WO1992007896A1 - FORMULE DE SILICONE DURCISSABLE A L'HUMIDITE ET UTILISANT UN PROMOTEUR D'ADHESION η-UREIDO-PROPYLTRIALCOXYSILANE - Google Patents

FORMULE DE SILICONE DURCISSABLE A L'HUMIDITE ET UTILISANT UN PROMOTEUR D'ADHESION η-UREIDO-PROPYLTRIALCOXYSILANE Download PDF

Info

Publication number
WO1992007896A1
WO1992007896A1 PCT/US1991/008122 US9108122W WO9207896A1 WO 1992007896 A1 WO1992007896 A1 WO 1992007896A1 US 9108122 W US9108122 W US 9108122W WO 9207896 A1 WO9207896 A1 WO 9207896A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
weight
filler
amount
polyorganosiloxane
Prior art date
Application number
PCT/US1991/008122
Other languages
English (en)
Inventor
George D. Metz
M. Dale Beers
Original Assignee
Loctite Corporation
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 Loctite Corporation filed Critical Loctite Corporation
Publication of WO1992007896A1 publication Critical patent/WO1992007896A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group

Definitions

  • R 1 is a C (1-7) monovalent hydrocarbon radical
  • R 2 is a C (1-4) alkyl radical, C (1-4) acyl radical or a radical of the formula -CH 2 CH 2 O) n R 4 , where n is 1 or 2 and R 4 is a C (1-4) alkyl radical.
  • R 3 is a C (1-18) divalent hydrocarbon radical free of aliphatic unsaturation attached to a nitrogen atom of the urea nucleus through a non- aromatic carbon atom
  • Z is hydrogen or a C (1-4) alkyl radical and y equals 0 or 1.
  • Such compounds are disclosed as coupling agents for improving bonding of organic polymers to glass substrates. Use of these compounds in RTV silicone formulations or for bonding to metal substrates is not suggested by this reference.
  • urea compounds disclosed in US 3,675,562 may be employed as adhesion promoters in RTV silicone substrates giving superior metal bonding performance to the bis-silyl urea compounds of US 4,506,058 and 4,847,396, in similar formulations. Therefore, in one aspect there is provided a moisture curing RTV silicone formulation employing an adhesive promoting effective amount of a compound of the formula:
  • R' is a one-to-seven carbon atom monovalent hydrocarbon group
  • R" is a monovalent hydrocarbon radical, optionally interrupted by one or more ether oxygen atoms
  • R'" is a divalent hydrocarbon radical and x is 0 or 1.
  • a silicone composition which is storage stable in the substantial absence of moisture and which composition vulcanizes at room temperature on exposure to moisture comprising in admixture:
  • R is a hydrocarbon or halohydrocarbon group, said reactive polyorganosiloxane having moisture curable end groups thereon,
  • R' is a one-to-seven-carbon atom monovalent hydrocarbon group
  • R" is a monovalent hydrocarbon radical, optionally interrupted by one or more ether oxygen atoms
  • R'" is a divalent hydrocarbon radical and x is 0 or 1.
  • polyorganosiloxane (A) can be any polyorganosiloxane consisting essentially of repeating units of formula (1) and which is terminated with radicals which will effect crosslinking upon exposure to moisture.
  • Such polyorganosiloxanes are well known to those skilled in the art, but of particular interest in the present invention are polyorganosiloxanes wherein the silicone at each chain end is silanol terminated.
  • the polyorganosiloxane (D) is a silanol terminated polydimethylsiloxane which has a viscosity at 25° C of 2,000 cps - 250,000 cps, preferably about 4,000 cps to about 50,000 cps.
  • condensation catalysts which can be used in the practice of the present invention to facilitate the cure of the room temperature vulcanizable compositions are, for example, from about 0.001 % to about 1 % based on the weight of polyorganosiloxane (A).
  • the condensation catalyst is a tin compound such as dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, stannous octoate, stannous oieat, stannous naphthenate and the like. Dimethyltinbis-neodecanoate is particularly preferred.
  • Titanium compounds which can be used are, for example,
  • the present invention is based on the surprising discovery that a self- bonding room temperature vulcanizable composition is obtained when an effective amount of a mono-silyl urea compound of formula (5) is also included in the RTV composition.
  • an effective amount of adhesion promoter of formula (5) will range from about 0.05 to about 10 parts by weight per 100 parts by weight of polyorganosiloxane (A).
  • the bis-silyl urea adhesion promoter of the present invention have two or three OR" radicals bonded to each silicon atom.
  • R" be a methyl or ethyl group; e.g. each silicon atom preferably has three methoxy or ethoxy radicals bonded thereto.
  • R" can generally be any alkyl radical of 1 to 4 carbon atoms such as formyl, acetyl or propionyl; or any alkoxyethyl radical such as ⁇ -methoxyethyl, ⁇ - ethoxyethyl or ⁇ -butoxyethyl; or any radical of the formula -CH 2 CH 2 O) n R"" where n is 1 or 2 and R"" is a C (1-4) alkyl radical such as -CH 2 CH 2 O) 2 CH 3 or -CH 2 CH 2 O) 2 C 4 H 9 .
  • R' if present, can be any monovalent hydrocarbon radical of up to 7 carbon atoms such as methyl, ethyl, hexyl, vinyl, allyl, hexenyl, phenyl, cyclohexyl, cyclopentyl and cyclopentenyl.
  • R'" can be any divalent hydrocarbon radical most suitably a C 1 - C 8 alkylene group.
  • crosslinking silane compound there is also incorporated into the RTV composition of the invention a crosslinking silane compound.
  • Various crosslinkers are known, all characterized by the presence of three or four hydrolyzable groups attached to the silane silicon atom. Most common are the trialkoxy, triamino, triacetoxy or trioxime substituted silanes.
  • trioxime silanes such as methyltris-methylethylketoximosilane or vinyltris-methylethylketoximosilane are preferred, suitably at levels of about 3 to about 9, preferably about 4 to about 6, ketoxime groups per silanol group.
  • the composition may also employ a plasticizer.
  • the plasticizer is a trimethylsilyl terminated dimethylsiloxane employed at levels of up to about 40% by weight of the composition.
  • a thixotropic agent is added to the overall composition.
  • This agent which also adds physical strength to the system desirably is a treated or an untreated silica filler with a treated fumed silica filler being preferred.
  • Treated or untreated silica fillers are well known to the art and generally any such conventional filler can be utilized. Suitable levels range from about 0.1% to about
  • the silica filler has a very high surface area such as about 100-300M 2 /gram.
  • a thermal aging additive can be utilized.
  • This optional component functions to reduce oxidation and thermal rearrangement of polymers at elevated temperatures.
  • These antioxidants may include materials like cerium neodecanoate, rare earth octoates and iron octoates.
  • Representative samples can also usually include thermal aging additives such as carbon black, iron oxide powder, and titanium dioxide. Naturally, other pigments can be utilized.
  • Another optional ingredient is an inert non-reinforcing filler such as ground quartz, calcium carbonate, talc, clay, various silicate compounds and other materials well known in the art.
  • the amount utilized is from about 5% to about 60% by weight bases upon the total weight of the sealant composition.
  • Especially preferred fillers are stearic acid treated calcium carbonate fillers having particle sizes below about 0.06 microns, suitably 0.04-0.05 microns.
  • Such fillers are commercially available and may be conveniently employed at levels of about 5% to about 70% of the total weight of the composition, preferably about 15% - 40% of the total composition.
  • iron aluminum silicate which further improves the fluid immersion properties of the cured compositions particularly in engine coolant.
  • a suitable filler is Ferrosil 14, sold by Kaopolite, Inc., Union, NJ, 98% of which has a particle size of 14 microns or less. Preserved levels of iron aluminum silicate range from 5% to 40% based on the total weight of the composition.
  • the compositions of the invention may further comprise other additives known in the art such as pigments, odor masks or other additives known to improve the properties of RTV silicones for particular applications.
  • compositions of the instant invention are formed by mixing the various ingredients together in the substantial absence of moisture. This mixing is carried out in the substantial absence of moisture because moisture will cause the ingredients to prematurely vulcanize. After mixing the composition is storage stable as long as moisture is prevented from contacting the composition. The physical properties of the composition will remain essentially unchanged for one year or more after packaging.
  • compositions of this invention can also be utilized as a two component system.
  • Such two component systems generally comprise as the basic ingredients as polyorganosiloxane base polymer and a filler in one package, and an alkyl silicate crosslinking agent mixed with a condensation catalyst as the second package.
  • the compositions prepared in this manner are stored as such and when it is desired to cure the composition the two packages are mixed together and cured to form a silicone elastomeric composition.
  • the inventive formulations are especially useful in hot oily environments such as in automotive gasketing applications, where they give comparable or even improved properties compared to prior art formulations employing bis-urea compounds and existing commercial automotive gasketing silicones.
  • the invention may be illustrated by the following non-limiting examples.
  • composition of the invention was prepared as follows:
  • a master batch silicone formulation J was prepared as follows:
  • Example 2 A master batch as in Example 2 was prepared to which was added the adhesion promoters and amounts listed in Table 3. Peel adhesion and % cohesive failure on aluminum lap shears were determined as for the examples in Table 2 except that both one week and two week values were obtained. Results are shown in Table 3.
  • Specimens were prepared from the formulations prepared in Example 3 according to ASTM D-412, Die C, after 1 week curing at 25°C, 50% relative humidity. Physical property testing results on these samples (initial values) and on cured specimens which were subsequently immersed in 50° C motor oil for 1 week (final values) are reported in Table 4. The results show good property retention under the test condition.
  • a RTV silicone master batch formulation was prepared as follows:
  • the polymer, plasticizers, fillers and pigments were mixed together under high shear mixing conditions in a vertical change can mixer at 120°C under vacuum for three hours. The batch was then cooled and the vinyltris-methylethylketoximosilane and tin catalyst added in sequence.

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)

Abstract

Silicone RTV durcissable à l'humidité, à un seul constituant et utilisant comme promoteur d'adhésion un composé de la formule (I) dans laquelle R' représente un groupe hydrocarbure monovalent constitué de un à sept atomes de carbone, R'' représente un radical hydrocarbure monovalent, éventuellement interrompu par un ou plusieurs atomes d'oxygène éther, R''' représente un radical hydrocarbure divalent et x est 0 ou 1. Ce produit possède des propriétés d'adhésion aux métaux particulièrement favorables, spécialement dans des milieux chargés de vapeurs d'huile tels que dans des applications d'étanchéité de moteurs automobiles.
PCT/US1991/008122 1990-11-01 1991-10-31 FORMULE DE SILICONE DURCISSABLE A L'HUMIDITE ET UTILISANT UN PROMOTEUR D'ADHESION η-UREIDO-PROPYLTRIALCOXYSILANE WO1992007896A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60757190A 1990-11-01 1990-11-01
US607,571 1990-11-01

Publications (1)

Publication Number Publication Date
WO1992007896A1 true WO1992007896A1 (fr) 1992-05-14

Family

ID=24432857

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/008122 WO1992007896A1 (fr) 1990-11-01 1991-10-31 FORMULE DE SILICONE DURCISSABLE A L'HUMIDITE ET UTILISANT UN PROMOTEUR D'ADHESION η-UREIDO-PROPYLTRIALCOXYSILANE

Country Status (1)

Country Link
WO (1) WO1992007896A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1147296B1 (fr) * 1999-01-25 2003-05-07 Henkel Loctite Deutschland GmbH Procede pour monter le carter d'huile ou le couvercle de soupape sur un bloc moteur ou un couvercle d un boitier de commande ou d un carter de boite de vitesse d un moteur a combustion interne, moteur a combustion interne sur lequel le carter d'huile, le couvercle de soupape ou le couvercle du boitier de commande ou du carter de boite de vitesse est fixe selon ce procede
WO2019107196A1 (fr) * 2017-11-30 2019-06-06 ダウ・東レ株式会社 Composition de caoutchouc de silicone durcissable

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671562A (en) * 1968-09-12 1972-06-20 Union Carbide Corp Urea silicon product and the preparation thereof
US4506058A (en) * 1984-03-14 1985-03-19 General Electric Company Self-bonding room temperature vulcanizable silicone compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671562A (en) * 1968-09-12 1972-06-20 Union Carbide Corp Urea silicon product and the preparation thereof
US4506058A (en) * 1984-03-14 1985-03-19 General Electric Company Self-bonding room temperature vulcanizable silicone compositions

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1147296B1 (fr) * 1999-01-25 2003-05-07 Henkel Loctite Deutschland GmbH Procede pour monter le carter d'huile ou le couvercle de soupape sur un bloc moteur ou un couvercle d un boitier de commande ou d un carter de boite de vitesse d un moteur a combustion interne, moteur a combustion interne sur lequel le carter d'huile, le couvercle de soupape ou le couvercle du boitier de commande ou du carter de boite de vitesse est fixe selon ce procede
US7040274B1 (en) 1999-01-25 2006-05-09 Henkel Loctite Deutschland Gmbh Process for attaching the oil sump to an engine block of a combustion engine
WO2019107196A1 (fr) * 2017-11-30 2019-06-06 ダウ・東レ株式会社 Composition de caoutchouc de silicone durcissable
JPWO2019107196A1 (ja) * 2017-11-30 2020-11-26 ダウ・東レ株式会社 硬化性シリコーンゴム組成物
JP7116085B2 (ja) 2017-11-30 2022-08-09 ダウ・東レ株式会社 硬化性シリコーンゴム組成物
US11505703B2 (en) 2017-11-30 2022-11-22 Dow Toray Co., Ltd. Curable silicone rubber composition

Similar Documents

Publication Publication Date Title
EP0157580B2 (fr) Composition d'étanchéité résistant à l'huile, avec module bas, à base de silicone
US4973623A (en) Fast curing oximo-ethoxy functional siloxane sealants
US5840794A (en) Alkoxy functional sealants with rapid development of green strength
EP0438221B1 (fr) Masses d'étanchéité à base de siloxanes ayant une adhésion améliorée
EP0368455B1 (fr) Contrôle de module pour un joint à base de silicone
US4261758A (en) Room temperature vulcanizable silicone rubber compositions with sag-control
US3542901A (en) Organosilicon compositions
US4748166A (en) RTV storage stable, water-free organopolysiloxanes
EP0371666B1 (fr) Joints à base de silicone de couleur atténuée
US4735979A (en) Auto-adhering one-component RTV silicone sealant composition utilizing an adhesion promoter
US4673750A (en) Auto-adhering one-component RTV silicone sealant composition utilizing glycidoxyalkyl substituted alkoxy-oxime silane as an adhesion promoter
US6288143B1 (en) Filler/silicone oil masterbatch with treating agent for RTV polysiloxanes
US4657967A (en) Room temperature curing compositions containing tetrafunctional ethoxy-ketoximo silane crosslinkers
US7094858B2 (en) Process for the preparation of crosslinkable materials based on organosilicon compounds
KR950005316B1 (ko) 실온 경화성 오르가노폴리실록산 조성물
EP0884351A2 (fr) Composition d'étanchéité de silicone résistante à l'huile contenant un acétate métallique
US5300611A (en) Room temperature curable organopolysiloxane compositions
US5688840A (en) Process for preparing room temperature-curable organopolysiloxane composition
GB2053255A (en) Shelf-stable one-part room temperature vulcanizable silicone rubber compositions
JPH0323106B2 (fr)
US6103804A (en) Process for the sealing components exposed to aggressive functional fluids and RTV silicone compositions suitable for use therein
JPH0645755B2 (ja) 室温でエラストマーに架橋する材料、その製造方法および該材料を含有する塗料相溶性封止剤
AU8708198A (en) Organosiloxane compositions
US4847396A (en) Auto-adhering one-component RTV silicone sealant composition utilizing an adhesion promoter
JPH04214764A (ja) 室温硬化性オルガノポリシロキサン組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE