weight.
Fourier's infrared spectrum of this embodiment synthetic silicone resin fire retardant as a comparison, is also painted the infrared spectrum of dihydroxyphenyl propane in the step 1 and containing hydrogen silicone oil to Fig. 6 shown in the curve c among Fig. 6, respectively shown in curve a and curve b.Visible by Fig. 6, curve a goes up 3360cm
-1Corresponding is the phenolic group in the dihydroxyphenyl propane; Curve b goes up 2164cm
-1The strong peak at place is corresponding to the charateristic avsorption band of si-h bond in the containing hydrogen silicone oil; Yet in curve c, 3360cm
-1Corresponding phenolic group completely dissolve, and 2164cm
-1The corresponding silicon hydrogen group in place still exists, just intensity relatively a little less than.Dehydrogenation reaction has taken place in this explanation dihydroxyphenyl propane and containing hydrogen silicone oil, but the silicon hydrogen base in the containing hydrogen silicone oil has remaining.In institute's sintetics, the charateristic avsorption band 1607 and the 3074cm of phenyl ring
-1There is obvious absorption to explain that also institute's sintetics is the reticulated structure of the crosslinked containing hydrogen silicone oil of dihydroxyphenyl propane.
Evenly sneak into this embodiment synthetic silicone resin fire retardant in the polycarbonate; The polycarbonate fire retardant material that both can have high flame resistance, this polycarbonate fire retardant material good flame resistance, oxygen index reaches 34.3%; The test of UL-94 vertical combustion is through the V0 level; And the polycarbonate fire retardant material is pollution-free, and siliceous resin fire retardant addition is low, and mechanical property is excellent.Wherein, Concrete preparation method with polycarbonate fire retardant material of high flame resistance is: press mass percent; Take by weighing 3% siliceous resin fire retardant of this embodiment synthetic and 97% polycarbonate, then with polycarbonate at 240 ℃ of following heating and meltings, more siliceous resin fire retardant is added in the polycarbonate of molten state; Through melt blending 10min, reshaping promptly obtains the polycarbonate fire retardant material of high flame resistance.
Oxygen index is pressed the GB/T2408-1996 test in this embodiment, and the GB/T2406-1994 test is pressed in the UL94 test.
Claims (10)
1. silicone resin fire retardant; It is characterized in that the silicone resin fire retardant is to be obtained by 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene prepared in reaction by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride or iron trichloride.
2. a kind of silicone resin fire retardant according to claim 1 is characterized in that the silicone resin fire retardant is to be obtained by 2.5～10 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1.5 part catalyzer and 72～80 parts toluene prepared in reaction by weight.
3. a kind of silicone resin fire retardant according to claim 1 is characterized in that the silicone resin fire retardant is to be obtained by 3～6 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1 part catalyzer and 72～80 parts toluene prepared in reaction by weight.
4. the compound method of silicone resin fire retardant as claimed in claim 1; The compound method that it is characterized in that the silicone resin fire retardant realizes through following steps: one, take by weighing 2～15 parts dihydroxyphenyl propane, 10～30 parts containing hydrogen silicone oil, 0.05～2 part catalyzer and 50～100 parts toluene by weight; Wherein the quality percentage composition of active hydrogen is 0.1%～10% in the containing hydrogen silicone oil, and said catalyzer is stannous octoate, tin protochloride, platinum dioxide, Platinic chloride or iron trichloride; Two, the dihydroxyphenyl propane that step 1 is taken by weighing, containing hydrogen silicone oil, catalyzer and toluene add in the reaction vessel that whisking appliance and reflux exchanger are housed successively; Then reaction vessel is put into 30～70 ℃ constant temperature oil bath; Reacted 2～5 hours; Then oil bath is warming up to 70～120 ℃, isothermal reaction is 3～10 hours again, must react the back system; Three, the system rotary evaporation removes and desolvates and micromolecular compound after the reaction that step 2 is obtained, again with after the ether washing, dry white solid silicone resin fire retardant product, promptly accomplish the synthetic of silicone resin fire retardant.
5. the compound method of silicone resin fire retardant according to claim 4 is characterized in that taking by weighing by weight in the step 1 2.5～10 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1.5 part catalyzer and 72～80 parts toluene.
6. the compound method of silicone resin fire retardant according to claim 4 is characterized in that taking by weighing by weight in the step 1 3～6 parts dihydroxyphenyl propane, 20～30 parts containing hydrogen silicone oil, 0.1～1 part catalyzer and 72～80 parts toluene.
7. according to the compound method of claim 4,5 or 6 described silicone resin fire retardants, it is characterized in that in the step 1 that the quality percentage composition of active hydrogen is 0.15%～2% in the containing hydrogen silicone oil.
8. according to the compound method of claim 4,5 or 6 described silicone resin fire retardants, it is characterized in that in the step 1 that the quality percentage composition of active hydrogen is 0.18% in the containing hydrogen silicone oil.
9. according to the compound method of claim 4,5 or 6 described silicone resin fire retardants, it is characterized in that in the step 2 reaction vessel being put into 50～68 ℃ constant temperature oil bath, reacted 2.5～4 hours.Embodiment 11: this embodiment with
10. according to the compound method of claim 4,5 or 6 described silicone resin fire retardants, it is characterized in that then oil bath being warming up to 75～100 ℃ in the step 2, isothermal reaction is 3～8 hours again.
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| CN108129632A (en) * | 2017-12-21 | 2018-06-08 | 广东工业大学 | A kind of siliceous flame-proof polyol and its preparation and flame retardant polyurethane |
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| US6310145B1 (en) * | 1997-12-04 | 2001-10-30 | General Electric Company | Flame retardant polyetherimide resin composition with polycarbonate and polysiloxane |
| CN101874074A (en) * | 2007-11-29 | 2010-10-27 | 出光兴产株式会社 | Polycarbonate resin composition, polycarbonate resin molded article, and method for producing same |
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| US6310145B1 (en) * | 1997-12-04 | 2001-10-30 | General Electric Company | Flame retardant polyetherimide resin composition with polycarbonate and polysiloxane |
| CN101874074A (en) * | 2007-11-29 | 2010-10-27 | 出光兴产株式会社 | Polycarbonate resin composition, polycarbonate resin molded article, and method for producing same |
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| 董全霄等: "聚碳酸酯用无卤阻燃剂研究进展", 《工程塑料应用》, vol. 34, no. 10, 31 December 2006 (2006-12-31) * |
| 贾修伟，刘治国: "硅系阻燃剂研究进展", 《化工进展》, vol. 22, no. 8, 31 December 2003 (2003-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129632A (en) * | 2017-12-21 | 2018-06-08 | 广东工业大学 | A kind of siliceous flame-proof polyol and its preparation and flame retardant polyurethane |
| CN108129632B (en) * | 2017-12-21 | 2021-03-16 | 广东工业大学 | Silicon-containing flame-retardant polyol, preparation thereof and flame-retardant polyurethane |
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| CN102391513B (en) | 2013-05-29 |
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