CN102731553A - Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof - Google Patents
Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof Download PDFInfo
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- CN102731553A CN102731553A CN2012102472578A CN201210247257A CN102731553A CN 102731553 A CN102731553 A CN 102731553A CN 2012102472578 A CN2012102472578 A CN 2012102472578A CN 201210247257 A CN201210247257 A CN 201210247257A CN 102731553 A CN102731553 A CN 102731553A
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Abstract
The invention relates to a tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound which is a silicon-halogen synergistic fire retardant, and a preparation method of the compound. The compound has a structure shown in a formula described in the specification; and in the formula, OC3H5Cl2 is OCH2CHClCH2Cl or OCH (CH2Cl) 2. The preparation method of the compound comprises the following steps: reacting tribromophenyl glycidyl ether and silicon tetrachloride according to the same molar ratio in an organic solvent for 4-6h at 60-80 DEG C; then dropwise adding dichloropropanol according to a certain molar ratio, reacting for 4-8h at 50-100 DEG C; and finally purifying to obtain faint yellow liquid which is the tris(dichloropropyl) tribromophenoxy chloropropyl silicate. The compound is applicable to fire retardants for polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and other materials; and the production process is simple, low in equipment investment and cost, and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester cpds and preparation method thereof.Silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester belongs to silicon halogen synergistic fire retardant, is suitable for the fire retardant or the softening agent of materials such as SE, urethane, epoxy resin, unsaturated polyester.
Background technology
The application of macromolecular material more and more widely still because its inflammable characteristic often causes fire, thereby has promoted the fast development of fire-retardant science and technology.Flame-retardant plasticizer is the processing of high molecular material auxiliary agent that has anti-flaming function and plastification simultaneously, and it can overcome because the adding of softening agent makes the more inflammable problem of macromolecular material.At present good flame-retardant plasticizer is of less types, and that the total expectation of people is developed is new and effective, low toxicity and cheap flame-retardant plasticizer.To achieve these goals, the exploitation to multielement cooperative flame retardant softening agent becomes the hot research problem.The excellent properties that press down cigarette owing to the silicon-type flame-retardant plasticizer has, promotes into carbon obtains people's attention.But the existence of silicon-type product costs an arm and a leg, use range is narrow, is restricted.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 (two a chloropropyls) tribromophenoxy chloropropyl ester.The present invention can solve the difficult problem of silicon tetrachloride comprehensive utilization, has opened up cheap good flame-retardant plasticizer new variety again, and has had good economic implications.
Summary of the invention
One of the object of the invention is that its fire-retardant plasticity is good, can effectively overcome deficiency of the prior art with synthetic a kind of silicon halogen cooperative flame retardant plasticized compound silicic acid three (two chloropropyls) the tribromophenoxy chloropropyl ester of the silicon tetrachloride as by-product of polysilicon industry.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester cpds is characterized in that the structure of this compound is shown below:
OC in its formula
3H
5Cl
2Be OCH
2CHClCH
2Cl or OCH (CH
2Cl)
2
Another object of the present invention is to propose the preparation method of a kind of silicic acid as stated three (two chloropropyls) tribromophenoxy chloropropyl ester, 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, and is with low cost, and this method is:
Stir down, in the silicon tetrachloride with mol ratios such as being added drop-wise under 20 ℃ of the organic solvent solutions of tribromo-benzene basic ring oxygen propyl ether, drip process temperature and be no more than 35 ℃, be warmed up to 60-80 ℃ after dripping off; Insulation reaction 4-6h cools to 40 ℃ again, the dichlorohydrine of certain mol proportion is added drop-wise in the above-mentioned reaction soln, after dripping off; Be warmed up to 50-100 ℃, insulation reaction 4-8h, the acid binding agent of adding quality product 1%-3%; Transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester.
Organic solvent is THF, acetonitrile, ethylene dichloride or dioxane as stated.
The dichlorohydrine of certain mol proportion is a silicon tetrachloride as stated: tribromo-benzene basic ring oxygen propyl ether: dichlorohydrine=1: 1: 3-1: 1: 4;
Aforesaid dichlorohydrine is 2,3-dichlorohydrine, 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine and 1, the mixture of 3-two chloro-2-propyl alcohol.
Aforesaid acid binding agent is triethylamine, N, accelerine, trimeric cyanamide or pyridine.
Silicic acid three of the present invention (2,3-two chloropropyls) tribromophenoxy chloropropyl ester is a light yellow viscous liquid, its flash-point (open cup): 228 ± 5 ℃, and decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.858g/cm
3, refractive index: n
D 25=1.6625; Silicic acid three (1,3-two chloropropyls) tribromophenoxy chloropropyl ester is a light yellow viscous liquid, its flash-point (open cup): 228 ± 5 ℃, and decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.856g/cm
3, refractive index: n
D 25=1.6629; Productive rate is 94.3%～98.0%, and it is suitable as the usefulness of the flame-retardant plasticizer of materials such as SE, Z 150PH, epoxy resin, unsaturated polyester, urethane.
The synthesis technique principle of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester is shown below:
OC in its formula
3H
5Cl
2Be OCH
2CHClCH
2Cl or OCH (CH
2Cl)
2
Compared with prior art, innovation part of the present invention is:
1. because the structure of silicon halogen cooperative flame retardant softening agent silicic acid of the present invention three (two chloropropyls) tribromophenoxy chloropropyl ester has symmetry characteristic preferably; Its physical and chemical performance is stable; Good with the macromolecular material intermiscibility; Good processability, element cooperative flame retardant usefulness 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 (two chloropropyls) the tribromophenoxy chloropropyl ester of raw material with polysilicon industry silicon tetrachloride as by-product; Can solve the difficult problem of silicon tetrachloride comprehensive utilization, open up cheap good flame-retardant plasticizer new variety 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.
The contriver thinks that mostly industrial dichlorohydrine is alcohol mixture, and it has application value most, and the spy will beat following spectrogram with the dichlorohydrine synthetic product that mixes that epoxy chloropropane and hydrochloric acid addition open loop make.
1, the infrared spectrogram of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester, see Figure of description Fig. 1 for details:
Fig. 1 shows, 2959.5cm
-1The place is the stretching vibration peak of methylene radical c h bond; 1630cm
-1The place is the skeleton stretching vibration peak of phenyl ring; 3080cm
-1The place is the C-H stretching vibration peak of phenyl ring; 1104cm
-1The place is the stretching vibration peak of Si-O-C key; 1046cm
-1The place is the stretching vibration peak of C-Br key; 492cm
-1The place is the stretching vibration peak of C-Cl key; 1248cm
-1The place is the stretching vibration peak of Ar-O key.
2, the nuclear magnetic spectrum figure of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester, see Figure of description Fig. 2 for details:
Fig. 2 shows that deuterochloroform is a solvent, and δ 3.61～3.77 is Si-OCH (CH
2Cl)
2Go up the methyl hydrogen peak and the Si-OCH that link to each other with chlorine
2CHClCH
2The last methyl hydrogen peak that links to each other with chlorine of Cl; δ 3.78～3.88 is Si-OCH
2CHClCH
2The last methylene radical hydrogen peak that links to each other with chlorine of Cl; δ 3.88～3.98 is Ar-OCH
2CHClCH
2The last methylene radical hydrogen peak that links to each other with chlorine of O-Si; δ 4.02～4.23 is Ar-OCH
2CHClCH
2Last methylene radical hydrogen peak and the Si-OCH that links to each other with silica of O-Si
2CHClCH
2The last methylene radical hydrogen peak that links to each other with silica of Cl; δ 4.40～4.57 is Si-OCH (CH
2Cl)
2Go up the methyne hydrogen peak that links to each other with oxygen; δ 4.67～4.78 is Ar-OCH
2CHClCH
2The methylene radical hydrogen peak that the last and fragrant oxygen of O-Si links to each other; δ 7.55～7.70 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.
Stir down, under 20 ℃, in the silicon tetrachloride with mol ratios such as the organic solvent solution of tribromo-benzene basic ring oxygen propyl ether are added drop-wise to, the dropping process is no more than 35 ℃; Be warmed up to 60-80 ℃ after dripping off, insulation reaction 4-6h cools to 40 ℃ again, and the dichlorohydrine of certain mol proportion is added drop-wise in the above-mentioned reaction soln; After dripping off, be warmed up to 50-100 ℃, insulation reaction 4-8h, the acid binding agent of adding quality product 1%-3%; Transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester.
Embodiment 2 adds acetonitrile 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, insulation 5h with 50ml acetonitrile dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Then under cooling conditions, drip 2 in the 1h, 3-dichlorohydrine 12.77g (0.099mol) is after dripping off; 70 ℃ of insulation reaction 7h, reaction finishes, and cools to 40 ℃, adds about 0.5g N; The accelerine acid binding agent transfers to pH=5-6, stirs 1h, filters; Filtrating distills out organic solvent (reclaiming use), and decompression steams excessive dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (2,3-two chloropropyls) tribromophenoxy chloropropyl ester; Product yield 95.1%, its flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.858g/cm
3, refractive index: n
D 25=1.6625.
Embodiment 3 adds ethylene dichloride 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 70 ℃ in the 1h with 50ml ethylene dichloride dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Insulation 4h then under cooling conditions, drips 1 in the 1h, 3-dichlorohydrine 13.93g (0.108mol); After dripping off, 80 ℃ of insulation reaction 6h, reaction finishes, and cools to 40 ℃; 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 dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (1,3-two chloropropyls) tribromophenoxy chloropropyl ester; Product yield 97.0%, its flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.856g/cm
3, refractive index: n
D 25=1.6629.
Embodiment 4 adds dioxane 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 80 ℃ in the 1h with 50ml dioxane dissolved 11.6g (0.03mol) tribromo-benzene basic ring oxygen propyl ether; Insulation 4h then under cooling conditions, drips 1 in the 1h, 3-dichlorohydrine 14.71g (0.114mol); After dripping off, 90 ℃ of insulation reaction 5h, reaction finishes, and cools to 40 ℃; 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 dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (1,3-two chloropropyls) tribromophenoxy chloropropyl ester; Product yield 97.5%, its flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.856g/cm
3, refractive index: n
D 25=1.6629.
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 then under cooling conditions, drips homemade as stated mixing dichlorohydrine 15.48g (0.120mol) in the 1h; After dripping off, 100 ℃ of insulation reaction 5h, reaction finishes; Cool to 40 ℃, add about 0.5g trimeric cyanamide acid binding agent, transfer to pH=5-6; Stir 1h, filter, filtrating distills out organic solvent (reclaim and use); Decompression steams excessive dichlorohydrine (reclaim and use) and a small amount of low boilers again, gets weak yellow liquid silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester, product yield 98.0%; Its flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 302 ± 5 ℃, density (25 ℃): 1.857g/cm
3, refractive index: n
D 25=1.6628.
The routine main technologic parameters of table 1 preparation
This case contriver also is applied to above-mentioned synthetic silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester in the SE.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " test sample article.After getting product silicon halogen cooperative flame retardant softening agent silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester, plasticizer phthalic acid dioctyl ester, synergistic flame retardant Antimony Trioxide: 99.5Min and SE and mixing in varing proportions; Extrude with forcing machine; Process the batten that diameter is 3mm, and its flame retardant properties is tested, experiment shows that different isomer product flame retardant propertiess is identical; Thereby experimental result do not indicate concrete isomer structure, and the part test result is as shown in table 2:
The flame retardant properties data of table 2 silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester
Claims (6)
1. a silicon halogen cooperative flame retardant softening agent silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester cpds is characterized in that the structure of this compound is shown below:
OC in its formula
3H
5Cl
2Be OCH
2CHClCH
2Cl or OCH (CH
2Cl)
2
2. the preparation method of silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester according to claim 1 is characterized in that this method is:
Under 20 ℃, the organic solvent solution of tribromo-benzene basic ring oxygen propyl ether is added drop-wise to etc. in the silicon tetrachloride of mol ratio, the dropping process is no more than 35 ℃, is warmed up to 60-80 ℃ after dripping off; Insulation reaction 4-6h cools to 40 ℃ again, the dichlorohydrine of certain mol proportion is added drop-wise in the above-mentioned reaction soln, after dripping off; Be warmed up to 50-100 ℃, insulation reaction 4-8h, the acid binding agent of adding quality product 1%-3%; Transfer to pH=5-6, stir 1h, filter; Filtrating distills out organic solvent, and decompression steams excessive dichlorohydrine and a small amount of low boilers again, gets weak yellow liquid silicic acid three (two chloropropyls) tribromophenoxy chloropropyl ester.
3. like the preparation method of the said silicic acid three of claim 2 (two chloropropyls) tribromophenoxy chloropropyl ester, it is characterized in that: said organic solvent is THF, acetonitrile, ethylene dichloride or dioxane.
4. like the preparation method of the said silicic acid three of claim 2 (two chloropropyls) tribromophenoxy chloropropyl ester, it is characterized in that: the dichlorohydrine of said certain mol proportion is a silicon tetrachloride: tribromo-benzene basic ring oxygen propyl ether: dichlorohydrine=1: 1: 3-1: 1: 4.
5. like the preparation method of the said silicic acid three of claim 2 (two chloropropyls) tribromophenoxy chloropropyl ester; It is characterized in that: described dichlorohydrine is 2,3-dichlorohydrine, 1,3-two chloro-2-propyl alcohol or 2; 3-dichlorohydrine and 1, the mixture of 3-two chloro-2-propyl alcohol.
6. like the preparation method of the said silicic acid three of claim 2 (two chloropropyls) tribromophenoxy chloropropyl ester, it is characterized in that: described acid binding agent is triethylamine, N, accelerine, trimeric cyanamide or pyridine.
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