CN103432961A - Acetylene bond-containing polyether modified polysiloxane surfactant and synthetic method thereof - Google Patents
Acetylene bond-containing polyether modified polysiloxane surfactant and synthetic method thereof Download PDFInfo
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- CN103432961A CN103432961A CN2013101060359A CN201310106035A CN103432961A CN 103432961 A CN103432961 A CN 103432961A CN 2013101060359 A CN2013101060359 A CN 2013101060359A CN 201310106035 A CN201310106035 A CN 201310106035A CN 103432961 A CN103432961 A CN 103432961A
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- oxyalkylene copolymers
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Abstract
The invention relates to an acetylene bond-containing polyether modified polysiloxane surfactant and a synthetic method thereof. The synthetic method comprises the following steps of adding a catalyst in an acetylene bond-containing polyether; activating for 0-3 h at a temperature of 80-140 DEG C; dropwise adding hydrogen-containing polysiloxane; reacting for 6-20 h; and filtering to obtain transparent liquid with a color ranging from light yellow to red brown. The transparent liquid is the acetylene bond-containing polyether modified polysiloxane surfactant. The polyether modified polysiloxane surfactant is prepared by a direct hydrosilylation method without solvent by using the acetylene bond-containing polyether and the hydrogen-containing polysiloxane. The method is simple in process, and can be easily industrialized. No solvent is used in the reaction process; and the purity of a product is high, without crosslinked polymer by-products.
Description
Technical field
The present invention relates to a kind of organic silicon surfactant and synthetic method thereof, relate in particular to a kind of acetylene bond polyether-modified polyoxy alkane surfactant and synthetic method thereof of containing, belong to the synthesis technical field of silicon-containing surfactant in fine chemistry industry.
Background technology
Organic silicon surfactant is given its unique performance because of its unique molecular structure, as can be, significantly by the near about 21mN/m of surface tension, had excellent wettability etc.These unique performances make it be widely used in the numerous areas such as polyurethane foam products, weaving, paint and coating, cosmetics and agricultural chemicals.At present, the maximum organic silicon surfactant of industrial application is Siloxane-Oxyalkylene Copolymers surfactant (polyether modified silicon oil).
The Siloxane-Oxyalkylene Copolymers surfactant is generally by allyl polyether and hydrogen containing siloxane, by the addition of silicon hydrogen, make, but present production technology has weak point: almost invariably the Si-H key is crosslinked, makes hydraulic performance decline, and accessory substance hydrogen makes equipment produce hydrogen embrittlement.In order to prevent the crosslinked of Si-H key, often adopt following two kinds of methods in industrialized production, 1., before hydrosilation, first the hydroxyl in unsaturated polyether is carried out to end-blocking, make like this course of reaction tediously long, product cost increases; 2. add a large amount of benzene kind solvents in reaction, these solvents are all inflammable explosive articles, dangerous high, and contaminated environment.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of containing acetylene bond polyether-modified polyoxy alkane surfactant and synthetic method thereof for the deficiencies in the prior art, adopt the polyethers and the hydrogen containing siloxane that contain acetylene bond solvent-free, directly silicon hydrogen addition process prepares the Siloxane-Oxyalkylene Copolymers surfactant.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant that contains, it is characterized in that, and the described structural formula containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant is as follows:
Wherein, R
1for H, CH
2oH, CH
2oCH
2cH
2oH or CH
2o (CH
2cH
2o)
2h, R
2for H or OCH
3, x is that 1～10, y is that 0～10, m is that 1～20, n is 1～25.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the described aqueous solution that is 0.5% containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant preparation percetage by weight, the surface tension of the described aqueous solution is 20.0～22.0mN/m, the minimal contact angle of the described aqueous solution on paraffin is 0～15 °.
The beneficial effect that adopts above-mentioned further scheme is that surface-active of the present invention is good, the surface tension that its percetage by weight is 0.5% aqueous solution is 20.0～22.0mN/m, be less than like product, spreading property of the present invention is good simultaneously, minimal contact angle on its aqueous solution paraffin is 0～15 °, can be used as the agricultural chemicals wetting aid to promote agricultural chemicals sprawling on plant leaf surface, improve drug effect.
Another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of synthetic method containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant comprises the following steps:
(1) add catalyst in the acetylene bond polyethers, activated 0～3h;
(2) drip hydrogen containing siloxane again, reacted 6～20h, filtration obtains light yellow to the rufous transparency liquid, is containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant.
It is solvent-free that the beneficial effect that adopts such scheme is that the present invention adopts containing polyethers and the hydrogen containing siloxane of acetylene bond, directly silicon hydrogen addition process prepares the Siloxane-Oxyalkylene Copolymers surfactant, the method technique is simple, be easy to industrialization, do not use solvent in course of reaction, product purity is high, without the cross-linked polymer accessory substance.
Further, the chemical structural formula of described acetylene bond polyethers is:
R wherein
1for H, CH
2oH, CH
2oCH
2cH
2oH or CH
2o (CH
2cH
2o)
2h, R
2for H or OCH
3, x is that 1～10, y is 0～10.
Further, the chemical structural formula of described hydrogen containing siloxane is:
Wherein m is that 1～20, n is 1～25.
Further, the mol ratio of described acetylene bond polyethers and hydrogen containing siloxane addition is 1～10:1.
Further, 1～100ppm that the consumption of described catalyst is acetylene bond polyethers and hydrogen containing siloxane mole sum.
Further, described catalyst is transition-metal catalyst.
Further, described catalyst is one or more the mixture in chloroplatinic acid, radium chloride or palladium bichloride.
Further, described activation and the temperature that reacts are 80～140 ℃.
Adopt the beneficial effect of above-mentioned further scheme for adopting the product prepared under above condition, lighter color, the reaction time is short, and the product serviceability is good.
The specific embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Add propargyl alcohol polyethers 14.5kg and 1.8g chloroplatinic acid catalyst in reactor, slowly be warming up to 80 ℃ of direct activations, the hydrogen containing siloxane that adds again 22.3kg, control temperature at 80～100 ℃, react after 10 hours, reaction mixture becomes after clear, continues the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 20.2mN/m, and the contact angle on paraffin is 5 °.
Embodiment 2
In reactor, add butynediols monosubstituted ethoxy ether 13.5kg and 1.5g chloroplatinic acid catalyst, slowly be warming up to 100 ℃ of activation 1 hour, the hydrogen containing siloxane that adds again 18.6kg, control temperature at 100～120 ℃, after reacting 15 hours, reaction mixture becomes after clear, continue the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 20.0mN/m, and the contact angle on paraffin is 0 °.
Embodiment 3
In reactor, add butynediols diethoxy ether 19.1kg and 1.4g radium chloride catalyst, slowly be warming up to 120 ℃ of activation 2 hours, the hydrogen containing siloxane that adds again 25.7kg, control temperature at 120～140 ℃, after reacting 6 hours, reaction mixture becomes after clear, continue the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 21.5mN/m, and the contact angle on paraffin is 10 °.
Embodiment 4
In reactor, add allyl alcohol polyether end-blocking 17.4kg and 1.1g radium chloride catalyst, slowly be warming up to 90 ℃ of activation 3 hours, the hydrogen containing siloxane that adds again 22.3kg, control temperature at 90～110 ℃, after reacting 20 hours, reaction mixture becomes after clear, continue the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 20.8mN/m, and the contact angle on paraffin is 5 °.
Embodiment 5
In reactor, add allyl alcohol polyether end-blocking 14.5kg and 0.8g palladium chloride catalyst, slowly be warming up to 110 ℃ of activation 1.5 hours, splash into again the hydrogen containing siloxane of 31.5kg, control temperature at 110～130 ℃, after reacting 18 hours, reaction mixture becomes after clear, continue the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 21.0mN/m, and the contact angle on paraffin is 8 °.
Embodiment 6
In reactor, add a certain amount of butynediols monosubstituted ethoxy ether 19.5kg and 1.0g palladium chloride catalyst, slowly be warming up to 140 ℃ of activation 2.5 hours, the hydrogen containing siloxane that adds again 42.8kg, control temperature at 120～140 ℃, after reacting 12 hours, reaction mixture becomes after clear, continue the insulation certain hour, then cooling discharge, filter to obtain product.The lowest surface tension that records its 0.5% aqueous solution by surface tension instrument is 20.2mN/m, and the contact angle on paraffin is 5 °.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. one kind contains acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, the described structural formula containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant is as follows:
Wherein, R
1for H, CH
2oH, CH
2oCH
2cH
2oH or CH
2o (CH
2cH
2o)
2h, R
2for H or OCH
3, x is that 1～10, y is that 0～10, m is that 1～20, n is 1～25.
2. according to claim 1 containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, the described aqueous solution that is 0.5% containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant preparation percetage by weight, the surface tension of the described aqueous solution is 20.0～22.0mN/m, and the minimal contact angle of the described aqueous solution on paraffin is 0～15 °.
3. the synthetic method containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, is characterized in that, comprises the following steps:
(1) add catalyst in the acetylene bond polyethers, activated 0～3h;
(2) drip hydrogen containing siloxane again, reacted 6～20h, filtration obtains light yellow to the rufous transparency liquid, is containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant.
4. according to claim 3 containing the synthetic method of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, the chemical structural formula of described acetylene bond polyethers is:
R wherein
1for H, CH
2oH, CH
2oCH
2cH
2oH or CH
2o (CH
2cH
2o)
2h, R
2for H or OCH
3, x is that 1～10, y is 0～10.
5. according to claim 3 containing the synthetic method of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, the chemical structural formula of described hydrogen containing siloxane is:
Wherein m is that 1～20, n is 1～25.
6. according to the described synthetic method containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant of claim 3 to 5 any one, it is characterized in that, the mol ratio of described acetylene bond polyethers and hydrogen containing siloxane addition is 1～10:1.
7. according to claim 3 containing the synthetic method of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that 1～100ppm that the consumption of described catalyst is acetylene bond polyethers and hydrogen containing siloxane mole sum.
8. according to the described synthetic method containing acetylene bond Siloxane-Oxyalkylene Copolymers surfactant of claim 3 or 7, it is characterized in that, described catalyst is transition-metal catalyst.
9. according to claim 8 containing the synthetic method of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, described catalyst is one or more the mixture in chloroplatinic acid, radium chloride or palladium bichloride.
10. according to claim 3 containing the synthetic method of acetylene bond Siloxane-Oxyalkylene Copolymers surfactant, it is characterized in that, described activation and the temperature reacted are 80～140 ℃.
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Cited By (4)
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| CN112280046A (en) * | 2020-11-13 | 2021-01-29 | 杭州崇耀科技发展有限公司 | Preparation method of alkyne bond-containing polyether modified organic silicon |
| CN112280029A (en) * | 2020-10-26 | 2021-01-29 | 上海麦豪新材料科技有限公司 | Preparation method of alkynyl polyether |
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| CN114106854A (en) * | 2021-11-26 | 2022-03-01 | 江苏钟山新材料有限公司 | Modified organic silicon surfactant and application thereof |
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