WO2016101568A1 - 一种有机硅组合物及其制备、应用 - Google Patents

一种有机硅组合物及其制备、应用 Download PDF

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Publication number
WO2016101568A1
WO2016101568A1 PCT/CN2015/082284 CN2015082284W WO2016101568A1 WO 2016101568 A1 WO2016101568 A1 WO 2016101568A1 CN 2015082284 W CN2015082284 W CN 2015082284W WO 2016101568 A1 WO2016101568 A1 WO 2016101568A1
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Prior art keywords
integer
parts
silicone
polyether
content
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English (en)
French (fr)
Inventor
侯伟
吴飞
曹添
黄伟
杨有忠
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Jiangsu SIXIN Scientific Technological Application Research Institute Co Ltd
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Jiangsu SIXIN Scientific Technological Application Research Institute Co Ltd
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Priority to EP15871643.1A priority Critical patent/EP3210663B1/en
Publication of WO2016101568A1 publication Critical patent/WO2016101568A1/zh
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention provides a high-content foam control agent for liquid detergents, which has better foam control effect in detergents and better maintains the clarity of detergents, and belongs to the field of fine chemical technology.
  • Liquid detergent is a daily necessities for people. It has the unique advantages of convenient use, rapid dissolution, and mildness to fabrics and skin. Due to the stabilizing effect of the surfactant, the foam is difficult to rinse, which not only wastes water resources, increases the cost of washing, but also causes large-scale water pollution, which is not conducive to energy saving, emission reduction and environmental protection. At present, this problem is usually solved by adding a silicone antifoaming agent to the detergent mixture component. However, in addition to the foam control effect, the stability and clarity of silicone antifoams in detergents are two other important properties to be considered.
  • EP 1 753 853 B1 discloses a low-foaming liquid detergent composition which, by adding an ethoxylated fatty acid diester to a liquid detergent, can exert a certain foam control effect without causing turbidity, but its foam control effect is not up to The effect of silicone defoamer.
  • CN 103272411 A relates to a foam inhibitor and a preparation method thereof, and the hydrogen-containing polyorganosiloxane and the unsaturated polyether and the ⁇ -olefin are obtained by an acidic catalyst to obtain an alkyl group, an unsaturated polyether co-modified polyorganism.
  • the obtained foam inhibitor active ingredient is further prepared by an emulsifier to prepare an O/W type antifoam emulsion, which is added to the non-structural detergent, and can effectively solve the clear Degree problem.
  • EP 1 075 683 and EP 1 075 684 disclose a foam control agent for liquid detergents comprising an organopolysiloxane material, a silicone resin and a hydrophobic filler, wherein the organopolysiloxane material comprises the molecular formula X- At least one silicon-bonded substituent organopolysiloxane of Ar, wherein X represents a divalent aliphatic group bonded to silicon through a carbon atom and Ar represents an aromatic group.
  • the organic-based resin is selected from the group consisting of siloxane units having the formula RaSiO (4-a)/2 , wherein R represents a hydroxyl group, a hydroxyl group or a hydroxyl group and a has an average value of 0.5 to 2.4.
  • CN102307978 A discloses a foam inhibitor comprising, based on EP 1075684, an organopolysiloxane resin having at least one polyoxyalkylene group, comprising a tetrafunctional siloxane unit having the formula RSiO4/2 and having the formula Monofunctional siloxane unit of R3SiO4/2.
  • the total number of tetrafunctional siloxane units in the silicone resin is at least 50% based on the total number of siloxane units and R represents a hydroxyl group.
  • This liquid foam inhibitor in heavy duty liquid (HDL) detergents solves the stability and foam control properties of the composition in detergents, but also increases the turbidity of liquid detergents in appearance.
  • CN1215162C discloses a silicone-based foam control composition
  • a silicone antifoaming agent and silica dispersed in a detergent compatible carrier by mixing a silicone based antifoaming agent with silica The mixture is then added to a continuous phase consisting of an alkyl polyglycoside formulation, a branched alcohol ethoxylate, a silicone polyether, and water, with a good density match between them exhibiting a low phase delamination rate.
  • the invention adopts the compounding of the crosslinked polyether-polydiorganosiloxane and the branched polyether-polydiorganosiloxane, and further cooperates with the synergistic action of the polyether polyol to have an alkyl structure.
  • the silicone composition has good encapsulation and dispersion, and a high-content silicone antifoam composition having a specific assembly structure is prepared to have excellent clarity and stability in a liquid detergent. In liquid detergents, it has a better foam control effect with less added amount.
  • a silicone antifoam composition characterized in that it consists of the following materials:
  • the silicone active of the present invention is prepared by a technique known to those skilled in the art using hydrogen-containing polyorganosiloxanes, acrylates, ⁇ -olefins, catalysts, silica, and silicone resins.
  • the silicone component of the antifoam composition is contained in an amount of from 5 to 40 parts by weight, preferably from 5 to 35 parts, more preferably from 8 to 25 parts by weight.
  • Me is a methyl group, subscript k is 0 or 1, v is an integer of 2 to 100, w is an integer of 20 to 300, and each molecule has at least 2 silicon-bonded hydrogen atoms; the organosilicon composition
  • the hydrogen-containing polyorganosiloxane is contained in an amount of 40 to 80 parts by weight.
  • Vi is a vinyl group
  • t is an integer of from 1 to 36, preferably an integer of from 6 to 18.
  • the content of the ⁇ -olefin in the silicone composition is from 10 to 30 parts.
  • the acrylate is an ester of acrylic acid and its homologues, including methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate or 2 - butyl methacrylate; in one embodiment, the acrylate content of the silicone composition is from 3 to 15 parts by weight.
  • the catalyst is selected from the group consisting of a platinum-alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, and a platinum-ketone.
  • a complex a chloroplatinic acid isopropanol solution or a platinum-vinyl complex; preferably a chloroplatinic acid isopropanol solution having a platinum content of 1 to 20 ppm; in one embodiment, the quality of the catalyst in the silicone composition
  • the dosage is 0.01 to 0.2%.
  • the silica comprises fumed silica or precipitated silica having a specific surface area of from 50 to 500 m 2 /g and may or may not be hydrophobized.
  • precipitated silica or fumed silica having a specific surface area of from 90 to 300 m 2 /g is preferred; in one embodiment, the silica is present in the silicone composition in an amount of from 1 to 15 parts by weight.
  • the silicone resin refers to a highly crosslinked spatial network structure polyorganosiloxane, and the network structure polyorganosiloxane is usually composed of methyltrichlorosilane, dimethyldichlorosilane, benzene.
  • the silicone resin is an MQ resin composed of a unit of CH 3 SiO 1/2 (referred to as M unit in silicone chemistry) and a chain SiO 4/2 (Q unit), and the molar ratio therebetween is (0.4). ⁇ 1.2): 1.0, preferably (0.5 to 0.8): 1.0.
  • the MQ resin is present in the silicone composition in an amount of from 5 to 20 parts by weight.
  • the silicone composition A (ie, component A) can be prepared by using the prior art, and the invention also provides a specific preparation method: firstly mixing the above hydrogen-containing organopolysiloxane with acrylate. The catalyst was added at 70 ° C and the system was heated to 100 ° C for 1 hour, and then ⁇ -olefin was added thereto for further 2 hours. Finally, silica was added to the silicone resin to obtain a silicone composition.
  • the polyether-polydiorganosiloxane is a combination of three or more of the following structural formulae, and at least two c ⁇ 0; polyether-poly in the antifoam composition
  • the diorganosiloxane is contained in an amount of 10 to 70 parts by weight, preferably 15 to 60 parts, more preferably 15 to 40 parts by weight:
  • Me is a methyl group
  • a is an integer of 20 to 300
  • b is an integer of 2 to 100
  • c is an integer of 0-100
  • d is an integer of 2 to 100
  • R 1 represents a polyether segment, which is a ring a copolymer obtained by copolymerization of oxyethylene-propylene oxide
  • R 2 is an aliphatic hydrocarbon group having the structural formula -(CH 2 ) z H, z is an integer of from 1 to 36
  • R 3 is a crosslinking agent, preferably a double vinyl seal.
  • the R 1 segment is grafted to the siloxane backbone by a hydrosilylation reaction of a polyether containing an unsaturated double bond and Si-H, and the polyether having an unsaturated double bond has the formula:
  • R 4 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an ester group, an epoxy group or an amino group; EO is ethylene oxide, PO is propylene oxide, x and y are degrees of polymerization, and x is 0.
  • An integer of -150 is preferably an integer of 0 to 40; y is an integer of 0 to 150, preferably an integer of 0 to 100; and x and y are not 0 at the same time.
  • the R 2 is an aliphatic hydrocarbon group having the structural formula -(CH 2 ) z H, which is grafted onto the siloxane backbone by a hydrosilylation reaction of an olefin having an unsaturated double bond and Si-H.
  • the R 3 is a hydrosilylation reaction with Si-H by a divinyl-terminated polyorganosiloxane to obtain a modified polysiloxane having a crosslinked structure, a divinyl terminated polyorganosiloxane Oxyalkanes have the following structural formula:
  • n is an integer of 100 to 500, preferably an integer of 200 to 400; and the divinyl-terminated polyorganosiloxane has a kinematic viscosity at 25 ° C of 50 to 2,000 mPa ⁇ s.
  • the polyether-polydiorganosiloxane in the present invention is obtained by reacting the above-mentioned modifying groups R 1 , R 2 and R 3 with a hydrogen-containing polyorganosiloxane under the action of a catalyst, wherein various The modifying group is grafted onto the hydrogen-containing polyorganosiloxane backbone by random polymerization.
  • the hydrogen-containing polyorganosiloxane is at least one hydrogen-containing polyorganosiloxane having the following structural formula:
  • Me is a methyl group
  • p is an integer of 2 to 100, preferably an integer of 10 to 70
  • q is an integer of 20 to 300, preferably an integer of 40 to 200
  • each molecule has at least 2 silicon-bonded hydrogen atoms
  • the hydrogen-containing polyorganosiloxane has a kinematic viscosity at 25 ° C of 20 to 5,000 mPa ⁇ s.
  • the catalyst is selected from the group consisting of a platinum-alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, a platinum-ketone complex, a chloroplatinic acid isopropanol solution or One of the platinum-vinyl complexes.
  • the catalyst in the method is preferably a chloroplatinic acid isopropanol solution having a platinum content of 1 to 20 ppm.
  • the mass of the catalyst in the polyether-polydiorganosiloxane is from 0.01 to 0.2% by weight based on the total mass.
  • the silicone active material is a defoaming active material, however, it is not preferable to directly disperse it into the laundry liquid, and it is also required to act by means of a polyether-polydiorganosiloxane; the inventors found in the experiment that the polyether - Polydiorganosiloxane has good encapsulation and dispersing ability for organosilicon actives having aliphatic hydrocarbon groups, and can be prepared by compounding polyether-polydiorganosiloxanes of three different structures. A stable high level of silicone defoamer is obtained.
  • polyether-polydiorganosiloxanes of the three different structures used in the present invention are each a substance having the following structural formula.
  • R 1 represents a polyether segment obtained by copolymerization of ethylene oxide-propylene oxide
  • x is an integer of 0 to 150, preferably an integer of 0 to 40
  • y is an integer of 0 to 150, preferably 0 to 100.
  • An integer; x, y are not 0 at the same time
  • R 2 is an aliphatic hydrocarbon group having the structural formula -(CH 2 ) z H, and z is an integer of 6-18.
  • R 3 is a divinyl terminated polyorganosiloxane, and m is an integer of from 200 to 400.
  • the B1 content of the antifoaming agent composition is from 5 to 40 parts, preferably from 5 to 35 parts, more preferably from 8 to 25 parts by weight.
  • B2 a is an integer of 20 to 300, b is an integer of 2 to 100, c is an integer of 2 to 100, and d is an integer of 2 to 100.
  • R 1 represents a polyether segment obtained by copolymerization of ethylene oxide-propylene oxide, x is an integer of 0 to 150, preferably an integer of 0 to 40; and y is an integer of 0 to 150, preferably 0 to 100. An integer; x, y are not 0 at all; R 2 is a methyl group.
  • R 3 is a divinyl terminated polyorganosiloxane, and m is an integer of from 200 to 400.
  • the amount by weight of B2 in the antifoaming composition is from 2 to 30 parts, preferably from 5 to 25 parts, more preferably from 5 to 20 parts.
  • R 1 represents a polyether segment obtained by copolymerization of ethylene oxide-propylene oxide
  • x is an integer of 0 to 150, preferably an integer of 0 to 40
  • y is an integer of 0 to 150, preferably 0 to 100.
  • An integer; x, y are not 0 at the same time
  • R 2 is an aliphatic hydrocarbon group having the structural formula -(CH 2 ) z H, and z is an integer of 6-18.
  • the polyether-polydiorganosiloxane has an average kinematic viscosity at 25 ° C of 10 to 30,000 mPa ⁇ s, preferably 100 to 3,000 mPa ⁇ s.
  • the content of B3 in the antifoam composition is from 2 to 20 parts, preferably from 2 to 15 parts, more preferably from 2 to 10 parts by weight.
  • B1 and B2 are cross-linked polyether-polydiorganosiloxanes which are added to the divinyl-terminated polyorganosiloxane during the preparation of the branched polyether-polydiorganosiloxane (also It is obtained by reacting a crosslinking agent.
  • the crosslinked polyether-polydiorganosiloxane has an average kinematic viscosity at 25 ° C of 20 to 40,000 mPa ⁇ s, preferably 100 to 4,000 mPa ⁇ s.
  • the crosslinked polyether-polydiorganosiloxane has excellent emulsifying and encapsulating ability. This excellent emulsifying and encapsulating ability enables the silicone active to be dispersed to a certain extent in the laundry liquid and through the component C. Further strengthened so that it is stably dispersed in the laundry liquid.
  • the polyether polyol structure is a combination having three or more of the following formulas; the polyether polyol is contained in the antifoam composition in an amount of 10 to 80 parts by weight, preferably 20 to 70 parts by weight, More preferably, it is 35-65 parts.
  • the subscript g is an integer of 1 to 6, preferably an integer of 1 to 3;
  • EO is ethylene oxide
  • PO is propylene oxide;
  • R 5 is a reaction residue of a polyether initiator, and the initiator is C1 a linear or branched alkyl alcohol of -C30, preferably a C16-C18 linear alkyl alcohol, ethylene glycol, propylene glycol, glycerol, glycerol trimethylolpropane;
  • m, n is a degree of polymerization, m is 1
  • An integer of ⁇ 100 is preferably an integer of 1 to 40, and n is an integer of 0 to 80, and preferably an integer of 0 to 60.
  • the addition of the polyether is added in two steps. This order of addition may be advantageous for the layered assembly structure of the silicone antifoaming agent.
  • the defoaming agent combination is destroyed.
  • the layer assembly of the material will eventually affect the stability of the defoamer, causing uneven density distribution and delamination.
  • C1 g is 1, m is 0, n is preferably an integer from 5 to 40, and the initiator is propylene glycol.
  • the C1 content of the antifoaming agent is from 5 to 50 parts by weight, preferably from 10 to 40 parts, more preferably from 15 to 35 parts by weight.
  • the second step is to add:
  • C2 g is 3, m is preferably an integer of 10 to 40, n is preferably an integer of 0 to 80, and the initiator is glycerol.
  • the C2 content of the antifoaming agent is from 2 to 40 parts by weight, preferably from 5 to 35 parts, more preferably from 5 to 20 parts by weight.
  • C3 g is 1, m is preferably an integer of 10 to 40, n is preferably an integer of 0 to 80, and the initiator is a C16 to C18 linear alkyl alcohol.
  • the amount of C3 in the antifoam composition is from 2 to 40 parts, preferably from 5 to 35 parts, more preferably from 5 to 20 parts by weight.
  • the antifoaming agent of the present invention may be specifically formulated by a method comprising the following steps:
  • the inventors used a cross-linked modified polyorganosiloxane B1, B2 and a branched modified polyorganosiloxane B3 in the preparation of an antifoaming agent for an organosilicon composition having an alkyl group-modified group.
  • a stable high content of antifoaming agent can be prepared, and the prepared defoaming agent is added to the liquid detergent with ideal clarity. And stability, it has a better foam control effect with less added amount. This is due to the special structure of B1.
  • the modified polyorganosiloxane of the crosslinked structure has strong emulsifying and dispersing ability, and can effectively encapsulate and disperse the silicone composition A, and the alkyl group on the side chain.
  • the structure is similar to the structure of the side chain alkyl group on the silicone composition, has good affinity, and ensures the stability of the defoaming agent.
  • the role of the polyether polyol is primarily to further disperse the antifoam component, reducing the viscosity of the composition, making it easier to disperse in the laundry liquor.
  • the compounding effect of two or more polyether polyols is significantly better than that of the single use.
  • the order of addition of the polyether polyols also has an effect on the properties of the antifoam composition, especially in terms of stability, which may be advantageous for the layered assembly structure of the silicone defoamer.
  • the order of addition of the polyether will destroy the layer assembly of the defoamer composition, which will eventually affect the stability of the defoamer, causing uneven density distribution and delamination.
  • Component A Silicone active
  • the silicone active A1 was prepared as follows:
  • the silicone active A2 was prepared as follows:
  • the silicone active A3 was prepared as follows:
  • Component B Polyether-polydiorganosiloxane:
  • the corresponding modified groups R 1 , R 2 and R 3 having an unsaturated double bond shown in Table 1 are reacted with hydrogen-containing polyorganisms in the presence of a solution of chloroplatinic acid isopropanol having a platinum content of 1 to 20 ppm.
  • the siloxane reaction is obtained in which various modifying groups are grafted onto the hydrogen-containing polyorganosiloxane backbone by random polymerization.
  • Component C Polyether polyol
  • the antifoam products of Examples 1-10 were prepared according to the formulations in Table 3.
  • the component A prepared by the well-known technique shown in Table 3 was mixed with the component B and heated to 55 ° C, stirred at 150 rpm for 0.5 h, kept at the same temperature and added to C1, stirred uniformly, and homogenized by a colloid mill. After the treatment, C2 and C3 were added and stirred to obtain the antifoam composition.
  • the component A prepared by the known technique shown in Table 3 was mixed with the component B and heated to 145 ° C, stirred at 550 rpm for 1.5 h, kept at the same temperature and added to C1, stirred uniformly, and homogenized by a colloid mill. After the treatment, C2 and C3 were added and stirred to obtain the antifoam composition.
  • Comparative Examples 1-7 were similar to the preparation methods of the examples: Component A prepared by the well-known technique shown in Table 3 was mixed with Component B and heated to 55 ° C, stirred at 150 rpm for 0.5 h, and maintained at a temperature of After changing and adding C1, the mixture was uniformly stirred, and after homogenization treatment by a colloid mill, C2 and C3 were added and stirred uniformly to obtain the antifoam composition.
  • Comparative Example 8 Component A prepared in the same manner as in Example 1 was mixed with Component B and heated to 55 ° C, stirred at 150 rpm for 0.5 h, and then the order of addition of the polyether polyol was changed, and C2 was first added. After stirring evenly with C3, C1 is further homogenized by a colloid mill, and then uniformly stirred to obtain the antifoam composition.
  • Comparative Example 9 Component A prepared in the same manner as in Example 1 was mixed with Component B and heated to 55 ° C, After stirring at 150 rpm for 0.5 h, C1, C2 and C3 were simultaneously added, and after stirring uniformly, the mixture was homogenized by a colloid mill, and stirred uniformly to obtain the antifoam composition.
  • Example 5 13 19 twenty four 26 29 32 36 38 39 40 Comparative example 1 13 19 twenty four 26 29 32 36 38 39 40 Comparative example 2 17 twenty four 29 33 39 44 49 53 57 64 Comparative example 3 15 twenty one 25 30 33 35 38 40 42 45 Comparative example 4 16 twenty one 27 32 35 37 41 44 46 49 Comparative example 5 13 20 twenty three 26 29 32 35 38 39 40 Comparative example 10 17 twenty four 29 33 37 43 48 54 56 59
  • Examples 1-5 have similar bubble control effects and have smaller haze values; Comparative Examples 1-7 indicate that changes and substitutions in the structure of any of these components result in stability and clarity. A large effect; Comparative Examples 8 and 9 show that changing the order of addition of the polyether polyol results in delamination of the composition, thus indicating that the prepared antifoaming agent may be a layer-assembled structure, changing this The order of addition disrupts the structure of the antifoam composition, resulting in delamination.
  • Comparative Example 10 is an oil-in-water emulsion product which has a weaker clarity and foam control effect than the prepared product, and is disadvantageous for transportation, energy saving and environmental protection.

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Abstract

一种有机硅消泡剂组合物，它由以下物质组成：A、有机硅活性物，在消泡剂组合物中有机硅活性物的重量份含量为5～40份；B、聚醚-聚二有机基硅氧烷，聚醚-聚二有机基硅氧烷具有结构通式 (I) 在消泡剂组合物中聚醚-聚二有机基硅氧烷的重量份含量为10～70份：C、聚醚多元醇，聚醚多元醇结构具有通式：R 5[(EO) m(PO) nH] g；在消泡剂组合物中聚醚多元醇的重量份含量为10-80份。

Description

一种有机硅组合物及其制备、应用 技术领域
本发现提供了一种用于液体洗涤剂的高含量泡沫控制剂，在洗涤剂中具有较好的控泡效果，同时能较好的保持洗涤剂的清澈度，属于精细化工技术领域。
背景技术
液体洗涤剂是人们的日常生活用品，具有产品使用方便、溶解迅速、对织物和肌肤更加温和等独特优势。由于表面活性剂的稳泡作用，造成泡沫多难漂洗，不仅浪费水资源，增加洗衣成本，还会造成大规模水体污染，不利于节能减排和绿色环保。目前，这个问题通常是寄托于通过将硅氧烷消泡剂加入到洗涤剂混合物组分中来解决。然而，除了泡沫控制效果外，硅氧烷消泡剂在洗涤剂中的稳定性和清澈度是另外两个需要重点考察的性能。
EP1753853B1公开了一种低泡液体洗涤剂组合物，通过向液体洗涤剂中添加乙氧基脂肪酸二酯，能够起到一定的控泡作用，同时不会引起浑浊，但是其控泡效果还达不到有机硅消泡剂的效果。CN 103272411 A涉及一种泡沫抑制剂及其制备方法，将含氢聚有机硅氧烷和不饱和聚醚、α-烯烃在酸性催化剂作用下，得到烷基、不饱和聚醚共改性聚有机硅氧烷；然后加入疏水粒子与有机硅树脂混合处理，得到的泡沫抑制剂活性成分再通过乳化剂作用制备O/W型消泡剂乳液，添加到非结构型洗涤剂中，能够有效解决清澈度问题。
EP1075683和EP1075684公开了一种用于液体洗涤剂的泡沫控制剂，它包括有机基聚硅氧烷材料，有机硅树脂和疏水填料，其中所述的有机基聚硅氧烷材料包括具有分子式X-Ar的至少一个与硅键合的取代基的有机聚硅氧烷，其中X表示通过碳原子键合到硅上的二价脂族基团和Ar表示芳族基团。有机基树脂选自选自具有式RaSiO(4-a)/2的硅氧烷单元组成，其中R表示羟基，羟氧基或羟基且a具有0.5～2.4的平均值。CN102307978 A公开了一种泡沫抑制剂，在EP1075684的基础上包括具有至少一个聚氧亚烷基的有机基聚硅氧烷树脂，其中包含具有式RSiO4/2的四官能硅氧烷单元和具有式R3SiO4/2的单官能硅氧烷单元。其中硅树脂中四官能硅氧烷单元的总数基于硅氧烷单元总数计为至少50％和R表示羟基。将此液体泡沫抑制剂用于重垢液体(HDL)洗涤剂中，解决了组合物在洗涤剂中的稳定性和泡沫控制性能，但是在外观上还是增加了液体洗涤剂的浊度。CN1215162C公开了一种包括分散于洗涤剂相容的载体中的硅氧烷防沫剂和二氧化硅的硅氧烷基控泡组合物，通过将硅氧烷基防沫剂和二氧化硅混合，然后将混合物加入到由烷基聚苷制剂、支链醇乙氧基化物、硅氧烷聚醚和水组成连续相中，它们之间的密度匹配良好而表现出低相分层速率。
从洗涤产品的发展趋势来看，未来环保型和浓缩型洗涤产品将是整个日化洗涤市场的发展趋势，高浓度的产品对于企业和环境也有着巨大的好处，比如减少运输、包装费用、减少 能源消耗，降低二氧化碳的排放量。对于消泡剂产品也是一样，浓缩型消泡剂具有低成本、高性能的特点，但鉴于高含量消泡剂的稳定性问题和添加到液体洗涤剂中的浊度较高的原因，市场上此类产品一直处于紧缺状态。
发明内容
本发明通过采用交联型聚醚-聚二有机基硅氧烷和支链型聚醚-聚二有机基硅氧烷的复配，再配合聚醚多元醇的协同作用，对具有烷基结构的有机硅组合物有很好的包裹和分散作用，制备出具有特定组装结构的高含量有机硅消泡剂组合物，使其在液体洗涤剂中具有优异的清澈度和稳定性，将其加入到液体洗涤剂中，在较少添加量下就具有较理想的泡沫控制效果。
本发明采取的技术方案：一种有机硅消泡剂组合物，其特征在于，它由以下物质组成：
A、有机硅活性物
本发明所述的有机硅活性物，是采用含氢聚有机硅氧烷、丙烯酸酯、α-烯烃、催化剂、二氧化硅和有机硅树脂，通过本领域技术人员公知技术制备得到的。
在一种方案中，消泡剂组合物中有机硅组合物的重量份含量为5～40份，优选5～35份，更优选8～25份。
A(Ⅰ)：含氢聚有机硅氧烷：
至少一种结构通式为如下的含氢聚有机硅氧烷：
HkMe3-kSiO(MeHSiO)v(Me2SiO)wSiMe3-kHk
Me为甲基，下标k是0或1，v是2～100的整数，w是20～300的整数，每个分子具有至少2个硅键合的氢原子；所述的有机硅组合物中含氢聚有机硅氧烷的重量份为40～80份。
A(Ⅱ)：α-烯烃
所述的α-烯烃的结构通式如下：
Vi(CH2)tH
Vi为乙烯基，t为1～36的整数，优选6～18的整数；在一种方案中，有机硅组合物中α-烯烃的含量为10～30份。
A(Ⅲ)：丙烯酸酯
所述的丙烯酸酯是丙烯酸及其同系物的酯类，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异丁酯、2-甲基丙烯酸甲酯、2-甲基丙烯酸乙酯或2-甲基丙烯酸丁酯；在一种方案中，有机硅组合物中丙烯酸酯的重量份含量为3～15份。
A(Ⅳ)：催化剂
所述的催化剂选自铂-醇络合物、铂-烯烃络合物、铂-醇盐络合物、铂-醚络合物、铂-酮 络合物、氯铂酸异丙醇溶液或铂-乙烯基络合物；优选铂含量为1～20ppm的氯铂酸异丙醇溶液；在一种方案中，有机硅组合物中催化剂的质量用量为0.01～0.2％。
A(Ⅴ)：二氧化硅
所述的二氧化硅包括气相二氧化硅或沉淀二氧化硅，比表面积为50～500m2/g,可以经过或未经过疏水化处理的。本发明优选比表面积为90～300m2/g的沉淀二氧化硅或气相二氧化硅；在一种方案中，有机硅组合物中二氧化硅的重量份含量为1～15份。
A(Ⅵ)：有机硅树脂
所述的有机硅树脂指高度交联的空间网状结构的聚有机硅氧烷，这种网状结构的聚有机硅氧烷通常是由甲基三氯硅烷、二甲基二氯硅烷、苯基三氯硅烷、二苯基二氯硅烷或甲基苯基二氯硅烷的各种混合物在有机溶剂如甲苯中水解，得到酸性水解物，然后经水洗除去酸，得到产品；本发明使用的有机硅树脂为由链节CH3SiO1/2(有机硅化学中称为M单元)和链节SiO4/2(Q单元)的单元组成的MQ树脂，二者之间的摩尔比为(0.4～1.2)：1.0，优选(0.5～0.8)：1.0。在一种方案中，有机硅组合物中MQ树脂的重量份含量为5～20份。
所述的有机硅组合物A(即组分A)可采用现有技术进行制备，本发明也提供一种具体的制备方法为：先将上述的含氢有机聚硅氧烷与丙烯酸酯混合均匀，于70℃加入催化剂并将体系升温至100℃保温1小时，再向其中加入α-烯烃继续保温2小时，最后加入二氧化硅与有机硅树脂混合处理得到有机硅组合物。
B、聚醚-聚二有机基硅氧烷
所述的聚醚-聚二有机基硅氧烷为具有如下的结构通式中的三种或三种以上的组合，且至少两种c≠0；在消泡剂组合物中聚醚-聚二有机基硅氧烷的重量份含量为10～70份，优选15～60份，更优选15～40份：
Figure PCTCN2015082284-appb-000001
其中：Me为甲基，a是20～300的整数，b是2～100的整数，c是0-100的整数，d是2-100的整数；R1表示聚醚链段，是由环氧乙烷-环氧丙烷共聚得到的共聚物，R2为具有结构式-(CH2)zH的脂肪烃基，z为1～36的整数，R3为交联剂，优选为双乙烯基封端的聚二甲基硅氧烷；
更具体的：
所述R1链段是通过含有不饱和双键的聚醚和Si-H发生硅氢加成反应而接枝到硅氧烷主链 上，含有不饱和双键的聚醚具有通式：
CH2＝CHCH2O(EO)x(PO)yR4
其中R4为氢原子、碳原子数为1～6的烷基、酯基、环氧基或氨基；EO为环氧乙烷，PO为环氧丙烷，x、y为聚合度，x为0～150的整数，优选0～40的整数；y为0～150的整数，优选0～100的整数；x，y不同时为0。
所述R2为具有结构式-(CH2)zH的脂肪烃基，该脂肪基是通过含有不饱和双键的烯烃和Si-H发生硅氢加成反应而接枝到硅氧烷主链上，含有不饱和双键的烯烃优选具有结构式CH2＝CH(CH2)zH的α-烯烃,z为1～36的整数，优选1或6～18的整数。
所述的R3是通过双乙烯基封端聚有机硅氧烷与Si-H发生硅氢加成反应，从而得到具有交联结构的改性聚硅氧烷，双乙烯基封端聚有机硅氧烷具有结构通式如下:
CH2＝CH(CH3)2SiO((CH3)2SiO)mSi(CH3)2CH＝CH2
m为100～500的整数，优选200～400的整数；所述的双乙烯基封端聚有机硅氧烷在25℃时的运动粘度为50～2,000mPa·s。
本发明中的聚醚-聚二有机基硅氧烷是由上述的改性基团R1、R2和R3在催化剂的作用下与含氢聚有机硅氧烷反应得到的,其中各种改性基团是通过无规聚合接枝到含氢聚有机硅氧烷主链上。
所述含氢聚有机硅氧烷为至少一种结构通式为如下的含氢聚有机硅氧烷：
Me3SiO(MeHSiO)p(Me2SiO)qSiMe3
Me为甲基，p是2～100的整数，优选10～70的整数；q是20～300的整数，优选40～200的整数；每个分子具有至少2个硅键合的氢原子；所述的含氢聚有机硅氧烷在25℃时的运动粘度为20～5,000mPa·s。
所述的催化剂选自铂-醇络合物、铂-烯烃络合物、铂-醇盐络合物、铂-醚络合物、铂-酮络合物、氯铂酸异丙醇溶液或铂-乙烯基络合物中的一种。本方法中的催化剂优选铂含量为1～20ppm的氯铂酸异丙醇溶液。在一种方案中，聚醚-聚二有机基硅氧烷中催化剂的质量用量为总质量的0.01～0.2％。
有机硅活性物是消泡活性物质，然而将其直接分散到洗衣液中是不可取的，还需要借助于聚醚-聚二有机基硅氧烷的作用；发明人在实验中发现，聚醚-聚二有机基硅氧烷对具有脂肪烃基团的有机硅活性物的具有较好的包裹和分散能力，而通过三种不同结构的聚醚-聚二有机基硅氧烷的复配可以制备出稳定的高含量的有机硅消泡剂。
所述的用于本发明中的三种不同结构的聚醚-聚二有机基硅氧烷分别为具有如下结构式的物质。
B1：a是20～300的整数，b是2～100的整数，c是2-100的整数，d为2～100的整数。R1表示聚醚链段，是由环氧乙烷-环氧丙烷共聚得到的，x为0～150的整数，优选0～40的整数；y为0～150的整数，优选0～100的整数；x，y不同时为0；R2为具有结构式-(CH2)zH的脂肪烃基，z为6～18的整数。R3为双乙烯基封端聚有机硅氧烷，m为200～400的整数。在一种技术方案中，消泡剂组合物中B1的重量份含量为5～40份，优选5～35份，更优选8-25份。
B2：a是20～300的整数，b是2～100的整数，c是2-100的整数，d为2～100的整数。R1表示聚醚链段，是由环氧乙烷-环氧丙烷共聚得到的，x为0～150的整数，优选0～40的整数；y为0～150的整数，优选0～100的整数；x，y不同时为0；R2为甲基。R3为双乙烯基封端聚有机硅氧烷，m为200～400的整数。在一种技术方案中，消泡剂组合物中B2的重量份含量为2～30份，优选5～25份，更优选5-20份。
B3:a是20～300的整数，b是2～100的整数，c为0，d为2～100的整数。R1表示聚醚链段，是由环氧乙烷-环氧丙烷共聚得到的，x为0～150的整数，优选0～40的整数；y为0～150的整数，优选0～100的整数；x，y不同时为0；R2为具有结构式-(CH2)zH的脂肪烃基，z为6～18的整数。所述聚醚-聚二有机基硅氧烷在25℃下的平均运动粘度为10～30，000mPa·s，优选为100～3，000mPa·s。在一种技术方案中，消泡剂组合物中B3的重量份含量为2～20份，优选2～15份，更优选2-10份。
B1和B2是交联型聚醚-聚二有机基硅氧烷，是在支链型聚醚-聚二有机基硅氧烷制备的过程中加入双乙烯基封端聚有机硅氧烷(也就是交联剂)进行反应得到的。
所述交联型聚醚-聚二有机基硅氧烷在25℃下的平均运动粘度为20～40，000mPa·s，优选为100～4，000mPa·s。
交联型聚醚-聚二有机基硅氧烷具有优异的乳化和包裹能力，这种优异的乳化和包裹能力能使有机硅活性物在一定程度上分散于洗衣液中，并通过组分C进一步强化，从而使其稳定的分散于洗衣液中。
C、聚醚多元醇
所述聚醚多元醇结构为具有如下通式中的三种或三种以上的组合；在消泡剂组合物中聚醚多元醇的重量份含量为10-80份，优选20-70份，更优选35-65份。
R5[(EO)m(PO)nH]g，
其中：下标g为1～6的整数,优选1～3的整数；EO为环氧乙烷，PO为环氧丙烷；R5为聚醚起始剂的反应残基，起始剂为C1～C30的直链或支链烷基醇，优选C16-C18的直链烷基醇、乙二醇、丙二醇、丙三醇、甘油三羟甲基丙烷；m、n为聚合度，m为1～100的整数，优选1～40的整数，n为0～80的整数，优选0-60整数。
在本发明中，聚醚的加入是分两步加入的，这种加料顺序可能有利于有机硅消泡剂的层层组装结构，当改变这种聚醚的加料顺序，会破坏消泡剂组合物的层层组装，最终会影响消泡剂的稳定性，引起密度分布不均匀、分层等现象。
第一步加入：
C1：g为1，m为0，n优选5-40的整数,起始剂为丙二醇。在一种技术方案中，消泡剂组合物中C1的重量份含量为5～50份，优选10～40份，更优选15-35份。
第二步加入：
C2：g为3，m优选10～40的整数，n优选0-80整数，起始剂为丙三醇。在一种技术方案中，消泡剂组合物中C2的重量份含量为2～40份，优选5～35份，更优选5-20份。
C3：g为1，m优选10～40的整数，n优选0-80整数，起始剂为C16～C18的直链烷基醇。在一种技术方案中，消泡剂组合物中C3的重量份含量为2～40份，优选5～35份，更优选5-20份。
在一种技术方案中，本发明的消泡剂具体可采用包括下述步骤的方法配制：
(1)将上述有机硅活性物A和聚醚-聚二有机基硅氧烷B1、B2、B3和混合，升温至50～150℃，搅拌0.5～1.5h，搅拌转速为100～600rpm；
(2)保持温度不变，边搅拌边加入聚醚多元醇C1；
(3)将上述混合物通过胶体磨进行均质化后，用聚醚多元醇C2和C3复配搅拌均匀，得到所述消泡剂产品。
发明人在制备带有烷基改性基团的有机硅组合物的消泡剂过程中，采用交联型改性聚有机硅氧烷B1、B2和支链型改性聚有机硅氧烷B3，通过三者之间的配伍和协同作用，并通过聚醚多元醇的进一步分散，可以制备出稳定的高含量消泡剂，制备的消泡剂添加到液体洗涤剂中具有较理想的清澈度和稳定性，在较少添加量下就具有较理想的泡沫控制效果。这是由于B1特殊的结构所导致的，交联结构的改性聚有机硅氧烷具有较强的乳化分散能力，可以对有机硅组合物A进行有效的包裹分散，同时侧链上的烷基结构，与有机硅组合物上的侧链烷基的结构相似，具有较好的亲和力，保证了消泡剂的稳定性。
聚醚多元醇的作用主要是对消泡剂组分进一步分散，降低组合物的粘度，使其易于在洗衣液中分散。两者或两种以上的聚醚多元醇的复配效果要明显好于单独使用。同时聚醚多元醇的加料顺序也会对消泡剂组合物的性能产生影响，尤其是在稳定性上，这种加料顺序可能有利于有机硅消泡剂的层层组装结构，当改变这种聚醚的加料顺序，会破坏消泡剂组合物的层层组装，最终会影响消泡剂的稳定性，引起密度分布不均匀、分层等现象。
具体实施方式
组分A：有机硅活性物
有机硅活性物A1按如下方法制备：
取50g含氢聚有机硅氧烷Me3SiO(MeHSiO)15(Me2SiO)45SiMe3与12g丙烯酸甲酯混合均匀，于70℃加入催化剂氯铂酸异丙醇溶液(铂含量10～15ppm)，用量为组合物质量的0.05％，并将体系升温至100℃保温1小时，再向其中加入28gα-烯烃Vi(CH2)8H，最后加入13g沉淀二氧化硅(60m2/g)与5g MQ硅树脂(M:Q摩尔比0.5∶1.0)混合处理，即得。
有机硅活性物A2按如下方法制备：
取60g含氢聚有机硅氧烷HMe2SiO(MeHSiO)65(Me2SiO)190SiMe2H与14g丙烯酸甲酯混合均匀，于69℃加入催化剂氯铂酸异丙醇溶液(铂含量10～15ppm)，用量为组合物质量的0.05％，并将体系升温至100℃保温1小时，再向其中加入20gα-烯烃Vi(CH2)16H，最后加入10g气相二氧化硅(80m2/g)与10g MQ硅树脂(M:Q摩尔比0.6∶1.0)混合处理，即得。
有机硅活性物A3按如下方法制备：
取70g含氢聚有机硅氧烷HMe2SiO(MeHSiO)100(Me2SiO)170SiMe2H与10g丙烯酸乙酯混合均匀，于71℃加入催化剂氯铂酸异丙醇溶液(铂含量10～15ppm)，用量为组合物质量的0.05％，并将体系升温至100℃保温1小时，再向其中加入12gα-烯烃Vi(CH2)12H，最后加入3g气相二氧化硅(100m2/g)与20g MQ硅树脂(M:Q摩尔比0.7∶1.0)混合处理，即得。
组分B：聚醚-聚二有机基硅氧烷：
表1聚醚-聚二有机基硅氧烷各变量取值
Figure PCTCN2015082284-appb-000002
Figure PCTCN2015082284-appb-000003
组分B的制备方法：
由表1所示的相应的带有不饱和双键的改性基团R1、R2和R3在铂含量为1～20ppm的氯铂酸异丙醇溶液的作用下与含氢聚有机硅氧烷反应得到的,其中各种改性基团是通过无规聚合接枝到含氢聚有机硅氧烷主链上。所述含氢聚有机硅氧烷为至少一种结构通式为如下的含氢聚有机硅氧烷：Me3SiO(MeHSiO)p(Me2SiO)qSiMe3,其中，相应的取值为：Me为甲基，b+c+d＝p，a＝q；每个分子具有至少2个硅键合的氢原子；在25℃时的运动粘度为20～5,000mPa·s。
组分C：聚醚多元醇
表2不同聚醚多元醇各变量取值
  m n g 起始剂
C1-1 0 7 1 丙二醇
C1-2 0 14 1 丙二醇
C1-3 0 35 1 丙二醇
C2-1 12 0 3 丙三醇
C2-2 25 70 3 丙三醇
C2-3 38 40 3 丙三醇
C3-1 40 0 1 C16-C18直链烷基醇
C3-2 35 65 1 C16-C18直链烷基醇
C3-3 12 10 1 C16-C18直链烷基醇
C4 40 50 3 甘油三羟甲基丙烷
C5 25 30 2 乙二醇
实施例1-10
按表3中的配方制备实施例1-10的消泡剂产品。
表3消泡剂组分及配比
Figure PCTCN2015082284-appb-000004
实施例1-2的制备方法：
将表3所示计量的公知技术制备的组分A与组分B混合并加热至55℃，150rpm转速下搅拌0.5h后，保持温度不变并加入C1，搅拌均匀后，通过胶体磨均质化处理后，加入C2和C3，搅拌均匀，得到所述消泡剂组合物。
实施例3-5的制备方法：
将表3所示计量的公知技术制备的组分A与组分B混合并加热至145℃，550rpm转速下搅拌1.5h后，保持温度不变并加入C1，搅拌均匀后，通过胶体磨均质化处理后，加入C2和C3，搅拌均匀，得到所述消泡剂组合物。
对比例1-7的制备方法和实施例制备方法类似：将表3所示计量的公知技术制备的组分A与组分B混合并加热至55℃，150rpm转速下搅拌0.5h后，保持温度不变并加入C1，搅拌均匀后，通过胶体磨均质化处理后，加入C2和C3，搅拌均匀，得到所述消泡剂组合物。
对比例8：将同实施例1相同计量的公知技术制备的组分A与组分B混合并加热至55℃，150rpm转速下搅拌0.5h后，改变聚醚多元醇的加料顺序，先加入C2和C3，搅拌均匀后，再加入C1通过胶体磨均质化处理后，搅拌均匀，得到所述消泡剂组合物。
对比例9：将同实施例1相同计量的公知技术制备的组分A与组分B混合并加热至55℃， 150rpm转速下搅拌0.5h后，同时加入C1、C2和C3，搅拌均匀后，通过胶体磨均质化处理后，搅拌均匀，得到所述消泡剂组合物。
对比例10：参考CN 104130879A实施例1
有机硅消泡剂性能测试：
(1)稳定性测试：将有机硅消泡剂组合物于-18℃-40℃12小时间隔循环放置一周、二周、四周后，目测消泡剂组合物状态。测试结果见表4。
根据以下等级目测：
1＝流动性好，未析出、分层。
2＝流动性好；有可见的较小的硅氧烷析出。
3＝密度分布不均匀，有较大的硅氧烷聚集团。
4＝明显分层
表4稳定性测试结果
Figure PCTCN2015082284-appb-000005
(2)在液体洗涤剂中的机洗性能测试
往金章牌滚筒洗衣机(ZWH6125)里加入50g市售的洗涤剂、0.1g制备的有机硅组合物和20kg水，测试程序为棉麻程序。洗衣机的视窗上标有0％-100％度量标示，分别为视窗高的0，25％，50％，75％，100％。“0”为起始，表示无泡沫，“100％”表示充满泡沫。每5min记录一次泡沫高度，停机时记录。数值越大，表明洗衣机中的泡沫刻度值越高，抑泡性就越差；相同时间内泡沫刻度值越低，说明产品抑泡性能越好。测试结果见表5
表5在液体洗涤剂中的机洗性能测试结果
时间/min 5 10 15 20 25 30 35 40 45 50
实施例1 12 16 19 23 24 26 29 31 33 35
实施例2 10 16 20 22 23 25 27 29 31 33
实施例3 12 17 22 24 25 28 31 34 36 36
实施例4 13 17 22 24 25 27 29 33 35 38
实施例5 13 19 24 26 29 32 36 38 39 40
对比例1 13 19 24 26 29 32 36 38 39 40
对比例2 17 24 29 33 39 44 49 53 57 64
对比例3 15 21 25 30 33 35 38 40 42 45
对比例4 16 21 27 32 35 37 41 44 46 49
对比例5 13 20 23 26 29 32 35 38 39 40
对比例10 17 24 29 33 37 43 48 54 56 59
(3)浊度测试：将有机硅消泡剂组合物以0.2％的添加量添加到液体洗涤剂样品中，搅拌均匀并放置到无气泡后，用HK-288型台式浊度分析仪测试浊度值(单位：NTU)；浊度值越大，混合物越浑浊，测试结果见表6。
表6浊度测试结果
  浊度/NTU
市售洗衣液 5.4
实施例1 11.3
实施例2 10.8
实施例3 11.7
实施例4 13.9
实施例5 14.1
对比例1 19.3
对比例3 35.7
对比例4 29.1
对比例5 21.8
对比例10 24.8
实施例1-5具有相近的控泡效果，且具有较小的浊度值；对比例1-7表明，对其中的任一组分的结构进行改变和替换，会对稳定性和清澈度造成很大的影响；对比例8和9表明，当改变聚醚多元醇的加料顺序会导致组合物分层，因此说明了所制备的消泡剂可能是一种层层组装的结构，改变这种加料顺序会破坏消泡剂组合物的结构，导致分层。对比例10是一种水包油乳液产品，与所制备的产品相比，在清澈度和控泡效果上都有所减弱，而且不利于运输和节能环保。

Claims (10)

  1. 一种有机硅消泡剂组合物，其特征在于，它由以下物质组成：
    A、有机硅活性物，在消泡剂组合物中有机硅活性物的重量份含量为5～40份；
    B、聚醚-聚二有机基硅氧烷
    所述的聚醚-聚二有机基硅氧烷具有如下的结构通式，在消泡剂组合物中聚醚-聚二有机基硅氧烷的重量份含量为10～70份：
    Figure PCTCN2015082284-appb-100001
    其中：Me为甲基，a是20～300的整数，b是2～100的整数，c是0-100的整数，d是2-100的整数；
    R1表示聚醚链段，由环氧乙烷-环氧丙烷共聚得到的共聚物，是通过含有不饱和双键的聚醚和Si-H发生硅氢加成反应而接枝到硅氧烷主链上，含有不饱和双键的聚醚具有通式：CH2＝CHCH2O(EO)x(PO)yR4；其中：R4为氢原子、碳原子数为1～6的烷基、酯基、环氧基或氨基；EO为环氧乙烷，PO为环氧丙烷，x、y为聚合度，x为0～150的整数，优选0～40的整数；y为0～150的整数，优选0～100的整数；x，y不同时为0；
    R2为具有结构式-(CH2)zH的脂肪烃基，z为1～36的整数；具体是通过含有不饱和双键的烯烃和Si-H发生硅氢加成反应而接枝到硅氧烷主链上，含有不饱和双键的烯烃为具有结构式CH2＝CH(CH2)zH的α-烯烃,z为1～36的整数，优选1或6～18的整数；
    R3为双乙烯基封端的聚二甲基硅氧烷，是通过双乙烯基封端聚有机硅氧烷与Si-H发生硅氢加成反应，从而得到具有交联结构的改性聚硅氧烷，双乙烯基封端聚有机硅氧烷具有结构通式如下：CH2＝CH(CH3)2SiO((CH3)2SiO)mSi(CH3)2CH＝CH2；其中m为100～500的整数，优选200～400的整数；所述的双乙烯基封端聚有机硅氧烷在25℃时的运动粘度为50～2,000mPa·s；
    且：组分B包括如下三种不同结构的聚醚-聚二有机基硅氧烷：
    B1：c是2-100的整数，z为6～18的整数，m为200～400的整数；
    B2：c是2-100的整数，R2为甲基，m为200～400的整数；
    B3：c为0，z为6～18的整数；在25℃下的平均运动粘度为10～30，000mPa·s，优选为100～3，000mPa·s；
    C、聚醚多元醇
    所述聚醚多元醇结构具有通式：R5[(EO)m(PO)nH]g；在消泡剂组合物中聚醚多元醇的重量 份含量为10-80份；
    其中：下标g为1～6的整数，优选1～3的整数；m、n为聚合度，m为1～100的整数，优选1～40的整数，n为0～80的整数，优选0-60整数；EO为环氧乙烷，PO为环氧丙烷；R5为聚醚起始剂的反应残基，起始剂为C1～C30的直链或支链烷基醇，优选C16-C18的直链烷基醇、乙二醇、丙二醇、丙三醇、甘油三羟甲基丙烷；
    且：组分C包括如下三种不同结构的聚醚多元醇：
    C1：g为1，m为0，n为5-40的整数，起始剂为丙二醇；
    C2：g为3，m为10～40的整数，n为0-80整数，起始剂为丙三醇；
    C3：g为1，m为10～40的整数，n为0-80整数，起始剂为C16～C18的直链烷基醇。
  2. 根据权利要求1所述的有机硅消泡剂组合物，其特征在于，B1和B2是交联型聚醚-聚二有机基硅氧烷；在25℃下的平均运动粘度为20～40，000mPa·s，优选为100～4，000mPa·s。
  3. 根据权利要求2所述的有机硅消泡剂组合物，其特征在于，消泡剂组合物中B1的重量份含量为5～40份，优选5～35份，更优选8-25份；消泡剂组合物中B2的重量份含量为2～30份，优选5～25份，更优选5-20份；消泡剂组合物中B3的重量份含量为2～20份，优选2～15份，更优选2-10份；消泡剂组合物中C1的重量份含量为5～50份，优选10～40份，更优选15-35份；消泡剂组合物中C2的重量份含量为2～40份，优选5～35份，更优选5-20份；消泡剂组合物中C3的重量份含量为2～40份，优选5～35份，更优选5-20份。
  4. 根据权利要求3所述的有机硅消泡剂组合物，其特征在于，其物质组成比例为：
    A、有机硅活性物，在消泡剂组合物中有机硅活性物的重量份含量为5～35份；
    B、聚醚-聚二有机基硅氧烷，在消泡剂组合物中聚醚-聚二有机基硅氧烷的重量份含量为15～60份；
    C、聚醚多元醇，在消泡剂组合物中聚醚多元醇的重量份含量为20-70份。
  5. 根据权利要求4所述的有机硅消泡剂组合物，其特征在于，其物质组成比例为：
    A、有机硅活性物，在消泡剂组合物中有机硅活性物的重量份含量为8～25份；
    B、聚醚-聚二有机基硅氧烷，在消泡剂组合物中聚醚-聚二有机基硅氧烷的重量份含量为15～40份；
    C、聚醚多元醇，在消泡剂组合物中聚醚多元醇的重量份含量为35-65份。
  6. 根据权利要求1所述的有机硅消泡剂组合物，其特征在于，所述组分B的制备方法是由改性基团R1、R2和R3在催化剂的作用下与含氢聚有机硅氧烷反应得到的,其中各种改性基团是通过无规聚合接枝到含氢聚有机硅氧烷主链上；所述含氢聚有机硅氧烷为至少一种结构通式为如下的含氢聚有机硅氧烷：
    Me3SiO(MeHSiO)p(Me2SiO)qSiMe3
    其中Me为甲基，p是2～100的整数，优选10～70的整数；q是20～300的整数，优选40～200的整数；每个分子具有至少2个硅键合的氢原子；所述的含氢聚有机硅氧烷在25℃时的运动粘度为20～5,000mPa·s。
  7. 根据权利要求6所述的有机硅消泡剂组合物，其特征在于，所述的催化剂选自铂-醇络合物、铂-烯烃络合物、铂-醇盐络合物、铂-醚络合物、铂-酮络合物、氯铂酸异丙醇溶液或铂-乙烯基络合物中的一种；优选铂含量为1～20ppm的氯铂酸异丙醇溶液；聚醚-聚二有机基硅氧烷中催化剂的质量用量为总质量的0.01～0.2％。
  8. 根据权利要求1所述的有机硅消泡剂组合物，其特征在于，所述组分A的有机硅活性物是采用含氢聚有机硅氧烷、丙烯酸酯、α-烯烃、催化剂、二氧化硅和有机硅树脂制备得到；
    A(Ⅰ)：含氢聚有机硅氧烷：
    至少一种结构通式为如下的含氢聚有机硅氧烷：
    HkMe3-kSiO(MeHSiO)v(Me2SiO)wSiMe3-kHk
    Me为甲基，下标k是0或1，v是2～100的整数，w是20～300的整数，每个分子具有至少2个硅键合的氢原子；所述的有机硅活性物中含氢聚有机硅氧烷的重量份为40～80份；
    A(Ⅱ)：α-烯烃
    所述的α-烯烃的结构通式如下：
    Vi(CH2)tH
    Vi为乙烯基，t为1～36的整数，优选6～18的整数；所述有机硅活性物中α-烯烃的含量为10～30份；
    A(Ⅲ)：丙烯酸酯
    所述的丙烯酸酯是丙烯酸及其同系物的酯类，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异丁酯、2-甲基丙烯酸甲酯、2-甲基丙烯酸乙酯或2-甲基丙烯酸丁酯；所述有机硅活性物中丙烯酸酯的重量份含量为3～15份；
    A(Ⅳ)：催化剂
    所述的催化剂选自铂-醇络合物、铂-烯烃络合物、铂-醇盐络合物、铂-醚络合物、铂-酮络合物、氯铂酸异丙醇溶液或铂-乙烯基络合物；优选铂含量为1～20ppm的氯铂酸异丙醇溶液；所述有机硅活性物中催化剂的质量用量为0.01～0.2％；
    A(Ⅴ)：二氧化硅
    所述的二氧化硅包括气相二氧化硅或沉淀二氧化硅，比表面积为50～500m2/g,优选比表面积为90～300m2/g的沉淀二氧化硅或气相二氧化硅；所述有机硅活性物中二氧化硅的重量份含 量为1～15份；
    A(Ⅵ)：有机硅树脂
    所述有机硅树脂为由链节CH3SiO1/2，即M单元和链节SiO4/2，即Q单元的单元组成的MQ树脂，M单元和Q单元之间的摩尔比为(0.4～1.2)：1.0，优选(0.5～0.8)：1.0；所述有机硅活性物中MQ树脂的重量份含量为5～20份。
  9. 权利要求1-8任一项所述的消泡剂组合物的制备方法，其特征在于，所述组分C分两步加入，第一步加入组分C1，第二步加入组分C2和C3。
  10. 根据权利要求9所述的消泡剂组合物的制备方法，其特征在于，包括如下步骤：
    (1)将上述有机硅活性物A和组分B混合，升温至50～150℃，搅拌0.5～1.5h，搅拌转速为100～600rpm；
    (2)保持温度不变，边搅拌边加入组分C1；
    (3)将上述混合物通过胶体磨进行均质化后，用组分C2和组分C3复配搅拌均匀，得到所述消泡剂产品。
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