CN105384776B - Dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds and preparation method thereof - Google Patents
Dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds and preparation method thereof Download PDFInfo
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- CN105384776B CN105384776B CN201510707358.2A CN201510707358A CN105384776B CN 105384776 B CN105384776 B CN 105384776B CN 201510707358 A CN201510707358 A CN 201510707358A CN 105384776 B CN105384776 B CN 105384776B
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- silicic acid
- methyl
- ester
- phosphine heterocyclic
- heterocyclic methyl
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 35
- BMYXFDYLULLPCA-UHFFFAOYSA-N dodecoxy(trihydroxy)silane Chemical compound CCCCCCCCCCCCO[Si](O)(O)O BMYXFDYLULLPCA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- -1 ester compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000002195 synergetic effect Effects 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 150000004702 methyl esters Chemical class 0.000 claims 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000003610 charcoal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 5
- 239000004677 Nylon Substances 0.000 abstract description 3
- 239000007977 PBT buffer Substances 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 229920001778 nylon Polymers 0.000 abstract description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 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 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 241000272517 Anseriformes Species 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- 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
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of (phosphine heterocyclic methyl) ester compounds of phosphorus silicon synergistic fire retardant dodecyl silicic acid three and preparation method thereof, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of fire retardant dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds and preparation method thereof, tool
Body is related to a kind of fire retardant dodecyl three (1- oxygen -1- methyl -4- ethyl -1- phospha -2,6- dioxa-cyclohexyls -<4>-
Methoxyl group) silane compound and preparation method thereof, the compound contains the dual ignition-proof element of phosphorus, silicon, and the collaboration of phosphorus silicon has higher
Flame-retarded efficiency, is suitable as the fire retardant of the materials such as polyester PBT, PET, polyurethane, nylon, polypropylene.
Background technology
With the progress of industrial expansion and technology, high polymer material kind is more and more, using also more and more extensive, gives
Because its inflammability also brings great disaster hidden-trouble while people offer convenience, this promotes the fast of fire retardant industry
Speed development.In recent years, with the continuous enhancing of safety and environmental protection consciousness of people, limit got over using the cry of halogenated flame retardant in the world
Come higher, therefore, the agent of exploitation novel halogen-free flame-retardant turns into the focus that current fire retardant develops.Phosphorus flame retardant is with its Halogen, poison
Relatively low, smoke amount is few, flame retarding efficiency is high for property, advantages of environment protection receives the concern of people, a series of based on organophosphor
The novel halogen-free flame-retardant agent of composition is wanted to be widely deployed utilization；Silicone flame retardant with its unique flame retardant effect also by
Gradually it is subject to the people's attention.Research shows, if phosphorus, two kinds of ignition-proof elements of silicon are designed in same molecular structure, Ji Nengshi
The compounding of existing intramolecular ignition-proof element, can produce more preferable synergistic function, it will obtain performance more excellent fire retardant.
The invention discloses a kind of fire retardant dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds and preparation method thereof.
Contain phosphorus, two kinds of ignition-proof elements of silicon in the molecular structure of compounds, phosphorus, silicon cooperative flame retardant efficiency are high；It possesses phosphorus flame retardant
With the advantage of silicon-series five-retardant, show again preferably into charcoal and friendly processing characteristics, and stability is good, it is applied widely
It is general, it is a kind of efficient, suppression cigarette, nontoxic fire retardant, with vast potential for future development.
The content of the invention
An object of the present invention is to propose a kind of phosphorus, silicon synergistic fire retardant dodecyl silicic acid three (phosphine heterocyclic methyl)
Ester compounds.Its physical and chemical performance is stable, and decomposition temperature is high, has preferable compatibility with high polymer material, and has into charcoal and prevents
The effect of drippage, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
A kind of dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds, it is characterised in that the structure of the compound is as follows
Shown in formula：
Another object of the present invention is to propose a kind of system of dodecyl silicic acid three as described above (phosphine heterocyclic methyl) ester
Preparation Method, its technique is simple, is adapted to large-scale production, and raw material is cheap and easy to get, with good development prospect, this method
For：
Under nitrogen protection, control dodecyltrimethoxysilane and 4- ethyls -2,6,7- trioxa -1- phosphabicyclos
[2.2.2] octane is (referred to as：Young laying ducks in cage) mol ratio be 1: 3-1: 3.3, add catalyst and organic solvent, be warming up to
140-160 DEG C, insulation reaction 16-22h is cooled to 50 DEG C, vacuum distillation removes organic solvent, is cooled to 50 DEG C, purified place
Reason, obtains product dodecyl silicic acid three (phosphine heterocyclic methyl) ester.
This method is：
Under nitrogen protection, control dodecyltrimethoxysilane and 4- ethyls -2,6,7- trioxa -1- phosphabicyclos
[2.2.2] octane is (referred to as：Young laying ducks in cage) mol ratio be 1: 3-1: 3.3, add catalyst, be heated to backflow, start
Reaction, gradually rises with the carry out reflux temperature of reaction, at 150-190 DEG C, backflow and insulation reaction 14-18h, is cooled to 50
DEG C, purified processing obtains product dodecyl silicic acid three (phosphine heterocyclic methyl) ester.
Organic solvent as described above is diethylene glycol dimethyl ether, methyl phenyl ethers anisole or dimethylformamide (DMF), and its consumption is
The volume milliliter number of organic solvent is 2-5 times of dodecyltrimethoxysilane quality grams.
Catalyst as described above is dimethyl suflfate, methyl tosylate or ethyl p-toluenesulfonate, and its consumption is
The 4%-7% of dodecyltrimethoxysilane quality.
Purification treating method as described above is to add the petroleum ether with product Theoretical Mass grams same volume milliliter number,
Stirring makes solid be scattered in petroleum ether, suction filtration, drying.
Dodecyl silicic acid three (phosphine heterocyclic methyl) ester of the present invention is white solid, and its yield is 83.8%-88.6%, is melted
Point：126 ± 2 DEG C, decomposition temperature：312 ± 5 DEG C, it is suitable as the materials such as polyester PBT, PET, polyurethane, nylon, polypropylene
Fire retardant.
The synthesis technique principle of dodecyl silicic acid three (phosphine heterocyclic methyl) ester is shown below：
Compared with prior art, innovation of the invention is：
1. dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds of the present invention contain phosphorus, two kinds of ignition-proof elements of silicon, high temperature
Under, P elements are converted into phosphoric acid or polyphosphoric acid can be catalyzed the formation for facilitating charcoal, and the polyphosphoric acid film of formation has heat-insulated anoxybiotic to act on；Silicon
The silicon layer of charcoal of densification is formed with carbon, the generation that can effectively prevent melting from dripping.Phosphorus, silicon can be sent out from different mechanism cooperative flame retardants
Wave higher flame-retarded efficiency.
2. C-P keys, C-Si keys are contained in dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds molecular structure of the present invention
And three six-membered ring structures, these design features cause the compound physical stable chemical performance, and decomposition temperature is high, adapts to
In the high temperature process of engineering plastics；Containing chain alkyl so that it has good compatibility, and good dispersion with material, to material
The Effect on Mechanical Properties of material is smaller, while also assigning the preferable plasticity of product.
3. the preparation of dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds of the present invention be by bimolecular rearrangement reaction,
The organic phosphine compound that inorganic phosphorous compound is changed into, its heat endurance and fire resistance are obtained for very big raising.
4. dodecyl silicic acid three (phosphine heterocyclic methyl) ester compounds preparation method of the present invention, contracts without any small molecule
Go, atom utilization 100%, three-waste free discharge is friendly process.
Brief description of the drawings
In order to which the structure and performance spy that further illustrate product provide drawings described below.
Fig. 1 is the infrared spectrogram of dodecyl silicic acid three (phosphine heterocyclic methyl) ester；Fig. 1 shows：3021cm-1With
2923cm-1(stretching vibration of c h bond)；1436cm-1(flexural vibrations of c h bond)；1250cm-1(stretching vibration of P=O keys)；
1172cm-1(stretching vibration of Si-O-C keys)；998cm-1(flexural vibrations of Si-O-C keys)；941cm-1(P-O-C keys it is flexible
Vibration)；794cm-1(stretching vibration of Si-C keys).
Fig. 2 is the nuclear magnetic spectrum figure of dodecyl silicic acid three (phosphine heterocyclic methyl) ester；Fig. 2 shows：Deuterochloroform is solvent,
δ 0.45-0.53 are Si-CH2CH3The upper methylene hydrogen peak being connected with silicon；δ 0.71-0.75 are C-CH2CH3The first of upper and carbon phase even
Ji Qingfeng；δ 0.77-0.84 are Si- (CH2)11CH3The methyl hydrogen peak of upper and carbon phase even；δ 1.10-1.19 are C-CH2CH3Upper and carbon
Connected methylene hydrogen peak；δ 1.25-1.36 are Si- (CH2)11CH3The methylene hydrogen peak of upper and carbon phase even；δ 1.52-1.76 are O
=P-CH3The upper methyl hydrogen peak being connected with phosphorus oxygen；δ 4.03-4.27 are Si-OCH2The upper methylene hydrogen peaks being connected with silica of C；δ
4.33-4.52 is (CH2O)2- P=O (- CH3) the methylene epoxide hydrogen peak that is connected with oxygen on phosphine ring；δ 7.26 is solvent carbon deuterium chloride
The proton peak of exchange.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 uses nitrogen displacement in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of high performance reflux condenser
Air in bottle falling, adds 52.68g (0.325mol) young laying ducks in cage, 100ml diethylene glycol dimethyl ethers, 29.06g (0.10mol)
Dodecyltrimethoxysilane and 1.16g dimethyl suflfates, are warming up to 160 DEG C, insulation reaction 16h, vacuum distillation removes two
Glycol dimethyl ether (recovery is used), is cooled to 50 DEG C, adds 75ml petroleum ether, and stirring makes solid be scattered in petroleum ether
In, suction filtration, drying obtain white solid dodecyl silicic acid three (phosphine heterocyclic methyl) ester, product yield 88.6%, its decomposition temperature
Degree：312±5℃.
Embodiment 2 uses nitrogen displacement in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of high performance reflux condenser
Air in bottle falling, adds 53.49g (0.33mol) young laying ducks in cage, 29.06g (0.10mol) dodecyltrimethoxysilane
With 1.55g dimethyl suflfates, 155 DEG C are warming up to, is flowed back and insulation reaction 18h, is cooled to 50 DEG C, adds 75ml oil
Ether, stirring makes solid be scattered in petroleum ether, and suction filtration, drying obtain white solid dodecyl silicic acid three (phosphine heterocyclic methyl) ester,
Product yield 87.2%, its decomposition temperature：312±5℃.
Embodiment 3 uses nitrogen displacement in equipped with agitator, thermometer, the 200ml four-hole boiling flasks of high performance reflux condenser
Air in bottle falling, adds 51.87g (0.32mol) young laying ducks in cage, 60ml methyl phenyl ethers anisoles, 29.06g (0.10mol) dodecyl three
Methoxy silane and 1.85g methyl tosylates, are warming up to 150 DEG C, insulation reaction 20h, vacuum distillation removes methyl phenyl ethers anisole and (returned
Receipts are used), 50 DEG C are cooled to, 75ml petroleum ether is added, stirring makes solid be scattered in petroleum ether, and suction filtration, drying obtain white
Color solid dodecyl silicic acid three (phosphine heterocyclic methyl) ester, product yield 86.0%, its decomposition temperature：312±5℃.
Embodiment 4 uses nitrogen displacement in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of high performance reflux condenser
Air in bottle falling, adds 48.63g (0.30mol) young laying ducks in cage, 90mlDMF, 29.06g (0.10mol) dodecyl front three
TMOS and 2.0g ethyl p-toluenesulfonates, are warming up to 140 DEG C, insulation reaction 22h, and vacuum distillation removes DMF, and (recovery makes
With), 50 DEG C are cooled to, 75ml petroleum ether is added, stirring makes solid be scattered in petroleum ether, and suction filtration, drying obtain white solid
Body dodecyl silicic acid three (phosphine heterocyclic methyl) ester, product yield 83.8%, its decomposition temperature：312±5℃.
Embodiment 5 uses nitrogen displacement in equipped with agitator, thermometer, the 200ml four-hole boiling flasks of high performance reflux condenser
Air in bottle falling, adds 50.25g (0.31mol) young laying ducks in cage, 29.06g (0.10mol) dodecyltrimethoxysilane
With 1.9g methyl tosylates, 155 DEG C of backflows are heated to, starts reaction, 190 is gradually raised to the trip temperature that enters of reaction
DEG C, backflow and insulation reaction 14h are cooled to 50 DEG C, add 75ml petroleum ether, and stirring makes solid be scattered in petroleum ether,
Suction filtration, drying, obtain white solid dodecyl silicic acid three (phosphine heterocyclic methyl) ester, product yield 85.4%, its decomposition temperature：
312±5℃。
The preparation example main technologic parameters of table 1
Dodecyl silicic acid three (phosphine heterocyclic methyl) ester of above-mentioned synthesis is also applied in polyester PBT by inventor.
Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limited oxygen index of test sample product.Take product phosphorus
After (phosphine heterocyclic methyl) ester of silicon synergistic fire retardant dodecyl silicic acid three and polyester PBT are well mixed with different weight percentage,
Extruded with extruder at 230 DEG C, a diameter of 3mm batten is made, and its fire resistance is tested, result of the test is such as
Shown in table 2：
Table 2 dodecyl silicic acid three (phosphine heterocyclic methyl) ester is applied to the fire resistance data in PBT
As can be seen from Table 2 when (phosphine heterocyclic methyl) the ester addition of fire retardant dodecyl silicic acid three of the present invention is up to 25%
When, the limited oxygen index of flame-retardant PBT reaches 30%, is provided with good flame retardant effect, and to its it is heated or when burning it is meltable
The defect for melting drippage makes moderate progress.Therefore, fire retardant of the present invention has good fire resistance and into charcoal anti-drip energy, before
Scape is very wide.
Claims (4)
1. a kind of (phosphine heterocyclic methyl) ester compounds of phosphorus silicon synergistic fire retardant dodecyl silicic acid three, it is characterised in that the chemical combination
The structure of thing is shown below：
2. a kind of preparation method of (phosphine heterocyclic methyl) ester of phosphorus silicon synergistic fire retardant dodecyl silicic acid three, it is characterised in that should
Method is：
Under nitrogen protection, control dodecyltrimethoxysilane and 4- ethyls -2,6,7- trioxa -1- phosphabicyclos
The mol ratio of [2.2.2] octane is 1: 3-1: 3.3, adds dodecyltrimethoxysilane quality 4%-7% sulfuric acid two
Methyl esters, methyl tosylate or ethyl p-toluenesulfonate catalyst and organic solvent, are warming up to 140-160 DEG C, insulation reaction
16-22h, vacuum distillation removes organic solvent, is cooled to 50 DEG C, adds and product Theoretical Mass grams equal volume milliliter number
Petroleum ether, stirring makes solid be scattered in petroleum ether, and suction filtration, drying obtain product dodecyl silicic acid three (phosphine heterocyclic methyl) ester.
3. a kind of preparation method of (phosphine heterocyclic methyl) ester of phosphorus silicon synergistic fire retardant dodecyl silicic acid three, it is characterised in that should
Method is：
Under nitrogen protection, control dodecyltrimethoxysilane and 4- ethyls -2,6,7- trioxa -1- phosphabicyclos
The mol ratio of [2.2.2] octane is 1: 3-1: 3.3, adds dodecyltrimethoxysilane quality 4%-7% sulfuric acid two
Methyl esters, methyl tosylate or ethyl p-toluenesulfonate catalyst, are heated to backflow, start reaction, with the progress of reaction
Reflux temperature gradually rises, at 150-190 DEG C, backflow and insulation reaction 14-18h, is cooled to 50 DEG C, adds and the theoretical matter of product
The petroleum ether of grams equal volume milliliter number is measured, stirring makes solid be scattered in petroleum ether, and suction filtration, drying obtain product dodecane
Base silicic acid three (phosphine heterocyclic methyl) ester.
4. the preparation method of dodecyl silicic acid three (phosphine heterocyclic methyl) ester as claimed in claim 2, it is characterised in that：Described
Organic solvent is diethylene glycol dimethyl ether, methyl phenyl ethers anisole or dimethylformamide, and its consumption is that the volume milliliter number of organic solvent is
2-5 times of dodecyltrimethoxysilane quality grams.
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