CN106492514A - A kind of hyperbranched polyether modified organic silicon defoamer for keeping alkaline environment and preparation method thereof - Google Patents
A kind of hyperbranched polyether modified organic silicon defoamer for keeping alkaline environment and preparation method thereof Download PDFInfo
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- CN106492514A CN106492514A CN201610903976.9A CN201610903976A CN106492514A CN 106492514 A CN106492514 A CN 106492514A CN 201610903976 A CN201610903976 A CN 201610903976A CN 106492514 A CN106492514 A CN 106492514A
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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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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The present invention discloses a kind of hyperbranched polyether modified organic silicon defoamer for keeping alkaline environment, is made up of the raw material of following weight portion：28 40 parts of polysiloxanes, 18 26 parts of hyperbranched polyether, 20 27 parts of allyl glycidyl ether, 40 60 parts of expoxy propane, 0.3 0.7 parts of bimetallic cyaniding complex, 50 70 parts of isopropanol, 0.3 0.8 parts of chloroplatinic acid catalyst, 36 parts of superfine alumina silicate, 12 parts of D-sorbite, 12 parts of polysorbate60,14 parts of sodium carboxymethylcellulose, appropriate deionized water, 13 parts of sodium metasilicate, 0.5 2 parts of calcined soda for industry.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, more particularly to a kind of hyperbranched polyether modified organic silicon for keeping alkaline environment
Defoamer 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 hyperbranched polyether modified organic silicon for keeping alkaline environment and disappears
Infusion and preparation method thereof.
A kind of hyperbranched polyether modified organic silicon defoamer for keeping alkaline environment, is made up of the raw material of following weight portion：
Polysiloxanes 28-40 parts, hyperbranched polyether 18-26 parts, allyl glycidyl ether 20-27 parts, expoxy propane 40-60 parts are double
Metal cyanide complex 0.3-0.7 parts, isopropanol 50-70 parts, chloroplatinic acid catalyst 0.3-0.8 parts, superfine alumina silicate 3-6 parts,
D-sorbite 1-2 parts, polysorbate60 1-2 parts, sodium carboxymethylcellulose 1-4 parts, appropriate deionized water, sodium metasilicate 1-3 parts, work
Industry soda ash 0.5-2 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）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane for obtaining is uniformly mixed with superfine alumina silicate,
150-170 DEG C is warming up to, insulation reaction 1-3 hour obtains polyethers silicon cream；
（4）Calcined soda for industry is added in deionized water, 35-40 DEG C of stirring 5-10 minute is warming up to, is added D-sorbite, tween
60,60-90 DEG C is warming up to, 10-25 minutes is stirred so as to be completely dissolved, sodium carboxymethylcellulose is added afterwards, is well mixed
Afterwards, above-mentioned silicon cream is added, quick stirring 50-70 minutes under the conditions of 600-800r/min, is eventually adding sodium metasilicate stirring 15-25
Minute, with high-shear emulsion machine under the conditions of 9000-10000r/min high speed shear 20-40 minute, be down to room temperature, obtain final product needed for
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 0.2-0.6, 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）Used in defoamer of the present invention, sodium metasilicate and calcined soda for industry maintain defoamer in the environment of alkalescence so that super
Branch polyether graft polysiloxane can destroy the surface tension of formation of foam completely so that foam moment while producing breaks
Go out, in addition the unique molecular structure of sodium metasilicate can prevent foam from setting with the bur on eliminating equipment surface from root
Standby surface adhesion, prepared defoamer have excellent froth breaking, suds suppressing properties and alkali resistance.
Specific embodiment
A kind of hyperbranched polyether modified organic silicon defoamer for keeping alkaline environment, by following weight portion（Kilogram）Raw material
Composition：Polysiloxanes 34, hyperbranched polyether 20, allyl glycidyl ether 23, expoxy propane 50, bimetallic cyaniding complex
0.4, isopropanol 62, chloroplatinic acid catalyst 0.4, superfine alumina silicate 5, D-sorbite 1, polysorbate60 2, sodium carboxymethylcellulose 3,
Appropriate deionized water, sodium metasilicate 2, calcined soda for industry 1.
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）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane for obtaining is uniformly mixed with superfine alumina silicate,
160 DEG C are warming up to, insulation reaction 2 hours obtains polyethers silicon cream；
（4）Calcined soda for industry is added in deionized water, 35 DEG C is warming up to and is stirred 8 minutes, add D-sorbite, polysorbate60, heat up
To 70 DEG C, stir 20 minutes so as to be completely dissolved, add sodium carboxymethylcellulose afterwards, after being well mixed, add above-mentioned silicon
Cream, quick stirring 60 minutes under the conditions of 800r/min, is eventually adding sodium metasilicate and stirs 20 minutes, existed with high-shear emulsion machine
Under the conditions of 9000r/min, high speed shear 30 minutes, 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. a kind of keep alkaline environment hyperbranched polyether modified organic silicon defoamer, it is characterised in that by following weight portion
Raw material is constituted：Polysiloxanes 28-40 parts, hyperbranched polyether 18-26 parts, allyl glycidyl ether 20-27 parts, expoxy propane
40-60 parts, bimetallic cyaniding complex 0.3-0.7 parts, isopropanol 50-70 parts, chloroplatinic acid catalyst 0.3-0.8 parts, ultra-fine silicon
Sour aluminium 3-6 parts, D-sorbite 1-2 parts, polysorbate60 1-2 parts, sodium carboxymethylcellulose 1-4 parts, appropriate deionized water, metasilicic acid
Sodium 1-3 parts, calcined soda for industry 0.5-2 parts.
2. the preparation of the hyperbranched polyether modified organic silicon defoamer of a kind of holding alkaline environment 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 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）By step（2）The end-allyl group hyperbranched poly ether grafted polysiloxane for obtaining is uniformly mixed with superfine alumina silicate,
150-170 DEG C is warming up to, insulation reaction 1-3 hour obtains polyethers silicon cream；
（4）Calcined soda for industry is added in deionized water, 35-40 DEG C of stirring 5-10 minute is warming up to, is added D-sorbite, tween
60,60-90 DEG C is warming up to, 10-25 minutes is stirred so as to be completely dissolved, sodium carboxymethylcellulose is added afterwards, is well mixed
Afterwards, above-mentioned silicon cream is added, quick stirring 50-70 minutes under the conditions of 600-800r/min, is eventually adding sodium metasilicate stirring 15-25
Minute, with high-shear emulsion machine under the conditions of 9000-10000r/min high speed shear 20-40 minute, be down to room temperature, obtain final product needed for
Defoamer.
3. the system of the hyperbranched polyether modified organic silicon defoamer of a kind of holding alkaline environment according to claims 1,2
Preparation Method, it is characterised in that the hyperbranched polyether is 3- ethyls -3- methylols epoxy butane or 3- methyl -3- methylol rings
Oxygen 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019140A (en) * | 2019-12-30 | 2020-04-17 | 江苏美思德化学股份有限公司 | Hyperbranched organic silicon foam stabilizer, and preparation method and application thereof |
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 |
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- 2016-10-18 CN CN201610903976.9A patent/CN106492514A/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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019140A (en) * | 2019-12-30 | 2020-04-17 | 江苏美思德化学股份有限公司 | Hyperbranched organic silicon foam stabilizer, and preparation method and application thereof |
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