CN104710457B - Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds and preparation method thereof - Google Patents
Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds and preparation method thereof Download PDFInfo
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- CN104710457B CN104710457B CN201510100442.8A CN201510100442A CN104710457B CN 104710457 B CN104710457 B CN 104710457B CN 201510100442 A CN201510100442 A CN 201510100442A CN 104710457 B CN104710457 B CN 104710457B
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- ethyl
- propoxyl group
- dimethyl chloride
- group silicon
- isocyanurate
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 49
- 239000010703 silicon Substances 0.000 title claims abstract description 48
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title claims abstract description 31
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000010792 warming Methods 0.000 claims abstract description 15
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 12
- 238000009413 insulation Methods 0.000 claims abstract description 12
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims abstract description 11
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- -1 isocyanuric acid ester Chemical class 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 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 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003610 charcoal Substances 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 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
- 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
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 235000013877 carbamide Nutrition 0.000 description 6
- IVQVCMFLKPVKEC-UHFFFAOYSA-N 2-isocyanoethane-1,1,1-triol Chemical compound OC(O)(O)C[N+]#[C-] IVQVCMFLKPVKEC-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 229920000728 polyester Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of three [2 (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds and preparation method thereof, and the structure of the compound is shown below：OC in formula3H6Cl is OCH2CHClCH3Or OCH (CH2Cl)CH3.Preparation method is：Tris(2-hydroxy ethyl)isocyanurate is dissolved in organic solvent, 3 times moles of dimethyldichlorosilane is added, 5~9h is reacted at 50 DEG C~70 DEG C；Certain mole of propylene oxide is added dropwise under liquid level, after dripping off, is warming up to 50 DEG C~80 DEG C, 6~10h of insulation reaction；It is purified to handle to obtain three [2 (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters.Fire retardant efficiency of the present invention is high, good at charcoal effect, 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, nitrogen, three element synergistic fire retardant of chlorine, three [2- (dimethyl chloride propoxyl group silicon acyloxy) second
Base] isocyanurate compound and preparation method thereof, which is suitable as polyvinyl chloride, polyurethane, epoxy resin, insatiable hunger
With the flame-retardant plasticizer of resin etc..
Background technology
With the fast development of Macromolecular materials industry, obtained in daily life, manufacture and engineering construction more next
More it is widely applied.Fire occurs since high molecular material is easily ignited, seriously endangers the safety to people's life and property,
Therefore the research and extensive use of fire retardant are promoted.Wherein silicon systems hinder right agent with its excellent thermal stability, effectively prevent molten
Body drips and flame retarding and smoke suppressing properties, and as one of the new technology of current low-smoke low-toxicity fire proofing exploitation；Nitrogenated flame retardant is
The emphasis of expansible fire retardant exploitation, some products are applied；Halogenated flame retardant flame retarding efficiency height, production technology
Maturation is widely used in many fields.If silicon, nitrogen, halogen these three excellent ignition-proof elements are designed into same
In molecule, the effect of silicon, nitrogen, halogen cooperative flame retardant is just will produce, flame-retarded efficiency can be greatly improved.Thus develop new and effective, ring
Guarantor's type silicon, nitrogen, halogen synergistic fire retardant are a projects being of great significance.
The invention discloses be with tris(2-hydroxy ethyl)isocyanurate (THEIC), dimethyldichlorosilane, propylene oxide (PO)
Primary raw material prepares silicon, nitrogen, chlorine three element synergistic fire retardant three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanide urea
Ester compound.Fire retardant of the present invention, which combines the expandable flame retardant of nitrogen, silicon, can generate fine and close silicon layer of charcoal and halogen element
The fire-retardant mechanism of gas phase, flame-retarded efficiency is high, good at charcoal effect, has a wide range of application, there is good development prospect.
Invention content
It is an object of the present invention to a kind of silicon of proposition, nitrogen, [2- (the dimethyl chloride propoxyl group silicon of chlorine synergistic fire retardant three
Acyloxy) ethyl] isocyanurate compound, flame-retarded efficiency is high, can overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions：
Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds, which is characterized in that the chemical combination
The structure of object is shown below：
OC in formula3H6Cl is OCH2CHClCH3Or OCH (CH2Cl)CH3。
Another object of the present invention is to propose a kind of silicon, nitrogen, [2- (the dimethyl chloride propoxyl group silicon of chlorine synergistic fire retardant three
Acyloxy) ethyl] isocyanurate compound preparation method, simple for process, equipment investment is few, is easy to large-scale production,
And raw material is cheap and easy to get, of low cost, this method is：
Drying tube and hydrogen chloride absorption device are housed equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading
Reactor in, tris(2-hydroxy ethyl)isocyanurate is dissolved in organic solvent, addition rubs again relative to tris(2-hydroxy ethyl)isocyanurate 3
Your dimethyldichlorosilane, is warming up to 50 DEG C~70 DEG C, 5~9h of insulation reaction；After HCl is discharged, be cooled to 20 DEG C hereinafter,
By drying tube be changed to can great expansion sealing shroud, certain mole of propylene oxide is added dropwise under liquid level, it is anti-with rate of addition control
Temperature is answered to be not higher than 40 DEG C, 1~2h is warming up to 50 DEG C~80 DEG C after dripping off, 6~10h of insulation reaction；Air-distillation removes excessive
Propylene oxide, then be evaporated under reduced pressure and remove solvent and a small amount of low boilers, obtain three [2- (dimethyl chloride propoxyl group silicon acyloxy) second
Base] isocyanuric acid ester.
Certain mole of propylene oxide is tris(2-hydroxy ethyl)isocyanurate as described above: dimethyldichlorosilane: epoxy third
Alkane molar ratio is 1: 3: 3~1: 3: 4.
Organic solvent as described above is dioxane, tetrahydrofuran, acetonitrile or dichloroethanes, dosage volume ml
It is 5~15 times of tris(2-hydroxy ethyl)isocyanurate quality grams.
Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of the present invention are colourless or light yellow liquid
Body, yield are 91.4%~97.3%, and decomposition temperature is 293 ± 5 DEG C, index of refraction nD 25=1.4573, density (25 DEG C) is
1.28g/cm3.It is suitable as the flame-retardant plasticizer of the materials such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin.It should
The preparation process principle of three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters is shown below：
OC in formula3H6Cl is OCH2CHClCH3Or OCH (CH2Cl)CH3。
Compared with prior art, the beneficial effects of the present invention are：
1. three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of the invention are siliceous, nitrogen, three kinds of chlorine hinder
Element is fired, cooperative flame retardant efficiency is high, and there is nitrogen expansion heat insulation, element silicon to have into charcoal effect, can effectively prevent
Material melted by heating is dripped and the second-time burning of generation.
2. connecting on silicon atom in three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate structures of the invention
There are two methyl, there is C-Si keys, be organosilicon structures, organosilicon structures stability is good, water resistance is strong, and when burning is easier to give birth to
At fine and close charcoal-silicon layer, flame retardant effect is better.
3. three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid ester molecular weight of the invention are big, volatility
It is low, symmetry is good, physical and chemical performance is stablized, and belongs to more silicon, more nitrogen, more chlorine, polyester structure, ignition-proof element content is high, molecule
In atom vector construction each other, it is good with high molecular material compatibility, adapt to the high temperature process in engineering material.
4. three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of the invention belong to heterocycle highly branched chain silicon
Acid esters compound is transparent viscous liquid, has good plasticity.
5. it is ring that three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of the invention, which prepare one of raw material,
Ethylene Oxide, atom utilization 100%, is more advantageous to environmental protection, has good energy economy ＆ environment benefit.
6. three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of the invention are simple for process, preparation process
In do not introduce impurity without adding catalyst, equipment is simple, of low cost, is suitable for large-scale production, there is good application and development
Foreground.
Description of the drawings
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
1, the infrared spectrogram of three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters, refers to specification
Attached drawing Fig. 1；
Fig. 1 shows 2958.3cm-1And 2901.2cm-1For the stretching vibration absworption peak of C-H, 1714.2cm-1For carbonyl
Stretching vibration absworption peak, 1183.8cm-1For the stretching vibration absworption peak of C-O, 1004.9cm-1For the characteristic absorption peak of Si-O-C,
824.5cm-1For the characteristic absorption peak of C-Cl, 801.6cm-1For the characteristic absorption peak of Si-C.
2, the nuclear magnetic spectrogram of three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters, it is attached to refer to specification
Figure Fig. 2；
Fig. 2 shows that deuterochloroform makees solvent, and δ 1.19-1.29 are OCH (CH2Cl)CH3Upper methyl hydrogen peak, δ 1.43-1.50
For OCH2CHClCH3Upper methyl hydrogen peak, δ 3.33-3.50 are OCH (CH2Cl)CH3Upper methylene hydrogen peak, δ 4.07-4.16 are OCH
(CH2Cl)CH3Last time methyl hydrogen peak, δ 3.53-3.59 are OCH2CHClCH3Upper methylene hydrogen peak, δ 3.96-3.99 are
OCH2CHClCH3Last time methyl hydrogen peak, δ 3.99-4.07 are NCH2CH2The upper methylene hydrogen peaks being connected with oxygen O, δ 3.76-3.91
For NCH2CH2The upper methylene hydrogen peaks being connected with nitrogen O, δ 0.02-0.24 are SiCH3Upper methyl hydrogen peak, δ 7.28 are the deuterated chlorine of solvent
Paraabelian proton peak.
Specific embodiment
Technical scheme of the present invention is described further below in conjunction with specific implementation mode.
Embodiment 1 is inhaled equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading equipped with drying tube and hydrogen chloride
In the 250ml four-hole bottles of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 80ml dioxane are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 5h；
After HCl is discharged, be cooled to 20 DEG C hereinafter, by drying tube be changed to can great expansion sealing shroud, 5.81g is added dropwise under liquid level
(0.1mol) propylene oxide is not higher than 40 DEG C with rate of addition controlling reaction temperature, drips off rear 2h and be warming up to 80 DEG C, insulation reaction
6h；Vacuum distillation removes solvent and a small amount of low boilers, obtains three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanide ureas
Acid esters, yield 94.1%.
Embodiment 2 is inhaled equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading equipped with drying tube and hydrogen chloride
In the 250ml four-hole bottles of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 100ml tetrahydrofurans are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 50 DEG C, insulation reaction 9h；
After HCl is discharged, be cooled to 20 DEG C hereinafter, by drying tube be changed to can great expansion sealing shroud, 6.20g is added dropwise under liquid level
(0.1067mol) propylene oxide is not higher than 40 DEG C with rate of addition controlling reaction temperature, drips off rear 1h and is warming up to 50 DEG C, heat preservation
React 10h；Air-distillation removes excessive propylene oxide, then is evaporated under reduced pressure and removes solvent and a small amount of low boilers, obtains three [2-
(dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid ester, yield 91.4%.
Embodiment 3 is inhaled equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading equipped with drying tube and hydrogen chloride
In the 250ml four-hole bottles of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 120ml acetonitriles are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 65 DEG C, insulation reaction 7h；It waits for
After HCl is discharged, be cooled to 20 DEG C hereinafter, by drying tube be changed to can great expansion sealing shroud, 6.78g is added dropwise under liquid level
(0.1167mol) propylene oxide is not higher than 40 DEG C with rate of addition controlling reaction temperature, drips off rear 2h and is warming up to 70 DEG C, heat preservation
React 7h；Air-distillation removes excessive propylene oxide, then is evaporated under reduced pressure and removes solvent and a small amount of low boilers, obtains three [2- (two
Methyl chloropropanol oxygen radical silicon acyloxy) ethyl] isocyanuric acid ester, yield 96.1%.
Embodiment 4 is inhaled equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading equipped with drying tube and hydrogen chloride
In the 250ml four-hole bottles of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 100ml dichloroethanes are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 60 DEG C, insulation reaction 9h；
After HCl is discharged, be cooled to 20 DEG C hereinafter, by drying tube be changed to can great expansion sealing shroud, 6.97g is added dropwise under liquid level
(0.12mol) propylene oxide is not higher than 40 DEG C with rate of addition controlling reaction temperature, drips off rear 2h and is warming up to 70 DEG C, heat preservation is anti-
Answer 6h；Air-distillation removes excessive propylene oxide, then is evaporated under reduced pressure and removes solvent and a small amount of low boilers, obtains three [2- (diformazans
Base chloropropanol oxygen radical silicon acyloxy) ethyl] isocyanuric acid ester, yield 96.6%.
Embodiment 5 is inhaled equipped with blender, thermometer and condenser pipe, and condenser pipe is suitable for reading equipped with drying tube and hydrogen chloride
In the 250ml four-hole bottles of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 150ml acetonitriles are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 6h；It waits for
After HCl is discharged, be cooled to 20 DEG C hereinafter, by drying tube be changed to can great expansion sealing shroud, 7.74g is added dropwise under liquid level
(0.1333mol) propylene oxide is not higher than 40 DEG C with rate of addition controlling reaction temperature, drips off rear 1h and is warming up to 60 DEG C, heat preservation
React 8h；Air-distillation removes excessive propylene oxide, then is evaporated under reduced pressure and removes solvent and a small amount of low boilers, obtains three [2- (two
Methyl chloropropanol oxygen radical silicon acyloxy) ethyl] isocyanuric acid ester, yield 97.3%.
1 preparation example main technologic parameters of table
Inventor is also by three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters of above-mentioned preparation
Applied in polyvinyl chloride (PVC).Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》Sample
Limit oxygen index.Take product three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid ester, plasticizer neighbour benzene two
Formic acid dioctyl ester (DOP), synergistic flame retardant antimony oxide (Sb2O3) and polyvinyl chloride is in varing proportions after mixing, with squeezing
Go out machine extrusion, the batten of a diameter of 3mm is made, and be tested to its flame retardant property, lists part test result such as table 2
It is shown：
The flame retardant property data of table 2 three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid ester
According to table 2 as can be seen that when the additive amount of fire retardant of the present invention reaches 20%, limit oxygen index reaches
29%, it is provided with good flame retardant effect, and overcome the defect that pvc material burning is easily dripped completely.Therefore, this hair
Bright three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid ester has good flame retardant property and antidrip at charcoal
Fall performance.Meanwhile it has also been found that the compound can replace DOP, you can go easy in right amount with certain plasticity in experiment
DOP。
Claims (3)
1. a kind of silicon, nitrogen, chlorine three element synergistic fire retardant three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid
The preparation method of ester, which is characterized in that this method is：
Equipped with blender, thermometer and condenser pipe, and it is suitable for reading anti-equipped with drying tube and hydrogen chloride absorption device in condenser pipe
It answers in device, tris(2-hydroxy ethyl)isocyanurate is dissolved in organic solvent, be added relative to 3 times moles of tris(2-hydroxy ethyl)isocyanurate
Dimethyldichlorosilane is warming up to 50 DEG C~70 DEG C, 5~9h of insulation reaction；After HCl is discharged, 20 DEG C are cooled to hereinafter, will do
Dry pipe be changed to can great expansion sealing shroud, certain mole of propylene oxide is added dropwise under liquid level, reaction temperature is controlled with rate of addition
Degree is not higher than 40 DEG C, and 1~2h is warming up to 50 DEG C~80 DEG C after dripping off, 6~10h of insulation reaction；Air-distillation removes excessive ring
Ethylene Oxide, then be evaporated under reduced pressure and remove solvent and a small amount of low boilers, obtain three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyls]
The structure of isocyanuric acid ester, the compound is shown below：
OC in formula3H6Cl is OCH2CHClCH3Or OCH (CH2Cl)CH3。
2. the preparation side of three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters according to claim 1
Method, which is characterized in that the organic solvent is dioxane, tetrahydrofuran, acetonitrile or dichloroethanes, dosage volume milliliter
Number is 5~15 times of tris(2-hydroxy ethyl)isocyanurate quality grams.
3. the preparation side of three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanuric acid esters according to claim 1
Method, which is characterized in that certain mole of the propylene oxide is tris(2-hydroxy ethyl)isocyanurate: dimethyldichlorosilane: ring
Ethylene Oxide molar ratio is 1: 3: 3~1: 3: 4.
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