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WO2025087455A1 - Composition démoussante de silicium organique et son procédé de préparation - Google Patents

Composition démoussante de silicium organique et son procédé de préparation Download PDF

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Publication number
WO2025087455A1
WO2025087455A1 PCT/CN2024/136726 CN2024136726W WO2025087455A1 WO 2025087455 A1 WO2025087455 A1 WO 2025087455A1 CN 2024136726 W CN2024136726 W CN 2024136726W WO 2025087455 A1 WO2025087455 A1 WO 2025087455A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
platinum
temperature
organosilicon
containing polyorganosiloxane
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Pending
Application number
PCT/CN2024/136726
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English (en)
Chinese (zh)
Inventor
董飞
黄伟
刘树龙
孙超
曹添
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Sixin Scientific-Technological Application Research Institute Co Ltd
Original Assignee
Jiangsu Sixin Scientific-Technological Application Research Institute Co Ltd
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Publication of WO2025087455A1 publication Critical patent/WO2025087455A1/fr
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Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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

Definitions

  • the invention relates to an organosilicon defoaming composition and a preparation method thereof.
  • the organosilicon defoaming composition belongs to fine chemicals, so the invention belongs to the technical field of fine chemical preparations.
  • defoaming agents to eliminate foam is one of the chemical methods.
  • defoaming agents have been widely promoted and applied.
  • defoaming agents on the market are classified by active ingredients, mainly polyethers, silicones, mineral oils, fatty alcohols and other polymers. Among them, silicone defoaming agents are widely favored by consumers due to their stable chemical properties, small side effects, and strong defoaming and suppression properties.
  • the organosilicon defoaming composition is the core component of the organosilicon defoamer. Its defoaming speed and antifoaming performance directly affect the performance of the final product. For organosilicon defoamers, the improvement of the defoaming and antifoaming performance of its active ingredients is the main optimization direction of the organosilicon defoamer.
  • the original organosilicon defoaming composition was prepared by polydimethylsiloxane and silicon dioxide through a specific processing technology. For example, the defoamer composition introduced in GB1051687A was prepared by heating polydimethylsiloxane and hydrophilic silicon dioxide, but its antifoaming performance was poor.
  • DE-OS2925722 replaced hydrophilic silicon dioxide with hydrophobic silicon dioxide;
  • US-A4145308 introduced (CH 3 ) 3 SiO 1/2 and SiO 2 units;
  • US4395352 describes an antifoaming agent composition containing a high viscosity polydimethylsiloxane fluid and finely dispersed hydrophobic particles, which can be used as a defoaming agent itself or in the form of an emulsion;
  • US3691091 discloses an organosilicon emulsion of an aqueous liquid defoaming agent, wherein the organosilicon consists of a polydimethylsiloxane fluid, silicon dioxide, and an organosilicon compound or oligomer containing an alkoxy group and/or a silanol group;
  • EP0163541 discloses a method for preparing an organosilicon defoaming agent by reacting a mixture of components including a preformed polyorganosiloxane polymer with
  • EP163541B1, CN102698475A, and CN104274998A introduce the use of terminal hydroxyl-containing polysiloxanes to react with polyorganosiloxanes containing other active functional groups under the action of a catalyst to form branched polyorganosiloxanes, and use this to replace ordinary polysiloxanes and hydrophilic silica for mixed treatment.
  • the prepared organosilicon defoaming composition has improved crosslinking degree, but the viscosity is too high and it is difficult to emulsify and disperse it in water.
  • US5153258 introduces the introduction of slightly crosslinked polyorganosiloxanes into the system to improve the defoaming and defoaming performance of the composition, for example, vinyl polyorganosiloxane and hydrogen-containing polyorganosiloxane, hydroxyl-containing polyorganosiloxane and alkyl silicate undergo crosslinking reaction under the action of a catalyst, but the degree of crosslinking is difficult to control.
  • US5486306 introduces a defoamer synthesized directly by reacting hydrogen-containing polyorganosiloxane with ⁇ -olefins. This process is simple to synthesize, but the defoamer obtained has poor defoaming performance and is only used in washing powder.
  • WO2007137948A1 introduces that after the reaction of hydrogen-containing polyorganosiloxane and vinyl polyorganosiloxane, trimethylsiloxy-terminated polydimethylsiloxane is added for dilution, but the contribution of the diluent to the defoaming performance is small, and when the hydrogen-containing polyorganosiloxane and vinyl polyorganosiloxane react, the viscosity is large and difficult to control, and the obtained defoamer composition has poor defoaming and antifoaming performance.
  • CN105107237A synthesizes terminal alkyl polysiloxane and side alkyl polysiloxane with terminal hydrogen-containing polysiloxane and side hydrogen-containing polysiloxane respectively, and finally introduces silanol polymer as a crosslinking agent to improve the crosslinking degree of the composition.
  • the above patents all improve the defoaming and antifoaming performance by improving the crosslinking degree of the composition, but the aggregation and precipitation problems of hydrophobic particles still exist.
  • the invention relates to an organosilicon defoaming composition and a preparation method thereof.
  • the invention comprises the following steps: reacting a high hydrogen-containing polyorganosiloxane and a high vinyl-content vinyl polysiloxane under the action of a catalyst to form a solid organosilicon powder; reacting a terminal hydrogen-containing polyorganosiloxane with an alpha-olefin under the action of a catalyst to form a terminal alkyl hydrogen-containing polyorganosiloxane; reacting a side hydrogen-containing polyorganosiloxane with an alpha-olefin under the action of a catalyst to form a side alkyl hydrogen-containing polyorganosiloxane; mixing the solid organosilicon powder, the side alkyl hydrogen-containing polyorganosiloxane and the terminal alkyl polyorganosiloxane into a reactor, so that the solid organosilicon powder reacts with the remaining hydrogen in the terminal and side alkyl hydrogen-containing
  • a polymer with an intermediate structure is then added to a silicone resin to obtain an organosilicon defoaming composition.
  • the organosilicon solid powder can be completely compatible with the organosilicon system during the reaction process, which solves the defoaming and antifoaming performance attenuation and compatibility problems caused by the aggregation of hydrophobic particles.
  • it is obtained by the reaction of hydrogen-containing polysiloxane and vinyl polysiloxane containing high-active groups, and the molecular structure has high density, which can greatly improve the cross-linking density of the organosilicon defoaming composition and greatly improve the defoaming and antifoaming performance of the defoaming agent.
  • This organosilicon defoaming composition can be prepared into a solid defoaming agent and a liquid defoaming agent, and has good defoaming and antifoaming performance in the papermaking and pulping, textile printing and dyeing, petroleum extraction, daily chemical washing and industrial cleaning industries.
  • the organosilicon defoaming composition of the present invention is composed of the following substances:
  • the substituents R0 are the same or different, and are hydrocarbon groups with 1 to 12 carbon atoms, selected from alkyl, cycloalkyl, and aryl, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, and n-dodecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; preferably R0 is methyl; the subscript a is an integer of 10 to 200; and the amount thereof is 20-40% of the total mass of the def
  • the substituent R1 is the same or different, and is a hydrocarbon group with 1 to 18 carbon atoms, selected from alkyl, cycloalkyl, and aryl, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; preferably R1 is methyl; the subscript b is an integer of 10 to 100; the subscript
  • the ⁇ -olefin is a mixture of any one or more of linear ⁇ -olefins, ⁇ -aromatic olefins or branched ⁇ -olefins, including ⁇ -octene, ⁇ -decene, ⁇ -dodecene, ⁇ -tetradecene, ⁇ -hexadecene, ⁇ -octadecene, ⁇ -eicosene, a C20-C24 linear ⁇ -olefin mixture, a C24-C28 linear ⁇ -olefin mixture, ⁇ -triacontene, ⁇ -methylstyrene, and ⁇ -styrene.
  • the ⁇ -olefin can be used alone or mixed in any proportion.
  • the ⁇ -olefin is added in two parts, the first part is used in an amount of 1-5% of the total mass of the defoaming composition, and the second part is used in an amount of 10-30% of the total mass of the defoaming composition.
  • Solid organosilicon powder is formed by reacting high hydrogen polyorganosiloxane D1 and high vinyl content vinyl polysiloxane D2 under the action of platinum catalyst D3, and finally ground to obtain solid organosilicon powder, the amount of which is 10-20% of the total mass of the defoaming composition;
  • R3 is an alkyl group having 1 to 5 carbon atoms, which may be the same or different; subscript c is 0, 1 or 2, subscript d is an integer of 100 to 300; subscript b is an integer of 50 to 1600; the hydrogen content of the high hydrogen polysiloxane is ⁇ 0.1%; the amount used accounts for 10 to 30% of the total mass of the solid organosilicon powder;
  • R 4 The value range of R 4 is the same as that of R 3 ; Vi is vinyl, subscript e is 0 or 1, subscript f is 30-80; subscript g is 20-80; the molecular weight of the high vinyl content vinyl polysiloxane D2 is less than 10000; the amount used accounts for 70-90% of the total mass of the solid silicone powder
  • the platinum catalyst D3 is selected from platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution, and platinum-vinyl complexes; the amount used is 0.01%-0.05% of the total mass of the high hydrogen-containing polysiloxane and the high vinyl content vinyl polysiloxane.
  • the catalyst is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution, platinum-vinyl complex, preferably chloroplatinic acid isopropanol solution; the amount of the catalyst is 3 to 20 ppm (in terms of platinum) of the total mass of the terminal hydrogen-containing polyorganosiloxane A, the side hydrogen-containing polyorganosiloxane B, the ⁇ -olefin C and the solid organosilicon powder D, and is used in three parts.
  • the MQ silicone resin is an MQ resin composed of chain segments (CH3)3SiOl/2 (M unit) and chain segments SiO4/2 (Q unit), the molar ratio between the two is (0.4-1.2):1.0, and the dosage is 2-8% of the total mass of the defoaming composition.
  • the preparation method of the organosilicon defoaming composition of the present invention is as follows:
  • the organosilicon defoaming composition of the present invention can be prepared into an emulsion defoaming agent or a solid defoaming agent for use.
  • silicone defoaming composition of the present invention is prepared into an emulsion defoaming agent, it can be prepared using the techniques for preparing silicone emulsions that are well known to those skilled in the art.
  • silicone emulsions contain the silicone defoaming composition as an oil phase, one or more surfactants, water and standard additives (such as preservatives, viscosity improvers, anti-gelling agents and/or thickeners); the surfactant can be selected from anionic, cationic, nonionic or amphoteric materials, or one or more mixtures thereof can be used.
  • the organosilicon defoaming composition of the present invention is prepared into a solid powder or granular defoaming agent.
  • the preparation of the solid powder or granular defoaming agent can be carried out using methods well known to those skilled in the art, such as spray drying or agglomeration granulation, and additives well known to those skilled in the art.
  • the organosilicon defoamer compositions prepared in Examples 7 to 13 and the organosilicon defoamer compositions prepared in Comparative Examples 5 to 9 were used to prepare solid defoamers G1 to G7 and DG1 to DG5, respectively.
  • the preparation methods are as follows:
  • the organosilicon defoamer compositions prepared in Examples 7 to 13 and the organosilicon defoamer compositions prepared in Comparative Examples 5 to 9 were used to prepare liquid defoamers Y1 to Y7 and DY1 to DY5, respectively.
  • the preparation methods are as follows:
  • a silicone defoaming composition 100 g of a silicone defoaming composition, 30 g of sorbitan monostearate (span 60) and 20 g of polyoxyethylene (20) sorbitan monostearate were mixed at 70°C for 10 minutes, and 500 g of water were added in batches; 2 g of polyacrylic acid was then added to the mixture, and the pH was adjusted to 6-7 with 10% NaOH, followed by adding 345 g of water; finally, the emulsion was homogenized with a high-pressure homogenizer, and the pH was adjusted to 6-7 with 10% NaOH again, and then 3 g of an isothiazolinone-based preservative was added to obtain an emulsion defoaming agent.
  • the organosilicon defoaming composition prepared by the present invention can be prepared into solid defoaming agent and liquid defoaming agent, and has good defoaming and defoaming performance in paper pulping, textile printing and dyeing, oil extraction, daily chemical washing and industrial cleaning industries. The following tests are selected in washing powder, papermaking black liquor and textile pulp.
  • This test uses a Jinzhang drum washing machine, model: ZWH6125, with a capacity of 7kg.
  • Test method Add 150g of commercially available laundry detergent, 0.75g of solid defoamer and 20kg of water into the washing machine.
  • the test procedure is the cotton and linen procedure.
  • Table 1 The test results are shown in Table 1:
  • the solid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in machine washing in a washing powder solution than the solid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.
  • Test 1 Papermaking black liquor system tested at 85°C
  • Test method First, add 600mL of black liquor (from pine wood) into the circulating bubbler, set the temperature to 85°C and the flow rate to 6L/min, then turn on the temperature control switch, heat the foaming liquid to the set temperature, turn on the circulation pump, start impact foaming, wait for the foam to rise to 300mL, add 0.1% defoamer, and record the change of foam height over time.
  • the better the defoaming performance of the defoamer the lower the minimum scale reached by the foam; the better the anti-foaming performance of the defoamer, the longer it takes for the foam to reach 300mL again.
  • the liquid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in black liquor than the liquid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.
  • Test method Take a 250ml stoppered measuring cylinder and add 160ml of prepared textile pulp, then add 0.05g of emulsion defoamer, shake the bottle up and down at a speed of 2s/time, shake each group of bottles 10 times, and record the defoaming time of each group. The shorter the defoaming time in each group of shaking bottles, the better the defoaming and defoaming performance of the defoamer sample.
  • the liquid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in textile slurry than the liquid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne une composition démoussante de silicium organique et son procédé de préparation. Un polyorganosiloxane à haute teneur en hydrogène et un polysiloxane vinylique à haute teneur en vinyle sont mis à réagir sous l'action d'un catalyseur, de manière à former une poudre de silicium organique solide ; un polyorganosiloxane contenant de l'hydrogène sur un groupe terminal et une α-oléfine réagissent sous l'action d'un catalyseur pour former un polyorganosiloxane contenant de l'hydrogène sur un groupe alkyle terminal ; un polyorganosiloxane contenant de l'hydrogène sur un groupe pendant et une α-oléfine réagissent sous l'action d'un catalyseur pour former un polyorganosiloxane contenant de l'hydrogène au niveau d'un groupe alkyle pendant ; et la poudre de silicium organique solide, le polyorganosiloxane contenant de l'hydrogène sur un groupe alkyle pendant et le polyorganosiloxane contenant de l'hydrogène sur un groupe alkyle terminal sont mélangés et chargés dans un réacteur, de telle sorte que la poudre de silicium organique solide est soumise à une réaction de réticulation avec l'hydrogène résiduel dans le polyorganosiloxane contenant de l'hydrogène sur un groupe alkyle terminal et le polyorganosiloxane contenant de l'hydrogène sur un groupe alkyle pendant, de manière à former un polymère ayant une structure spatiale SiOSi, puis une résine de silicium organique est ajoutée à celui-ci pour préparer une composition démoussante de silicium organique, ce qui permet d'améliorer la densité de réticulation de la composition démoussante de silicium organique et d'améliorer considérablement les performances démoussante et anti-moussage de l'agent démoussant.
PCT/CN2024/136726 2023-10-27 2024-12-04 Composition démoussante de silicium organique et son procédé de préparation Pending WO2025087455A1 (fr)

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CN202311403742.4 2023-10-27
CN202311403742.4A CN119896882A (zh) 2023-10-27 2023-10-27 一种有机硅消泡组合物及其制备方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009262080A (ja) * 2008-04-25 2009-11-12 San Nopco Ltd 界面活性剤
CN105107237A (zh) * 2015-10-12 2015-12-02 江苏四新科技应用研究所股份有限公司 一种有机硅消泡组合物及其制备方法
CN105498304A (zh) * 2015-12-15 2016-04-20 江苏四新科技应用研究所股份有限公司 一种消泡组合物及其制备方法
CN106215465A (zh) * 2016-08-12 2016-12-14 中国海洋石油总公司 一种油气分离用消泡剂
CN109107229A (zh) * 2018-08-23 2019-01-01 南京瑞思化学技术有限公司 有机硅组合物
CN113797600A (zh) * 2020-06-16 2021-12-17 江苏四新科技应用研究所股份有限公司 一种有机硅消泡组合物及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009262080A (ja) * 2008-04-25 2009-11-12 San Nopco Ltd 界面活性剤
CN105107237A (zh) * 2015-10-12 2015-12-02 江苏四新科技应用研究所股份有限公司 一种有机硅消泡组合物及其制备方法
CN105498304A (zh) * 2015-12-15 2016-04-20 江苏四新科技应用研究所股份有限公司 一种消泡组合物及其制备方法
CN106215465A (zh) * 2016-08-12 2016-12-14 中国海洋石油总公司 一种油气分离用消泡剂
CN109107229A (zh) * 2018-08-23 2019-01-01 南京瑞思化学技术有限公司 有机硅组合物
CN113797600A (zh) * 2020-06-16 2021-12-17 江苏四新科技应用研究所股份有限公司 一种有机硅消泡组合物及其制备方法

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