Search

CN-121991119-A - Isocyanatosilane compositions and methods of making the same

CN121991119ACN 121991119 ACN121991119 ACN 121991119ACN-121991119-A

Abstract

The present application relates to isocyanatosilane compositions and methods of making the same. The isocyanate silane composition comprises isocyanate silane and a stabilizer, wherein the content of the stabilizer in the isocyanate silane composition is 10 ppm-300 ppm, and the stabilizer is one or more selected from alcohol compounds, amine compounds, amide compounds, sulfonamide compounds and phenol compounds. The above-described isocyanatosilane composition is advantageous in improving the storage stability of isocyanatosilane.

Inventors

  • YE ZHIYANG
  • ZHANG YIQIANG
  • WU QIAN
  • HUO BIN
  • Niu Kangning
  • LI JIANFENG

Assignees

  • 万华化学集团股份有限公司

Dates

Publication Date
20260508
Application Date
20260104

Claims (10)

  1. 1. The isocyanate silane composition is characterized by comprising isocyanate silane and a stabilizer, wherein the content of the stabilizer in the isocyanate silane composition is 10 ppm-300 ppm, and the stabilizer is one or more selected from alcohol compounds, amine compounds, amide compounds, sulfonamide compounds and phenol compounds.
  2. 2. The isocyanatosilane composition of claim 1, wherein the stabilizer is selected from one or more of an amide compound and a sulfonamide compound, optionally one or more of p-toluenesulfonamide, m-toluenesulfonamide, N-methylbenzenesulfonamide and benzamide, and/or, In the isocyanatosilane composition, the content of the stabilizer is 10 ppm-150 ppm.
  3. 3. The isocyanatosilane composition of claim 1, wherein the isocyanatosilane has the structural formula (1): ; In the formula (1), R 1 、R 2 and R 3 are each independently selected from saturated alkyl of C 1 ~C 6 or saturated alkoxy of C 1 ~C 6 , at least one of which is saturated alkoxy of C 1 ~C 6 , and R 4 is selected from alkylene of C 1 ~C 12 , cycloalkylene of C 1 ~C 12 , arylene of C 6 ~C 10 or benzylene of C 7 ~C 10 ; Alternatively, R 4 is alkylene of C 1 ~C 12 ; optionally, the isocyanatosilane includes one or more of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, and 3-isocyanatopropyl methyl dimethoxysilane.
  4. 4. An isocyanatosilane composition according to any of claims 1-3, wherein the isocyanatosilane composition has a color number of 11 Hazan-15 Hazan, a chromatographic purity of 95.0% or more, and/or, After the isocyanate silane composition is stored for 90 days at 30 ℃, the color number change range is less than 20% of the initial color number, and the chromatographic purity change range is less than 1%.
  5. 5. A method of preparing an isocyanatosilane composition comprising the steps of: Reacting halogenated silane with isocyanic acid under the action of a catalyst and an auxiliary agent; Removing the catalyst and at least part of the auxiliary agent after the reaction is finished to obtain an isocyanate silane composition, wherein the isocyanate silane composition comprises isocyanate silane and a stabilizer, the content of the stabilizer in the isocyanate silane composition is 10 ppm-300 ppm, and the stabilizer is one or more selected from alcohol compounds, amine compounds, amide compounds, sulfonamide compounds and phenolic compounds; Wherein the auxiliary agent comprises a stabilizer, or the auxiliary agent does not comprise a stabilizer, after the reaction is finished, all the auxiliary agent is removed, and the stabilizer is added into the system to obtain the isocyanatosilane composition.
  6. 6. The method for producing an isocyanatosilane composition according to claim 5, wherein in the step of reacting a halosilane with isocyanic acid under the action of a catalyst and an auxiliary agent, the reaction temperature is-20 ℃ to 20 ℃ and the reaction time is 1.5h to 2h, and optionally, the reaction temperature is-10 ℃ to 10 ℃.
  7. 7. The method of preparing an isocyanatosilane composition of claim 5, wherein one or more of the following conditions are satisfied: (1) The mol ratio of the isocyanic acid to the halogenated silane is (0.9-10) 1, and optionally, the mol ratio of the isocyanic acid to the halogenated silane is (2.5-5) 1; (2) The molar ratio of the catalyst to the halogenated silane is (0.001-0.05): 1, and optionally, the molar ratio of the catalyst to the halogenated silane is (0.005-0.01): 1; (3) The auxiliary agent is selected from one or more of amide compounds and sulfonamide compounds, the ratio of the molar quantity of-NH bonds in the auxiliary agent to the molar quantity of the catalyst is (1.5-3) 1, and optionally, the ratio of the molar quantity of-NH bonds in the auxiliary agent to the molar quantity of the catalyst is (1.8-2.2) 1.
  8. 8. The method for producing an isocyanatosilane composition according to any one of claims 5 to 7, wherein the structural formula of the halosilane is represented by formula (2): ; In the formula (2), R 1 、R 2 and R 3 are each independently selected from saturated alkyl of C 1 ~C 6 or saturated alkoxy of C 1 ~C 6 , and at least one is saturated alkoxy of C 1 ~C 6 , R 4 is selected from straight-chain or branched alkylene of C 1 ~C 12 , cycloalkylene of C 1 ~C 12 , arylene of C 6 ~C 10 or benzylene of C 7 ~C 10 , X is halogen, and/or, The catalyst comprises one or more of cyclic crown ether, quaternary ammonium salt, quaternary phosphonium salt and metal chloride, optionally one or more of tetrabutylammonium chloride, 18-crown ether, zinc chloride and aluminum chloride, and optionally one or more of 18-crown ether, zinc chloride and aluminum chloride.
  9. 9. The method for preparing an isocyanatosilane composition according to any one of claims 5 to 7, wherein the catalyst and at least part of the auxiliary agent are removed by means of distillation; optionally, the process of rectification satisfies one or more of the following conditions: (1) The theoretical plate number of the rectifying tower is 2-50, alternatively, the theoretical plate number of the rectifying tower is 6-50, further alternatively, the theoretical plate number of the rectifying tower is 6-30; (2) The top pressure of the rectifying tower is 0.1kPa to 4kPa, alternatively, the top pressure of the rectifying tower is 0.15kPa to 4kPa, further alternatively, the top pressure of the rectifying tower is 0.15kPa to 2.5kPa; (3) The top reflux ratio of the rectifying tower is (0.01-60): 1, alternatively the top reflux ratio of the rectifying tower is (0.1-60): 1, further alternatively the top reflux ratio of the rectifying tower is (0.1-40): 1; (4) The temperature of the top of the rectifying tower is 50-60 ℃ and the temperature of the bottom of the rectifying tower is 130-150 ℃; (5) The rectification time is 1.5-4 hours.
  10. 10. The method for producing an isocyanatosilane composition according to any one of claims 5 to 7, further comprising, after the step of removing the catalyst and at least part of the auxiliary agent after the completion of the reaction: Introducing protective gas into the reaction liquid to purge and remove hydrogen chloride and unreacted isocyanic acid generated by the reaction; optionally, the temperature is-20 ℃ to 20 ℃ in the step of blowing the shielding gas, and optionally, the temperature is-10 ℃ to 10 ℃ in the step of blowing the shielding gas.

Description

Isocyanatosilane compositions and methods of making the same Technical Field The application relates to the field of silane coupling agents, in particular to an isocyanate silane composition and a preparation method thereof. Background Isocyanatosilanes are an important class of silane coupling agents and are widely used in a variety of articles such as coatings, sealants, adhesives, and elastomeric materials. The isocyanatosilane contains isocyanate groups and silane or siloxane groups, is active in nature, and is easy to undergo side reactions such as polymerization, hydrolysis and the like, so that the quality of the product is influenced. For example, the existing isocyanatosilanes have poor storage stability, and have the problem of slow increase of color number during storage, which not only affects the appearance of the product, but also can have adverse effects on the performance of the product in application fields such as coating. Disclosure of Invention Based on this, some embodiments of the present application provide an isocyanatosilane composition and a method for preparing the same, which are advantageous for improving storage stability of isocyanatosilane. An isocyanatosilane composition comprises isocyanatosilane and a stabilizer, wherein the content of the stabilizer in the isocyanatosilane composition is 10 ppm-300 ppm, and the stabilizer is one or more selected from alcohol compounds, amine compounds, amide compounds, sulfonamide compounds and phenol compounds. In some embodiments, the stabilizer is selected from one or more of an amide compound and a sulfonamide compound. In some embodiments, the stabilizer is selected from one or more of p-toluenesulfonamide, m-toluenesulfonamide, N-methylbenzenesulfonamide, and benzamide. In some embodiments, the content of the stabilizer in the isocyanatosilane composition is 10 ppm-150 ppm. In some of these embodiments, the isocyanatosilane has the following structural formula: ; In formula (1), R 1、R2 and R 3 are each independently selected from saturated alkyl of C 1~C6 or saturated alkoxy of C 1~C6, and at least one is saturated alkoxy of C 1~C6, and R 4 is selected from straight or branched alkylene of C 1~C12, cycloalkylene of C 1~C12, arylene of C 6~C10, or benzylene of C 7~C10. In some of these embodiments, R 4 is a linear or branched C 1~C12 alkylene group. In some of these embodiments, the isocyanatosilane includes one or more of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, and 3-isocyanatopropyl methyl dimethoxysilane. In some embodiments, the isocyanatosilane composition has a color number of 11Hazan to 15Hazan, a chromatographic purity of greater than or equal to 95.0%, and/or, After the isocyanate silane composition is stored for 90 days at 30 ℃, the color number change range is less than 20% of the initial color number, and the chromatographic purity change range is less than 1%. A method of preparing an isocyanatosilane composition comprising the steps of: Reacting halogenated silane with isocyanic acid under the action of a catalyst and an auxiliary agent; Removing the catalyst and at least part of the auxiliary agent after the reaction is finished to obtain an isocyanate silane composition, wherein the isocyanate silane composition comprises isocyanate silane and a stabilizer, the content of the stabilizer in the isocyanate silane composition is 10 ppm-300 ppm, and the stabilizer is one or more selected from alcohol compounds, amine compounds, amide compounds, sulfonamide compounds and phenolic compounds; Wherein the auxiliary agent comprises a stabilizer, or the auxiliary agent does not comprise a stabilizer, after the reaction is finished, all the auxiliary agent is removed, and the stabilizer is added into the system to obtain the isocyanatosilane composition. In some embodiments, in the step of reacting halosilane with isocyanic acid under the action of a catalyst and an auxiliary agent, the reaction temperature is-20 ℃ to 20 ℃ and the reaction time is 1.5h to 2h. In some embodiments, the reaction temperature is-10 ℃ to 10 ℃. In some embodiments, the molar ratio of the isocyanic acid to the halosilane is (0.9-10): 1. In some embodiments, the molar ratio of the isocyanic acid to the halosilane is (2.5-5): 1; In some embodiments, the molar ratio of the catalyst to the halosilane is (0.001-0.05): 1, alternatively, the molar ratio of the catalyst to the halosilane is (0.005-0.01): 1; In some embodiments, the auxiliary agent is selected from one or more of amide compounds and sulfonamide compounds, and the ratio of the molar amount of-NH bond in the auxiliary agent to the molar amount of the catalyst is (1.5-3): 1. In some embodiments, the ratio of the molar amount of-NH bond in the auxiliary agent to the molar amount of the catalyst is (1.8-2.2): 1. In some of these embodiments, the halosilane has the structural formula shown in formula (2): ; In the formula (2), R 1、R2 and R 3 are each independently sele