Silane modified polyether flame-retardant adhesive and preparation process thereof

Abstract

The invention discloses a silane modified polyether flame-retardant adhesive and a preparation process thereof, and relates to the technical field of sealants, a phosphate plasticizer is selected as a plasticizer, a flame-retardant filler is selected from any one or two of aluminum hydroxide and magnesium hydroxide, and silane modified polyether resin is added as flame-retardant resin. All the components are compounded and mixed to obtain the modified flame-retardant adhesive, and the flame-retardant resin, the flame-retardant filler and the plasticizer have a good synergistic flame-retardant effect, so that the flame-retardant adhesive achieves a good flame-retardant effect. According to the invention, mercaptoacetic acid modified silicon resin microspheres are prepared, then the mercaptoacetic acid modified silicon resin microspheres react with lead acetate and zinc acetate by utilizing the adsorbability of sulfydryl to prepare modified silicon resin, and the silicon resin is an anti-dripping flame retardant and can form a stable and compact carbon layer structure after combustion; lead acetate and zinc acetate are beneficial to dehydrogenation and charring in the combustion process, so that the flame retardant property is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of sealants, in particular to a silane-modified polyether flame-retardant sealant and a preparation process thereof. Background Art

[0002] In the field of modern construction, qualified and effective fireproof sealing systems are particularly important, and flame retardant sealants are an important part of the entire fireproof sealing system. Silane-modified polyether sealants are mainly silane-modified prepolymers, with fillers, plasticizers and other functional additives, and are prepared by high-speed stirring and shear mixing. It has good adhesion to various materials, can be painted on the surface, has no pollution to the substrate surface, is low in VOC, and has no irritating odor.

[0003] However, the carbon-oxygen bonds mainly contained in silane-modified sealants have poor flame retardant effects on their own, and simply adding conventional flame retardants on the market cannot make silane-modified sealants achieve better flame retardant effects, and will also have a certain impact on the mechanical properties of silane-modified sealants.

[0004] In order to solve the above problems and improve the flame retardancy of silane-modified polyether flame retardant adhesive, the present invention provides a silane-modified polyether flame retardant adhesive and a preparation process thereof. Summary of the invention

[0005] The purpose of the present invention is to provide a silane-modified polyether flame retardant adhesive and a preparation process thereof, so as to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions: A silane-modified polyether flame-retardant adhesive, comprising the following components, measured in parts by weight: 20-30 parts of silane-modified polyether resin, 15-20 parts of plasticizer, 40-60 parts of flame-retardant filler, 5-10 parts of reinforcing filler, 0.3-1 parts of ultraviolet absorber, 0.3-1 parts of light stabilizer, 2-3 parts of thixotropic agent, 1-2 parts of silane coupling agent, 1-2.5 parts of dewatering agent, and 0.5-1 parts of catalyst.

[0007] More optimally, the plasticizer is a phosphate plasticizer; the flame retardant filler is any one or two of aluminum hydroxide and magnesium hydroxide; and the reinforcing filler is any one or two of light nano calcium carbonate and heavy calcium carbonate.

[0008] More optimally, the production process of the silane-modified polyether resin comprises the following steps: Step S1: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120° C. for 1-3 hours, add diisocyanate when the moisture is less than 200 ppm, and react at 90° C. for 4-6 hours; Step S2: Cool down to 40-50° C., add isocyanate silane, and react for 8-10 hours to obtain silane-modified polyether resin. More optimally, the silane-modified polyether resin is composed of the following raw materials, calculated by weight: 80-90 parts of polyether polyol, 3-10 parts of halogen-free phosphorus-containing polyol, 3-10 parts of diisocyanate, and 3-10 parts of isocyanate silane.

[0009] More optimally, the polyether polyol is polypropylene oxide with two functionalities and a molecular weight of 8000; the halogen-free phosphorus-containing polyol has a total phosphorus content of 7.5-9.5% and a hydroxyl value of 6-8; the diisocyanate is any one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; the isocyanate silane is any one or more of isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, and isocyanate propyl dimethoxy silane.

[0010] More optimally, the phosphate plasticizer is selected from any one or more of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, triethyl phosphate, tricresyl phosphate, trioctyl phosphate, and toluene diphenyl phosphate; the light stabilizer is a hindered amine light stabilizer; and the ultraviolet absorber is a benzotriazole ultraviolet absorber. A preparation process of a silane-modified polyether flame retardant adhesive comprises the following steps: Step 1: Take silane-modified polyether resin, plasticizer, flame retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, thixotropic agent, stir for 60-70 minutes, heat to 110°C, continue to stir for 2-3 hours to dehydrate, and cool the mixture to 45°C after stirring; Step 2: Add dehydrating agent and stir evenly; Step 3: adding a silane coupling agent and a catalyst, stirring and mixing them evenly, and then dispersing them in a vacuum, discharging and packaging them to obtain a silane-modified polyether flame retardant adhesive.

[0011] More optimally, in step 1, flame retardant silicone resin microspheres are further added, and the preparation method of the flame retardant silicone resin microspheres comprises the following steps: S1: Preparation of modified silicone resin microspheres: Take deionized water, add sodium hydroxide, stir evenly, heat to 45-50°C, add OP-10 emulsifier, stir evenly, add vinyl trimethoxy silane, heat to 45-50°C and stir for 1-2h, add acetic acid solution, let stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of Thioglycolic Acid Modified Silicone Resin Microspheres: Take vinyl silicone resin microspheres and ethanol, ultrasonically disperse for 30 - 40 min, add benzoin dimethyl ether, stir evenly, add mercaptoacetic acid, stir for 10 - 15 min under ultraviolet light, centrifuge, wash, and dry to obtain mercaptoacetic acid - modified silicone resin microspheres; S3: Preparation of flame - retardant silicone resin microspheres: Take lead acetate, zinc acetate, and deionized water, stir evenly, add mercaptoacetic acid - modified silicone resin microspheres, ultrasonically disperse for 30 - 40 min, heat up to 40 - 45 °C, stir for 24 - 26 h, wash, and dry to obtain flame - retardant silicone resin microspheres.

[0012] Preferably, the flame - retardant filler is a modified flame - retardant filler, and its preparation method is: take maleimide - modified flame - retardant agent, flame - retardant filler, and absolute ethanol, react for 10 - 14 h under nitrogen protection and at the ethanol reflux temperature, filter by suction, and dry to obtain the modified flame - retardant filler.

[0013] The preparation method of the maleimide - modified flame - retardant agent is: take azobisisobutyronitrile and toluene, stir evenly to obtain an azobisisobutyronitrile solution; take 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, vinyltrimethoxysilane, and toluene, heat up to 80 - 82 °C, dropwise add the azobisisobutyronitrile solution, react for 10 - 14 h, and perform rotary evaporation to obtain the maleimide - modified flame - retardant agent.

[0014] Compared with the prior art, the beneficial effects of the present invention are: 1. In the present invention, the plasticizer is selected from phosphate plasticizers, the flame - retardant filler is selected from any one or two of aluminum hydroxide and magnesium hydroxide, and a silane - modified polyether resin is also added as a flame - retardant resin. By adopting the above technical scheme, each component is compounded and mixed to obtain a modified flame - retardant adhesive, in which there is a good synergistic flame - retardant effect among the flame - retardant resin, flame - retardant filler, and plasticizer, so that the flame - retardant adhesive achieves a very good flame - retardant effect. 2. The present invention prepares a mercaptoacetic acid - modified silicone resin microsphere, and then utilizes the adsorption of mercapto groups to react the mercaptoacetic acid - modified silicone resin microsphere with lead acetate and zinc acetate to prepare a modified silicone resin. The silicone resin is a type of anti - dripping flame - retardant, and it can form a stable and dense carbon layer structure after combustion, while lead acetate and zinc acetate are beneficial for dehydrogenation and carbon formation during combustion, further improving the flame - retardant performance.

[0015] 3. The present invention also prepares a maleimide - modified 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide as a flame - retardant agent, and then uses this flame - retardant agent to modify the flame - retardant filler, further enhancing the flame - retardant performance. At the same time, the maleimide group has very good compatibility with the mercapto groups on the flame - retardant silicone resin microspheres, which can improve the compatibility of the modified flame - retardant filler in the matrix. Specific embodiments

[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] The material models and sources used in the present invention are not particularly limited, and exemplary include: silane-modified polyether resin: model 3368T, from Jiangsu Ruiyang Antai New Material Technology Co., Ltd.; UV absorber: UV-326 model UV absorber; light stabilizer: hindered amine light stabilizer 770; thixotropic agent: polyamide wax; silane coupling agent: KH-792; dewatering agent: vinyl trimethoxy silane; catalyst: KRA-1 catalyst; aluminum hydroxide, particle size: 0.5-1µm; heavy calcium carbonate, particle size: 1-2µm; magnesium hydroxide, particle size: 1-2µm; light nano calcium carbonate, particle size: 40-60nm; polyether polyol: model: DDL-8000D, provided by Zibo Dexin Federal Chemical Industry Co., Ltd., with a functionality of 2 and a number average molecular weight of 8000; halogen-free phosphorus-containing polyol: model: Exolit OP, provided by Clariant, Germany; diisocyanate: isophorone diisocyanate, provided by Covestro; isocyanate silane: isocyanate propyltrimethoxysilane, provided by Hangzhou Jessica Chemical Co., Ltd.

[0018] Embodiment 1: A process for preparing a silane-modified polyether flame retardant adhesive, comprising the following steps: Step 1: Preparation method of silane-modified polyether resin: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120°C for 2h, add diisocyanate when the moisture is lower than 200ppm, and react at 90°C for 5h; cool to 45°C, add isocyanate silane, and react for 9h to obtain silane-modified polyether resin; The silane-modified polyether resin is composed of raw materials, in parts by weight: 85 parts of polyether polyol, 8 parts of halogen-free phosphorus-containing polyol, 5 parts of diisocyanate, and 5 parts of isocyanate silane; Step 2: Preparation of silane-modified polyether flame retardant adhesive: Silane-modified polyether resin, plasticizer, flame retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer and thixotropic agent are stirred at a stirring speed of 900 rpm for 60 minutes under vacuum, and then the mixed mixture is heated to 110°C, and continued to be stirred at a speed of 900 rpm for 2 hours for dehydration, and the mixture is cooled to 45°C after stirring; a dehydrating agent is added, and then stirred at a speed of 500 rpm for 20 minutes; a silane coupling agent and a catalyst are added, and stirred at a speed of 300 rpm for 25 minutes, and then vacuum dispersed after stirring, and the material is discharged and packaged to obtain a silane-modified polyether flame retardant adhesive; The plasticizer is tri(2-chloroethyl) phosphate; the flame retardant filler is aluminum hydroxide; the reinforcing filler is heavy calcium carbonate; A silane-modified polyether flame-retardant adhesive comprises the following components, measured by weight: 3kg of silane-modified polyether resin, 1.5kg of plasticizer, 5kg of flame-retardant filler, 0.5kg of reinforcing filler, 0.03kg of ultraviolet absorber, 0.03kg of light stabilizer, 0.2kg of thixotropic agent, 0.1kg of silane coupling agent, 0.1kg of dehydrating agent and 0.05kg of catalyst.

[0019] Example 2: The model of the silane-modified polyether resin is 3368T, and the rest is the same as Example 1.

[0020] Example 3: The flame retardant plasticizer is tricresyl phosphate, and the rest is the same as Example 1.

[0021] Example 4: The flame retardant plasticizer is trioctyl phosphate, and the rest is the same as Example 1.

[0022] Example 5: The flame retardant filler is magnesium hydroxide, and the rest is the same as Example 1.

[0023] Example 6: The reinforcing filler is lightweight nano calcium carbonate, and the rest is the same as Example 1.

[0024] Embodiment 7: A process for preparing a silane-modified polyether flame retardant adhesive, comprising the following steps: Step 1: Preparation method of silane-modified polyether resin: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120°C for 2h, add diisocyanate when the moisture is lower than 200ppm, and react at 90°C for 5h; cool to 45°C, add isocyanate silane, and react for 9h to obtain silane-modified polyether resin; The silane-modified polyether resin is composed of raw materials, in parts by weight: 85 parts of polyether polyol, 8 parts of halogen-free phosphorus-containing polyol, 5 parts of diisocyanate, and 5 parts of isocyanate silane; Step 2: Preparation of flame retardant silicone resin microspheres, comprising the following steps: S1: Preparation of modified silicone resin microspheres: Take 100 mL of deionized water, add 0.13 g of sodium hydroxide, stir evenly, heat to 48 ° C, add 0.05 g of OP-10 emulsifier, stir evenly, add 3 g of vinyl trimethoxysilane, heat to 47 ° C and stir for 1.5 h, add 0.5 mL of 10% acetic acid solution, let stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of Thioglycolic Acid Modified Silicone Resin Microspheres: Take 2 g of vinyl silicone resin microspheres and 100 mL of ethanol, ultrasonically disperse for 35 min, add 0.1 g of benzoin dimethyl ether, stir evenly, add 5 g of thioglycolic acid, stir under ultraviolet light for 12 min, centrifuge, wash, and dry to obtain thioglycolic acid-modified silicone resin microspheres; S3: Preparation of flame retardant silicone microspheres: Take 6g of lead acetate, 4g of zinc acetate, and 100mL of deionized water, stir evenly, add 4g of thioglycolic acid-modified silicone resin microspheres, ultrasonically disperse for 35min, heat to 42°C, stir for 25h, wash, and dry to obtain flame-retardant silicone resin microspheres; Step 3: Preparation of maleimide modified flame retardant: Take 0.2g of azobisisobutyronitrile and 25mL of toluene, stir evenly to obtain an azobisisobutyronitrile solution; take 22.5g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 32g of vinyltrimethoxysilane, and 100mL of toluene, heat to 81°C, dropwise add the azobisisobutyronitrile solution, react for 12h, and rotary evaporate to obtain a maleimide modified flame retardant; Step 4: Preparation of modified filler: Preparation of modified flame retardant filler: Take 30g of maleimide modified flame retardant, 30g of flame retardant filler, and 500mL of anhydrous ethanol, react for 12h at ethanol reflux temperature under nitrogen protection, filter and dry to obtain a modified flame retardant filler; Step 5: Preparation of silane-modified polyether flame retardant adhesive: Silane-modified polyether resin, plasticizer, flame-retardant silicone resin microspheres, modified flame-retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, and thixotropic agent are stirred at a stirring speed of 900 rpm for 60 minutes under vacuum, and then the mixed mixture is heated to 110° C., and continued to be stirred at a speed of 900 rpm for 2 hours for dehydration, and the mixture is cooled to 45° C. after stirring; a dehydrating agent is added, and then stirred at a speed of 500 rpm for 20 minutes; a silane coupling agent and a catalyst are added, and stirred at a speed of 300 rpm for 25 minutes, and then vacuum dispersed after stirring, and the material is discharged and packaged to obtain a silane-modified polyether flame-retardant adhesive; The plasticizer is tri(2-chloroethyl) phosphate; the flame retardant filler is aluminum hydroxide; the reinforcing filler is heavy calcium carbonate; A silane-modified polyether flame-retardant adhesive, comprising the following components by weight: 3 kg of silane-modified polyether resin, 1.5 kg of plasticizer, 0.6 kg of flame-retardant silicone resin microspheres, 5 kg of modified flame-retardant filler, 0.5 kg of reinforcing filler, 0.03 kg of ultraviolet absorber, 0.03 kg of light stabilizer, 0.2 kg of thixotropic agent, 0.1 kg of silane coupling agent, 0.1 kg of water remover, and 0.05 kg of catalyst.

[0025] Example 8: A preparation process of a silane-modified polyether flame-retardant adhesive, comprising the following steps: Step 1: Preparation method of silane-modified polyether resin: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate under vacuum at 120 °C for 1 h, add diisocyanate when the water content is lower than 200 ppm, and react at 90 °C for 4 h; cool down to 40 °C, add isocyanate silane, and react for 8 h to obtain silane-modified polyether resin; The silane-modified polyether resin is composed of raw materials, by weight: 80 parts of polyether polyol, 3 parts of halogen-free phosphorus-containing polyol, 3 parts of diisocyanate, and 3 parts of isocyanate silane; Step 2: Preparation of flame-retardant silicone resin microspheres, comprising the following steps: S1: Preparation of modified silicone resin microspheres: Take 100 mL of deionized water, add 0.13 g of sodium hydroxide, stir evenly, heat up to 45 °C, add 0.05 g of OP-10 emulsifier, stir evenly, add 3 g of vinyltrimethoxysilane, heat up to 45 °C and stir for 1 h, add 0.5 mL of 10% acetic acid solution by mass fraction, let it stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of mercaptoacetic acid-modified silicone resin microspheres: Take 2 g of vinyl silicone resin microspheres and 100 mL of ethanol, ultrasonically disperse for 30 min, add 0.1 g of benzoin dimethyl ether, stir evenly, add 5 g of mercaptoacetic acid, stir under ultraviolet light for 10 min, centrifuge, wash, and dry to obtain mercaptoacetic acid-modified silicone resin microspheres; S3: Preparation of flame-retardant silicone resin microspheres: Take 6 g of lead acetate, 4 g of zinc acetate, and 100 mL of deionized water, stir evenly, add 4 g of mercaptoacetic acid-modified silicone resin microspheres, ultrasonically disperse for 30 min, heat up to 40 °C, stir for 24 h, wash, and dry to obtain flame-retardant silicone resin microspheres; Step 3: Preparation of maleimide-modified flame retardant: Take 0.2g of azobisisobutyronitrile and 25mL of toluene, stir evenly to obtain an azobisisobutyronitrile solution; take 22.5g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 32g of vinyltrimethoxysilane, and 100mL of toluene, heat to 81°C, dropwise add the azobisisobutyronitrile solution, react for 10h, and rotary evaporate to obtain a maleimide modified flame retardant; Step 4: Preparation of modified filler: Preparation of modified flame retardant filler: Take 30g of maleimide modified flame retardant, 30g of flame retardant filler, and 500mL of anhydrous ethanol, react for 10h at ethanol reflux temperature under nitrogen protection, filter and dry to obtain a modified flame retardant filler; Step 5: Preparation of silane-modified polyether flame retardant adhesive: Silane-modified polyether resin, plasticizer, flame-retardant silicone resin microspheres, modified flame-retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, and thixotropic agent are stirred at a stirring speed of 900 rpm for 60 minutes under vacuum, and then the mixed mixture is heated to 110° C., and continued to be stirred at a speed of 900 rpm for 2 hours for dehydration, and the mixture is cooled to 45° C. after stirring; a dehydrating agent is added, and then stirred at a speed of 500 rpm for 20 minutes; a silane coupling agent and a catalyst are added, and stirred at a speed of 300 rpm for 25 minutes, and then vacuum dispersed after stirring, and the material is discharged and packaged to obtain a silane-modified polyether flame-retardant adhesive; The plasticizer is tri(2-chloroethyl) phosphate; the flame retardant filler is aluminum hydroxide; the reinforcing filler is heavy calcium carbonate; A silane-modified polyether flame-retardant adhesive comprises the following components, measured by weight: 2kg of silane-modified polyether resin, 1.8kg of plasticizer, 0.5kg of flame-retardant silicone resin microspheres, 4kg of modified flame-retardant filler, 0.8kg of reinforcing filler, 0.05kg of ultraviolet absorber, 0.05kg of light stabilizer, 0.25kg of thixotropic agent, 0.15kg of silane coupling agent, 0.15kg of dehydrating agent and 0.08kg of catalyst.

[0026] Embodiment 9: A process for preparing a silane-modified polyether flame retardant adhesive, comprising the following steps: Step 1: Preparation method of silane-modified polyether resin: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120°C for 3 hours, add diisocyanate when the moisture is lower than 200 ppm, and react at 90°C for 6 hours; cool to 50°C, add isocyanate silane, and react for 10 hours to obtain silane-modified polyether resin; The silane-modified polyether resin is composed of raw materials, in parts by weight: 90 parts of polyether polyol, 10 parts of halogen-free phosphorus-containing polyol, 10 parts of diisocyanate, and 10 parts of isocyanate silane; Step 2: Preparation of flame-retardant silicone resin microspheres, including the following steps: S1: Preparation of modified silicone resin microspheres: Take 100 mL of deionized water, add 0.13 g of sodium hydroxide, stir evenly, heat up to 50 °C, add 0.05 g of OP-10 emulsifier, stir evenly, add 3 g of vinyltrimethoxysilane, heat up to 50 °C and stir for 2 h, add 0.5 mL of 10% acetic acid solution by mass fraction, let stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of mercaptoacetic acid-modified silicone resin microspheres: Take 2 g of vinyl silicone resin microspheres and 100 mL of ethanol, ultrasonically disperse for 40 min, add 0.1 g of benzoin dimethyl ether, stir evenly, add 5 g of mercaptoacetic acid, stir under ultraviolet light for 15 min, centrifuge, wash, and dry to obtain mercaptoacetic acid-modified silicone resin microspheres; S3: Preparation of flame-retardant silicone resin microspheres: Take 6 g of lead acetate, 4 g of zinc acetate, and 100 mL of deionized water, stir evenly, add 4 g of mercaptoacetic acid-modified silicone resin microspheres, ultrasonically disperse for 40 min, heat up to 45 °C, stir for 26 h, wash, and dry to obtain flame-retardant silicone resin microspheres; Step 3: Preparation of maleimide-modified flame retardant: Take 0.2 g of azobisisobutyronitrile and 25 mL of toluene, stir evenly to obtain an azobisisobutyronitrile solution; take 22.5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 32 g of vinyltrimethoxysilane, and 100 mL of toluene, heat up to 82 °C, dropwise add the azobisisobutyronitrile solution, react for 14 h, rotary evaporate to obtain maleimide-modified flame retardant; Step 4: Preparation of modified filler: Preparation of modified flame-retardant filler: Take 30 g of maleimide-modified flame retardant, 30 g of flame-retardant filler, and 500 mL of absolute ethanol, react under nitrogen protection at the ethanol reflux temperature for 14 h, filter by suction, and dry to obtain modified flame-retardant filler; Step 5: Preparation of silane-modified polyether flame retardant glue: Take silane-modified polyether resin, plasticizer, flame-retardant silicone resin microspheres, modified flame-retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, and thixotropic agent, stir at a stirring speed of 900 rpm under vacuum for 60 min, then heat the mixed mixture to 110 °C, continue to stir at a speed of 900 rpm for 2 h for dehydration, cool the mixture to 45 °C after stirring; add a water remover, and then stir at a speed of 500 rpm for 20 min; add a silane coupling agent and a catalyst, stir at a speed of 300 rpm for 25 min, disperse under vacuum after stirring, discharge and pack to obtain a kind of silane-modified polyether flame retardant glue; The plasticizer is tri(2-chloroethyl) phosphate; the flame retardant filler is aluminum hydroxide; the reinforcing filler is heavy calcium carbonate; A silane-modified polyether flame-retardant adhesive comprises the following components, measured by weight: 3kg of silane-modified polyether resin, 2kg of plasticizer, 0.6kg of flame-retardant silicone resin microspheres, 6kg of modified flame-retardant filler, 1kg of reinforcing filler, 0.1kg of ultraviolet absorber, 0.1kg of light stabilizer, 0.3kg of thixotropic agent, 0.2kg of silane coupling agent, 0.25kg of dehydrating agent, and 0.1kg of catalyst.

[0027] Comparative Example 1: The model of the silane-modified polyether resin is 280R, and the rest is the same as Example 1: Comparative Example 2: The plasticizer is dioctyl phthalate, and the rest is the same as Example 1: Comparative Example 3: No maleimide-modified 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is used as a flame retardant, and the rest is the same as Example 7: Step 1: Preparation method of silane-modified polyether resin: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120°C for 2h, add diisocyanate when the moisture is lower than 200ppm, and react at 90°C for 5h; cool to 45°C, add isocyanate silane, and react for 9h to obtain silane-modified polyether resin; The silane-modified polyether resin is composed of raw materials, in parts by weight: 85 parts of polyether polyol, 8 parts of halogen-free phosphorus-containing polyol, 5 parts of diisocyanate, and 5 parts of isocyanate silane; Step 2: Preparation of flame retardant silicone resin microspheres, comprising the following steps: S1: Preparation of modified silicone resin microspheres: Take 100 mL of deionized water, add 0.13 g of sodium hydroxide, stir evenly, heat to 48 ° C, add 0.05 g of OP-10 emulsifier, stir evenly, add 3 g of vinyl trimethoxysilane, heat to 47 ° C and stir for 1.5 h, add 0.5 mL of 10% acetic acid solution, let stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of Thioglycolic Acid Modified Silicone Resin Microspheres: Take 2 g of vinyl silicone resin microspheres and 100 mL of ethanol, ultrasonically disperse for 35 min, add 0.1 g of benzoin dimethyl ether, stir evenly, add 5 g of thioglycolic acid, stir under ultraviolet light for 12 min, centrifuge, wash, and dry to obtain thioglycolic acid-modified silicone resin microspheres; S3: Preparation of flame retardant silicone resin microspheres: Take 6g of lead acetate, 4g of zinc acetate, and 100mL of deionized water, stir evenly, add 4g of thioglycolic acid-modified silicone resin microspheres, ultrasonically disperse for 35min, heat to 42°C, stir for 25h, wash, and dry to obtain flame-retardant silicone resin microspheres; Step 3: Preparation of silane-modified polyether flame retardant adhesive: Silane-modified polyether resin, plasticizer, flame-retardant silicone resin microspheres, flame-retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, and thixotropic agent are stirred at a stirring speed of 900 rpm for 60 minutes under vacuum, and then the mixed mixture is heated to 110° C., and continued to be stirred at a speed of 900 rpm for 2 hours for dehydration, and the mixture is cooled to 45° C. after stirring; a dehydrating agent is added, and then stirred at a speed of 500 rpm for 20 minutes; a silane coupling agent and a catalyst are added, and stirred at a speed of 300 rpm for 25 minutes, and after stirring, vacuum dispersed, and the material is discharged and packaged to obtain a silane-modified polyether flame-retardant adhesive; The plasticizer is tri(2-chloroethyl) phosphate; the flame retardant filler is aluminum hydroxide; the reinforcing filler is heavy calcium carbonate; A silane-modified polyether flame-retardant adhesive comprises the following components, measured by weight: 3kg of silane-modified polyether resin, 1.5kg of plasticizer, 0.6kg of flame-retardant silicone resin microspheres, 5kg of flame-retardant filler, 0.5kg of reinforcing filler, 0.03kg of ultraviolet absorber, 0.03kg of light stabilizer, 0.2kg of thixotropic agent, 0.1kg of silane coupling agent, 0.1kg of dehydrating agent and 0.05kg of catalyst.

[0028] experiment: The silane-modified polyether flame retardant adhesive prepared in Example 1 to Example 9 and Comparative Example 1 to Comparative Example 3 was tested for performance, and the mechanical properties and flame retardant properties were tested with reference to GB / T 24267-2009 "Flame Retardant Sealant for Building", and the obtained data are as follows: Conclusion: From the comparison of the data in the table, it can be seen that Example 1, Example 2, and Comparative Example 1 that the flame retardant adhesive made of flame retardant silane-modified polyether resin 0 used in this application has better flame retardant effect than the flame retardant adhesive made of ordinary silane-modified polyether resin on the market, and has excellent mechanical properties. The flame retardancy of the homemade silane-modified polyether in Example 1 is better.

[0029] Combining Example 1, Example 3, Example 4 and Comparative Example 2, it can be seen that the flame retardant effect of the phosphate plasticizer in the flame retardant system is significantly better than that of the conventional phthalate plasticizer. It can be seen from Example 1 and Example 5 that both aluminum hydroxide and magnesium hydroxide have good flame retardant effects, and the mechanical properties provided by aluminum hydroxide in the system are slightly higher than those of magnesium hydroxide.

[0030] It can be seen from Example 1 and Example 6 that the mechanical properties of the flame retardant sealant can be adjusted without affecting the flame retardant performance by adding different reinforcing powders.

[0031] It can be seen from Example 1 and Examples 7-9 that the flame retardant properties are further enhanced by adding thioglycolic acid-modified silicone microspheres and using maleimide-modified 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a flame retardant to modify the flame retardant filler.

[0032] Combining Example 7 and Comparative Example 3, it can be seen that Comparative Example 3 does not use maleimide-modified 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a flame retardant, the compatibility of the flame retardant filler in the matrix is ​​poor, and the mechanical properties and flame retardant properties are reduced.

[0033] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A silane-modified polyether flame retardant adhesive, characterized in that: The silane-modified polyether flame retardant adhesive comprises the following components, in parts by weight: 20-30 parts of silane-modified polyether resin, 15-20 parts of plasticizer, 40-60 parts of flame retardant filler, 5-10 parts of reinforcing filler, 0.3-1 parts of ultraviolet absorber, 0.3-1 parts of light stabilizer, 2-3 parts of thixotropic agent, 1-2 parts of silane coupling agent, 1-2.5 parts of dehydrating agent, and 0.5-1 parts of catalyst; The production process of the silane-modified polyether resin comprises the following steps: Step S1: Take polyether polyol and halogen-free phosphorus-containing polyol, mix them evenly, dehydrate them under vacuum at 120° C. for 1-3 hours, add diisocyanate when the moisture is less than 200 ppm, and react at 90° C. for 4-6 hours; Step S2: Cool down to 40-50° C., add isocyanate silane, and react for 8-10 hours to obtain silane-modified polyether resin.

2. The silane-modified polyether flame retardant adhesive according to claim 1, characterized in that: The plasticizer is a phosphate plasticizer; the flame retardant filler is any one or two of aluminum hydroxide and magnesium hydroxide; and the reinforcing filler is any one or two of light nano calcium carbonate and heavy calcium carbonate.

3. The silane-modified polyether flame retardant adhesive according to claim 1, characterized in that: The silane-modified polyether resin is composed of the following raw materials, calculated by weight: 80-90 parts of polyether polyol, 3-10 parts of halogen-free phosphorus-containing polyol, 3-10 parts of diisocyanate, and 3-10 parts of isocyanate silane.

4. The silane-modified polyether flame retardant adhesive according to claim 3, characterized in that: The diisocyanate is any one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; the isocyanate silane is any one or more of isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, and isocyanate propyl dimethoxy silane.

5. The silane-modified polyether flame retardant adhesive according to claim 1, characterized in that: The phosphate plasticizer is selected from any one or more of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, triethyl phosphate, tricresyl phosphate, trioctyl phosphate, and tolylene diphenyl phosphate.

6. A process for preparing a silane-modified polyether flame retardant adhesive according to any one of claims 1 to 5, characterized in that: The following steps are involved: Step 1: Take silane-modified polyether resin, plasticizer, flame retardant filler, reinforcing filler, ultraviolet absorber, light stabilizer, thixotropic agent, stir for 60-70 minutes, heat to 110°C, continue to stir for 2-3 hours to dehydrate, and cool the mixture to 45°C after stirring; Step 2: Add dehydrating agent and stir evenly; Step 3: adding a silane coupling agent and a catalyst, stirring and mixing them evenly, and then dispersing them in a vacuum, discharging and packaging them to obtain a silane-modified polyether flame retardant adhesive.

7. The preparation process of a silane-modified polyether flame retardant adhesive according to claim 6, characterized in that: In step 1, flame retardant silicone resin microspheres are also added, and the preparation method of the flame retardant silicone resin microspheres comprises the following steps: S1: Preparation of modified silicone resin microspheres: Take deionized water, add sodium hydroxide, stir evenly, heat to 45-50°C, add OP-10 emulsifier, stir evenly, add vinyl trimethoxy silane, heat to 45-50°C and stir for 1-2h, add acetic acid solution, let stand, wash, and dry to obtain vinyl silicone resin microspheres; S2: Preparation of Thioglycolic Acid Modified Silicone Resin Microspheres: Take vinyl silicone resin microspheres and ethanol, ultrasonically disperse for 30-40 minutes, add benzoin dimethyl ether, stir evenly, add thioglycolic acid, stir under ultraviolet light for 10-15 minutes, centrifuge, wash, and dry to obtain thioglycolic acid-modified silicone resin microspheres; S3: Preparation of flame retardant silicone microspheres: Take lead acetate, zinc acetate and deionized water, stir evenly, add thioglycolic acid modified silicone resin microspheres, ultrasonically disperse for 30-40 minutes, heat to 40-45° C., stir for 24-26 hours, wash and dry to obtain flame-retardant silicone resin microspheres.

8. The preparation process of a silane-modified polyether flame retardant adhesive according to claim 6, characterized in that: The flame retardant filler is a modified flame retardant filler, and its preparation method is: taking maleimide modified flame retardant, flame retardant filler, and anhydrous ethanol, reacting for 10-14 hours at ethanol reflux temperature under nitrogen protection, filtering, and drying to obtain the modified flame retardant filler.

9. The process for preparing a silane-modified polyether flame retardant adhesive according to claim 8, characterized in that: The preparation method of the maleimide modified flame retardant comprises the following steps: taking azobisisobutyronitrile and toluene, stirring evenly to obtain an azobisisobutyronitrile solution; taking 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, vinyltrimethoxysilane and toluene, heating to 80-82° C., dropping the azobisisobutyronitrile solution, reacting for 10-14 hours, and rotary evaporating to obtain the maleimide modified flame retardant.

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