CN104725413B - Flame-retardant plasticizer dimethyl silicic acid halogen propyl ester compound and preparation method thereof - Google Patents
Flame-retardant plasticizer dimethyl silicic acid halogen propyl ester compound and preparation method thereof Download PDFInfo
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- CN104725413B CN104725413B CN201510102101.4A CN201510102101A CN104725413B CN 104725413 B CN104725413 B CN 104725413B CN 201510102101 A CN201510102101 A CN 201510102101A CN 104725413 B CN104725413 B CN 104725413B
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- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000004014 plasticizer Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 dimethyl silicic acid halogen propyl ester compound Chemical class 0.000 title abstract description 31
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000002367 halogens Chemical class 0.000 claims abstract description 20
- ONCIQCKBUSMDIK-UHFFFAOYSA-N dihydroxy(dimethoxy)silane Chemical compound CO[Si](O)(O)OC ONCIQCKBUSMDIK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006073 displacement reaction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 11
- 238000009413 insulation Methods 0.000 description 10
- 238000004064 recycling Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 7
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of flame-retardant plasticizer dimethyl silicic acid halogen propyl ester compounds and preparation method thereof, and the structure of the compound is shown below：OC in formula3H6X is OCH2CHXCH3With OCH (CH2X)CH3, X=Cl or Br.Preparation method is：Two halosilanes of dimethyl are added in the reactor, the propylene oxide compared with 2~3 times moles of two halosilanes of dimethyl is added dropwise, and with rate of addition controlling reaction temperature not higher than 30 DEG C, react 6~11h after dripping off at 30 DEG C~70 DEG C；It is purified to handle to obtain dimethyl silicic acid halogen propyl ester.Dimethyl silicic acid halogen propyl ester flame-retarded efficiency of the present invention is high, and plasticity is good, is suitable as the flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin etc., and simple production process, at low cost, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of silicon, halogen dual element cooperative flame retardant plasticizer dimethyl silicic acid halogen propyl ester compound and its preparations
Method, the compound are suitable as the flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin etc..
Background technology
For many years, the yield for synthesizing high molecular material is all exponentially increasing.The application of high molecular material has been one
The symbol whether prosperity of country.But high molecular material is inflammable mostly, and the fire to grow in intensity promotes fire-retardant material
The research and development of material and fire retardant.In fire retardant, yield is maximum, using it is most wide be halogenated flame retardant.But with society
Progress and the enhancing of environmental protection consciousness, halogenated flame retardant can release substantial amounts of pernicious gas in burning, receive people
Query, thus the application in some fields is limited by very large.Simultaneously as halogenated flame retardant has good synthesis
Cost performance, although non-halogen cry is very high, its preferable fire retardant can be substituted completely by temporarily finding not yet, so halogen system
Still in flame retardant area in occupation of leading position, new and effective, the less toxic halogenated flame retardant of research and development becomes existing fire retardant
Stage important problem.
The invention discloses a kind of silicon, halogen dual element cooperative flame retardant plasticizer dimethyl silicic acid halogen propyl ester compound and its sides
Method.Silicon and halogen dual element cooperative flame retardant, element silicon can promote high molecular material to generate fine and close silicon charcoal into charcoal under hot conditions
Layer；Halogen element generates hydrogen halides when heated, and acting on generation antimony halides with retardant synergist antimony oxide is covered in material
Surface, have anoxybiotic effect or its heat can be taken away with gas releasing, reduce the temperature of material and non-ignitable.Fire retardant of the present invention is
Two kinds of ignition-proof element cooperative flame retardants, flame-retarded efficiency is high, has a wide range of application, there is good application and development prospect.
The content of the invention
It is an object of the present invention to propose a kind of flame-retardant plasticizer dimethyl silicic acid halogen propyl ester compound, fire-retardant effect
Can be high, plasticity is good, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical solutions：
Dimethyl silicic acid halogen propyl ester compound, which is characterized in that the structure of the compound is shown below：
OC in formula3H6X is OCH2CHXCH3With OCH (CH2X)CH3, X=Cl or Br.
It is simple for process another object of the present invention is to propose the preparation method of dimethyl silicic acid halogen propyl ester compound,
Equipment investment is few, is easy to large-scale production, and raw material is cheap and easy to get, of low cost, and this method is：
In the reactor equipped with blender, thermometer and condenser pipe, the air in reactor is fallen with nitrogen displacement, is added in
Two halosilanes of dimethyl, are cooled to less than 10 DEG C, and the propylene oxide compared with 2~3 times moles of two halosilanes of dimethyl is added dropwise, with
Rate of addition controlling reaction temperature is not higher than 30 DEG C, reacts 6~11h after dripping off at 30 DEG C~70 DEG C；Air-distillation removed
The propylene oxide (recycling uses) of amount, then be evaporated under reduced pressure and remove a small amount of low boilers, obtain dimethyl silicic acid halogen propyl ester.
Two halosilanes of dimethyl as described above are two bromo-silicane of dimethyldichlorosilane or dimethyl.
The dimethyl silicic acid bromine propyl ester of the present invention is colourless transparent liquid, and yield is 89.7%~94.3%, decomposition temperature
For 229 DEG C ± 5 DEG C, index of refraction nD 25=1.4735, (25 DEG C) of density is 1.46g/cm3；Dimethyl silicic acid chlorine propyl ester is colourless
Transparency liquid, yield are 86.5%~92.6%, and decomposition temperature is 218 DEG C ± 5 DEG C, index of refraction nD 25=1.4268, density
(25 DEG C) are 1.09g/cm3.It is suitable as the fire-retardant increasing of the materials such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin
Mould agent.The preparation process principle of the dimethyl silicic acid halogen propyl ester is shown below：
OC in formula3H6X is OCH2CHXCH3With OCH (CH2X)CH3, X=Cl or Br.
Compared with prior art, the beneficial effects of the present invention are：
1. dimethyl silicic acid halogen propyl ester of the present invention is siliceous, two kinds of ignition-proof elements of halogen, cooperative flame retardant efficiency is high, element silicon tool
There is into charcoal effect, the second-time burning that can effectively prevent material melted by heating drippage and generate.
2. connecting on silicon atom in dimethyl silicic acid halogen propyl ester structure of the present invention there are two methyl, there is C-Si keys, be organic
Silicon structure, organosilicon structures stability is good, water resistance is strong, and when burning is more easily generated fine and close charcoal-silicon layer, and flame retardant effect is more excellent
It is different；Since with branched chain propyl structure, intermolecular electrostatic force is smaller, and product viscosity is small, there is preferable plasticity in molecule.
3. there is no any small molecule to release in dimethyl silicic acid halogen propyl ester preparation process of the present invention, atom utilization 100%,
It is of low cost, there is good energy economy ＆ environment benefit.
4. dimethyl silicic acid halogen propyl ester of the present invention is simple for process, preparation process need not add catalyst and not introduce impurity, if
It is standby simple, it is of low cost, suitable for large-scale production, there is good application and development prospect.
Description of the drawings
Drawings described below is provided in order to further illustrate the structure and performance spy of product.
1st, the infrared spectrogram of dimethyl silicic acid chlorine propyl ester, refers to Figure of description Fig. 1；
Fig. 1 shows 2976.6cm-1, 2933.8cm-1, 2906.1cm-1Locate the stretching vibration absworption peak for C-H,
1007.5cm-1Locate the characteristic absorption peak for Si-O-C, 1093.6cm-1Locate the stretching vibration absworption peak for C-O, 832.3cm-1Place
For the stretching vibration absworption peak of C-Cl, 800.2cm-1Locate the characteristic absorption peak for Si-C.
2nd, the nuclear magnetic spectrogram of dimethyl silicic acid chlorine propyl ester, refers to Figure of description Fig. 2；
Fig. 2 shows that deuterochloroform makees solvent, and δ 0.15-0.22 are SiCH3Upper methyl hydrogen peak, δ 1.24-1.33 are OCH
(CH2Cl)CH3Upper methyl hydrogen peak, δ 1.47-1.54 are OCH2CHClCH3Upper methyl hydrogen peak, δ 3.37-3.53 are OCH (CH2Cl)
CH3The upper methylene hydrogen peak being connected with chlorine, δ 4.10-4.19 are OCH (CH2Cl)CH3The upper methine hydrogen peak being connected with oxygen, δ
3.68-3.87 for OCH2CHClCH3The upper methylene hydrogen peak being connected with oxygen, δ 3.99-4.08 are OCH2CHClCH3It is upper to be connected with chlorine
Methine hydrogen peak, δ 7.28 be solvent carbon deuterium chloride exchange proton peak.
3rd, the infrared spectrogram of dimethyl silicic acid bromine propyl ester, refers to Figure of description Fig. 3；
Fig. 3 shows 2983.4cm-1, 2931.9cm-1And 2907.2cm-1Locate the stretching vibration absworption peak for C-H,
1005.3cm-1Locate the characteristic absorption peak for Si-O-C, 1084.7cm-1Locate the stretching vibration absworption peak for C-O, 623.7cm-1Place
For the stretching vibration absworption peak of C-Br, 800.6cm-1Locate the characteristic absorption peak for Si-C.
Specific embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, two bromo-silicane of 109g (0.5mol) dimethyl, drop are added in
58.1g (1mol) propylene oxide is added dropwise to less than 10 DEG C in temperature, with rate of addition controlling reaction temperature not higher than 30 DEG C, after dripping off
1.5h is warming up to 60 DEG C, insulation reaction 8h；Vacuum distillation removes a small amount of low boilers, obtains dimethyl silicic acid bromine propyl ester, yield
91.2%.
Embodiment 2 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, two bromo-silicane of 109g (0.5mol) dimethyl, drop are added in
63.9g (1.1mol) propylene oxide is added dropwise to less than 10 DEG C in temperature, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
0.5h is warming up to 40 DEG C afterwards, insulation reaction 10h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure
A small amount of low boilers are removed, obtain dimethyl silicic acid bromine propyl ester, yield 89.7%.
Embodiment 3 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, two bromo-silicane of 109g (0.5mol) dimethyl, drop are added in
72.6g (1.25mol) propylene oxide is added dropwise to less than 10 DEG C in temperature, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
1.5h is warming up to 70 DEG C afterwards, insulation reaction 6h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure and removes
A small amount of low boilers are gone, obtain dimethyl silicic acid bromine propyl ester, yield 93.5%.
Embodiment 4 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, two bromo-silicane of 109g (0.5mol) dimethyl, drop are added in
81.3g (1.4mol) propylene oxide is added dropwise to less than 10 DEG C in temperature, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
1.5h is warming up to 60 DEG C afterwards, insulation reaction 8h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure and removes
A small amount of low boilers are gone, obtain dimethyl silicic acid bromine propyl ester, yield 94.3%.
Embodiment 5 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, two bromo-silicane of 109g (0.5mol) dimethyl, drop are added in
87.1g (1.5mol) propylene oxide is added dropwise to less than 10 DEG C in temperature, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
Afterwards at 30 DEG C, insulation reaction 11h；The excessive propylene oxide of air-distillation removing (recycling uses), then it is evaporated under reduced pressure removing less
Low boilers are measured, obtain dimethyl silicic acid bromine propyl ester, yield 90.8%.
Embodiment 6 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilane is added in, it is cold
But to less than 10 DEG C, 58.1g (1mol) propylene oxide is added dropwise, with rate of addition controlling reaction temperature not higher than 30 DEG C, after dripping off
1.5h is warming up to 70 DEG C, insulation reaction 6h；Vacuum distillation removes a small amount of low boilers, obtains dimethyl silicic acid chlorine propyl ester, yield
90.3%.
Embodiment 7 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilane is added in, it is cold
But to less than 10 DEG C, 63.9g (1.1mol) propylene oxide is added dropwise, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
0.5h is warming up to 45 DEG C afterwards, insulation reaction 10h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure
A small amount of low boilers are removed, obtain dimethyl silicic acid chlorine propyl ester, yield 87.9%.
Embodiment 8 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilane is added in, it is cold
But to less than 10 DEG C, 72.6g (1.25mol) propylene oxide is added dropwise, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
1.5h is warming up to 60 DEG C afterwards, insulation reaction 8h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure and removes
Solvent and a small amount of low boilers are gone, obtain dimethyl silicic acid chlorine propyl ester, yield 92.6%.
Embodiment 9 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilane is added in, it is cold
But to less than 10 DEG C, 81.3g (1.4mol) propylene oxide is added dropwise, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
1h is warming up to 50 DEG C afterwards, insulation reaction 8h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure removing
Solvent and a small amount of low boilers obtain dimethyl silicic acid chlorine propyl ester, yield 91.4%.
Embodiment 10 equipped with blender, thermometer and condenser pipe, and condenser pipe it is suitable for reading equipped with can great expansion it is close
In the 250ml four-hole bottles of big envelope, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilane is added in, it is cold
But to less than 10 DEG C, 87.1g (1.5mol) propylene oxide is added dropwise, with rate of addition controlling reaction temperature not higher than 30 DEG C, drips off
After be warming up to 30 DEG C, insulation reaction 11h；Air-distillation removes excessive propylene oxide (recycling uses), then is evaporated under reduced pressure removing
Solvent and a small amount of low boilers obtain dimethyl silicic acid chlorine propyl ester, yield 86.5%.
The dimethyl silicic acid halogen propyl ester of preparation is applied in polyvinyl chloride (PVC) by inventor.Reference：GB/
T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limit oxygen index of sample.Take product dimethyl silicic acid
Halogen propyl ester, plasticizer phthalic acid dioctyl ester (DOP), synergist antimony oxide (Sb2O3) and polyvinyl chloride is in varing proportions
After mixing, squeezed out with extruder, the batten of a diameter of 3mm is made, test its flame retardant property, part test result such as table 1
And shown in table 2：
The flame retardant property data of 1 dimethyl silicic acid bromine propyl ester of table
The flame retardant property data of 2 dimethyl silicic acid chlorine propyl ester of table
It is generally acknowledged that oxygen index (OI) reach 27% its be fire proofing.From upper table 1 and table 2, dimethyl silicic acid halogen propyl ester
There is good flame retardant property to pvc material.It has also been found that dimethyl silicic acid halogen propyl ester has one to polyvinyl chloride in experiment
Fixed plasticity can replace DOP, you can go easy plasticizer in right amount in.
Claims (1)
1. a kind of preparation method of flame-retardant plasticizer dimethyl silicic acid halogen propyl ester, which is characterized in that this method is：
In the reactor equipped with blender, thermometer and condenser pipe, the air in reactor is fallen with nitrogen displacement, adds in diformazan
Two bromo-silicane of base, is cooled to less than 10 DEG C, and the propylene oxide compared with 2~3 times moles of two bromo-silicane of dimethyl is added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 30 DEG C, reacts 6~11h after dripping off at 30 DEG C~70 DEG C；Air-distillation removes excessive
Propylene oxide, then be evaporated under reduced pressure and remove a small amount of low boilers, obtain dimethyl silicic acid halogen propyl ester, the structure such as following formula institute of the compound
Show：
OC in formula3H6X is OCH2CHXCH3With OCH (CH2X)CH3, X=Br.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140113A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Tri(chloroproply) methyl silicate compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140113A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Tri(chloroproply) methyl silicate compound and preparation method thereof |
Non-Patent Citations (3)
| Title |
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