CN104004022A - Caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester compound and preparation method thereof - Google Patents
Caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester compound and a preparation method thereof. The structure of the compound is shown in the specification. The preparation method comprises the steps that dimethyldichlorosilane is dropwise added into a solution of 1-oxy-phospha-4-hydroxymethyl-2,6,7-trioxabicyclo [2.2.2]octane (PEPA) and an organic solvent under 40 DEG C, the mixture is heated to 80-140 DEG C, is stirred and reacts for 4-9 h, a certain amount of acid-binding agent is added, the mixture is mixed with the temperature being kept for 1h, and the reaction is ended when the pH value of the solution is 5-6. After reduced pressure distillation, the white solid caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester can be obtained through purification treatment. The compound is a good phosphorus-silicon integrated flame-retardant charring agent and can be applied to polyolefin, polyolefin, polyvinyl chloride, polyurethane, epoxy resin, unsaturated polyester resin and the like, the process is simple, the equipment investment is small, and industrial production can be easily achieved.
Description
Technical field
The present invention relates to a kind of two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester cpds and preparation method thereof, be specifically related to a kind of fire-retardant char-forming agent dimethyl silicic acid two { 1-oxygen base phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane-(4)-first } ester cpds and preparation method thereof, this compound contains phosphorus, the two ignition-proof elements of silicon, can be used as the fire-retardant char-forming agent of polyolefine, polyester, urethane, polyvinyl chloride, epoxy resin and unsaturated polyester etc.
Background technology
The progress of science and technology has promoted the fast development of Polymeric Industry; the consumption of organic synthesis material has become the important indicator of weighing a country prosperity; but macromolecular material is inflammable mostly; often can cause fire; people's the security of the lives and property is caused to serious threat; fire safety problem has caused people's great attention; the fire-retardant rate of synthesized polymer material becomes again weighs a country prosperity as no new standard, has therefore greatly promoted the progress of fire retardant material and flame-retarded technology.Along with the enhancing of Environmental Safety consciousness, at present fire retardant material is proposed again to non-halogen requirement.Phosphorus, nitrogenated flame retardant are to realize non-halogen main body, and silicon-series five-retardant is the up-and-coming youngster of new development.When phosphonium flame retardant burning, can form the heat insulation anoxybiotic of polyphosphoric acid film, when the burning of silicon fire retardant, can form fine and close silicon charcoal layer, can effectively prevent material melted by heating drippage and the secondary combustion of generation.The synergy of phosphorus silicon cooperative flame retardant, can bring into play better flame-retarded efficiency, thereby phosphorus silicon synergistic fire retardant has become one of focus of current research and development.
The two cage loop resistance combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester, phosphorus, silicon are designed in same molecular structure, more be of value to the synergism of performance phosphorus silicon cooperative flame retardant, phosphorus silicon produces fire retardation from different fire retardant mechanisms, can effectively improve the flame retardant resistance of material, the one-tenth charcoal that increases material, effectively overcomes melting and drips the secondary combustion causing.Because molecular structure is two cage ring symmetrical structures, there is very high thermostability again, can be used as the fire-retardant char-forming agent of most of macromolecular materials, have a good application prospect.
Summary of the invention
One of object of the present invention is to propose a kind of two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester cpds, and its physical and chemical performance is stable, and nontoxic, flame-retarded efficiency is high, good with macromolecular material consistency, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester cpds, is characterized in that, the structure of this compound is shown below:
The preparation method who another object of the present invention is to propose a kind of pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester, its raw material is cheap and easy to get, with low cost, and technique is simple, and facility investment is few, is easy to large-scale production, and the method is:
Control dimethyldichlorosilane(DMCS) and 1-oxygen base phospha-4-methylol-2,6, the certain mol ratio of 7-trioxa-l-phosphabicyclo [2.2.2] octane (PEPA), by dimethyldichlorosilane(DMCS) at 40 DEG C, be added drop-wise in the solution of PEPA and organic solvent, drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 80～140 DEG C, stirring reaction 4～9h, after hydrogen chloride gas discharges, then adds the acid binding agent of product Theoretical Mass (g) 2%～6%, stir 1h, detection pH value of solution=5-6 is reaction end; Vacuum distillation recovered solvent, solids crude product is stayed in reactor, and purified processing obtains dimethyl silicic acid PEPA ester.
Organic solvent as above is glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, dioxane, dimethyl formamide or dimethylbenzene, and volume (ml) number of its organic solvent is 4～14 times of PEPA quality (g) number.
Control dimethyldichlorosilane(DMCS) as above and 1-oxygen base phospha-4-methylol-2, the certain mol ratio of 6,7-trioxa-l-phosphabicyclo [2.2.2] octane (PEPA) is that dimethyldichlorosilane(DMCS): PEPA is 1: 2～1: 3.
Acid binding agent as above is triethylamine, pyridine, xylidine.
Purified being treated to toward the dehydrated alcohol that adds 5 times of volumes of product Theoretical Mass (g) (ml) in solids crude product as above, stirring heating, cooling, suction filtration, add again the dehydrated alcohol drip washing of 2-4 times of volume of product Theoretical Mass (g) (ml), suction filtration, dries, and obtains the two cage loop resistance combustion of white solid char-forming agent dimethyl silicic acid PEPA ester.
The two cage loop resistance combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester is white powder solid, is dissolved in most polar organic solvents and 70 DEG C of above hot water but is insoluble to cold water.Product yield is 80.2%～93.4%, decomposition temperature: 298 ± 5 DEG C, and 167 ± 2 DEG C of fusing points, it is suitable as the fire-retardant char-forming agent of polyolefine, polyester, polyvinyl chloride, urethane, epoxy resin and unsaturated polyester etc.The preparation principle of its pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester cpds is shown below:
Compared with prior art, usefulness of the present invention is:
1. the two cage loop resistance combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester structure novelty, phosphorous, the two ignition-proof elements of silicon, and structural symmetry is good, and stability is high, can be applicable to the high temperature process of various engineering plastics.
2. the two cage loop resistance combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester is not halogen-containing, belongs to eco-friendly fire-retardant char-forming agent.
3. the two cage loop resistances combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester becomes charcoal good, also has swelling property, can overcome PEPA and do that char-forming agent easily absorbs water, decomposition temperature is low, the shortcoming of poor processability.
4. the preparation method of the two cage loop resistance combustion of the present invention char-forming agent dimethyl silicic acid PEPA ester is single step reaction, and technique is simple, and building-up process is not introduced impurity without adding catalyzer, and equipment is simple, with low cost, is suitable for large-scale production, has good application and development prospect.
Brief description of the drawings
For the structure and the performance spy that further illustrate product provide following accompanying drawing.
1, the infrared spectrogram of two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, refers to Figure of description Fig. 1:
Fig. 1 shows, 2960.5cm
-1, 2912.5cm
-1for the stretching vibration absorption peak of the C-H of methyl and methylene radical; 1470.9cm
-1, 1410.5cm
-1for the flexural vibration absorption peak of the C-H of methyl and methylene radical; 1321.2cm
-1for the charateristic avsorption band of P=O; 1037.4cm
-1for the charateristic avsorption band of P-O-C; 1085.3cm
-1, 802.4cm
-1for the absorption peak of Si-O-C; 921.3cm
-1, 862.2cm
-1, 762.9cm
-1for the charateristic avsorption band of ring texture; 1262.8cm
-1for Si-CH
3charateristic avsorption band.
2, the nuclear magnetic spectrum figure of two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, refers to Figure of description Fig. 2:
Fig. 2 shows, deuterated dimethyl sulfoxide makees solvent, and δ 4.59～4.64 is O=P (OCH
2)
3-on methylene radical H peak, δ 3.51～3.54 is-CH
2the H peak of the methylene radical on OSi-, δ 0.06-0.09 is the CH being connected with Si
3on H peak, δ 3.36 is H
2the H peak of O, δ 2.50 is the proton peak of solvent deuterated dimethyl sulfoxide exchange.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1 is being equipped with magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 100ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 4.5g (0.025mol) PEPA and 60ml glycol dimethyl ether, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 85 DEG C, reaction 8h, after HCl gas discharges, add again 0.1g triethylamine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 12ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 80.2%, 298 ± 5 DEG C of decomposition temperatures.
Embodiment 2 is being equipped with magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 100ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 4.95g (0.0275mol) PEPA and 30ml acetonitrile, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 80 DEG C, reaction 9h, after HCl gas discharges, add again 0.15g triethylamine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 15ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 93.4%, 298 ± 5 DEG C of decomposition temperatures.
Embodiment 3 is being equipped with magnetic magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 5.85g (0.0325mol) PEPA and 70ml dioxane, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 100 DEG C, reaction 7h, after HCl gas discharges, add again 0.2g pyridine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 18ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 92.6%, 298 ± 5 DEG C of decomposition temperatures.
Embodiment 4 is being equipped with magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 100ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 6.3g (0.035mol) PEPA and 50ml dimethyl formamide, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 130 DEG C, reaction 5h, after HCl gas discharges, add again 0.25g pyridine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 20ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 88.7%, 298 ± 5 DEG C of decomposition temperatures.
Embodiment 5 is being equipped with magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 100ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 6.75g (0.0375mol) PEPA and 40ml dimethylbenzene, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 120 DEG C, reaction 5h, after HCl gas discharges, add again 0.3g xylidine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 20ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 86.5%, 298 ± 5 DEG C of decomposition temperatures.
Embodiment 6 is being equipped with magnetic stirring apparatus, thermometer and efficient backflow prolong, and in the prolong 100ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 5.4g (0.03mol) PEPA and 50ml diethylene glycol dimethyl ether, stir, at 40 DEG C, splash into 1.61g (1.50ml, 0.0125mol) dimethyldichlorosilane(DMCS), drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 140 DEG C, reaction 4h, after HCl gas discharges, add again 0.2g xylidine, insulated and stirred 1h, detection pH value of solution=5-6 is reaction end.Vacuum distillation recovered solvent, solids crude product is stayed in reactor, adds the dehydrated alcohol of 25ml, stirring heating, cooling, suction filtration, then add the dehydrated alcohol drip washing of 15ml, suction filtration, dry, obtain two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters, productive rate is 90.4%, 298 ± 5 DEG C of decomposition temperatures.
Table 1 preparation example main technologic parameters
This case contriver is applied to two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters in polybutylene terephthalate (PBT), adds two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters of different ratios in PBT; Extrude at 230 DEG C with XJ-01 type forcing machine again, make diameter 3mm, the batten of length 15mm, the limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample bar.Test-results is as shown in table 2:
Table 2 pair cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester fire-retardant carbon-forming performance in PBT
As shown in Table 2, two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters have certain fire retardation to PBT, have into the antidrip drop of charcoal.
This case contriver is also fired two cage loop resistances char-forming agent dimethyl silicic acid PEPA esters and diethyl hypo-aluminum orthophosphate (1240) composite usage in polybutylene terephthalate (PBT), adds two cage loop resistances combustion char-forming agent dimethyl silicic acid PEPA esters and 1240 of different ratios in PBT; Extrude at 230 DEG C with XJ-01 type forcing machine, batten is of a size of diameter 3mm, length 15mm again.Then it is carried out to flame retardant properties mensuration, reference: the limiting oxygen index(LOI) of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.Test-results is as shown in table 3:
Table 3 dimethyl silicic acid PEPA ester and 1240 composite fire-retardant carbon-forming performances in PBT
As shown in Table 3, two cage loop resistances combustion char-forming agent dimethyl silicic acid PEPA esters with 1240 composite to PBT have good fire-retardant become the anti-drip effect of charcoal, and expansion effect is good, shows and has good synergetic.When two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester contents are in 5%, its fire-retardant one-tenth charcoal expansion effect is good, can replace 1240 of part costliness, can reduce costs.And appropriate two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters and the 1240 composite mechanical properties that do not reduce PBT, do not affect the processing of material.
This case contriver is also applied to two cage loop resistances combustion char-forming agent dimethyl silicic acid PEPA esters in polybutylene terephthalate (PBT) with diethyl hypo-aluminum orthophosphate (1240) and melamine cyanurate (MCA) ternary built, adds the two cage loop resistances that are not listed as on year-on-year basis to fire char-forming agent dimethyl silicic acid PEPA esters, 1240 and MCA in PBT.Extrude at 230 DEG C with XJ-01 type forcing machine again, make diameter 3mm, the batten of length 15mm, the limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample bar.Test-results is as shown in table 4:
Table 4 dimethyl silicic acid PEPA ester and 1240 and the composite fire-retardant carbon-forming performance in PBT of MCA
As shown in Table 4, two cage loop resistances combustion char-forming agent dimethyl silicic acid PEPA esters with 1240 and MCA ternary built be applied to and gather in PBT, there is good fire-retardant one-tenth charcoal effect, in the time that 1240 replace 39.7% (the 3rd row), its limiting oxygen index(LOI) can also reach 25%, equate (the 1st row) with 1240 o'clock limiting oxygen index(LOI)s that add 20%, reduce costs highly significant for 1240 of alternative costliness.
Claims (6)
1. two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester cpds, is characterized in that, the structure of this compound is shown below:
2. the preparation method of according to claim 1 pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester, is characterized in that, the method is:
Control dimethyldichlorosilane(DMCS) and 1-oxygen base phospha-4-methylol-2,6, the certain mol ratio of 7-trioxa-l-phosphabicyclo [2.2.2] octane (PEPA), by dimethyldichlorosilane(DMCS) at 40 DEG C, be added drop-wise in the solution of PEPA and organic solvent, drip process control temp not higher than 50 DEG C, after dripping off, be warming up to 80～140 DEG C, stirring reaction 4～9h, after hydrogen chloride gas discharges, then adds the acid binding agent of product Theoretical Mass (g) 2%～6%, stir 1h, detection pH value of solution=5-6 is reaction end; Vacuum distillation recovered solvent, solids crude product is stayed in reactor, and purified processing obtains two cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA esters.
3. the preparation method of according to claim 2 pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester, it is characterized in that: described organic solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, dioxane, dimethyl formamide or dimethylbenzene, volume (ml) number of its organic solvent is 4～14 times of PEPA quality (g) number.
4. the preparation method of according to claim 2 pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester, it is characterized in that: described control dimethyldichlorosilane(DMCS) and 1-oxygen base phospha-4-methylol-2, the certain mol ratio of 6,7-trioxa-l-phosphabicyclo [2.2.2] octane (PEPA) is that dimethyldichlorosilane(DMCS): PEPA is 1: 2～1: 3.
5. the preparation method of according to claim 2 pair of cage loop resistance combustion char-forming agent dimethyl silicic acid PEPA ester, is characterized in that: described acid binding agent is triethylamine, pyridine, xylidine.
6. the preparation method that two cage loop resistances fire char-forming agent dimethyl silicic acid PEPA esters according to claim 2, it is characterized in that: described purified being treated to toward the dehydrated alcohol that adds 5 times of volumes of product Theoretical Mass (g) (ml) in solids crude product, stirring heating, cooling, suction filtration, add again the dehydrated alcohol drip washing of 2-4 times of volume of product Theoretical Mass (g) (ml), suction filtration, dry, obtain the two cage loop resistance combustion of white solid char-forming agent dimethyl silicic acid PEPA ester.
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| CN201410264047.9A CN104004022B (en) | 2014-06-11 | Double cage rings fire-retardant carbon forming agent dimethyl silicic acid PEPA ester compounds and preparation method thereof |
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| CN201410264047.9A CN104004022B (en) | 2014-06-11 | Double cage rings fire-retardant carbon forming agent dimethyl silicic acid PEPA ester compounds and preparation method thereof |
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