CN113750577A - Defoamer for rhamnolipid fermentation liquor and preparation method and application thereof - Google Patents
Defoamer for rhamnolipid fermentation liquor and preparation method and application thereof Download PDFInfo
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- CN113750577A CN113750577A CN202110907769.1A CN202110907769A CN113750577A CN 113750577 A CN113750577 A CN 113750577A CN 202110907769 A CN202110907769 A CN 202110907769A CN 113750577 A CN113750577 A CN 113750577A
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Abstract
The invention provides a defoaming agent for rhamnolipid fermentation liquor and a preparation method and application thereof. The defoamer for the rhamnolipid fermentation liquid has strong defoaming capability, and can effectively control foams generated in the rhamnolipid fermentation process only by using extremely low dosage. In addition, the defoaming agent has long-acting performance, the requirement of 48h fermentation process on foam control can be met by adding the defoaming agent once, and labor and cost are greatly saved. In addition, the used raw materials are mild, and due to the extremely low addition amount, the organic silicon chain segment and the polyether chain segment can be decomposed into a culture medium carbon source component by zymophyte in the later fermentation period, and no additional defoaming agent separation and removal procedure is needed after the use. Because other surfactants are not introduced, the purity of the rhamnolipid after purification cannot be influenced. The antifoaming agent for the rhamnolipid fermentation liquor can obviously improve the extraction rate of the rhamnolipid, but can not reduce the purity of the rhamnolipid, and improves the production efficiency.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a defoaming agent for rhamnolipid fermentation liquor, and a preparation method and application thereof.
Background
The rhamnolipid is a nontoxic, pollution-free and biodegradable anionic surfactant with good selectivity and specificity, has good surface activity, and has unique application prospect in a plurality of industrial fields such as medicine, food, cosmetics, environmental protection and the like.
The biological fermentation of rhamnolipid adopts an aerobic biological fermentation method, and the aerobic biological fermentation process is mostly carried out along with aeration. The combination of the air introduced and the surfactant in the culture medium often produces foam which is difficult to break. Although foams play an important role in the fields of food technology, medicine, cosmetics, marine technology, environmental technology, fire fighting and the like, during the biological fermentation process, the generation of foams can cause the damage of loss of fermentation products, bacterial contamination, pollution sensors, reduction of working volume, environmental pollution and the like. Particularly, when the fermentation product is a surfactant, the foam generated in the fermentation process is more stable, and the industrial production of the whole industry is limited. For aerobic biological fermentation, the requirement of foam control is to remove excessive foam while maintaining a certain amount of foam, and the ability of foam control is not reduced by the prolonged fermentation time, so that the elimination of excessive foam during fermentation is important. In the related art, the defoaming methods mainly include a chemical defoaming method, a physical defoaming method and a mechanical defoaming method. The defoaming effect of the physical defoaming method and the mechanical defoaming method is not obvious after a plurality of team experiments. Patent CN103966282B introduces a physical defoaming method, the foam in the fermentation cylinder is led into the top of a defoaming tank, and spray into the defoaming tank through a foam spray head with the aperture of 1-2mm, simultaneously, aseptic air with the pressure 0.1-0.25MPa higher than the pressure in the defoaming tank is released into the defoaming tank instantly, the release is stopped after the foam is eliminated, the fermentation liquid after the foam liquefaction is led back to the fermentation tank by a peristaltic pump, although the method can realize defoaming, but a whole set of defoaming system is added, the method comprises the defoaming tank, a defoaming loop and a defoaming device, pressure control is needed, the possibility of bacteria contamination and the types of complex chemical defoaming agents of operation are increased, the efficiency is high, and the application is most extensive in the fermentation production. In the ventilation fermentation, the chemical defoaming agent is generally natural vegetable oil, polyether, higher alcohol, silicone oil, surfactant-containing composite defoaming agent and the like.
In industry, the process with high rhamnolipid yield mainly uses vegetable oil as a carbon source, because the vegetable oil can also be used as an antifoaming agent while being used as the carbon source. However, there is a certain risk in using vegetable oil as the defoaming agent, and under the condition of the existence of a large amount of foam, the increase of the vegetable oil dosage can result in the increase of the oil content of the fermentation liquor, and the fermentation liquor is easy to emulsify and difficult to separate. The defoaming efficiency of the polyether defoamer is low, the addition amount is high, and the later separation and purification process is required to be added when the polyether defoamer is used excessively. Although simple dimethyl silicone oil has good defoaming property, the dispersibility and the foam inhibition property are poor, and the requirement of foam control in the fermentation process for dozens of hours is difficult to meet. The existence of the surfactant-containing composite antifoaming agent introduces a new surfactant into the fermentation liquor, and influences the purity of rhamnolipid.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides the defoamer for the rhamnolipid fermentation liquor, which has extremely strong defoaming capability and can effectively control foam generated in the rhamnolipid fermentation process only by extremely low using amount.
The invention also provides a preparation method of the antifoaming agent for the rhamnolipid fermentation liquor.
The invention also provides application of the antifoaming agent for the rhamnolipid fermentation liquor
The invention provides a defoaming agent for rhamnolipid fermentation liquor, which is prepared from raw materials including terminal polyether modified polysiloxane, polyether modified heptamethyltrisiloxane and a solvent;
the terminal polyether modified polysiloxane has the following structure:
wherein R is- (CH)2)3(OCH(CH3)CH2)a(OCH2CH2)bOR1，R1is-COCH3、-COCH2CH2CH2CH3N is 10 to 100, a is 3 to 15, and b is 3 to 10;
the polyether modified heptamethyltrisiloxane has the structure shown as follows:
wherein G is- (CH)2)3(OCH(CH3)CH2)e(OCH2CH2)fOR2，R2is-COCH3、-COCH2CH2CH2CH3E is 8 to 15, and f is 0 to 5.
The antifoaming agent for the rhamnolipid fermentation liquor provided by the invention at least has the following beneficial effects:
for the defoaming agent, the defoaming agent needs to have certain incompatibility with a foaming system, so that the defoaming agent can exist on a gas-liquid interface, namely a bubble surface, in the foaming system in droplets/particles with certain structures and particle sizes, the surface tension of the defoaming agent needs to be lower than that of the foaming liquid, the defoaming agent component on the bubble surface breaks bubbles due to lower surface tension, and the bubbles are eliminated due to the difference of the surface tension of the bubbles. Meanwhile, the surface tension and the incompatibility are lower, and the problem of poor foam inhibition capability caused by the fact that the defoaming agent component loses the defoaming effect because of being emulsified and coated by the surfactant of a foaming system is avoided to a greater extent. In addition, the defoaming agent also needs to have good migration capability, and can rapidly migrate to a gas-liquid interface, namely a bubble surface, so as to play a role in rapid defoaming.
In the raw materials for preparing the defoamer for the rhamnolipid fermentation liquor, the structural formulA of the end polyether modified polysiloxane is an R-A-R structure, wherein A is A polysiloxane chain segment which belongs to A hydrophobic chain segment (not hydrophilic), and R is A polyether chain segment, wherein the structure of R can be divided into A-PO-EO structure or A-EO-PO structure. PO is (OCH (CH)3)CH2) Is a hydrophobic segment, EO is (OCH)2CH2) Is a hydrophilic segment). The hydrophobic A chain segment and the hydrophobic PO are linked together to form A whole hydrophobic chain segment, and the hydrophilic EO chain segment is arranged at the two ends of the molecular chain to form an EO-PO-A-PO-EO structure. The structure is characterized in that regular 'staple-shaped' arrangement can be automatically formed in a water system, EO enters a water phase, and PO and A chain segments face the air or the inside of bubbles, so that quick and lasting bubble suppression is realized. However, if the structure is PO-EO-A-EO-PO, regular 'staple-like' arrangement cannot be formed, disorder is caused in the system, and defoaming performance is greatly reduced.
In the raw materials for preparing the antifoaming agent for the rhamnolipid fermentation liquor, the polyether modified heptamethyltrisiloxane is in an umbrella-shaped structure, one of the structural characteristics is that the surface tension is very low and is lower than 22mN/m, and the surface tension of the rhamnolipid fermentation liquor is 26.2mN/m, so that the requirement of lower surface tension than a foaming system in a defoaming mechanism is met; the second structural characteristic is that the moving ability is strong, the moving ability is very strong, and the requirement of 'good moving ability' in the defoaming mechanism is satisfied.
Therefore, the action of the preparation raw materials ensures that the defoamer for the rhamnolipid fermentation liquor has extremely strong defoaming capability, and can effectively control the foam generated in the rhamnolipid fermentation process only by extremely low dosage. In addition, the defoaming agent has long-acting performance, the requirement of 48h fermentation process on foam control can be met by adding the defoaming agent once, and labor and cost are greatly saved.
The raw materials used by the defoamer for the rhamnolipid fermentation liquor are mild, and due to the extremely low addition amount, the organosilicon chain segment and the polyether chain segment can be decomposed into a culture medium carbon source component by zymophyte in the later fermentation stage, and no additional defoamer separation and removal procedure is needed after use.
The antifoaming agent for the rhamnolipid fermentation liquor provided by the invention does not introduce other surfactants, so that the purity of the rhamnolipid after purification is not influenced.
The antifoaming agent for the rhamnolipid fermentation liquor can obviously improve the extraction rate of the rhamnolipid, but can not reduce the purity of the rhamnolipid, and improves the production efficiency.
According to some embodiments of the present invention, the raw material for preparing includes 20 to 40 parts by weight of the terminal polyether modified polysiloxane.
According to some embodiments of the present invention, the raw material for preparing includes 25 to 32 parts by weight of the terminal polyether modified polysiloxane.
The terminal polyether modified polysiloxane with a specific structure is beneficial to forming regular 'book nail-shaped' arrangement, and other polyether modified silicone oil is 'comb-shaped' polyether modified silicone oil, cannot form regular 'book nail-shaped' arrangement and has poor defoaming capability.
According to some embodiments of the invention, the raw material for preparation comprises 5-10 parts by weight of polyether modified heptamethyltrisiloxane.
According to some embodiments of the invention, the raw material for preparation comprises 5-8 parts by weight of polyether modified heptamethyltrisiloxane.
According to some embodiments of the present invention, the CAS number of the polyether-modified heptamethyltrisiloxane is 27306-78-1.
According to some embodiments of the present invention, the raw material for preparation includes 50 to 75 parts by weight of a solvent.
According to some embodiments of the invention, the solvent is a lower alcohol.
According to some embodiments of the invention, the lower alcohol comprises at least one of ethanol, isopropanol, and n-butanol.
The second aspect of the invention provides a method for preparing the antifoaming agent for rhamnolipid fermentation liquor, wherein the terminal polyether modified polysiloxane, the polyether modified heptamethyltrisiloxane and the solvent are mixed uniformly.
According to some embodiments of the invention, the blending process is performed at ambient temperature.
According to some embodiments of the invention, the ambient temperature is 10 ℃ to 40 ℃.
According to some embodiments of the invention, the blending process applies agitation at a speed of 100rpm to 500 rpm.
According to some embodiments of the invention, the time of stirring during the blending process is 10min to 60 min.
The method for preparing the antifoaming agent for the rhamnolipid fermentation liquor has the advantages of mild preparation conditions, low equipment requirements and easy industrial popularization.
The third aspect of the invention provides application of the antifoaming agent for the plum glycolipid fermentation liquor in preparation of a biosurfactant.
According to some embodiments of the invention, the biosurfactant comprises a polymeric biosurfactant.
According to some embodiments of the invention, the biosurfactant comprises an acyl peptide-based biosurfactant.
According to some embodiments of the invention, the biosurfactant comprises a glycolipid, a lipopeptide and a phospholipid.
According to some embodiments of the invention, the biosurfactant comprises sophorolipids, algal glycolipids and lipopeptides.
When the antifoaming agent for the plum glycolipid fermentation liquor is used, the addition amount is 0.01-0.02% of the mass of the fermentation liquor.
Drawings
FIG. 1 is a schematic representation of the staple-like structure of the end polyether modified polysiloxane.
FIG. 2 is a schematic representation of the comb structure of the terminal polyether-modified polysiloxane.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process comprises the following steps: 256g of end polyether modified polysiloxane, 64g of polyether modified heptamethyltrisiloxane and 480g of absolute ethyl alcohol are stirred, mixed and reacted for 30min at the room temperature at the rotating speed of 300 r/min. Wherein the terminal polyether modified polysiloxane and the polyether modified heptamethyltrisiloxane are respectively purchased from C-9960 and SP-5160 of Guangdong golden cypress chemical Co.
Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH(CH3)CH2)10(OCH2CH2)5OCOCH3，n＝50；
The structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)8OCOCH2CH2CH2CH3)。
Example 2
The embodiment prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process comprises the following steps: 200g of end polyether modified polysiloxane, 40g of polyether modified heptamethyltrisiloxane and 560g of absolute ethyl alcohol are stirred, mixed and reacted for 60min at room temperature at the rotating speed of 100 r/min. Wherein the terminal polyether modified polysiloxane and the polyether modified heptamethyltrisiloxane are respectively purchased from C-9935 and SP-5186 of Guangdong golden cypress chemical Co.
Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH(CH3)CH2)3(OCH2CH2)5OCOCH3，n＝100；
The structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)15OCOCH3。
Example 3
The embodiment prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process comprises the following steps: 240g of end polyether modified polysiloxane, 40g of polyether modified heptamethyltrisiloxane and 520g of absolute ethyl alcohol are stirred, mixed and reacted for 10min at the room temperature at the rotating speed of 500 r/min. Wherein the terminal polyether modified polysiloxane and the polyether modified heptamethyltrisiloxane are respectively purchased from C-9978 and SP-5122 of Guangdong golden cypress chemical Co. Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH(CH3)CH2)15(OCH2CH2)3OCOCH2CH2CH2CH3，n＝10；
The structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)15(OCH2CH2)2OCOCH3。
Example 4
The embodiment prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process comprises the following steps: 200g of end polyether modified polysiloxane, 64g of polyether modified heptamethyltrisiloxane and 536g of absolute ethyl alcohol are stirred and mixed at the room temperature of 250r/min for reaction for 25 min. Wherein the terminal polyether modified polysiloxane and the polyether modified heptamethyltrisiloxane are respectively purchased from C-9909 and SP-5108 of Guangdong golden cypress chemical Co.
Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH(CH3)CH2)15(OCH2CH2)10OCOCH2CH2CH2CH3，n＝75；
The structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)10(OCH2CH2)5OCOCH2CH2CH2CH3。
Comparative example 1
The comparative example prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process is as follows: 256g of end polyether modified polysiloxane, 64g of polyether modified heptamethyltrisiloxane and 480g of absolute ethyl alcohol are stirred, mixed and reacted for 30min at the room temperature at the rotating speed of 300 r/min. Wherein the terminal polyether modified polysiloxane and the polyether modified heptamethyltrisiloxane are respectively purchased from C-6309 and SP-5108 of Guangdong golden cypress chemical Co.
Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH2CH2)5(OCH(CH3)CH2)10OCOCH3，n＝50；
The structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)8OCOCH2CH2CH2CH3。
Comparative example 2
The comparative example prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process is as follows: 240g of end polyether modified polysiloxane and 560g of absolute ethyl alcohol are stirred, mixed and reacted for 60min at room temperature at the rotating speed of 100 r/min. Wherein the terminal polyether modified polysiloxane is purchased from C-9935 of Guangdong golden cypress chemical Co.
Wherein, the structure of the end polyether modified polysiloxane is shown as the following formula:
r is- (CH)2)3(OCH(CH3)CH2)3(OCH2CH2)5OCOCH3，n＝100。
Comparative example 3
The comparative example prepares the antifoaming agent for the rhamnolipid fermentation liquor, and the specific process is as follows: 280g of polyether modified heptamethyltrisiloxane and 520g of absolute ethyl alcohol are stirred, mixed and reacted for 10min at the room temperature at the rotating speed of 500 r/min. Among them, polyether-modified heptamethyltrisiloxane was purchased from SP-5122 of Juniperus horizontalis Chemicals, Inc.
Wherein, the structure of the polyether modified heptamethyltrisiloxane is shown as the following formula:
g is- (CH)2)3(OCH(CH3)CH2)15(OCH2CH2)2OCOCH3。
And (3) performance testing:
1. defoaming capability test: adding 100mL of rhamnolipid fermentation liquor serving as foaming liquid into a 500mL graduated cylinder, blowing air at the speed of 3L/min, stopping blowing when the air bubble amount reaches the height of 500mL, immediately dropping a mixture of 10mg of antifoaming agent accurately weighed in net weight and 0.5mL of rhamnolipid fermentation liquor into the graduated cylinder once, and measuring the time for eliminating the foam completely.
2. And (3) testing the foam inhibition capability: 100mL of rhamnolipid fermentation liquor is added into a graduated measuring cylinder with scales as foaming, the net weight is accurately weighed to be 10mg of antifoaming agent, the antifoaming agent is placed into the rhamnolipid fermentation liquor, air is continuously blown in at the speed of 3L/min, and the foam heights of 1h, 12h, 24h, 36h and 48h are respectively recorded. If the intermediate foam height reaches 500mL, the time for the foam height to reach 500mL is recorded.
The detection methods used for the yield, extraction yield and purity of rhamnolipids are well known in the art. The results are shown in Table 1.
TABLE 1 antifoam Performance test results
As can be seen from Table 1, the defoaming agent for the rhamnolipid fermentation liquid prepared in the embodiments 1-4 of the invention has greatly better performances than the comparative examples and the commercially available samples. Wherein:
(1) as can be seen from the defoaming capability test results, the defoaming time of examples 1-4 is completed within 15s, which is greatly superior to that of comparative examples and commercially available samples. Among them, soybean oil has the worst defoaming power.
(2) As can be seen from the results of the foam inhibition capability test, the foam inhibition time of the examples 1-4 exceeds 48h, the foam at 48h does not reach 500mL, and the foam control requirement of the whole fermentation process can be ensured by adding the foam at one time. The comparative example and the commercial sample did not exceed 24 hours, and the foam inhibition ability was insufficient. Wherein, the soybean oil has the worst foam inhibition capability and is only kept for 9 min.
(3) As can be seen from the results of the foam inhibition capability tests of examples 2 and 3 and comparative examples 2 and 3, the terminal polyether modified polysiloxane and polyether modified heptamethyltrisiloxane with specific structures adopted by the invention have synergistic effect which is far better than that of a single component.
(4) As can be seen from the table 1, the antifoaming agent for the rhamnolipid fermentation liquor can significantly improve the yield and extraction rate of rhamnolipid, and has no obvious influence on the purity. And the purity of rhamnolipid is reduced because the surfactant of other components is introduced into the commercial fermentation antifoaming agent.
The terminal polyether modified polysiloxane with a specific structure is beneficial to forming a regular 'nail-shaped' arrangement shown in figure 1, and other polyether modified silicone oil is 'comb-shaped' polyether modified silicone oil shown in figure 2, cannot form the regular 'nail-shaped' arrangement and has poor defoaming capability.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. The antifoaming agent for the rhamnolipid fermentation liquor is characterized in that the preparation raw materials comprise terminal polyether modified polysiloxane, polyether modified heptamethyltrisiloxane and a solvent;
the terminal polyether modified polysiloxane has the following structure:
wherein R is- (CH)2)3(OCH(CH3)CH2)a(OCH2CH2)bOR1，R1is-COCH3、-COCH2CH2CH2CH3N is 10 to 100, a is 3 to 15, and b is 3 to 10;
the polyether modified heptamethyltrisiloxane has the structure shown as follows:
wherein G is- (CH)2)3(OCH(CH3)CH2)e(OCH2CH2)fOR2，R2is-COCH3、-COCH2CH2CH2CH3E is 8 to 15, and f is 0 to 5.
2. The antifoaming agent according to claim 1, wherein the raw materials for preparation comprise 20-40 parts by weight of the terminal polyether modified polysiloxane.
3. The antifoaming agent according to claim 2, wherein the raw materials for preparation comprise 25-32 parts by weight of the terminal polyether modified polysiloxane.
4. The antifoaming agent according to claim 1, wherein the raw materials for preparation comprise 5-10 parts by weight of polyether modified heptamethyltrisiloxane.
5. The antifoaming agent for rhamnolipid fermentation broth according to claim 4, characterized in that the raw material for preparation comprises 5-8 parts by weight of polyether modified heptamethyltrisiloxane.
6. The antifoaming agent for rhamnolipid fermentation broth according to claim 1, wherein the raw material for preparation includes 50-75 parts by weight of solvent.
7. The antifoaming agent for rhamnolipid fermentation broth according to any of claims 1 to 6, characterized in that the solvent includes at least one of ethanol, isopropanol and n-butanol.
8. A method for preparing the antifoaming agent for rhamnolipid fermentation broth according to any of claims 1 to 7, characterized in that the terminal polyether modified polysiloxane, polyether modified heptamethyltrisiloxane and solvent are mixed well.
9. Use of the rhamnolipid fermentation broth of any one of claims 1 to 7 with an antifoaming agent in the preparation of biosurfactant.
10. The use of claim 9, wherein the biosurfactant comprises a polymeric biosurfactant; preferably, the biosurfactant comprises an acyl peptide-based biosurfactant; preferably, the biosurfactant comprises a glycolipid, a lipopeptide and a phospholipid.
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| DE19936289A1 (en) * | 1999-08-02 | 2001-02-15 | Wacker Chemie Gmbh | Defoamer formulation |
| DE10314853A1 (en) * | 2003-04-02 | 2004-10-14 | Goldschmidt Ag | New organofunctional modified polysilanes are useful for the defoaming of liquid fuels, preferably diesel fuel |
| 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 |
| CN102643565A (en) * | 2012-05-04 | 2012-08-22 | 浙江润禾有机硅新材料有限公司 | Terminal modified organic silicone coating flatting agent and preparation method thereof |
| CN103214895A (en) * | 2013-04-26 | 2013-07-24 | 广东省石油化工研究院 | Organic silicon coating leveling agent and preparation method thereof |
| CN107216457A (en) * | 2017-04-21 | 2017-09-29 | 苏州博纳化学科技有限公司 | Defoamer of fluorine richness organosilicon and preparation method thereof |
| CN111040176A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Organic silicon polyether copolymer and preparation method and application thereof |
| CN111118088A (en) * | 2020-01-08 | 2020-05-08 | 万华化学集团股份有限公司 | Foam control method in rhamnolipid fermentation process |
| CN111151033A (en) * | 2020-01-17 | 2020-05-15 | 广东轻工职业技术学院 | Preparation method of novel polyether modified organic silicon defoaming agent |
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