NZ264321A

NZ264321A - Polyorganosiloxane composition comprising an alkoxysilane containing an alkyl group substituted by halo, arylamino, hydroxy or etherified hydroxy as adhesion promoter

Info

Publication number: NZ264321A
Application number: NZ264321A
Authority: NZ
Inventors: Robert Friebe; Wilhelm Weber; Karl-Heinz Sockel
Original assignee: Bayer Ag
Priority date: 1993-08-31
Filing date: 1994-08-26
Publication date: 1997-01-29
Also published as: DE4329263A1; EP0640659A3; JPH0797518A; KR950005909A; EP0640657A2; EP0640659A2; AU682197B2; AU7157294A; HU214044B; HUT70862A; HU9402496D0

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £64321 2 6 4 3 2 Patents Form 5 Priority Date(s):.., Complete Specification Fite^r: Class. (6) ,GG>$ W5.3k). S .. £QS. &S] SH .. .QftfJ. & 3>. \ .1P 2'g"JA'NW? Publication Date: P.O. Je-urn?' No: ?*»* rn it fc.ji IjV ; rl V * . U t* L ^ <«■** *?c/ M.g. FATfVn" OFFICE 2G AUG 1994 •••» -• ' -r.i ..- i . - rr-j i .- T- ■ i , :.. mmm. N.Z. No. NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION SINGLE-COMPONENT POLYSILOXANE COMPOUNDS We, BAYER AKTIENGESELLSCHAFT, a company registered under the laws of the Federal Republic of Germany, of D-51368 Leverkusen, Federal Republic of Germany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 - (Followed by 1A) .•m 'V 2fi4321 The invention relate* to single-component silicone systems, hereinafter identified as IK-RTV compositions, which can be stored with the exclusion of moisture and which cure as room temperature under the effect of moisture and thereby release 5 alcohols aa reaction product*. This type of composition can be prepared from polyargano-siloxanes with reactive £ terminal groups, slane cross-linking agents and optional fillers by using condensation catalysts. According to the prior art; organic titanium compounds are suitable aa catalysts. PblyaUaxane compounds which contain titanium compounds 1Q as condensation catalysts am known. A few examples only are mentioned here as being representative of those which are prepared using this type of titanium catalyst and aikoxysilanccros®4inltfng agents of the general formula. RSi(ORV US 3334067., U$3i29*,739i DE-A J 125 881, DE-A 3 512 337, US 3,499,85* and US 4,433.03* 15 A. prerequisite for the successful use of these IK-RTV compositions, e.g. as sealing compounds, is good: and long-lasting adhesion to the substrate. Therefore the broadest possible adhesion spectrum is desirable for the compositions as this opens up a wide range of applications. To improve the adhesive properties of IK-RTV compounds, adhesion promoters 20 are generally added to the pastes, these preferably being organo-functional si lanes of the type (R'0)3.llR,'nSi'X, wherein X represents any organic group, which is substituted in any position by a functional group such as, for example, an amino, cyano, mercapto, glycidyloxy or methacryloxy group. There are numerous patents which describe the use of such compounds in alkoxy-25 hardening, titanium catalyzed polysiloxane compounds. For instance, DOS 2 063 630 describes adhesives which contain carboxyl groups, such as, for instance, the compound (CHjO^SilCH^SCCH^COOH. US 4, 460,739, for instance, describes - 1 - I hx r "t or ] ~ i r/-]p >r]34 1 I i i .' L. rJw ' \ t 2*4321 makwniriylpropyltrictho*y-ailaag and (SB 2 079 745A inscribes 1,3-bis-rrtmcthoxy-«ilylpropyl-Uocyanarate. GE1137217A describes, inter alia, acyloxy, acryloxy, cyano, isocyasaaor amino and epoxy fiiaclkwial aUcoxyalaces as adhoion promoters. Mercaptoai lanes ate described la EP-A 345 645 and 5 epoxyaDboxysilams are described in EP-A 175 134* Combinations of functional silanes such aa epoxysilanes and anrinotrialkoxysiliiies (EP-A 221 644) are also described. These known adheatoa promoteo. however, have n number of disadvantages in practice. Ite adhesion promoting effect of stlaney is. sometime* restricted to only a 10 few substrates aad frequently, after storage of ftlly cored test bodies in water, a loss of adhesion is observed. Furthermore, cross-linking distortions and discoloration phenomena ,^>ca^*^^jBdany- itt titanium-catalyzed IK-RTV compositions* whkte ave sn^eg^ to-be- du»'^ieactiona between the titanium ctfrfytts nCtte often have IS short shelf Eves. Therefore it is the object of the invention to find suitable adhesion promoters which avoid the disadvantages mentioned above and which produce good adhesion of IK-RTV compounds. Unexpectedly, it was found that particularly suitable adhesion promoters for the 20 polysdloxane compositions according to die invention are organo-functional alkoxysilanes of die general formula (R'0)VnR"1,Si-(CHj)I-X, in which the functional group X is a halogen atom, especially chlorinc, a hydroxyl group or an aminoaryl group, especially an aminophcnyl group. Examples of such compounds are 3-chloro-propyItriethoxysilane, 3-chloropropyldimethoxymethyIsilaoe, 3-25 hydroxypropyltricthoxysilane and 3-(N-phcnylanjino}-propyltriethoxysilane. The IK-RTV compositions produced with the aid of the adhesion promoters according to the invention have a surprisingly wide adhesion spectrum, the cured product has good mechanical properties, full curing takes place rapidly and UM ft B3 gJtegg - 2 - i 1 2«4 321 without distortion, there is no tendency to discolor and the shelf lives are very long. The invention provides a polyorganosiloxAne composition, which cum at ambient temperature under the effect of water or moisture to give an elastomer, and which 5 can be stored with tile exclusion of water, prepared by mixing a) a polyorganosaioxaner with reactive terminal groups and having a viscosity of 1.0 to 1000 at 25°C, b) optionally polyorganodloxans with non-reactive terminal groups, c) a silane cross-linking agent of fonnula R'^SiCOR.2),, wherein R1 end Rz 10' each independently is a mono-valent optionally substituted hydrocarbon group with 2-8 eastern atoms and n is 2,3 or 4, d) a titanium compound: as a condensation catalyst, e) optionally a filler, f) an adhesion promoter of the formula IS (R30)3H1R4.Si-(CH2),-X wherein R3 and R4 each independently is a Cj-C^, alkyl or alkoxyalkyl group, X is a halogen atom, an aminoaryt group optionally substituted on the aromatic moiety, n Si? 33Sjm - 3 - 2«A32f or a hydraxyl group, or a 0,-Cjo alkoxyalkyl group which is substituted at one or mote carbon atoms at any position by one or more hydroxyl groups, n is 0,1 or 2, and and g) optionally other additives and auxiliary agents. In the prefeiied embodiment of the present invention the polysiloxane composition which hardens at ambient temperature under the effect of water or moisture and which are obtainable by mixing a) 100 parts by wl of polyoiganositoxanes with reactive terminal groups, b) 0 to 50 parts by wt. of polyoiganosiloxanes with non-reactive terminal groups, c) 0 to 20, preferably 5 to 20 parts by wt. of alkoxysilane cross-linking agents, d) 0.01 to 2 parts by wt of organic titanium compounds as condensation catalysts, e) 10 to 120 parts by wt of fillers, f) adhesion promoters according to the invention, and g) optionally, other additives and auxiliary agents, such as, e.g. stabilizers, dyes and fungicides, in amounts of up to 5 paits by wt 119 ti *9 j?3S_Efl - 4 - z is from I to 20, 2fi43 PolydiiMthylriloxues can be used aa polydiorganoaloxanca with reactive terminal groups a), wherein the methyl groups can be partly replaced by vinyl, phenyl, C,-C,*alkyl or haloalkyl groups. The polydimethylsiloxanes should be essentially linear. Small proportions of branching organostloxy units may, however, be 5 present The viscosity of the polymers is preferably between 1.0 and 1000 P&s, preferably less than 100 Pa£. Suitable reactive terminal groups are triaDcoxysiloxy or dialkoxyalkylsiloxy groups, wherein the alkyl group may optionally cany, at any position, halogen atoms or amino, axyl, alkyl or hydroxyl groups, or any other functional groups. In the latter case, diethoxymctfaylsiloxy, diethoxyvinylsiloxy, 10 dimethoxymetbylsiloxy, dtmetboxy-3-chloropropyisiIoxy (-OSiCOCHj^CCCH^JjCI]) or dimethoxy-3-(N-phenylaminopropy1)-5iloxy (-OSiCOCTjJjKCHjJsNHPhJ) groups are preferred. In a preferred embodiment of the present invention the polyorganosiloxane a) preferably carries at least one of hydtoxydimethyl, methyldimethoxy, vinyldiethoxy, triethoxysiloxy and 3-chloropropyl-15 dimethoxyailoxy terminal groups. In another embodiment of the present invention wherein the polyorganosiloxane a) preferably carries at least one of hydroxydimethyl, methyldimethoxy, vinyldiethoxy, triethoxysiloxy and 3-chloropropyl-dimethoxysiloxy terminal groups, the adhesion promoter is present in from about 0.01 to 10 wt.% with 20 respect to the amount of polyorganosiloxane (a), and the alkoxysilane cross-linking agent c) comprises a partial hydrolyzate of methyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane or tetraethoxysilane, methyltriethoxy-silane or tetraethoxysilane and the number of silicon atoms in the polyorganosiloxane a) and b) is from 2 to 12. 25 Suitable polyorganosiloxanes with non-reactive terminal groups are all silicone plasticizers known from the prior art. Poly dimctby I si loxanes with trimethylsiloxy terminal groups and a viscosity of 0.1 - 5 Pas are preferably used as component b). ft ng 93ti re - 5 - 3 1 AUG r.:-34 I 264321 Alkoxysilanea are suitable u sUane cmw-Hnlring agents c). AHcoxysilanes have the general formula R'^SitOR3),,, wherein R1 and R* each independently are a monovalent optionally substituted hydrocarbon groups with 2-8 carbon atoms, and n is 2, 3 or 4. Picfciied stlane crosa-linlting agents ace aDcoxysilanes such *s 5 teraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane or vinyltriethoxysilane or partial hydrolyzates of such alkoxysi lanes. Any conventional confounds which ate partly known front the cited literature are used aa organic titanium catalysts d), audi aa tetraalkyl thanates, e.g. TICOCjHj)*, Ti[OCH(CH0il4. HIOCn-C+H,)^, HIOC^CEKCHjJjl,, TitOCHaCH(C2HJ)-C4H9]4 10 and complexes of titanium with various chelating agents such as, e.g. fj-dicarbonyl compounds soch as ethyl acetoaoetate or acetylacetone: ethyl diisobutyl-diacetoacetate titanate, diisopropyl-titaTiiiimdiacetylaceto titanate, ethyl propane-1 ,2-dioxottiaaetOMTtatc titanate. ethyl propane-l,3-dioxodiacetoacetate titanate or ethyl propane-1 ^-dioxoacetoacctatBi-tiiethylcitrate titanate. Tetraisobutyl titanate. 15 ethyl propane-1,2-dioxodiaceto-acetate titanate, ethyl propane-1,2-. dioxoftcctoacctate-triethy Icitrate rftanwtr and ethyl diisobutyl-bis-acetoacetate titanate are particularly suitable- Suitable fillers e) which can be uaed are reinforcing fillers such as pyrogenic or precipitated silicas and carbon black or weak or non-reinforcing mineral materials 20 with a carbonate, silicate or oxide composition. The filler surface may be pie-treated. Silanized pyrogenic silicas and milted natural chalk or precipitated chalk coated with stearic acid are particularly preferred. The adhesion promoters f) according to the invention have the following general structure: 25 (R'0)3JEt".SHCHa),-X wherein fca ft fit? 3Jg-ffr MZ. PATE . 7 ^ 31 AUt 10 j. 2 £Li R'JR" represent Identical or different linear or branched C,-Cjo alkyl group* m- awox groups, X represent! a halogen atom, or an antinoaryl group. wherein the aromatic portion may optionally carry C,-5 C» alkyl groups or alkoxyalkyl groups, halogen atoms, or other functional groups on one or more carbon atoms at any position, or a hydroxyl group or a C,-^ alkoxyalkyl group which is substituted, at one or more carbon atoms in any position, by one or more hydroxyl groups, 10 n is 0,1 or 2 and z is 1 to 20, particularly preferably 1 to 8, in particular 3. 3~Ch1oropropylteietboxysilane, 3-chloropropyltrimethoxy-silane, 3-chloropropyl-diethyoxymethyl si lane, 2-chloroethyl-triethoxysiIane, 3-(N-phenylamino>propy!tri-methoxysilane, 3-(N-{4-iiicthylphcnyl)-amiiio)-propy1triethyoxysiIane, 3-hydroxy -15 propyltriethoxysilaoe and 3-(2-hydroxyethoxy)-propyltriethoxysilane are particularly suitable. The adhesion promoters according to the invention are used in amounts of 0.01 to 10 wt.%, preferably 0.1 to 6 wt%» with respect to the amount of polyorganosiloxane (component a). 20 The compositions according to the invention, as is usual with IK-RTV compositions, may be prepared in planetary mixers, buttcifly mixers, dissolvers, continuously operating mixing screws or other equipment suitable for preparing pastes. The compositions m.isi be protected from atmospheric moisture during 03 m - 7 - i'J.Z. pate 31 AUt': 1304 2*432 pwpimioB and storage. Any sequence may b» uicd for mixing the individual components. The inveation is explained in mem detail by the following examples. lu a no oaa-ge* - 8 - 2 i .4 v L, 2rh32H t to 7 55.0 puts by weight of a polydimetbylidloxanc with -OSKOCH^CH,) terminal groups, which had a viscosity of 50 Pa* at 25 °C, were mixed with 29.0 parts by wt of a-polydimethylsiloxane with -OSi(CHj), termiiial groups (viscosity O.t Pu 5 at 25°C) and 2J parts by wL of methyltrimcthoxysilane. Then 9J5 parts by wt of a hydrophobic, pyrogenic silica were incorporated. Finally die titanium catalyst and the corresponding adhesion promoter were added (see Table 1). To test die mechanical data, 2 mm thick sheets were applied to a smooth, plane base and tested after coring for 14- days at 25°C and 50% relative humidity in 10 accordance with DIN 53504 (standard test piece). In addition, the Shore A hardness of die cured elastomers was determined after 21 days in accordance with DIN 53505. Hie dcin-fonning time of die compounds is determined, ije., the time which elapses until a skin forms on the stufrce of the sample layer. The adhesion is determined by applying the IK-RTV compositions in the shape of a bead with 15 the approximate dimensions 50x50x10 mm to test plates of various substrates and then, after a curing time of 7 days, testing die adhesion to the corresponding substrate by means of a powerful tug on the cared material. After passing this test the test specimen are stored for a farther 7 days in water at room temperature and subjected to an adhesion test again. 20 Example 8 55.0 parts by weight of a polydimethylsiloxane with -OSi(CX^HJ)2l(CH2)3Cl]) terminal groups, which had a viscosity of 80 Pa.s at 25°C, were mixed with 29.0 parts by weight of a polydimethylsiloxane with -OSi(CH,)3 terminal groups (viscosity 1.0 Pa.s at 25°C) and 2.5 parts by weight of mcthyltr i methoxysi lane in a 25 planetary mixer. Then 9 J parts by weight of a hydrophobic, pyrogenic silica were incorporated. Finally, the titanium catalyst and adhesion promoter as cited in Table 1 were added. SO 938TQ - 9 - I'.Ti! :'■! i 31 AUG 1394 R»«nnla« 9 tfl 13 3510 parts by weight of a polydhnethylsHoxane with -OSiCCHg^OH terminal groups, which had a viscosity of 80 Paj at 25°C were mixed with 2?J) parts by weight of & polydiinethylailoxanc with -OSi(CHj)j terminal groups (viscosity 0.01 P&j at 23*Q and with 30.0 parts by weight of a chalk filler treated with stearic acid. Then die titanium catalyst (see Table 2) was incorporated. The batch was completed by incorporating 2.5 parts by weight of methyltrimetboxysilane and 5.5 parts by weight of a hydrophflic, pyrogenic silica and the amount of adhesion promoter given in Table 2. - 10 N.Z. PA iCE 31 AUG 1304 Tahte 1 10 15 1» 2 3 4* 5 6 7 8 | Ti catalyst A A A B B B C A | puts by weight 1-0 1.0 ijo 0.9 03 0.9 1 JO 1J> 1 Adhesion promoter • D B • D B F D \ para by weight 1.0 1.0 1.0 1j0 03 OS I Skin-forming time 10 10 12 5 15 12 • 17 | (minutes) Shore A hardness 19 21 20 16 19 18 20 19 ■Iter 21 days DIN 53504 standard test picce 8 Hear atreugili 1 (N/mm1) 1.36 1.60 1.78 1.75 1.70 1.68 1.50 1.77 1 1 Elongation (%) 541 482 598 586 536 521 520 643 | ( B-modulna (N/mnr1) 0.2s 035 039 031 035 032 038 035 | Adhesion 2 2 £ Glass 2 2 2 1 2 2 2 2 I Ttet 2 2 2 1 2 2 2 2 | Ataminont 0 2 2 0 2 2 2 U V^A steel • - - - - . 2 2 I Copper 0 2 2 0 2 2 2 2 | 1 PVC 0 2 2 0 2 2 2 2 | | Plexiglass 1 2 2 0 2 2 2 2 1 Q Macrolon 0 2 2 1 9. 2 2 20 25 30 35 * Comparison example A = ethyl piopaae-1 ,2-dloxoducctoacetate titan Me B = tecmiaobuiyl titanate C » ethyl diiaovotyl-bis-acetoacetate titanate D - 3-chloropropyltricthoxysilane E a 3-chloropropyItriethoxyjiIanc P = 3-(N-phCTiylamino)-propyltrirnBthQxy»ilane Adhesion: 0 = no adhesion after caring for 7 days 1 = adhesion after curing for 7 days 2 = adhesion after curing for 7 days followed by 7 days in water at RT t i iii ir ri - ii - 4 3 21 Example No. 9» 10 11* 12 13 14* 19 Ti catalyst C c A A A a G pans by weight IjO 1.0 1.0 1.0 IX) 13 S Adhesion promuta • F • D C • D | paits by weight 05 IjO 0.5 IjO | Sin-fomniig rime • - 10 12 11 9 11 1 minutes | Shore A liaitlueia 27 29 23 30 28 27 29 10 after 21 days DIN 53504 standard test piece Tfear tfxength (N/mni2) 1.43 IM IJO 1-49 131 139 1.43 Elongation (%) 424 450 463 473 465 421 42° J 15 E-modnlus (N/znm1) 046 045 045 0.44 0/43 046 0.43 | Adhe^OQ/cateipUlar trade test ; Class 2 Z 2 2 2 2 . 2 Hies Z 2 2 2 2 2 2 20 1 Alirminnm Z 2 1 Z 2 1 2 V«A StOOl 2 2 0 2 I - 1 Copper 0 2 1 2 2 0 2 FVC 0 2 0 2 2 0 2 Plexiglass 0 2 0 2 2 0 2 25 Macroloo 0 2 1 2 2 0 2 30 * Comparison example A m ethyl ptopano-t,2-riinxn<HM!wtoacctato titanate C = ethyl diiaobutyl-bis-acetpacetate titanate D = 3-chloropropylttietfaoxy»iUne F « 3-(N-phenylamiiio)-propyitrimethoxysilinie Q - ethyl propane-1 ^-diaxQ-acetoacetitc-tritthyl-citrate titanate Adhesion: 0 ■ no adhesion alter curing for 7 days 1 ■ adhesioa after coring for 7 days 2 = adhesioa after caring for 7 days followed by 7 days in water at RT hi] ft BO PJfegg - 12 - 1 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> It is understood that the specification and examples are ill limitative of the prescul inveotioii and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art 2 1 i.a ft aa en a fo - 13 - I 3 1 AUG 1354 WHAT WE CLAIM IS: 2*4321

1. A polyorganosiloxane composition, which cures at ambient temperature under die effect of water or moisture to give an elastomer, and which can be stored with the exclusion of water, prepared by mixing a) a polyorganosiloxane with reactive terminal groups and having a viscosity of 1.0 to 1000 Fa.s at 25°C, b) optionally polyorganosiloxans with non-reactive terminal groups, c) a silane cross-linking agent of the formula R'^SKOR2),, wherein R1 and R3 each independently is a mono-valent optionally substituted hydrocarbon group with 2-8 carbon atoms and n is 2, 3 or 4, d) a titanium compound as a condensation catalyst, e) optionally a filler, f) an adhesion promoter of the formula (R30)3^R4»Si-(CH2)I-X wherein R3 and R4 each independently is a Cj-C^, alkyl or alkoxyalkyl group, X is a halogen atom, an aminoaiyl group optionally substituted on the aromatic moiety, i *■ 'cv - -—•- ■ • ■ 2R4321 or a hydroxyl group, or a C,-Ca alkoxyalkyl group which it substituted at one or mora carbon atoms at any position by one or mote hydroxyl groups, n is 0,1 or 2, and z is from 1 to 20, and g) optionally other additives and auxiliary agents.

2. A composition according to Claim 1, wherein the adhesion promoter f) comprises at least on» of 3-chloxopropyltricthoxyalanc and 3-chloropropyl-trimethoxy ulane. 10

3. A composition according to Claim 1, wherein the adhesion promoter f) comprises at least one of 3KN-phenylamino)-propyltrimetboxysUane and 3-' (N-(4-methylphenyl)-amino>propy ltrietboxysilane.

4. A composition according to Claim 1, wherein the promoter f) comprises 3-hydroxypropyltrimethoxysiiane. 15

5. A composition according to Claim 1, wherein the adhesion promoter is present in from about 0.01 to 10 wt.% with respect to the amount of polyorganosiloxane (a).

6. A composition according to Claim 1, wherein the si lane cross-linking agent c) comprises at least one of me&yltrimethoxysilane, vinyltriethoxysilane, 2 0 methyltriethoxysilane and tetraethoxysHane. ha ft 3Q Qa-a-gg. - 15 - 1 ;•■■]]{* 10.04 | i ;•» L ^ I J %j"t f I » 2«432i

7. A composition according to Claim 1, wherein die riUne cross-linking agent c) comprises a partial hydrolyzate of methyltrimethoxyalane, vinyl-triethoxysilane methyltriethoxysilane or tetraethoxysilane, and tl» number of silicon atoms in the polyorganosiloxane a) and b) ia from 2 to 12. 5

8. A composition according to Claim 1, wherein the polyorganosiloxane a) carries at least one of hydroxydimethyl, methyldimethoxy, vinyldiethoxy, triethoxysiloxy and 3-chloropfopyHUmethoxysiloxy terminal groups.

9. A composition according to Claim 4* wherein the polyorganosiloxane a) carries at least one of hydroxydimethyl, methyldimethoxy, vinyldiethoxy, 10 triethoxysiloxy and 3-chloropropyl-dimethoxysiioxy terminal groups, the adhesion promoter is present in from about 0.01 to 10 wt.% with respect to the amount of polyorganosiloxane (a), and the alkoxyalane cross-linking agent c) comprises a. partial hydrolyzate of methyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane or tetraethoxysilane, methyl- 15 triethoxysilane or tetraethoxysilane and the number of silicon atoms in the polyorganosiloxane a) and b) is from 2 to 12.

10. In a single-component silicone composition comprising a silicone, a titanium compound and an adhesion promoter, the improvement wherein such adhesion promoter comprises a compound of die formula 20 (R30)>#R4ftSi-(CH2)J8-X wherein R3 and R4 each independently is a Cj-C^ alkyl or alkoxyalkyl group, X is a halogen atom, BQ QQB - 16 - n.z. patent off 31 AUG 1994 264 321 or a hydroxyl group, or a CrCV} alkoxyalkyl group which is substituted at one or more carbon atoms at any position by one or more hydroxyl groups, n is 0, 1 or 2, and z is an integer from 1 to 20.

11. A composition according to claim 1 or 10, substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES Per: </div>