CN106492515A - Modified organic silicon defoamer of a kind of MQ silicone grafts containing hydrogen silicone oil and preparation method thereof - Google Patents
Modified organic silicon defoamer of a kind of MQ silicone grafts containing hydrogen silicone oil and preparation method thereof Download PDFInfo
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- CN106492515A CN106492515A CN201610903979.2A CN201610903979A CN106492515A CN 106492515 A CN106492515 A CN 106492515A CN 201610903979 A CN201610903979 A CN 201610903979A CN 106492515 A CN106492515 A CN 106492515A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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Abstract
The present invention discloses a kind of modified organic silicon defoamer of MQ silicone grafts containing hydrogen silicone oil, is made up of the raw material of following weight portion：22 38 parts of polysiloxanes, 12 20 parts of hyperbranched polyether, 15 24 parts of allyl glycidyl ether, 35 58 parts of expoxy propane, 0.2 0.5 parts of bimetallic cyaniding complex, 50 65 parts of isopropanol, 0.4 0.9 parts of chloroplatinic acid catalyst, 26 parts of superfine alumina silicate, 12 parts of D-sorbite, 0.8 1 parts of polysorbate60,13 parts of sodium carboxymethylcellulose, appropriate deionized water, 25 parts of MQ silicones, 27 parts of containing hydrogen silicone oil.The present invention contains the hyperbranched polyether of great amount of hydroxy group as raw material with end, prepare end-allyl group hyperbranched polyether, there is hydrosilylation using the double bond structure and polysiloxanes of modified hyperbranched polyether end group, synthesis of super branched Siloxane-Oxyalkylene Copolymers, the defoamer in order to prepare have excellent anti-shear performance.
Description
Technical field
The present invention relates to chemicals field, the modified organosilicon of more particularly to a kind of MQ silicone grafts containing hydrogen silicone oil disappears
Infusion and preparation method thereof.
Technical background
Defoamer, is also called defrother or foamicide, can produce many bubbles for affecting production during industrial production
Foam, needs to add defoamer.It is widely used in removing latex, textile sizing, food fermentation, biological medicine, coating, oil
The unwanted bubbles produced during the industry productions such as work, papermaking, industry cleaning link, sewage disposal.
Existing defoamer can be divided into two big class of organic silicon type and polyether-type according to composition, and organic silicon defoamer is due to emulsification
The addition of the auxiliary agents such as agent, easily occurs the defects such as breakdown of emulsion, floating oil at relatively high temperatures；Polyether-type defoamer be mostly by initiator and
The polymer that oxirane, expoxy propane ring-opening polymerisation are formed, its maximum advantage are that suds power is strong, but fatal defects are brokenly bubbles
Rate is low, and froth breaking is not slowly thorough.Higher with regard to the new applicability of exploitation in recent years, the research layer of the higher defoamer of defoaming effectiveness
Go out not poor.Polyether modified polysiloxan defoaming agent passes through to introduce polyether segment on silicone oil segment, common so as to have two kinds of defoamers concurrently
Advantage, froth breaking effect is strong, and heat resistance, shear resistant and acid-proof alkaline are good.But the polyether modified silicon oil of research disappears at present
Infusion is not satisfactory in terms of anti-shear performance, limits its application on some fields such as coating, petrochemical industry, papermaking.
Dissaving polymer is the highly branched macromolecular that a class has torispherical structure, containing a large amount of functional end-groups,
The characteristics of there is low melt and solution viscosity.After linear polymer is sheared, molecular backbone is interrupted, under causing molecular weight significantly
Drop, and after dissaving polymer is sheared, can interrupt a certain branched structure, not interfere with main chain performance, therefore hyperbranched polymerization
Thing can have more preferable anti-shear ability than linear polymer in theory.
Xu Junqi, Huang Tong, Lv Xin et al. are at which《The synthesis of water-soluble high shear hyperbranched poly acrylamide and sign》
In one text, raw radical polymerization is issued in cerium salt-hydroxyl initiator system with hyperbranched polyglycidyl ether, acrylamide, is obtained
Highly branched water-soluble ultrabranching polyacrylamide HPG-star-PAM, as a result shows highly branched polyacrylamide sample
Product have excellent anti-shear performance.
Therefore, the present invention prepares end-allyl group hyperbranched poly ethoxylated polyhydric alcohol by the terminal groups modification to hyperbranched polyether, profit
There is hydrosilylation with the double bond structure and polysiloxanes of modified hyperbranched polyether, prepare hyperbranched polyether modified poly-
Siloxanes, improves anti-shear performance, the froth breaking suds suppressing properties of defoamer.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of MQ silicone grafts containing hydrogen silicone oil modified organosilicon froth breaking
Agent and preparation method thereof.
A kind of modified organic silicon defoamer of MQ silicone grafts containing hydrogen silicone oil, is made up of the raw material of following weight portion：Poly-
Siloxanes 22-38 parts, hyperbranched polyether 12-20 parts, allyl glycidyl ether 15-24 parts, expoxy propane 35-58 parts, double gold
Category cyanide complex 0.2-0.5 parts, isopropanol 50-65 parts, chloroplatinic acid catalyst 0.4-0.9 parts, superfine alumina silicate 2-6 parts, mountain
Pears sugar alcohol 1-2 parts, polysorbate60 0.8-1 parts, sodium carboxymethylcellulose 1-3 parts, appropriate deionized water, MQ silicones 2-5 parts contain
Hydrogen silicone oil 2-7 parts.
Comprise the following steps that：
（1）The preparation of end-allyl group hyperbranched polyether：
Hyperbranched polyether and bimetallic cyaniding complex are added in autoclave, dehydration is vacuumized, and with nitrogen displacement 3
Secondary, after being warming up to 120 DEG C, 2/3 part of expoxy propane is passed through, course of reaction temperature is controlled at 130-140 DEG C or so, when pressure in kettle
During decline, allyl glycidyl ether and residual epoxide propane is added to continue polymerization a period of time, pressure no longer changes to kettle,
Vacuumize and slough unreacted monomer, that is, prepare end-allyl group hyperbranched polyether；
（2）End-allyl group hyperbranched poly ether grafted polysiloxane：
In equipped with magnetic stirring apparatus, thermometer, the there-necked flask of reflux condensing tube, polysiloxanes, isopropanol and step is added
（1）The end-allyl group hyperbranched polyether of preparation, under agitation, leads to nitrogen purging 20-40 minutes, adds chloroplatinic acid at 40-60 DEG C
Catalyst, under nitrogen protection, is warming up to 100-130 DEG C of reaction 3-6 hour, and vacuum distillation removes isopropanol, obtains holding allyl
Base hyperbranched poly ether grafted polysiloxane；
（3）The preparation of MQ silicone graft containing hydrogen silicone oils：
Containing hydrogen silicone oil and MQ silicones are mixed to join in reactor, when being heated to 100 DEG C while stirring under nitrogen protection,
Add remaining chloroplatinic acid catalyst to be reacted, 2-4 hours are incubated at 110-130 DEG C, obtain thick MQ silicones
Grafting containing hydrogen silicone oil；
（4）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane that obtains, step（3）The MQ silicones of preparation connects
Branch containing hydrogen silicone oil is uniformly mixed with superfine alumina silicate, is warming up to 150-170 DEG C, and insulation reaction 1-3 hour obtains polyethers silicon
Cream；
（5）Add D-sorbite, polysorbate60 in deionized water, be warming up to 60-90 DEG C, stir 10-25 minutes so as to completely molten
Solution, adds sodium carboxymethylcellulose afterwards, after being well mixed, adds above-mentioned silicon cream, quickly stirs under the conditions of 600-800r/min
50-70 minutes, with high-shear emulsion machine under the conditions of 9000-10000r/min high speed shear 20-40 minute, be down to room temperature, i.e.,
Defoamer needed for obtaining.
Wherein, the hyperbranched polyether is 3- ethyls -3- methylols epoxy butane or 3- methyl -3- methylol epoxy butanes
Self condense under initiator, then cation ring-opening polymerization is obtained, the degree of branching is 0.2-0.6, and number-average molecular weight is 10000-
30000.
Compared with prior art, the present invention has advantages below：
（1）The present invention contains the hyperbranched polyether of great amount of hydroxy group as raw material with end, using the allyl glycidyl containing double bond structure
There is ring-opening polymerisation with hydroxyl and prepare end-allyl group hyperbranched polyether in the epoxide group on glycerin ether, using modified hyperbranched poly
There is hydrosilylation with polysiloxanes in the double bond structure of ether end group, synthesis of super branched Siloxane-Oxyalkylene Copolymers, in order to make
Standby defoamer has excellent anti-shear performance, can be suitable for multiple occasions.
（2）The present invention prepare hyperbranched polyether modified polyorganosiloxane be Si -- C type, in aqueous chemical stability compared with
Good, can preserve for a long time, while being conducive to improving its prolonged defoaming effectiveness.
（3）MQ silicones of the present invention and the graft reaction of containing hydrogen silicone oil, draw on the basis of the layer structure of MQ silicones
Enter silicone oil chain link, increase dispersiveness of the MQ silicones in hyperbranched poly ether grafted polysiloxane, also increase its defoamer excellent
Different suds suppressing properties.
Specific embodiment
A kind of modified organic silicon defoamer of MQ silicone grafts containing hydrogen silicone oil, by following weight portion（Kilogram）Raw material group
Into：Polysiloxanes 32, hyperbranched polyether 18, allyl glycidyl ether 22, expoxy propane 52, bimetallic cyaniding complex 0.3,
Isopropanol 60, chloroplatinic acid catalyst 0.6, superfine alumina silicate 5, D-sorbite 2, polysorbate60 1, sodium carboxymethylcellulose 2, go from
Sub- appropriate amount of water, MQ silicones 4, containing hydrogen silicone oil 7.
Comprise the following steps that：
（1）The preparation of end-allyl group hyperbranched polyether：
Hyperbranched polyether and bimetallic cyaniding complex are added in autoclave, dehydration is vacuumized, and with nitrogen displacement 3
Secondary, after being warming up to 120 DEG C, 2/3 part of expoxy propane is passed through, course of reaction temperature is controlled at 135 DEG C or so, when pressure drop in kettle
When, add allyl glycidyl ether and residual epoxide propane to continue polymerization a period of time, to kettle, pressure no longer changes, and takes out true
Sky sloughs unreacted monomer, that is, prepare end-allyl group hyperbranched polyether；
（2）End-allyl group hyperbranched poly ether grafted polysiloxane：
In equipped with magnetic stirring apparatus, thermometer, the there-necked flask of reflux condensing tube, polysiloxanes, isopropanol and step is added
（1）The end-allyl group hyperbranched polyether of preparation, under agitation, leads to nitrogen and purges 30 minutes, add chloroplatinic acid catalyst at 50 DEG C,
Under nitrogen protection, it is warming up to 110 DEG C to react 4 hours, vacuum distillation removes isopropanol, obtains end-allyl group hyperbranched polyether and connects
Branch polysiloxanes；
（3）The preparation of MQ silicone graft containing hydrogen silicone oils：
Containing hydrogen silicone oil and MQ silicones are mixed to join in reactor, when being heated to 100 DEG C while stirring under nitrogen protection,
Add remaining chloroplatinic acid catalyst to be reacted, 3 hours are incubated at 120 DEG C, obtain thick MQ silicone grafts and contain
Hydrogen silicone oil；
（4）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane that obtains, step（3）The MQ silicones of preparation connects
Branch containing hydrogen silicone oil is uniformly mixed with superfine alumina silicate, is warming up to 160 DEG C, and insulation reaction 2 hours obtains polyethers silicon cream；
（5）Add D-sorbite, polysorbate60 in deionized water, be warming up to 80 DEG C, stir 20 minutes so as to be completely dissolved, it
Add sodium carboxymethylcellulose afterwards, after being well mixed, add above-mentioned silicon cream, quick stirring 60 minutes, use under the conditions of 800r/min
High-shear emulsion machine high speed shear 30 minutes under the conditions of 9000r/min, are down to room temperature, obtain final product required defoamer.
Wherein, the hyperbranched polyether is 3- ethyls -3- methylols epoxy butane or 3- methyl -3- methylol epoxy butanes
Self condense under initiator, then cation ring-opening polymerization is obtained, the degree of branching is 0.5, number-average molecular weight is 20000.
The antifoam performance of defoamer of the present invention is evaluated with Bubbling method：
At 85-150 DEG C, basicity>In the bubbling system of 10mg/L, antifoam performance is less than 110mm foam heights, and suds suppressing properties are less than
220mm foam heights.
Claims (3)
1. the modified organic silicon defoamer of a kind of MQ silicone grafts containing hydrogen silicone oil, it is characterised in that by the original of following weight portion
Material composition：Polysiloxanes 22-38 parts, hyperbranched polyether 12-20 parts, allyl glycidyl ether 15-24 parts, expoxy propane 35-
58 parts, bimetallic cyaniding complex 0.2-0.5 parts, isopropanol 50-65 parts, chloroplatinic acid catalyst 0.4-0.9 parts, superfine alumina silicate
2-6 parts, D-sorbite 1-2 parts, polysorbate60 0.8-1 parts, sodium carboxymethylcellulose 1-3 parts, appropriate deionized water, MQ silicones
2-5 parts, containing hydrogen silicone oil 2-7 parts.
2. a kind of preparation side of the modified organic silicon defoamer of MQ silicone grafts containing hydrogen silicone oil according to claims 1
Method, it is characterised in that comprise the following steps that：
（1）The preparation of end-allyl group hyperbranched polyether：
Hyperbranched polyether and bimetallic cyaniding complex are added in autoclave, dehydration is vacuumized, and with nitrogen displacement 3
Secondary, after being warming up to 120 DEG C, 2/3 part of expoxy propane is passed through, course of reaction temperature is controlled at 130-140 DEG C or so, when pressure in kettle
During decline, allyl glycidyl ether and residual epoxide propane is added to continue polymerization a period of time, pressure no longer changes to kettle,
Vacuumize and slough unreacted monomer, that is, prepare end-allyl group hyperbranched polyether；
（2）End-allyl group hyperbranched poly ether grafted polysiloxane：
In equipped with magnetic stirring apparatus, thermometer, the there-necked flask of reflux condensing tube, polysiloxanes, isopropanol and step is added
（1）The end-allyl group hyperbranched polyether of preparation, under agitation, leads to nitrogen purging 20-40 minutes, adds 1/2 chlorine at 40-60 DEG C
Platinic acid catalyst, under nitrogen protection, is warming up to 100-130 DEG C of reaction 3-6 hour, and vacuum distillation removes isopropanol, held
Pi-allyl hyperbranched poly ether grafted polysiloxane；
（3）The preparation of MQ silicone graft containing hydrogen silicone oils：
Containing hydrogen silicone oil and MQ silicones are mixed to join in reactor, when being heated to 100 DEG C while stirring under nitrogen protection,
Add remaining chloroplatinic acid catalyst to be reacted, 2-4 hours are incubated at 110-130 DEG C, obtain thick MQ silicones
Grafting containing hydrogen silicone oil；
（4）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane that obtains, step（3）The MQ silicones of preparation connects
Branch containing hydrogen silicone oil is uniformly mixed with superfine alumina silicate, is warming up to 150-170 DEG C, and insulation reaction 1-3 hour obtains polyethers silicon
Cream；
（5）Add D-sorbite, polysorbate60 in deionized water, be warming up to 60-90 DEG C, stir 10-25 minutes so as to completely molten
Solution, adds sodium carboxymethylcellulose afterwards, after being well mixed, adds above-mentioned silicon cream, quickly stirs under the conditions of 600-800r/min
50-70 minutes, with high-shear emulsion machine under the conditions of 9000-10000r/min high speed shear 20-40 minute, be down to room temperature, i.e.,
Defoamer needed for obtaining.
3. a kind of preparation of the modified organic silicon defoamer of MQ silicone grafts containing hydrogen silicone oil according to claims 1,2
Method, it is characterised in that the hyperbranched polyether is 3- ethyls -3- methylols epoxy butane or 3- methyl -3- methylol epoxies
Butane is self condensed under initiator, and then cation ring-opening polymerization is obtained, and the degree of branching is 0.2-0.6, and number-average molecular weight is
10000-30000.
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| CN201610903979.2A CN106492515A (en) | 2016-10-18 | 2016-10-18 | Modified organic silicon defoamer of a kind of MQ silicone grafts containing hydrogen silicone oil and preparation method thereof |
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| CN201610903979.2A CN106492515A (en) | 2016-10-18 | 2016-10-18 | Modified organic silicon defoamer of a kind of MQ silicone grafts containing hydrogen silicone oil and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705355A (en) * | 2019-01-11 | 2019-05-03 | 湖北新四海化工股份有限公司 | A kind of preparation process of hydrophily MQ silicone resin |
| CN113144678A (en) * | 2020-12-09 | 2021-07-23 | 金湖金凌新材料科技有限公司 | Composite defoaming agent with lasting foam inhibition performance and preparation method thereof |
| CN117417661A (en) * | 2023-11-17 | 2024-01-19 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891894A (en) * | 2008-10-29 | 2010-11-24 | 赢创戈尔德施米特有限公司 | Silicone-polyether copolymer systems and process for preparing them by means of an alkoxylation reaction |
| CN103768834A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Defoaming agent composition |
-
2016
- 2016-10-18 CN CN201610903979.2A patent/CN106492515A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891894A (en) * | 2008-10-29 | 2010-11-24 | 赢创戈尔德施米特有限公司 | Silicone-polyether copolymer systems and process for preparing them by means of an alkoxylation reaction |
| CN103768834A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Defoaming agent composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705355A (en) * | 2019-01-11 | 2019-05-03 | 湖北新四海化工股份有限公司 | A kind of preparation process of hydrophily MQ silicone resin |
| CN113144678A (en) * | 2020-12-09 | 2021-07-23 | 金湖金凌新材料科技有限公司 | Composite defoaming agent with lasting foam inhibition performance and preparation method thereof |
| CN117417661A (en) * | 2023-11-17 | 2024-01-19 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
| CN117417661B (en) * | 2023-11-17 | 2024-04-09 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
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Application publication date: 20170315 |