CN105110356B - Silicon-magnesium composite oxide and preparation method thereof - Google Patents
Silicon-magnesium composite oxide and preparation method thereof Download PDFInfo
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- CN105110356B CN105110356B CN201510510854.9A CN201510510854A CN105110356B CN 105110356 B CN105110356 B CN 105110356B CN 201510510854 A CN201510510854 A CN 201510510854A CN 105110356 B CN105110356 B CN 105110356B
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Abstract
The invention discloses a silicon-magnesium composite oxide and a preparation method thereof, wherein the silicon-magnesium composite oxide comprises the following magnesium elements: the molar ratio of the silicon element is 5:1-1.5:1 or 1:2-1: 5. The invention has the beneficial effects that: the raw materials are rich in source, the magnesium-rich brine is fully utilized, the production process is simple without modification treatment and easy to industrialize, the silicon-magnesium composite oxide has the advantages of less impurities, high whiteness, controllable appearance and quality and the like, the silicon-magnesium content is adjustable, the synergistic effect of the silicon-magnesium composite oxides with different silicon-magnesium contents on an expansion flame-retardant system is convenient to control, the flame-retardant performance of the expansion flame-retardant polymer can be improved, and a good synergistic effect is shown. The silicon-magnesium composite oxide is an amorphous composite oxide, can conveniently realize industrial amplification during production, and has low production cost.
Description
Technical field
The present invention relates to technical field of chemistry, more particularly to a kind of silicon Magnesium coumpoud oxide and preparation method thereof.
Background technology
Contain substantial amounts of magnesium resource in China's Brine resources, but comprehensive utilization ratio is relatively low, and especially preparing salt by working up seawater is bitter
Halogen, its product is generally magnesium chloride hexahydrate and epsom salt, and added value is relatively low, and production capacity surplus.It is large batch of per existing every year
Rich magnesium bittern fully, cannot be comprehensively utilized effectively, cause the wasting of resources, then as discharging of waste liquid, be influenceed again ecological
Efficient, the higher value application of magnesium resource become important the grinding in Brine Chemistry comprehensive utilization of resources field in environment, therefore bittern
Study carefully problem.With the low value-added magnesium -based products such as magnesium chloride hexahydrate, epsom salt as raw material, it is attached that preparation possesses New function, height
Value added magnesium salts product is a kind of important method of bittern magnesium resource comprehensive utilization.
Intumescent Retardant System has the advantages that low cigarette, low toxicity, without molten drop, have become the fire-retardant research neck of current most active
One of domain, general principle is that ammonium polyphosphate (APP) is heated and reacted with carbon forming agent (CA), discharges ammonia and vapor, hair
Bubble forms the foamed char with iris action, completely cuts off heat and mass transfer, so as to reach fire-retardant effect.But intumescent
Fire retardant efficiency need to be improved, the combination property of the very big easily influence body of addition.
Compared with natural minerals, silicon Magnesium coumpoud oxide is the artificial silicon Magnesium coumpoud oxide for preparing, with impurity it is few,
Whiteness is high, pattern and it is quality controllable the advantages of, can equally improve the fire resistance of expandable flame retardant polymer, show good
Synergistic effect.The silicon content of magnesium of the artificial silicon Magnesium coumpoud oxide for preparing is adjustable.The silicon magnesium composite oxygen of different silicon content of magnesium
There is not been reported for synergistic effect of the compound to Intumescent Retardant System.To be utilized with magnesium chloride hexahydrate and sodium silicate as raw material herein
Hydro-thermal method prepares the silicon Magnesium coumpoud oxide of different silicon content of magnesium, is then applied in expansion flame-retarded polyolefin system, grinds
Study carefully its synergistic effect to Intumescent Retardant System.
The content of the invention
Bittern comprehensive utilization ability is improved in order to meet, the flame retarding efficiency of Intumescent Retardant System is improved, addition is reduced, carried
Carrier mechanical property demand high, the embodiment of the invention provides a kind of adjustable can the facilitating of silicon content of magnesium and controls flame retarding efficiency
Silicon Magnesium coumpoud oxide and preparation method thereof.
In order to realize foregoing invention purpose, the invention provides a kind of silicon Magnesium coumpoud oxide, the silicon magnesium combined oxidation
Magnesium elements in thing：Element silicon mol ratio is 5:1-1.5:1 or 1:2-1:5.
In order to goal of the invention is better achieved, the present invention also provides a kind of preparation method of silicon Magnesium coumpoud oxide, described
Preparation method is comprised the following steps：Magnesium chloride hexahydrate and sodium silicate are configured to solution, magnesium chloride hexahydrate solution is placed in container
In, sodium silicate solution is added dropwise while stirring, pH value is adjusted with alkali lye after being added dropwise to complete, mother liquor is persistently stirred to obtain at room temperature, by institute
Mother liquor is fitted into the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining and is reacted, taken out after the completion of reaction reaction solution oneself
Room temperature so is cooled to, reaction solution is discarded and filter after supernatant liquor, filtrate is washed and silicon magnesium combined oxidation is obtained after drying
Thing.
The mol ratio of the magnesium chloride hexahydrate and sodium silicate is 5:1-1.5:1, or magnesium chloride hexahydrate and sodium silicate mole
Than being 1:2-1:5
The alkali lye is sodium hydroxide solution, and the span of the pH value is 9-11.
Reaction temperature in the high-temperature high-pressure reaction kettle is 120-160 DEG C, and the time of reaction is 18-30h.
The mixing time for obtaining the mother liquor is 1-5 hours.
The dry temperature is 100-110 DEG C, and the dry time is 10-15h.
In order to goal of the invention is better achieved, the present invention also provides a kind of expansion flame-retarded polyolefin, and the expandable flame retardant gathers
The recipe ingredient of alkene is：Silicon Magnesium coumpoud oxide, expansion type flame retardant and polyolefin.
The recipe ingredient of the expansion flame-retarded polyolefin is calculated by weight as：0.5-3 parts of silicon Magnesium coumpoud oxide, expansion
17-25 parts and polyolefin 75-90 parts of type fire retardant.
In order to goal of the invention is better achieved, the present invention also provides a kind of preparation method of expansion flame-retarded polyolefin, described
Preparation method is comprised the following steps：The silicon Magnesium coumpoud oxide, expansion type flame retardant and polyolefin are taken in proportion, after drying
It is well mixed, expansion flame-retarded polyolefin is obtained by double-screw extruding pelletizing.
The drying temperature of the polyolefin is 70-90 DEG C, and drying time is 100-180min.
The silicon Magnesium coumpoud oxide, expansion type flame retardant drying temperature are 90-110 DEG C, and drying time is 1.5-3h.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：Raw material sources enrich, and take full advantage of richness
Magnesium bittern, without modification, simple production process is easy to industrialization, and silicon Magnesium coumpoud oxide has that impurity is few, whiteness is high, shape
Looks and it is quality controllable the advantages of, silicon content of magnesium is adjustable, and the silicon Magnesium coumpoud oxide of different silicon content of magnesium is to expandable flame retardant body
The synergistic effect of system is convenient to be controlled, it is possible to increase the fire resistance of expandable flame retardant polymer, shows good synergistic effect.Silicon
Magnesium coumpoud oxide is that industrial amplification, low production cost can be easily realized during production for unformed composite oxides.
And polyolefin Effect on Mechanical Properties is small after silicon Magnesium coumpoud oxide addition of the invention, addition very little, but fire resistance
It is high.
Brief description of the drawings
Fig. 1 is the infrared spectrum of silicon Magnesium coumpoud oxide,
Fig. 2 is the XRD spectra of silicon Magnesium coumpoud oxide, 1, M5S；2、M3S；3、MS；4、MS2；5、MS3；6、MS5.
Fig. 3 is the scanning electron microscopic picture of the silicon Magnesium coumpoud oxide MS3 of embodiment 4
Fig. 4 is the scanning electron microscopic picture of the silicon Magnesium coumpoud oxide MS2 of embodiment 3
Fig. 5 is the scanning electron microscopic picture of the silicon Magnesium coumpoud oxide MS of embodiment 2
Fig. 6 is the scanning electron microscopic picture of the silicon Magnesium coumpoud oxide M3S of embodiment 1
Specific embodiment
Relatively low for bittern comprehensive utilization ratio, Intumescent Retardant System flame retarding efficiency is not high, the big influence carrier power of addition
The problem of performance is learned, the present invention provides a kind of silicon Magnesium coumpoud oxide and preparation method thereof.
Sodium silicate, Shandong Eastern Mountain group, modulus 3.28；Remaining chemical reagent is analyzes pure, purchased from Chinese medicines group；
Polypropylene (PP), S2040, Shanghai Sai Ke petrochemical industries Co., Ltd；
Magnesium chloride hexahydrate, Solution on Chemical Reagents in Shanghai company of magnesia Chinese Medicine group；
Expansion type flame retardant, Shandong Sunris New Materials Co., Ltd., 201A is made up of ammonium polyphosphate and triazine carbon forming agent, matter
Measuring ratio is:3：1:
Polypropylene (PP), S2040, Shanghai Sai Ke petrochemical industries Co., Ltd；
The Taiwan of high density polyethylene (HDPE) 7200 is moulded；
Ethylene-vinyl acetate copolymer EVA7350M Taiwans are moulded.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 1
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 3:1, pH11 is adjusted with sodium hydroxide solution after being added dropwise to complete, 2 are persistently stirred at room temperature
Hour obtains mother liquor, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, and 24h is reacted at 160 DEG C,
Then take out reactor and naturally cool to room temperature, discard supernatant liquor, then filtering gained precipitation is washed with distilled water to nothing
Cl-, 110 DEG C dry 12h after obtain silicon Magnesium coumpoud oxide, be designated as M3S, be put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 2
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 1:1.PH value is adjusted to 11 with sodium hydroxide solution after being added dropwise to complete, and is persistently stirred at room temperature
Mix 1 hour, be fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, 30h is reacted at 120 DEG C, so
Reactor being taken out afterwards and naturally cooling to room temperature, discard supernatant liquor, then filtering gained precipitation is washed with distilled water to without Cl-,
100 DEG C dry 15h after obtain silicon Magnesium coumpoud oxide, be designated as MS, be put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 3
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 1:2.PH value to 10.5 is adjusted with sodium hydroxide solution after being added dropwise to complete, is continued at room temperature
Stirring 5 hours, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, and 26h is reacted at 130 DEG C,
Then take out reactor and naturally cool to room temperature, discard supernatant liquor, then filtering gained precipitation is washed with distilled water to nothing
Cl-, 110 DEG C dry 10h after obtain silicon Magnesium coumpoud oxide, be designated as MS2, be put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 4
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 1:3.PH value is adjusted to 9 with sodium hydroxide solution after being added dropwise to complete, and is persistently stirred at room temperature
Mix 4 hours, be fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, 18h is reacted at 140 DEG C, so
Reactor being taken out afterwards and naturally cooling to room temperature, discard supernatant liquor, then filtering gained precipitation is washed with distilled water to without Cl-,
110 DEG C to dry and obtain silicon Magnesium coumpoud oxide after 11h and be designated as MS3, are put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 5
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 2:1, pH value is adjusted to 9 with sodium hydroxide solution after being added dropwise to complete, persistently stir at room temperature
Mother liquor is mixed 2 hours to obtain, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, reacted at 160 DEG C
24h, then takes out reactor and naturally cools to room temperature, discards supernatant liquor, and then filtering gained precipitation is washed with distilled water to
Without Cl-, 110 DEG C dry 12h after obtain silicon Magnesium coumpoud oxide, be designated as M2S, be put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 6
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 5:1, pH value is adjusted to 11 with sodium hydroxide solution after being added dropwise to complete, persistently stir at room temperature
Mother liquor is mixed 3 hours to obtain, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, reacted at 160 DEG C
24h, then takes out reactor and naturally cools to room temperature, discards supernatant liquor, and then filtering gained precipitation is washed with distilled water to
Without Cl-, 110 DEG C dry 12h after obtain silicon Magnesium coumpoud oxide, be designated as M5S, be put into drier standby.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 7
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure magnesium chloride molten
Liquid and sodium silicate solution, magnesium chloride solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls magnesium chloride and flower bulb
The mol ratio of alkali is 1:5.PH value to 11 is adjusted with sodium hydroxide solution after being added dropwise to complete, persistently stirs 3 hours female at room temperature
Liquid, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, and 18h is reacted at 140 DEG C, then takes out
Reactor naturally cools to room temperature, discards supernatant liquor, and then filtering gained precipitation is washed with distilled water to without Cl-,105℃
Silicon Magnesium coumpoud oxide is obtained after drying 12h, drier is put into standby.The silicon Magnesium coumpoud oxide for obtaining is multiple for unformed silicon magnesium
Oxide is closed, MS5 is designated as.
The preparation of the silicon Magnesium coumpoud oxide of embodiment 8
By magnesium chloride hexahydrate and sodium silicate, add deionized water to be configured to the solution of 0.5mol/L respectively, measure six water chlorinations
Magnesium solution and sodium silicate solution, magnesium chloride hexahydrate solution is placed in container, and sodium silicate solution is added dropwise while stirring, controls six water
The mol ratio of magnesium chloride and sodium silicate is 1.5:1, pH value to 9 is adjusted with sodium hydroxide solution after being added dropwise to complete, continue at room temperature
Stirring obtains mother liquor in 2 hours, is fitted into mother liquid obtained in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, anti-at 130 DEG C
28h is answered, reactor is then taken out and is naturally cooled to room temperature, discard supernatant liquor, filtering gained precipitation, then with distillation water washing
To without Cl-, 110 DEG C dry 12h after obtain silicon Magnesium coumpoud oxide, be designated as M1.5S, be put into drier standby.
The preparation of the expansion flame-retarded polyolefin of embodiment 9
Polypropylene dries 2h at 70 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 2h at 100 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M3S10g, expansion type flame retardant IFR240g and polypropylene 750g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 10
Polypropylene dries 110min at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide are dried at 110 DEG C
1.5h。
Recipe ingredient is：Silicon Magnesium coumpoud oxide MS10g, expansion type flame retardant IFR240g and polypropylene 750g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 3 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 190 DEG C, and injection pressure is 70Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 11
Polypropylene dries 100min at 90 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide are dried at 100 DEG C
2h。
Recipe ingredient is：Silicon Magnesium coumpoud oxide MS2 10g, expansion type flame retardant IFR240g and polypropylene 750g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 10 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 12
Polypropylene dries 2h at 70 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide are dried at 110 DEG C
2.5h。
Recipe ingredient is：Silicon Magnesium coumpoud oxide MS3 10g, expansion type flame retardant IFR240g and polypropylene 750g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 210 DEG C, and injection pressure is 60Mpa.
Embodiment 13
Other are identical with embodiment 10, and difference is to be formulated difference：
Recipe ingredient is：Silicon Magnesium coumpoud oxide M3S 5g, expansion type flame retardant IFR245g and polypropylene 750g.
The preparation of the expansion flame-retarded polyolefin of embodiment 14
Other are identical with embodiment 10, and difference is to be formulated difference：
Recipe ingredient is：Silicon Magnesium coumpoud oxide M3S 15g, expansion type flame retardant IFR235g and polypropylene 750g.
The preparation of the expansion flame-retarded polyolefin of embodiment 15
Other are identical with embodiment 10, and difference is to be formulated difference：
Recipe ingredient is：Silicon Magnesium coumpoud oxide M3S 20g, expansion type flame retardant IFR230g and polypropylene 750g.
The preparation of the expansion flame-retarded polyolefin of embodiment 16
Other are identical with embodiment 10, and difference is to be formulated difference：
Recipe ingredient is：Silicon Magnesium coumpoud oxide M3S 30g, expansion type flame retardant IFR220g and polypropylene 750g.
The preparation of the expansion flame-retarded polyolefin of embodiment 17
Polypropylene dries 3h at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M2S 10g, expansion type flame retardant IFR200g and polypropylene 800g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
200 DEG C are set to, screw speed is 90r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 18
Polypropylene dries 3h at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M5S 10g, expansion type flame retardant IFR170g and polypropylene 900g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
180 DEG C are set to, screw speed is 70r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 210 DEG C, and injection pressure is 70Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 19
Polypropylene dries 3h at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide MS5 5g, expansion type flame retardant IFR170g and polypropylene 850g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 190 DEG C, and injection pressure is 60Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 20
Polypropylene dries 3h at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M1.5S 30g, expansion type flame retardant IFR170g and polypropylene 870g.
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polypropylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 21
Polyethylene dries 3h at 80 DEG C, and expansion type flame retardant IFR and silicon Magnesium coumpoud oxide dry 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M5S 10g, expansion type flame retardant IFR170g and high density polyethylene (HDPE)
7200 840g。
By in silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and polyethylene addition high-speed mixer, mix 5 minutes and mix
After closing uniformly, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process parameter：Head temperature sets
190 DEG C are set to, screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
The preparation of the expansion flame-retarded polyolefin of embodiment 22
Ethylene-vinyl acetate copolymer EVA7350M dries 3h, expansion type flame retardant IFR and silicon magnesium composite oxygen at 80 DEG C
Compound dries 3h at 90 DEG C.
Recipe ingredient is：Silicon Magnesium coumpoud oxide M2S 20g, expansion type flame retardant IFR170g and ethene-vinyl acetate are total to
Polymers EVA7350M 840g.
Silicon Magnesium coumpoud oxide, expansion type flame retardant IFR and ethylene-vinyl acetate copolymer EVA are added into mixed at high speed
In machine, mix after being well mixed within 5 minutes, cut by Screw Extrusion and granulated, obtain expansion flame-retarded polyolefin.Extruding-out process
Parameter：Head temperature is set to 190 DEG C, and screw speed is 80r/min.
Required test bars will be molded into after the expansion flame-retarded polyolefin particle drying of granulation, be then detected.Injection
The technological parameter of shaping is：Nozzle temperature is 200 DEG C, and injection pressure is 65Mpa.
Comparative example 1：It is pure PP to be formulated
Comparative example 2：It is IFR250g and polypropylene 750g to be formulated.
Wherein magnesium chloride hexahydrate obtains product for what salt manufacturing bittern treatment was obtained, it is also possible to use other magnesium chloride hexahydrates.
The formula (g) of the expansion flame-retarded polyolefin composite of table 1
Characterize and test
Using gravimetric detemination SiO2Content, using EDTA titration measuring content of MgO；Using German Brooker company
The type spectrometers of Tensor 27 carry out infrared spectrum analysis, and KBr pressed disc methods, test scope is 400-4000cm-1；Using German cloth
The Bruker D8 types diffractometers of Lu Ke companies carry out X-ray diffraction analysis, voltage 40kV, electric current 40mA, and 0.02 ° of step-length/
Step, speed 6 °/min, 2 θ=10-60 °.
Using the SEM-101 types intelligence oxygen index instrument of Southeast China University's Mechanical Academy, tested according to GB/T 2406.2-2009
Oxygen index (OI) (LOI), batten size is 130 × 6.5 × 3.2mm3。
Using the CZF-2 horizontal vertical burning testers of Jiangning, Nanjing analytical instrument factory, vertical burn test is according to GB/T
2408-2008 is measured, and batten size is 130 × 13 × 3.2mm3。
Using the cone calorimetry of UK fire detection technique Co., Ltd, tested according to standard ISO 5660.Sample
Product size is 100 × 100 × 3mm3, by sample parcel to aluminium foil during test, horizontal positioned applies external radiation, heat flux
It is 35KW/m2。
The heat endurance of PP composite material is tested using the STA449 thermogravimetric analyzers of German Nai Chi companies.Weigh about
The sample of 10mg is put into alumina crucible, and thermogravimetric analysis is carried out under nitrogen atmosphere, and nitrogen circulation is 20Ml/min, and heat up speed
Rate is 10K/min, and temperature range is 50-700 DEG C.
Using the carbon residue pattern of the S-4800 scanning electron microscopic observation samples of HIT, using Japanese Horiba companies
EMAX 7593-H energy spectrometer analysis carbon residues element and content.
Using Mei Tesi CMT4104 universal testing machines, tensile property test, experiment speed are carried out according to GB/T1040-2006
It is 5mm/min to spend, and sample is dumbbell shape.
Using Mei Tesi ZBC1400-B Charpy test machines, Chalpy impact is carried out according to GB/T1843-2008
Can test.
(1) sign of silicon Magnesium coumpoud oxide
By three kinds of silicon magnesium ratios of silicon Magnesium coumpoud oxide of gravimetric method and EDTA complexometric titrations, table is as a result listed in
In 2.As seen from table, three kinds of actual Si/Mg mol ratios of silicon Magnesium coumpoud oxide, are more or less the same with target Si/Mg.
The silicon content of magnesium of the silicon Magnesium coumpoud oxide of table 2
Referring to Fig. 1-6, the silicon Magnesium coumpoud oxide of embodiment 1-4 is characterized using FT-IR, be as a result listed in Fig. 1
In.As shown in figure 1, with Mg/Si than increase, 795cm-1Place's absworption peak weakens and 673cm-1Place's absworption peak enhancing, explanation
The degree of order of Si-O-Si skeleton structures gradually weakens, i.e., Si-O-Si keys are reduced；3698cm in M3S spectrograms-1There is sharp Mg- in place
The stretching vibration absworption peak of OH.In order to further analyze the structure of silicon Magnesium coumpoud oxide, characterized using XRD, as a result
As shown in Figure 2.
Occur in the range of 2 θ=23-25 ° and 2 θ=35-36 ° in the diffraction spectrogram of all of silicon Magnesium coumpoud oxide
Diffraction maximum wider, matches with the diffraction maximum of magnesium silicate；Meanwhile, in 2 θ=18.56 °, 2 θ=38 °, 2 θ in M3S diffraction spectrograms
Strong and sharp diffraction maximum is occurred in that at=50.82 ° and 2 θ=58.59 °.Both contain undefined structure in M3S, crystal is contained again
Structure.Diffraction maximums of the MS in 2 θ=20 °, 2 θ=35 °, 2 θ=60 ° is stronger, and now magnesia octahedron is interconnected to form short distance and has
The magnesium hydroxide crystal structure of sequence, with Si/Mg than increase, these diffraction maximums die down, and the degree of order of Mg-O-Mg structures subtracts
It is small.Three kinds of MS3, MS2, MS etc. is the silicon Magnesium coumpoud oxide of impalpable structure.
Determined both to contain undefined structure in M5S, M3S, M2S, M1.5S according to testing result, crystal structure is contained again.And
MS5, MS3, MS2, MS are the silicon Magnesium coumpoud oxide of impalpable structure.
The pattern of the silicon Magnesium coumpoud oxide of embodiment 1-4 is observed using SEM, as seen in figures 3-6.MS3 and MS2 is ball
Shape particle, the mixture of MS then spheric granules and flat particle, this is because the Mg-O-Mg structures of shortrange order make part ball
Shape particle extends turns into flat.
(2) limited oxygen index and vertical burn test
Limited oxygen index (LOI) and vertical burn test (UL-94) are usually used in the combustibility of evaluating combined material.Poly- third
The limited oxygen index of alkene and its flame-proof composite material is listed in Table 3 below.As shown in Table 3, the oxygen index (OI) of PP is only 19.00, adds IFR
Afterwards, oxygen index (OI) increases to 38.1；After addition silicon Magnesium coumpoud oxide, oxygen index (OI) is further improved, maximum during addition M3S, is added
Plus take second place during MS3, it is minimum during addition MS, illustrate that adding silicon Magnesium coumpoud oxide can significantly improve the oxygen index (OI) of material, improve
Fire resistance.
For vertical burn test, as seen from table, after addition silicon Magnesium coumpoud oxide, UL-94 grades bring up to V-0, say
Bright addition silicon Magnesium coumpoud oxide is remarkably improved the self-extinguishment of PP composite material.
The limited oxygen index and vertical combustion grade of the expansion flame-retarded polyolefin of table 3
The burning time parameter of the PP composite material of table 4
| Sample | Burning time (s) | Fall time (s) | Flaming combustion time (s) |
| PP | 65 | 385 | 320 |
| PP/IFR | 25 | 710 | 685 |
| PP/IFR/M3S10 | 28 | 875 | 847 |
It can be seen from table 4, after addition M3S, the layer of charcoal protectiveness of formation is stronger, and heat endurance more preferably, can undergo longer
The high temperature sintering of time.
The heat release parameter of the PP composite material of table 5
Remarks：PHRR refers to the peak value of heat release rate curve, TPHRR for HRR reach corresponding to peak value when
Between.
The thermogravimetric analysis data of the PP composite material of table 6
| Sample | ||||
| PP | 325 | 408 | 423 | 0 |
| PP/IFR | 348 | 437 | 447 | 6.3 |
| PP/IFR/M3S10 | 373 | 451 | 459 | 12.5 |
CRαRefer to 700 DEG C of carbon lefts.
The integrator decomposition temperature of the PP composite material of table 7
The mechanical property of the PP composite material of table 9
| Sample number into spectrum | Tensile strength MPa | Impact strength |
| PP | 29.33 | 3.34 |
| PP/IFR | 25.9 | 3.2 |
| PP/IFR/M3S05 | 26.03 | 3.0 |
| PP/IFR/M3S10 | 28.04 | 2.95 |
| PP/IFR/M3S15 | 27.74 | 2.87 |
| PP/IFR/M3S20 | 27.78 | 3.12 |
| PP/IFR/M3S30 | 26.55 | 2.74 |
| PP/IFR/M2S10 | 28.93 | 3.24 |
| PP/IFR/M5S10 | 29.13 | 3.30 |
The fire development index of the PP composite material of table 9
| Sample | FGI |
| PP | 2.32 |
| PP/IFR | 0.53 |
| PP/IFR/M3S10 | 0.36 |
As known from Table 9 compared with virgin pp, after addition expansion type flame retardant, fire development index decreased 77.2% adds
Plus after M3S, fire development index lower about 84.5%, with only add expansion type flame retardant when compared with, fire development index reduction
About 32.1%, after illustrating addition M3S, the fire resistance of PP composite material is further strengthened, and fire hazard further drops
It is low.
In sum, the addition synergistic effect enhancing of silicon Magnesium coumpoud oxide, oxygen index (OI) is 47.7 to the maximum；Silicon magnesium composite oxygen
Compound reduces the heat release of composite, HRR reduction by 13.6%, heat release premier reduction by 9.6%；Can strengthen multiple
The smoke suppressing of condensation material, gives birth to cigarette rate reduction 13%, cigarette total volume reduction by 3.4%；The fire of composite can be reduced
Calamity harmfulness, fire development index reduction by 32.1%；Intumescent Retardant System can be effectively facilitated to be reacted into charcoal, increase the cause of layer of charcoal
It is close, improve layer of charcoal protectiveness.Silicon Magnesium coumpoud oxide can improve temperature of initial decomposition 7.2%, half longevity temperature 3.2%, maximum
Decomposition rate temperature 8.5%, raising broken down into program temperature 16.0%, while 700 DEG C of carbon lefts for being are greatly increased, illustrate its energy
Enough effectively improve the heat endurance of PP composite material.Silicon Magnesium coumpoud oxide can be improved and with the addition of expandable flame retardant type polyene
The tensile property of hydrocarbon.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (1)
1. a kind of silicon Magnesium coumpoud oxide does the expansion flame-retarded polyolefin of synergistic flame retardant, it is characterised in that the expandable flame retardant
The recipe ingredient of polyolefin is：Silicon Magnesium coumpoud oxide, expansion type flame retardant and polyolefin;
The recipe ingredient of the expansion flame-retarded polyolefin is calculated by weight as：0.5-3 parts of silicon Magnesium coumpoud oxide, intumescent resistance
17-25 parts and polyolefin 75-90 parts of combustion agent;
The expansion type flame retardant is made up of ammonium polyphosphate and triazine carbon forming agent, the ammonium polyphosphate:Triazine carbon forming agent matter
Measuring ratio is:3：1;The expansion type flame retardant, model 201A, Shandong Sunris New Materials Co., Ltd.,
Magnesium elements in the silicon Magnesium coumpoud oxide：Element silicon mol ratio is 5:1-5:0.5 or 1:2;
The preparation method of the silicon Magnesium coumpoud oxide is comprised the following steps：Magnesium chloride hexahydrate solution is placed in container, while stirring
Mix side and sodium silicate solution is added dropwise, pH value is adjusted with alkali lye after being added dropwise to complete, mother liquor is persistently stirred to obtain at room temperature, by mother liquid obtained dress
To enter reacted in high-temperature high-pressure reaction kettle, reaction solution is taken out after the completion of reaction and naturally cools to room temperature, reaction solution is discarded
Filtered after layer clear liquid, filtrate is washed and silicon Magnesium coumpoud oxide is obtained after drying;
The mol ratio of the magnesium chloride hexahydrate and sodium silicate is 5:1-5:0.5, or the mol ratio of magnesium chloride hexahydrate and sodium silicate is
1:2;
The alkali lye is sodium hydroxide solution, and the span of the pH value is 9-11;
The temperature of the reaction in the high-temperature high-pressure reaction kettle is 120-160 DEG C, and the time of reaction is 18-30h;
The mixing time for obtaining the mother liquor is 1-5 hours;
The dry temperature is 100-110 DEG C, and the dry time is 10-15 h;
The preparation method of described expansion flame-retarded polyolefin is comprised the following steps：The silicon Magnesium coumpoud oxide, swollen is taken in proportion
Swollen type fire retardant and polyolefin, are well mixed after drying, and expansion flame-retarded polyolefin is obtained by double-screw extruding pelletizing.
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| CN102351207A (en) * | 2011-08-22 | 2012-02-15 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing nano attapulgite by solvothermal process |
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