Metal-free catalytic silicon resin-polyether emulsifier as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic silicon emulsion, in particular to a metal-free catalytic silicon resin-polyether emulsifier as well as a preparation method and application thereof. The silicon resin-polyether copolymer emulsifier disclosed by the invention is prepared by taking SH-containing silicon resin and unsaturated polyether as raw materials and carrying out sulfydryl-alkene reaction. The problem of poor emulsion stability caused by Si-O-C bond connection is avoided, and the prepared organic silicon emulsion has excellent storage stability. In addition, the preparation method provided by the invention is rapid in reaction, the reaction time can be reduced to 0.5 h, the conversion rate is high, and the preparation method has a good application prospect.

Description

Technical Field

[0001] This invention relates to the field of organosilicon emulsion technology, specifically to a metal-free catalytic silicone resin-polyether emulsifier, its preparation method, and its application. Background Technology

[0002] Organosilicon emulsions refer to polymer emulsions formed by mechanically dispersing polysiloxanes or silicone resins containing Si-O-Si repeating units through the addition of emulsifiers or the introduction of hydrophilic groups. These emulsions are environmentally friendly and widely used in water-based high-temperature coatings, waterproof coatings, water-based adhesives, daily chemical products, textile treatment, paper and leather finishing, and other fields. However, traditional emulsifiers have low molecular weights and poor emulsion stability, especially prone to demulsification under high-temperature or high-salt environments. Furthermore, the higher the molecular weight of the polysiloxane and silicone resin, the more difficult it is to disperse and emulsify. Therefore, developing efficient emulsifiers suitable for high molecular weight organosilicon materials is particularly important. It is generally believed that silicone resin emulsifiers, due to their three-dimensional structure, provide superior emulsification effects and stability. Patent CN202110012062.4 (An Organosilicon Emulsifier and Its Preparation Method and Application) proposes to prepare an emulsifier by dehydration condensation reaction of silicone resin and polyether. This emulsifier can be used to emulsify high-viscosity polysiloxanes, and the resulting emulsion has good stability, remaining intact for 4-6 months at room temperature. However, the MQ-type silicone resin and polyether in this emulsifier structure are linked by easily hydrolyzable Si–O–C bonds, which limits the emulsion stability. It can be stored for a maximum of 6 months at room temperature and a maximum of 3 months at 60°C without demulsification, which greatly limits its practical application.

[0003] Currently, the preparation of modified silicone resins mainly relies on hydrosilylation reactions. However, this method requires the use of noble metal catalysts such as platinum, which are easily poisoned and deactivated by impurities containing sulfur, phosphorus, and nitrogen. Furthermore, hydrosilylation reactions are often accompanied by isomerization, affecting the control of the addition site and the purity of the final product. Therefore, there is an urgent need to introduce novel reactions to prepare organosilicon compounds with superior performance.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] In view of the technical problems existing in the background art, the present invention provides a metal-free catalytic silicone resin-polyether emulsifier, its preparation method and application.

[0006] In a first aspect, the present invention provides a metal-free catalytic silicone resin-polyether emulsifier, wherein the structural formula of the metal-free catalytic silicone resin-polyether emulsifier is: (Me3SiO 0.5 ) a (R'Me2SiO 0.5 ) b (Me2SiO) c(R'MeSiO) d (MeSiO 1.5 ) e (R'SiO 1.5 ) f (SiO2) g ; where a, b, c, d, e, and f each take values ​​from 0 to 50 independently, and b, d, and f cannot be zero simultaneously; g takes values ​​from 10 to 100; and the structural formula of R' is: C3H6SC3H6O(CH2CH2O). x (CH3CHCH2O) y R1 is H or CH3; the numerical ratio of x to y is (5-40):1; the molecular weight of R' is 300-20000.

[0007] Preferably, the metal-free catalytic silicone resin-polyether emulsifier is prepared by reacting thiol with SH-containing silicone resin and unsaturated polyether. The thiol reaction is a free radical addition reaction. Under photoinitiator and UV light irradiation, free radicals (or thermal initiators) are generated to initiate the generation of sulfur free radicals from thiols. The sulfur free radicals attack the double bonds of olefins to generate carbon free radical intermediates. These intermediates then abstract hydrogen atoms from another thiol molecule to generate addition products and new sulfur free radicals, thus realizing a chain reaction.

[0008] The metal-free catalytic silicone resin-polyether emulsifier of this invention is prepared by reacting SH-containing silicone resin and unsaturated polyether as raw materials with mercaptoene, thus avoiding the problem of poor emulsion stability caused by Si–O–C bond linkage. The resulting organosilicon emulsion exhibits excellent storage stability. Furthermore, the preparation method provided by this invention features mild reaction conditions, efficient and rapid reaction process, reducing the reaction time to 0.5 hours, high conversion rate, and promising application prospects.

[0009] In this invention, the SH-containing silicone resin has the structure shown in formula (I); Formula (I): (Me3SiO 0.5 ) a (RMe2SiO 0.5 ) b (Me2SiO) c (RMeSiO) d (MeSiO 1.5 ) e (RSiO 1.5 ) f (SiO2) g In formula (I), R is CH2CH2CH2SH; the values ​​of a, b, c, d, e, and f are each independent from 0 to 50, and b, d, and f cannot be zero simultaneously; the value of g is 10 to 100; the unsaturated polyether has the structure shown in formula (II); Formula (II): CH2=CHCH2O(CH2CH2O)x (CH3CHCH2O) y R1, where R1 is H or CH3; wherein the numerical ratio of x to y is (5 to 40):1; the total molecular weight of formula (II) is 300 to 20000.

[0010] Preferably, in formula (I), the value of a is 8 to 18; the value of f is 4 to 10; and the value of g is 45 to 55.

[0011] Preferably, in formula (II), the value of x is 30 to 50; and the value of y is 4 to 6.

[0012] Preferably, the molar ratio of SH in the silicone resin to the double bond in the unsaturated polyether is 1 to 1.05:1.

[0013] Secondly, the present invention provides a method for preparing the metal-free catalytic silicone resin-polyether emulsifier, comprising: mixing the SH-containing silicone resin, the unsaturated polyether and a solvent, and reacting them under UV light irradiation and photoinitiator conditions.

[0014] Preferably, the photoinitiator is selected from benzoin dimethyl ether, photoinitiator 1173; and / or, the solvent is ethyl acetate.

[0015] Thirdly, the present invention provides the application of the metal-free catalytic silicone resin-polyether emulsifier or the metal-free catalytic silicone resin-polyether emulsifier prepared by the preparation method in the preparation of emulsions.

[0016] Fourthly, the present invention provides an organosilicon emulsion comprising the metal-free catalytic silicone resin-polyether emulsifier or the metal-free catalytic silicone resin-polyether emulsifier prepared by the method, and further comprising a silicone polymer and deionized water.

[0017] Preferably, based on the total mass of the organosilicon emulsion, the mass percentage of the metal-free catalytic silicone resin-polyether emulsifier is 3-10 wt%.

[0018] Beneficial effects:

[0019] This invention provides a metal-free catalytic silicone resin-polyether emulsifier, its preparation method, and its applications. The silicone resin-polyether copolymer emulsifier of this invention is prepared by reacting SH-containing silicone resin with unsaturated polyether as raw materials via a mercaptoene reaction. This invention avoids the problem of poor emulsion stability caused by Si–O–C bond linkage, and the resulting organosilicon emulsion exhibits excellent storage stability. Furthermore, the preparation method provided by this invention features rapid reaction, reducing the reaction time to 0.5 hours, and high conversion rate, demonstrating promising application prospects. Detailed Implementation

[0020] This invention provides a metal-free catalytic silicone resin-polyether emulsifier, its preparation method, and its application. Specifically, the emulsifier is prepared by reacting thiol-based silicone resins containing SH (MQ, MDQ, MTQ, or MDTQ) with unsaturated polyethers under UV irradiation and photoinitiator (benzoin dimethyl ether, etc.) to prepare silicone resin-based emulsifiers, which are then applied to the preparation of organosilicon material (polysiloxane, silicone resin) emulsions.

[0021] In this invention, the silicone resin structure can be: (Me3SiO) 0.5 ) a (RMe2SiO 0.5 ) b (Me2SiO) c (RMeSiO) d (MeSiO 1.5 ) e (RSiO 1.5 ) f (SiO2) g R is CH2CH2CH2SH; a, b, c, d, e, f are 0-50; g is 10-100.

[0022] In this invention, the structural formula of the unsaturated polyether can be:

[0023] CH2=CHCH2O(CH2CH2O) x (CH3CHCH2O) y R1, R1 is H or CH3, molecular weight is 300 to 20000, x:y = (5 to 40):1.

[0024] In this invention, the raw materials involved include: MQ, MDQ, MTQ or MDTQ silica resin containing SH, unsaturated polyether, photoinitiator, solvent (methanol, ethanol, toluene, xylene, ethyl acetate, butyl acetate, etc.); the equipment involved includes: a glass reactor with a UV device.

[0025] In one more specific embodiment provided by the present invention, the reaction process involved includes:

[0026] (1) Place 100 parts of SH-containing silicone resin (M-SH, D-SH, T-SH, or a mixture of two or three types of SH) in a reaction vessel, add an appropriate amount (e.g., 60 parts) of solvent, and start stirring to dissolve;

[0027] (2) Add metered unsaturated polyether (Vi mol%: SH mol% = 1:1~1.05) and catalyst (0.2~3wt% (unsaturated polyether)), stir to dissolve evenly, and after UV-initiated reaction (0.5~4 hours), remove the solvent to obtain silicone resin-based emulsifier.

[0028] (3) Emulsification of Organosilicon Material: Take 80 parts of organosilicon material (polysiloxane, silicone resin, or a mixture of the two), 2-10 parts of metal-catalyzed silicone resin-polyether emulsifier, and 120-160 parts of deionized water, and put them into a disperser to emulsify and prepare an organosilicon emulsion. The stability of the organosilicon emulsion obtained in the above steps was tested. The test results showed that the emulsion did not break down after being stored at room temperature for 6-12 months, and had good stability.

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0030] The endpoints and any values ​​of the ranges disclosed in this specification are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0031] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "specific implementation," or "some specific implementations," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0032] Unless otherwise specified, all materials and reagents used in the following examples are commercially available. Experimental methods not specifically described in the examples are generally performed under standard conditions or as recommended by the manufacturer.

[0033] Example 1

[0034] (1) Preparation of metal-free catalytic silicone resin-polyether emulsifier

[0035] Take 100 parts by weight (Me3SiO) 0.5 ) 13(RSiO 1.5 )8(SiO2) 50 329 parts by weight of unsaturated polyether CH2=CHCH2O(CH2CH2O) 40 (CH3CHCH2O)5H, 6.6 parts by weight of benzoin dimethyl ether, and 60 parts by weight of ethyl acetate were stirred until homogeneous. The mixture was then irradiated with 365nm UV for 2 hours to remove the ethyl acetate, yielding a metal-free catalytic silicone resin-polyether emulsifier. In this example, the molar ratio of SH in the silicone resin to the double bonds in the unsaturated polyether was 1:1.

[0036] (2) Preparation of silicone emulsion

[0037] Take 80 parts by weight of high molecular weight (750,000) polysiloxane, 2.5 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 124 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 3 wt%.

[0038] Note: The mass fraction of emulsifier = (weight parts of emulsifier) ​​ / (weight parts of high molecular weight polysiloxane + weight parts of emulsifier) ​​* 100%. Water is not included in the calculation. The same applies to other examples.

[0039] Example 2

[0040] The only difference between Example 2 and Example 1 is:

[0041] Take 80 parts by weight of high molecular weight (750,000) polysiloxane, 5.1 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 128 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 6 wt%.

[0042] Example 3

[0043] The only difference between Example 3 and Example 1 is:

[0044] Take 80 parts by weight of high molecular weight (750,000) polysiloxane, 7.9 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 132 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 9 wt%.

[0045] Example 4

[0046] The only difference between Example 4 and Example 1 is:

[0047] Take 80 parts by weight of high molecular weight (750,000) polysiloxane, 8.9 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 134 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 10 wt%.

[0048] Example 5

[0049] The only difference between Example 5 and Example 1 is that the silicone resin containing SH has the molecular formula (Me3SiO2). 0.5 )9(RSiO 1.5 )8(SiO2) 55 The dosage is 100 parts; the molecular formula of the unsaturated polyether is CH2=CHCH2O(CH2CH2O). 35 (CH3CHCH2O)4H, the dosage is 280 parts; the molar ratio of SH in silicone resin to double bond in unsaturated polyether is 1.04:1.

[0050] Take 80 parts by weight of high molecular weight (550,000) polysiloxane, 10 parts by weight of MQ resin (8,000 molecular weight), 3.8 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 141 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 4 wt%.

[0051] Example 6

[0052] The only difference between Example 6 and Example 1 is that the silicone resin containing SH has the molecular formula (Me3SiO2). 0.5 ) 15 (RMeSiO)2(RSiO 1.5 )7(SiO2) 45 The dosage is 100 parts; the molecular formula of the unsaturated polyether is CH2=CHCH2O(CH2CH2O). 38 (CH3CHCH2O)2CH3, with an amount of 330 parts; the molar ratio of SH in the silicone resin to the double bond in the unsaturated polyether is 1:1.

[0053] Take 80 parts by weight of high molecular weight (550,000) polysiloxane, 15 parts by weight of MQ resin (8,000 molecular weight), 4 parts by weight of metal-free catalytic silicone resin-polyether emulsifier and 149 parts by weight of deionized water and put them into a high-speed disperser to emulsify and prepare an organosilicon emulsion. The mass fraction of the emulsifier is 4 wt%.

[0054] Comparative Example 1

[0055] Comparative Example 1 used commercially available 1310 emulsifier.

[0056] The only difference between the preparation process of the silicone emulsion and that in Example 1 is that the mass fraction of the 1310 emulsifier is 12 wt%.

[0057] The performance of the silicone emulsions in the examples and comparative examples was tested, and the specific results are shown in Table 1.

[0058] Table 1

[0059]

[0060] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A metal-free catalyst silicone resin-polyether emulsifier, characterized in that, The structural formula of the metal-free catalytic silicone resin-polyether emulsifier is: (Me3SiO) 0.5 ) a (R'Me2SiO 0.5 ) b (Me2SiO) c (R'MeSiO) d (MeSiO 1.5 ) e (R'SiO 1.5 ) f (SiO2) g ; in The values ​​of a, b, c, d, e, and f are each independent and range from 0 to 50, and b, d, and f cannot be zero simultaneously; the value of g ranges from 10 to 100; and the structural formula of R' is: C3H6SC3H6O(CH2CH2O). x (CH3CHCH2O) y R1 is H or CH3; the numerical ratio of x to y is (5-40):1; the molecular weight of R' is 300-20000.

2. The metal-free catalytic silicone resin-polyether emulsifier according to claim 1, characterized in that, The metal-free catalytic silicone resin-polyether emulsifier is prepared by reacting SH-containing silicone resin and unsaturated polyether with mercaptoene; the SH-containing silicone resin has the structure shown in formula (I); Formula (I): (Me3SiO 0.5 ) a (RMe2SiO 0.5 ) b (Me2SiO) c (RMeSiO) d (MeSiO 1.5 ) e (RSiO 1.5 ) f (SiO2) g In formula (I), R is CH2CH2CH2SH; the values ​​of a, b, c, d, e, and f are each independent from 0 to 50, and b, d, and f cannot be zero simultaneously; the value of g is 10 to 100; the unsaturated polyether has the structure shown in formula (II); Formula (II): CH2=CHCH2O(CH2CH2O) x (CH3CHCH2O) y R1, where R1 is H or CH3; wherein the numerical ratio of x to y is (5 to 40):1; the total molecular weight of formula (II) is 300 to 20000.

3. The metal-free catalytic silicone resin-polyether emulsifier according to claim 1 or 2, characterized in that, In formula (I), the value of a is 8 to 18; the value of f is 4 to 10; and the value of g is 45 to 55.

4. The metal-free catalytic silicone resin-polyether emulsifier according to any one of claims 1-3, characterized in that, In equation (II), x takes values ​​of 30 to 50; y takes values ​​of 4 to 6.

5. The metal-free catalytic silicone resin-polyether emulsifier according to any one of claims 1-4, characterized in that, The molar ratio of SH in silicone resin to double bonds in unsaturated polyether is 1 to 1.05:

1.

6. The method for preparing the metal-free catalytic silicone resin-polyether emulsifier according to any one of claims 1-5, characterized in that, include: The SH-containing silicone resin, the unsaturated polyether, and the solvent are mixed and reacted under UV light and photoinitiator conditions.

7. The preparation method according to claim 6, characterized in that, The photoinitiator is selected from benzoin dimethyl ether, photoinitiator 1173; and / or, the solvent is ethyl acetate.

8. The use of the metal-free catalytic silicone resin-polyether emulsifier according to any one of claims 1-5 or the metal-free catalytic silicone resin-polyether emulsifier prepared by the preparation method according to any one of claims 6-7 in the preparation of emulsions.

9. An organosilicon emulsion, characterized in that, The product includes the metal-free catalytic silicone resin-polyether emulsifier according to any one of claims 1-5 or the metal-free catalytic silicone resin-polyether emulsifier prepared by the method according to any one of claims 6-7, and further includes a silicone polymer and deionized water.

10. The silicone emulsion according to claim 9, characterized in that, Based on the total mass of the organosilicon emulsion, the mass percentage of the metal-free catalytic silicone resin-polyether emulsifier is 3-10 wt%.

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