WO2022233411A1 - Mixtures containing a silirane-functionalized compound and a polymer - Google Patents
Mixtures containing a silirane-functionalized compound and a polymer Download PDFInfo
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- WO2022233411A1 WO2022233411A1 PCT/EP2021/061920 EP2021061920W WO2022233411A1 WO 2022233411 A1 WO2022233411 A1 WO 2022233411A1 EP 2021061920 W EP2021061920 W EP 2021061920W WO 2022233411 A1 WO2022233411 A1 WO 2022233411A1
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- WIPO (PCT)
- Prior art keywords
- radical
- group
- silirane
- independently
- hydrogen
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 title claims abstract description 18
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- JPBJMYVOQWDQNS-UHFFFAOYSA-N silirane Chemical group C1C[SiH2]1 JPBJMYVOQWDQNS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 229920000620 organic polymer Polymers 0.000 claims abstract description 5
- 229920000592 inorganic polymer Polymers 0.000 claims abstract description 4
- -1 siloxanes Chemical class 0.000 claims description 25
- 239000012876 carrier material Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 238000007725 thermal activation Methods 0.000 claims description 5
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000005624 silicic acid group Chemical class 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 abstract 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000000879 imine group Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000013005 condensation curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000011410 subtraction method Methods 0.000 description 1
- 229920005612 synthetic inorganic polymer Polymers 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08K5/549—Silicon-containing compounds containing silicon in a ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Definitions
- the present invention describes mixtures containing, as adhesion promoter, at least one silirane-functionalized compound from a substrate to which at least two silirane groups of the formula (I) are covalently bonded, and at least one polymer. Also included are moldings containing at least one mixture according to the invention and a slightly polar to non-polar substrate, as well as a method for curing the mixtures and the use of the mixtures.
- Silicones also called poly(organo)siloxanes or siloxanes for short
- silicones can be used in a variety of ways due to their chemical and physical properties. Unlike carbon-based plastics, the van der Waals forces between siloxane polymer chains are weak, which is why high molecular weight siloxane polymers are still flowable.
- the polymer components In order to obtain dimensionally stable, rubber-elastic silicones, the polymer components have to be crosslinked with one another.
- addition crosslinking condensation crosslinking and free-radical crosslinking.
- vinyl-functionalized polyorganosiloxanes react with hydridosiloxanes (hydrosilylation).
- condensation crosslinking terminal Si-OH or Si-OR groups with typically multifunctional siloxane building blocks (containing, for example, Si-O-CH 3 , Si-OC 2 H 5 , Si-O-COCH 3 ) are cured by atmospheric moisture and in the presence a metal-based catalyst (e.g. based on tin) reacted.
- a metal-based catalyst e.g. based on tin
- condensation-curing systems can be handled as one-component systems.
- Radical crosslinking uses organic peroxides, for example, which decompose into highly reactive radicals as a result of thermal or photolysis and link functional polyorganosiloxanes (eg vinyl-methyl-siloxanes) with one another in a free-radical manner.
- organic peroxides for example, which decompose into highly reactive radicals as a result of thermal or photolysis and link functional polyorganosiloxanes (eg vinyl-methyl-siloxanes) with one another in a free-radical manner.
- polyorganosiloxanes can be applied to solid surfaces, for example textiles, paper and plastics, to render the surfaces water-repellent, non-stick or to impart lubricity.
- the polyorganosiloxanes most commonly used for these purposes are functional polymethylsiloxanes or blends with methylhydrogenpolysiloxanes. While the polyorganosiloxanes provide the desired surface properties, they often lack adequate durability. For example, they can be removed by washing or by contact with organic solvents.
- silicones show only limited adhesion to plastic substrates such as polyolefins (eg polyethylene (PE) and polypropylene (PP)), polyethylene terephthalate (PET) or polycarbonate (PC), which is due to the non-polar nature of the plastics.
- PET polyethylene terephthalate
- PC polycarbonate
- Adhesion to plastic substrates can currently only be achieved by complex manipulations of the substrate, for example by pretreatment with solvents, a multi-stage oxygen plasma treatment and/or by applying a priming can be achieved (U. Stschreib, Vacuum in Research and Practice 2015, 27, 16-21).
- PCT/EP2019/083744 describes silirane-functionalized compounds as thermally and photochemically activatable crosslinkers for the catalyst-free production of elastomeric silicones.
- This technology represents a sustainable alternative to established crosslinking technologies such as addition or condensation crosslinking, which require the use of platinum, titanium or tin-based catalysts.
- silirane-containing substrates are used as storage-stable silylene sources that can be activated in a controlled manner.
- the three-membered silacyclopropane structure motive is under high ring strain and can be thermally converted from 140°C into an intermediate silylene derivative, which reacts with other functional silicone components of the mixtures to form an elastomeric network (see Scheme 1).
- Scheme 1 Siliranes can be cleaved by thermolysis or photolysis to give an olefin and a silylene.
- PCT/EP2019/083737 describes silirane-functionalized compounds for the production of elastomeric silicones by nucleophilic ring-opening polymerization.
- the silirane-containing compounds are potential sources of silylene, the reactive silicon center upon activation is siloxane skeleton is separated, neither crosslinking nor an adhesion-promoting effect can be achieved.
- JP 63048674 A2 describes a method for coating metallic or ceramic surfaces with hexamethyldisilazane with reference to a silylene reaction. In terms of content, however, the silylation of OH groups on the substrate surface is carried out with hexamethyldisilazane. Reaction conditions which lead to the release of silylenes are not mentioned.
- the object of the invention was to improve the adhesion of silicones to plastic surfaces without having to subject the plastic surface to an expensive pretreatment.
- R 2 , R 3 , R 4 , R 5 are independently selected from the group consisting of hydrogen, halogen and C 1 -C 20 hydrocarbon radical, where R 2 and R 4 can be part of a cyclic radical; b) at least one natural or synthetic polymer selected from the group consisting of bl) addition-crosslinking silicone compositions, b2) condensation-crosslinking silicone compositions, b3) hybrid materials/silyl-terminated polymers (STP) and b4) inorganic polymers and organic polymers and combinations of bl to b4.
- silane-containing compounds as adhesion promoters for existing silicone products or as a component of self-adhesive crosslinkable silicone (hybrid) compositions for plastics with little or no polarity is not known to date.
- addition-crosslinking silicone masses generally designates hydrosilylatable mixtures containing hydridopolysiloxanes, alkenyl-containing polyorganosiloxanes and fillers (eg silicas). These mixtures can only be crosslinked thermally or photochemically to form elastomeric silicones in the presence of catalysts (eg the platinum-based Karstedt catalyst) and inhibitors. Such mixtures are, for example, in EP 0651 019 A1 or EP 0 444 960 A2.
- the addition-crosslinking silicone compositions therefore contain metal catalysts.
- the condensation-crosslinking silicone masses contain metal catalysts.
- hybrid materials / STP are generally reactive silane-terminated organic polymers (e.g.
- Polyether which are used, for example, as adhesives, sealants and coating materials. Such materials are described by way of example in WO 2017/137281 A1.
- inorganic polymers are generally natural and synthetic inorganic polymers (e.g. silicic acids, silicate structures, polysilanes and polysiloxanes).
- organic polymers are generally natural and synthetic organic polymers suitable for producing molded articles, coatings or laminates. Examples of such polymers can be found in US 5,792,812; US 2007/0141250 A1 and US 4,686,124.
- the silirane-functionalized compounds thus act as adhesion promoters between the inert polymer carrier body and the applied crosslinkable siloxane mixture
- the mixture is therefore, with particular advantage, a self-adhesive mixture for the coating of, in particular, chemically inert materials.
- the silirane functionalized compounds are stable
- Scheme 2 Top: The Si atoms of the silirane-functionalized compound are bridged through a structural backbone, resulting in a crosslinkable reactive bis-silylene species upon activation. Bottom: The silirane groups are not bridged via the Si atoms, resulting in non-crosslinking cleavage products upon activation.
- the substrate of the silirane-functionalized compound is preferably selected from the group consisting of silanes, organosilicon compounds, hydrocarbons, silicic acids, carbon-based oligomers and polymers.
- the substrate of the silirane-functionalized compound is particularly preferably selected from the group consisting of siloxanes, precipitated silica, pyrogenic silica, polyolefins, acrylates, polyacrylates, polyvinyl acetates, polyurethanes and polyethers made from propylene oxide and/or ethylene oxide units
- the substrate is organosilicon compounds of the general formula
- R x is independently selected from the group consisting of hydrogen, halogen, an unsubstituted or substituted C 1 -C 20 hydrocarbyl radical and an unsubstituted or substituted C 1 -C 20 hydrocarbyloxy radical.
- the indices a, b, b′, c, c′, c′′, d, d′, d′′, d′′′′ indicate the number of the respective siloxane unit in the compound and are independently zero or an integer from 1 to 10,000, provided that the sum of a, b, b', c, c', c'', d, d', d'', d''' is at least 2 and at least one of the indices b', c', d'> 2 or at least one of the indices c'', d'' or d , '' is not equal to zero.
- the radical R' is the silirane group of the formula (I).
- the radical R a in the formula (I) is preferably a C 1 -C 3 - alkylene radical, particularly preferably an ethylene radical.
- R 1 is preferably a C 1 -C 6 hydrocarbyl radical or amine radical -N(SiR a R b R c ) 2 , where R a , R b , R c are independently a C 1 -C 6 hydrocarbyl radical.
- R 1 is particularly preferably a C 1 -C 6 -alkyl radical or -N(SiMe 3 ) 2 .
- the indices a, b, b', c, c', c'', d, d'' and d''' are preferably zero and the index d' has the value 2, where in formula (I) the index n is 1, R a is a C 1 -C 3 alkylene group and R 1 is a C 1 -C 6 hydrocarbyl group or an amine group -N(SiR a R b R c ) 2 wherein R a ,R b ,R c are independently C 1 -C 6 hydrocarbon radicals.
- the radicals R 2 , R 3 , R 4 , R 5 are, independently of one another, hydrogen or a C 1 -C 6 -alkyl radical, where R 2 and R 4 can also be part of a cyclic radical.
- the indices a, b, b', c, c', c'', d, d'' and d''' are particularly preferably zero and the index d' has the value 2, where in formula (I) the Index n is 1, R a is an ethylene radical and R 1 is a C 1 -C 6 alkyl radical or -N(SiMe 3 ) 2 .
- the radicals R 2 , R 3 , R 4 , R 5 are, independently of one another, hydrogen or a C 1 -C 6 - alkyl radical, where R 2 and R 4 can also be part of a cyclic radical.
- the radical R x in the formula (II) is preferably selected independently from the group consisting of methyl, ethyl,
- the silirane-functionalized compound is particularly preferably selected from the group with SV1, SV2 and SV3, where SV1, SV2 and SV3 have the following structures:
- the proportion of the silirane-functionalized compound in the mixture is preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, in particular 0.5 to 2% by weight.
- a further aspect of the invention relates to moldings comprising at least one of the mixtures according to the invention and a slightly polar to non-polar carrier material.
- the molding is preferably selected from the group consisting of extrusion or injection molding, single or multi-layer laminates (e.g. produced by spin coating, calendering or dipping processes), encapsulated moldings (e.g. produced in electrocasting by filling, dipping or plasticizing), adhesive or sealable shaped bodies (reactive adhesives) and transitions between identical or different shaped bodies of the same or different carrier materials.
- the latter means in particular jointing compounds for bonding several dissimilar materials.
- the shaped body can contain the carrier material in the form of a coating.
- the shaped body can consist of the carrier material to which the mixture is applied.
- the carrier material preferably comprises at least one synthetic hydrocarbon polymer selected from the Group with polyolefins made from mono- or polyenes, polyhaloolefin, polyether, polyvinyl chloride, polyvinylidene difluoride, polytetrafluoroethene, polycarbonate, polyester and copolymers thereof. Furthermore, the carrier material can consist of or comprise polymer blends of the hydrocarbon polymers mentioned.
- the copolymers can be, for example, ethylene propylene diene monomer rubber (EPDM) or acrylonitrile butadiene styrene (ABS).
- EPDM ethylene propylene diene monomer rubber
- ABS acrylonitrile butadiene styrene
- a further aspect of the invention relates to a method for curing the mixture according to the invention by thermal and/or photochemical activation.
- the mixture is brought into contact with a slightly polar to non-polar carrier material as described above.
- thermal activation requires a temperature above the decomposition temperature of the silirane compound.
- the wavelength required for photochemical activation is in the UV range.
- the reactivity of the siliranes is identical for both activation methods.
- the activated silirane-functionalized compounds can react with a variety of functional groups due to their high reactivity. Possible reaction partners are, for example, Si-H, Si-OR, Si-OH, C-OH, CH, -NH 2 and vinyl. This covers all typical functional groups of silicones as well as slightly polar to non-polar carrier materials. Curing can take place by means of a one-stage or multi-stage thermal activation in a temperature range from 0 to 200°C, preferably from 10 to 180°C, particularly preferably from 15 to 160°C.
- Curing preferably takes place by means of a two-stage thermal activation, comprising the following steps: a) setting a temperature T1 in a temperature range from 0 to 140° C. and b) setting a temperature T2 in a temperature range from 120 to 180° C., with the following that T1 ⁇ T2.
- the mixture to be cured is preferably a component of the molding according to the invention.
- the process is therefore preferably used in a shaped body according to the invention, with adhesion being promoted between the carrier material and the mixture component b).
- Another object of the invention is the use of the silirane-functionalized compound according to a) of the mixture according to the invention as an adhesion promoter, in particular as an adhesion promoter between a slightly polar to non-polar carrier material as described above and a polymer according to b) of the mixture according to the invention .
- Also covered by the invention is the use of the mixture of the invention as a self-adhesive coating material for low-polarity to non-polar carrier materials as described above.
- the XPS analysis was carried out with a KRATOS Axis Supra spectrometer. The spectra were recorded at a pressure of ⁇ 3*10 -8 Torr with a focused scan using a monochromatic Al-K ⁇ source. The penetration energy in the hybrid lens mode with charge neutralization was 15 eV and the spot size was 800 x 300 ⁇ m. The data were analyzed with the program CasaXPS (version 2.3.15). The signals were integrated using the Shirley background subtraction method. The elemental proportions were quantified using CASA XPS and IMFP data from the NIST database. Sensitivity factors were calculated using published ionization crossing (Scofield, J.
- Hönel (illuminance: max. 250 mW/cm 2 ) is used.
- ELASTOSIL® RT604 A/B (from Wacker Chemie AG): Room-temperature-curing silicone rubber (RTV-2).
- Adhesion promoter SV3 The silirane-functionalized compound SV3 was synthesized as described in PCT/EP2019/083744. 1. Coating of polypropylene with SV3
- Polypropylene was provided as a square plate with a side length of 2 cm and cleaned three times with isopropanol in an ultrasonic bath for 20 minutes.
- the coating was carried out by spin-coating n-hexane solutions (concentration 13% by weight) of Siliran SV3. Layer thicknesses of approx. 1/100 mm were obtained.
- the reaction crosslinking/curing was triggered either by UV-C treatment (at least 15 min at approx. 4-5 raW/cm 2 ) or by heat treatment (1 h at 140°C). Each sample was then extracted three times with THF/diethyl ether and dried in a gas stream.
- mixtures A and B are mixed in a mass ratio of 1:1 (e.g. with a "DAC-150.1" speed mixer from Hausschild).
- a) 1, 5 and 10% by weight are used for the additives.
- of the silirane-functionalized siloxane SV3 was added and mixed with the ELASTOSIL® by hand or using a speed mixer
- Polypropylene specimens were primed with a 10% by weight solution of SV3 in pentane, which evaporates rapidly at room temperature
- the amounts used and all of the crosslinking conditions can be found in Table 2. The adhesion of the crosslinked silicone coating to the specimens was evaluated via the detachment stability of the coating.
- Peel stability was tested by peeling off the crosslinked silicone coating. If, like the reference, it could be released in one piece without tearing, there was no improvement in adhesion. If the material tore because it stuck particularly firmly to the carrier material and had to be removed piecemeal, the adhesion was rated as better than the reference.
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Abstract
The invention relates to mixtures containing a), as an adhesion promoter, at least one silirane-functionalized compound of a substrate to which at least two silirane groups of the formula (I) are covalently bonded, wherein n = 0 or 1, Ra is a divalent C1-C20 hydrocarbon group and R1 is selected from the group including (i) a C1-C20 hydrocarbon group, (ii) a C1-C20 hydrocarbon oxy group, (iii) a silyl group -SiRaRbRc, wherein Ra, Rb, Rc independently of each other represents a C1-C6 hydrocarbon group, (iv) an amine group -NRx
2, wherein Rx independently of each other is selected from the group including (iv.i) hydrogen, (iv.ii) a C1-C20 hydrocarbon group and (iv.iii) the silyl group -SiRaRbRc, and (v) an imine group -N=CR1R2, wherein R1, R2 independently of each other are selected from the group including (v.i) hydrogen, (v.ii) a C1-C20 hydrocarbon group and (v.iii) the silyl group -SiRaRbRc; and wherein R2, R3, R4, R5 independently of each other are selected from the group including hydrogen, halogen and a C1-C20 hydrocarbon group, with R2 and R4 being potentially part of a cyclic group; b) at least one polymer, selected from the group including addition cross-linking silicone compounds, condensation cross-linking silicone compounds, hybrid materials/STP, inorganic and organic polymers and corresponding combinations.
Description
Mischungen enthaltend eine Siliran-funktionalisierte Verbindung und ein Polymer Mixtures containing a silirane-functionalized compound and a polymer
Die vorliegende Erfindung beschreibt Mischungen, enthaltend als Haftvermittler mindestens eine Siliran-funktionalisierte Verbindung aus einem Substrat, an das mindestens zwei Silirangruppen der Formel (I) kovalent gebunden sind, und mindestens ein Polymer. Darüber hinaus umfasst sind Formkörper, enthaltend mindestens eine erfindungsgemäße Mischung und ein wenig polares bis unpolares Substrat, sowie ein Verfahren zur Aushärtung der Mischungen und die Verwendung der Mischungen. The present invention describes mixtures containing, as adhesion promoter, at least one silirane-functionalized compound from a substrate to which at least two silirane groups of the formula (I) are covalently bonded, and at least one polymer. Also included are moldings containing at least one mixture according to the invention and a slightly polar to non-polar substrate, as well as a method for curing the mixtures and the use of the mixtures.
Silicone (auch Poly(organo)siloxane oder kurz: Siloxane) sind aufgrund ihrer chemischen und physikalischen Eigenschaften in vielfältiger Weise einsetzbar. Anders als bei kohlenstoff- basierten Kunststoffen sind die Van-der-Waals-Kräfte zwischen Siloxan-Polymerketten schwach, weshalb hochmolekulare Siloxan- polymere noch fließfähig sind. Um formstabile, gummielastische Silicone zu erhalten, müssen die polymeren Bestandteile miteinander vernetzt werden. Silicones (also called poly(organo)siloxanes or siloxanes for short) can be used in a variety of ways due to their chemical and physical properties. Unlike carbon-based plastics, the van der Waals forces between siloxane polymer chains are weak, which is why high molecular weight siloxane polymers are still flowable. In order to obtain dimensionally stable, rubber-elastic silicones, the polymer components have to be crosslinked with one another.
Generell kann zwischen Additionsvernetzung, Kondensations- vernetzung und radikalischer Vernetzung unterschieden werden. Bei der Additionsvernetzung reagieren Vinyl-funktionalisierte Polyorganosiloxane mit Hydridosiloxanen (Hydrosilylierung).In general, a distinction can be made between addition crosslinking, condensation crosslinking and free-radical crosslinking. During addition crosslinking, vinyl-functionalized polyorganosiloxanes react with hydridosiloxanes (hydrosilylation).
Die Reaktion erfordert den Einsatz von edelmetallhaltigen Katalysatoren (z.B. auf Basis von Platin), welche nicht zurückgewonnen werden können. Im Fall der Kondensations- vernetzung werden endständige Si-OH oder Si-OR-Gruppen mit typischerweise multifunktionellen Siloxanbausteinen (enthaltend z.B. Si-O-CH3, Si-O-C2H5, Si-O-COCH3) durch Luftfeuchtigkeit und in Gegenwart eines metallbasierten Katalysators (z.B. auf Basis von Zinn) zur Reaktion gebracht.
Hierbei kommt es zur Abspaltung kleiner, flüchtiger Verbindungen (z.B. Essigsäure oder Alkohole) und folglich zu einem Materialverlust (Schrumpfung). Kondensationsvernetzende Systeme können im Gegensatz zu den meisten additions- vernetzenden Formulierungen als Einkomponentensysteme gehandhabt werden. Die radikalische Vernetzung hingegen bedient sich beispielsweise organischer Peroxide, welche durch Thermo- oder Photolyse in hochreaktive Radikale zerfallen und funktionelle Polyorganosiloxane (z.B. Vinyl-Methyl-Siloxane) radikalisch miteinander verknüpfen. The reaction requires the use of catalysts containing noble metals (e.g. based on platinum), which cannot be recovered. In the case of condensation crosslinking, terminal Si-OH or Si-OR groups with typically multifunctional siloxane building blocks (containing, for example, Si-O-CH 3 , Si-OC 2 H 5 , Si-O-COCH 3 ) are cured by atmospheric moisture and in the presence a metal-based catalyst (e.g. based on tin) reacted. This leads to the elimination of small, volatile compounds (e.g. acetic acid or alcohols) and consequently to a loss of material (shrinkage). In contrast to most addition-curing formulations, condensation-curing systems can be handled as one-component systems. Radical crosslinking, on the other hand, uses organic peroxides, for example, which decompose into highly reactive radicals as a result of thermal or photolysis and link functional polyorganosiloxanes (eg vinyl-methyl-siloxanes) with one another in a free-radical manner.
Es ist bekannt, dass Polyorganosiloxane auf feste Oberflächen, zum Beispiel Textilien, Papier und Kunststoffe, aufgebracht werden können, um die Oberflächen wasserabweisend oder nicht- haftend zu machen oder ihnen Gleitfähigkeit zu verleihen. Die für diese Zwecke am häufigsten verwendeten Polyorganosiloxane sind funktionelle Polymethylsiloxane oder Mischungen mit Methylhydrogenpolysiloxanen. Die Polyorganosiloxane ergeben zwar die gewünschte Oberflächeneigenschaften, es fehlt ihnen jedoch häufig an ausreichender Dauerhaftfähigkeit. Sie können z.B. durch Waschen oder beim Kontakt mit organischen Lösungsmitteln entfernt werden. It is known that polyorganosiloxanes can be applied to solid surfaces, for example textiles, paper and plastics, to render the surfaces water-repellent, non-stick or to impart lubricity. The polyorganosiloxanes most commonly used for these purposes are functional polymethylsiloxanes or blends with methylhydrogenpolysiloxanes. While the polyorganosiloxanes provide the desired surface properties, they often lack adequate durability. For example, they can be removed by washing or by contact with organic solvents.
Generell zeigen Silicone nur eine begrenzte Haftung auf Kunst- stoffSubstraten wie Polyolefinen (z.B. Polyethylen (PE) und Polypropylen (PP)), Polyethylenterephthalat (PET) oder Poly- carbonat (PC), was auf die unpolare Stoffnatur der Kunststoffe zurückzuführen ist. Es kann zu keiner mechanisch stabilen Verbindung durch polare Wechselwirkung oder kovalente Bindung kommen. Eine Haftung auf KunststoffSubstraten kann gegenwärtig nur durch aufwendige Manipulationen des Substrates z.B. durch eine Vorbehandlung mit Lösungsmitteln, einer mehrstufigen Sauerstoff-Plasmabehandlung und/oder durch Aufbringen einer
Grundierung erreicht werden (U. Stöhr, Vakuum in Forschung und Praxis 2015, 27, 16-21). In general, silicones show only limited adhesion to plastic substrates such as polyolefins (eg polyethylene (PE) and polypropylene (PP)), polyethylene terephthalate (PET) or polycarbonate (PC), which is due to the non-polar nature of the plastics. There can be no mechanically stable connection through polar interaction or covalent bonding. Adhesion to plastic substrates can currently only be achieved by complex manipulations of the substrate, for example by pretreatment with solvents, a multi-stage oxygen plasma treatment and/or by applying a priming can be achieved (U. Stöhr, Vacuum in Research and Practice 2015, 27, 16-21).
PCT/EP2019/083744 beschreibt Siliran-funktionalisierte Verbindungen als thermisch und photochemisch aktivierbare Vernetzer zur katalysatorfreien Erzeugung von elastomeren Siliconen. Diese Technologie stellt eine nachhaltige Alternative zu etablierten Vernetzungstechnologien wie Additions- oder Kondensationsvernetzung dar, welche den Einsatz von platin-, titan- oder zinnbasierten Katalysatoren erfordern. Im konkreten Fall werden siliranhaltige Substrate als lagerstabile und kontrolliert aktivierbare Silylenquellen genutzt. Das dreigliedrige Silacyclopropan-Struktur otiv steht unter hoher Ringspannung und kann thermisch ab 140°C in ein intermediäres Silylenderivat überführt werden, welches mit weiteren funktionellen Siliconbestandteilen der Mischungen zu einem elastomeren Netzwerk reagiert (vgl. Schema 1).
Schema 1: Silirane können durch Thermolyse oder Photolyse unter Entstehung eines Olefins und Silylens gespalten werden. PCT/EP2019/083744 describes silirane-functionalized compounds as thermally and photochemically activatable crosslinkers for the catalyst-free production of elastomeric silicones. This technology represents a sustainable alternative to established crosslinking technologies such as addition or condensation crosslinking, which require the use of platinum, titanium or tin-based catalysts. In this specific case, silirane-containing substrates are used as storage-stable silylene sources that can be activated in a controlled manner. The three-membered silacyclopropane structure motive is under high ring strain and can be thermally converted from 140°C into an intermediate silylene derivative, which reacts with other functional silicone components of the mixtures to form an elastomeric network (see Scheme 1). Scheme 1: Siliranes can be cleaved by thermolysis or photolysis to give an olefin and a silylene.
PCT/EP2019/083737 beschreibt Siliran-funktionalisierte Verbindungen zur Herstellung von elastomeren Siliconen durch nukleophile Ringöffnungspolymerisation. Die siliranhaltigen Verbindungen stellen zwar potenzielle Silylenquellen dar, da das reaktive Siliciumzentrum bei einer Aktivierung jedoch vom
Siloxangerüst getrennt wird, kann weder eine Vernetzung nocheine haftvermittelnde Wirkung erzielt werden. JP 63048674 A2 beschreibt ein Verfahren zur Beschichtung vonmetallischen oder keramischen Oberflächen mit Hexamethyl-disilazan mit dem Verweis auf eine Silylenreaktion. Inhaltlichwird jedoch die Silylierung von OH-Gruppen auf der Substrat-oberfläche mit Hexamethyldisilazan durchgeführt. Reaktions-bedingungen, welche zur Freisetzung von Silylenen führen, sindnicht genannt. Die Aufgabe der Erfindung bestand darin, die Haftung vonSiliconen auf Kunststoffoberflächen zu verbessern, ohne dieKunststoffOberfläche einer aufwendigen Vorbehandlungunterziehen zu müssen. Diese Aufgabe wird gelöst durch Mischungen, enthaltenda) mindestens eine Siliran-funktionalisierte Verbindung aus einem Substrat, an das mindestens zwei Silirangruppen der Formel (I)
kovalent gebunden sind, wobei n = 0 oder 1 ist; wobei Ra ein zweibindiger C1-C20-Kohlenwasserstoffrest ist; wobei R1 ausgewählt ist aus der Gruppe mit (i) C1-C20-Kohlen- wasserstoffrest, (ii) C1-C20-Kohlenwasserstoffoxyrest, (iii) Silylrest -SiRaRbRc, worin Ra,Rb,Rc unabhängig voneinander ein C1-C6-Kohlenwasserstoffrest sind, (iv) Aminrest -NRX2, worin Rx unabhängig voneinander ausgewählt ist aus der Gruppe mit (iv.i) Wasserstoff, (iv.ii) C1-C20-Kohlenwasser- stoffrest und (iv.iii) dem Silylrest -SiRaRbRc, und (v)
Iminrest — N=CR1R2 , worin R1 R2 unabhängig voneinander ausgewählt ist aus der Gruppe mit (v.i) Wasserstoff, (v.ii) C1-C20~Kohlenwasserstoffrest und (v.iii) dem SilylrestPCT/EP2019/083737 describes silirane-functionalized compounds for the production of elastomeric silicones by nucleophilic ring-opening polymerization. Although the silirane-containing compounds are potential sources of silylene, the reactive silicon center upon activation is siloxane skeleton is separated, neither crosslinking nor an adhesion-promoting effect can be achieved. JP 63048674 A2 describes a method for coating metallic or ceramic surfaces with hexamethyldisilazane with reference to a silylene reaction. In terms of content, however, the silylation of OH groups on the substrate surface is carried out with hexamethyldisilazane. Reaction conditions which lead to the release of silylenes are not mentioned. The object of the invention was to improve the adhesion of silicones to plastic surfaces without having to subject the plastic surface to an expensive pretreatment. This object is achieved by mixtures containinga) at least one silirane-functionalized compound from a substrate to which at least two silirane groups of the formula (I) are covalently bonded, where n = 0 or 1; wherein R a is a C 1 -C 20 divalent hydrocarbon radical; where R 1 is selected from the group consisting of (i) C 1 -C 20 hydrocarbyl, (ii) C 1 -C 20 hydrocarbyloxy, (iii) silyl -SiR a R b R c , wherein R a ,R b ,R c are independently a C 1 -C 6 hydrocarbon radical, (iv) amine radical -NR X 2, wherein R x is independently selected from the group with (iv.i) hydrogen, (iv.ii) C 1 -C 20 -hydrocarbon radical and (iv.iii) the silyl radical -SiR a R b R c , and (v) Imine radical — N=CR 1 R 2 where R 1 R 2 is independently selected from the group consisting of (vi) hydrogen, (v.ii) C 1 -C 20 ~hydrocarbon radical and (v.iii) the silyl radical
-SiRaRbRc; wobei R2 , R3 , R4 , R5 unabhängig voneinander ausgewählt sind aus der Gruppe mit Wasserstoff, Halogen und C1-C20- Kohlenwasserstoffrest, wobei R2 und R4 Bestandteil eines zyklischen Restes sein können; b) mindestens ein natürliches oder synthetisches Polymer, ausgewählt aus der Gruppe mit bl) additionsvernetzende Siliconmassen, b2) kondensationsvernetzende Siliconmassen, b3) Hybridmaterialien / Silyl-terminierte Polymere (STP) und b4) anorganische Polymere und organische Polymere und Kombinationen aus bl bis b4. -SiR a R b R c ; where R 2 , R 3 , R 4 , R 5 are independently selected from the group consisting of hydrogen, halogen and C 1 -C 20 hydrocarbon radical, where R 2 and R 4 can be part of a cyclic radical; b) at least one natural or synthetic polymer selected from the group consisting of bl) addition-crosslinking silicone compositions, b2) condensation-crosslinking silicone compositions, b3) hybrid materials/silyl-terminated polymers (STP) and b4) inorganic polymers and organic polymers and combinations of bl to b4.
Bisher wurden Silirane bzw. die hieraus generierbaren Silylene nur als metallfreie Vernetzer für funktionelle Polyorgano- siloxane zur Darstellung von elastomeren Siliconen beschrieben. Eine Nutzung siliranhaltiger Verbindungen als Haftvermittler für bestehende Siliconprodukte oder als Bestandteil von selbsthaftenden vernetzbaren Silicon (hybrid)massen für wenig polare bis unpolare Kunststoffe ist bisher nicht bekannt. So far, siliranes and the silylenes that can be generated from them have only been described as metal-free crosslinkers for functional polyorganosiloxanes for the preparation of elastomeric silicones. The use of silane-containing compounds as adhesion promoters for existing silicone products or as a component of self-adhesive crosslinkable silicone (hybrid) compositions for plastics with little or no polarity is not known to date.
Der Begriff additionsvernetzende Siliconmassen bezeichnet im Sinne der vorliegenden Erfindung generell hydrosilylierbare Mischungen, enthaltend Hydridopolysiloxane, alkenylhaltige Polyorganosiloxane und Füllstoffe (z.B. Kieselsäuren). Diese Mischungen können nur in Gegenwart von Katalysatoren (z.B. dem platinbasierten Karstedt-Katalysator) und Inhibitoren thermisch oder photochemisch zu elastomeren Siliconen vernetzt werden. Solche Mischungen sind z.B. in EP 0651 019 Al oder EP
0 444 960 A2 beschrieben. Die additionsvernetzenden Silicon- massen enthalten also Metallkatalysatoren. For the purposes of the present invention, the term addition-crosslinking silicone masses generally designates hydrosilylatable mixtures containing hydridopolysiloxanes, alkenyl-containing polyorganosiloxanes and fillers (eg silicas). These mixtures can only be crosslinked thermally or photochemically to form elastomeric silicones in the presence of catalysts (eg the platinum-based Karstedt catalyst) and inhibitors. Such mixtures are, for example, in EP 0651 019 A1 or EP 0 444 960 A2. The addition-crosslinking silicone compositions therefore contain metal catalysts.
Kondensationsvernetzende Siliconmassen sind im Sinne der Erfindung generell Mischungen, enthaltend OH- oder Alkoxy- terminierte Polyorganosiloxane und multifunktionelle Polysiloxan-Vernetzer (z.B. R-SiX3 mit X = Alkoxy, Carboxy oder Amino) . Diese kondensieren durch Luftfeuchtigkeit und in Gegenwart eines Metallkatalysators (z.B. organische Zinn- oder Titanverbindungen) unter Freisetzung von Wasser, Alkoholen, Essigsäure oder Aminen zu dreidimensionalen Netzwerken. Solche Mischungen sind z.B. in DE 1026 520 oder US 3,696,090 beschrieben. Die kondensationsvernetzenden Siliconmassen enthalten Metallkatalysatoren. In the context of the invention, condensation-crosslinking silicone compositions are generally mixtures containing OH- or alkoxy-terminated polyorganosiloxanes and multifunctional polysiloxane crosslinkers (e.g. R-SiX3 with X=alkoxy, carboxy or amino). These condense into three-dimensional networks due to atmospheric moisture and in the presence of a metal catalyst (e.g. organic tin or titanium compounds) with the release of water, alcohols, acetic acid or amines. Such mixtures are described, for example, in DE 1026 520 or US Pat. No. 3,696,090. The condensation-crosslinking silicone masses contain metal catalysts.
Hybridmaterialen / STP sind im Sinne der Erfindung generell reaktive Silan-terminierte organische Polymere (z.B. In the context of the invention, hybrid materials / STP are generally reactive silane-terminated organic polymers (e.g.
Polyether) die beispielsweise als Kleb-, Dicht- und Beschichtungsstoffe zum Einsatz kommen. Solche Materialien sind exemplarisch in WO 2017/137281 Al beschrieben. Polyether) which are used, for example, as adhesives, sealants and coating materials. Such materials are described by way of example in WO 2017/137281 A1.
Anorganische Polymere sind im Sinne der Erfindung generell natürliche und synthetische anorganische Polymere (z.B. Kieselsäuren, silikatische Strukturen, Polysilane und Polysiloxane) . Organische Polymere sind im Sinne der Erfindung generell natürliche und synthetische organische Polymere, geeignet zur Herstellung von Formkörpern, Beschichtungen oder Laminaten. Beispiele für derartige Polymere finden sich in US 5,792,812; US 2007/0141250 Al und US 4,686,124. In the context of the invention, inorganic polymers are generally natural and synthetic inorganic polymers (e.g. silicic acids, silicate structures, polysilanes and polysiloxanes). For the purposes of the invention, organic polymers are generally natural and synthetic organic polymers suitable for producing molded articles, coatings or laminates. Examples of such polymers can be found in US 5,792,812; US 2007/0141250 A1 and US 4,686,124.
Es wurde erkannt, dass die Siliran-funktionalisierten Verbindungen gemäß a) der Mischung, bzw. die aus diesen erzeugten reaktiven Silylene, neben ihrer bekannten Verwendung als edelmetallfreie Vernetzer für Polyorganosiloxane, geeignet
sind, anderweitig vernetzbare Silicone (Technologiebasis: It was recognized that the silirane-functionalized compounds according to a) of the mixture, or the reactive silylenes produced from them, are suitable in addition to their known use as noble-metal-free crosslinkers for polyorganosiloxanes are otherwise crosslinkable silicones (technology basis:
Hydrosilylierung oder Kondensationsvernetzung) auf unreaktivenhydrosilylation or condensation crosslinking) on unreactive ones
Polymerträgerkörpern wie PE, PP, PET und PC zur Haftung zu bringen. Die Siliran-funktionalisierten Verbindungen fungieren also als Haftvermittler zwischen dem inerten Polymerträgerkörper und dem aufgebrachten vernetzbaren Siloxangemisch durchTo bring polymer carrier bodies such as PE, PP, PET and PC to liability. The silirane-functionalized compounds thus act as adhesion promoters between the inert polymer carrier body and the applied crosslinkable siloxane mixture
Ausbildung kovalenter Bindungen. Bei der erfindungsgemäßenformation of covalent bonds. In the case of the invention
Mischung handelt es sich also mit besonderem Vorteil um eine selbsthaftende Mischung zur Beschichtung von insbesondere chemisch-inerteren Materialien. The mixture is therefore, with particular advantage, a self-adhesive mixture for the coating of, in particular, chemically inert materials.
Die Siliran-funktionalisierten Verbindungen sind stabile The silirane functionalized compounds are stable
Vorstufen der hochreaktiven Silylene. Aus der Silirangruppe entsteht nach thermischer oder photochemischer Aktivierung einPrecursors of highly reactive silylenes. After thermal or photochemical activation, a siliran group is formed
Silylen-Intermdiat . Die Siliran-funktionalisierten silylene intermediate . The siliran-functionalized
Verbindungen müssen mindestens über zwei Silirangruppen verfügen, um als Haftvermittler fungieren zu können. Dabei ist es zwingend erforderlich, dass die Si-Atome der Silirangruppen über ein Grundgerüst miteinander verbrückt sind (vgl. Compounds must have at least two silirane groups to function as an adhesion promoter. It is imperative that the Si atoms of the silirane groups are bridged to one another via a backbone (cf.
Schema 2)
scheme 2)
Schema 2: Oben: Die Si-Atome der Siliran-funktionalisierten Verbindung sind über ein Strukturgerüst verbrückt, wodurch sich bei Aktivierung eine vernetzungsfähigereaktive Bis- Silylen-Spezies ergibt. Unten: Die Silirangruppen sind nicht über die Si-Atome verbrückt, wodurch bei Aktivierung nicht vernetzende Spaltungsprodukte entstehen.
Vorzugsweise ist das Substrat der Siliran-funktionalisierten Verbindung ausgewählt aus der Gruppe mit Silane, Organo- siliciumverbindungen, Kohlenwasserstoffe, Kieselsäuren, kohlenstoffbasierte Oligomere und Polymere. Scheme 2: Top: The Si atoms of the silirane-functionalized compound are bridged through a structural backbone, resulting in a crosslinkable reactive bis-silylene species upon activation. Bottom: The silirane groups are not bridged via the Si atoms, resulting in non-crosslinking cleavage products upon activation. The substrate of the silirane-functionalized compound is preferably selected from the group consisting of silanes, organosilicon compounds, hydrocarbons, silicic acids, carbon-based oligomers and polymers.
Besonders bevorzugt ist das Substrat der Siliran- funktionalisierten Verbindung ausgewählt aus der Gruppe mit Siloxane, gefällte Kieselsäure, pyrogene Kieselsäure, Polyolefine, Acrylate, Polyacrylate, Polyvinylacetate, Polyurethane und Polyether aus Propylenoxid- und/oder Ethylenoxideinheiten The substrate of the silirane-functionalized compound is particularly preferably selected from the group consisting of siloxanes, precipitated silica, pyrogenic silica, polyolefins, acrylates, polyacrylates, polyvinyl acetates, polyurethanes and polyethers made from propylene oxide and/or ethylene oxide units
Gemäß einer weiteren Ausführungsform handelt es sich bei dem Substrat um Organosiliciumverbindungen der allgemeinen FormelAccording to a further embodiment, the substrate is organosilicon compounds of the general formula
(II): (II):
(SiO4/2) a (RxSiO3/2) b (R ' SiO3/2) b' (Rx 2SiO2/2) c (RXR ' SiO2/2) C' (SiO 4/2 ) a (R x SiO 3/2 ) b (R ' SiO 3/2 ) b' (R x 2 SiO 2/2 ) c (R X R ' SiO 2/2 ) C '
(R '2SiO2/2) o” (Rx 3SiO1/2) d (R 'Rx 2SiO1/2) d' (R '2RxSiO1/2) d' ' (R ' 2 SiO 2/2 ) o” (R x 3 SiO 1/2 ) d (R 'R x 2 SiO 1/2 ) d ' (R ' 2 R x SiO 1/2 ) d '''
(R '3SiO1/2)d"' (II) (R ' 3 SiO 1/2 ) d "' (II)
Dabei ist Rx unabhängig voneinander ausgewählt aus der Gruppe mit Wasserstoff, Halogen, unsubstituierter oder substituierter C1-C20-Kohlenwasserstoffrest und unsubstituierter oder substituierter C1-C20-Kohlenwasserstoffoxyrest. R x is independently selected from the group consisting of hydrogen, halogen, an unsubstituted or substituted C 1 -C 20 hydrocarbyl radical and an unsubstituted or substituted C 1 -C 20 hydrocarbyloxy radical.
Die Indices a, b, b', c, c', c'', d, d', d'', d''' geben die Anzahl der jeweiligen Siloxaneinheit in der Verbindung an und bedeuten unabhängig voneinander Null oder eine ganze Zahl von 1 bis 10.000, mit der Maßgabe, dass die Summe aus a, b, b', c, c', c'', d, d', d'', d''' mindestens den Wert 2 annimmt und wenigstens einer der Indices b', c', d' > 2 ist oder wenigstens einer der Indices c'', d'' oder d,'' ungleich Null ist.
Der Rest R' ist dabei die Siliran-Gruppe der Formel (I). The indices a, b, b′, c, c′, c″, d, d′, d″, d″″ indicate the number of the respective siloxane unit in the compound and are independently zero or an integer from 1 to 10,000, provided that the sum of a, b, b', c, c', c'', d, d', d'', d''' is at least 2 and at least one of the indices b', c', d'> 2 or at least one of the indices c'', d'' or d , '' is not equal to zero. The radical R' is the silirane group of the formula (I).
Bevorzugt ist der Rest Ra in der Formel (I) ein C1-C3- Alkylenrest, besonders bevorzugt ein Ethylenrest. The radical R a in the formula (I) is preferably a C 1 -C 3 - alkylene radical, particularly preferably an ethylene radical.
Über den Substituenten R1 am Si-Atom in der Formel (I) kann kinetisch und thermodynamisch Einfluss auf die Reaktivität und Stabilität der Siliran-funktionalisierten Verbindungen ausgeübt werden. Bevorzugt ist R1 ein C1-C6-Kohlenwasserstoff- rest oder Aminrest -N (SiRaRbRc)2, wobei Ra,Rb,Rc unabhängig voneinander ein C1-C6-Kohlenwasserstoffrest sind. Besonders bevorzugt ist R1 ein C1-C6-Alkylrest oder -N(SiMe3)2. The reactivity and stability of the silirane-functionalized compounds can be influenced kinetically and thermodynamically via the substituent R 1 on the Si atom in the formula (I). R 1 is preferably a C 1 -C 6 hydrocarbyl radical or amine radical -N(SiR a R b R c ) 2 , where R a , R b , R c are independently a C 1 -C 6 hydrocarbyl radical. R 1 is particularly preferably a C 1 -C 6 -alkyl radical or -N(SiMe 3 ) 2 .
Bevorzugt sind die Indices a, b, b ', c, c', c'', d, d'' und d''' Null und der Index d' nimmt den Wert 2 an, wobei in Formel (I) der Index n den Wert 1 annimmt, Ra ein C1-C3- Alkylenrest ist und R1 ein C1-C6-Kohlenwasserstoffrest oder ein Aminrest -N (SiRaRbRc)2 ist, worin Ra,Rb,Rc unabhängig voneinander C1-C6-Kohlenwasserstoffreste sind. Die Reste R2,R3,R4,R5 sind unabhängig voneinander Wasserstoff oder C1-C6-Alkylrest, wobei R2 und R4 auch Bestandteil eines zyklischen Restes sein können. The indices a, b, b', c, c', c'', d, d'' and d''' are preferably zero and the index d' has the value 2, where in formula (I) the index n is 1, R a is a C 1 -C 3 alkylene group and R 1 is a C 1 -C 6 hydrocarbyl group or an amine group -N(SiR a R b R c ) 2 wherein R a ,R b ,R c are independently C 1 -C 6 hydrocarbon radicals. The radicals R 2 , R 3 , R 4 , R 5 are, independently of one another, hydrogen or a C 1 -C 6 -alkyl radical, where R 2 and R 4 can also be part of a cyclic radical.
Besonders bevorzugt sind die Indices a, b, b', c, c', c'', d, d'' und d''' Null und der Index d' nimmt den Wert 2 an, wobei in Formel (I) der Index n den Wert 1 annimmt, Ra ein Ethylen- rest und R1 ein C1-C6-Alkylrest oder -N(SiMe3)2 ist. Die Reste R2,R3,R4,R5 sind unabhängig voneinander Wasserstoff oder C1-C6- Alkylrest, wobei R2 und R4 auch Bestandteil eines zyklischen Restes sein können. The indices a, b, b', c, c', c'', d, d'' and d''' are particularly preferably zero and the index d' has the value 2, where in formula (I) the Index n is 1, R a is an ethylene radical and R 1 is a C 1 -C 6 alkyl radical or -N(SiMe 3 ) 2 . The radicals R 2 , R 3 , R 4 , R 5 are, independently of one another, hydrogen or a C 1 -C 6 - alkyl radical, where R 2 and R 4 can also be part of a cyclic radical.
Vorzugsweise ist der Rest Rx in der Formel (II) unabhängig voneinander ausgewählt aus der Gruppe mit Methyl, Ethyl,The radical R x in the formula (II) is preferably selected independently from the group consisting of methyl, ethyl,
Vinyl, Wasserstoff und Phenyl.
Die Siliran-funktionalisierte Verbindung ist besonders bevorzugt ausgewählt aus der Gruppe mit SVl, SV2 und SV3, wobei SVl, SV2 und SV3 folgende Strukturen aufweisen:
vinyl, hydrogen and phenyl. The silirane-functionalized compound is particularly preferably selected from the group with SV1, SV2 and SV3, where SV1, SV2 and SV3 have the following structures:
Vorzugsweise beträgt der Anteil der Siliran-funktionalisierten Verbindung in der Mischung 0,5 bis 10 Gew.-%, besonders bevorzugt 0,5 bis 5 Gew.-%, insbesondere 0,5 bis 2 Gew.~%. The proportion of the silirane-functionalized compound in the mixture is preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, in particular 0.5 to 2% by weight.
Ein weiterer Aspekt der Erfindung betrifft Formkörper, umfassend mindestens eine der erfindungsgemäßen Mischung und ein wenig polares bis unpolares Trägermaterial. A further aspect of the invention relates to moldings comprising at least one of the mixtures according to the invention and a slightly polar to non-polar carrier material.
Der Formkörper ist vorzugsweise ausgewählt aus der Gruppe mit Extrusions- oder Spritzgussformkörper, ein- oder mehr- schichtige Laminate (z.B. hergestellt durch Spincoating, Kalandrieren oder Tauchverfahren), verkapselbare Formkörper (z.B. hergestellt im Elektroguss durch Verfüllen, Tauchen oder Plastifizieren), verklebungs- oder dichtungsfähige Formkörper (reaktive Klebmassen) und Übergänge zwischen gleichen oder verschiedenen Formkörpern gleicher oder verschiedener Trägermaterialien. Mit letzterem sind insbesondere Fügemassen zum Verkleben mehrerer ungleicher Materialien gemeint. The molding is preferably selected from the group consisting of extrusion or injection molding, single or multi-layer laminates (e.g. produced by spin coating, calendering or dipping processes), encapsulated moldings (e.g. produced in electrocasting by filling, dipping or plasticizing), adhesive or sealable shaped bodies (reactive adhesives) and transitions between identical or different shaped bodies of the same or different carrier materials. The latter means in particular jointing compounds for bonding several dissimilar materials.
Der Formkörper kann das Trägermaterial in Form einer Beschichtung enthalten. Der Formkörper kann aus dem Trägermaterial, auf welches die Mischung aufgetragen ist, bestehen. The shaped body can contain the carrier material in the form of a coating. The shaped body can consist of the carrier material to which the mixture is applied.
Das Trägermaterial umfasst vorzugsweise mindestens ein synthetisches Kohlenwasserstoffpolymer, ausgewählt aus der
Gruppe mit Polyolefine aus Mono- oder Polyenen, Polyhalogen- olefin, Polyether, Polyvinylchlorid, Polyvinylidendifluorid, Polytetrafluorethen, Polycarbonat, Polyester und Copolymere daraus. Ferner kann das Trägermaterial aus Polymerblends der genannten Kohlenwasserstoffpolymere bestehen oder diese umfassen. The carrier material preferably comprises at least one synthetic hydrocarbon polymer selected from the Group with polyolefins made from mono- or polyenes, polyhaloolefin, polyether, polyvinyl chloride, polyvinylidene difluoride, polytetrafluoroethene, polycarbonate, polyester and copolymers thereof. Furthermore, the carrier material can consist of or comprise polymer blends of the hydrocarbon polymers mentioned.
Bei den Copolymeren kann es sich z.B. um Ethylen-Propylen- Dien-Monomer-Kautschuk (EPDM) oder Acrylnitril-Butadien-Styrol (ABS) handeln. The copolymers can be, for example, ethylene propylene diene monomer rubber (EPDM) or acrylonitrile butadiene styrene (ABS).
Ein weiterer Aspekt der Erfindung betrifft ein Verfahren zur Aushärtung der erfindungsgemäßen Mischung durch thermische und/oder photochemische Aktivierung. A further aspect of the invention relates to a method for curing the mixture according to the invention by thermal and/or photochemical activation.
Zur Aushärtung wird die Mischung mit einem wenig polaren bis unpolaren Trägermaterial wie es oben beschrieben ist in Kontakt gebracht. For curing, the mixture is brought into contact with a slightly polar to non-polar carrier material as described above.
Generell erfordert die thermische Aktivierung eine Temperatur oberhalb der Zersetzungstemperatur der Siliranverbindung. Die dafür benötigte Wellenlänge bei der photochemischen Aktivierung liegt im UV-Bereich. Die Reaktivität der Silirane ist bei beiden Aktivierungsmethoden identisch. In general, thermal activation requires a temperature above the decomposition temperature of the silirane compound. The wavelength required for photochemical activation is in the UV range. The reactivity of the siliranes is identical for both activation methods.
Die aktivierten Siliran-funktionalisierten Verbindungen können aufgrund ihrer hohen Reaktivität mit einer Vielzahl von funktionellen Gruppen reagieren. Mögliche Reaktionspartner sind beispielsweise Si-H, Si-OR, Si-OH, C-OH, C-H, -NH2 und Vinyl. Es werden dadurch alle typischen funktionellen Gruppen von Siliconen sowie wenig polaren bis unpolaren Träger- materialien abgedeckt.
Die Aushärtung kann durch eine ein- oder mehrstufige thermische Aktivierung in einem Temperaturbereich von 0 bis 200°C, bevorzugt von 10 bis 180°C, besonders bevorzugt von 15 bis 160°C, erfolgen. The activated silirane-functionalized compounds can react with a variety of functional groups due to their high reactivity. Possible reaction partners are, for example, Si-H, Si-OR, Si-OH, C-OH, CH, -NH 2 and vinyl. This covers all typical functional groups of silicones as well as slightly polar to non-polar carrier materials. Curing can take place by means of a one-stage or multi-stage thermal activation in a temperature range from 0 to 200°C, preferably from 10 to 180°C, particularly preferably from 15 to 160°C.
Vorzugsweise erfolgt die Aushärtung durch eine zweistufige thermische Aktivierung, umfassend die folgenden Schritte: a) Einstellen einer Temperatur T1 in einem Temperaturbereich von 0 bis 140°C und b) Einstellen einer Temperatur T2 in einem Temperaturbereich von 120 bis 180°C, wobei gilt, dass T1 < T2 ist. Curing preferably takes place by means of a two-stage thermal activation, comprising the following steps: a) setting a temperature T1 in a temperature range from 0 to 140° C. and b) setting a temperature T2 in a temperature range from 120 to 180° C., with the following that T1 < T2.
Vorzugsweise ist die auszuhärtende Mischung Bestandteil des erfindungsgemäßen Formkörpers. Das Verfahren wird also vorzugsweise bei einem erfindungsgemäßen Formkörper angewendet, wobei es zu einer Haftvermittlung zwischen dem Trägermaterial und der Mischungskomponente b) kommt. The mixture to be cured is preferably a component of the molding according to the invention. The process is therefore preferably used in a shaped body according to the invention, with adhesion being promoted between the carrier material and the mixture component b).
Ein weiterer Gegenstand der Erfindung ist die Verwendung der Siliran-funktionalisierten Verbindung gemäß a) der erfindungs- gemäßen Mischung als Haftvermittler, insbesondere als Haft- vermittler zwischen einem wenig polaren bis unpolaren Träger- material wie oben beschrieben und einem Polymer gemäß b) der erfindungsgemäßen Mischung. Another object of the invention is the use of the silirane-functionalized compound according to a) of the mixture according to the invention as an adhesion promoter, in particular as an adhesion promoter between a slightly polar to non-polar carrier material as described above and a polymer according to b) of the mixture according to the invention .
Ferner umfasst von der Erfindung ist die Verwendung der erfindungsgemäßen Mischung als selbsthaftender Beschichtungs- stoff für wenig polare bis unpolare Trägermaterialen wie sie oben beschrieben sind. Also covered by the invention is the use of the mixture of the invention as a self-adhesive coating material for low-polarity to non-polar carrier materials as described above.
Beispiele examples
Geräte:
Die XPS-Analyse wurde mit einem Axis Supra-Spektrometer der Fa. KRATOS durchgeführt. Die Spektren wurden bei einem Druck von <3*10-8 Torr mit einer fokussierten Abtastung unter Nutzung einer monochromatischen Al-Kα-Quelle aufgenommen. Die Durch- trittsenergie im Hybrid-lens-mode mit Ladungsneutralisation betrug 15 eV und die Spotgröße 800 x 300 μm. Die Daten wurden mit dem Programm CasaXPS (Version 2.3.15) analysiert. Die Signale wurden nach der Shirley-Hintergrundsubstraktions- methode integriert. Die Quantifizierung der Elementanteile erfolgte mittels CASA XPS und IMFP-Daten aus der NIST- Datenbank. Sensitivitätsfaktoren wurden mit Hilfe der veröffentlichten Ionisationskreuzung berechnet (Scofield, J.Devices: The XPS analysis was carried out with a KRATOS Axis Supra spectrometer. The spectra were recorded at a pressure of <3*10 -8 Torr with a focused scan using a monochromatic Al-Kα source. The penetration energy in the hybrid lens mode with charge neutralization was 15 eV and the spot size was 800 x 300 μm. The data were analyzed with the program CasaXPS (version 2.3.15). The signals were integrated using the Shirley background subtraction method. The elemental proportions were quantified using CASA XPS and IMFP data from the NIST database. Sensitivity factors were calculated using published ionization crossing (Scofield, J.
H. J. J. Elec. Spec. Rel. Phen. 1976, 8, 129.) und korrigiert für Dämpfung, Übertragungsfunktion des Instruments und Winkel von Probe zum Analysator. Infolgedessen werden die gemessenen Mengen als scheinbar normierte atomare Konzentration angegeben, wobei die Genauigkeit unter den gewählten Bedingungen ca. ± 10% beträgt. H.J.J. Elec. Spec. Rel. Phen. 1976, 8, 129.) and corrected for attenuation, instrument transfer function and sample to analyzer angle. As a result, the amounts measured are given as apparently normalized atomic concentrations, with an accuracy of approx. ± 10% under the chosen conditions.
Zur Härtung wurde eine UV-Lampe „UVahand 250" der Fa. Dr. A UV lamp "UVahand 250" from Dr.
Hönel (Beleuchtungsstärke: max. 250 mW/cm2) verwendet. Hönel (illuminance: max. 250 mW/cm 2 ) is used.
Zur thermischen Härtung wurde ein Trockenschrank „LHT6/30" der Fa. Carbolite-Gero verwendet. An "LHT6/30" drying cabinet from Carbolite-Gero was used for thermal curing.
Chemikalien : Chemicals :
ELASTOSIL® RT604 A/B (Fa. Wacker Chemie AG): Raumtemperatur- vernetzender Siliconkautschuk (RTV-2). ELASTOSIL® RT604 A/B (from Wacker Chemie AG): Room-temperature-curing silicone rubber (RTV-2).
Haftvermittler SV3: Die Synthese des der Siliran- funktionalisierten Verbindung SV3 erfolgte wie in PCT/EP2019/083744 beschrieben.
1. Beschichtung von Polypropylen mit SV3 Adhesion promoter SV3: The silirane-functionalized compound SV3 was synthesized as described in PCT/EP2019/083744. 1. Coating of polypropylene with SV3
Polypropylen wurde als quadratisches Plättchen mit einer Seitenlänge von 2 cm bereitgestellt und dreimal für 20 min mit Isopropanol im Ultraschallbad gereinigt. Die Beschichtung erfolgte mittels Spin-Coating von n-Hexan-Lösungen (Konzentration 13 Gew.-%-ig) des Silirans SV3. Es wurden Schichtdicken von ca. 1/100 mm erhalten. Die Reaktion (Vernetzung/Aushärtung) wurde entweder durch UV-C-Behandlung (mind. 15 min bei ca. 4-5 raW/cm2) oder durch Wärmebehandlung (1 h bei 140°C) ausgelöst. Im Anschluss wurde ede Probe dreimal mit THF/Diethylether extrahiert und im Gasstrom getrocknet. Die Elementarzusammensetzung der Polypropylen- Oberfläche wurde mittels XPS-Analyse untersucht, wobei die experimentellen mit den theoretisch zu erwartenden Element- Gehalten (C, N, 0, Si) verglichen wurden. Die Ergebnisse sind in der Tabelle 1 zusammengefasst.
2. Haftvermittlung von SV3 in thermisch vernetzender RTV2- Masse (Elastosil® RT604 A/B) Polypropylene was provided as a square plate with a side length of 2 cm and cleaned three times with isopropanol in an ultrasonic bath for 20 minutes. The coating was carried out by spin-coating n-hexane solutions (concentration 13% by weight) of Siliran SV3. Layer thicknesses of approx. 1/100 mm were obtained. The reaction (crosslinking/curing) was triggered either by UV-C treatment (at least 15 min at approx. 4-5 raW/cm 2 ) or by heat treatment (1 h at 140°C). Each sample was then extracted three times with THF/diethyl ether and dried in a gas stream. The elemental composition of the polypropylene surface was examined using XPS analysis, whereby the experimental element contents (C, N, O, Si) to be expected theoretically were compared. The results are summarized in Table 1. 2. Adhesion promotion of SV3 in thermally crosslinking RTV2 mass (Elastosil® RT604 A/B)
Zur Herstellung der RTV-2-Siliconmasse werden Mischung A und B im Massenverhältnis 1:1 gemischt (z.B. mit einem Speedmixer „DAC-150.1" der Fa. Hausschild). a) Für die Additivierung werden 1, 5 und 10 Gew.-% des Siliran-funktionalisierten Siloxans SV3 zugegeben und per Hand oder unter Verwendung eines Speedmixers mit dem ELASTOSIL® vermischt. b) Eine Grundierung von Polypropylen-Probenkörpern erfolgte mit einer 10 Gew.-%-igen Lösung von SV3 in Pentan, welches bei Raumtemperatur rasch abdampft. Die eingesetzten Mengen sind ebenso wie alle Vernetzungsbedingungen der Tabelle 2 zu entnehmen. Die Haftung des vernetzten Silicon-Überzugs auf den Probenkörpern wurde über die Ablösestabilität der Beschichtung bewertet .
To produce the RTV-2 silicone mass, mixtures A and B are mixed in a mass ratio of 1:1 (e.g. with a "DAC-150.1" speed mixer from Hausschild). a) 1, 5 and 10% by weight are used for the additives. of the silirane-functionalized siloxane SV3 was added and mixed with the ELASTOSIL® by hand or using a speed mixer b) Polypropylene specimens were primed with a 10% by weight solution of SV3 in pentane, which evaporates rapidly at room temperature The amounts used and all of the crosslinking conditions can be found in Table 2. The adhesion of the crosslinked silicone coating to the specimens was evaluated via the detachment stability of the coating.
Die Ablösestabilität wurde durch ein Abziehen des vernetzten Silicon-Überzugs getestet. Konnte dieser wie die Referenz ohne Reißen in einem Stück gelöst werden, gab es keine Verbesserung der Haftung. Riss das Material, weil es besonders fest am Trägermaterial klebte, und musste stückweise entfernt werden, wurde die Haftung als besser gegenüber der Referenz bewertet.
Peel stability was tested by peeling off the crosslinked silicone coating. If, like the reference, it could be released in one piece without tearing, there was no improvement in adhesion. If the material tore because it stuck particularly firmly to the carrier material and had to be removed piecemeal, the adhesion was rated as better than the reference.
Claims
1. Mischungen, enthaltend a) mindestens eine Siliran-funktionalisierte Verbindung aus einem Substrat, an das mindestens zwei Silirangruppen der Formel (I)
kovalent gebunden sind, wobei n = 0 oder 1 ist; wobei Ra ein zweibindiger C1-C20-Kohlenwasserstoffrest ist; wobei R1 ausgewählt ist aus der Gruppe mit (i) C1-C20- Kohlenwasserstoffrest , (ii) C1-C20-Kohlenwasserstoff- oxyrest, (iii) Silylrest -SiRaRbRc, worin Ra,Rb,Rc unabhängig voneinander ein C1-C6-Kohlenwasserstoffrest sind, (iv) Aminrest -NRX2, worin Rx unabhängig voneinander ausgewählt ist aus der Gruppe mit (iv.i) Wasserstoff, (iv.ii) C1-C20~Kohlenwasserstoffrest und (iv.iii) dem Silylrest -SiRaRbRc, und (v) Iminrest 1. Mixtures containing a) at least one silirane-functionalized compound from a substrate to which at least two silirane groups of the formula (I) are covalently bonded, where n = 0 or 1; wherein R a is a C 1 -C 20 divalent hydrocarbon radical; where R 1 is selected from the group consisting of (i) C 1 -C 20 hydrocarbyl, (ii) C 1 -C 20 hydrocarbyl oxy, (iii) silyl -SiR a R b R c , wherein R a ,R b ,R c are independently a C 1 -C 6 hydrocarbon radical, (iv) amine radical -NR X 2, wherein R x is independently selected from the group with (iv.i) hydrogen, (iv.ii) C 1 -C 20 ~hydrocarbon radical and (iv.iii) the silyl radical -SiR a R b R c , and (v) imine radical
-N=CR1R2, worin R1 ,R2 unabhängig voneinander ausgewählt ist aus der Gruppe mit (v.i) Wasserstoff, (v.ii) C1-C20- Kohlenwasserstof frest und (v.iii) dem Silylrest-N=CR 1 R 2 wherein R 1 ,R 2 is independently selected from the group consisting of (vi) hydrogen, (v.ii) C 1 -C 20 hydrocarbon radical and (v.iii) the silyl radical
-SiRaRbRc; wobei R2,R3,R4,R5 unabhängig voneinander ausgewählt sind aus der Gruppe mit Wasserstoff, Halogen und C1-C20- Kohlenwasserstoffrest , wobei R2 und R4 Bestandteil eines zyklischen Restes sein können; b) mindestens ein Polymer, ausgewählt aus der Gruppe mit bl) additionsvernetzende Siliconmassen, b2) kondensationsvernetzende Siliconmassen, b3) Hybridmaterialien / STP und
b4) anorganische und organische Polymere und Kombinationen aus bl bis b4. -SiR a R b R c ; where R 2 , R 3 , R 4 , R 5 are independently selected from the group consisting of hydrogen, halogen and C 1 -C 20 hydrocarbon radical, where R 2 and R 4 can be part of a cyclic radical; b) at least one polymer selected from the group consisting of bl) addition-crosslinking silicone compositions, b2) condensation-crosslinking silicone compositions, b3) hybrid materials/STP and b4) inorganic and organic polymers and combinations of bl to b4.
2. Mischungen nach Anspruch 1, dadurch gekennzeichnet, dass das Substrat der Siliran-funktionalisierten Verbindung ausgewählt ist aus der Gruppe mit Silane, Organosilicium- verbindungen, Kohlenwasserstoffe, Kieselsäuren, kohlenstoffbasierte Oligomere und Polymere. 2. Mixtures according to claim 1, characterized in that the substrate of the silirane-functionalized compound is selected from the group consisting of silanes, organosilicon compounds, hydrocarbons, silicic acids, carbon-based oligomers and polymers.
3. Mischungen nach Anspruch 2, dadurch gekennzeichnet, dass das Substrat ausgewählt ist aus der Gruppe mit Siloxane, gefällte Kieselsäure, pyrogene Kieselsäure, Polyolefine, Acrylate, Polyacrylate, Polyvinylacetate, Polyurethane und Polyether aus Propylenoxid- und/oder Ethylenoxideinheiten. 3. Mixtures according to claim 2, characterized in that the substrate is selected from the group consisting of siloxanes, precipitated silica, pyrogenic silica, polyolefins, acrylates, polyacrylates, polyvinyl acetates, polyurethanes and polyethers made from propylene oxide and/or ethylene oxide units.
4. Mischungen nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei dem Substrat um Organosiliciumverbindungen der allgemeinen Formel ( II ) handelt 4. Mixtures according to Claim 1, characterized in that the substrate is an organosilicon compound of the general formula (II).
(SiO4/2) a (RxSiO3/2) b (R 'SiO3/2) b' (Rx 2SiO2/2) G (RxR 'SiO2/2) c' (SiO 4/2 ) a (R x SiO 3/2 ) b (R 'SiO 3/2 ) b' (R x 2 SiO 2/2 ) G (R x R 'SiO 2/2 ) c '
(R '2SiO2/2) c" (Rx 3SiO1/2) d (R 'Rx 2SiO1/2) d' (R '2RxSiO1/2) d' ' (R ' 2 SiO 2/2 ) c" (R x 3 SiO 1/2 ) d (R 'R x 2 SiO 1/2 ) d ' (R ' 2 R x SiO 1/2 ) d '''
(R '3SiO1/2)d' " (II), wobei Rx unabhängig voneinander ausgewählt ist aus der Gruppe mit Wasserstoff, Halogen, unsubstituierter oder substituierter C1-C20-Kohlenwasserstoffrest und unsubstituierter oder substituierter C1~C2o-Kohlenwasser- stoffoxyrest; wobei die Indices a, b, b', c, c', c'', d, d', d'', d''' die Anzahl der jeweiligen Siloxaneinheit in der Verbindung angeben und unabhängig voneinander Null oder eine ganze Zahl von 1 bis 10.000 bedeuten, mit der Maßgabe, dass die Summe aus a, b, b', c, c', c'', d, d',
d'', d''' mindestens den Wert 2 annimmt und wenigstens einer der Indices b', c', d' h 2 ist oder wenigstens einer der Indices c'', d'' oder d''' ungleich Null ist; wobei R' die Siliran-Gruppe der Formel (I) ist. (R ' 3 SiO 1/2 ) d '" (II), wherein R x is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C 1 -C 20 hydrocarbyl and unsubstituted or substituted C 1 ~ C 2 o-hydrocarbonoxy radical, where the indices a, b, b', c, c', c'', d, d', d'', d''' indicate the number of the respective siloxane unit in the compound and independently of one another mean zero or an integer from 1 to 10,000, provided that the sum of a, b, b', c, c', c'', d, d', d'', d''' has at least the value 2 and at least one of the indices b', c', d'h is 2 or at least one of the indices c'', d'' or d''' is non-zero; where R' is the silirane group of formula (I).
5. Mischungen nach Anspruch 4, dadurch gekennzeichnet, dass die Indices a, b, b', c, c', c'', d, d'' und d''' Null sind und der Index d' den Wert 2 annimmt; und wobei in Formel (I) der Index n den Wert 1 annimmt, Ra ein C1-C3-Alkylenrest ist und R1 ein C1-C6-Kohlenwasserstofir- rest oder ein Aminrest -N (SiRaRbRc)2 ist, worin Ra,Rb,Rc unabhängig voneinander C1-C6-Kohlenwasserstoffreste sind; und wobei R2,R3,R4,R5 unabhängig voneinander Wasserstoff oder C1-C6-Alkylrest ist, wobei R2 und R4 Bestandteil eines zyklischen Restes sein können. 5. Mixtures according to claim 4, characterized in that the indices a, b, b', c, c', c'', d, d'' and d''' are zero and the index d' has the value 2 ; and where in formula (I) the index n is 1, R a is a C 1 -C 3 alkylene radical and R 1 is a C 1 -C 6 hydrocarbon radical or an amine radical -N (SiR a R b R c )2, wherein R a ,R b ,R c are independently C 1 -C 6 hydrocarbon radicals; and where R 2 ,R 3 ,R 4 ,R 5 are independently hydrogen or C 1 -C 6 alkyl radical, where R 2 and R 4 can be part of a cyclic radical.
6. Mischungen nach Anspruch 4, dadurch gekennzeichnet, dass die Indices a, b, b', c, c', c'', d, d'' und d''' Null sind und der Index d' den Wert 2 annimmt; wobei in Formel (I) der Index n den Wert 1 annimmt, Ra ein Ethylenrest und R1 ein C1-C6-Alkylrest oder -N(SiMe3)2 ist; und wobei R2,R3,R4,R5 unabhängig voneinander Wasserstoff oder C1-C6-Alkylrest ist, wobei R2 und R4 Bestandteil eines zyklischen Restes sein können. 6. Mixtures according to claim 4, characterized in that the indices a, b, b', c, c', c'', d, d'' and d''' are zero and the index d' has the value 2 ; where in formula (I) the index n is 1, R a is ethylene and R 1 is C 1 -C 6 alkyl or -N(SiMe 3 ) 2 ; and where R 2 ,R 3 ,R 4 ,R 5 are independently hydrogen or C 1 -C 6 alkyl radical, where R 2 and R 4 can be part of a cyclic radical.
7. Mischungen nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass Rx unabhängig voneinander ausgewählt ist aus der Gruppe mit Methyl, Ethyl, Vinyl, Wasserstoff und Phenyl. 7. Mixtures according to any one of claims 4 to 6, characterized in that R x is independently selected from the group consisting of methyl, ethyl, vinyl, hydrogen and phenyl.
8. Mischungen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Siliran- funktionalisierte Verbindung ausgewählt ist aus der Gruppe mit
8. Mixtures according to one of the preceding claims, characterized in that the silirane-functionalized compound is selected from the group with
9. Formkörper, enthaltend mindestens eine Mischung nach einem der Ansprüche 1 bis 8 und ein wenig polares bis unpolares Trägermaterial. 9. Moldings containing at least one mixture as claimed in any of claims 1 to 8 and a slightly polar to non-polar carrier material.
10. Formkörper nach Anspruch 9, dadurch gekennzeichnet, dass das Trägermaterial mindestens ein synthetisches Kohlen- wasserstoffpoly er umfasst, ausgewählt aus der Gruppe mit Polyolefin aus Mono- oder Polyenen, Polyhalogenolefin, Polyether, Polyvinylchlorid, Polyvinylidendifluorid, Polytetrafluorethen, Polycarbonat, Polyester und Copolymere daraus. 10. Shaped body according to claim 9, characterized in that the carrier material comprises at least one synthetic hydrocarbon polymer selected from the group consisting of polyolefins made from mono- or polyenes, polyhaloolefins, polyethers, polyvinyl chloride, polyvinylidene difluoride, polytetrafluoroethene, polycarbonate, polyesters and copolymers thereof .
11. Verfahren zur Aushärtung einer Mischung nach zumindest einem der Ansprüche 1 bis 8 durch thermische und/oder photochemische Aktivierung. 11. A method for curing a mixture according to at least one of claims 1 to 8 by thermal and/or photochemical activation.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass die Aushärtung durch eine einstufige oder mehrstufige thermische Aktivierung in einem Temperaturbereich von 0 bis 200°C, bevorzugt von 10 bis 180°C, besonders bevorzugt von 15 bis 160°C, erfolgt. 12. The method according to claim 11, characterized in that curing takes place by a single-stage or multi-stage thermal activation in a temperature range from 0 to 200°C, preferably from 10 to 180°C, particularly preferably from 15 to 160°C.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass die Aushärtung durch eine zweistufige thermische Aktivierung erfolgt, umfassend die Schritte c) Einstellen einer Temperatur TI in einem Temperatur- bereich von 0 bis 140°C und
d) Einstellen einer Temperatur T2 in einem Temperatur- bereich von 120 bis 180°C, wobei gilt T1 < T2. 13. The method according to claim 11 or 12, characterized in that the curing takes place by a two-stage thermal activation, comprising the steps c) setting a temperature TI in a temperature range of 0 to 140 ° C and d) Setting a temperature T2 in a temperature range from 120 to 180°C, where T1<T2 applies.
14. Verwendung einer Siliran-funktionalisierten Verbindung aus einem Substrat, an das mindestens zwei Silirangruppen der Formel (I)
kovalent gebunden sind als Haftvermittler, wobei n = 0 oder 1 ist; wobei Ra ein zweibindiger C1-C20-Kohlenwasserstoffrest ist; wobei R1 ausgewählt ist aus der Gruppe mit (i) C1-C20- Kohlenwasserstoffrest, (ii) C1-C20-14. Use of a silirane-functionalized compound from a substrate to which at least two silirane groups of the formula (I) are covalently bonded as adhesion promoters, where n = 0 or 1; wherein R a is a C 1 -C 20 divalent hydrocarbon radical; where R 1 is selected from the group with (i) C 1 -C 20 - hydrocarbyl, (ii) C 1 -C 20 -
Kohlenwasserstoffoxyrest, (iii) Silylrest -SiRaRbRc, worin Ra, Rb, Rc unabhängig voneinander ein C1-C6-Kohlen- wasserstoffrest sind, (iv) Aminrest -NRX2, worin Rx unabhängig voneinander ausgewählt ist aus der Gruppe mit (iv.i) Wasserstoff, (iv.ii) C1-C20-Kohlenwasserstoffrest und (iv.iii) dem Silylrest -SiRaRbRc, und (v) Iminrest - N=CR1-R2, worin R1,R2 unabhängig voneinander ausgewählt ist aus der Gruppe mit (v.i) Wasserstoff, (v.ii) C1-C20- Kohlenwasserstoffrest und (v.iii) dem Silylrest -SiRaRbRc; wobei R2 , R3 , R4 , R5 unabhängig voneinander ausgewählt sind aus der Gruppe mit Wasserstoff, Halogen und C1-C20- Kohlenwasserstoffrest, wobei R2 und R4 Bestandteil eines zyklischen Restes sein können. hydrocarbyloxy radical, (iii) silyl radical -SiR a R b R c where R a , R b , R c are independently a C 1 -C 6 hydrocarbon radical, (iv) amine radical -NR X 2 where R x independently is selected from each other from the group with (iv.i) hydrogen, (iv.ii) C 1 -C 20 hydrocarbyl radical and (iv.iii) the silyl radical -SiR a R b R c , and (v) imine radical - N= CR 1 -R 2 wherein R 1 ,R 2 is independently selected from the group consisting of (vi) hydrogen, (v.ii) C 1 -C 20 hydrocarbon radical and (v.iii) the silyl radical -SiR a R b RC ; where R 2 , R 3 , R 4 , R 5 are independently selected from the group consisting of hydrogen, halogen and C 1 -C 20 hydrocarbon radical, where R 2 and R 4 can be part of a cyclic radical.
15. Verwendung der Mischungen nach einem der Ansprüche 1 bis 8 als selbsthaftender Beschichtungsstoff für wenig polare bis unpolare Trägermaterialien.
15. Use of the mixtures according to any one of claims 1 to 8 as a self-adhesive coating material for slightly polar to non-polar carrier materials.
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