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WO2025147791A1 - Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication - Google Patents

Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication

Info

Publication number
WO2025147791A1
WO2025147791A1 PCT/CN2024/071028 CN2024071028W WO2025147791A1 WO 2025147791 A1 WO2025147791 A1 WO 2025147791A1 CN 2024071028 W CN2024071028 W CN 2024071028W WO 2025147791 A1 WO2025147791 A1 WO 2025147791A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
silicone rubber
silane compound
sealant
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/071028
Other languages
English (en)
Inventor
Yalong QI
Hongyu CHU
Xuan XU
Wenyan SUN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Adhesive Technologies Shanghai Co Ltd
Henkel AG and Co KGaA
Original Assignee
Henkel Adhesive Technologies Shanghai Co Ltd
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Adhesive Technologies Shanghai Co Ltd, Henkel AG and Co KGaA filed Critical Henkel Adhesive Technologies Shanghai Co Ltd
Priority to PCT/CN2024/071028 priority Critical patent/WO2025147791A1/fr
Publication of WO2025147791A1 publication Critical patent/WO2025147791A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

Definitions

  • the curing speed of the condensation type (especially the single-component type) is related to the concentration and temperature of the moisture in the air, and heating alone cannot accelerate the curing.
  • a type such as dealcoholization type, deoxime type and deacetone type.
  • the present invention is related to a one-component silicone rubber composition
  • a reactive or curable silicone comprises: a reactive or curable silicone, an effective amount of deacetone type crosslinker, an effective amount of organometallic catalyst, and a silane compound, the silane compound being represented by the following formulas:
  • the silicone (silicone resin) in present invention includes reactive or curable silicone.
  • the reactive or curable silicone works as backbone after curing of the silicone rubber composition, and can provide the composition with necessary mechanical strength, bonding strength, aging resistance, and other functional performance after curing.
  • the reactive or curable silicone contains active groups such as hydroxyl group and/or alkoxyl group and can therefore carry out the curing or crosslinking reaction with the crosslinker upon exposure to moisture.
  • the reactive or curable silicone may comprise at least one selected from a group comprising a hydroxyl-containing silicone, an alkoxyl-containing silicone, and the combination thereof, and preferably a hydroxyl-containing silicone.
  • R1 and R2 are independently selected from a group consisting of H, substituted or unsubstituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C1-12 alkoxyl, and C6-12 aryl; and n is an integer of from 1,000 to 3,000,000, preferably from 100,000 to 2,000,000, more preferably from 500,000 to 2,000,000.
  • the alkoxyl-containing silicone may comprise a moiety of formula (II)
  • each R is independently selected from a group consisting of substituted or unsubstituted C1-12 alkyl, particularly C1-10 alkyl, more particularly C1-6 alkyl, even more particularly methyl or ethyl.
  • the crosslinker may comprise at least one selected from a group including an alkoxy functional curing agent, an acetoxy functional curing agent, an oxime functional curing agent, a keto functional curing agent, and the combination thereof.
  • the crosslinker comprises at least one selected from a group including vinyltriisopropensilane, phenyltriisopropenoxysilane, methyltriisopropyloxysilane, tetraisopropyloxysilane, etc.
  • Deketone type room temperature curing silicone rubber has good adhesion, meanwhile , it is odorless and non-corrosive. Because the released acetone has a low boiling point, it is easy to diffuse and volatilize, then the surface and interior could be solidified quickly.
  • the silane compounds have a formula as below:
  • 3 A being a linear or branched, aliphatic or alicyclic or substituted alicyclic or aromatic divalent hydrocarbon residue having 1 to 20 carbon atoms, preferably having 2 to 6 carbon atoms, more preferably 3 A being -CH 2 -CH 2 -or -CH 2 -CH 2 -CH 2 -.
  • 4 A, 5 A may being the same or different, and each representing a linear or branched alkyl group having 1 to 5 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably 4 A, 5 A, each representing methyl, ethyl or isopropyl;
  • n an integer of 0 to 2.
  • the silane compounds include ( (Triethoxysilyl) propyl) methylisobutylimine, ( (Trimethoxysilyl) propyl) methylisobutylimine, ( (methyl dimethoxysilyl) propyl) methylisobutylimine and the like.
  • the silane compounds in present invention have a reaction speed quite lower than traditional deacetone type organosilicon crosslinking agent in the moisture curing reaction (about two orders of magnitude lower) .
  • moisture/water that penetrated into the cured silicone can react preferentially with the imine bond of silane compounds rather than reacting with Si-O groups of the cured silicone rubber, thus the cured silicone rubber has an improved aging resistance service life in oil resistance.
  • the rate of curing or crosslinking may be slow. Therefore, it is needed to add a catalyst to the composition in order to accelerate the curing or crosslinking of the composition such that the reactive or curable silicone may form a network structure with the crosslinker within a shorter time upon exposure to moisture.
  • Curing catalysts include organic tin compounds, such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin dioctoate; titanates. Titanium chelates are also suitable catalysts, such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonato) titanium, and titanium isopropoxyoctylene glycol.
  • the catalytic amount of the catalyst may be added into the composition depending on the amount of the reactive or curable silicone.
  • the catalyst may be incorporated into the one-component silicone rubber composition in an amount of from 0.05 to 0.5%by weight, preferably in an amount of from 0.06%to 0.3%, such as 0.08%, 0.09%, 0.11%by weight, based on the total amount of the composition.
  • the silicone rubber composition of the present invention may contain, if necessary, various additives, in a range that does not inhibit the object of the present technology, such as fillers, plasticizers, antiaging agents, antioxidants, pigments (dyes) , thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents) , dispersing agents, dehydrating agents, adhesion promoters, and antistatic agents.
  • various additives in a range that does not inhibit the object of the present technology, such as fillers, plasticizers, antiaging agents, antioxidants, pigments (dyes) , thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents) , dispersing agents, dehydrating agents, adhesion promoters, and antistatic agents.
  • fillers examples include organic or inorganic fillers of any form. Specific examples include hollow glass bubbles, fumed silica, calcined silica, precipitated silica, pulverized silica, molten silica; attapulgite, diatomaceous earth; aluminum powder, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate) , colloidal calcium carbonate, magnesium carbonate, zinc carbonate; pyrophyllite clay, kaolin clay, calcined clay; fatty acid treated products, resin acid treated products, urethane compound treated products, PVC powder, and fatty acid ester treated products thereof; and the like. One type of these may be used alone, or two or more types of these may be used in combination.
  • the invention further provides a method of sealing, comprising the steps of:
  • the moisture required for the curing of the moisture-curable silicone rubber composition preferably gets into the composition through diffusion from the air (atmospheric moisture) .
  • air atmospheric moisture
  • a solid layer of cured composition is formed on the surfaces of the composition which come into contact with air ( “skin” ) .
  • the curing continues in the direction of diffusion from the outside inward, the skin becoming increasingly thick and ultimately encompassing the entire composition applied.
  • the moisture on one or more substrate (s) preferentially react with the silicone rubber to form cross-linking structures in the presence of tin catalyst.
  • the catalyst accelerates the curing or crosslinking of the silicone rubber such that the reactive or curable silicone may form a network structure with the crosslinker within a shorter time upon exposure to moisture.
  • the silane compound of present invention Due to low reaction speed, most of the silane compound of present invention, maybe haven't had time to react, were embedded in the composition matrix. It is surprisingly found that the reaction of imine group of the silane compound with the moisture is prior to the hydrolysis of silico-oxygen bond of cured silicone rubber in the hydrolysis reaction in storage, thus unreacted imine group of the silane compound improve the water-resistant and then improve storage stability. Meanwhile, the cured silicone rubber sealant composition has good anti medium properties (oil/ethylene glycol) in later use.
  • the moisture-curable silicone rubber sealant composition is preferably likewise cured at ambient temperature.
  • the substrates are preferably inorganic substrates including glass, ceramics, metals, etc.
  • Metal includes carbon steel, galvanized steel, stainless steel, tin plate.
  • the substrates of present invention may also include plastic substrates such as polycarbonate; powder coated substrates such as automotive electrophoretic paint treated substrates. Particularly suitable substrates are bare metal.
  • a one-component silicone rubber composition comprises:
  • 1 A, 2 A being the same or different, and each being hydrogen, C1-C10, linear or branched, aliphatic or alicyclic or substituted alicyclic or aromatic hydrocarbons, and 1 A, 2 A not being hydrogen simultaneously,
  • A being a linear or branched, aliphatic or alicyclic or substituted alicyclic or aromatic divalent hydrocarbon residue having 1 to 20 carbon atoms
  • n an integer of 0 to 2.
  • A being a linear aliphatic alkylene having 2 to 6 carbon atoms
  • 1 A, 2 A each being hydrogen C1-C6, linear or branched, aliphatic or alicyclic or substituted alicyclic or aromatic hydrocarbons, and 1 A, 2 A not being hydrogen simultaneously,
  • n an integer of 0 to 1.
  • composition according to any one of preceding embodiments, wherein the composition comprises 30 to 60 parts by weight of the reactive or curable silicone.
  • the deacetone type crosslinker comprises an organic isopropenoxysilane selected from methyl triisopropenoxy silane, vinyl triisopropenoxy silane, and phenyl triisopropeneoxysilane and tetraisopropoxysilane.
  • composition according to any one of preceding embodiments, wherein the organometallic catalyst is selected from a group consisting of tin, platinum, palladium, rhodium, nickel, iridium, ruthenium catalyst, and mixtures thereof.
  • An article includes a sealant on a surface of the article, wherein the sealant is a cured product of the composition of anyone of claims 1-11.
  • a method of using a one-component silicone rubber sealant which comprises:
  • the curable one-component silicone rubber sealant compositions of E2 to E5, CE1 to CE4 were prepared in reference to Example 1.
  • the curable one-component silicone rubber sealant compositions of E1 to E5 and CE1 to CE4 were cured in reference to Example 1. More details are listed in below result part.
  • the cured sealant samples were subjected to various of tests.
  • test speed is 500mm/min.
  • CE1 Compared with E1, CE1 comprise ureidosilane instead of claimed silane compound. Although the initial strength of the composition is improved due to the addition of ureidosilane as coupling agent, the anti-aging performance of the composition of CE1 is worse than E1.
  • the tensile strength value after medium (ethylene glycol) aging of CE1 is 72%of initial tensile strength value, meanwhile, the composition turned cured within only 24 hours storage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

Une composition de caoutchouc de silicone durcissable à l'humidité à un composant comprend une silicone réactive ou durcissable, une quantité efficace d'un agent de réticulation de type deacétone, une quantité efficace de catalyseur et un composé de silane. Les compositions peuvent être utilisées comme agent d'étanchéité qui présente une propriété d'adhérence, une propriété de résistance à l'huile, une stabilité au stockage améliorées. L'agent d'étanchéité de caoutchouc de silicone peut être durci à température ambiante et présente une faible émission de COV.
PCT/CN2024/071028 2024-01-08 2024-01-08 Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication Pending WO2025147791A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/071028 WO2025147791A1 (fr) 2024-01-08 2024-01-08 Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/071028 WO2025147791A1 (fr) 2024-01-08 2024-01-08 Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication

Publications (1)

Publication Number Publication Date
WO2025147791A1 true WO2025147791A1 (fr) 2025-07-17

Family

ID=96386047

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/071028 Pending WO2025147791A1 (fr) 2024-01-08 2024-01-08 Composition de caoutchouc de silicone à un composant, article associé et son procédé de fabrication

Country Status (1)

Country Link
WO (1) WO2025147791A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797446A (en) * 1985-10-15 1989-01-10 Dow Corning Corporation Adhesion of silicone sealant
US5118755A (en) * 1989-03-29 1992-06-02 Toshiba Silicone Co., Ltd. Room temperature-curable polyorganosiloxane composition
JP2001152092A (ja) * 1999-11-26 2001-06-05 Konishi Co Ltd ２成分形シリコーン系シーリング材への打継ぎ用プライマー組成物
US20090191375A1 (en) * 2006-06-30 2009-07-30 Sika Technology Ag Adhesive joint sealed with silicone
CN105121012A (zh) * 2013-03-04 2015-12-02 阿绍尼特罗开米有限公司 用于制备硅橡胶材料的组合物
CN111278924A (zh) * 2017-10-31 2020-06-12 信越化学工业株式会社 有机聚硅氧烷组合物以及有机硅化合物及其制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797446A (en) * 1985-10-15 1989-01-10 Dow Corning Corporation Adhesion of silicone sealant
US5118755A (en) * 1989-03-29 1992-06-02 Toshiba Silicone Co., Ltd. Room temperature-curable polyorganosiloxane composition
JP2001152092A (ja) * 1999-11-26 2001-06-05 Konishi Co Ltd ２成分形シリコーン系シーリング材への打継ぎ用プライマー組成物
US20090191375A1 (en) * 2006-06-30 2009-07-30 Sika Technology Ag Adhesive joint sealed with silicone
CN105121012A (zh) * 2013-03-04 2015-12-02 阿绍尼特罗开米有限公司 用于制备硅橡胶材料的组合物
CN111278924A (zh) * 2017-10-31 2020-06-12 信越化学工业株式会社 有机聚硅氧烷组合物以及有机硅化合物及其制造方法

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