CA1336215C - Moulding and sealing compound - Google Patents
Moulding and sealing compoundInfo
- Publication number
- CA1336215C CA1336215C CA000599240A CA599240A CA1336215C CA 1336215 C CA1336215 C CA 1336215C CA 000599240 A CA000599240 A CA 000599240A CA 599240 A CA599240 A CA 599240A CA 1336215 C CA1336215 C CA 1336215C
- Authority
- CA
- Canada
- Prior art keywords
- compound according
- stabilizer
- dibutyl tin
- compound
- compounds
- 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.)
- Expired - Fee Related
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0239—Oxides, hydroxides, carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
- C09K2200/0247—Silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0458—Nitrogen-containing compounds
- C09K2200/0464—Isocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0657—Polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
A one-component moulding and sealing compound based on prepolymers, having terminal silyl groups with at least one hydrolyzable substituent at the Si atom, organometallic tin compounds as catalysts and inorganic fillers, comprises an isocyanate and/or a carboxylic acid chloride as stabilizer.
Description
Mouldinq and Sealinq Compound The present invention relates to a one-component moulding and sealing compound, which is storable on excluding moisture, but which is crosslinkable to elastomers in the case of water access, whilst having an improved stability.
Moisture-hardening one-component moulding and sealing compounds are already known per se. A known group of such compounds contains as prepolymers, which are crosslinkable by atmospheric moisture, compounds with term; n~ 1 silyl 10 groups having at least one hydrolyzable substituent at the Si-atom. Such prepolymers and sealing compounds produced therefrom are e.g. known from US Patent 3 971 751 and EP
application 217 289 published April 8, 1987.
15 In particular on incorporating larger quantities of inorganic fillers, particularly thixotropic fillers, such as micro-fine silica, problems occur. Particularly in the case of prolonged storage, the compounds have an inadequate stability and this can lead to a complete collapse of the 20 thixotropic characteristics. However, for practical uses a stable sealant is vital and it must have no flow or levelling tendency.
It has surprisingly been found that the stability of the 25 known sealing compounds can be significantly improved if an isocyanate or a carboxylic acid chloride is added as stabilizer. Particular preference is given to p-toluyl sulphonyl isocyanate of formula I
CH3 ~ S2 ~ NCO
, .
- - -- 2 - 133~215 but it is also possible to use other isocyanates, such as toluylene diisocyanate (TDI ), diphenyl methane-4,4-diisocyanate (MDI), naphthalene diisocyanate (NDI ), isophorone diisocyanate ( IPDI ), hexamethylene diisocyanate 5 (HDI), etc. Preferred acid chlorides are benzoylchloride and 3,5-dinitrobenzoyl chloride. Based on the total weight of the compound, added quantities of approximately 0.01 to 1 and preferably 0.05 to 0.10% by weight are adequate for obt~ini~g the desired stability. Hitherto p-toluyl 10 sulphonyl isocyanate, which is commercially available under the name "Zusatzmittel TI" from Bayer AG, Leverkusen, has only been used as an agent for trapping water traces in polyurethane materials. This problem does not occur in the case of the materials or compounds according to the 15 invention and no explanation can be given as to why said compounds lead to the observed increase in the stability of the highly filled sealants, without impairing other characteristics of the compounds.
20 The silyl-modified prepolymers are polyethers, polyesters, ether-ester block copolymers, vinyl polymers, diallyl phthalates and their prepolymers, as well as diallyl phthalate copolymers, which can in each case contain at least one silyl group of the following formula II in the 5 molecule 1 2 (R )a I
X -Si~ H- , (II) in which Rl and R2, independently of one another, can 30 represent hydrogen atoms or alkyl, aryl or aralkyl radicals with up to 10 carbon atoms, X a hydrolyzable group and a 0, 1 or 2. X can be a halogen atom or an alkoxy, aminoxy, phenoxy, thioalkoxy, acyloxy, acid amide, mercapto or ketoximato group. It is preferably an alkoxy group with 1 35 to 5 carbon atoms in the alkyl radical. A particularly preferred silyl terminal group is the dimethoxymethylsilyl ~ 3 ~ 1 33621 5 group.
The prepolymer molecular weight can be between 500 and 20,000, preferably between 500 and 15,000. A particularly 5 preferred molecular weight is 3000 t~ 12,000. Particularly preferred prepolymers are silyl-modified polyethers, which can be obtained by hydrosilylation of polyethers with olefinically unsaturated terminal groups, cf. US Patent 3 971 751. Suitable silyl-modified polyethers are those of 10 formula III
3 (CH2)3 - (0CH2 - CH ~ )n -(CH2)3 ~ Si - OCH3 III
OCH ~~ OCH3 For producing moisture-hardening moulding and sealing compounds, organometallic tin compounds are added as catalysts to the known silyl-modified polymers, e.g.
tin(II)octoate or dibutyl tin laurate and dibutyl tin 2~ maleate (US Patent 3 971 751). However, the use charac-teristics of the present compounds are also influenced by the choice of the organometallic tin compound. Particularly preferred catalysts are the reaction products obtained at approximately 150C of dibutyl tin oxide with dioctyl 25 phthalate and dibutyl tin acetate. Surprisingly dibutyl tin dialkylates of C3 to C6-alcohols, particularly dibutyl tin dibutylate are particularly suitable.
In addition, inorganic fillers such as carbon black, 30 calcium carbonate, titanium dioxide and the like, as well as plasticizers, particularly phthalates, such as dioctyl phthalate and butylbenzyl phthalate or phosphates, such as tricresyl phosphate are added.
35 The preferred inorganic fillers according to the invention are highly disperse silica and in particular fumed or _ 4 _ l 3 3 6 2 1 5 precipitated silica which have a thixotropic effect and whose thixotropic characteristics are retained even after prolonged storage in the compounds according to the invention. Finally the compounds can contain conventional 5 W-stabilizers and antioxydants (anti-agers). Amino silanes, such as e.g. ~-glycidyloxypropyl or Y-aminopropyl-trimethoxysilane are in particular used for improving the adhesion to glass, metals, etc. They simultaneously trap any moisture in the fillers, ensure a good storage 10 stability and to a certain extent act as a co-catalyst.
It has proved particularly advantageous in the production of the inventive compounds, if the organometallic tin compounds and the stabilizer are jointly added following 15 the mixing of the remaining components. This avoids the collapse of the thixotropy which is otherwise frequently encountered on adding tin compounds.
The following examples further illustrate the invention 20 without restricting the same.
Example l Within the scope of this example, various organometallic tin compounds were checked as regards their catalytic 25 activity. For this purpose, a basic mixture of the following components was prepared:
30.0% by weight of a polyether prepolymer with dimethoxy-methylsilyl terminal groups (viscosity 100-260 P), 6.34% dioctylphthalate, 30 11.83% titanium dioxide paste (52% TiO2 in dioctyl-phthalate), 0.30% antioxydant (anti-ager), 0.30~ W-protective agent, 45.39% calcium carbonate, 35 4.34% hydrogenated castor oil.
In each case 200 g of the above basic mixture were filled _ 5 l 3 3 62 1 ~
into a 310 ml cartridge and mixed with 0.2 to 0.8 g of the particular catalyst composition to be tested. The mixture was then stirred under vacuum for`approximately 2 minutes in a cartridge mixing apparatus.
The sealants were then applied to glass plates or poly-ethylene film-covered boards for determin;ng the skin formation time (in minutes) and the surface tackiness (after 24 hours). The results obtained are given in the 10 following Table 1. Apart from the reaction product of dibutyl tin oxide with dioctyl phthalate (at 150C), dibutyl tin dibutylate was surprisingly found to be very effective. The tests also revealed that, apart from the organometallic tin compound, a silane such as y-glycidyl-15 oxypropyl-trimethoxysilane or y-aminopropyl-trimethoxy-silane is particularly useful for obtaining good adhesion characteristics and also for the storage stability.
_ -- 6 -- ' , ,t O O I '~
~o I ~ O ' O O ~ + + a ~
O o I
V ~3 O ~ + +~ 3 u o O I~ r ~ ~ o co I I I ~o + + u~
o o a~ ta o o .
o o ~ ~ ., r~ I I I I i I o c,~3 ~ ~ Qr~
r ~ I_ o I ~ 1' 1' 1' c~ _( c~ o ~
co . . . I I ~ + + ~ +
o o o u~ +
o o c~
o I I I o~ + +
o o o o c~
~o I I I ~ I +
,t O O
~ I
E~ O O O
~ ~ ` ~ ~ ~ + + - o o o o o o ~ r ,t c O O O
~O ~CS` CJ~ I ~ + I O
I I ~ + + ~
O O O +
c"
o cs~ .
O l l ~ l O
r o - ., o oo i -~
I I ~ I o o o o ~ o o a~ ~ ,-O I I I J, I ~ t` ` ' c~ ~ . , ~ ~ ,t ~ o r - c r o J
~ r c~
. `" ., ,~', ,r .' ~ ~ 8 ~ 8 o o ,- ,-~ E ~ r z ~ rt ~ ._r ~ . O U~
JJ ~ C~ rt ~ C ~ U~
U~ rrt~ O r~ ~ rt E ~ ~ ,t V ~rt rt~5 -;,_ C~ ~ + ~ + + O
_ 7 _ l 33621 5 ExamPle 2 Sealants A to D were produced which differ from one another in that the sealants B to D additionally contain an isocyanate or acid chloride:
A B C D
MS polymer* 20 A 19.00 19.00 19.00 19.00 10 MS polymer* 300 13.00 13.00 13.00 13.00 Dioctylphthalate 29.03 28.53 21.09 21.09 Di(N-methylbenzamido)-15 methyl-ethoxysilane 0.50 0.50 0.50 0.50 Y-Aminopropyl-trimeth-oxysilane 0.80 0.80 0.80 0.80 20 Vinyltrimethoxysilane 0.60 0.60 0.60 0.60 Antioxydant (Anti-ager) 0.30 0.30 0.30 0.30 25 W -protective agent 0.30 0.30 0.30 .30 Highly disperse silica4.50 4.50 4.50 4.50 Calcium carbonate 24.52 24.52 32.06 32.06 Butyl tin dibutylate 0.70 Intermediate 1 6.75 6.75 6.75 6.75 Intermediate 2 - 1.20 Intermediate 3 - - 1.20 35 Intermediate 4 - - - 1.20 -100.00 100.00 100.00 100.00 Intermediate Dioctylphthalate 43.530 Iron oxides 56.470 100 . 00 * Bis[3-(methyldimethoxysilyl)propyl]-polyoxypropylene - - 1 3 3 ~ 2 1 5 Intermediate 2 3 4 Dioctylphthalate 34.723 34.723 34.723 Dibutyl tin dibutylate58.333 58.333 58.333 p-Toluol sulphonyl isocyanate 6.944 Diphenylmethane-4,4'-diisocyanate - 6.944 Benzoylchloride - - 6.944 100.00 100.00 100.00 All the sealants had a very short skin formation time of 10 to 20 15 minutes and showed a good adhesion to different substrates.
However, the formulations differed significantly as regards their stability. Whereas even after prolonged storage sealants B
to D had an excellent stability, sealant A proved not to be stable. Despite the addition of thixotropic highly disperse 25 silica, the thixotropic characteristics had disappeared after only a short time, so that on a smooth substrate sealant A
flowed, i.e. had a levelling tendency.
Moisture-hardening one-component moulding and sealing compounds are already known per se. A known group of such compounds contains as prepolymers, which are crosslinkable by atmospheric moisture, compounds with term; n~ 1 silyl 10 groups having at least one hydrolyzable substituent at the Si-atom. Such prepolymers and sealing compounds produced therefrom are e.g. known from US Patent 3 971 751 and EP
application 217 289 published April 8, 1987.
15 In particular on incorporating larger quantities of inorganic fillers, particularly thixotropic fillers, such as micro-fine silica, problems occur. Particularly in the case of prolonged storage, the compounds have an inadequate stability and this can lead to a complete collapse of the 20 thixotropic characteristics. However, for practical uses a stable sealant is vital and it must have no flow or levelling tendency.
It has surprisingly been found that the stability of the 25 known sealing compounds can be significantly improved if an isocyanate or a carboxylic acid chloride is added as stabilizer. Particular preference is given to p-toluyl sulphonyl isocyanate of formula I
CH3 ~ S2 ~ NCO
, .
- - -- 2 - 133~215 but it is also possible to use other isocyanates, such as toluylene diisocyanate (TDI ), diphenyl methane-4,4-diisocyanate (MDI), naphthalene diisocyanate (NDI ), isophorone diisocyanate ( IPDI ), hexamethylene diisocyanate 5 (HDI), etc. Preferred acid chlorides are benzoylchloride and 3,5-dinitrobenzoyl chloride. Based on the total weight of the compound, added quantities of approximately 0.01 to 1 and preferably 0.05 to 0.10% by weight are adequate for obt~ini~g the desired stability. Hitherto p-toluyl 10 sulphonyl isocyanate, which is commercially available under the name "Zusatzmittel TI" from Bayer AG, Leverkusen, has only been used as an agent for trapping water traces in polyurethane materials. This problem does not occur in the case of the materials or compounds according to the 15 invention and no explanation can be given as to why said compounds lead to the observed increase in the stability of the highly filled sealants, without impairing other characteristics of the compounds.
20 The silyl-modified prepolymers are polyethers, polyesters, ether-ester block copolymers, vinyl polymers, diallyl phthalates and their prepolymers, as well as diallyl phthalate copolymers, which can in each case contain at least one silyl group of the following formula II in the 5 molecule 1 2 (R )a I
X -Si~ H- , (II) in which Rl and R2, independently of one another, can 30 represent hydrogen atoms or alkyl, aryl or aralkyl radicals with up to 10 carbon atoms, X a hydrolyzable group and a 0, 1 or 2. X can be a halogen atom or an alkoxy, aminoxy, phenoxy, thioalkoxy, acyloxy, acid amide, mercapto or ketoximato group. It is preferably an alkoxy group with 1 35 to 5 carbon atoms in the alkyl radical. A particularly preferred silyl terminal group is the dimethoxymethylsilyl ~ 3 ~ 1 33621 5 group.
The prepolymer molecular weight can be between 500 and 20,000, preferably between 500 and 15,000. A particularly 5 preferred molecular weight is 3000 t~ 12,000. Particularly preferred prepolymers are silyl-modified polyethers, which can be obtained by hydrosilylation of polyethers with olefinically unsaturated terminal groups, cf. US Patent 3 971 751. Suitable silyl-modified polyethers are those of 10 formula III
3 (CH2)3 - (0CH2 - CH ~ )n -(CH2)3 ~ Si - OCH3 III
OCH ~~ OCH3 For producing moisture-hardening moulding and sealing compounds, organometallic tin compounds are added as catalysts to the known silyl-modified polymers, e.g.
tin(II)octoate or dibutyl tin laurate and dibutyl tin 2~ maleate (US Patent 3 971 751). However, the use charac-teristics of the present compounds are also influenced by the choice of the organometallic tin compound. Particularly preferred catalysts are the reaction products obtained at approximately 150C of dibutyl tin oxide with dioctyl 25 phthalate and dibutyl tin acetate. Surprisingly dibutyl tin dialkylates of C3 to C6-alcohols, particularly dibutyl tin dibutylate are particularly suitable.
In addition, inorganic fillers such as carbon black, 30 calcium carbonate, titanium dioxide and the like, as well as plasticizers, particularly phthalates, such as dioctyl phthalate and butylbenzyl phthalate or phosphates, such as tricresyl phosphate are added.
35 The preferred inorganic fillers according to the invention are highly disperse silica and in particular fumed or _ 4 _ l 3 3 6 2 1 5 precipitated silica which have a thixotropic effect and whose thixotropic characteristics are retained even after prolonged storage in the compounds according to the invention. Finally the compounds can contain conventional 5 W-stabilizers and antioxydants (anti-agers). Amino silanes, such as e.g. ~-glycidyloxypropyl or Y-aminopropyl-trimethoxysilane are in particular used for improving the adhesion to glass, metals, etc. They simultaneously trap any moisture in the fillers, ensure a good storage 10 stability and to a certain extent act as a co-catalyst.
It has proved particularly advantageous in the production of the inventive compounds, if the organometallic tin compounds and the stabilizer are jointly added following 15 the mixing of the remaining components. This avoids the collapse of the thixotropy which is otherwise frequently encountered on adding tin compounds.
The following examples further illustrate the invention 20 without restricting the same.
Example l Within the scope of this example, various organometallic tin compounds were checked as regards their catalytic 25 activity. For this purpose, a basic mixture of the following components was prepared:
30.0% by weight of a polyether prepolymer with dimethoxy-methylsilyl terminal groups (viscosity 100-260 P), 6.34% dioctylphthalate, 30 11.83% titanium dioxide paste (52% TiO2 in dioctyl-phthalate), 0.30% antioxydant (anti-ager), 0.30~ W-protective agent, 45.39% calcium carbonate, 35 4.34% hydrogenated castor oil.
In each case 200 g of the above basic mixture were filled _ 5 l 3 3 62 1 ~
into a 310 ml cartridge and mixed with 0.2 to 0.8 g of the particular catalyst composition to be tested. The mixture was then stirred under vacuum for`approximately 2 minutes in a cartridge mixing apparatus.
The sealants were then applied to glass plates or poly-ethylene film-covered boards for determin;ng the skin formation time (in minutes) and the surface tackiness (after 24 hours). The results obtained are given in the 10 following Table 1. Apart from the reaction product of dibutyl tin oxide with dioctyl phthalate (at 150C), dibutyl tin dibutylate was surprisingly found to be very effective. The tests also revealed that, apart from the organometallic tin compound, a silane such as y-glycidyl-15 oxypropyl-trimethoxysilane or y-aminopropyl-trimethoxy-silane is particularly useful for obtaining good adhesion characteristics and also for the storage stability.
_ -- 6 -- ' , ,t O O I '~
~o I ~ O ' O O ~ + + a ~
O o I
V ~3 O ~ + +~ 3 u o O I~ r ~ ~ o co I I I ~o + + u~
o o a~ ta o o .
o o ~ ~ ., r~ I I I I i I o c,~3 ~ ~ Qr~
r ~ I_ o I ~ 1' 1' 1' c~ _( c~ o ~
co . . . I I ~ + + ~ +
o o o u~ +
o o c~
o I I I o~ + +
o o o o c~
~o I I I ~ I +
,t O O
~ I
E~ O O O
~ ~ ` ~ ~ ~ + + - o o o o o o ~ r ,t c O O O
~O ~CS` CJ~ I ~ + I O
I I ~ + + ~
O O O +
c"
o cs~ .
O l l ~ l O
r o - ., o oo i -~
I I ~ I o o o o ~ o o a~ ~ ,-O I I I J, I ~ t` ` ' c~ ~ . , ~ ~ ,t ~ o r - c r o J
~ r c~
. `" ., ,~', ,r .' ~ ~ 8 ~ 8 o o ,- ,-~ E ~ r z ~ rt ~ ._r ~ . O U~
JJ ~ C~ rt ~ C ~ U~
U~ rrt~ O r~ ~ rt E ~ ~ ,t V ~rt rt~5 -;,_ C~ ~ + ~ + + O
_ 7 _ l 33621 5 ExamPle 2 Sealants A to D were produced which differ from one another in that the sealants B to D additionally contain an isocyanate or acid chloride:
A B C D
MS polymer* 20 A 19.00 19.00 19.00 19.00 10 MS polymer* 300 13.00 13.00 13.00 13.00 Dioctylphthalate 29.03 28.53 21.09 21.09 Di(N-methylbenzamido)-15 methyl-ethoxysilane 0.50 0.50 0.50 0.50 Y-Aminopropyl-trimeth-oxysilane 0.80 0.80 0.80 0.80 20 Vinyltrimethoxysilane 0.60 0.60 0.60 0.60 Antioxydant (Anti-ager) 0.30 0.30 0.30 0.30 25 W -protective agent 0.30 0.30 0.30 .30 Highly disperse silica4.50 4.50 4.50 4.50 Calcium carbonate 24.52 24.52 32.06 32.06 Butyl tin dibutylate 0.70 Intermediate 1 6.75 6.75 6.75 6.75 Intermediate 2 - 1.20 Intermediate 3 - - 1.20 35 Intermediate 4 - - - 1.20 -100.00 100.00 100.00 100.00 Intermediate Dioctylphthalate 43.530 Iron oxides 56.470 100 . 00 * Bis[3-(methyldimethoxysilyl)propyl]-polyoxypropylene - - 1 3 3 ~ 2 1 5 Intermediate 2 3 4 Dioctylphthalate 34.723 34.723 34.723 Dibutyl tin dibutylate58.333 58.333 58.333 p-Toluol sulphonyl isocyanate 6.944 Diphenylmethane-4,4'-diisocyanate - 6.944 Benzoylchloride - - 6.944 100.00 100.00 100.00 All the sealants had a very short skin formation time of 10 to 20 15 minutes and showed a good adhesion to different substrates.
However, the formulations differed significantly as regards their stability. Whereas even after prolonged storage sealants B
to D had an excellent stability, sealant A proved not to be stable. Despite the addition of thixotropic highly disperse 25 silica, the thixotropic characteristics had disappeared after only a short time, so that on a smooth substrate sealant A
flowed, i.e. had a levelling tendency.
Claims (8)
1. A one-component moulding and sealing compound based on prepolymers having terminal silyl groups with at least one hydrolyzable substituent at the Si atom, organometallic tin compounds as catalysts and inorganic fillers, characterized in that it comprises an isocyanate and/or a carboxylic acid chloride as stabilizer.
2. A compound according to claim 1, characterized in that it comprises 0.01 to 1% by weight of stabilizer.
3. A compound according to claim 1, characterized in that it comprises p-toluyl sulphonyl isocyanate as stabilizer.
4. A compound according to claim 1, characterized in that it comprises as the organometallic tin compound the reaction product of dibutyl tin oxide with dioctyl phthalate and/or dibutyl tin acetate and/or a dibutyl tin dialkylate of a C3 to C6-alkyl alcohol.
5. A compound according to claim 4, characterized in that it comprises dibutyl tin dibutylate.
6. A compound according to claim 1, characterized in that it comprises highly disperse silica as the inorganic filler.
7. A compound according to claim 1, characterized in that it comprises a silane-modified polyether prepolymer.
8. A method of preparing a one-component moulding and sealing compound according to anyone of claims 1 to 7, characterized in that the organometallic tin compounds and the stabilizer are jointly added to the compound following the mixing of the remaining components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3816808A DE3816808C1 (en) | 1988-05-14 | 1988-05-14 | |
| DEP3816808.1 | 1988-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336215C true CA1336215C (en) | 1995-07-04 |
Family
ID=6354557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000599240A Expired - Fee Related CA1336215C (en) | 1988-05-14 | 1989-05-10 | Moulding and sealing compound |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0342411B1 (en) |
| JP (1) | JPH0224363A (en) |
| AT (1) | ATE113640T1 (en) |
| CA (1) | CA1336215C (en) |
| DE (2) | DE3816808C1 (en) |
| ES (1) | ES2063069T3 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991013928A1 (en) * | 1990-03-09 | 1991-09-19 | Kanegafuchi Chemical Industry Co., Ltd. | Curable composition |
| DE4019074C1 (en) * | 1990-06-15 | 1991-07-18 | Teroson Gmbh, 6900 Heidelberg, De | |
| DE4119484C2 (en) * | 1991-06-13 | 1993-12-23 | Teroson Gmbh | Sealants and adhesives based on silane-modified prepolymers |
| EP0844266B1 (en) * | 1991-09-12 | 2004-12-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition |
| US5703146A (en) * | 1991-09-12 | 1997-12-30 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition containing an oxypropylene polymer and calcium carbonate which has been surface treated with a fatty acid |
| DE4223468A1 (en) * | 1992-07-16 | 1994-01-20 | Wacker Chemie Gmbh | Stabilization of organosiloxanes with SiOC-bound residues |
| US5902863A (en) * | 1997-07-21 | 1999-05-11 | Dow Corning Corporation | Dendrimer-based networks containing lyophilic organosilicon and hydrophilic polyamidoamine nanoscopic domains |
| US5938934A (en) * | 1998-01-13 | 1999-08-17 | Dow Corning Corporation | Dendrimer-based nanoscopic sponges and metal composites |
| PL1672161T3 (en) | 2004-12-20 | 2009-09-30 | Gabriel Pichler | Joint sealing and method of producing the same |
| DE102006006974A1 (en) * | 2006-02-14 | 2007-08-30 | Bostik Gmbh | Coating composition based on modified silane polymer useful to seal built structures, is composed of mixture of silane-terminated polyoxyalkylenes of different viscosities, chalk powder, drying agent, curing catalyst and adhesion promoter |
| DE102006006973C5 (en) * | 2006-02-14 | 2014-10-23 | Bostik Gmbh | One-component, water-free coating material for building waterproofing |
| DE102006006975A1 (en) * | 2006-02-14 | 2007-08-30 | Bostik Gmbh | One-component, solvent-free contact adhesive |
| WO2024017969A1 (en) | 2022-07-22 | 2024-01-25 | Merz + Benteli Ag | Silane-terminated polymers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3971751A (en) * | 1975-06-09 | 1976-07-27 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vulcanizable silylether terminated polymer |
| JPS60206812A (en) * | 1984-03-31 | 1985-10-18 | Dainippon Ink & Chem Inc | Room temperature-setting resin composition containing vinyl polymer having silyl group of improved hydrolyzability |
| JPS6274959A (en) * | 1985-09-30 | 1987-04-06 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
| JPS6383160A (en) * | 1986-09-26 | 1988-04-13 | Toshiba Silicone Co Ltd | Room temperature-curable composition |
-
1988
- 1988-05-14 DE DE3816808A patent/DE3816808C1/de not_active Expired
-
1989
- 1989-04-28 EP EP89107718A patent/EP0342411B1/en not_active Expired - Lifetime
- 1989-04-28 AT AT89107718T patent/ATE113640T1/en not_active IP Right Cessation
- 1989-04-28 ES ES89107718T patent/ES2063069T3/en not_active Expired - Lifetime
- 1989-04-28 DE DE58908579T patent/DE58908579D1/en not_active Expired - Lifetime
- 1989-05-10 CA CA000599240A patent/CA1336215C/en not_active Expired - Fee Related
- 1989-05-12 JP JP1117633A patent/JPH0224363A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0342411A2 (en) | 1989-11-23 |
| DE3816808C1 (en) | 1989-10-26 |
| ATE113640T1 (en) | 1994-11-15 |
| ES2063069T3 (en) | 1995-01-01 |
| DE58908579D1 (en) | 1994-12-08 |
| JPH0224363A (en) | 1990-01-26 |
| EP0342411B1 (en) | 1994-11-02 |
| EP0342411A3 (en) | 1990-10-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |