CN110156826A - Diphenyl cyclotrisiloxane and the preparation method and application thereof - Google Patents
Diphenyl cyclotrisiloxane and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110156826A CN110156826A CN201910536793.1A CN201910536793A CN110156826A CN 110156826 A CN110156826 A CN 110156826A CN 201910536793 A CN201910536793 A CN 201910536793A CN 110156826 A CN110156826 A CN 110156826A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- trifluoro propyl
- diphenyl
- organic solvent
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UNPFADACPKMIHX-UHFFFAOYSA-N 2,2-diphenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C1(=CC=CC=C1)[Si]1(O[SiH2]O[SiH2]O1)C1=CC=CC=C1 UNPFADACPKMIHX-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OHABWQNEJUUFAV-UHFFFAOYSA-N dichloro-methyl-(3,3,3-trifluoropropyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)F OHABWQNEJUUFAV-UHFFFAOYSA-N 0.000 claims abstract description 20
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- -1 3,3,3- trifluoro propyl Chemical group 0.000 claims description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 13
- 238000007363 ring formation reaction Methods 0.000 claims description 12
- 229920005560 fluorosilicone rubber Polymers 0.000 claims description 11
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000013517 stratification Methods 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 238000009835 boiling Methods 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 11
- 239000005457 ice water Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 6
- QTRQFVAKGZFBRT-UHFFFAOYSA-N 2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[SiH]1O[SiH2]O[SiH2]O1 QTRQFVAKGZFBRT-UHFFFAOYSA-N 0.000 description 5
- 239000005046 Chlorosilane Substances 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- YLGFLAGIVRJQTC-UHFFFAOYSA-N ethenyl-[hydroxy(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(O)O[Si](C)(C)C=C YLGFLAGIVRJQTC-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- OGPNXGJLKXGASM-UHFFFAOYSA-N [Si].CC=C Chemical compound [Si].CC=C OGPNXGJLKXGASM-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- REPWJCMYAKEVRF-UHFFFAOYSA-N phenyl(silyloxysilyloxy)silane Chemical class [SiH3]O[SiH2]O[SiH2]C1=CC=CC=C1 REPWJCMYAKEVRF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The present invention relates to diphenyl cyclotrisiloxane and the preparation method and application thereof, the trisiloxanes that both ends are chlorine is prepared for using trifluoropropylmethyldichlorosilane and diphenyl silanediol reaction, the trisiloxanes hydrolytic condensation is then made into its intramolecular cyclization, by two-step reaction beam system for target product.This method not only inhibits the generation of side reaction, and substantially increases the yield of cyclotrisiloxane, has many advantages, such as that high-efficient, easy to operate, product purity is high.
Description
Technical field
The invention belongs to the synthesis fields of organo-silicon compound, and in particular to 1,3- of one kind dimethyl -1,3- bis- (3,3,3-
Trifluoro propyl) -5,5- diphenyl cyclotrisiloxane and the preparation method and application thereof.
Background technique
Fluorine silicone rubber be a kind of main chain be silica structure, the extraordinary synthetic material that side chain is methyl and trifluoro propyl structure,
Mainly pass through 1,3,5- trimethyl -1,3,5- three (3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) ring-opening polymerisation obtains.It is this
The special chemical structure of material makes it have many unique functions, and it is submissive that the Si-O-Si structure of main chain imparts fluorine silicone rubber
Property and thermal stability, and the side-chain structure of trifluoro propyl then gives the good oil resistant of fluorine silicone rubber, solvent resistance.But with first
Base phase ratio, trifluoro propyl are easy to decompose at high operating temperatures, generate fluoride, make its heat resistance not as good as methyl ethylene silicon rubber
Glue, using being subject to certain restrictions.
With the continuous development of fluorine silicone rubber application field, to its heat resistance, more stringent requirements are proposed, how to improve fluorine
The heat-resisting and ageing-resistant performance of silicon rubber is the important developing direction of fluorine silicone rubber.And phenyl siloxane rubber then has good hot oxygen
Stability not only increases the interior rotational resistance of silicon rubber strand due to the introducing of phenyl, moreover it is possible to stablize and produce in pyroprocess
Raw free radical, to improve the high temperature resistance of material.
Currently, being directed to the resistance to heat problem of fluorine silicone rubber, there is data to point out, by the cyclosiloxane containing phenyl and 1,3,5- tri-
Methyl-1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) by way of copolymerization, with excellent heat resistance
Phenyl is introduced into the strand of fluorine silicone rubber, and the heat resistance of fluorine silicone rubber is improved with this.But in polymerization process, by
In the different ring body structurc of two kinds of monomers and side-chain radical difference, the open loop activity of the two has a long way to go, the poor effect of copolymerization,
Not the problem of not can effectively solve fluorine silicone rubber poor heat resistance.Therefore, a kind of and 1,3,5- trimethyls -1,3,5- tri- are invented
(3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) open loop activity is close and the cyclosiloxane containing phenyl is even more important.
Chinese patent CN1181081C has invented a kind of fluorine-containing hybrid ring siloxane, with fluorine-containing alkyl methyl dichlorosilane with
Dialkyl dichlorosilane mixed raw material and metal oxide or alkali carbonate react dechlorination preparation at -20 DEG C~80 DEG C.
The structural formula of the fluorine-containing cyclosiloxane is as follows:
Wherein R1=C1~4Alkyl, phenyl；R2=methyl, phenyl；M=0,1,2；The integer of n=3~10；X=2,3；Y
=0~11 integer.The cyclosiloxane could form cyclotrisiloxane only as m=0, n=3, but the cyclotrisiloxane
Only there was only fluoro-containing group, mixed structure can not be formed；When m=1 or 2, n=3~10 integer when, which at least contains
There are four silicon oxygen chain link, i.e., minimum cyclotetrasiloxane is equally also unable to get the cyclotrisiloxane of mixed structure.
Chinese patent CN105085567A discloses a kind of cyclosiloxane that polyfunctional group replaces altogether, ring siloxane mixture
Preparation method.Using dimethyl dichlorosilane (DMCS) or methyl dialkyl silane, in the mixed system of water and organic solvent composition,
Weak base or metal oxide or metal carbonate is added, for maintenance system temperature at 0~80 DEG C, cohydrolysis reaction obtains cyclosiloxane
Mixture.This method carries out cohydrolysis reaction using a variety of chlorosilanes, obtains different ring siloxane mixtures, to wherein special
The selectivity for determining the cyclosiloxane of structure is very poor, and product is generally the mixture of various cyclosiloxane, can not efficiently obtain target
Product.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides 1,3- of one kind dimethyl -1,3- bis- (3,3,3- trifluoropropyls
Base) -5,5- diphenyl cyclotrisiloxane and preparation method thereof.The method comprises the steps of firstly, preparing the trisiloxanes that a kind of end group is chlorine, and
The trisiloxanes hydrolytic condensation is made into its intramolecular cyclization afterwards, by two-step reaction beam system for target product, this method is not only
The generation of side reaction is inhibited, and substantially increases the yield of cyclotrisiloxane.
Technical scheme is as follows:
1,3- of one kind dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane has following knot
Structure:
According to the present invention, above-mentioned 1,3- dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane
Preparation method, comprise the following steps that
The organic solvent system of diphenyl silanediol and triethylamine is added dropwise to the organic of trifluoropropylmethyldichlorosilane
In dicyandiamide solution, it is stirred to react；
After the reaction was completed, chloro- 1,5- dimethyl -1,5- bis- (3,3,3- trifluoro propyl) -3, the 3- bis- of 1,5- bis- that will be obtained
Phenyl trisiloxanes solution is added drop-wise in water, and cyclization is hydrolyzed to get (3,3, the 3- trifluoros of 1,3- dimethyl -1,3- bis-
Propyl) -5,5- diphenyl cyclotrisiloxane.
, according to the invention it is preferred to, the organic solvent system and trifluoro propyl methyl two of diphenyl silanediol and triethylamine
Organic solvent type is identical in the organic solvent system of chlorosilane；Have in the organic solvent system of diphenyl silanediol and triethylamine
The inventory of solvent is that diphenyl silanediol feeds intake 2-3 times of quality, the organic solvent body of trifluoropropylmethyldichlorosilane
The inventory of organic solvent is that trifluoropropylmethyldichlorosilane feeds intake 2-3 times of quality in system；
Preferred organic solvent is ethyl acetate.
, according to the invention it is preferred to, the organic solvent system and trifluoro propyl methyl two of diphenyl silanediol and triethylamine
The hybrid reaction of the organic solvent system of chlorosilane carries out under protective gas protection, and preferred protective gas is nitrogen or argon
Gas；
Preferably, reaction temperature is 0-20 DEG C, reaction time 1-3h；
Preferably, the molar ratio of diphenyl silanediol and trifluoropropylmethyldichlorosilane is 1:(2.0-2.2), three
The molar ratio of ethamine and trifluoropropylmethyldichlorosilane is 1:(1.0-1.2).
According to the present invention, after fully reacting, system is filtered into removal triethylamine hydrochloride, obtains chloro- 1, the 5- bis- of 1,5- bis-
Methyl-1,5- bis- (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes solution；
Preferably, hydrolytic cyclization reaction temperature is 0-10 DEG C, reaction time 1-2h；
Preferably, the inventory of water is that trifluoropropylmethyldichlorosilane feeds intake 2-5 times of quality.
According to the present invention, hydrolytic cyclization takes out organic phase and is washed to neutrality after the reaction was completed by system stratification；
Under vacuum condition, organic phase is subjected to rectifying, (3,3, the 3- trifluoros of 1,3- dimethyl -1,3- bis- after being purified
Propyl) -5,5- diphenyl cyclotrisiloxane；
Preferably, washing temperature is 20-50 DEG C, washing time 0.5-1h；
Preferably, rectifying condition is pressure -0.099MPa, 174-176 DEG C of temperature；174-176 is intercepted in distillation process
DEG C/fraction of -0.099MPa, as product 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- hexichol basic ring, three silicon
Oxygen alkane；It is further preferred that distillation process control reflux ratio is (8-10): 1.
The system of 1,3- dimethyl -1,3- two (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane according to the present invention
A kind of Preparation Method, preferred embodiment, includes the following steps:
(1) under inert gas shielding, by organic solvent, diphenyl silanediol and triethylamine be uniformly mixed formed it is transparent molten
Liquid, and be slowly added dropwise to the system of trifluoropropylmethyldichlorosilane and identical organic solvent, it quickly stirs, maintains reaction
It carries out, is added dropwise at 0-20 DEG C, kept for 0-20 DEG C continue to stir 1-3h；
(2) after fully reacting, system is filtered into removal triethylamine hydrochloride, obtains chloro- 1, the 5- dimethyl -1,5- of 1,5- bis-
Two (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes solution；
(3) at 0-10 DEG C, chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoropropyls of 1,5- bis- that step (2) is obtained
Base) -3,3- diphenyl trisiloxanes solution is added dropwise in water and cyclization is hydrolyzed, after being added dropwise to complete, maintain 0-10 DEG C after
Continuous stirring 1-2h；
(4) stratification takes out organic phase and is washed to neutrality；
(5) under vacuum condition, organic phase is subjected to rectifying, obtains 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -
5,5- diphenyl cyclotrisiloxane.
According to the present invention, 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane is used for
Application in the preparation of thermostable fluorine silicon rubber, especially with 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) ring three
Siloxanes ring opening copolymer prepares thermostable fluorine silicon rubber.
Reaction equation of the invention are as follows:
What the present invention did not elaborate, press this field routine techniques.
Compared with prior art, it technical characterstic of the invention and has the beneficial effect that:
1. the present invention is prepared for both ends using trifluoropropylmethyldichlorosilane and diphenyl silanediol reaction as the three of chlorine
Then reaction is hydrolyzed in the trisiloxanes by siloxanes under low-temperature condition, compare dichlorosilane, and both ends are three silicon oxygen of chlorine
Alkane is easier intramolecular condensation, reduces the generation of linear polymer, is conducive to the generation of cyclotrisiloxane, passes through two-step reaction
Beam system is high-efficient for target product.
2. the invention avoids different chlorosilanes because of the difference of respective hydrolysing activity compared with a variety of chlorosilane cohydrolysis reactions
It is different, product complexity, the defect of target product poor selectivity are caused, has the advantages that impurity is few, with high purity, with clearly defined objective.
3. preparation method of the invention, technique is simple and direct, easy to operate, and solvent is recyclable to be applied, and reduces production cost, easily
In realization industrialized production.
4. 1,3- dimethyl -1,3- two (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane and 1 of the invention,
3,5- trimethyl -1,3,5- three (3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) open loop activity is close and contains phenyl, the two
Copolyreaction works well, obtained fluorine silicone rubber Good Heat-resistance.
Detailed description of the invention
Fig. 1 is the product that 1 reactive distillation of the embodiment of the present invention obtains1H-NMR spectrum.
Fig. 2 is the TGA curve graph of fluorine silicon raw rubber prepared by application examples 1 of the present invention and common fluorine silicon raw rubber.
Specific embodiment
Below with reference to following embodiment, the present invention is further illustrated, can not limit the contents of the present invention.
Raw material as described in the examples is conventional raw material, can market buy or obtained by prior art preparation.
Embodiment 1
The preparation method of 1,3- dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane, including
Steps are as follows:
(1) under nitrogen protection, to equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 5L four-hole boiling flask
Middle addition 1055g trifluoropropylmethyldichlorosilane and 540g ethyl acetate, by 1080g ethyl acetate, 540g diphenyl silicon two
Pure and mild 555.5g triethylamine is uniformly mixed and forms clear solution and be then added in constant pressure funnel, stirring is opened, by constant pressure
Material in dropping funel is slowly added dropwise to flask, and system is cooled down using ice-water bath, and reaction is maintained to carry out at 0-20 DEG C,
Until material dropping finishes, 0-20 DEG C is then kept to continue to stir 2h；
(2) after fully reacting, system is filtered into removal triethylamine hydrochloride, wherein filter cake is washed using 200g ethyl acetate
It washs, collects filtrate, obtain chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes of 1,5- bis-
Solution；
(3) to it is another equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 10L four-hole boiling flask in be added
4220g water, by constant pressure funnel, chloro- 1,5- dimethyl -1,5-, bis- (3,3, the 3- trifluoros of 1,5- bis- that step (2) is obtained
Propyl) -3,3- diphenyl trisiloxanes solution is added dropwise in water and cyclization is hydrolyzed, and system is cooled down using ice-water bath, dimension
0-10 DEG C of dropping temperature is held, until material dropping finishes, then keeps 0-10 DEG C to continue to stir 1h；
(4) stratification, separates lower layer's organic phase, and organic phase is washed 1h under conditions of 20-30 DEG C, until system becomes
For neutrality, organic phase crude product is obtained；
(5) organic phase is collected, is separated and recovered from ethyl acetate under condition of negative pressure, essence is then carried out using the reflux ratio of 10:1
Purification is evaporated, the fraction of 174-176 DEG C/- 0.099MPa, as product 1, (3,3, the 3- trifluoropropyls of 3- dimethyl -1,3- bis- are intercepted
Base) -5,5- diphenyl cyclotrisiloxane, purity 99.12%, yield 82.4%.
The nucleus magnetic hydrogen spectrum spectrogram of product is as shown in Figure 1, be the chemical potential of hydrogen in typical silicon phenyl at 7.41-7.67ppm
Peak is moved, is wherein the chemical shift of the H at the ortho position for the carbon being connected with silicon, integral area 1,7.41- at 7.64-7.67ppm
It is the chemical shift of the meta position, the H of contraposition of the carbon being connected with silicon at 7.51ppm, integral area 1.5, the two represents phenyl
In hydrogen；It is Si-CH at 2.00-2.13ppm2CH2CF3In close-CF3Methylene H chemical shift, integral area 1,
It is Si-CH at 0.87-0.95ppm2CH2CF3In close to Si methylene H chemical shift, integral area 1；0.20-
It is Si-CH at 0.33ppm3The chemical shift of middle H, integral area 1.5；The integral area ratio of H is 2:3:2 in three kinds of groups:
2:3, it may be determined that product is 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane.
Embodiment 2
The preparation method of 1,3- dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane, including
Steps are as follows:
(1) under nitrogen protection, to equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 5L four-hole boiling flask
Middle addition 1107.8g trifluoropropylmethyldichlorosilane and 540g ethyl acetate, by 1080g ethyl acetate, 540g diphenyl silicon
Two pure and mild 583.3g triethylamines are uniformly mixed and form clear solution and be then added in constant pressure funnel, open stirring, will be permanent
Pressure dropping funel in material be slowly added dropwise to flask, system using ice-water bath cool down, maintain react at 0-20 DEG C into
Then row keeps 0-20 DEG C to continue to stir 2h until material dropping finishes；
(2) after fully reacting, system is filtered into removal triethylamine hydrochloride, wherein filter cake is washed using 200g ethyl acetate
It washs, collects filtrate, obtain chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes of 1,5- bis-
Solution；
(3) to it is another equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 10L four-hole boiling flask in be added
4432g water, by constant pressure funnel, chloro- 1,5- dimethyl -1,5-, bis- (3,3, the 3- trifluoros of 1,5- bis- that step (2) is obtained
Propyl) -3,3- diphenyl trisiloxanes solution is added dropwise in water and cyclization is hydrolyzed, and system is cooled down using ice-water bath, dimension
0-10 DEG C of dropping temperature is held, until material dropping finishes, then keeps 0-10 DEG C to continue to stir 1h；
(4) stratification, separates lower layer's organic phase, and organic phase is washed 1h under conditions of 20-30 DEG C, until system becomes
For neutrality, organic phase crude product is obtained；
(5) organic phase is collected, is separated and recovered from ethyl acetate under condition of negative pressure, essence is then carried out using the reflux ratio of 10:1
Purification is evaporated, the fraction of 174-176 DEG C/- 0.099MPa, as product 1, (3,3, the 3- trifluoropropyls of 3- dimethyl -1,3- bis- are intercepted
Base) -5,5- diphenyl cyclotrisiloxane, purity 99.08%, yield 81.5%.
Embodiment 3
The preparation method of 1,3- dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane, including
Steps are as follows:
(1) under nitrogen protection, to equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 5L four-hole boiling flask
Middle addition 1160.5g trifluoropropylmethyldichlorosilane and 540g ethyl acetate, by 1080g ethyl acetate, 540g diphenyl silicon
Two pure and mild 611.1g triethylamines are uniformly mixed and form clear solution and be then added in constant pressure funnel, open stirring, will be permanent
Pressure dropping funel in material be slowly added dropwise to flask, system using ice-water bath cool down, maintain react at 5-15 DEG C into
Then row keeps 5-15 DEG C to continue to stir 2h until material dropping finishes；
(2) after fully reacting, system is filtered into removal triethylamine hydrochloride, wherein filter cake is washed using 200g ethyl acetate
It washs, collects filtrate, obtain chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes of 1,5- bis-
Solution；
(3) to it is another equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 10L four-hole boiling flask in be added
4642g water, by constant pressure funnel, chloro- 1,5- dimethyl -1,5-, bis- (3,3, the 3- trifluoros of 1,5- bis- that step (2) is obtained
Propyl) -3,3- diphenyl trisiloxanes solution is added dropwise in water and cyclization is hydrolyzed, and system is cooled down using ice-water bath, dimension
0-10 DEG C of dropping temperature is held, until material dropping finishes, then keeps 0-10 DEG C to continue to stir 2h；
(4) stratification, separates lower layer's organic phase, and organic phase is washed 1h under conditions of 20-30 DEG C, until system becomes
For neutrality, organic phase crude product is obtained；
(5) organic phase is collected, is separated and recovered from ethyl acetate under condition of negative pressure, essence is then carried out using the reflux ratio of 10:1
Purification is evaporated, the fraction of 174-176 DEG C/- 0.099MPa, as product 1, (3,3, the 3- trifluoropropyls of 3- dimethyl -1,3- bis- are intercepted
Base) -5,5- diphenyl cyclotrisiloxane, purity 99.25%, yield 80.8%.
Embodiment 4
The preparation method of 1,3- dimethyl -1,3-, bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane, including
Steps are as follows:
(1) under nitrogen protection, to equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 5L four-hole boiling flask
Middle addition 1107.8g trifluoropropylmethyldichlorosilane and 540g ethyl acetate, by 1080g ethyl acetate, 540g diphenyl silicon
Two pure and mild 636.3g triethylamines are uniformly mixed and form clear solution and be then added in constant pressure funnel, open stirring, will be permanent
Pressure dropping funel in material be slowly added dropwise to flask, system using ice-water bath cool down, maintain react at 0-10 DEG C into
Then row keeps 0-10 DEG C to continue to stir 2h until material dropping finishes；
(2) after fully reacting, system is filtered into removal triethylamine hydrochloride, wherein filter cake is washed using 200g ethyl acetate
It washs, collects filtrate, obtain chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoro propyl) -3,3- diphenyl trisiloxanes of 1,5- bis-
Solution；
(3) to it is another equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 10L four-hole boiling flask in be added
4432g water, by constant pressure funnel, chloro- 1,5- dimethyl -1,5-, bis- (3,3, the 3- trifluoros of 1,5- bis- that step (2) is obtained
Propyl) -3,3- diphenyl trisiloxanes solution is added dropwise in water and cyclization is hydrolyzed, and system is cooled down using ice-water bath, dimension
0-10 DEG C of dropping temperature is held, until material dropping finishes, then keeps 0-10 DEG C to continue to stir 2h；
(4) stratification, separates lower layer's organic phase, and organic phase is washed 1h under conditions of 20-30 DEG C, until system becomes
For neutrality, organic phase crude product is obtained；
(5) organic phase is collected, is separated and recovered from ethyl acetate under condition of negative pressure, essence is then carried out using the reflux ratio of 10:1
Purification is evaporated, the fraction of 174-176 DEG C/- 0.099MPa, as product 1, (3,3, the 3- trifluoropropyls of 3- dimethyl -1,3- bis- are intercepted
Base) -5,5- diphenyl cyclotrisiloxane, purity 99.32%, yield 82.6%.
Comparative example
Under nitrogen protection, to equipped with mechanical stirring, thermometer, constant pressure funnel, snorkel 10L four-hole boiling flask in
4220g water and 540g ethyl acetate is added, by 1080g ethyl acetate, 1055g trifluoropropylmethyldichlorosilane, 632.5g bis-
Diphenyl dichlorosilane is uniformly mixed and is added in constant pressure funnel, opens stirring, and the material in constant pressure funnel is slow
It is added dropwise among flask and carries out cohydrolysis reaction, system is cooled down using ice-water bath, maintains reaction to carry out at 0-10 DEG C, until object
Material is added dropwise, and is kept for 0-10 DEG C continue to stir 1-2h.Then, stratification separates lower layer's organic phase and is washed to neutrality, does
Cohydrolysis object is obtained after dry.
Cohydrolysis object is subjected to GC-MS analysis, the line style comprising different cyclosiloxane and different chain numbers is poly- in product
Siloxanes, component is many and very mixed and disorderly, target product 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- hexichol
The selectivity of basic ring trisiloxanes is very poor, and yield is very low.
Application examples 1
Under nitrogen protection, to equipped with mechanical stirring, thermometer, condenser pipe, snorkel 1L four-hole boiling flask in be added 1,
3,5- trimethyl -1,3,5- three (3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) 530.4g, 1,3- bis- made from embodiment 1
Methyl-1,3- bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane 102g, 1- vinyl -3- hydroxyl -1,1,3,3-
Tetramethyl disiloxane (purity 96%) 7.2g and sodium hydroxide silicon alkoxide (NaOH content 4.05%) 0.48g, stirs evenly；
Heating is opened, kettle temperature is risen to 125 DEG C, after minute bubbles occurs in system, copolyreaction 3h is maintained, is maintained during copolyreaction
Pressure -0.04MPa to -0.08MPa；After fully reacting, 0.6g silicon substrate phosphate catalyst neutralisation is added into bottle ,-
Under the pressure of 0.099MPa, system is warming up to 200~220 DEG C, low-boiling small molecule is removed, is down to room temperature, obtain product
Fluorine silicon raw rubber containing phenyl.
Product appearance: clear, yield: 96.5%, viscosity: 21600cp (25 DEG C), volatile matter: 1.02% (200 DEG C
× 4h), vinyl mass fraction: 0.138%.
Application examples 2
Under nitrogen protection, to equipped with mechanical stirring, thermometer, condenser pipe, snorkel 1L four-hole boiling flask in be added 1,
3,5- trimethyl -1,3,5- three (3,3,3- trifluoro propyl) cyclotrisiloxane (D3F) 530.4g, methyl phenyl ring siloxane
(DnPh, n=3~5) 102g, 1- vinyl -3- hydroxyl -1,1,3,3- tetramethyl disiloxanes (purity 96%) 7.2g and hydrogen
Sodium oxide molybdena silicon alkoxide (NaOH content 4.05%) 0.48g, stirs evenly；Heating is opened, kettle temperature is risen to 125 DEG C and maintains 3h,
System is very dilute, reactionless sign；Kettle temperature is risen to 160 DEG C, continues to 3h, the still reactionless sign of system；Heating is closed, by system
It is down to room temperature, material is very dilute, and appearance is milky turbidity shape.
In reaction process, D3F and DnThere are great differences for the opposite open-loop rate of Ph, cannot be copolymerized well；Even if by anti-
It answers temperature to be increased to 160 DEG C, can not also solve D3F and DnThe reactivity ratio difference problem of Ph is difficult to cause under the catalyst system
DnPh ring-opening polymerisation.
Fluorine silicon raw rubber (sample 1) containing phenyl and common fluorine silicon raw rubber (sample 2) prepared by application examples 1 are placed in drum
Heat resistance test is carried out in wind drying box, experiment condition is 260 DEG C × 5h, and test result is as shown in table 1.
Table 1
Fluorine silicon raw rubber (sample 1) containing phenyl and common fluorine silicon raw rubber (sample 2) prepared by application examples 1 is in oxygen atmosphere
Lower carry out thermogravimetic analysis (TGA) is enclosed, as a result as shown in Fig. 2, the temperature of initial decomposition of sample 1 is 394.1 DEG C, the initial decomposition of sample 2
Temperature is 343.2 DEG C, and the temperature of initial decomposition of sample 1 improves 50.9 DEG C compared with sample 2.
In summary test result, in the molecular structure of fluorine silicon raw rubber, due to the introducing of phenyl group, to the heat of raw rubber
Oxygen degradation plays inhibiting effect, and the whole heat resistance of polymer is improved, and the temperature of initial decomposition of fluorine silicon raw rubber is shown as
It is greatly enhanced；Also, raw rubber keeps stablizing under conditions of 260 DEG C, is not crosslinked, not gum deposit, still has flowing
Property, illustrate of the invention 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane is to fluorine silicon rubber
The high temperature resistance of glue, which has, is obviously improved effect.
Claims (10)
1. one kind 1,3- dimethyl -1,3- bis- (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane, which is characterized in that
It has the following structure:
2. 1,3- dimethyl -1,3- two (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane described in claim 1
Preparation method comprises the following steps that
The organic solvent system of diphenyl silanediol and triethylamine is added dropwise to the organic solvent of trifluoropropylmethyldichlorosilane
In system, it is stirred to react；
After the reaction was completed, chloro- 1,5- dimethyl -1,5-, bis- (3,3,3- trifluoro propyl) -3, the 3- diphenyl of 1,5- bis- that will be obtained
Trisiloxanes solution is added drop-wise in water, and cyclization is hydrolyzed to get (3,3, the 3- trifluoropropyls of 1,3- dimethyl -1,3- bis-
Base) -5,5- diphenyl cyclotrisiloxane.
3. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that the organic solvent system of diphenyl silanediol and triethylamine and trifluoro propyl methyl dichloro
Organic solvent type is identical in the organic solvent system of silane；It is organic in the organic solvent system of diphenyl silanediol and triethylamine
The inventory of solvent is that diphenyl silanediol feeds intake 2-3 times of quality, the organic solvent system of trifluoropropylmethyldichlorosilane
The inventory of middle organic solvent is that trifluoropropylmethyldichlorosilane feeds intake 2-3 times of quality.
4. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that organic solvent is ethyl acetate.
5. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that the organic solvent system of diphenyl silanediol and triethylamine and trifluoro propyl methyl dichloro
The hybrid reaction of the organic solvent system of silane carries out under protective gas protection, and preferred protective gas is nitrogen or argon gas；
Preferably, reaction temperature is 0-20 DEG C, reaction time 1-3h；
Preferably, the molar ratio of diphenyl silanediol and trifluoropropylmethyldichlorosilane is 1:(2.0-2.2), triethylamine
Molar ratio with trifluoropropylmethyldichlorosilane is 1:(1.0-1.2).
6. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that hydrolytic cyclization reaction temperature is 0-10 DEG C, reaction time 1-2h.
7. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that the inventory of hydrolytic cyclization reaction water is that trifluoropropylmethyldichlorosilane feeds intake quality
2-5 times.
8. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 2
The preparation method of alkane, which is characterized in that hydrolytic cyclization takes out organic phase and be washed to after the reaction was completed by system stratification
Property；
Under vacuum condition, organic phase is subjected to rectifying, (3,3, the 3- trifluoropropyls of 1,3- dimethyl -1,3- bis- after being purified
Base) -5,5- diphenyl cyclotrisiloxane.
9. two (3,3,3- trifluoro propyl) -5,5- hexichol basic ring of 1,3- dimethyl -1,3-, three silicon oxygen according to claim 8
The preparation method of alkane, which is characterized in that washing temperature is 20-50 DEG C, washing time 0.5-1h；
Preferably, rectifying condition is pressure -0.099MPa, 174-176 DEG C of temperature, and it is (8-10) that distillation process, which controls reflux ratio:
1。
10. 1,3- dimethyl -1,3- two (3,3,3- trifluoro propyl) -5,5- diphenyl cyclotrisiloxane described in claim 1
Application in the preparation of thermostable fluorine silicon rubber；
Preferably, with 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane ring opening copolymer prepares resistance to
Application in high temperature fluorine silicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536793.1A CN110156826B (en) | 2019-06-20 | 2019-06-20 | Diphenyl cyclotrisiloxane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536793.1A CN110156826B (en) | 2019-06-20 | 2019-06-20 | Diphenyl cyclotrisiloxane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110156826A true CN110156826A (en) | 2019-08-23 |
| CN110156826B CN110156826B (en) | 2021-08-31 |
Family
ID=67625345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910536793.1A Active CN110156826B (en) | 2019-06-20 | 2019-06-20 | Diphenyl cyclotrisiloxane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110156826B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE635644A (en) * | 1961-12-18 | |||
| EP0538062A2 (en) * | 1991-10-17 | 1993-04-21 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing cyclotrisiloxane and process for preparing the same |
| JPH09221489A (en) * | 1996-02-14 | 1997-08-26 | Shin Etsu Chem Co Ltd | Organohydrogen cyclotetrasiloxane containing fluorine |
| WO1999062916A1 (en) * | 1998-05-29 | 1999-12-09 | Archimica (Florida) Inc. | Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
| US6284906B1 (en) * | 1999-10-12 | 2001-09-04 | University Of Southern California | Cyclotrisiloxanes, new siloxane polymers and their preparation |
| CN1378549A (en) * | 1999-10-12 | 2002-11-06 | 南加州大学 | Novel fluoroalkyl sabstituted cyclotrisiloxanes, their use for preparation of new polymers and novel polymers |
| CN1456564A (en) * | 2003-05-28 | 2003-11-19 | 中国科学院上海有机化学研究所 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
| CN101111567A (en) * | 2005-02-24 | 2008-01-23 | 株式会社艾迪科 | Silicon-containing curable composition and its cured product |
| CN102701191A (en) * | 2012-06-06 | 2012-10-03 | 渤海大学 | Preparation method of fluorosilane surface finished grapheme for supercapacitor |
| CN104004191A (en) * | 2014-06-18 | 2014-08-27 | 山东大学 | Fluorosiloxane copolymer and preparing method thereof |
| WO2015069271A1 (en) * | 2013-11-08 | 2015-05-14 | Empire Technology Development Llc | Fluorinated siloxanes and methods for their preparation |
| CN105085567A (en) * | 2015-08-25 | 2015-11-25 | 浙江大学 | Multiple functional groups co-substituted cyclosiloxane, cyclosiloxane mixture, and preparation method and application of cyclosiloxane mixture |
| CN105837617A (en) * | 2016-04-20 | 2016-08-10 | 中国科学院上海有机化学研究所 | Preparation and application of trifluorovinyl-ether-containing cyclosiloxane capable of direct heat curing |
| CN106986890A (en) * | 2017-06-07 | 2017-07-28 | 威海新元化工有限公司 | A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 |
| CN107698617A (en) * | 2017-09-04 | 2018-02-16 | 北京航空航天大学 | Organosilicon polymer containing silica octatomic ring, its synthesis and application |
| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
-
2019
- 2019-06-20 CN CN201910536793.1A patent/CN110156826B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE635644A (en) * | 1961-12-18 | |||
| EP0538062A2 (en) * | 1991-10-17 | 1993-04-21 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing cyclotrisiloxane and process for preparing the same |
| JPH09221489A (en) * | 1996-02-14 | 1997-08-26 | Shin Etsu Chem Co Ltd | Organohydrogen cyclotetrasiloxane containing fluorine |
| WO1999062916A1 (en) * | 1998-05-29 | 1999-12-09 | Archimica (Florida) Inc. | Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
| US6284906B1 (en) * | 1999-10-12 | 2001-09-04 | University Of Southern California | Cyclotrisiloxanes, new siloxane polymers and their preparation |
| CN1378549A (en) * | 1999-10-12 | 2002-11-06 | 南加州大学 | Novel fluoroalkyl sabstituted cyclotrisiloxanes, their use for preparation of new polymers and novel polymers |
| KR100684549B1 (en) * | 1999-10-12 | 2007-02-20 | 유니버시티 오브 서던 캘리포니아 | Fluoroalkylsubstituted cyclotrisiloxanes, their use for preparation of new polymers and novel polymers |
| CN1456564A (en) * | 2003-05-28 | 2003-11-19 | 中国科学院上海有机化学研究所 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
| CN101111567A (en) * | 2005-02-24 | 2008-01-23 | 株式会社艾迪科 | Silicon-containing curable composition and its cured product |
| CN102701191A (en) * | 2012-06-06 | 2012-10-03 | 渤海大学 | Preparation method of fluorosilane surface finished grapheme for supercapacitor |
| WO2015069271A1 (en) * | 2013-11-08 | 2015-05-14 | Empire Technology Development Llc | Fluorinated siloxanes and methods for their preparation |
| CN104004191A (en) * | 2014-06-18 | 2014-08-27 | 山东大学 | Fluorosiloxane copolymer and preparing method thereof |
| CN105085567A (en) * | 2015-08-25 | 2015-11-25 | 浙江大学 | Multiple functional groups co-substituted cyclosiloxane, cyclosiloxane mixture, and preparation method and application of cyclosiloxane mixture |
| CN105837617A (en) * | 2016-04-20 | 2016-08-10 | 中国科学院上海有机化学研究所 | Preparation and application of trifluorovinyl-ether-containing cyclosiloxane capable of direct heat curing |
| CN106986890A (en) * | 2017-06-07 | 2017-07-28 | 威海新元化工有限公司 | A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 |
| CN107698617A (en) * | 2017-09-04 | 2018-02-16 | 北京航空航天大学 | Organosilicon polymer containing silica octatomic ring, its synthesis and application |
| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110156826B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2128164B1 (en) | Silicone compound, a process for the preparation thereof and a process for the preparation of an ophthalmic device therefrom | |
| CN104045831B (en) | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof | |
| TWI668272B (en) | A thermoplastic resin composion comprising silsesquioxane composite polymer | |
| CN104350088A (en) | Process for producing functional siloxanes of controlled structure | |
| CN104610549B (en) | A kind of modified fluoride-containing silicone oil and preparation method thereof | |
| EP0728793A1 (en) | Method for preparation of polyorganosiloxane resin, optionally alkoxylated, through non-hydrolytic condensation | |
| US7956125B2 (en) | (Thio)phenoxy phenyl silane compostion and method for making same | |
| KR20160014595A (en) | Phenyl-containing functional polysiloxanes and polycarbonate-polysiloxane copolymers made therefrom | |
| CN106674528B (en) | A kind of preparation method of Polycarbosilane | |
| JP5990909B2 (en) | One-end functional group-containing organopolysiloxane and method for producing the same | |
| CN108997582A (en) | A kind of preparation method of the single-ended polysiloxane fluid containing active hydrogen | |
| KR20010041184A (en) | Silyl and siloxyl substituted carborane compositions with unsaturated organic end groups | |
| KR20050047713A (en) | Siloxane monomers containing trifluorovinylether group, sol-gel hybrid polymers prepared by using the siloxane monomers | |
| CN102863465A (en) | Preparation method for methyl phenyl di-alkoxy silane | |
| CN108164707A (en) | A kind of novel fluorescence polysiloxane group ionic liquid and its application | |
| CN108586747A (en) | A kind of preparation method of middle high phenyl content methyl phenyl silicone oil | |
| CN107312175A (en) | A kind of preparation method of line style polyborosiloxane | |
| JP2002533324A5 (en) | ||
| CN110156826A (en) | Diphenyl cyclotrisiloxane and the preparation method and application thereof | |
| GB1581850A (en) | Thermoplastic polysiloxane elastomers filling containers | |
| CN101597303A (en) | The preparation method of Hexaethyl cyclotrisiloxane or triethyl trimethyl cyclotrisiloxane | |
| CN111072716A (en) | Preparation method of tetramethyl tetravinylcyclotetrasiloxane | |
| US8093345B2 (en) | Method of preparing a silicone resin | |
| JP2005517749A (en) | Aminomethylene functional siloxane | |
| TWI606055B (en) | Alternating phenylene and oxonane structural polymer and its precursor preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 264204 no.985 Fenghuangshan Road, Yangting industrial new area, Huancui District, Weihai City, Shandong Province Patentee after: Xinyuan chemical (Shandong) Co.,Ltd. Address before: 264204 no.985 Fenghuangshan Road, Yangting industrial new area, Huancui District, Weihai City, Shandong Province Patentee before: WEIHAI NEWERA CHEMICAL Co.,Ltd. |