CN107459044B - A kind of inorganic agent and preparation method thereof for white carbon - Google Patents
A kind of inorganic agent and preparation method thereof for white carbon Download PDFInfo
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- CN107459044B CN107459044B CN201710612879.9A CN201710612879A CN107459044B CN 107459044 B CN107459044 B CN 107459044B CN 201710612879 A CN201710612879 A CN 201710612879A CN 107459044 B CN107459044 B CN 107459044B
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- PQXAPVOKLYINEI-JAMMHHFISA-N CCC1C[C@@H](C)CC1 Chemical compound CCC1C[C@@H](C)CC1 PQXAPVOKLYINEI-JAMMHHFISA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of inorganic agents for white carbon, the inorganic agent can improve the compatibility between white carbon surface group and polyether modified silicon oil, inhibit the generation of sedimentation, and then improve the appearance and application performance of antifoaming agent, to reach the balance of superior defoaming and lasting suds.The present invention discloses a kind of preparation method of the inorganic agent for white carbon again, and step is few, and flow is simple, safe operation.
Description
Technical field
The present invention relates to technical field of organic chemistry more particularly to a kind of inorganic agents and its preparation side for white carbon
Method.
Background technology
Antifoaming agent can substantially be divided into non-silicon systems and silicon systems two major classes according to the difference of main component.Non- silicon systems are to defoam
Agent includes mainly polyethers antifoaming agent, mineral oil antifoam agent and higher alcohols antifoaming agent；And the main component of silicon systems antifoaming agent is then
Silicone oil, white carbon silicone oil cream or special modified silicon oil.Silicon systems antifoaming agent is current most widely used a kind of antifoaming agent.
In modified silicon oil antifoaming agent, polyether modified silicon oil is to apply and produce at present most one kind.Polyether-modified silicon
Oil is to introduce polyether siloxane copolymers made from polyether segment by hydrosilylation in siloxane molecule.Compared to
The polyethers obtained after simply silicone oil is mixed with polyethers and other auxiliary agents-silicone oil Compounded Antifoamer is found in practical application poly-
The suds ability of ethers antifoaming agent is strong, but the relatively general polysiloxane-based antifoaming agent of defoaming capacity is far short of what is expected.
In many application fields, such as papermaking, textile printing and dyeing, oil product processing, sewage disposal, oil exploitation and conveying, need
Antifoaming agent is wanted to be provided simultaneously with good defoaming function and suds function.White carbon is added in polyether modified silicon oil to be greatly improved
Its antifoaming speed optimizes the suds balance that disappears.
But existing white carbon has the following defects：It is anti-heavy in surname silicone oil system that existing white carbon changes in polyethers
Drop property is poor, it is easy to layering precipitation phenomenon occur, influence the appearance and application performance of antifoaming agent.
Invention content
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of processing for white carbon
Agent, which can be modified white carbon, affine between white carbon surface and polyether modified silicon oil to improve
Property, inhibit the generation of sedimentation, and then improve the appearance and application performance of antifoaming agent, to reach superior defoaming and persistently
The balance of suds.
The second object of the present invention is to provide a kind of preparation method of the inorganic agent for white carbon, and step is few, flow
Simply, safe operation.
An object of the present invention adopts the following technical scheme that realization：
A kind of inorganic agent for white carbon, the molecular structural formula of the inorganic agent is as shown in structural formula I：
Wherein, n=0-100；R is hydroxyl, carboxyl, epoxy group, hydrogen-based or the group for having reactivity with other silicone hydroxyls；
R1、R2、R3It is alkyl.
Further, n=10-50；R1、R2、R3It is methyl, ethyl or propyl.
The second object of the present invention adopts the following technical scheme that realization：
A kind of preparation method of inorganic agent for white carbon, including：
It is primary that step is added：Hydroxyl three (trialkylsiloxy) silane monomer is added in reaction vessel；
Secondary addition step：Under conditions of nitrogen protection, difunctional silicone oil is added, stirs evenly；
Reaction step：Catalyst, temperature reaction is added；
Discharge step：It vacuumizing, reflux condensation mode, removes small molecule by-product, it is ensured that reaction carries out complete, cooling discharge,
Up to the inorganic agent.
Further, in the primary addition step, the molecular structure of hydroxyl three (trialkylsiloxy) silane monomer
Formula is as shown in structural formula II：
Wherein, X1、X2、X3It is methyl, ethyl or propyl.
Further, in the secondary addition step, difunctional silicone oil and hydroxyl three (trialkylsiloxy) silane
The molar ratio of monomer is 1:1.
Further, in the secondary addition step, one end of the difunctional silicone oil carries silicone hydroxyl or silicon hydrogen
The other end of base, the difunctional silicone oil is the hydroxyl with blocking group or without blocking group, carboxyl, epoxy group, hydrogen-based
Or other have the group of reactivity with silicone hydroxyl.
Further, in the reaction step, it is warming up to 40-95 DEG C, reacts 2-18h.
Further, in the reaction step, the dosage of the catalyst is difunctional silicone oil and (three alkane of hydroxyl three
Base siloxy) the sum of silane monomer weight 0.01-2.0%.
Further, in the reaction step, the catalyst is organic acid.
Further, the organic acid is one kind in acetic acid, caproic acid, octanoic acid, enanthic acid and chloroplatinic acid or arbitrary combination.
Compared with prior art, the beneficial effects of the present invention are：
(1) inorganic agent provided by the present invention for white carbon improves white carbon surface base by process of surface treatment
Compatibility between group and polyether modified silicon oil, inhibits the generation of sedimentation, and then improves the appearance and application performance of antifoaming agent,
To reach the balance of superior defoaming and lasting suds.
(2) preparation method of the inorganic agent provided by the present invention for white carbon, step is few, and flow is simple, operation peace
Entirely.
Description of the drawings
The hydrophobic silicic aerogels that Fig. 1 is provided by the embodiment of the present invention 1 change the mixed design sketch of surname silicone oil with polyethers；
Fig. 2 changes the mixed design sketch of surname silicone oil for the hydrophobic silicic aerogels that comparative example 1 of the present invention is provided with polyethers.
Specific implementation mode
In the following, in conjunction with attached drawing and specific implementation mode, the present invention is described further, it should be noted that not
Under the premise of conflicting, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
A kind of inorganic agent for white carbon, the molecular structural formula of inorganic agent is as shown in structural formula I：
Wherein, n=0-100, preferably 10-50；R be hydroxyl, carboxyl, epoxy group, hydrogen-based or other have instead with silicone hydroxyl
Answer active group；R1、R2、R3It is alkyl, short hydrocarbon, preferably methyl, ethyl or propyl.
A kind of preparation method of inorganic agent for white carbon, including：
It is primary that step is added：Hydroxyl three (trialkylsiloxy) silane monomer is added in reaction vessel；
Secondary addition step：Under conditions of nitrogen protection, be added equimolar than difunctional silicone oil, stir evenly；
Reaction step：Organic acid catalyst, temperature reaction is added；
Discharge step：It vacuumizing, reflux condensation mode, removes small molecule by-product, it is ensured that reaction carries out complete, cooling discharge,
Up to inorganic agent.
As further embodiment, in secondary addition step, one end of difunctional silicone oil with silicone hydroxyl or
Silicon hydrogen-based, the other end is with blocking group or the hydroxyl without blocking group, carboxyl, epoxy group, hydrogen-based or has instead with silicone hydroxyl
Answer active group.
As further embodiment, in reaction step, it is warming up to 40-95 DEG C, reacts 2-18h；The use of catalyst
Amount is the 0.01-2.0% of the sum of difunctional silicone oil and hydroxyl three (trialkylsiloxy) silane monomer weight；Catalyst is to have
Machine acid, preferably one kind in acetic acid, caproic acid, octanoic acid, enanthic acid and chloroplatinic acid or arbitrary combination.
This is used for the preparation flow of the inorganic agent of white carbon as shown in reaction equation I：
Wherein, X1、X2、X3It is methyl, ethyl or propyl；Y is hydroxyl, carboxyl, epoxy group, hydrogen-based or other and silicon hydroxyl
It is hydroxyl or hydrogen-based that base, which has the group of reactivity, Z,.
Hydroxyl three (trialkylsiloxy) silane monomer is added in reactor first, then in the condition of nitrogen protection
Under, be added equimolar than difunctional silicone oil, stir evenly；It is subsequently added into organic acid catalyst, is warming up to 40-95 DEG C, control
Reaction time processed is 2-18h, and during which, reactant carries out condensation reaction, generates target product and by-product；It finally vacuumizes, returns
Stream condensation, removes small molecule by-product, it is ensured that reaction progress is complete, and cooling discharge is to get inorganic agent.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained by buying pattern outside fixed.
Embodiment 1
A kind of inorganic agent for white carbon, preparation method are as follows：
1, (three silyloxies) silane body of hydroxyl three (structural formula III) is added in reaction vessel；
2, under nitrogen protection, be added equimolar than both-end silicone hydroxyl silicone oil (structural formula IV), stir evenly；
Wherein n=40；
3, the octanoic acid of total reactant weight 0.2% is added as catalyst, is warming up to 75 DEG C；
4, it vacuumizes, reflux condensation mode 9h, removes small molecule product, it is ensured that reaction carries out completely, and cooling discharge obtains white carbon
Inorganic agent.
The reaction process of embodiment 1 is as shown in reaction equation II：
Wherein, R1、R2、R3It is methyl, n=40.
The inorganic agent of above-mentioned acquisition is uniformly mixed with hydrophily white carbon, 3- aminopropyl dimethyl methyl oxygroup silicon is added
Alkane reacts 7h at 140 DEG C, vacuumizes removing small molecule by-product, obtains hydrophobic silicic aerogels；Wherein, inorganic agent and 3- aminopropyls
The dosage of dimethyl methoxy silane is respectively the 10% and 1% of hydrophilic white carbon weight.
Embodiment 2
A kind of inorganic agent for white carbon, preparation method are as follows：
1, (three silyloxies) silane body of hydroxyl three (structural formula III) is added in reaction vessel；
2, under nitrogen protection, be added equimolar than both-end containing hydrogen silicone oil (structural formula V), stir evenly；
Wherein n=60；
3, the chloroplatinic acid of total reactant weight 0.01% is added as catalyst, is warming up to 55 DEG C；
4, it vacuumizes, reflux condensation mode 9h, removes small molecule product, it is ensured that reaction carries out completely, and cooling discharge obtains white carbon
Inorganic agent.
The reaction process of embodiment 2 is as shown in reaction equation III：
Wherein, R1、R2、R3It is methyl, n=60.
The inorganic agent of above-mentioned acquisition is uniformly mixed with hydrophily white carbon, N- (β-aminoethyl)-γ-aminopropyl first is added
Base dimethoxysilane reacts 18h at 60 DEG C, vacuumizes removing small molecule by-product, obtains hydrophobic silicic aerogels；Wherein, it handles
The dosage of agent and N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilanes is respectively 30% He of hydrophilic white carbon weight
2%.
Embodiment 3
A kind of inorganic agent for white carbon, preparation method are as follows：
1, (three silyloxies) silane body of hydroxyl three (structural formula III) is added in reaction vessel；
2, under nitrogen protection, be added equimolar than end alkoxy end hydroxyl silicone oil (structural formula VI), stir evenly；
Wherein n=50；
3, the octanoic acid of total reactant weight 0.2% is added as catalyst, is warming up to 70 DEG C；
4, it vacuumizes, reflux condensation mode 9h, removes small molecule product, it is ensured that reaction carries out completely, and cooling discharge obtains white carbon
Inorganic agent.
The reaction process of embodiment 3 is as shown in reaction equation IV：
Wherein R1、R2、R3It is methyl, n=50.
The inorganic agent of above-mentioned acquisition is uniformly mixed with hydrophily white carbon, N- (β-aminoethyl)-γ-aminopropyls two are added
Methylmethoxysilane reacts 10h at 200 DEG C, vacuumizes removing small molecule by-product, obtains hydrophobic silicic aerogels；Wherein, it handles
The dosage of agent and N- (β-aminoethyl)-γ-aminopropyl dimethyl methoxy silanes is respectively 20% He of hydrophilic white carbon weight
0.5%.
Comparative example 1
300ml octamethylcy-clotetrasiloxanes are added in the there-necked flask of 500ml and are slowly added into gas phase under agitation
Until mixture is in starchiness in flask, according to the amount of white carbon be added, water is added in 4% ratio, at room temperature in white carbon
1h is stirred, 10% hexamethyldisilazane is added, keeps the temperature 2h；The ammonia generated in solvent and elimination reaction is steamed, is obtained
Hydrophobic silicic aerogels.
Effect assessment and performance detection
The hydrophobic silicic aerogels that Example 1-3 and comparative example 1 obtain, are added to according to 5% additive amount same respectively
In organosilicon modified polyether antifoaming agent, room temperature is stored 4 weeks, observes delamination, the result is shown in Figure 1 and Fig. 2.
Fig. 1 is the design sketch of embodiment 1, and Fig. 2 is the design sketch of comparative example 1.
It can be seen from figure 1 that the hydrophobic silicic aerogels of embodiment 1 and polyethers change after surname silicone oil system mixes, it is placed at room temperature for 4 weeks
Afterwards without there is layering precipitation phenomenon, sample appearance is uniform, this illustrates that the hydrophobic silicic aerogels resistance to settling of embodiment 1 can be good,
The appearance and application performance of antifoaming agent are not interfered with.The design sketch of embodiment 2-3 is close with embodiment 1, and details are not described herein.
As can be seen from Figure 2, the hydrophobic silicic aerogels with polyethers of comparative example 1 change after surname silicone oil system mixes, and are placed at room temperature for 4 weeks
After there is layering precipitation phenomenon, the hydrophobic silicic aerogels anti-settling poor performance of comparative example 1.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (7)
1. a kind of inorganic agent for white carbon, which is characterized in that the molecular structural formula of the inorganic agent is as shown in structural formula I：
；
Structural formula I
Wherein, n=10-50；R1、R2、R3It is methyl, ethyl or propyl.
2. a kind of preparation method of the inorganic agent as described in claim 1 for white carbon, it is characterised in that including：
It is primary that step is added：Hydroxyl three (trialkylsiloxy) silane monomer is added in reaction vessel；
Secondary addition step：Under conditions of nitrogen protection, difunctional silicone oil is added, stirs evenly；
One end of the difunctional silicone oil carries silicone hydroxyl or silicon hydrogen-based, and the other end of the difunctional silicone oil carries hydroxyl
Base, carboxyl, epoxy group or hydrogen-based；
Reaction step：Catalyst, temperature reaction is added；The catalyst is organic acid；
Discharge step：It vacuumizes, reflux condensation mode, removes by-product, cooling discharge is to get the inorganic agent.
3. the preparation method for the inorganic agent of white carbon as claimed in claim 2, which is characterized in that in the primary addition
In step, the molecular structural formula of hydroxyl three (trialkylsiloxy) silane monomer is as shown in structural formula II：
；Structural formula II；
Wherein, X1、X2、X3It is methyl, ethyl or propyl.
4. the preparation method for the inorganic agent of white carbon as claimed in claim 2, which is characterized in that in the secondary addition
In step, the molar ratio of difunctional silicone oil and hydroxyl three (trialkylsiloxy) silane monomer is 1:1.
5. the preparation method for the inorganic agent of white carbon as claimed in claim 2, which is characterized in that in the reaction step
In, it is warming up to 40-95 DEG C, reacts 2-18h.
6. the preparation method for the inorganic agent of white carbon as claimed in claim 2, which is characterized in that in the reaction step
In, the dosage of the catalyst is the sum of difunctional silicone oil and hydroxyl three (trialkylsiloxy) silane monomer weight
0.01-2.0%。
7. the preparation method for the inorganic agent of white carbon as claimed in claim 2, which is characterized in that the organic acid is vinegar
One kind in acid, caproic acid, octanoic acid, enanthic acid and chloroplatinic acid or arbitrary combination.
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| CN101884852A (en) * | 2010-06-30 | 2010-11-17 | 南京四新科技应用研究所有限公司 | Method for improving properties of polyether defoaming agent |
| JP6000640B2 (en) * | 2011-05-30 | 2016-10-05 | 東レ・ダウコーニング株式会社 | Novel organopolysiloxane elastomer and use thereof |
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