CN106478726B - Fire retardant diphenyl silicic acid disulfide group phospha trioxa-l-phosphabicyclo [2.2.2] octyl methyl compound and preparation method thereof - Google Patents
Fire retardant diphenyl silicic acid disulfide group phospha trioxa-l-phosphabicyclo [2.2.2] octyl methyl compound and preparation method thereof Download PDFInfo
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- CN106478726B CN106478726B CN201610850679.2A CN201610850679A CN106478726B CN 106478726 B CN106478726 B CN 106478726B CN 201610850679 A CN201610850679 A CN 201610850679A CN 106478726 B CN106478726 B CN 106478726B
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- trioxa
- phosphabicyclo
- sulfenyl
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- silicic acid
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- -1 octyl methyl compound Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000005194 fractionation Methods 0.000 claims abstract description 13
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- NQFNREAPSWQXCD-UHFFFAOYSA-N C1C2(COP(=S)(O1)OC2)PO Chemical compound C1C2(COP(=S)(O1)OC2)PO NQFNREAPSWQXCD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- IPUPHKDDBISGRH-UHFFFAOYSA-N dihydroxy(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](O)(O)OC1=CC=CC=C1 IPUPHKDDBISGRH-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004886 process control Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 6
- 238000004508 fractional distillation Methods 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 11
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 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 class 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 description 15
- 239000000463 material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of fire retardant diphenyl silicic acid disulfide group phospha trioxa-l-phosphabicyclo [2.2.2] octyl methyl compounds and preparation method thereof, and the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of silicon, phosphorus, the double -1- sulfenyl phosphas -2,6 of sulphur element synergistic fire retardant diphenyl silicic acid, 7-
Trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound and preparation method thereof, which is suitable as polyester, polyurethane, ring
The fire-retardant carbon forming agent of oxygen resin, unsaturated-resin etc..
Background technique
The extensive use of the high molecular materials such as China's expanding economy and plastic products has driven the rapid development of fire retardant.
Fire retardant has developed into plastic additive the second largest auxiliary agent for being only second to plasticizer, and using increasingly extensive, new varieties constantly increase
Add.Meanwhile the requirement to fire retardant comprehensive performance is higher and higher, and proposes matter in certain fields to applying for halogenated flame retardant
It doubts, therefore develops the hot spot that new and effective, less toxic halogen-free flame retardants has become current fire retardant research.Silicon is a kind of nontoxic
Element, silicon-series five-retardant can be by generating fine and close silicon layer of charcoal in solid phase, and starvation has anti-molten drop to act on；Phosphorous flame-retardant
Agent is also the emphasis of halogen-free flame retardants exploitation, and phosphorus flame retardant can be fire-retardant by the polyphosphoric acid condensed phase of generation or be caught in the gas phase
Living radical is caught to improve the flame retardant property of material；Sulphur ignition-proof element can change the decomposition course of material, fire-retardant in condensed phase.
Therefore, three kinds of silicon, phosphorus and sulphur excellent ignition-proof elements are embedded into molecular structure, develop silicon, phosphorus and a variety of fire-retardant members of sulphur
The excellent flame retardant of plain cooperative flame retardant is the project with application value.
The invention discloses with dimethoxydiphenylsilane or diphenyl dichlorosilane, 1- sulfenyl phospha -4- methylol -
2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane is that primary raw material prepares silicon, phosphorus, sulphur element synergistic fire retardant diphenyl silicic acid
Double -1- sulfenyl phosphas -2,6, the method for 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound.Fire retardant of the present invention has
Multiple fire retardant mechanism, three element cooperative flame retardants can generate excellent flame retardant effect.Fire retardant efficiency of the present invention is high, imitates at charcoal
Fruit is good, has a wide range of application, and has good development prospect.
Summary of the invention
It is an object of the present invention to propose the double -1- sulfenyls of a kind of silicon, phosphorus, sulphur cooperative flame retardant carbon forming agent diphenyl silicic acid
Phospha -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound, flame-retarded efficiency is high, can overcome in the prior art
It is insufficient.
For achieving the above object, present invention employs following technical solutions:
Double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound are special
Sign is that the structure of the compound is shown below:
Another object of the present invention is to propose the double -1- sulfenyl phosphorus of a kind of silicon, phosphorus, sulphur synergistic fire retardant diphenyl silicic acid
Miscellaneous -2, the preparation method of 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl -4- methyl compound, simple process, equipment investment is few,
It is easy to large-scale production, and raw material is cheap and easy to get, low in cost, this method are as follows:
In the reactor equipped with blender, thermometer and fractionating device, most air is caught up with nitrogen, at 25 DEG C of temperature,
Dimethoxydiphenylsilane is added and a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] are pungent
Alkane is warming up to 120 DEG C -160 DEG C, and solids gradually dissolves, and is finally in colourless transparent liquid, and fractionation reaction 5h-10h was fractionated
Process control tower top temperature is not higher than 65 DEG C, constantly fractionates out the methanol of generation, and the last 1h of fractionation keeps micro-vacuum in reactor
(- 0.02Mpa) so that the methanol of generation is completely segregated out, and breaks balance, makes to react thorough progress, separates theory
After the methanol of amount, 40 DEG C are cooled to, the methanol or ethyl alcohol stirring for adding product theory quality 1-2 times of volume ml of grams are washed
1h is washed, is filtered, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2]
Octyl -4- methyl esters.
This method may be used also are as follows:
In the reactor equipped with blender, thermometer and hydrogen chloride absorption device, most air is caught up with nitrogen, in temperature 25
At DEG C, a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and volume ml is added
Relative to 1- sulfenyl phospha -4- methylol -2,6,2~8 times of grams of 7- trioxa-l-phosphabicyclo [2.2.2] octane quality organic molten
Diphenyl dichlorosilane is slowly added dropwise in agent, 60 DEG C is not higher than with rate of addition control reaction temperature, 80 DEG C~120 after dripping off
5h~8h is reacted at DEG C, after hydrogen chloride discharges, reaction is completed, and is cooled to 25 DEG C, is filtered, with 1-2 times of grams of product theory quality
The methanol or ethanol washing of volume ml, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7-
Trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters.
A certain amount of 1- sulfenyl phospha -4- methylol -2,6 as described above, 7- trioxa-l-phosphabicyclo [2.2.2] octane is two
Phenyidimethoxysilane or diphenyl dichlorosilane: 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2]
The molar ratio of octane is 1: 2~1: 4.
Organic solvent as described above is acetonitrile, dioxane or diethylene glycol dimethyl ether.
Double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid of the invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters are
White solid powder, product yield are 90.3%~98.1%, and fusing point is 187 ± 2 DEG C, and decomposition temperature is 352 ± 5 DEG C.It is suitable
Share the fire-retardant carbon forming agent for making the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin.Double -1- the sulfenyls of the diphenyl silicic acid
The preparation process principle of phospha -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters is shown below:
Compared with prior art, the beneficial effects of the present invention are:
1. double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters contain
Three kinds of silicon, phosphorus, sulphur ignition-proof elements, cooperative flame retardant efficiency is high, and wherein element silicon can generate fine and close silicon layer of charcoal, can effectively prevent
Material melted by heating is dripped and the second-time burning of generation, and P elements can generate polyphosphoric acid film in burning, block combustible and sky
Gas, element sulphur can change the decomposition course of high molecular material, and condensed phase is fire-retardant.
2. double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters knot
Connecting on silicon atom in structure there are two phenyl, there is C-Si key, is organosilicon structures, organosilicon structures stability is good, water resistance is strong,
Fine and close charcoal-silicon layer is more easily generated when burning, flame retardant effect is more excellent.
3. double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters pair
Title property is good, physical and chemical performance is stablized, and decomposition temperature is high, and the phenyl ring contained has the polytropism of electronic structure, with macromolecule
Material compatibility is good, is conducive to the mechanical property for improving material, adapts to the high temperature process of engineering material.
4. double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters
Preparation process is simple, does not introduce impurity without adding catalyst, and equipment is simple, low in cost, is suitable for large-scale production, has very well
Application and development prospect.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the double -1- sulfenyl phosphas -2,6 of diphenyl silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters it is infrared
Spectrogram；Fig. 1 shows 991cm-1Place is the stretching vibration peak of P-O key, 2963cm-1、2906cm-1Place is methyl and methylene
The stretching vibration peak of C-H, 3031cm-1Place is the stretching vibration peak of C-H on phenyl ring, 698cm-1Place is the characteristic absorption peak of P=S,
1027cm-1Place is the stretching vibration peak of C-O key, 804cm-1Place is the stretching vibration peak of Si-C key, 1491cm-1、1521cm-1And
1684cm-1Place is the characteristic absorption peak of phenyl ring skeleton, 1107cm-1Place is the characteristic absorption peak of Si-O-C key.
Fig. 2 is the double -1- sulfenyl phosphas -2,6 of diphenyl silicic acid, the nuclear-magnetism of 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters
Spectrogram；Fig. 2 shows to make solvent with deuterated dimethyl sulfoxide, is hydrogen peak on phenyl ring at chemical shift δ 7.41-7.63；δ4.65-
It is C (CH at 4.712O hydrogen peak on the methylene being connected on) with oxygen；It is CCH at δ 3.59-3.682On the methylene that OSi is connected with O
Hydrogen peak, is water peak at δ 3.34, is the proton peak of solvent deuterated dimethyl sulfoxide exchange at δ 2.50.
Fig. 3 is the double -1- sulfenyl phosphas -2,6 of diphenyl silicic acid, the thermogravimetric of 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters
Figure；Fig. 3 shows to start weightlessness when being warming up to 330 DEG C of products；When temperature is increased to 350 DEG C or so, weight loss rate reaches maximum
Value, and DTA curve has an apparent exothermic peak, this may be the decomposition due to cage structure, and weight-loss ratio is about 51% at this time；
When temperature reaches 700 DEG C, weight-loss ratio levels off to stabilization substantially, still there is about 34% surplus charcoal rate at this time.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen
Air, at 25 DEG C of temperature, be added 21.56g (0.11mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo
[2.2.2] octane and 12.22g (0.05mol) dimethoxydiphenylsilane, are warming up to 140 DEG C, solids gradually dissolves, most
It is eventually in colourless transparent liquid, 7h is reacted in fractionation, and fractional distillation process controls tower top temperature and is not higher than 65 DEG C, constantly fractionates out the first of generation
The last 1h of alcohol, fractionation keeps micro-vacuum (- 0.02Mpa) in reactor, so that the methanol of generation is completely segregated out, and
Break balance, make to react thorough progress, after the methanol for separating theoretical amount, is cooled to 40 DEG C, adds 40mL absolute ethyl alcohol and stirring
Disperse 1h, filters, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
[2.2.2] octyl -4- methyl esters, yield 94.5%.
Embodiment 2 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen
Air, at 25 DEG C of temperature, be added 19.62g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo
[2.2.2] octane and 12.22g (0.05mol) dimethoxydiphenylsilane, are warming up to 160 DEG C, solids gradually dissolves, most
It is eventually in colourless transparent liquid, 10h is reacted in fractionation, and fractional distillation process controls tower top temperature and is not higher than 65 DEG C, constantly fractionates out generation
The last 1h of methanol, fractionation keeps micro-vacuum (- 0.02Mpa) in reactor, so that the methanol of generation is completely segregated out,
And break balance, make to react thorough progress, after the methanol for separating theoretical amount, is cooled to 40 DEG C, adds the stirring point of 30mL methanol
1h is dissipated, is filtered, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2]
Octyl -4- methyl esters, yield 90.3%.
Embodiment 3 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen
Air, at 25 DEG C of temperature, be added 39.23g (0.2mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo
[2.2.2] octane and 12.22g (0.05mol) dimethoxydiphenylsilane, are warming up to 120 DEG C, solids gradually dissolves, most
It is eventually in colourless transparent liquid, 5h is reacted in fractionation, and fractional distillation process controls tower top temperature and is not higher than 65 DEG C, constantly fractionates out the first of generation
The last 1h of alcohol, fractionation keeps micro-vacuum (- 0.02Mpa) in reactor, so that the methanol of generation is completely segregated out, and
Break balance, make to react thorough progress, after the methanol for separating theoretical amount, is cooled to 40 DEG C, adds 50mL absolute ethyl alcohol and stirring
Disperse 1h, filters, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
[2.2.2] octyl -4- methyl esters, yield 98.1%.
Embodiment 4 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen
Air, at 25 DEG C of temperature, be added 29.42g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo
[2.2.2] octane and 12.22g (0.05mol) dimethoxydiphenylsilane, are warming up to 130 DEG C, solids gradually dissolves, most
It is eventually in colourless transparent liquid, 8h is reacted in fractionation, and fractional distillation process controls tower top temperature and is not higher than 65 DEG C, constantly fractionates out the first of generation
The last 1h of alcohol, fractionation keeps micro-vacuum (- 0.02Mpa) in reactor, so that the methanol of generation is completely segregated out, and
Break balance, make to react thorough progress, after the methanol for separating theoretical amount, is cooled to 40 DEG C, adds 45mL ethyl alcohol and be dispersed with stirring
1h is filtered, dry, obtains the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, and 7- trioxa-l-phosphabicyclo [2.2.2] is pungent
Base -4- methyl esters, yield 95.8%.
Embodiment 5 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, is added 23.54g (0.12mol) 1- sulfenyl phospha -4- methylol -2,6, and 7- trioxa-l-phosphabicyclo [2.2.2] is pungent
12.67g (0.05mol) diphenyl dichlorosilane is slowly added dropwise in alkane and 80mL acetonitrile, not high with rate of addition control reaction temperature
In 60 DEG C, 8h is reacted at 80 DEG C after dripping off, after discharging hydrogen chloride, reaction is completed, is cooled to 25 DEG C, filter, filter cake is used again
40mL ethanol washing filters, dry, obtains the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
[2.2.2] octyl -4- methyl esters, yield 95.4%.
Embodiment 6 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, is added 19.62g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6, and 7- trioxa-l-phosphabicyclo [2.2.2] is pungent
12.67g (0.05mol) diphenyl dichlorosilane is slowly added dropwise in alkane and 40mL dioxane, controls reaction temperature with rate of addition
Not higher than 60 DEG C, 6h is reacted at 100 DEG C after dripping off, after discharging hydrogen chloride, reaction is completed, is cooled to 25 DEG C, filter, filter cake
It is washed, is filtered with 30mL methanol again, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa
Bicyclic [2.2.2] octyl -4- methyl esters, yield 92.5%.
Embodiment 7 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, is added 35.30g (0.18mol) 1- sulfenyl phospha -4- methylol -2,6, and 7- trioxa-l-phosphabicyclo [2.2.2] is pungent
Alkane and 100mL diethylene glycol dimethyl ether are slowly added dropwise 12.67g (0.05mol) diphenyl dichlorosilane, are controlled with rate of addition
Reaction temperature is not higher than 60 DEG C, reacts 5h at 120 DEG C after dripping off, and after discharging hydrogen chloride, completes reaction, is cooled to 25 DEG C,
It filtering, filter cake uses 60mL ethanol washing again, filters, and it is dry, double -1- sulfenyl phospha -2 of white solid powder diphenyl silicic acid are obtained,
6,7- trioxa-l-phosphabicyclos [2.2.2] octyl -4- methyl esters, yield 97.2%.
Embodiment 8 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, is added 29.43g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6, and 7- trioxa-l-phosphabicyclo [2.2.2] is pungent
12.67g (0.05mol) diphenyl dichlorosilane is slowly added dropwise in alkane and 60mL diethylene glycol dimethyl ether, anti-with rate of addition control
It answers temperature not higher than 60 DEG C, reacts 6h at 120 DEG C after dripping off, after discharging hydrogen chloride, complete reaction, be cooled to 25 DEG C, take out
Filter, filter cake are washed with 40mL methanol again, are filtered, dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid,
7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters, yield 96.1%.
Inventor is by the double -1- sulfenyl phosphas -2,6 of the diphenyl silicic acid of above-mentioned preparation, 7- trioxa-l-phosphabicyclo [2.2.2]
Octyl -4- methyl esters (DPSSPE) individually or with melamine polyphosphate (MPP) carries out composite usage in fire-retardant poly- terephthaldehyde
In sour butanediol ester (PBT).Reference: the pole of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " sample
Limited oxygen index (LOI).DPSSPE is taken to be uniformly mixed or take DPSSPE, MPP and PBT to mix in varing proportions in varing proportions with PBT
It closes uniformly, is squeezed out with extruder, diameter is made and is the batten of 3mm, and its fire-retardant melt-dropping property is tested, lists portion
Separating tests result is as shown in table 1~2:
The flame retardant property data of the independent flame-retardant PBT of 1 DPSSPE of table
| Sequence | Additive amount/% | LOI/% | Molten drop situation | At charcoal situation |
| 1 | 0 | 21 | Drippage | Not at charcoal |
| 2 | 10 | 24 | Slow drippage | At charcoal |
| 3 | 20 | 28 | It does not drip | At charcoal |
| 4 | 30 | 30 | It does not drip | At charcoal |
Table 1 is as can be seen that work as the double -1- sulfenyl phosphas -2,6 of diphenyl silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4-
When additive amount of the methyl esters (DPSSPE) individually in PBT reaches 20%, flame-retardant PBT can not be dripped in burning at charcoal, and PBT
LOI 27% or more, reach fire retardant rank.This illustrates the double -1- sulfenyl phosphas -2,6 of diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
[2.2.2] octyl -4- methyl esters has PBT material fire-retardant at charcoal effect well.
The flame retardant property data of 2 DPSSPE of table and MPP compositional flame-retardant PBT
Table 2 is as can be seen that be added total amount in PBT when DPSSPE is compounded with MPP as 20%, DPSSPE and MPP matter
When amount is than being 2: 3, LOI 28% has slight molten drop phenomenon；When mass ratio is 3: 2, the LOI of flame-retardant PBT reaches 34%,
And melting can be effectively prevent to drip rapidly at charcoal.It can be seen that double -1- sulfenyl the phosphas -2,6 of diphenyl silicic acid, 7- trioxa are double
Ring [2.2.2] octyl -4- methyl esters and MPP composite usage show good synergetic in PBT.
Claims (2)
1. double -1- sulfenyl the phosphas -2,6 of a kind of silicon, phosphorus, sulphur element synergistic fire retardant diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
The preparation method of [2.2.2] octyl -4- methyl esters, which is characterized in that this method are as follows:
In the reactor equipped with blender, thermometer and fractionating device, most air is caught up with nitrogen, at 25 DEG C of temperature, is added
Dimethoxydiphenylsilane and a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane,
120 DEG C~160 DEG C are warming up to, solids gradually dissolves, and is finally in colourless transparent liquid, fractionation reaction 5h~10h, fractional distillation process
Control tower top temperature and be not higher than 65 DEG C, constantly fractionate out the methanol of generation, the last 1h of fractionation keep micro-vacuum in reactor (-
0.02Mpa), so that the methanol of generation is completely segregated out, and break balance, make to react thorough progress, separate theoretical amount
Methanol after, be cooled to 40 DEG C or so, add product theory quality 1-2 times of volume ml of grams methanol or ethyl alcohol stirring
1h is washed, is filtered, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder diphenyl silicic acid, 7- trioxa-l-phosphabicyclo
[2.2.2] octyl -4- methyl esters, the structure of the compound are shown below:
2. double -1- sulfenyl the phosphas-of a kind of silicon according to claim 1, phosphorus, sulphur element synergistic fire retardant diphenyl silicic acid
The preparation method of 2,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl -4- methyl esters, which is characterized in that a certain amount of 1- as described above
Sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane is dimethoxydiphenylsilane: 1- sulfenyl phospha -
4- methylol -2,6, the molar ratio of 7- trioxa-l-phosphabicyclo [2.2.2] octane are 1: 2~1: 2.2.
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