CN101768273B - Method for preparing multifunctional or non-functional end group polyorganosiloxane by ring-opening polymerization of cyclosiloxane - Google Patents
Method for preparing multifunctional or non-functional end group polyorganosiloxane by ring-opening polymerization of cyclosiloxane Download PDFInfo
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- CN101768273B CN101768273B CN2010100289776A CN201010028977A CN101768273B CN 101768273 B CN101768273 B CN 101768273B CN 2010100289776 A CN2010100289776 A CN 2010100289776A CN 201010028977 A CN201010028977 A CN 201010028977A CN 101768273 B CN101768273 B CN 101768273B
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Abstract
The invention relates to a method for preparing multifunctional or non-functional end group polyorganosiloxane by ring-opening polymerization of cyclosiloxane, which is used for preparing the functional or non-functional end group polyorganosiloxane by taking heteropolyacid as a catalyst and using the ring-opening polymerization of a body or solution and belongs to the field of ring-opening polymerization of cations. The functional or non-functional end group polyorganosiloxane is prepared by adopting green and environment-friendly solid heteropolyacid as the catalyst, carrying out the ring-opening polymerization of the body or the solution of the cyclosiloxane and purifying a polymer. With the invention, the functional or non-functional end group polyorganosiloxane with different molecular weights can be obtained by controlling reaction conditions. Compared with the traditional ring-opening polymerization of the cations, the invention adopts solid acid with little consumption, not only cannot corrode equipment, but also cannot damage the environment; and in addition, the invention has low cost and convenient recovery of the catalyst.
Description
Technical field
The present invention relates to a kind of cyclosiloxane ring-opening polymerization and prepare method multi-functional or NOT-function end group ZGK 5.
Background technology
The anionic ring-opening polymerization of cyclosiloxane is the domestic method of industry and prepared in laboratory ZGK 5.Compare with anionic ring-opening polymerization, the research of positively charged ion ring-opening polymerization and application are less relatively, and some are contained the unsettled (as: SiH of functional group under the alkaline condition
2Cl ,-SiR
2COOH,
Deng) the cyclosiloxane ring-opening polymerization, the positively charged ion ring-opening polymerization particularly important that just seems.Need adopt the positively charged ion ring-opening polymerization in this case.Strong protonic acid (H is generally adopted in the ring-opening polymerization of cyclosiloxane positively charged ion
2SO
4, CF
3SO
3H etc.), Lewis acid (AlCl
3, FeCl
3, SnCl
4Deng) and superpower protonic acid etc. carry out ring-opening polymerization.Not only consumption is big owing to use liquid strong acid, and corrodibility is strong, and dangerous and contaminate environment and difficult defective such as is removed and limited its application.Or with acid-treated kaolin, polynite, zeolite and the ring-opening polymerization of spot holder soil catalysis cyclosiloxane; When polymer viscosity was big, catalyzer was difficult to separate and removes, and acidic white earth commonly used is made catalyzer in the industry; Aftertreatment ten minutes difficulty when molecular weight is big, same etching apparatus.
Heteropolyacid is a kind of solid acid stronger than common mineral acid, and cost is low.Water-soluble, non-corrosiveness, safety non-pollution are considered to a kind of new environmental protection catalyzer, have been widely used in organic synthesis.It is very few that heteropolyacid is used for cyclosiloxane ring-opening polymerization research, and mainly studied tetrahydrofuran ring opening polymerization reaction and existing the application.Find that it can not only improve transformation efficiency, and can control molecular weight preferably, and have high reactivity, particularly consumption is few, and reaction conditions is gentle, and non-corrosiveness is prone to advantages such as recovery.Do not see at present report and patent with the ring-opening polymerization of heteropoly acid catalysis cyclosiloxane.
Summary of the invention
The objective of the invention is to above-mentioned present situation, it is few to aim to provide a kind of solid acid consumption, etching apparatus neither, and non-environmental-pollution, and cost again is low, and catalyst recovery cyclosiloxane ring-opening polymerization easily prepares method multi-functional or NOT-function end group siloxanes.
The implementation of the object of the invention is that the cyclosiloxane ring-opening polymerization prepares method multi-functional or NOT-function end group ZGK 5, follows these steps to carry out:
(1) cyclosiloxane positively charged ion ring-opening polymerization,
Under nitrogen protection; The catalyzer of monomer mass 0.05% ~ 0.7% is joined in the cyclosiloxane monomer; Under 70 ~ 130 ℃, carry out body or solution ring-opening polymerization 0.5 ~ 5 hour, and made both-end hydroxyl ZGK 5 and required function or NOT-function end group ZGK 5.
The polymer ends hydroxyl adds the different functionalities end-capping reagent under these conditions, obtains the multi-function terminal radical siloxane.
Said siloxanyl monomers is octamethylcyclotetrasiloxane (D
4), hybrid ring siloxane (DMC), hydrogeneous cyclosiloxane or vinyl cyclosiloxane,
Said catalyzer is a phospho-wolframic acid, silicon dioxide carried phospho-wolframic acid, phospho-wolframic acid/acetate mixture etc.
Said end-capping reagent is a vinyl-dimethyl base chlorosilane, vinyl-dimethyl base silicol, vinyl-dimethyl methoxylsilane; Vinyl-dimethyl base oxethyl silane, phenyl dimethylchlorosilane, phenyl dimethyl-organoalkoxysilane; Trimethylchlorosilane or trimethylammonium organoalkoxysilane
2) purifying of polymkeric substance
Body ring-opening polymerization resulting polymers adds water, and amount of water is removed catalyzer for separating.
Solution ring-opening polymerization resulting polymers boils off solvent earlier, and underpressure distillation gets ZGK 5 again.
Through the control reaction conditions, adopt the present invention can obtain the function or the NOT-function end group ZGK 5 of different molecular weight.The present invention compares with traditional anionic ring-opening polymerization, adopts solid acid, and consumption is few, etching apparatus neither, and non-environmental-pollution, and cost again is low, and catalyst recovery is convenient.
Embodiment
It is catalysis that the present invention adopts the solid heteropoly acid of environmental protection, and cyclosiloxane is carried out body or solution ring-opening polymerization, and polymkeric substance is purified, prepares functional or NOT-function end group ZGK 5.
The silicon dioxide carried phospho-wolframic acid PWA/SiO of catalyzer
2The preparation method be: the 10g tetraethoxy, 5g propyl carbinol, 4g water, 3.5g phospho-wolframic acid drop in the three-necked bottle; 80 ℃ of refluxed 2h, teos hydrolysis generates vitreosol, and 80 ℃ of following water bath with thermostatic control 2h of colloidal sol get clear gel; The clear gel oven dry is ground, and gets product.
Through specific embodiment the present invention is detailed below:
Embodiment 1: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.03g phospho-wolframic acid (PWA), and isothermal reaction 1h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and it is M that GPC records polymericular weight
w=69073.
Embodiment 2: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA), and isothermal reaction 1h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and it is M that GPC records polymericular weight
w=378950.
Embodiment 3: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 70 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA), and isothermal reaction 1h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and it is M that GPC records polymericular weight
w=43151.
Embodiment 4: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA), and isothermal reaction 0.5h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and it is M that GPC records polymericular weight
w=120450.
Embodiment 5: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA), Si (CH
3)
3Cl, isothermal reaction 3.5h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and monomer conversion reaches 85.09%.
Embodiment 6: adopt sol-gel method to prepare H
3PW
12O
40/ SiO: with the 10g tetraethoxy, the 5g propyl carbinol, 4g water, 3.5g phospho-wolframic acid drop in the three-necked bottle, and 80 ℃ of refluxed 2h make teos hydrolysis generate vitreosol.Take out colloidal sol, 80 ℃ of following water bath with thermostatic control 2h obtain clear gel.With the clear gel oven dry, grind, obtain solid-carrying heteropolyacid silicon-dioxide.
With 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2Be heated to 120 ℃, constant temperature 30min adds the silicon dioxide carried phospho-wolframic acid PWA/SiO of 0.2g
2, isothermal reaction 12h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, obtains containing SiO2 particulate ZGK 5, and monomer conversion is 45.34%.
Embodiment 7: with 30g octamethylcyclotetrasiloxane (D
4) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA) and 0.375g acetate, and isothermal reaction 4h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer.Monomer conversion reaches 83.91%.
Embodiment 8: 30g hybrid ring siloxane (DMC) is added be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA), and isothermal reaction 1h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer, and it is M that GPC records polymericular weight
w=286920.
Embodiment 9: with 30g eight vinyl cyclotetrasiloxane (D
4 V1) add and be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA) and 0.375g acetate, and isothermal reaction 4h takes out product, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation removes and anhydrates and unreacted monomer.
Embodiment 10: with 30g octamethylcyclotetrasiloxane (D
4) and 20ml toluene add and to be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA) and 0.375g acetate, and isothermal reaction 4h takes out product after steaming solvent, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation is except that anhydrating and unreacted monomer.Monomer conversion reaches 86.91%.
Embodiment 11: proportioning raw materials, and solvent and catalyst treatment are with example 10, and solvent is a 30ml toluene, and temperature is 60 ℃, and monomer conversion reaches 87.53%.
Embodiment 12: proportioning raw materials, and solvent and catalyst treatment are with example 10, and solvent is the 20ml normal hexane, and temperature is 60 ℃, and monomer conversion reaches 87.71%.
Embodiment 13: proportioning raw materials, and solvent and catalyst treatment are with example 10, and solvent is the 30ml normal hexane, and temperature is 60 ℃, and monomer conversion reaches 88.63%.
Embodiment 14: proportioning raw materials, and solvent and catalyst treatment are with example 10, and solvent is the 20ml hexanaphthene, and temperature is 60 ℃, and monomer conversion reaches 85.5%.
Embodiment 15: proportioning raw materials, and solvent and catalyst treatment are with example 10, and solvent is the 30ml hexanaphthene, and temperature is 60 ℃, and monomer conversion reaches 86.4%.
Embodiment 16: with 30g tetramethyl-tetrahydrochysene cyclotetrasiloxane (D
H 4) and 20ml toluene add and to be equipped with in the four-hole bottle of prolong, TM, whisking appliance, feed N
2, being heated to 100 ℃, constant temperature 30min adds 0.075g phospho-wolframic acid (PWA) and 0.375g acetate, and isothermal reaction 4h takes out product after steaming solvent, pours separating funnel into, and supernatant liquid is got in washing after the layering, and underpressure distillation is except that anhydrating and unreacted monomer.Monomer conversion reaches 87.2%.
Claims (2)
1. the cyclosiloxane ring-opening polymerization prepares method multi-functional or NOT-function end group ZGK 5, it is characterized in that following these steps to carrying out:
(1) cyclosiloxane positively charged ion ring-opening polymerization,
Under nitrogen protection; The catalyzer of monomer mass 0.05%～0.7% is joined in the cyclosiloxane monomer; Under 70～130 ℃, carry out body or solution ring-opening polymerization 0.5～5 hour, and made both-end hydroxyl ZGK 5 and required function or NOT-function end group ZGK 5
The polymer ends hydroxyl adds the different functionalities end-capping reagent under these conditions, obtains function end group ZGK 5, or adds a certain amount of non-functional end-capping reagent, obtains NOT-function end group ZGK 5,
The add-on of end-capping reagent by formula
Calculate,
In the formula: X=0.25～2;
m
1: the ZGK 5 quality;
m
2: the quality that should add end-capping reagent;
Said end-capping reagent is vinyl-dimethyl base chlorosilane, vinyl-dimethyl base silicol, vinyl-dimethyl methoxylsilane, trimethylchlorosilane or trimethylammonium organoalkoxysilane,
Said cyclosiloxane monomer is an octamethylcyclotetrasiloxane, hybrid ring siloxane, and hydrogeneous cyclosiloxane or vinyl cyclosiloxane,
Said catalyzer is a phospho-wolframic acid, silicon dioxide carried phospho-wolframic acid, and phospho-wolframic acid/acetate mixture,
The solvent that carries out the solution ring-opening polymerization is toluene, normal hexane or hexanaphthene,
2) purifying of polymkeric substance
Body ring-opening polymerization resulting polymers adds water, and amount of water is removed catalyzer for separating,
Solution ring-opening polymerization resulting polymers boils off solvent earlier, and underpressure distillation gets ZGK 5 again.
2. cyclosiloxane ring-opening polymerization according to claim 1 prepares method multi-functional or NOT-function end group ZGK 5, it is characterized in that silicon dioxide carried phospho-wolframic acid PWA/SiO
2The preparation method be: the 10g tetraethoxy, 5g propyl carbinol, 4g water, 3.5g phospho-wolframic acid drop in the three-necked bottle; 80 ℃ of refluxed 2h, teos hydrolysis generates vitreosol, and 80 ℃ of following water bath with thermostatic control 2h of colloidal sol get clear gel; The clear gel oven dry is ground, and gets product.
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|---|---|---|---|
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| CN102952270B (en) * | 2011-08-29 | 2015-03-25 | 比亚迪股份有限公司 | Polysiloxane polymer and preparation method thereof, as well as single-component dealcoholized silicon rubber and preparation method thereof |
| CN102442660B (en) * | 2011-10-14 | 2013-08-28 | 苏州大学 | Surface modified carbon nanotube and preparation method thereof |
| CN105885050A (en) * | 2016-06-06 | 2016-08-24 | 湖北新海鸿化工有限公司 | Method for preparing greenhouse vulcanized methyl silicone rubber |
| CN110527098A (en) * | 2019-09-27 | 2019-12-03 | 东莞市贝特利新材料有限公司 | The post-processing approach and polysiloxanes of polysiloxanes synthesis |
| CN110938207B (en) * | 2019-12-10 | 2022-02-22 | 烟台开发区金宏化工有限公司 | Preparation method of hydrogen-containing silicone oil |
| CN112250867A (en) * | 2020-10-28 | 2021-01-22 | 湖北新海鸿化工有限公司 | Preparation method of methyl silicone oil |
| CN112679736B (en) * | 2020-12-28 | 2022-04-19 | 江苏美思德化学股份有限公司 | Phenyl hydrogen-containing silicone oil and preparation method thereof |
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