CN109912843A - Double thio phosphono heterocycle shape silicate ester compounds of fire retardant and preparation method thereof - Google Patents

Double thio phosphono heterocycle shape silicate ester compounds of fire retardant and preparation method thereof Download PDF

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Publication number
CN109912843A
CN109912843A CN201910195460.7A CN201910195460A CN109912843A CN 109912843 A CN109912843 A CN 109912843A CN 201910195460 A CN201910195460 A CN 201910195460A CN 109912843 A CN109912843 A CN 109912843A
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fire retardant
heterocycle shape
phosphono heterocycle
thio phosphono
preparation
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CN201910195460.7A
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仲柿成
王世杰
王彦林
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Suzhou University of Science and Technology
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Suzhou University of Science and Technology
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Abstract

The present invention relates to double thio phosphono heterocycle shape silicate ester compounds of a kind of fire retardant and preparation method thereof, and the structure of the compound is shown below:

Description

Double thio phosphono heterocycle shape silicate ester compounds of fire retardant and preparation method thereof
Technical field
The present invention relates to double thio phosphono heterocycle shape silicate ester compounds of a kind of fire retardant and preparation method thereof, and in particular to A kind of fire retardant dimethyl silicic acid two [1,1- dimethyl -1- sila -2,6- dioxa -4- sulfenyl -4- phosphine miscellaneous-(4)-methylene] Ester compounds and preparation method thereof, the compound contain three kinds of phosphorus, silicon, sulphur ignition-proof elements, can be used as polyamide, polyester, poly- ammonia The fire-retardant carbon forming agent of ester, polyolefin, epoxy resin and unsaturated-resin etc..
Background technique
The progress of science and technology promotes the fast development of Macromolecular materials industry, and the application of high-molecular organic material is more next It is more universal.But mostly high molecular material be it is inflammable, often cause fire, the security of the lives and property of people caused seriously Threat, fire safety problem cause people great attention, synthesize high molecular material fire-retardant rate have become measure a country or Regional flourishing such as no standard, therefore it is greatly promoted the progress of fire proofing and flame-retarded technology.As Environmental Safety is realized Enhancing, non-halogen requirement is had also been proposed to fire proofing at present.Phosphorus, nitrogenated flame retardant are to realize non-halogen main body, silicon Flame retardant is the up-and-coming youngster of new development.Phosphonium flame retardant can form the heat-insulated anoxybiotic of polyphosphoric acid film, the combustion of silicon fire retardant when burning Fine and close silicon layer of charcoal can be formed when burning, can effectively prevent the second-time burning of material melted by heating drippage and generation.The collaboration of phosphorus silicon Fire-resistant synergistic can play better flame-retarded efficiency, thus phosphorus silicon synergistic fire retardant has become one of the hot spot researched and developed at present.
The double thio phosphono heterocycle shape esters of silicon acis of fire retardant of the present invention more have by phosphorus, silicon, sulphur design in same molecular structure Beneficial to playing cooperative flame retardant synergistic effect, phosphorus, silicon, sulphur play fire retardation from different fire retardant mechanisms, can effectively improve material Flame retardant property, increase material at charcoal, effectively overcome melting drip caused by second-time burning.Again since molecular structure is Bicyclic symmetrical structure has very high thermal stability, adapts to the high temperature process of material, can be used as most of high molecular materials Fire-retardant carbon forming agent, has a good application prospect.
Summary of the invention
It is an object of the present invention to propose a kind of double thio phosphono heterocycle shape silicate ester compounds of fire retardant, materialization Performance is stablized, nontoxic, and flame-retarded efficiency is high, good with high molecular material compatibility, can overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
A kind of double thio phosphono heterocycle shape silicate ester compounds of fire retardant, which is characterized in that the structure of the compound is as follows Shown in formula:
Another object of the present invention is to propose a kind of preparation of double thio phosphono heterocycle shape silicate ester compounds of fire retardant Method, raw material are easy to get, and simple process, equipment investment is few, are easy to large-scale production, this method are as follows:
Blender, thermometer and high efficiency reflux condenser are being housed, and suitable for reading equipped with hydrogen chloride absorption device in condenser In reactor, the air in reactor is displaced with nitrogen, and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester and organic is added Solvent, then dimethyldichlorosilane is added dropwise, control dimethyldichlorosilane and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester Molar ratio 1: 2-1: 2.4, limit and process temperature is added dropwise is not higher than 50 DEG C, be warming up to 75 DEG C, insulation reaction 5h after dripping off, then Reflux is warming up to 110-150 DEG C of heat preservation, reacts 7-11h, hydrogen chloride is allowed to discharge, and stops reaction, is cooled to room temperature, vacuum distillation removes Solvent is removed, muddy viscous liquid is obtained;Crude product is poured into again in product Theoretical Mass grams 2.5 times mls ice water, Quickly stirring 30min is filtered, and filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant.
Dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxy Miscellaneous miscellaneous -4- methylol the hexamethylene of -4- sulfenyl -4- phosphine, chemical structural formula are as follows:
Organic solvent as described above is ethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrachloroethanes, methyl phenyl ethers anisole, diformazan Benzene or dimethyl sulfoxide, the volume ml of organic solvent are dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester quality grams 4~6 times.
The double thio phosphono heterocycle shape esters of silicon acis of fire retardant of the present invention are white powder solid, 186 ± 2 DEG C of fusing point, decompose temperature Degree is 330 ± 5 DEG C, and product yield is 90.2%~93.1%, is suitble to polyamide, polyester, polyurethane, polyolefin, epoxy The fire-retardant carbon forming agent of resin and unsaturated-resin etc..The preparation principle of the double thio phosphono heterocycle shape silicate ester compounds of its fire retardant It is shown below:
Compared with prior art, the invention has the beneficial effects that:
1. the double thio phosphono heterocycle shape silicate structures of fire retardant of the present invention are novel, phosphorous, silicon, three ignition-proof element of sulphur, knot Structure symmetry is good, and stability is high, and decomposition temperature is up to 330 ± 5 DEG C, can be suitably used for the high temperature process of various engineering plastics.
2. the double thio phosphono heterocycle shape esters of silicon acis of fire retardant of the present invention are halogen-free, belong to environmental-friendly fire-retardant carbon forming agent.
3. the double thio phosphono heterocycle shape esters of silicon acis of fire retardant of the present invention prepare raw materials used dimethyl silicic acid trihydroxy methyl sulphur Changing phosphine cyclic ester, itself is a outstanding fire-retardant carbon forming agents, but its reaction sealed with dimethyl silicon dichloride pole of hydroxyl Property overcomes its hygroscopic deficiency, and increases the content of fire-retardant element silicon, improve with the compatibility of material, improve It is fire-retardant at charcoal efficiency.
4. the preparation method of the double thio phosphono heterocycle shape esters of silicon acis of fire retardant of the present invention is single step reaction, simple process is closed Impurity is not introduced without adding catalyst at process, equipment is simple, and it is low in cost, it is suitable for large-scale production, there is good application Development prospect.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of the double thio phosphono heterocycle shape esters of silicon acis of fire retardant;Fig. 1 shows 698cm-1It is P=S key Stretching vibration peak;843cm-1It is the stretching vibration peak of C-P;2998cm-1And 2896cm-1It is the stretching vibration peak of c h bond; 1032cm-1Place is the stretching vibration peak of Si-O-C key;1498cm-1It is the flexural vibrations peak of c h bond;1106cm-1Place is C-O key Stretching vibration peak;750cm-1Place is the stretching vibration peak of C-Si key.
Fig. 2 is the nuclear magnetic spectrum figure of the double thio phosphono heterocycle shape esters of silicon acis of fire retardant;Fig. 2 show be at δ 0.1-0.25 with Si connected-CH3The peak H;It is-the CH that is connected with O at δ 3.75-4.12The peak H;It is solvent peak at δ 7.25.
Fig. 3 is the differential thermal spectrogram of the double thio phosphono heterocycle shape esters of silicon acis of fire retardant;Fig. 3 shows that temperature reaches 330 DEG C of products Start weightless;Temperature reaches 350 DEG C, and product weight-loss ratio is about 50%;When reaching 800 DEG C of final temperature, still there is about 34% carbon Residue, it can be seen that, which has excellent thermal stability.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, 21.2g (0.10mol) dimethyl silicic acid trihydroxy methyl is added Phosphine sulfide cyclic ester and 90ml ethylene glycol diethyl ether, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control was added dropwise Cheng Wendu is not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 110 DEG C, insulation reaction 11h allows Hydrogen chloride discharges, and stops reaction, is cooled to room temperature, and vacuum distillation removes solvent, obtains muddy viscous liquid;Crude product is fallen again Enter in 60ml ice water, quickly stir 30min, filter, filter cake is dried in vacuo to obtain the double thio miscellaneous cyclic silicates of phosphono of product fire retardant Ester.Yield is 90.2%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
Embodiment 2 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, three hydroxyl first of 22.16g (0.105mol) dimethyl silicic acid is added Base phosphine sulfide cyclic ester and 100ml diethylene glycol dimethyl ether, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control drop Add process temperature not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 130 DEG C, insulation reaction 10h allows hydrogen chloride to discharge, and stops reaction, is cooled to room temperature, and vacuum distillation removes solvent, obtains muddy viscous liquid;It again will be thick Product pours into 60ml ice water, quickly stirs 30min, filters, and filter cake is dried in vacuo to obtain the double thio phosphono heterocycles of product fire retardant Shape esters of silicon acis.Yield is 93.1%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
Embodiment 3 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, three hydroxyl first of 23.32g (0.11mol) dimethyl silicic acid is added Base phosphine sulfide cyclic ester and 110ml tetrachloroethanes, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control dropwise addition process Temperature is not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 120 DEG C, insulation reaction 8h, allows chlorine Change hydrogen to discharge, stop reaction, be cooled to room temperature, vacuum distillation removes solvent, obtains muddy viscous liquid;Crude product is poured into again In 60ml ice water, 30min is quickly stirred, is filtered, filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant. Yield is 91.6%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
Embodiment 4 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, three hydroxyl first of 24.38g (0.115mol) dimethyl silicic acid is added Base phosphine sulfide cyclic ester and 120ml methyl phenyl ethers anisole, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control dropwise addition process temperature Degree is not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 140 DEG C, insulation reaction 8h, allows chlorination Hydrogen discharges, and stops reaction, is cooled to room temperature, and vacuum distillation removes solvent, obtains muddy viscous liquid;Crude product is poured into again In 60ml ice water, 30min is quickly stirred, is filtered, filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant. Yield is 92.7%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
Embodiment 5 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, three hydroxyl first of 25.44g (0.12mol) dimethyl silicic acid is added Base phosphine sulfide cyclic ester and 120ml dimethylbenzene, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control dropwise addition process temperature Degree is not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 130 DEG C, insulation reaction 9h, allows chlorination Hydrogen discharges, and stops reaction, is cooled to room temperature, and vacuum distillation removes solvent, obtains muddy viscous liquid;Crude product is poured into again In 60ml ice water, 30min is quickly stirred, is filtered, filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant. Yield is 92.5%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
Embodiment 6 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with drying tube in condenser pipe 250ml four-hole boiling flask in, with the air in nitrogen displacement bottle falling, three hydroxyl first of 23.32g (0.11mol) dimethyl silicic acid is added Base phosphine sulfide cyclic ester and 110ml dimethyl sulfoxide, then 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, control dropwise addition process Temperature is not higher than 50 DEG C, 75 DEG C, insulation reaction 5h is warming up to after dripping off, then flow back and be warming up to 150 DEG C, insulation reaction 7h, allows chlorine Change hydrogen to discharge, stop reaction, be cooled to room temperature, vacuum distillation removes solvent, obtains muddy viscous liquid;Crude product is poured into again In 60ml ice water, 30min is quickly stirred, is filtered, filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant. Yield is 93.0%, and fusing point is 186 ± 2 DEG C, and decomposition temperature is 330 ± 5 DEG C.
1 preparation example main technologic parameters of table
3mm is made with mold by the double thio phosphono heterocycle shape esters of silicon acis application epoxy resin of fire retardant in inventor Thick glass epoxy, then it is cut into the batten that long 15mm, width 7mm, thickness 3mm is made, reference: GB/T2406-2008 " Plastics Combustion Can test method-oxygen index method " limit oxygen index of test sample item.Test result is as shown in table 2:
2 pairs, table thio phosphono heterocycle shape esters of silicon acis application ethoxyline resin antiflaming test datas
When additive amount of the fire retardant in glass reinforced plastic is 12.5%, oxygen index (OI) has reached 29% fire retardant rank, When additive amount of the fire retardant in glass reinforced plastic is 16%, oxygen index (OI) is even more to reach 33%, this illustrates product to epoxy resin There is good fire-retardant effectiveness.

Claims (3)

1. a kind of double thio phosphono heterocycle shape silicate ester compounds of fire retardant, which is characterized in that the structure of the compound such as following formula It is shown:
2. the preparation method of the double thio phosphono heterocycle shape silicate ester compounds of a kind of fire retardant according to claim 1, special Sign is, this method are as follows:
Blender, thermometer and high efficiency reflux condenser are being housed, and suitable for reading equipped with hydrogen chloride absorption device reaction in condenser In device, the air in reactor is displaced with nitrogen, dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester and organic solvent is added, Dimethyldichlorosilane is added dropwise again, controls mole of dimethyldichlorosilane and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester Than limiting and process temperature being added dropwise not higher than 50 DEG C, 75 DEG C, insulation reaction 5h are warming up to after dripping off, then the liter that flows back 1: 2-1: 2.4 Temperature reacts 7-11h, hydrogen chloride is allowed to discharge to 110-150 DEG C of heat preservation, stops reaction, is cooled to room temperature, and vacuum distillation removes molten Agent obtains muddy viscous liquid, then crude product is poured into product Theoretical Mass grams 2.5 times mls ice water, quickly 30min is stirred, is filtered, filter cake is dried in vacuo to obtain the double thio phosphono heterocycle shape esters of silicon acis of product fire retardant;
Dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxa -4- Miscellaneous -4- methylol the hexamethylene of sulfenyl -4- phosphine, chemical structural formula are as follows:
3. the preparation method of the double thio phosphono heterocycle shape silicate ester compounds of a kind of fire retardant according to claim 2, special Sign is: the organic solvent is ethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrachloroethanes, methyl phenyl ethers anisole, dimethylbenzene or two First sulfoxide, the volume ml of organic solvent are the 4~6 of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester quality grams Times.
CN201910195460.7A 2019-03-04 2019-03-04 Double thio phosphono heterocycle shape silicate ester compounds of fire retardant and preparation method thereof Withdrawn CN109912843A (en)

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Application publication date: 20190621