Plasticizer and preparation method thereof, composition for polyether waterproof coating, polyether waterproof coating and preparation method thereof

Abstract

The invention relates to the field of building waterproofing, and discloses a plasticizer and a preparation method thereof, a composition for a polyether waterproof coating, the polyether waterproof coating and a preparation method of the polyether waterproof coating. The method for preparing the modified polyether plasticizer comprises the following steps: (1) in a protective atmosphere, in the presence of a base catalyst, stirring and mixing alpha, omega-dihydroxy polydimethylsiloxane and alkylene oxide to obtain an intermediate I; and (2) contacting and mixing a neutralizer with the intermediate I to obtain the modified polyether plasticizer, relative to 100 parts by weight of the alpha, omega-dihydroxy polydimethylsiloxane, the use amount of the base catalyst is 0.1 to 1 part by weight, the use amount of the alkylene oxide is 400 to 900 parts by weight, and the use amount of the neutralizer is 0.12 to 1.2 parts by weight. The silane modified polyether waterproof coating prepared from the modified polyether plasticizer provided by the invention has obviously better weather resistance.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing, specifically to a plasticizer and its preparation method, a composition for polyether waterproof coatings, and a polyether waterproof coating and its preparation method. Background Technology

[0002] Silane-modified polyether waterproof coating is a single-component, solvent-free waterproof coating made from modified polyether resin as the base polymer, combined with functional additives, fillers, pigments and catalysts. It has advantages such as high elongation, high tensile strength and good low-temperature flexibility.

[0003] Silane polyether resin, also known as silane-terminated modified polyether resin or organosilicon-modified polyether resin, initially appeared mainly in the form of silane-terminated polyether sealant. Silane-terminated polyether sealant is also known as MS sealant, organosilicon-modified polyether sealant, and modified silicone sealant.

[0004] Silane polyether building waterproof coatings are mainly used for waterproofing and moisture-proofing in kitchens, bathrooms, balconies, and other areas. When applied, it is coated onto the substrate and cures through a reaction with moisture, forming a continuous, seamless, high-polymer elastic waterproof membrane. With the application of a suitable protective layer, silane-modified polyether waterproof coatings can also be used on roofs and exterior walls. This coating can be applied by scraping, rolling, brushing, or spraying, and can be applied to the designed thickness in a single application, saving time and construction costs.

[0005] In the field of building waterproofing, weather-resistant silane-modified polyether waterproof coatings are widely used in waterproofing parts that need to be exposed for a long time, such as outdoor buildings, infrastructure, and special scenarios. They have good weather resistance and high elasticity waterproofing performance, strong resistance to ultraviolet rays, resistance to high and low temperature cycles, and resistance to water erosion and other harsh outdoor conditions. At the same time, they solve the problems of traditional exposed coatings being prone to aging, cracking, and leakage. As a new type of waterproof coating, they have been promoted.

[0006] However, in silane-modified polyether waterproof coatings, the plasticizers used include phthalate esters and polyether esters. Phthalate ester plasticizers, due to their low viscosity, can significantly reduce product viscosity, but their plasticizing effect is not ideal, resulting in low elongation, poor water resistance, and certain environmental risks. In addition, polyether polyols are also used as plasticizers on the market, which have good plasticizing effects, high product strength, and large elongation. However, since ordinary polyether plasticizers are hydrophilic molecules, their compatibility with silane polyether systems is limited. Under water immersion, "hydrophilic precipitation" can easily occur, causing the polyether plasticizer to migrate to the coating surface. This manifests as a sticky surface after soaking, the precipitation of oily substances, loss of coating weight, hardening of the coating, and shrinkage. In severe cases, the coating loses its elasticity, ultimately affecting the product's performance.

[0007] Therefore, it is of great significance to provide a new plasticizer suitable for silane-modified polyether waterproof coatings and a novel silane-modified polyether waterproof coating. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of poor compatibility and weather resistance of existing silane-modified polyether waterproof coatings.

[0009] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a modified polyether plasticizer, the method comprising: under a protective atmosphere, (1) In the presence of an alkaline catalyst, α,ω-dihydroxypolydimethylsiloxane and epoxide alkane were stirred and mixed to obtain intermediate I; (2) The neutralizing agent is contacted and mixed with the intermediate I to obtain the modified polyether plasticizer; Relative to 100 parts by weight of the α,ω-dihydroxypolydimethylsiloxane, the amount of the alkaline catalyst is 0.1-1 parts by weight, the amount of the epoxide is 400-900 parts by weight, and the amount of the neutralizing agent is 0.12-1.2 parts by weight.

[0010] A second aspect of the present invention provides a modified polyether plasticizer prepared by the method described in the first aspect above.

[0011] A third aspect of the present invention provides a composition for a silane-modified polyether waterproof coating, the composition comprising a main agent and an auxiliary agent, wherein the main agent contains an alkoxy-terminated polyether, an acryloxysilane, and a plasticizer; The content of the acryloxysilane is 2-3 parts by weight relative to 100 parts by weight of the alkoxy-terminated polyether, and the content of the plasticizer is 45-85 parts by weight. The plasticizer is the modified polyether plasticizer described in the second aspect above.

[0012] A fourth aspect of the present invention provides a method for preparing a silane-modified polyether waterproof coating, the method being carried out using the components of the composition described in the third aspect above, the method comprising: stirring and mixing the components of the composition to obtain the silane-modified polyether waterproof coating.

[0013] The fifth aspect of the present invention provides a silane-modified polyether waterproof coating prepared according to the method described in the fourth aspect above.

[0014] Through the above technical solution, the present invention has at least the following beneficial technical effects: (1) The present invention uses epoxy alkane to graft α,ω-dihydroxy polydimethylsiloxane to obtain a modified polyether plasticizer. Due to the introduction of hydrophobic segments in the grafted segments of the modified polyether plasticizer, its affinity and compatibility with other components are enhanced. At the same time, it has a synergistic effect with acryloyloxysilane in the system, further improving compatibility. It has good plasticizing effect and excellent tensile properties, and solves the problem of easy precipitation and migration of ordinary polyether plasticizers under water immersion conditions.

[0015] (2) The modified polyether plasticizer prepared by the present invention has good weather resistance. When used as a plasticizer in silane-modified polyether waterproof coating, it can significantly improve the weather resistance of silane-modified polyether waterproof coating. Detailed Implementation

[0016] The endpoints of the ranges and any values ​​disclosed herein are not limited to those precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, each… One or more new numerical ranges can be obtained by combining the endpoint values ​​of a range with each other, the endpoint values ​​of each range with individual point values, and individual point values ​​with each other, and these numerical ranges should be considered as specifically disclosed herein.

[0017] As previously described, a first aspect of the present invention provides a method for preparing a modified polyether plasticizer, the method comprising: under a protective atmosphere, (1) In the presence of an alkaline catalyst, α,ω-dihydroxypolydimethylsiloxane and epoxide alkane were stirred and mixed to obtain intermediate I; (2) The neutralizing agent is contacted and mixed with the intermediate I to obtain the modified polyether plasticizer; Relative to 100 parts by weight of the α,ω-dihydroxypolydimethylsiloxane, the amount of the alkaline catalyst is 0.1-1 parts by weight, the amount of the epoxide is 400-900 parts by weight, and the amount of the neutralizing agent is 0.12-1.2 parts by weight.

[0018] According to a preferred embodiment, the α,ω-dihydroxypolydimethylsiloxane has a viscosity of 350-750 cs at 25°C. The inventors of this invention have discovered that, in this preferred embodiment, when the modified polyether plasticizer provided by this invention is applied to a silane-modified polyether waterproof coating, the resulting silane-modified polyether waterproof coating exhibits superior weather resistance and compatibility.

[0019] According to one specific embodiment, the epoxide is selected from at least one of propylene oxide, ethylene oxide, butane oxide, epichlorohydrin, and cyclohexane oxide.

[0020] In some embodiments, the protective atmosphere is a nitrogen atmosphere.

[0021] According to a specific implementation, in step (1), the stirring and mixing conditions include: a temperature of 100-110℃ and a time of 2-4h.

[0022] According to one specific embodiment, in step (1), the alkaline catalyst is selected from at least one of potassium hydroxide, sodium hydroxide, cesium hydroxide and quaternary ammonium bases.

[0023] In some embodiments, before stirring and mixing in step (1), the α,ω-dihydroxypolydimethylsiloxane is subjected to vacuum drying; the conditions for vacuum drying include: a temperature of 100-120°C, a pressure of -0.08MPa to -0.1MPa, and a time of 2-3h.

[0024] According to one specific implementation, in step (2), the conditions for contact mixing include: a temperature of 60-70°C and a time of 1-2 hours.

[0025] According to one specific embodiment, in step (2), the neutralizing agent is selected from at least one of phosphoric acid, hydrochloric acid, sulfuric acid, acetic acid and citric acid.

[0026] In some embodiments, step (2) further includes separating and drying the preproduct obtained after contact mixing to obtain the modified polyether plasticizer.

[0027] As previously stated, a second aspect of the present invention provides a modified polyether plasticizer prepared by the method described in the first aspect.

[0028] As previously described, a third aspect of the present invention provides a composition for a silane-modified polyether waterproof coating, the composition comprising a main agent and an auxiliary agent, wherein the main agent contains an alkoxy-terminated polyether, an acryloxysilane, and a plasticizer; The content of the acryloxysilane is 2-3 parts by weight relative to 100 parts by weight of the alkoxy-terminated polyether, and the content of the plasticizer is 45-85 parts by weight. The plasticizer is the modified polyether plasticizer described in the second aspect above.

[0029] According to one specific embodiment, the alkoxy-terminated polyether is a dialkoxy-terminated polyether and / or a trialkoxy-terminated polyether.

[0030] According to a preferred embodiment, the alkoxy-terminated polyether is a combination of dialkoxy-terminated polyether and trialalkoxy-terminated polyether in a weight ratio of 1:0.6-2. The inventors of this invention have discovered that, in this preferred embodiment, the silane-modified polyether waterproof coating provided by this invention exhibits superior weather resistance and mechanical properties.

[0031] According to one specific embodiment, the acryloyloxysilane is α-(methacryloyloxy)methyltriethoxysilane and / or γ-(methacryloyloxy)propyltrimethoxysilane.

[0032] In some embodiments, the additives include antioxidants, fillers, dehydrating agents, and coupling agents; relative to 100 parts by weight of the alkoxy-terminated polyether, the content of the antioxidant is 0.2-0.8 parts by weight, the content of the filler is 120-180 parts by weight, the content of the dehydrating agent is 2-5 parts by weight, and the content of the coupling agent is 1.5-3 parts by weight.

[0033] In some embodiments, the coupling agent is selected from at least one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(β-aminoethyl)aminopropyltrimethoxysilane, anilinemethyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, ureopropyltrimethoxysilane, and ureopropyltriethoxysilane.

[0034] According to one specific embodiment, the filler is selected from at least one of nano-calcium carbonate, talc, fumed silica, heavy calcium carbonate, mica powder, titanium dioxide, and carbon black.

[0035] In some embodiments, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 3114, antioxidant 168 and antioxidant 626.

[0036] In some embodiments, the dehydrating agent is selected from at least one of vinyltrimethoxysilane, vinyltriacetoxysilane, and vinyltriethoxysilane.

[0037] According to one specific embodiment, the additive further includes a catalyst, wherein the content of the catalyst is 0.3-1.5 parts by weight relative to 100 parts by weight of the alkoxy-terminated polyether.

[0038] According to one specific embodiment, the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and chelated tin catalysts.

[0039] A fourth aspect of the present invention provides a method for preparing a silane-modified polyether waterproof coating, the method being carried out using the components of the composition described in the third aspect above, the method comprising: stirring and mixing the components of the composition to obtain the silane-modified polyether waterproof coating.

[0040] According to one specific embodiment, the method for preparing the silane-modified polyether waterproof coating includes: S1: Alkoxy-terminated polyether, plasticizer, and some additives are stirred and dispersed to obtain material I; S2: Under conditions of temperature of 100-110℃ and pressure of -0.08MPa to -0.1MPa, the material I is dehydrated for 3-4 hours to obtain material II; S3: At 50-60℃, acryloyloxysilane, the remaining additives and material II are stirred for 0.5-2 hours to obtain the silane-modified polyether waterproof coating.

[0041] The fifth aspect of the present invention provides a silane-modified polyether waterproof coating prepared according to the method described in the fourth aspect above.

[0042] To provide a clearer understanding of the technical features, objectives, and beneficial effects of this invention, the invention is now described in detail through embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention, and the scope of protection of this invention is not limited to the following description. In the following examples, unless otherwise specified, all raw materials and reagents used are common commercially available products.

[0043] The following examples include some of the raw materials used and their sources: α,ω-dihydroxypolydimethylsiloxane-I: viscosity at 25℃ is 350cs, grade OH-035, purchased from Jiangsu Keqi Polymer Materials Co., Ltd. α,ω-dihydroxypolydimethylsiloxane-II: viscosity at 25℃ is 750cs, grade OH-075, purchased from Jiangsu Keqi Polymer Materials Co., Ltd. α,ω-dihydroxypolydimethylsiloxane-III: viscosity at 25℃ is 1500cs, grade is OH-1.5, purchased from Jiangsu Keqi Polymer Materials Co., Ltd.; Nano calcium carbonate: grade CCS-30c, purchased from Guangxi Huana New Materials Co., Ltd.; Filler I: A combination of nano-calcium carbonate, heavy calcium carbonate, and titanium dioxide in a weight ratio of 45:87:6; Antioxidant 1010, Antioxidant 1076 and Antioxidant 168 were all purchased from Guangzhou Aoying Trading Co., Ltd. Alkoxy-terminated polyether-I: A combination of diekoxy-terminated polyether and trialkoxy-terminated polyether in a weight ratio of 1:1.5; Alkoxy-terminated polyether-II: A combination of dialkoxy-terminated polyether and trialkoxy-terminated polyether in a weight ratio of 1:0.25; Dialkoxy-terminated polyether: brand name SAX350, purchased from Kaneka Trading (Shanghai) Co., Ltd.; Trialkoxy-terminated polyether: brand name SAX520, purchased from Kaneka Trading (Shanghai) Co., Ltd.; Commercially available plasticizer: polyether polyol, brand name DL-1000D, purchased from Shandong Lanxing Dongda Co., Ltd.

[0044] Preparation Example 1 This preparation example illustrates the preparation of the modified polyether plasticizer provided by the present invention, including the following steps: (1) Place α,ω-dihydroxy polydimethylsiloxane in a reaction vessel, control the reactor temperature to 100℃ and the pressure to -0.08MPa, and start stirring for 2h to perform vacuum drying on α,ω-dihydroxy polydimethylsiloxane. (2) Nitrogen gas was introduced into the reactor to restore the pressure to 0.1 MPa, the reactor temperature was controlled at 100 °C, an alkaline catalyst and epoxide were added, and the mixture was stirred for 3 h to obtain intermediate I; (3) Control the reactor temperature to 60℃, add neutralizing agent, stir for 2h, and dry the obtained preproduct at 100℃ and -0.08MPa for 1h to obtain the modified polyether plasticizer.

[0045] For the specific types and amounts of substances used in this preparation example, please refer to Table 1.

[0046] Unless otherwise specified, Preparation Example 2 and Preparation Example 3 were carried out in accordance with the method of Preparation Example 1, except that the types and amounts of substances used were different, as detailed in Table 1.

[0047] Table 1

[0048] Preparation Example 4 This preparation example was carried out using a method similar to that of Preparation Example 1. The difference is that in step (1), an equal mass of α,ω-dihydroxypolydimethylsiloxane-III was used to replace α,ω-dihydroxypolydimethylsiloxane-I in Preparation Example 1 to prepare modified polyether plasticizer-IV.

[0049] Comparative Preparation Example 1 This comparative preparation example was prepared using a method similar to that of Preparation Example 1, except that the amount of epoxide was adjusted to 1800g, while the amounts of the other components remained unchanged, to prepare the modified polyether plasticizer-DI.

[0050] Comparative Preparation Example 2 This comparative preparation example was prepared using a method similar to that of Preparation Example 1, except that the amount of epoxide was adjusted to 4800g, while the amounts of the other components remained unchanged, to prepare the modified polyether plasticizer-DII.

[0051] Comparative preparation example 3 This comparative preparation example was prepared using a method similar to that of Preparation Example 1. The difference is that in step (1), styrene oxide of equal mass was used to replace propylene oxide in Preparation Example 1 to prepare modified polyether plasticizer-DIII.

[0052] The following examples illustrate the preparation of silane-modified polyether waterproof coatings, specifically: Example 1 S1: In a disperser, alkoxy-terminated polyether, plasticizer, filler and antioxidant are stirred and dispersed for 1 hour to obtain material I; S2: Transfer the above material I into the reactor, adjust the temperature of the reactor to 100℃ and the pressure to -0.08MPa, and dehydrate for 3 hours to obtain material II; S3: Control the temperature of the reactor to 55°C, add dehydrating agent, acryloyloxysilane, coupling agent and catalyst, continue stirring for 1 hour, and obtain the silane-modified polyether waterproof coating after cooling.

[0053] For the specific types and amounts of substances used in this embodiment, please refer to Table 2.

[0054] Unless otherwise specified, Examples 2 and 3 are carried out with reference to the method of Example 1. The difference is that the types and amounts of substances used in the examples are not exactly the same, as detailed in Table 2.

[0055] Table 2

[0056] Example 4 This embodiment uses a method similar to that of Example 1, except that an equal weight portion of alkoxy-terminated polyether-II is used to replace alkoxy-terminated polyether-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0057] Example 5 This embodiment uses a method similar to that of Example 1, except that an equal part by weight of modified polyether plasticizer-IV is used to replace modified polyether plasticizer-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0058] Example 6 This embodiment uses a method similar to that of Example 1, except that an equal weight portion of trialkoxy-terminated polyether is used to replace the alkoxy-terminated polyether-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0059] Comparative Example 1 This comparative example was conducted using the same method as in Example 1, except that an equal part by weight of modified polyether plasticizer-DI was used to replace modified polyether plasticizer-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0060] Comparative Example 2 This comparative example was conducted using the same method as in Example 1, except that an equal part by weight of modified polyether plasticizer-DII was used to replace modified polyether plasticizer-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0061] Comparative Example 3 This comparative example was conducted using the same method as in Example 1, except that an equal part by weight of modified polyether plasticizer-DIII was used to replace modified polyether plasticizer-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0062] Comparative Example 4 This comparative example was conducted using the same method as in Example 1, except that an equal weight portion of commercially available plasticizer was used to replace the modified polyether plasticizer-I in Example 1 to obtain a silane-modified polyether waterproof coating.

[0063] Comparative Example 5 This comparative example was conducted according to the method of Example 1, except that modified polyether plasticizer-I was not added in this comparative example, resulting in a silane-modified polyether waterproof coating.

[0064] Test case This test example demonstrates the performance of the various silane-modified polyether waterproof coatings prepared above.

[0065] This test case was conducted in accordance with the standards T / CBMF 105-2021 and T / CWA 203-2021. The specific test results are shown in Table 3.

[0066] Table 3

[0067] As can be seen from the results in Table 3, the silane-modified polyether waterproof coating prepared using the modified polyether plasticizer provided by this invention has significantly better weather resistance and comprehensive physical and mechanical properties.

[0068] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing modified polyether plasticizers, characterized in that, The method includes: under a protective atmosphere, (1) In the presence of an alkaline catalyst, α,ω-dihydroxypolydimethylsiloxane and epoxide alkane were stirred and mixed to obtain intermediate I; (2) The neutralizing agent is contacted and mixed with the intermediate I to obtain the modified polyether plasticizer; Relative to 100 parts by weight of the α,ω-dihydroxypolydimethylsiloxane, the amount of the alkaline catalyst is 0.1-1 parts by weight, the amount of the epoxide is 400-900 parts by weight, and the amount of the neutralizing agent is 0.12-1.2 parts by weight.

2. The method according to claim 1, characterized in that, The viscosity of the α,ω-dihydroxypolydimethylsiloxane at 25°C is 350-750 cs. And / or, the epoxide is selected from at least one of propylene oxide, ethylene oxide, butane oxide, epichlorohydrin, and cyclohexane oxide.

3. The method according to claim 1 or 2, characterized in that, In step (1), the stirring and mixing conditions include: a temperature of 100-110℃ and a time of 2-4h; And / or, in step (2), the conditions for contact mixing include: a temperature of 60-70°C and a time of 1-2 hours.

4. A modified polyether plasticizer prepared by the method according to any one of claims 1-3.

5. A composition for a silane-modified polyether waterproof coating, characterized in that, The composition consists of a main agent and an auxiliary agent, wherein the main agent contains alkoxy-terminated polyether, acryloyloxysilane and plasticizer; The content of the acryloxysilane is 2-3 parts by weight relative to 100 parts by weight of the alkoxy-terminated polyether, and the content of the plasticizer is 45-85 parts by weight. The plasticizer is the modified polyether plasticizer as described in claim 4.

6. The composition according to claim 5, characterized in that, The alkoxy-terminated polyether is selected from dialkoxy-terminated polyether and / or trialkoxy-terminated polyether.

7. The composition according to claim 5 or 6, characterized in that, The alkoxy-terminated polyether is a combination of dialkoxy-terminated polyether and trialkoxy-terminated polyether in a weight ratio of 1:0.6-2; And / or, the acryloyloxysilane is α-(methacryloyloxy)methyltriethoxysilane and / or γ-(methacryloyloxy)propyltrimethoxysilane.

8. The composition according to claim 5 or 6, characterized in that, The additives include antioxidants, fillers, dehydrating agents, and coupling agents; Relative to 100 parts by weight of the alkoxy-terminated polyether, the content of the antioxidant is 0.2-0.8 parts by weight, the content of the filler is 120-180 parts by weight, the content of the dehydrating agent is 2-5 parts by weight, and the content of the coupling agent is 1.5-3 parts by weight. And / or, the coupling agent is selected from at least one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(β-aminoethyl)aminopropyltrimethoxysilane, anilinemethyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, ureopropyltrimethoxysilane, and ureopropyltriethoxysilane; And / or, the filler is selected from at least one of nano-calcium carbonate, talc, fumed silica, heavy calcium carbonate, mica powder, titanium dioxide and carbon black.

9. A method for preparing silane-modified polyether waterproof coating, characterized in that, The method is carried out using each component of the composition according to any one of claims 5-8, and the method includes: stirring and mixing each component of the composition to obtain the silane-modified polyether waterproof coating.

10. The silane-modified polyether waterproof coating prepared according to claim 9.

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