MULTI-COMPONENT CROSSLINKABLE MASSES BASED ON ORGANYLOXYSILANE-TERMINATED POLYMERS

Abstract

A multi-component crosslinkable composition includes at least one component (K1) and one component (K2). Component (K1) contains organosilicon compounds (A1) selected from compounds (A1a) of formula (Ia), the formula (Ia) being Y.sup.1—[B.sup.1—CR.sup.2.sub.2—SiR.sub.a(OR.sup.1).sub.3-a].sub.x, and compounds (A1b) of formula (Ib), the formula (Ib) being Y.sup.2—[B.sup.2—(CR.sup.4.sub.2).sub.b—Si(OR.sup.3).sub.3].sub.y. Component (K2), based in each case on 100 parts by weight of compounds (A1) in component (K1), includes at least 0.05 parts by weight of water and 10 to 1000 parts by weight of a component (A2) selected from compounds (A2a) of formula (IIa), the formula (IIa) being Y.sup.3—B.sup.3—CR.sup.7.sub.2—SiR.sup.5.sub.c(OR.sup.6).sub.3-c, and compounds (A2b) of formula (IIb), the formula (IIb) being Y.sup.4—[B.sup.4—(CR.sup.10.sub.2).sub.e—SiR.sup.8.sub.d(OR.sup.9).sub.3-d].sub.z.

Claims

1-13. (canceled)

14. A multicomponent crosslinkable composition (K) comprising at least one component (K1) and one component (K2), wherein component (K1) comprises organosilicon compounds (A1) selected from compounds (A1a) of the formula (Ia)
Y.sup.1—[B.sup.1—CR.sup.2.sub.2—SiR.sub.a(OR.sup.1).sub.3-a].sub.x  (Ia) and compounds (A1b) of the formula (Ib)
Y.sup.2—[B.sup.2—(CR.sup.4.sub.2).sub.b—Si(OR.sup.3).sub.3].sub.y  (Ib) where Y.sup.1 is an x-valent polymer radical bonded via carbon, Y.sup.2 is a y-valent polymer radical bonded via carbon, B.sup.1 and B.sup.2 each independently of one another may be identical or different and are a divalent linking group —O—, —NH—, —NR′—, —O—CO—NH—, —NH—CO—O—, —NH—CO—NH, —NH—CO—NR′—, —NR′—CO—NH—, —NH—CO—, —CO—NH—, —CO—O—, —O—CO—, —O—CO—O—, —S—CO—NH—, —NH—CO—S—, —CO—S—, —S—CO— or —S—, R′ may be identical or different and is a monovalent, optionally substituted hydrocarbon radical or a group —CH(COOR*)—CH.sub.2—COOR*, where R* is an alkyl radical, R may be identical or different and is a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.1 and R.sup.3 each independently of one another may be identical or different and are the hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, R.sup.2 and R.sup.4 each independently of one another may be identical or different and are the hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, x and y each independently of one another are an integer from 1 to 10, a may be identical or different and is 0, 1 or 2, with the proviso that if x=1 a=0, b may be identical or different and is an integer from 3 to 10, and component (K2), based in each case on 100 parts by weight of compounds (A1) in component (K1), comprises at least 0.05 part by weight of water and also 10 to 1000 parts by weight of a component (A2) selected from compounds (A2a) of the formula (IIa)
Y.sup.3—B.sup.3—CR.sup.7.sub.2—SiR.sup.5.sub.c(OR.sup.6).sub.3-c  (IIa) and compounds (A2b) of the formula (IIb)
Y.sup.4—[B.sup.4—(CR.sup.10.sub.2).sub.e—SiR.sup.8.sub.d(OR.sup.9).sub.3-d]_{(IIb) where Y.sup.3 is a monovalent polymer radical bonded via carbon, Y.sup.4 is a z-valent polymer radical bonded via carbon, B.sup.3 and B.sup.4 in each case independently of one another may be identical or different and are a divalent linking group —O—, —NH—, —NR″—, —O—CO—NH—, —NH—CO—O—, —NH—CO—NH, —NH—CO—NR″—, —NR″—CO—NH—, —NH—CO—, —CO—NH—, —CO—O—, —O—CO—, —O—CO—O—, —S—CO—NH—, —NH—CO—S—, —CO—S—, —S—CO— or —S—, R″ may be identical or different and is a monovalent, optionally substituted hydrocarbon radical or a group —CH(COOR*)—CH.sub.2—COOR*, where R* is an alkyl radical, R.sup.5 and R.sup.8 each independently of one another may be identical or different and are a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.6 and R.sup.9 each independently of one another may be identical or different and are the hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, R.sup.7 and R.sup.10 each independently of one another may be identical or different and are the hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, z is an integer from 1 to 10, c is 1 or 2, d may be identical or different and is 1 or 2, and e may be identical or different and is an integer from 3 to 10.}

15. The crosslinkable composition of claim 14, wherein the composition is a two-component composition consisting of components (K1) and (K2).

16. The crosslinkable composition of claim 14, wherein component (A1) comprises compounds (A1a) and component (A2) comprises compounds (A2b).

17. The crosslinkable composition of claim 14, wherein the polymer radicals Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 independently of one another have no groups that are reactive with water or moisture.

18. The crosslinkable composition of claim 14, wherein the composition comprises organosilicon compounds (B) containing basic nitrogen.

19. The crosslinkable composition of claim 14, wherein, if the composition comprises tin catalysts (E), the amounts involved are such that the weight fraction of tin is at most 500 ppm by weight, based on the total weight of the composition (K).

20. The crosslinkable composition of claim 14, wherein the composition is tin-free.

21. The crosslinkable composition of claim 14, wherein the composition is of the kind consisting of a component (K1) comprising (A1) organosilicon compounds selected from compounds (A1a) and (A1b), optionally (B) compounds containing basic nitrogen, optionally (C) fillers, optionally (D) silicone resins, optionally (E) catalysts, optionally (F) adhesion promoters, optionally (G) water scavengers, optionally (I) unreactive plasticizers, optionally (J) organic solvents, optionally (L) additives, and optionally (M) adjuvants, and also of a component (K2) comprising, based in each case on 100 parts by weight of compounds (A1) in component (K1), at least 0.05 part by weight of water and also (A2) 10 to 1000 parts by weight of organosilicon compounds selected from compounds (A2a) and (A2b), optionally (C) fillers, optionally (D) silicone resins, optionally (F) adhesion promoters, optionally (H) thickeners, optionally (I) unreactive plasticizers, optionally (J) organic solvents, optionally (L) additives, and optionally (M) adjuvants.

22. The crosslinkable composition of claim 14, wherein the proportions of (K1) to (K2) are between 5:1 and 1:5, based on the weight.

23. A method for producing a composition as claimed in claim 14 by mixing together components (K1) and (K2) and also optionally further components, the individual components having been produced by separately mixing together all of the constituents of the respective components in any order.

24. A shaped article produced by crosslinking a composition as claimed in claim 14.

25. A shaped article produced by crosslinking a composition as claimed in claim 23.

26. A method for bonding or sealing substrates, wherein components (K1) and (K2) and also optionally further components are first mixed with one another and subsequently applied to the surface of at least one substrate, then this surface is contacted with the second substrate to be bonded, and the composition as claimed in claim 14 is subsequently caused to crosslink.

27. A method for bonding or sealing substrates, wherein components (K1) and (K2) and also optionally further components are first mixed with one another and subsequently applied to the surface of at least one substrate, then this surface is contacted with the second substrate to be bonded, and the composition is produced as claimed in claim 23 and is subsequently caused to crosslink.

28. A method for producing coatings or encapsulations, wherein components (K1) and (K2) and also optionally further components are first mixed with one another and subsequently applied to at least one substrate and the composition as claimed in claim 14 is subsequently caused to crosslink.

29. A method for producing coatings or encapsulations, wherein components (K1) and (K2) and also optionally further components are first mixed with one another and subsequently applied to at least one substrate and the composition is produced as claimed in claim 23 and is subsequently caused to crosslink.

Description

EXAMPLES

[0240] Production example 1-1: producing a component (K1) for a 2K adhesive formulation (K1-1) 172.4 g of a double-sidedly silane-terminated polypropylene glycol having an average molar mass (M.sub.n) of 12 000 g/mol and end groups of the formula —O—C(═O)—NH—CH.sub.2—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name GENIOSIL® STP-E10 from Wacker Chemie AG, Munich (DE)) are homogenized for 2 minutes at 200 rpm in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-armed mixers, at around 25° C. with 34.4 g of a single-sidedly silane-terminated polypropylene glycol having an average molar mass (M.sub.n) of 5000 g/mol and end groups of the formula —O—C(═O)—NH—CH.sub.2—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name GENIOSIL® XM20 from Wacker Chemie AG, Munich (DE)), 10.4 g of vinyltrimethoxysilane and 3.6 g of a stabilizer mixture (mixture of 20% Irganox® 1135 (CAS No. 125643-61-0), 40% Tinuvin® 571 (CAS No. 23328-53-2) and 40% Tinuvin® 765 (CAS No. 41556-26-7), available commercially under the name TINUVIN® B 75 from BASF SE, Germany).

[0241] Thereafter, 69.2 g of a stearic acid-coated calcium carbonate having a mean particle diameter (D50%) of around 2.0 □m (available commercially under the name Omyabond 520 from Omya, Cologne (DE)) and 103.6 g of a fatty acid-coated precipitated chalk having a mean particle diameter (D50%) of around 0.07 □m (available commercially under the name Hakuenka CCR S10 from Shiraishi Omya GmbH, Gummem (AT)) are blended with stirring for one minute at 600 rpm. Lastly 6.4 g of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane are mixed in for 1 minute at 200 rpm. To conclude, homogenization and bubble-free stirring are carried out for 2 minutes at 600 rpm and for 1 minute at 200 rpm under a pressure of 100 mbar.

[0242] The completed component (K1-1) is transferred to a container with facility for airtight sealing.

[0243] Production example 2-1: producing a component (K2) for a 2K adhesive formulation (K2-1) 200.0 g of a single-sidedly silane-terminated polypropylene glycol having an average molar mass (M.sub.n) of 5000 g/mol and end groups of the formula —O—C(═O)—NH—CH.sub.2—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name GENIOSIL® XM20 from Wacker Chemie AG, Munich (DE)) are blended with stirring for one minute at 600 rpm in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-arm stirrers, at around 25° C. with 100.0 g of a stearic acid-coated calcium carbonate having a mean particle diameter (D50%) of around 2.0 □m (available commercially under the name Omyabond 520 from Omya, Cologne (DE)), 40.0 g of a fatty acid-coated precipitated chalk having a mean particle diameter (D50%) of around 0.07 □m (available commercially under the name Hakuenka CCR S10 from Shirai-shi Omya GmbH, Gummern (AT)) and 60 g of a thermally activated colloidal magnesium aluminum silicate (available commercially under the name Micro-sorb 300 LVM from BASF SE, Germany).

[0244] Thereafter, 10 g of water are mixed in for 1 minute at 200 rpm. To conclude, homogenization and bubble-free stirring are carried out for 2 minutes at 600 rpm and for 1 minute at 200 rpm under a pressure of 100 mbar.

[0245] The completed component (K2-1) is transferred to a container with facility for airtight sealing.

[0246] Production example 2-2: producing a component (K2) for a 2K adhesive formulation (K2-2) The procedure was exactly the same as for production example 2-1, but replacing the 200 g of GENIOSIL® XM20 with 200 g of a singly branched silane-terminated polypropylene glycol having end groups of the formula —O—(CH.sub.2).sub.3—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name MS 303H from Kaneka, Japan).

[0247] Production example 2-3: producing a component (K2) for a 2K adhesive formulation (K2-3) The procedure was exactly the same as for production example 2-1, but replacing the 200 g of GENIOSIL® XM20 with 200 g of a linear silane-terminated polypropylene glycol having end groups of the formula —O—(CH.sub.2).sub.3—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name SAX 750 from Kaneka, Japan).

[0248] Production example 2-4: producing a component (K2) for a 2K adhesive formulation (K2-4) The procedure was exactly the same as for production example 2-1, but replacing the 200 g of GENIOSIL® XM20 with 200 g of a mixture of a linear silane-terminated polypropylene glycol and of a silane-modified polyacrylate, both having silyl groups of the formula —O—(CH.sub.2).sub.3—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name MAX 951 from Kaneka, Japan).

Examples 1 to 4

[0249] 60 g in each case of the completed component K1-1 are mixed homogeneously with 40 g in each case of the completed components K2-1 (example 1), K2-2 (example 2), K2-3 (example 3) and K2-4 (example 4), respectively. The properties of the four compositions obtained are then determined.

Skin-Forming Time (SFT)

[0250] The skin-forming time is determined by applying the resultant two-componently crosslinking compositions, each in a layer 2 mm thick, to PE film and storing these assemblies under standard conditions (23° C. and 50% relative humidity). Testing for formation of a skin is performed once per minute in the course of curing. For this testing, a dry laboratory spatula is placed carefully onto the surface of the specimen and is drawn upward. If sample remains adhering on the spatula, a skin has not yet formed. If sample no longer remains adhering on the spatula, a skin has formed, and the time is recorded. The results are found in table 1.

Mechanical Properties

[0251] The 2-componently crosslinking compositions were each coated out onto milled-out Teflon plaques to a depth of 2 mm and cured for 2 weeks at 23° C. and 50 relative humidity.

[0252] The Shore A hardness is determined according to DIN EN 53505.

[0253] The tensile strength is determined according to DIN EN 53504-S1.

[0254] The elongation at break is determined according to DIN EN 53504-S1.

[0255] The 100% modulus is determined according to DIN EN 53504-S1.

[0256] The results are found in table 1

TABLE-US-00001 TABLE 1 Composition from example 1 2 3 4 Component (K1) (K1-1) (K1-1) (K1-1) (K1-1) Component (K2) (K2-1) (K2-2) (K2-3) (K2-4) Mixing ratio 60:40 60:40 60:40 60:40 SFT [min] 70 85 124 100 Shore A hardness 30 44 48 47 Tensile strength [N/mm.sup.2] 1.8 2.4 2.3 2.0 Elongation at break [%] 366 237 211 204 100% modulus [MPa] 0.7 1.3 1.3 1.3

[0257] Production example 1-5: producing a component (K1) for a 2K adhesive formulation (K1-5) 91 g of a single-sidedly silane-terminated polypropylene glycol having an average molar mass (M.sub.n) of 5000 g/mol and end groups of the formula —O—C(═O)—NH—CH.sub.2—SiCH.sub.3(OCH.sub.3).sub.3 (available commercially under the name GENIOSIL® XM25 from Wacker Chemie AG, Munich (DE)) are homogenized for 2 minutes at 200 rpm in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-arm stirrers, at around 25° C. 4.5 g of vinyltrimethoxysilane and 1.5 g of a stabilizer mixture (mixture of 20% Irganox® 1135 (CAS No. 125643-61-0), 40% Tinuvin® 571 (CAS No. 23328-53-2) and 40% Tinuvin® 765 (CAS No. 41556-26-7), available commercially under the name TINUVIN® B 75 from BASF SE, Germany).

[0258] Thereafter, successively, 305 g of a spherical aluminum oxide (available commercially under the name Alunabeads™ CB A50 from Showa Denko, Tokyo (JP)), 375 g of a calcined aluminum oxide (available commercially under the name Alumina CL 3000 SG from Almatis, Ludwigshafen (DE)) and 220 g of zinc oxide (available commercially under the name Zinc Oxide Grade AZO 66 from U.S. Zinc, Houston (US)) are digested with stirring for one minute at 600 rpm. Lastly 3 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane are mixed in for 1 minute at 200 rpm. To conclude, homogenization and bubble-free stirring are carried out for 2 minutes at 600 rpm and for 1 minute at 200 rpm under a pressure of 100 mbar.

[0259] The completed component (K1-5) is transferred to a container with facility for airtight sealing.

[0260] Production example 2-5: producing a component (K2) for a 2K adhesive formulation (K2-5) 96.2 g of a single-sidedly silane-terminated polypropylene glycol having an average molar mass (M.sub.n) of 5000 g/mol and end groups of the formula —O—C(═O)—NH—CH.sub.2—SiCH.sub.3(OCH.sub.3).sub.2 (available commercially under the name GENIOSIL® XM20 from Wacker Chemie AG, Munich (DE)) are blended with stirring for one minute at 600 rpm in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-arm stirrers, at around 25° C. with 305 g of a spherical aluminum oxide (available commercially under the name Alunabeads™ CB A50 from Showa Denko, Tokyo (JP)), 375 g of a calcined aluminum oxide (available commercially under the name Alumina CL 3000 SG from Almatis, Ludwigshafen (DE)) and 220 g of zinc oxide (available commercially under the name Zinc Oxide Grade AZO 66 from U.S. Zinc, Houston (US)). Subsequently, at a temperature of 55° C., 3.8 g of water homogenization and bubble-free stirring for 1 minute at 200 rpm under a pressure of 100 mbar.

[0261] The completed component (K2-5) is transferred to a container with facility for airtight sealing.

Example 5

[0262] An adhesive based on components (K1-5) and (K2-5) is mixed in a mixing ratio of 1:1, based on the weight, in a Speedmixer and the mixture is left to cure for 2 weeks at 23° C. and 50 relative humidity. Subsequently, in a number of trials, the composition is applied between two aluminum plaques with an area of 700 mm.sup.2 and measurements are made of the thermal conductivity according to ASTM 5470-12 at different gap thicknesses. A λ value of greater than 2.8 W/mK is ascertained.