CN104744504B - A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds - Google Patents
A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds Download PDFInfo
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- dimethyl
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- dihalo
- propyl alcohol
- halogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 60
- 239000010703 silicon Substances 0.000 title claims abstract description 59
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 35
- 239000003063 flame retardant Substances 0.000 title claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 150000002367 halogens Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims abstract description 8
- 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 abstract description 17
- 239000002955 immunomodulating agent Substances 0.000 title abstract description 4
- 229940121354 immunomodulator Drugs 0.000 title abstract description 4
- 230000002584 immunomodulator Effects 0.000 title abstract description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 95
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 57
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 43
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- 238000009413 insulation Methods 0.000 claims description 39
- -1 bromo- 2- propyl Chemical group 0.000 claims description 38
- 239000003208 petroleum Substances 0.000 claims description 37
- 238000010792 warming Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 230000006837 decompression Effects 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000006073 displacement reaction Methods 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 238000005292 vacuum distillation Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims description 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 5
- 239000003610 charcoal Substances 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 abstract description 4
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 36
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 22
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 150000002170 ethers Chemical class 0.000 description 16
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 14
- 238000011084 recovery Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 150000007974 melamines Chemical class 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- LIHMQSPBDBGMJW-UHFFFAOYSA-N 1,1-dibromopropan-1-ol Chemical class CCC(O)(Br)Br LIHMQSPBDBGMJW-UHFFFAOYSA-N 0.000 description 2
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention relates to a kind of silicon, nitrogen, halogen multielement cooperative flame retardant immunomodulator compounds preparation method, the structure of the compound is shown below：N=0 during m=1 in formula, n=1 during m=0；X=Cl or Br；Y=Cl or Br；OC3H5Y2For OCH (CH2Br)2、OCH2CHBrCH2Br、OCH(CH2Cl)2Or OCH2CHClCH2Cl.Preparation method is：In organic solvent, triglycidyl isocyanurate reacts 5~8h with the halosilanes of dimethyl two at 70 DEG C~100 DEG C；Dihalo- propyl alcohol is added dropwise again, 5~8h is reacted at 70 DEG C~110 DEG C, it is purified to handle to obtain isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester.Fire retardant efficiency of the present invention is high, good into charcoal effect, is suitable as the flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin etc., and simple production process, cost is low, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of silicon, nitrogen, halogen multielement cooperative flame retardant immunomodulator compounds preparation method, and in particular to isocyanide urea
The preparation method of sour three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) esters.The compound is suitable as polyvinyl chloride, gathered
The flame-retardant plasticizer of urethane, epoxy resin, unsaturated-resin etc..
Background technology
As European Union implements the propulsion of the fire-retardant non-halogen regulation of electronic product, China was proposed accordingly on July 1st, 2007
Flame retardant regulation, so as to be greatly promoted the research and development of China's fire retardant new varieties.The main path of preliminary halogen-free flameproof
It is addition magnesium hydroxide, aluminium hydroxide, Firebrake ZB and expanded graphite etc., but because its flame-retarded efficiency is low, it is necessary to very big in the substrate
Loading can be only achieved preferable flame retardant effect, often making the mechanical property of base material reduces.In addition, although P-N type is fire-retardant
The flame-retarded efficiency of agent is higher, but exist mostly easily move out, the deficiency such as the easy moisture absorption and poor processability.So, although it is non-halogen
Cry grows to even greater heights, but the development of halogen-free flame retardants at this stage is also difficult to the need for meeting society, and halogenated flame retardant will be
Flame retardant area is in occupation of consequence.Meanwhile, the halogen containing flame-retardant of many ignition-proof element collaborations is developed, by improving fire-retardant effect
Can, so as to reduce addition in the substrate, to reach the purpose of reduction halogen content, the class for practical application meaning that to be one have very much
Topic.
The invention discloses one kind with triglycidyl isocyanurate (TGIC), the halosilanes of dimethyl two, dihalo- propyl alcohol
Silicon, nitrogen, (the dimethyl dihalo- propoxyl group silicon acyloxy halogen third of halogen multielement synergistic fire retardant isocyanuric acid three are prepared for primary raw material
Base) ester compounds method.There is fire retardant of the present invention multiple fire retardant mechanism to act on, and wherein element silicon can generate the silicon charcoal of densification
Layer, nitrogen expandable flame retardant, halogen element gas phase is fire-retardant, and a variety of ignition-proof element cooperative flame retardants can produce excellent flame retardant effect.This
Invention fire retardant is a variety of ignition-proof element cooperative flame retardants, and its flame-retarded efficiency is high, good into charcoal effect, has a wide range of application, and has well
Application and development prospect.
The content of the invention
It is an object of the invention to propose isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) esterification conjunction
The preparation method of thing, its flame-retarded efficiency is high, and technique is simple, and equipment investment is few, it is easy to large-scale production, and raw material is cheap and easy to get,
It is with low cost, deficiency of the prior art can be overcome.
This method is：
Nitrogen displacement falls the air in reactor, adds triglycidyl isocyanurate, organic solvent and relative to different
The halosilanes of dimethyl two of 3 times moles of cyanurate three-glycidyl ester, stirring and dissolving, be warming up to 70 DEG C~100 DEG C, insulation reaction
5~8h；Less than 40 DEG C are cooled to, certain mole of dihalo- propyl alcohol is added dropwise, 60 DEG C are not higher than with rate of addition controlling reaction temperature,
5~8h is reacted after dripping off at 70 DEG C~110 DEG C；After hydrogen halide is discharged, add relative to product theory quality grams
Solvent, excessive dihalo- propyl alcohol is distilled off in 1%~5% melamine, regulation system pH to 5~6, suction filtration, filtrate decompression
(recovery is used) and a small amount of low boilers, add the oil of volume 1~3 times relative to product theory quality grams of number of milliliter
Ether, stirs 0.5h, stands, and separates lower floor's feed liquid, then vacuum distillation removes petroleum ether a small amount of in feed liquid, obtains isocyanuric acid three
(dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester.
Organic solvent as described above is dioxane, dichloroethanes, acetonitrile or diethylene glycol dimethyl ether, its consumption volume
Milliliter number is 5~15 times of triglycidyl isocyanurate quality grams.
Dihalo- propyl alcohol as described above certain mole is triglycidyl isocyanurate: the halosilanes of dimethyl two: two
Halogen propyl alcohol mol ratio is 1: 3: 3~1: 3: 4.
Dihalo- propyl alcohol as described above be the bromo- 2- propyl alcohol of 1,3- bis-, the bromo- 1- propyl alcohol of 2,3- bis-, the bromo- 2- propyl alcohol of 1,3- bis- and
The chloro- 2- propyl alcohol of mixture, 1,3- bis- of 2,3- bis- bromo- 1- propyl alcohol, the trimethylewne chlorohydrin 3-s of 2,3- bis- or the chloro- 2- propyl alcohol of 1,3- bis- and 2,
The mixture of the trimethylewne chlorohydrin 3-s of 3- bis-.
The halosilanes of dimethyl two as described above are dimethyldichlorosilane or the bromo-silicane of dimethyl two.
Isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester of the present invention is colourless or light yellow liquid
Body.It is suitable as the flame-retardant plasticizer of the materials such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin.The isocyanuric acid
The preparation technology principle of three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) esters is shown below：
N=0 during m=1 in formula, n=1 during m=0；X=Cl or Br；Y=Cl or Br；OC3H5Y2For OCH (CH2Br)2、
OCH2CHBrCH2Br、OCH(CH2Cl)2Or OCH2CHClCH2Cl。
Compared with prior art, the beneficial effects of the present invention are：
1. isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester of the present invention is nitrogenous, silicon, a variety of resistances of halogen
Element is fired, its cooperative flame retardant efficiency is high, nitrogen has expansion effect of heat insulation, element silicon has into charcoal effect, can effectively prevented
The second-time burning that material melted by heating is dripped and produced.
2. connect in isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester structure of the present invention on silicon atom
There are two methyl, be organosilicon structures with C-Si keys, organosilicon structures stability is good, water resistance strong, life is easier to during burning
Into fine and close charcoal-silicon layer, flame retardant effect is more excellent.
3. isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester molecule amount of the present invention is big, volatility
Low, symmetry is good, physical and chemical performance is stable, belongs to many silicon, many nitrogen, many halogen, many ester structures, and ignition-proof element content is high, molecule
In atom vector construction each other, it is good with high polymer material compatibility, adapt to the high temperature process in engineering material.
4. isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester of the present invention belongs to heterocycle highly branched chain silicon
Acid esters compound, is transparent viscous liquid, with good plasticity.
5. urged during prepared by isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester of the present invention without addition
Agent, does not introduce impurity, and process equipment is simple, suitable for large-scale production.
Brief description of the drawings
In order to which the structure and performance spy that further illustrate product provide drawings described below.
1st, the infrared spectrogram of isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester, in detail
See Figure of description Fig. 1；
Fig. 1 shows, 2960.7cm-1And 2906.2cm-1For C-H stretching vibration absworption peak, 1708.7cm-1For carbonyl
Stretching vibration absworption peak, 1474.8cm-1And 1426.1cm-1For C-H flexural vibrations absworption peak, 1008.9cm-1For Si-O-C's
Characteristic absorption peak, 878.2cm-1For C-Cl stretching vibration absworption peak, 692.6cm-1For C-Br stretching vibration absworption peak,
753.9cm-1For Si-C characteristic absorption peak.
2nd, the nuclear magnetic spectrogram of isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester, is referred to
Figure of description Fig. 2；
Fig. 2 shows that deuterochloroform makees solvent, and δ 3.39~3.54 is CH (CH2Br)2The upper methylene hydrogen peak being connected with bromine, δ
4.14~4.28 be CH (CH2Br)2Last time methyl hydrogen peak, δ 3.54~3.68 is NCH2CHClCH2The upper methylene being connected with nitrogen of O
Hydrogen peak, δ 3.98~4.14 is NCH2CHClCH2The upper methylene hydrogen peaks being connected with oxygen of O, δ 4.31~4.46 is NCH2CHClCH2O
The upper methine hydrogen peak being connected with chlorine, δ 0.12~0.34 is SiCH3Upper methyl hydrogen peak, δ 7.28 is what solvent carbon deuterium chloride was exchanged
Proton peak.
3rd, the infrared spectrogram of isocyanuric acid three (the chloro- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester, in detail
See Figure of description Fig. 3；
Fig. 3 shows, 2965.3cm-1、2911.2cm-1For C-H stretching vibration absworption peak, 1702.8cm-1For stretching for carbonyl
Contracting vibration absorption peak, 1471.8cm-1、1423.7cm-1For C-H flexural vibrations absworption peak, 1082.4cm-1For Si-O-C spy
Levy absworption peak, 826.3cm-1For C-Cl stretching vibration absworption peak, 801.9cm-1For Si-C characteristic absorption peak.
4th, the nuclear magnetic spectrogram of isocyanuric acid three (the chloro- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester, is referred to
Figure of description Fig. 4；
Fig. 4 shows that deuterochloroform makees solvent, and δ 3.58~3.72 is CH (CH2Cl)2Upper methylene hydrogen peak, δ 4.16~4.26
For CH (CH2Cl)2Last time methyl hydrogen peak, δ 3.47~3.58 is NCH2CHClCH2The upper methylene hydrogen peaks being connected with nitrogen of O, δ 4.03
~4.14 be NCH2CHClCH2The upper methylene hydrogen peaks being connected with oxygen of O, δ 4.29~4.38 is NCH2CHClCH2O is upper to be connected with chlorine
Methine hydrogen peak, δ 0.21~0.31 be SiCH3Upper methyl hydrogen peak, δ 1.56 is water peak, and δ 7.26 exchanges for solvent carbon deuterium chloride
Proton peak.
Specific embodiment
Technical scheme is described further below in conjunction with embodiment.
Embodiment 1 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 70ml are added
Dioxane and 12.91g (0.1mol) dimethyldichlorosilane, 1h are warming up to 90 DEG C, insulation reaction 6h；Be cooled to 40 DEG C with
Under, hydrogen chloride absorption device is connected on drying tube, the bromo- 2- propyl alcohol of 21.79g (0.1mol) 1,3- bis- is added dropwise, with rate of addition
Controlling reaction temperature is not higher than 60 DEG C, and 100 DEG C, insulation reaction 6h are warming up to after dripping off；After HCl gases are discharged, 0.4g is added
Solvent and a small amount of low boilers are distilled off in melamine, regulation system pH to 5~6, suction filtration, filtrate decompression, add 30ml
Petroleum ether, stirs 0.5h, stands, and separates lower floor's feed liquid, then vacuum distillation removes a small amount of petroleum ether, obtains isocyanuric acid three (two
Methyl isophthalic acid, the bromo- 2- propoxyl group silicon acyloxy chloropropyls of 3- bis-) ester.Yield 91.8%, 273 DEG C ± 5 DEG C of decomposition temperature, index of refraction
nD 25=1.5369, density (25 DEG C) 1.84g/cm3。
Embodiment 2 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
100ml acetonitriles and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 80 DEG C, insulation reaction 7h；Less than 40 DEG C are cooled to,
Hydrogen bromide absorption plant is connected on drying tube, the bromo- 2- propyl alcohol of 23.25g (0.1067mol) 1,3- bis- is added dropwise, with rate of addition
Controlling reaction temperature is not higher than 60 DEG C, and 80 DEG C, insulation reaction 7h are warming up to after dripping off；After HBr gases are discharged, 1g trimerizations are added
Cyanamide, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, (recovery makes the excessive bromo- 2- propyl alcohol of 1,3- bis-
With) and a small amount of low boilers, 50ml petroleum ethers are added, 0.5h is stirred, stood, lower floor's feed liquid is separated, then vacuum distillation is removed
A small amount of petroleum ether, obtains isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy bromopropyl of dimethyl -1,3- bis-) ester, yield
94.3%, 257 DEG C ± 5 DEG C of decomposition temperature, index of refraction nD 25=1.5438, density (25 DEG C) 1.96g/cm3。
Embodiment 3 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 50ml are added
Diethylene glycol dimethyl ether and 12.91g (0.1mol) dimethyldichlorosilane, 1h are warming up to 100 DEG C, insulation reaction 5h；It is cooled to
Less than 40 DEG C, hydrogen chloride absorption device is connected on drying tube, the bromo- 2- propyl alcohol of 25.43g (0.1167mol) 1,3- bis- is added dropwise, with
Rate of addition controlling reaction temperature is not higher than 60 DEG C, and 110 DEG C, insulation reaction 5h are warming up to after dripping off；After HCl gases are discharged,
1.2g melamines are added, solvent, the excessive bromo- 2- of 1,3- bis- is distilled off in regulation system pH to 5~6, suction filtration, filtrate decompression
Propyl alcohol (recovery is used) and a small amount of low boilers, add 80ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then subtract
A small amount of petroleum ether is distilled off in pressure, obtains isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-)
Ester, yield 95.8%.
Embodiment 4 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
150ml dioxane and 12.91g (0.1mol) dimethyldichlorosilane, 0.5h are warming up to 85 DEG C, insulation reaction 7h；It is cooled to
Less than 40 DEG C, hydrogen chloride absorption device is connected on drying tube, the bromo- 2- propyl alcohol of 29.04g (0.1333mol) 1,3- bis- is added dropwise, with
Rate of addition controlling reaction temperature is not higher than 60 DEG C, and 70 DEG C, insulation reaction 8h are warming up to after dripping off；After HCl gases are discharged, plus
Enter 2g melamines, solvent, the excessive bromo- 2- propyl alcohol of 1,3- bis- is distilled off in regulation system pH to 5~6, suction filtration, filtrate decompression
(recovery is used) and a small amount of low boilers, add 100ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then depressurize
A small amount of petroleum ether is distilled off, isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester is obtained,
Yield 94.9%.
Embodiment 5 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 90ml are added
Dichloroethanes and 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 8h；Less than 40 DEG C are cooled to,
Hydrogen chloride absorption device is connected on drying tube, the bromo- 1- propyl alcohol of 26.15g (0.12mol) 2,3- bis- is added dropwise, with rate of addition control
Reaction temperature processed is not higher than 60 DEG C, and 85 DEG C, insulation reaction 6h are warming up to after dripping off；After HCl gases are discharged, 1.6g trimerizations are added
Cyanamide, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, (recovery makes the excessive bromo- 1- propyl alcohol of 2,3- bis-
With) and a small amount of low boilers, 60ml petroleum ethers are added, 0.5h is stirred, stood, lower floor's feed liquid is separated, then vacuum distillation is removed
A small amount of petroleum ether, obtains isocyanuric acid three (the bromo- 1- propoxyl group silicon acyloxy chloropropyl of dimethyl -2,3- bis-) ester.Yield
93.7%, 254 DEG C ± 5 DEG C of decomposition temperature, index of refraction nD 25=1.5391, density (25 DEG C) 1.86g/cm3。
Embodiment 6 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
100ml acetonitriles and 12.91g (0.1mol) dimethyldichlorosilane, 0.5h are warming up to 80 DEG C, insulation reaction 7h；It is cooled to 40 DEG C
Hereinafter, hydrogen chloride absorption device is connected on drying tube, the bromo- 1- propyl alcohol of 21.79g (0.1mol) 2,3- bis- is added dropwise, so that speed is added dropwise
Degree controlling reaction temperature is not higher than 60 DEG C, and 90 DEG C, insulation reaction 7h are warming up to after dripping off；After HCl gases are discharged, 0.4g is added
Solvent and a small amount of low boilers are distilled off in melamine, regulation system pH to 5~6, suction filtration, filtrate decompression, add 30ml
Petroleum ether, stirs 0.5h, stands, and separates lower floor's feed liquid, then vacuum distillation removes a small amount of petroleum ether, obtains isocyanuric acid three (two
The bromo- 1- propoxyl group silicon acyloxy chloropropyl of methyl -2,3- bis-) ester, yield 90.4%.
Embodiment 7 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 60ml are added
Diethylene glycol dimethyl ether and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 100 DEG C, insulation reaction 5h；It is cooled to 40 DEG C
Hereinafter, hydrogen bromide absorption plant is connected on drying tube, the bromo- 1- propyl alcohol of 29.04g (0.1333mol) 2,3- bis- is added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 60 DEG C, and 100 DEG C, insulation reaction 6h are warming up to after dripping off；After HBr gases are discharged, add
Solvent, the excessive bromo- 1- propyl alcohol of 2,3- bis- is distilled off in 1.8g melamines, regulation system pH to 5~6, suction filtration, filtrate decompression
(recovery is used) and a small amount of low boilers, add 100ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then depressurize
A small amount of petroleum ether is distilled off, isocyanuric acid three (the bromo- 1- propoxyl group silicon acyloxy bromopropyl of dimethyl -2,3- bis-) ester is obtained,
Yield 97.2%.
Embodiment 8 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
120ml dichloroethanes and 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 8h；It is cooled to 40 DEG C
Hereinafter, hydrogen chloride absorption device is connected on drying tube, 25.43g (0.1167mol) mixing dibromo-propanols are added dropwise, so that speed is added dropwise
Degree controlling reaction temperature is not higher than 60 DEG C, and 110 DEG C, insulation reaction 5h are warming up to after dripping off；After HCl gases are discharged, add
1.2g melamines, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, (recovery makes excessive dibromo-propanol
With) and a small amount of low boilers, 80ml petroleum ethers are added, 0.5h is stirred, stood, lower floor's feed liquid is separated, then vacuum distillation is removed
A small amount of petroleum ether, obtains isocyanuric acid three (dimethyl dibromo propoxy silicon acyloxy chloropropyl) ester.Yield 96.9%, decomposes temperature
269 DEG C ± 5 DEG C of degree, index of refraction nD 25=1.5373, density (25 DEG C) 1.84g/cm3。
Embodiment 9 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
110ml dichloroethanes and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 80 DEG C, insulation reaction 8h；Be cooled to 40 DEG C with
Under, hydrogen bromide absorption plant is connected on drying tube, 29.04g (0.1333mol) mixing dibromo-propanols are added dropwise, with rate of addition
Controlling reaction temperature is not higher than 60 DEG C, and 80 DEG C, insulation reaction 8h are warming up to after dripping off；After HBr gases are discharged, 2g trimerizations are added
Cyanamide, regulation system pH to 5~6, suction filtration, filtrate decompression is distilled off solvent, excessive dibromo-propanol (recovery is used) and lacked
Low boilers are measured, 100ml petroleum ethers are added, 0.5h is stirred, stood, lower floor's feed liquid is separated, then vacuum distillation is removed on a small quantity
Petroleum ether, obtains isocyanuric acid three (dimethyl dibromo propoxy silicon acyloxy bromopropyl) ester, yield 94.3%.
Embodiment 10 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
100ml diethylene glycol dimethyl ethers and 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 100 DEG C, insulation reaction 5h；Cooling
To less than 40 DEG C, hydrogen chloride absorption device is connected on drying tube, the chloro- 2- propyl alcohol of 13.76g (0.1067mol) 1,3- bis- is added dropwise,
60 DEG C are not higher than with rate of addition controlling reaction temperature, after dripping off at 80 DEG C, insulation reaction 8h；After HCl gases are discharged, plus
Enter 0.6g melamines, solvent, the excessive chloro- 2- third of 1,3- bis- is distilled off in regulation system pH to 5~6, suction filtration, filtrate decompression
Alcohol (recovery is used) and a small amount of low boilers, add 30ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then depressurize
A small amount of petroleum ether is distilled off, isocyanuric acid three (the chloro- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester is obtained,
Yield 93.9%, 286 DEG C ± 5 DEG C of decomposition temperature, index of refraction nD 25=1.4927, density (25 DEG C) 1.34g/cm3。
Embodiment 11 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
120ml dioxane and 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 8h；It is cooled to 40 DEG C
Hereinafter, hydrogen chloride absorption device is connected on drying tube, the chloro- 2- propyl alcohol of 15.05g (0.1167mol) 1,3- bis- is added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 60 DEG C, and 100 DEG C, insulation reaction 6h are warming up to after dripping off；After HCl gases are discharged, add
Solvent, the excessive chloro- 2- propyl alcohol of 1,3- bis- is distilled off in 0.9g melamines, regulation system pH to 5~6, suction filtration, filtrate decompression
(recovery is used) and a small amount of low boilers, add 70ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then depressurize steaming
A small amount of petroleum ether is removed in distillation, obtains isocyanuric acid three (the chloro- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester, production
Rate 95.6%.
Embodiment 12 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
140ml dioxane and 12.91g (0.1mol) dimethyldichlorosilane, 1h are warming up to 90 DEG C, insulation reaction 6h；It is cooled to 40
Below DEG C, hydrogen chloride absorption device is connected on drying tube, the trimethylewne chlorohydrin 3-s of 15.48g (0.12mol) 2,3- bis- are added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 60 DEG C, and 90 DEG C, insulation reaction 5h are warming up to after dripping off；After HCl gases are discharged, 1g is added
Melamine, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, the excessive trimethylewne chlorohydrin 3-s of 2,3- bis- (are returned
Receipts are used) and a small amount of low boilers, 70ml petroleum ethers are added, 0.5h is stirred, stands, separates lower floor's feed liquid, then vacuum distillation
A small amount of petroleum ether is removed, isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy chloropropyl of dimethyl -2,3- bis-) ester, yield is obtained
96.8%, 272 DEG C ± 5 DEG C of decomposition temperature, index of refraction nD 25=1.4967, density (25 DEG C) 1.35g/cm3。
Embodiment 13 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
150ml dichloroethanes and 12.91g (0.1mol) dimethyldichlorosilane, 0.5h are warming up to 80 DEG C, insulation reaction 7h；It is cooled to
Less than 40 DEG C, hydrogen chloride absorption device is connected on drying tube, the trimethylewne chlorohydrin 3-s of 17.20g (0.1333mol) 2,3- bis- are added dropwise, with
Rate of addition controlling reaction temperature is not higher than 60 DEG C, and 70 DEG C, insulation reaction 8h are warming up to after dripping off；After HCl gases are discharged, plus
Enter 1.6g melamines, solvent, the excessive chloro- 1- third of 2,3- bis- is distilled off in regulation system pH to 5~6, suction filtration, filtrate decompression
Alcohol (recovery is used) and a small amount of low boilers, add 80ml petroleum ethers, stir 0.5h, stand, separate lower floor's feed liquid, then depressurize
A small amount of petroleum ether is distilled off, isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy chloropropyl of dimethyl -2,3- bis-) ester is obtained,
Yield 94.1%.
Embodiment 14 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 90ml are added
Diethylene glycol dimethyl ether and 12.91g (0.1mol) dimethyldichlorosilane, 1h are warming up to 100 DEG C, insulation reaction 5h；It is cooled to
Less than 40 DEG C, hydrogen chloride absorption device is connected on drying tube, 17.20g (0.1333mol) mixing dichlorohydrins are added dropwise, to drip
Acceleration Control reaction temperature is not higher than 60 DEG C, and 110 DEG C, insulation reaction 5h are warming up to after dripping off；After HCl gases are discharged, plus
Enter 1.6g melamines, solvent, the dichlorohydrin (recovery of excess is distilled off in regulation system pH to 5~6, suction filtration, filtrate decompression
Use) and a small amount of low boilers, 80ml petroleum ethers are added, 0.5h is stirred, stands, separates lower floor's feed liquid, then vacuum distillation is removed
A small amount of petroleum ether is removed, isocyanuric acid three (dimethyl compound silicon acyloxy chloropropyl) ester, yield 96.9% is obtained.
Embodiment 15 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
100ml diethylene glycol dimethyl ethers and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 100 DEG C, insulation reaction 5h；Cooling
To less than 40 DEG C, hydrogen bromide absorption plant is connected on drying tube, the chloro- 2- propyl alcohol of 12.9g (0.1mol) 1,3- bis- is added dropwise, to drip
Acceleration Control reaction temperature is not higher than 60 DEG C, after dripping off at 80 DEG C, insulation reaction 8h；After HBr gases are discharged, add
Solvent and a small amount of low boilers are distilled off in 0.6g melamines, regulation system pH to 5~6, suction filtration, filtrate decompression, add
30ml petroleum ethers, stir 0.5h, stand, and separate lower floor's feed liquid, then vacuum distillation removes a small amount of petroleum ether, obtains isocyanuric acid three
(the chloro- 2- propoxyl group silicon acyloxy bromopropyl of dimethyl -1,3- bis-) ester, yield 94.2%, 294 DEG C ± 5 DEG C of decomposition temperature, refractive power
Rate nD 25=1.5013, density (25 DEG C) 1.47g/cm3。
Embodiment 16 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
120ml dioxane and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 90 DEG C, insulation reaction 6h；Be cooled to 40 DEG C with
Under, hydrogen bromide absorption plant is connected on drying tube, the trimethylewne chlorohydrin 3-s of 17.20g (0.1333mol) 2,3- bis- are added dropwise, so that speed is added dropwise
Degree controlling reaction temperature is not higher than 60 DEG C, and 90 DEG C, insulation reaction 6h are warming up to after dripping off；After HBr gases are discharged, 1.5g is added
Melamine, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, the excessive trimethylewne chlorohydrin 3-s of 2,3- bis- (are returned
Receipts are used) and a small amount of low boilers, 80ml petroleum ethers are added, 0.5h is stirred, stands, separates lower floor's feed liquid, then vacuum distillation
A small amount of petroleum ether is removed, isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy bromopropyl of dimethyl -2,3- bis-) ester, yield is obtained
96.5%.
Embodiment 17 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, 9.91g (0.0333mol) triglycidyl isocyanurate, 70ml are added
Diethylene glycol dimethyl ether and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 90 DEG C, insulation reaction 6h；It is cooled to 40 DEG C
Hereinafter, hydrogen bromide absorption plant is connected on drying tube, 15.48g (0.12mol) mixing dichlorohydrins are added dropwise, with rate of addition
Controlling reaction temperature is not higher than 60 DEG C, and 110 DEG C, insulation reaction 5h are warming up to after dripping off；After HBr gases are discharged, 1.2g is added
Solvent, excessive dichlorohydrin is distilled off in melamine, regulation system pH to 5~6, suction filtration, filtrate decompression (recovery is used)
And a small amount of low boilers, 70ml petroleum ethers are added, 0.5h is stirred, stood, lower floor's feed liquid is separated, then vacuum distillation is removed on a small quantity
Petroleum ether, obtain isocyanuric acid three (dimethyl compound silicon acyloxy bromopropyl) ester, yield 97.6%.
Embodiment 18 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, add 9.91g (0.0333mol) triglycidyl isocyanurate,
150ml acetonitriles and the bromo-silicane of 21.8g (0.1mol) dimethyl two, are warming up to 70 DEG C, insulation reaction 8h；Less than 40 DEG C are cooled to,
Hydrogen bromide absorption plant is connected on drying tube, 17.20g (0.1333mol) mixing dichlorohydrins are added dropwise, with rate of addition control
Reaction temperature is not higher than 60 DEG C, and 80 DEG C, insulation reaction 8h are warming up to after dripping off；After HBr gases are discharged, 1.6g melamines are added
Amine, regulation system pH to 5~6, suction filtration, solvent is distilled off in filtrate decompression, excessive dichlorohydrin (recovery is used) and a small amount of
Low boilers, add 80ml petroleum ethers, stir 0.5h, stand, and separate lower floor's feed liquid, then vacuum distillation removes a small amount of oil
Ether, obtains isocyanuric acid three (dimethyl compound silicon acyloxy bromopropyl) ester, yield 95.1%.
Isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester various structures product of the present invention it is fire-retardant
Carbon-forming performance is basically identical.Therefore, inventor is only with (the bromo- 2- third of dimethyl -1,3- bis- of isocyanuric acid three of above-mentioned preparation
Epoxide silicon acyloxy chloropropyl) ester (sample 1), (the chloro- 1- propoxyl group silicon acyloxy chlorine third of dimethyl -2,3- bis- of isocyanuric acid three
Base) ester (sample 2) and isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy bromopropyl of dimethyl -2,3- bis-) ester (sample 3) be
Example, is applied in polyvinyl chloride (PVC).Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index (OI)
Method》The limited oxygen index of test sample product.Above-mentioned flame retardant products, plasticizer phthalic acid dioctyl ester (DOP), synergistic resistance are taken respectively
Fire agent antimony oxide (Sb2O3) and polyvinyl chloride in varing proportions be well mixed after, extruded with extruder, a diameter of 3mm be made
Batten, test its fire resistance, part test result is as shown in table 1, table 2 and table 3：
The fire resistance data of table 1 isocyanuric acid three (the bromo- 2- propoxyl group silicon acyloxy chloropropyl of dimethyl -1,3- bis-) ester
The fire resistance data of table 2 isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy chloropropyl of dimethyl -2,3- bis-) ester
The fire resistance data of table 3 isocyanuric acid three (the chloro- 1- propoxyl group silicon acyloxy bromopropyl of dimethyl -2,3- bis-) ester
According to table 1, table 2 and table 3 as can be seen that (the dimethyl dihalo- propoxyl group silicon acyloxy of isocyanuric acid three of the present invention
Halogen propyl group) ester has excellent fire resistance to pvc material and into charcoal anti-drip energy.Meanwhile, it also found in experiment
The compound has preferable plasticity, can in right amount replace or add some DOP less.
Claims (5)
1. many plain (the dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) esters of synergistic fire retardant isocyanuric acid three of a kind of silicon, nitrogen, halogen
The preparation method of compound, it is characterised in that this method is：
Nitrogen displacement falls the air in reactor, adds triglycidyl isocyanurate and organic solvent, add relative to
The halosilanes of dimethyl two of 3 times moles of triglycidyl isocyanurate, stirring and dissolving is warming up to 70 DEG C~100 DEG C, insulation is anti-
Answer 5~8h；Less than 40 DEG C are cooled to, dihalo- propyl alcohol of 3~4 times moles relative to triglycidyl isocyanurate is added dropwise, with
Rate of addition controlling reaction temperature is not higher than 60 DEG C, reacts 5~8h after dripping off at 70 DEG C~110 DEG C；Treat that hydrogen halide is put
After complete, the melamine relative to product theory quality 1%~5%, regulation system pH to 5~6, suction filtration, filtrate decompression are added
Solvent, excessive dihalo- propyl alcohol and a small amount of low boilers are distilled off, volume milliliter number are added relative to product theory quality
The petroleum ether that 1~3 times of grams, stirs 0.5h, stands, and separates lower floor's feed liquid, then vacuum distillation removes a small amount of oil in feed liquid
Ether, obtains isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester.
2. the preparation side of isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester according to claim 1
Method, it is characterised in that described organic solvent is dioxane, diethylene glycol dimethyl ether, acetonitrile or dichloroethanes, its consumption body
Product milliliter number is 5~15 times of triglycidyl isocyanurate quality grams.
3. the preparation side of isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester according to claim 1
Method, it is characterised in that described dihalo- propyl alcohol is the bromo- 2- propyl alcohol of 1,3- bis-, the bromo- 1- propyl alcohol of 2,3- bis-, the bromo- 2- propyl alcohol of 1,3- bis-
With the chloro- 2- propyl alcohol of mixture, 1,3- bis-, the trimethylewne chlorohydrin 3-s of 2,3- bis- or the chloro- 2- propyl alcohol of 1,3- bis- of the bromo- 1- propyl alcohol of 2,3- bis- and
The mixture of 2,3- bis- trimethylewne chlorohydrin 3-s.
4. the preparation side of isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester according to claim 1
Method, it is characterised in that the described halosilanes of dimethyl two are dimethyldichlorosilane or the bromo-silicane of dimethyl two.
5. the preparation side of isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester according to claim 1
Method, it is characterised in that it is the solvent and two that vacuum distillation goes out that solvent, excessive dihalo- propyl alcohol, which is distilled off, in described filtrate decompression
Halogen propyl alcohol is recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102137.2A CN104744504B (en) | 2015-03-06 | 2015-03-06 | A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102137.2A CN104744504B (en) | 2015-03-06 | 2015-03-06 | A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds |
Publications (2)
| Publication Number | Publication Date |
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| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN103554151A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Tris[2-tris(2,3-dichloropropoxy)silicon-acyloxy-ethyl]isocyanurate compound and preparation method thereof |
| CN103554148A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant cyclo-bromoethyl trisilicate compound and preparation method thereof |
| CN103554147A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant tris(hydroxyethyl) isocyanurate trisilicate propyl bromide compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN103554151A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Tris[2-tris(2,3-dichloropropoxy)silicon-acyloxy-ethyl]isocyanurate compound and preparation method thereof |
| CN103554148A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant cyclo-bromoethyl trisilicate compound and preparation method thereof |
| CN103554147A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant tris(hydroxyethyl) isocyanurate trisilicate propyl bromide compound and preparation method thereof |
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