CN102731546A - Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof - Google Patents

Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof Download PDF

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CN102731546A
CN102731546A CN2012102472597A CN201210247259A CN102731546A CN 102731546 A CN102731546 A CN 102731546A CN 2012102472597 A CN2012102472597 A CN 2012102472597A CN 201210247259 A CN201210247259 A CN 201210247259A CN 102731546 A CN102731546 A CN 102731546A
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tribromophenoxy
chloroethyl
chloro
silicic acid
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CN102731546B (en
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王彦林
徐玫
俞春雷
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Zhangjiagang Leyu Science And Technology Innovation Park Investment Development Co Ltd
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Suzhou University of Science and Technology
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Abstract

The invention relates to a silicon-halogen synergic flame retardant compound and a preparation method thereof. The compound has the structural formula shown in the specification. The preparation method comprises the following steps of: at 20 DEG C, dropwise adding equimolar organic solvent solution of tribromophenylepoxypropyl ester into silicon tetrachloride; after the solution is completely added dropwise, keeping temperature at 60-80 DEG C, and reacting for 4-6 hours; dropwise adding chloroethanol of a certain molar ratio at 35 DEG C; keeping temperature at 50-70 DEG C and reacting for 3-6 hours; and purifying to obtain a light yellow liquid product tri(2-chloroethyl)-2-chloro-3-(2,4,6-tribromophenoxy)propyl silicate. The compound is an efficient flame retardant and is suitable to be used as a flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and the like; and the production technology is simple, the equipment investment is low, and the industrial production is easy to realize.

Description

Fire retardant three chloroethyl tribromophenoxy chloropropyl silicate ester compounds and preparation method thereof
Technical field
The present invention relates to a kind of fire retardant three chloroethyl tribromophenoxy chloropropyl silicate ester compounds and preparation method thereof, be specifically related to a kind of silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl ester compound and preparation method thereof.This compound belongs to silicon halogen synergistic fire retardant, is suitable for the flame-retardant plasticizer of materials such as SE, urethane, epoxy resin, unsaturated polyester.
Background technology
Owing to synthesized polymer material the reach of science and application more and more widely, its inflammable problem often causes fire at present, brings serious threat for people's lives and properties, thereby has promoted the research of fire-retardant science and technology and the fast development of fire retardant industry.Again because the improving constantly of development of global economy and people's living standard; Environmental consciousness constantly strengthens; Environmental requirement to fire retardant also improves constantly; Though the fire retardant industry development is fast, can not satisfy the demand of material development far away, that people always hope to have is new and effective, low toxicity and cheap fire retardant or flame-retardant plasticizer occur on market.Flame retardant area technician thinks that the future of efficient flame-retarding agent exploitation is that polynary fire retardant is composite or designs to contain multiple ignition-proof element in the same molecular structure to produce synergistic function.To achieve these goals, the exploitation to the multielement synergistic fire retardant becomes the hot research problem.The silicon tetrachloride as by-product that the inventor has researched and developed out with the polysilicon industry is feedstock production novel silicon halogen cooperative flame retardant softening agent silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4; The 6-tribromophenoxy) propyl diester; Containing chlorine, bromine and three kinds of ignition-proof elements of silicon in this compound molecule, can bring into play cooperative flame retardant synergism preferably, is a good novel flame-retardant softening agent.The present invention has proposed a feasible technical basis to a difficult problem that solves the silicon tetrachloride comprehensive utilization, has opened up good flame-retardant plasticizer new variety again, promptly has good benefits in environment good economic benefits is arranged again.
Summary of the invention
One of the object of the invention is to propose a kind of silicon halogen cooperative flame retardant plasticizer compounds silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diesters, and its fire-retardant plasticising excellent property can overcome deficiency of the prior art.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl ester compound is characterized in that the structure of this compound is shown below:
Figure BSA00000750162600021
Another object of the present invention is to propose the preparation method of a kind of silicic acid as stated three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester; Its technology is simple, be easy to large-scale production, and low in raw material cost is easy to get, and facility investment is few; With low cost, this method is:
Stir down, in reactor drum, add silicon tetrachloride, under 20 ℃, drip the organic solvent solution of equimolar tribromo-benzene basic ring oxygen propyl ether, drip process control temp and be no more than 35 ℃; After dripping off, be warmed up to 60-80 ℃ in the 1h, insulation reaction 4-6h; Cool to 35 ℃ again, drip the glycol chlorohydrin of certain mol proportion, drip process control temp and be no more than 40 ℃; Drip off in the 1h of back and be warmed up to 50-70 ℃, insulation 3-6h, purified processing; Get weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester.
Aforesaid organic solvent is THF, chloroform, acetonitrile, 1,2-ethylene dichloride or 1,4-dioxane.
The glycol chlorohydrin of certain mol proportion is meant tribromo-benzene basic ring oxygen propyl ether as stated: silicon tetrachloride: the mol ratio of glycol chlorohydrin is 1: 1: 3～1: 1: 4.2.
Purification process transfers to pH=5-6 for adding the acid binding agent of quality product 1%-3% as stated, stirs 1h, filters, and filtrating distills out organic solvent (reclaim and use), and decompression steams excessive glycol chlorohydrin (reclaim and use) and a small amount of low boilers again.
Acid binding agent is triethylamine, N as stated, accelerine, trimeric cyanamide or pyridine.
Silicic acid three of the present invention (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester is a weak yellow liquid, and productive rate is 93.3%～97.4%, its flash-point (open cup): 225 ± 5 ℃, and decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.It is suitable as the usefulness of the flame-retardant plasticizer of materials such as SE, Z 150PH, epoxy resin, unsaturated polyester, urethane.
The composition principle of silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester is shown below:
Figure BSA00000750162600031
Compared with prior art, usefulness of the present invention is:
1. because the structure of silicon halogen cooperative flame retardant softening agent silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diesters of the present invention has symmetry characteristic preferably, its physical and chemical performance is stable, and is good with the macromolecular material intermiscibility, good processability; Again because its synthesis material tribromo-benzene basic ring oxygen propyl ether itself is exactly a good response type bromide fire retardant; It and chlorine, silicon element cooperative flame retardant; Stop burning to produce fire-resistant synergistic effect preferably from gas-solid phase fire retardant mechanism is complementary; Thereby this compound flame-retarded efficiency is high, and silicon ester structure plasticity is good.
2. the present invention is synthetic silicon halogen cooperative flame retardant softening agent silicic acid three (2-the chloroethyl)-2-chloro-3-(2 of raw material with polysilicon industry silicon tetrachloride as by-product; 4; The 6-tribromophenoxy) propyl diester can solve the difficult problem of silicon tetrachloride comprehensive utilization, has opened up cheap good flame-retardant plasticizer new variety again; Have good environmental benefit, have favorable economic benefit again.
3. preparation method of the present invention is simple, and low in raw material cost is easy to get, and cost is low, is easy to large-scale production.
Description of drawings
For structure and the performance spy who further specifies product provides following accompanying drawing.
1, the infrared spectrogram of silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester, see Figure of description Fig. 1 for details:
Fig. 1 shows, 2959.5cm -1Be the stretching vibration peak of methylene radical c h bond, 1630cm -1The place is the skeleton stretching vibration peak of phenyl ring, 3080cm -1Be the C-H stretching vibration peak of phenyl ring, 1104cm -1Stretching vibration peak for the Si-O-C key; 1046cm -1The place is the stretching vibration peak of C-Br key; 492cm -1Stretching vibration peak for the C-Cl key; 1248cm -1Stretching vibration peak for the Ar-O key.
2, the nuclear magnetic spectrum figure of silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester, see Figure of description Fig. 2 for details:
Fig. 2 shows that deuterochloroform is a solvent, and δ 3.59-3.66 is Si-OCH 2CH 2The last methylene radical hydrogen peak that links to each other with chlorine of Cl; δ 3.77-3.85 is Ar-OCH 2CHClCH 2The last methylene radical hydrogen peak that links to each other with chlorine of O-Si; δ 3.90-3.96 is Ar-OCH 2CHClCH 2The last methylene radical hydrogen peak that links to each other with silica of O-Si; δ 4.06-4.14 is Si-OCH 2CH 2The last methylene radical hydrogen peak that links to each other with silica of Cl; δ 4.60-4.69 is Ar-OCH 2CHClCH 2The methylene radical hydrogen peak that the last and fragrant oxygen of O-Si links to each other; δ 7.64-7.70 is hydrogen peak on the phenyl ring; δ 7.26 is the proton peak of solvent deuterochloroform exchange.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1 adds THF 10ml in the 100ml four-hole boiling flask that whisking appliance, TM, efficient reflux condensing tube are housed, and 5.1g (0.03mol, 3.4ml) silicon tetrachloride is under 20 ℃; Drip solution in the 60min, drip process control temp and be no more than 35 ℃, after dripping off, be warmed up to 60 ℃ in the 1h with 50ml THF dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Insulation 6h cools to 35 ℃ again, and cooling drips glycol chlorohydrin 7.25g (0.09mol) down; Drip process control temp and be no more than 40 ℃, then be warmed up to 50 ℃ of insulation 6h in the 1h, cool to 35 ℃, add about 0.5g triethylamine acid binding agent; Transfer to pH=5-6, stir 1h, filter, filtrating distills out organic solvent (reclaim and use); Decompression steams a small amount of low boilers again, gets weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester; Product yield 93.3%, its flash-point (open cup): 225 ± 5 ℃, decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.
Embodiment 2 adds chloroform 10ml, 5.1g (0.03mol, 3.4ml) silicon tetrachloride in the 100ml four-hole boiling flask that whisking appliance, TM, efficient reflux condensing tube are housed; Under 20 ℃, drip solution in the 60min, drip process control temp and be no more than 35 ℃, after dripping off with 11.6g (0.03mol) the tribromo-benzene basic ring oxygen propyl ether of 50ml dissolved in chloroform; Be warmed up to 60 ℃ in the 1h, insulation 5h cools to 35 ℃ again, and cooling down; Drip glycol chlorohydrin 7.97g (0.099mol), drip process control temp and be no more than 40 ℃, then be warmed up to 55 ℃ of insulation 5h in the 1h, cool to 35 ℃; Add about 0.5g N, the accelerine acid binding agent transfers to pH=5-6, stirs 1h; Filter, filtrating distills out organic solvent (reclaiming use), and decompression steams excessive glycol chlorohydrin (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4, the 6-tribromophenoxy) propyl diester, product yield 94.5%; Its flash-point (open cup): 225 ± 5 ℃, decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.
Embodiment 3 adds acetonitrile 10ml, 5.1g (0.03mol, 3.4ml) silicon tetrachloride in the 100ml four-hole boiling flask that whisking appliance, TM, efficient reflux condensing tube are housed; Under 20 ℃, drip solution in the 60min, drip process control temp and be no more than 35 ℃, after dripping off with 50ml acetonitrile dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Be warmed up to 70 ℃ in the 1h, insulation 4h cools to 35 ℃ again, and cooling down; Drip glycol chlorohydrin 8.70g (0.108mol), drip process control temp and be no more than 40 ℃, then be warmed up to 60 ℃ of insulation 4h in the 1h, cool to 35 ℃; Add about 0.5g trimeric cyanamide acid binding agent, transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive glycol chlorohydrin (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4, the 6-tribromophenoxy) propyl diester, product yield 96.2%; Its flash-point (open cup): 225 ± 5 ℃, decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.
Embodiment 4 adds ethylene dichloride 10ml, 5.1g (0.03mol, 3.4ml) silicon tetrachloride in the 100ml four-hole boiling flask that whisking appliance, TM, efficient reflux condensing tube are housed; Under 20 ℃, drip solution in the 60min, drip process control temp and be no more than 35 ℃, after dripping off with 50ml ethylene dichloride dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Be warmed up to 80 ℃ in the 1h, insulation 4h cools to 35 ℃ again, and cooling down; Drip glycol chlorohydrin 9.42g (0.117mol), drip process control temp and be no more than 40 ℃, then be warmed up to 65 ℃ of insulation 4h in the 1h, cool to 35 ℃; Add about 0.5g pyridine acid binding agent, transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive glycol chlorohydrin (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4, the 6-tribromophenoxy) propyl diester, product yield 97.0%; Its flash-point (open cup): 225 ± 5 ℃, decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.
Embodiment 5 adds dioxane 10ml, 5.1g (0.03mol, 3.4ml) silicon tetrachloride in the 100ml four-hole boiling flask that whisking appliance, TM, efficient reflux condensing tube are housed; Under 20 ℃, drip solution in the 60min, drip process control temp and be no more than 35 ℃, after dripping off with 50ml dioxane dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Be warmed up to 80 ℃ in the 1h, insulation 4h cools to 35 ℃ again, and cooling down; Drip glycol chlorohydrin 10.15g (0.126mol), drip process control temp and be no more than 40 ℃, then be warmed up to 70 ℃ of insulation 3h in the 1h, cool to 35 ℃; Add about 0.5g trimeric cyanamide acid binding agent, transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive glycol chlorohydrin (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4, the 6-tribromophenoxy) propyl diester, product yield 97.4%; Its flash-point (open cup): 225 ± 5 ℃, decomposition temperature: 300 ± 5 ℃, density (25 ℃): 1.830g/cm 3, refractive index: n D 25=1.6686.
The routine main technologic parameters of table 1 preparation
This case contriver also is applied to above-mentioned synthetic silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester in the SE (PVC).The limiting oxygen index(LOI) of reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " test sample article.Get product silicon halogen cooperative flame retardant softening agent silicic acid three (2-chloroethyl)-2-chloro-3-(2; 4; The 6-tribromophenoxy) after propyl diester, plasticizer phthalic acid dioctyl ester (DOP), synergistic flame retardant Antimony Trioxide: 99.5Min and SE mix in varing proportions, extrudes, process the batten that diameter is 3mm with forcing machine; And its flame retardant properties tested, it is as shown in table 2 to have listed the part test result:
The flame retardant properties data of table 2 silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester
Figure BSA00000750162600072

Claims (6)

1. silicon halogen cooperative flame retardant softening agent silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl ester compounds is characterized in that the structure of this compound is shown below:
Figure FSA00000750162500011
According to claim 1 silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester preparation method its, be characterised in that this method is:
Stir down, in reactor drum, add silicon tetrachloride, under 20 ℃, drip the organic solvent solution of equimolar tribromo-benzene basic ring oxygen propyl ether, drip process control temp and be no more than 35 ℃; After dripping off, be warmed up to 60-80 ℃ in the 1h, insulation reaction 4-6h; Cool to 35 ℃ again, drip the glycol chlorohydrin of certain mol proportion, drip process control temp and be no more than 40 ℃; Drip off in the 1h of back and be warmed up to 50-70 ℃, insulation 3-6h, purified processing; Get weak yellow liquid silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester.
As the said silicic acid three of claim 2 (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester preparation method its, be characterised in that: described organic solvent is THF, chloroform, acetonitrile, 1,2-ethylene dichloride or 1,4-dioxane.
4. like the said silicic acid three of claim 2 (2-chloroethyl)-2-chloro-3-(2; 4; The 6-tribromophenoxy) the propyl diester preparation method its, be characterised in that: the glycol chlorohydrin of said certain mol proportion is meant tribromo-benzene basic ring oxygen propyl ether: silicon tetrachloride: the mol ratio of glycol chlorohydrin is 1: 1: 3-1: 1: 4.2.
As the said silicic acid three of claim 2 (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester preparation method its; Be characterised in that: said purification process is for adding the acid binding agent of quality product 1%-3%; Transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent, and decompression steams excessive glycol chlorohydrin and a small amount of low boilers again.
As claim 2,5 said silicic acid three (2-chloroethyl)-2-chloro-3-(2,4, the 6-tribromophenoxy) propyl diester preparing methods its, be characterised in that: said acid binding agent is triethylamine, N, accelerine, trimeric cyanamide or pyridine.
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