CN108929341A - Four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent and preparation method thereof - Google Patents
Four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent and preparation method thereof Download PDFInfo
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- CN108929341A CN108929341A CN201810783081.5A CN201810783081A CN108929341A CN 108929341 A CN108929341 A CN 108929341A CN 201810783081 A CN201810783081 A CN 201810783081A CN 108929341 A CN108929341 A CN 108929341A
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- oxygroup
- benzoquinone
- forming agent
- carbon forming
- retardant carbon
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- 229940005561 1,4-benzoquinone Drugs 0.000 title claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- -1 oxygroup 1,4-benzoquinone compound Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims abstract description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 238000010792 warming Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003086 colorant Substances 0.000 abstract description 5
- 239000004677 Nylon Substances 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920001778 nylon Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 208000012641 Pigmentation disease Diseases 0.000 abstract 1
- 230000019612 pigmentation Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 12
- 239000003610 charcoal Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000012757 flame retardant agent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PBSSFJDGZRCHIX-UHFFFAOYSA-N BrC1=C(C(=C(OC=2C(C=CC(C2)=O)=O)C=C1)Br)Br Chemical compound BrC1=C(C(=C(OC=2C(C=CC(C2)=O)=O)C=C1)Br)Br PBSSFJDGZRCHIX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of four silicon cage oxygroup 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof, and the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of four silicon cage oxygroup 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof, specifically relate to
And a kind of four -1- methyl-1 of coloured flame-retardant carbon forming agent fire retardant-sila -2,6,7- trioxa-l-phosphabicyclo [2,2,2] octyl -<4>-
Methoxyl-p-benzoquinone compound and preparation method thereof.The compound be suitable as nylon, polyester, polyurethane, rubber, polyolefin,
The fire-retardant carbon forming agent agent of the materials such as unsaturated-resin and colorant.
Background technique
The progress of science and technology makes high-molecular organic material obtain universal application in people's production, life, gives people
While bring convenience, because its inflammable characteristic also makes people be faced with serious fire threat, thus fire-retardant product is ground
Hair is grown rapidly, and market demand constantly increases.And with increasingly strict, the fire safety mark of the fire-retardant legislation in the whole world
The successive promulgation of quasi- and relevant industries instruction, it is more and more fierce to the cry of flame-retardancy requirements, at present especially to new and effective, less toxic
The research and development of environment friendly flame retardant are increasingly urgent to.Since silicone flame retardant all has oil resistant, low toxicity, good at charcoal, no
The advantages that reducing the physical and chemical performance of material, the hot spot that fire-retardant research field is concerned is become.
The invention discloses one kind to be prepared with pentaerythritol methylsilicate sodium alkoxide as primary raw material using chloranil
Color blocking fires the preparation method of four silicon cage oxygroup 1,4-benzoquinone compound of carbon forming agent, and product is fire-retardant, good at charcoal effect, can give material
The color for increasing purple brown, can be used as pigment application, and when high-molecular organic material flame retardant treatment is not required to separately add pigment, eliminates and adds
The process that pigment is added during work, not only saves cost, but also reduce the additive amount of auxiliary agent, reduces the addition evil due to auxiliary agent
The deficiency for changing the mechanical property of materials or processing performance, be it is a kind of have it is fire-retardant, helped at charcoal and the multi-functional organic polymer of coloring
Agent, purposes is relatively broad, and preparation raw material used is easy to get, and simple process is easy to industrialized production, there is good application and development
Prospect.
Summary of the invention
It is an object of the present invention to proposing a kind of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent, it is
A kind of highly effective flame-retardant carbon forming agent, and be excellent organic pigment colorant.Its fire-retardant carbon-forming performance is excellent, and coloring is good, decomposes
Temperature is up to 400 DEG C, and physical and chemical performance is stablized, and adapts to the high temperature process of material, has a wide range of application, can overcome the prior art
In deficiency.
For achieving the above object, present invention employs following technical solutions:
A kind of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent, which is characterized in that the structure of the compound is such as
Shown in following formula:
Another object of the present invention is to propose a kind of system of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent
Preparation Method, raw material is cheap and easy to get, and equipment investment is few, low in cost, and simple process is easy to large-scale production, this method are as follows:
In the reactor that blender, thermometer, high performance reflux condenser are housed, suitable organic solvent, tetrachloro is added
1,4-benzoquinone adds the pentaerythritol methylsilicate sodium alkoxide relative to 4~5 times moles of chloranil, it is warming up to 100~
6~13h of insulation reaction at 160 DEG C is filtered, and removes sodium chloride, and filtrate crystallisation by cooling filters, and filter cake drying obtains purple brown powder
Last four silicon cage oxygroup 1,4-benzoquinone of coloured flame-retardant carbon forming agent,
Suitable organic solvent as described above is dioxane, toluene, dimethylbenzene, ethylene glycol diethyl ether, diethylene glycol
Dimethyl ether, methyl phenyl ethers anisole or dimethyl sulfoxide, dosage volume ml are 6 times -12 times of product Theoretical Mass grams.
(the dimethyl-silicon acid glyceride oxygroup) 1,4-benzoquinone of coloured flame-retardant carbon forming agent four of the invention is red-brown powder, yield
For 85.3%-92.8%, decomposition temperature: 390 ± 5 DEG C.It is suitable as nylon, polyester, polyurethane, rubber, polyolefin, insatiable hunger
With the fire-retardant carbon forming agent or colorant of the materials such as resin.
The composition principle of four (tribromophenoxy) 1,4-benzoquinone is shown below:
Compared with prior art, the invention has the beneficial effects that:
(1) since the structure of four silicon cage oxygroup 1,4-benzoquinone of the invention has preferable symmetric characteristics, physical chemistry
It can stablize, decomposition temperature is high, adapts to the high temperature process of material.
(2) four silicon cage oxygroup 1,4-benzoquinone intramoleculars of the invention contain multiple silicon atoms, multiple quaternary carbon atoms tool in structure
There is specific charing source, and the benzoquinones replaced also provides sufficient charcoal source structure point, so that four (dimethyl-silicon acid glycerols
Ester oxygroup) 1,4-benzoquinone has and preferably acts at charcoal and anti-drip.
(3) since four silicon cage oxygroup 1,4-benzoquinone of the present invention are purple browns, it is coloured flame-retardant carbon forming agent, has fire retardation to have again
Coloring effect.Namely pigment and fire retardant carrier each other, a kind of auxiliary agent is added and obtains multiple functions, eliminates the mistake that pigment is added
Journey and cost decrease the additional amount of filler in the material, can improve the physicochemical properties such as the transparency of material.
(4) preparation method of the present invention is simple, and raw material is cheap and easy to get, and equipment investment is few, is easy to large-scale production.
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 infrared spectrogram of four or four silicon cage oxygroup 1,4-benzoquinone；Fig. 1 shows 2962.8cm-1Place is methyl c h bond
Stretching vibration peak, 2884.8cm-1For the stretching vibration peak of methylene c h bond, 1681.6cm-1For the stretching vibration peak of C=O key；
1610.1cm-1For the stretching vibration peak of C=C key；1106.1cm-1Place and 1040.3cm-1Place is the stretching vibration peak of C-O key；
1017.3cm-1Place is the stretching vibration peak of Si-O key；779cm-1For the stretching vibration peak of C-Si key.
Fig. 2 is the nuclear magnetic spectrum figure of four silicon cage oxygroup 1,4-benzoquinone；Fig. 2 shows solvent for deuterated DMSO, at δ 0.10-0.15
By with Si hydrogen peak on company's methyl；It is and the hydrogen peak on the methylene that Si-O key is connected in cage at δ 3.55-3.65；δ3.80-
It is the hydrogen peak on the outer methylene being connected with C-O key of cage at 3.95；It is solvent deuterated DMSO hydrogen peak at δ 2.50.
Fig. 3 is the thermogravimetric map of four silicon cage oxygroup 1,4-benzoquinone；Fig. 3, which shows to have at 280 DEG C, significantly to be dissolved a little, so that producing
It can disperse with material molten in product high temperature process；When close to 400 DEG C, product starts slow weightlessness occur；Temperature is 405 DEG C
When, weight-loss ratio 10%；When temperature is 440 DEG C, weight-loss ratio is just 50%, when temperature reaches 800 DEG C, still there is 16% product
It is undecomposed, illustrate that product has preferable thermal stability.
Specific embodiment
Technical solution of the present invention is described further below in conjunction with specific embodiment.
60ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 1
Dioxane solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 7.92g
(0.04mol) is warming up to 100 DEG C of insulation reaction 13h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 84.4%, temperature of initial decomposition: 400 ± 5
℃。
70ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 2
Toluene solvant is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 8.32g
(0.042mol) is warming up to 110 DEG C of insulation reaction 512h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, and filter cake dries
It is dry, obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 87.5%, temperature of initial decomposition: 400
±5℃。
70ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 3
Toluene solvant is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 8.71g
(0.044mol) is warming up to 110 DEG C of insulation reaction 10h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 89.4%, temperature of initial decomposition: 400 ± 5
℃。
70ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 4
Ethylene glycol diethyl ether solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide
8.71g (0.044mo1) is warming up to 120 DEG C of insulation reaction 10h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake
Drying, obtains four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 90.2%, temperature of initial decomposition:
400±5℃。
80ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 5
Xylene solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 9.11g
(0.046mol) is warming up to 120 DEG C of insulation reaction 10h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 91.2%, temperature of initial decomposition: 400 ± 5
℃。
80ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 6
Toluene solvant is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 9.5g
(0.048mol) is warming up to 130 DEG C of insulation reaction 11h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 91.7%, temperature of initial decomposition: 400 ± 5
℃。
80ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 7
Xylene solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 9.90g
(0.05mol) is warming up to 140 DEG C of insulation reaction 11h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 91.2%, temperature of initial decomposition: 400 ± 5
℃。
70ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 8
Diethylene glycol dimethyl ether solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide
Salt 8.71 (0.044mol) is warming up to 160 DEG C of insulation reaction 10h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter
Cake drying, obtains four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 91.1%, initial decomposition temperature
Degree: 400 ± 5 DEG C.
60ml is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed in embodiment 9
Methyl phenyl ethers anisole solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide 8.71g
(0.044mol) is warming up to 150 DEG C of insulation reaction 5h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, filter cake drying,
Obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 90.5%, temperature of initial decomposition: 400 ± 5
℃。
Embodiment 10 is added in the 250ml three-necked flask that blender, thermometer, high performance reflux condenser are housed
60ml dimethylsulfoxide solvent is added 2.46g (0.01mol) chloranil, adds pentaerythritol methylsilicate sodium alkoxide
9.11g (0.04mol) is warming up to 160 DEG C of insulation reaction 8h, filters, and removes sodium chloride, and filtrate crystallisation by cooling filters, and filter cake dries
It is dry, obtain four silicon cage oxygroup 1,4-benzoquinone of purple brown powder coloured flame-retardant carbon forming agent, yield 85.3%, temperature of initial decomposition: 400
±5℃。
1 preparation example main technologic parameters of table
Four silicon cage oxygroup 1,4-benzoquinone of coloured flame-retardant carbon forming agent is applied in PP and PBT by inventor, and and and MPP
Compounding has studied cooperative flame retardant into charcoal situation, and the four silicon cage oxygroup 1,4-benzoquinone or compounding that different proportion is added in PP or PBI are not
MPP in proportion；The batten for squeezing out purple brown under melting with XJ-01 type single screw extrusion machine, is made length 15cm, diameter
The burning batten of 0.3cm, reference: the limit oxygen index (LOI) of the above-mentioned batten of GB/T 2406-2008 standard testing, test result
As shown in 2~table of table 5:
2 coloured flame-retardant agent of table, four silicon cage oxygroup 1,4-benzoquinone is applied to the oxygen index (OI) test result in PBT
As shown in Table 2, when the additive amount when four silicon cage oxygroup 1,4-benzoquinone of product in PBT is 15%, limit oxygen index
It is all larger than 27%, limit oxygen index when general halogen-free flame retardants additive amount is 25% has been had reached, has also had reached fire retardant grade
Not, when additive amount is all 20%, other than the oxygen index (OI) for being up to 30% or more, moreover it is possible to obviously observe by being modified
PBT material is very fast at charcoal speed, also without melting drippage when burning, it is possible to it is fire-retardant well to find out that product has PBT
Effectiveness.
The oxygen index (OI) test result of 3 coloured flame-retardant agent of table, four silicon cage oxygroup 1,4-benzoquinone and MPP composite usage in PBT
As shown in Table 3, when MPP being individually used for PBT with 20% additive amount, oxygen index (OI) is only 22%, is still fallen within flammable
Scope, and with melting drip phenomenon；Total amount of adding after compounding four silicon cage oxygroup 1,4-benzoquinone of product with MPP in PBT
For 20% and when ratio is 1: 1, limit oxygen index can reach 28% or more, and the PBT material being modified does not have in burning
There is melting to drip, it is also very fast at charcoal speed.This illustrates to be imitated at carbon flame-proof well using there is PBT after product is compounded with MPP
With.
4 coloured flame-retardant agent of table, four silicon cage oxygroup 1,4-benzoquinone is for the oxygen index (OI) test result in PP
As shown in Table 4, when additive amount of the four silicon cage oxygroup 1,4-benzoquinone of product in PP is all 20%, limit oxygen index
It is all larger than 31%, has had reached limit oxygen index when general fire retardant additive amount is 30%, when additive amount is 25%, is removed
Outside up to 33% or more oxygen index (OI), moreover it is possible to obviously observe the PBT material form stable by being modified, it is non-at charcoal speed
Often fastly, also without melting drippage when burning, it is possible to find out that product has good fire-retardant effectiveness to PP.
The oxygen index (OI) test result of 5 coloured flame-retardant agent of table, four silicon cage oxygroup 1,4-benzoquinone and MPP composite usage in PP
As shown in Table 5, when MPP being individually used for PP with 20% additive amount, oxygen index (OI) is only 22%, still falls within flammable model
Farmland, and with melting drip phenomenon；Total amount of adding after compounding four silicon cage oxygroup 1,4-benzoquinone of product with MPP in PP is
25% and ratio when being 1: 1, limit oxygen index can reach 30% or more, and the PP material by being modified in burning all
Drippage is not melted, it is also very fast at charcoal speed.This illustrates to be imitated at carbon flame-proof well using there is PP after product is compounded with MPP
With.
Claims (3)
1. a kind of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent, which is characterized in that the structure of the compound is as follows
Shown in formula:
2. a kind of preparation method of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent as described in claim 1, special
Sign is, this method are as follows:
In the reactor that blender, thermometer, high performance reflux condenser are housed, suitable organic solvent is added, tetrachloro is added
1,4-benzoquinone adds the pentaerythritol methylsilicate sodium alkoxide relative to 4~5 times moles of chloranil, it is warming up to 100~
6~13h of insulation reaction at 160 DEG C is filtered, and removes sodium chloride, and filtrate crystallisation by cooling filters, and filter cake drying obtains purple brown powder
Last four silicon cage oxygroup 1,4-benzoquinone of coloured flame-retardant carbon forming agent.
3. a kind of preparation method of four silicon cage oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent as claimed in claim 2, special
Sign is: suitable organic solvent is dioxane, toluene, dimethylbenzene, ethylene glycol diethyl ether, diethylene glycol diformazan
Ether, methyl phenyl ethers anisole or dimethyl sulfoxide, dosage volume ml are 6 times -12 times of product Theoretical Mass grams.
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| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146093A (en) * | 2011-02-23 | 2011-08-10 | 苏州科技学院 | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof |
| CN103880624A (en) * | 2014-04-16 | 2014-06-25 | 苏州科技学院相城研究院 | Tetraallyloxy p-benzoquinone compound and preparation method for same |
| CN104017025A (en) * | 2014-06-11 | 2014-09-03 | 苏州科技学院相城研究院 | Flame retardant charring agent-tetra-{1-oxyphospha-2,6,7-trioxabicyclo-[2.2.2]-octane-(4)-methyl} silicate compound and preparation method thereof |
| CN104710459A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Dimethyl silicate pentaerythritol ester compound as fire retardant and preparation method thereof |
-
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- 2018-07-06 CN CN201810783081.5A patent/CN108929341B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146093A (en) * | 2011-02-23 | 2011-08-10 | 苏州科技学院 | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof |
| CN103880624A (en) * | 2014-04-16 | 2014-06-25 | 苏州科技学院相城研究院 | Tetraallyloxy p-benzoquinone compound and preparation method for same |
| CN104017025A (en) * | 2014-06-11 | 2014-09-03 | 苏州科技学院相城研究院 | Flame retardant charring agent-tetra-{1-oxyphospha-2,6,7-trioxabicyclo-[2.2.2]-octane-(4)-methyl} silicate compound and preparation method thereof |
| CN104710459A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Dimethyl silicate pentaerythritol ester compound as fire retardant and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN111978351B (en) * | 2020-08-06 | 2022-04-26 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
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