CN109705333A - A kind of synthetic method of high molecular weight diallyl polyether - Google Patents
A kind of synthetic method of high molecular weight diallyl polyether Download PDFInfo
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- CN109705333A CN109705333A CN201910018894.XA CN201910018894A CN109705333A CN 109705333 A CN109705333 A CN 109705333A CN 201910018894 A CN201910018894 A CN 201910018894A CN 109705333 A CN109705333 A CN 109705333A
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Abstract
The preparation method of high molecular weight diallyl polyether provided by the invention, method provided by the invention is by obtaining macromolecule diallyl polyether for the diallyl polyether of formula (I) structure, chain extender and catalyst hybrid reaction；Wherein, by selecting the chain extender for one or more of tetramethyldihydrogendisiloxane, dimethyl diphenyl dihydro disiloxane, tetraphenyl dihydro disiloxane, (trifluoro propyl) the dihydro disiloxane of dimethyl two and dimethyl two (cyanogen propyl) dihydro disiloxane；So that method provided by the invention is easy to operate, pollution-free, it is at low cost, and the molecular weight of obtained diallyl polyether is 6000~20000, solve during traditional Williamson reaction preparation high molecular weight diallyl polyether that technique is cumbersome, post-processing is complicated, or the problem toxic etc. using dihalo- ethane chain extension raw material.
Description
Technical field
The present invention relates to technical field of macromolecules more particularly to a kind of synthetic methods of high molecular weight diallyl polyether.
Background technique
Polyethers is the important source material of a variety of chemical products, is addition when its end position is the allyl with greater activity
The ideal crosslinking agent of reaction can be used for synthesizing the organic silicon modified by polyether of Si-C key connection, be widely used in medicine, it is biochemical,
The industries such as papermaking, organosilicon new material.High molecular weight diallyl end capped polyether (Mn >=6000) can be with silane containing hydrogen simultaneously
Carry out addition reaction synthesizing silane modified polyether, be the base polymer of MS glue, be used for building sealant, excellent combination property,
With incomparable vast potential for future development.
Country's diallyl end capped polyether is usually using double hydroxy polyethers or allyl alcohol polyether as raw material, in sodium, hydrogen at present
Under the existence condition of the base metal catalysts such as sodium oxide molybdena or sodium methoxide, be added the halogenated end-capping reagent such as allyl chloride or allyl bromide, bromoallylene into
Row Williamson reaction is prepared, and during using Williamson reaction synthesis diallyl polyether, carries out alcohol
Salinization can generate water or methanol when reacting, and carry out having salt generation when allylation.When pfpe molecule amount increases, system
Viscosity increases, and the salt that when allylation generates further increases system viscosity, so that the water or methanol that generate are difficult to from body
Deviate from system, so that balanced reaction is difficult to mobile to high conversion, combined coefficient is low, while refining post-processing and also become to be stranded very much
Difficulty usually can only obtain one so that traditional Williamson reaction is difficult that the diallyl end capped polyether of high molecular weight is made
The polyethers of the diallyl sealing end of a little low molecular weights.
For this purpose, researchers change the method for preparing diallyl end capped polyether by Williamson reaction
Into；As: organic solvent is added using the azeotropic of organic solvent and water in CN200910057240.4 in alcohol salinization reaction process
Mode is gone out the water generated, is kept balanced reaction mobile to high conversion, is improved ending ratio, but needs to post-process work using solvent
Skill is more cumbersome；For another example CN201510455669.4 uses allyl alcohol polyether for raw material, alkoxidation reagent reaction is added, by adding
Enter methylene halide or dihalo- ethane chain extension preparation high molecular weight allyl capped polyethers, but the methylene halide or dihalo- second used
Alkane dosage is big, and toxicity is high.For another example CN201510977046.3 uses chloro polyethers for raw material, and it is molten that dihydroxy compounds heating is added
The diallyl end capped polyether that alkali reaction obtains 4000~13000 molecular weight is added in Xie Hou in three batches, but there is also alkali for the method
Salt by-product.As it can be seen that presently disclosed method is still difficult to realize the diallyl end capped polyether of high molecular weight in industrialization
Preparation.
Therefore it provides a kind of easy to operate, pollution-free, method of the diallyl polyether of preparation high molecular weight at low cost
It is of great significance.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in the diallyl polyethers for providing a kind of high molecular weight
Synthetic method, this method is easy to operate, diallyl end capped polyether that is pollution-free and can obtaining high molecular weight.
The present invention provides a kind of synthetic methods of macromolecule diallyl polyether, comprising:
By the diallyl polyether of formula (I) structure, chain extender and catalyst hybrid reaction, it is poly- to obtain macromolecule diallyl
Ether；
The chain extender is tetramethyldihydrogendisiloxane, dimethyl diphenyl dihydro disiloxane, tetraphenyl dihydro two
One of siloxanes, (trifluoro propyl) the dihydro disiloxane of dimethyl two and dimethyl two (cyanogen propyl) dihydro disiloxane or
It is several；
Wherein, the A is CH2CH(CH3)O；A is 10~70.
Preferably, the number-average molecular weight of the diallyl polyether of formula (I) structure is 600~5000.
Preferably, the pH of the diallyl polyether of formula (I) structure is 5~7.
Preferably, in the diallyl polyether of formula (I) structure ending ratio of allyl 90% or more.
Preferably, the diallyl polyether of formula (I) structure and the molar ratio of chain extender are (1~2): 1.
Preferably, the catalyst is the catalyst of platinum group metal.
Preferably, the catalyst of the platinum group metal is complex compound, the chlorine of chloroplatinic acid and unsaturated organosilicon compounds
One or more of platinic acid and platinum black.
Preferably, mass fraction of the dosage of the catalyst in terms of pt atom in the reaction system be calculated as 10~
100ppm。
Preferably, the temperature of the hybrid reaction is 50~90 DEG C.
Compared with prior art, the preparation method of high molecular weight diallyl polyether provided by the invention is by by formula (I)
Diallyl polyether, chain extender and the catalyst hybrid reaction of structure, obtain macromolecule diallyl polyether；Wherein, pass through choosing
Select the chain extender be tetramethyldihydrogendisiloxane, dimethyl diphenyl dihydro disiloxane, tetraphenyl dihydro disiloxane,
One or more of (trifluoro propyl) the dihydro disiloxane of dimethyl two and dimethyl two (cyanogen propyl) dihydro disiloxane；Make
Method provided by the invention is easy to operate, pollution-free, it is at low cost, and the molecular weight of obtained diallyl polyether 6000~
20000, solve during traditional Williamson reaction preparation high molecular weight diallyl polyether that technique is cumbersome, post-processing is multiple
Miscellaneous or toxic etc. using dihalo- ethane chain extension raw material problem.
Specific embodiment
The present invention provides a kind of synthetic methods of macromolecule diallyl polyether, comprising:
By the diallyl polyether of formula (I) structure, chain extender and catalyst hybrid reaction, it is poly- to obtain macromolecule diallyl
Ether；
The chain extender is tetramethyldihydrogendisiloxane, dimethyl diphenyl dihydro disiloxane, tetraphenyl dihydro two
One of siloxanes, (trifluoro propyl) the dihydro disiloxane of dimethyl two and dimethyl two (cyanogen propyl) dihydro disiloxane or
It is several；
Wherein, the A is CH2CH(CH3)O；A is 10~70.
According to the present invention, the present invention mixes the diallyl polyether of formula (I) structure, chain extender and catalyst, obtains height
Molecule diallyl polyether；Wherein, the number-average molecular weight of the diallyl polyether of formula (I) structure is 600~5000, more excellent
It is selected as 2000~5000；The pH of the diallyl polyether of formula (I) structure is preferably 5~7；The diene of formula (I) structure
The ending ratio of allyl is preferably 90% or more in propyl polyethers；The catalyst is preferably the catalyst of platinum group metal, more
Preferably one or more of the complex compound of chloroplatinic acid, chloroplatinic acid and unsaturated organosilicon compounds and platinum black, most preferably
The aqueous isopropanol of chloroplatinic acid.
In the present invention, the diallyl polyether of formula (I) structure and the molar ratio of chain extender are (1~2): 1；It is described to urge
Mass fraction of the dosage of agent in terms of pt atom in the reaction system is preferably 10~100ppm, more preferable 20~80ppm, most
Preferably 30~50ppm.
In the present invention, the present invention does not have particular/special requirement to the mixed method of hybrid reaction, and those skilled in the art can root
Suitable hybrid mode is selected according to actual conditions, the temperature of the hybrid reaction is preferably 50~90 DEG C, more preferably 70~90
℃；The time of the reaction is preferably 1~12 hour, and more preferably 2~6 hours.
The present invention, shown in the structure such as formula (II) for the macromolecule diallyl polyether that the present invention obtains, number-average molecular weight
It is 6000~20000.
Wherein, A CH2CH(CH3) O, a is 10~70；
R1、R2、R3And R4It is independent to be selected from methyl, phenyl, cyanogen propyl or trifluoro propyl.
The preparation method of high molecular weight diallyl polyether provided by the invention passes through the diallyl of formula (I) structure is poly-
Ether, chain extender and catalyst hybrid reaction, obtain macromolecule diallyl polyether；It wherein, is four by selecting the chain extender
Methyl dihydro disiloxane, dimethyl diphenyl dihydro disiloxane, tetraphenyl dihydro disiloxane, two (trifluoropropyl of dimethyl
Base) one or more of dihydro disiloxane and dimethyl two (cyanogen propyl) dihydro disiloxane；So that provided by the invention
Method is easy to operate, pollution-free, at low cost, solves traditional Williamson reaction preparation high molecular weight diallyl polyether mistake
Technique is cumbersome in journey, post-processing is complicated, or the problem toxic etc. using dihalo- ethane chain extension raw material.And obtained diallyl is poly-
The number-average molecular weight of ether can be used as the base polymer of synthesis MS glue 6000~20000, for building, the neck such as automobile, photovoltaic
Domain also can be used as crosslinking agent synthesis hydrophilic silicone elastomer gels.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
In the reaction vessel be added 100g diallyl end capped polyether (Mn=2454, ending ratio 96%, pH value 6) and
3.9g tetramethyldihydrogendisiloxane be stirred it is uniformly mixed, after being warming up to 80 DEG C, by concentration be 5000ppm (with containing for platinum
Amount calculate) chloroplatinic acid catalyst 0.5g into above-mentioned solution, after chain extending reaction 3h, obtain high molecular weight diallyl polyether.
Obtained high molecular weight diallyl polyether is detected, from infrared data as can be seen that in the product obtained
Without 2150cm-1The infrared peak of Si-H, there are 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is
Viscosity is 5600cp at 7630,25 DEG C.
Embodiment 2
In the reaction vessel be added 500g diallyl end capped polyether (Mn=4957, ending ratio 93%, pH value 5) and
20g tetraphenyl dihydro disiloxane be stirred it is uniformly mixed, after being warming up to 90 DEG C, by concentration be 8000ppm (with the content of platinum
Calculate) chloroplatinic acid catalyst 2g be added dropwise in above-mentioned solution, after chain extending reaction 5h, obtain high molecular weight diallyl polyether.
Obtained high molecular weight diallyl polyether is detected, from infrared data as can be seen that in the product obtained
Without 2150cm-1The infrared peak of Si-H, there are 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is
Viscosity is 12300cp at 10048,25 DEG C.
Embodiment 3
In the reaction vessel be added 200g diallyl end capped polyether (Mn=3868, ending ratio 93%, pH value 5) and
11.5g dimethyl two (trifluoro propyl) dihydro disiloxane is stirred uniformly mixed, after being warming up to 80 DEG C, is by concentration
The chloroplatinic acid catalyst 1.3g of 5000ppm (being calculated with the content of platinum) is added dropwise in above-mentioned solution, after chain extending reaction 6h, obtains height
Molecular weight diallyl polyether.
Obtained high molecular weight diallyl polyether is detected, from infrared data as can be seen that in the product obtained
Without 2150cm-1The infrared peak of Si-H, there are 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is
Viscosity is 14000cp at 11872,25 DEG C.
Embodiment 4
In the reaction vessel be added 250g diallyl end capped polyether (Mn=4957, ending ratio 93%, pH value 5) and
8.4g dimethyl two (cyanogen propyl) dihydro disiloxane be stirred it is uniformly mixed, after being warming up to 70 DEG C, by concentration be 8000ppm
The chloroplatinic acid catalyst 2.6g of (being calculated with the content of platinum) is added dropwise in above-mentioned solution, after chain extending reaction 6h, obtains high molecular weight
Diallyl polyether.
Obtained high molecular weight diallyl polyether is detected, from infrared data as can be seen that in the product obtained
Without 2150cm-1The infrared peak of Si-H, there are 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is
Viscosity is 21000cp at 15090,25 DEG C.
Embodiment 5
In the reaction vessel be added 300g diallyl end capped polyether (Mn=2454, ending ratio 96%, pH value 6) and
24g dimethyl diphenyl dihydro disiloxane be stirred it is uniformly mixed, after being warming up to 70 DEG C, by concentration be 3500ppm (with platinum
Content calculate) chloroplatinic acid catalyst 1.9g be added dropwise in above-mentioned solution, after chain extending reaction 6h, obtain high molecular weight diene third
Base polyethers.
Obtained high molecular weight diallyl polyether is detected, from infrared data as can be seen that in the product obtained
Without 2150cm-1The infrared peak of Si-H, there are 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is
Viscosity is 13200cp at 10590,25 DEG C.
Comparative example 1
In the reaction vessel be added 200g diallyl end capped polyether (Mn=4957, ending ratio 93%, pH value 5) and
6.5g dimethyl two (trifluoro propyl) dihydro disiloxane is stirred uniformly mixed, after being warming up to 40 DEG C, is by concentration
The chloroplatinic acid catalyst 0.2g of 3500ppm (being calculated with the content of platinum) is added dropwise in above-mentioned solution, after chain extending reaction 6h, is produced
Object.
Obtained product is detected, from infrared data as can be seen that through analyzing: in the product of acquisition there is also
2150cm-1The infrared peak of Si-H, 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is at 5240,25 DEG C
Viscosity is 2400cp (temperature and catalytic amount are too low, do not react).
Comparative example 2
In the reaction vessel be added 300g diallyl end capped polyether (Mn=2454, ending ratio 96%, pH value 6) and
The hydrogeneous dimethyl silicone polymer in the end 165g (H wt%=0.2) is stirred uniformly mixed, after being warming up to 50 DEG C, is by concentration
The chloroplatinic acid catalyst 1.3g of 3500ppm (being calculated with the content of platinum) is added dropwise in above-mentioned solution, after chain extending reaction 2h, is produced
Object.
Obtained product is detected, from infrared data as can be seen that through analyzing: in the product of acquisition there is also
2150cm-1The infrared peak of Si-H, 3077cm-1Neighbouring C=C feature peak position, GPC show that number-average molecular weight is at 2050,25 DEG C
Viscosity is 600cp.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (9)
1. a kind of synthetic method of macromolecule diallyl polyether, comprising:
By the diallyl polyether of formula (I) structure, chain extender and catalyst hybrid reaction, macromolecule diallyl polyether is obtained；
The chain extender is tetramethyldihydrogendisiloxane, dimethyl diphenyl dihydro disiloxane, two silicon oxygen of tetraphenyl dihydro
One of alkane, (trifluoro propyl) the dihydro disiloxane of dimethyl two and dimethyl two (cyanogen propyl) dihydro disiloxane are several
Kind；
Wherein, the A is CH2CH(CH3)O；A is 10~70.
2. synthetic method according to claim 1, which is characterized in that the number of the diallyl polyether of formula (I) structure
Average molecular weight is 600~5000.
3. synthetic method according to claim 1, which is characterized in that the pH of the diallyl polyether of formula (I) structure
It is 5~7.
4. synthetic method according to claim 1, which is characterized in that alkene in the diallyl polyether of formula (I) structure
The ending ratio of propyl is 90% or more.
5. synthetic method according to claim 1, which is characterized in that the diallyl polyether and expansion of formula (I) structure
The molar ratio of chain agent is (1~2): 1.
6. synthetic method according to claim 1, which is characterized in that the catalyst is the catalyst of platinum group metal.
7. synthetic method according to claim 6, which is characterized in that the catalyst of the platinum group metal be chloroplatinic acid with
One or more of complex compound, chloroplatinic acid and platinum black of unsaturated organosilicon compounds.
8. synthetic method according to claim 6, which is characterized in that the dosage of the catalyst is being reacted in terms of pt atom
Mass fraction in system is calculated as 10~100ppm.
9. synthetic method according to claim 1, which is characterized in that the temperature of the hybrid reaction is 50~90 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080221276A1 (en) * | 2006-09-01 | 2008-09-11 | Goldschmidt Gmbh | Silicone-containing graft copolymers of blockwise structure |
| CN101686901A (en) * | 2007-06-29 | 2010-03-31 | 陶氏康宁公司 | Silicone-organic gels with polyalkyloxylene crosslinked silicone elastomers |
| CN107987790A (en) * | 2017-12-11 | 2018-05-04 | 浙江工业大学 | A kind of silicone polyether base rubber of low viscosity and preparation method thereof |
-
2019
- 2019-01-09 CN CN201910018894.XA patent/CN109705333A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080221276A1 (en) * | 2006-09-01 | 2008-09-11 | Goldschmidt Gmbh | Silicone-containing graft copolymers of blockwise structure |
| CN101686901A (en) * | 2007-06-29 | 2010-03-31 | 陶氏康宁公司 | Silicone-organic gels with polyalkyloxylene crosslinked silicone elastomers |
| CN107987790A (en) * | 2017-12-11 | 2018-05-04 | 浙江工业大学 | A kind of silicone polyether base rubber of low viscosity and preparation method thereof |
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Application publication date: 20190503 |