CN104710464B - Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof - Google Patents
Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof Download PDFInfo
- Publication number
- CN104710464B CN104710464B CN201510100981.1A CN201510100981A CN104710464B CN 104710464 B CN104710464 B CN 104710464B CN 201510100981 A CN201510100981 A CN 201510100981A CN 104710464 B CN104710464 B CN 104710464B
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- propyl ester
- silicic acid
- flame
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof, the structure of the compound is shown below：ClXC in formula3H5O is CH2ClCHXCH2O or (CH2Cl)(CH2X) CHO, X=Cl or Br.Preparation method is：The halosilanes of dimethyl two are dissolved in organic solvent, epoxychloropropane of 2~3 times moles relative to two halosilanes of dimethyl is added, 70 DEG C~110 DEG C are warming up to, insulation reaction 5~13h is purified to handle to obtain dimethyl silicic acid dihalo- propyl ester.Dimethyl silicic acid dihalo- propyl ester flame-retarded efficiency of the present invention is high, and plasticity is good, is suitable as the flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin etc., and simple production process, cost is low, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of silicon, halogen element cooperative flame retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and its preparation
Method, the compound is suitable as the flame-retardant plasticizer of polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin etc..
Background technology
With Chinese society economy continue to develop and the wealth of society sharp increase, electronic apparatus, skyscraper etc.
Field is fast-developing, and occurrence index rises, and the Loss of Life and property that it is caused is huge, thereby promotes fire-retardant science and production
Industry is developed rapidly.At present, halogenated flame retardant is one of maximum organic fire-retardant of yield in the world, still, due to its burning
When discharge pernicious gas, its application in some fields is restricted.Meanwhile, also it is difficult in the recent period for comprehensive cost performance
Preferable substitute is found, so in the period of one considerably long, halogenated flame retardant is still in flame retardant area in occupation of leading
Status.But, requirement to halogenated flame retardant very clearly, the developing trend in its future be towards efficiently, the direction of low toxicity enters
OK.
Silicon, halogen element collaboration resistance are prepared the invention discloses raw material is wanted based on epoxychloropropane and the halosilanes of dimethyl two
Fire plasticizer dimethyl silicic acid dihalo- propyl ester compound.Element silicon can promote height under silicon and halogen element cooperative flame retardant, hot conditions
Molecular material generates fine and close silicon layer of charcoal into charcoal；Halogen element generates hydrogen halides when heated, itself and the oxidation of retardant synergist three two
Antimony effect generation antimony halides is covered in material surface, there is anoxybiotic effect, or can take away heat with gas releasing, reduces the temperature of material
Degree and it is non-ignitable.Fire retardant of the present invention is two kinds of ignition-proof element cooperative flame retardants, and flame-retarded efficiency is high, and plasticity is good, has a wide range of application, has
Good application and development prospect.
The content of the invention
An object of the present invention is to propose a kind of silicon, halogen cooperative flame retardant plasticizer dimethyl silicic acid dihalo- propyl ester chemical combination
Thing, its flame-retarded efficiency is high, and plasticity is good, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
Dimethyl-silicon acid dichloride propyl ester compound, it is characterised in that the structure of the compound is shown below：
ClXC in formula3H5O is CH2ClCHXCH2O or (CH2Cl)(CH2X) CHO, X=Cl or Br.
Another object of the present invention is to propose the preparation method of dimethyl silicic acid dihalo- propyl ester compound, the letter of its technique
Single, equipment investment is few, it is easy to large-scale production, and raw material is cheap and easy to get, and with low cost, this method is：
In the reactor equipped with agitator, thermometer and condenser pipe, the air in reactor is fallen with nitrogen displacement, by two
Methyl dihalo silane is dissolved in organic solvent, adds epoxychloropropane of 2~3 times moles relative to two halosilanes of dimethyl, adds
Afterwards, 70 DEG C~110 DEG C, 5~13h of insulation reaction are warming up to；Vacuum distillation removes solvent, (recovery makes excessive epoxychloropropane
With) and a small amount of low boilers, obtain dimethyl silicic acid dihalo- propyl ester.
Organic solvent as described above is acetonitrile, dichloroethanes, diethylene glycol dimethyl ether or dioxane, its consumption volume
Milliliter number is 0~10 times of the halosilanes quality grams of dimethyl two.
The halosilanes of dimethyl two as described above are dimethyldichlorosilane or the bromo-silicane of dimethyl two.
The dimethyl-silicon acid dichloride propyl ester of the present invention is colourless transparent liquid, and yield is 84.1%~92.6%, decomposes temperature
Spend for 207 DEG C ± 5 DEG C, index of refraction is nD 25=1.4628, (25 DEG C) of density is 1.32g/cm3；Dimethyl silicic acid chlorine bromine propyl ester is
Colourless or light yellow transparent liquid, product yield is 89.1%~94.7%, and decomposition temperature is 236 DEG C ± 5 DEG C, and index of refraction is
nD 25=1.4697, (25 DEG C) of density is 1.43g/cm3.It is suitable as polyvinyl chloride, polyurethane, epoxy resin, unsaturated tree
The flame-retardant plasticizer of the materials such as fat.The preparation technology principle of the dimethyl silicic acid dihalo- propyl ester is shown below：
XClC in formula3H5O is CH2ClCHXCH2O or (CH2Cl)(CH2X) CHO, X=Cl or Br.
Compared with prior art, the beneficial effects of the present invention are：
1. flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester of the present invention is siliceous, halogen ignition-proof element, and its cooperative flame retardant efficiency is high,
Element silicon has into charcoal effect, the second-time burning that can effectively prevent material melted by heating from dripping and produce.
2. two methyl are connected with silicon atom in flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester structure of the present invention, with C-
Si keys, are organosilicon structures, and organosilicon structures stability is good, water resistance strong, and charcoal-silicon layer of densification is more easily generated during burning,
Flame retardant effect is more excellent；Because with branched chain propyl structure, intermolecular electrostatic force is smaller, and product viscosity is small, with height in molecule
Molecular material compatibility is good, there is preferable plasticity.
3. released in flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester preparation process of the present invention without any small molecule, raw material is former
Sub- utilization rate 100%, with good energy economy ＆ environment benefit.
4. flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester technique of the present invention is simple, and reaction need not add catalyst and not introduce
Impurity, equipment is simple, with low cost, suitable for large-scale production, there is good application and development prospect.
Brief description of the drawings
In order to which the structure and performance spy that further illustrate product provide drawings described below.
1st, the infrared spectrogram of dimethyl-silicon acid dichloride propyl ester, refers to Figure of description Fig. 1；
Fig. 1 shows, 2846.9cm-1-2965.2cm-1Locate the stretching vibration suction for the C-H of methyl, methylene and methine
Receive peak, 1004.3cm-1Locate the characteristic absorption peak for Si-O-C, 1093.8cm-1Locate the stretching vibration absworption peak for C-O,
828.4cm-1Locate the stretching vibration absworption peak for C-Cl, 801.7cm-1Locate the characteristic absorption peak for Si-C.
2nd, the nuclear magnetic spectrogram of dimethyl-silicon acid dichloride propyl ester, refers to Figure of description Fig. 2；
Fig. 2 shows that deuterochloroform makees solvent, and δ 0.26-0.33 are SiCH3Upper methyl hydrogen peak, δ 3.59-3.73 are CH
(CH2Cl)2The upper methylene hydrogen peak being connected with chlorine, δ 4.18-4.26 are CH (CH2Cl)2Last time methyl hydrogen peak, δ 7.28 is solvent
The proton peak that deuterochloroform is exchanged.
Specific embodiment
Technical scheme is described further below in conjunction with embodiment.
Embodiment 1 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add 6.45g (0.05mol) dimethyldichlorosilane, 65ml dioxane and
9.25g (0.1mol) epoxychloropropane, is warming up to 100 DEG C, insulation reaction 8h；Vacuum distillation removes solvent and a small amount of low boiling
Thing, obtains dimethyl-silicon acid dichloride propyl ester, yield 86.9%.
Embodiment 2 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add 6.45g (0.05mol) dimethyldichlorosilane, 40ml acetonitriles and
10.18g (0.11mol) epoxychloropropane, is warming up to 70 DEG C, insulation reaction 13h；Vacuum distillation removes solvent, excessive epoxy
Chloropropane (recovery is used) and a small amount of low boilers, obtain dimethyl-silicon acid dichloride propyl ester, yield 84.1%.
Embodiment 3 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 6.45g (0.05mol) dimethyldichlorosilane, 20ml diethylene glycols two are added
Methyl ether and 11.57g (0.125mol) epoxychloropropane, are warming up to 110 DEG C, insulation reaction 5h；Vacuum distillation removes solvent, excess
Epoxychloropropane (recovery is used) and a small amount of low boilers, obtain dimethyl-silicon acid dichloride propyl ester, yield 91.2%.
Embodiment 4 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add 6.45g (0.05mol) dimethyldichlorosilane, 30ml dichloroethanes and
12.95g (0.14mol) epoxychloropropane, is warming up to 83 DEG C, insulation reaction 10h；Vacuum distillation removes solvent, excessive epoxy
Chloropropane (recovery is used) and a small amount of low boilers, obtain dimethyl-silicon acid dichloride propyl ester, yield 87.4%.
Embodiment 5 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 64.5g (0.5mol) dimethyldichlorosilanes and 138.8g (1.5mol) are added
Epoxychloropropane, is warming up to 90 DEG C, insulation reaction 8h；Vacuum distillation removes solvent, excessive epoxychloropropane (recovery is used)
And a small amount of low boilers, obtain dimethyl-silicon acid dichloride propyl ester, yield 92.6%.
Embodiment 6 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add the bromo-silicane of 10.9g (0.05mol) dimethyl two, 60ml acetonitriles and
9.25g (0.1mol) epoxychloropropane, is warming up to 70 DEG C, insulation reaction 13h；Vacuum distillation removes solvent and a small amount of low boiling
Thing, obtains dimethyl silicic acid chlorine bromine propyl ester, yield 89.1%.
Embodiment 7 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add the bromo-silicane of 10.9g (0.05mol) dimethyl two, 80ml dichloroethanes and
10.18g (0.11mol) epoxychloropropane, is warming up to 80 DEG C, insulation reaction 10h；Vacuum distillation removes solvent, excessive epoxy
Chloropropane (recovery is used) and a small amount of low boilers, obtain dimethyl silicic acid chlorine bromine propyl ester, yield 90.4%.
Embodiment 8 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 100ml tri- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, the bromo-silicane of 10.9g (0.05mol) dimethyl two, 20ml diethylene glycols two are added
Methyl ether and 11.57g (0.125mol) epoxychloropropane, are warming up to 100 DEG C, insulation reaction 8h；Vacuum distillation removes solvent, excess
Epoxychloropropane (recovery is used) and a small amount of low boilers, obtain dimethyl silicic acid chlorine bromine propyl ester, yield 93.5%.
Embodiment 9 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, add the bromo-silicane of 10.9 (0.05mol) dimethyl two, 100ml dioxane and
12.95g (0.14mol) epoxychloropropane, is warming up to 90 DEG C, insulation reaction 8h；Vacuum distillation removes solvent, excessive epoxy chlorine
Propane (recovery is used) and a small amount of low boilers, obtain dimethyl silicic acid chlorine bromine propyl ester, yield 93.4%.
Embodiment 10 is equipped with agitator, thermometer and condenser pipe, and in the condenser pipe 250ml suitable for reading equipped with drying tube
In four-hole bottle, with the air in nitrogen displacement bottle falling, the bromo-silicane of 109g (0.5mol) dimethyl two and 138.8g are added
(1.5mol) epoxychloropropane, is warming up to 110 DEG C, insulation reaction 5h；Vacuum distillation removes solvent, excessive epoxychloropropane
(recovery is used) and a small amount of low boilers, obtain dimethyl silicic acid chlorine bromine propyl ester, yield 94.7%.
The dimethyl silicic acid dihalo- propyl ester of above-mentioned preparation is applied in polyvinyl chloride (PVC) 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 dimethyl-silicon
Sour dihalo- propyl ester, plasticizer phthalic acid dioctyl ester (DOP), synergistic flame retardant antimony oxide (Sb2O3) and polyvinyl chloride with
After different proportion is well mixed, is extruded with extruder, a diameter of 3mm batten be made, and its fire resistance is tested,
Part test result is listed as shown in table 1 and table 2：
The fire resistance data of the dimethyl-silicon acid dichloride propyl ester of table 1
The fire resistance data of the dimethyl silicic acid chlorine bromine propyl ester of table 2
It is generally acknowledged that oxygen index (OI) reach 27% its be fire proofing.From table 1 and table 2, dimethyl silicic acid dihalo- propyl ester
There is excellent fire resistance to pvc material.It has also been found that dimethyl silicic acid dihalo- propyl ester has to polyvinyl chloride in experiment
Preferable plasticity, DOP can be replaced in right amount, you can go easy plasticizer in.
Claims (2)
1. a kind of preparation method of fire retardant dimethyl silicic acid dihalo- propyl ester, it is characterised in that this method is：
Fall the air in reactor with nitrogen displacement, the bromo-silicane of dimethyl two is dissolved in organic solvent, add relative to diformazan
The epoxychloropropane of 2~3 times moles of two bromo-silicane of base, is warming up to 70 DEG C~110 DEG C 5~13h of reaction, vacuum distillation removes molten
Agent, excessive epoxychloropropane and a small amount of low boilers, obtain dimethyl silicic acid dihalo- propyl ester, the structure such as following formula institute of the compound
Show：
ClXC in formula3H5O is CH2ClCHXCH2O or (CH2Cl)(CH2X) CHO, X=Br.
2. the preparation method of dimethyl silicic acid dihalo- propyl ester according to claim 1, it is characterised in that described organic solvent
For acetonitrile, dichloroethanes, diethylene glycol dimethyl ether or dioxane, its consumption volume milliliter number is the bromo-silicane matter of dimethyl two
Measure grams 0~10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510100981.1A CN104710464B (en) | 2015-03-06 | 2015-03-06 | Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510100981.1A CN104710464B (en) | 2015-03-06 | 2015-03-06 | Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104710464A CN104710464A (en) | 2015-06-17 |
| CN104710464B true CN104710464B (en) | 2017-10-17 |
Family
ID=53410242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510100981.1A Active CN104710464B (en) | 2015-03-06 | 2015-03-06 | Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710464B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830923A (en) * | 2010-05-27 | 2010-09-15 | 王彦林 | Silicic acid tetra (dichloropropyl) ester compound and preparation method thereof |
-
2015
- 2015-03-06 CN CN201510100981.1A patent/CN104710464B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830923A (en) * | 2010-05-27 | 2010-09-15 | 王彦林 | Silicic acid tetra (dichloropropyl) ester compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Reaction of epichlorohydrin and glycidol with organochlorosilanes;Adrianov K. A.等,;《Bull. Acad Sci. U.S.S.R., Div. Chem. Sci.》;19551231;第469-475页, 尤其是第471页最后一段 * |
| Reaction of epichlorohydrin and methyl glycidyl ether with organochlorosilanes;Malinovskii, M. S.等，;《Zhurnal Obshchei Khimii》;19571231;第1680-1685页, 尤其是第1681页反应式3、第1683页表1、第1682页实验1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104710464A (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104710464B (en) | Flame-retardant plasticizer dimethyl silicic acid dihalo- propyl ester compound and preparation method thereof | |
| CN104650136A (en) | Preparation method of flame retardant, namely tris (dimethylchloropropoxy silicon acyloxy ethyl) triazine compound | |
| CN104710457B (en) | Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds and preparation method thereof | |
| CN104710470B (en) | Fire retardant match gram three (dimethyl dihalo- propoxyl group silicic acid) ester compounds and preparation method thereof | |
| CN104710458B (en) | Three (2- dimethyl chloride ethyoxyl silicon trimethylammonium) isocyanurate compounds and preparation method thereof | |
| CN103554155B (en) | Fire retardant match gram three tetra-(chloroethyl) silicate compounds and preparation method thereof | |
| CN104693228A (en) | Flame retardant dibenzyl dimethylsilicate compound and preparation method thereof | |
| CN106632485A (en) | Flame retardant benzene siliconic acid bis-thiophospha-caged trioxacyclooctyl-4-methyl ester compound and preparation method thereof | |
| CN102731555B (en) | Tribromophenoxychloropropoxytri(dichloropropyl)silicate compound and preparation method thereof | |
| CN104650132B (en) | Fire retardant dimethyl silicic acid -2,4-PD ester compounds and preparation method thereof | |
| CN104788680B (en) | Poly dimethyl silicic acid tetrabromobisphenol A ester polymer and preparation method thereof | |
| CN104710468B (en) | Isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester compounds and preparation method thereof | |
| CN104710454B (en) | Dimethyl silicic acid two (2,4,6- tribromophenoxies chloropropyl) ester compounds and preparation method thereof | |
| CN103554149B (en) | Three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof | |
| CN104744504B (en) | A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds | |
| CN104672269B (en) | The preparation method of flame-retardant plasticizer dimethyl silicic acid two (1,3 dihalo- isopropyl) ester compounds | |
| CN104672272B (en) | Dimethyl silicic acid tribromophenoxy bromine propyl ester compound and preparation method thereof | |
| CN102140112A (en) | Halogenated organic silicate ester flame-retardant plasticizer compound and preparation method thereof | |
| CN104710465A (en) | Preparation method of dimethyl silicic acid (chlorine acrylate) diester as flame resistant plastifier | |
| CN104710467A (en) | Dimethyl silicon acid diester ( 2-chlorine ) compound serving as flame resistant plastifier and preparation method of dimethyl silicon acid diester (2-bromic ) compound | |
| CN104693230B (en) | A kind of preparation method of silicon, nitrogen, halogen cooperative flame retardant plasticizer | |
| CN104693444B (en) | Fire retardant poly dimethyl silicic acid -2,4,6- tribromo resorcinol ester polymers and preparation method thereof | |
| CN104672270B (en) | Isocyanuric acid three (dimethyl halogen propoxyl group silicon acyloxy halogen propyl group) ester compounds and preparation method thereof | |
| CN102731551B (en) | Novel silicon-halogen synergistic fire retardant plasticizer compound and preparation method thereof | |
| CN104710469B (en) | The preparation method of fire retardant dimethyl chloride propoxyl group silicon acyloxy halogen propyl group isocyanurate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170825 Address after: 313018, No. 188, Liang Shan Road, Ling Hu Town, Nanxun District, Zhejiang, Huzhou Applicant after: Huzhou Ruigao New Material Co., Ltd. Address before: 215131, No. 833, Xiangcheng Avenue, 1-2012 yuan street, Suzhou, Jiangsu, Xiangcheng District Applicant before: Suzhou Yang Qiao Chemical Industry Science Co., Ltd |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 313018 No. 188 Liangshan Road, Linghu Town, Nanxun District, Huzhou City, Zhejiang Province Patentee after: Zhejiang Rui hi tech materials Limited by Share Ltd Address before: 313018 No. 188 Liangshan Road, Linghu Town, Nanxun District, Huzhou City, Zhejiang Province Patentee before: Huzhou Ruigao New Material Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |