EP4263717A1 - Procédé de production de matériaux réticulables à base de polymères à terminaison organyloxysilane - Google Patents

Procédé de production de matériaux réticulables à base de polymères à terminaison organyloxysilane

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Publication number
EP4263717A1
EP4263717A1 EP20838918.9A EP20838918A EP4263717A1 EP 4263717 A1 EP4263717 A1 EP 4263717A1 EP 20838918 A EP20838918 A EP 20838918A EP 4263717 A1 EP4263717 A1 EP 4263717A1
Authority
EP
European Patent Office
Prior art keywords
optionally
weight
parts
radical
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20838918.9A
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German (de)
English (en)
Inventor
Volker Stanjek
Lars Zander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP4263717A1 publication Critical patent/EP4263717A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the invention relates to a method for the production of
  • Polymers preferably one-component, crosslinkable masses, and their use as adhesives and sealants, in particular as low-modulus sealants.
  • Adhesives and sealants based on alkoxysilane-crosslinking polymers show this in the cured state
  • a first special variant consists in the use of so-called a-silane-terminated prepolymers. These have reactive alkoxysilyl groups linked to an adjacent urethane unit by a methylene spacer. This class of compounds is highly reactive and requires neither tin catalysts nor strong acids or bases to achieve high cure speeds when exposed to air.
  • a-silane-terminated prepolymers are GENIOSIL® STP-E10 or -E30 from Wacker Chemie AG.
  • a second special variant, which is of particular interest for adhesives based on silane-crosslinking polymers, is described, for example, in EP 2 744 842 A, which also contains phenyl silicone resins in addition to the silane-crosslinking polymers.
  • the corresponding resin additives also lead to adhesives which, once fully cured, have significantly improved hardness and tensile shear strength.
  • a third special variant, which is of particular interest for sealants based on silane-crosslinking polymers, is described in EP 3 149095 A, for example.
  • formulations with a high thixotropy are desired, i.e. formulations that have a low viscosity at high shear rates and can therefore be applied from the cartridge or another container with little or at least moderate effort , but highly viscous at low shear rates, are ideally stable, so that the applied adhesive or sealant remains in place after its application until it has cured.
  • This property is indispensable, particularly in the case of sealants, which may also be used to seal vertical joints.
  • the desired thixotropy is usually achieved by adding a thixotropic agent, with polyamide waxes or derivatives thereof being particularly suitable.
  • a thixotropic agent with polyamide waxes or derivatives thereof being particularly suitable.
  • Such thixotropic agents and their use in formulations based on silane-crosslinking polymers have been described many times, including in EP 1767 584 A.
  • thixotropic agents are thixotropic agents that they generally have to be activated by thermal treatment of the formulation, during which at least partial melting of the thixotropic agent occurs.
  • This thermal treatment can take place either during or directly after the mixing of the formulation components or, as is described, for example, in EP 1 767 584 A, after the finished product has been filled Formulated in cartridges or other application containers.
  • the need for a thermal treatment represents an additional work step. If this takes place during or directly after the mixing step, which is usually carried out in large-volume mixers, this leads to a considerable increase in the plant occupancy time and is therefore too significant higher manufacturing costs. If, on the other hand, the thermal treatment is only carried out by heating the respective end container, this is associated with a considerable additional logistical effort and also requires additional heating chambers and/or other technical equipment, which in many cases are not available.
  • the object of the invention was therefore the development of a method which no longer has the disadvantages of the prior art.
  • the invention relates to a process for preparing crosslinkable compositions (M) by mixing (A) 100 parts by weight of compounds of the formula (I), whereby
  • Y is an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon
  • R may be the same or different and represents a monovalent, optionally substituted hydrocarbon radical
  • R 1 may be the same or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which can be linked via nitrogen, phosphorus, oxygen, sulfur or carbonyl group can be attached to the carbon atom
  • R 2 can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical
  • x is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2
  • a can be the same or different and 0 , 1 or 2, preferably 0 or 1
  • b can be the same or different and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1, and
  • at least one thixotropic agent selected from fatty acid amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, polyesteramides, polyureas, oxidized polyethylenes and metal soaps and optionally further components, optionally further subsequent process steps and subsequent storage of the resultant Mixture (M), characterized in that the period of time from the
  • the end of storage of the crosslinkable composition (M) is defined as the point in time at which the composition (M) is removed from a container (GB) for the purpose of crosslinking.
  • packages are cartridges, tubes, buckets, hoses or also large packages such as canisters or barrels, with packages (GB) preferably being cartridges.
  • Further process steps after the inventive mixing of (A) and (B) and optionally further components can include any further processing steps of the mixture, such as thermal treatment, degassing or further mixing steps following the thermal treatment and/or degassing.
  • Storage according to the invention in the method according to the invention preferably also includes filling and decanting the crosslinkable compositions (M) into containers (GB), it being possible for the filling to take place directly after the individual components have been mixed according to the invention or at any later point in time during storage. Transfer steps from one container (GB) for interim storage into other containers (GB) can also be carried out during storage. The last container (GB) is used for the final application, e.g. as an adhesive, sealant or coating material.
  • the mixing can be carried out in any manner known per se, such as methods which are customary for the production of moisture-curing compositions.
  • the order in which the various components are mixed with one another can be varied as desired.
  • the process according to the invention can be carried out at the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. Furthermore, it is possible to temporarily or permanently reduce the pressure, for example to 30 to 500 hPa absolute pressure, in order to remove volatile compounds and/or air.
  • the mixture is preferably mixed for a maximum of 3 hours, particularly preferably for a maximum of 2 hours, in particular for a maximum of 1 hour, optionally with heating by a heating device at temperatures below 80°C , preferably below 69°C, particularly preferably below 59°C, in particular below 49°C.
  • the inventive mixing of components (A) and (B) and optionally other components is heated only by the frictional heat unavoidably released during the mixing process and at no time by a heating device.
  • the period of time from the mixing of components (A) and (B) and, if appropriate, further components to the end of storage of the crosslinkable composition (M) is preferably at least 10 days, particularly preferably at least 15 days, in particular at least 20 days.
  • the storage can take place in any form, ie also in the final packaging for the end use. Storage preferably takes place at least partially in the final packaging for the end use.
  • Storage according to the invention is preferably carried out at a temperature of from -20 to 45.degree. C., in particular from 0 to 35.degree.
  • the method according to the invention is preferably carried out with the exclusion of (atmospheric) moisture.
  • the invention is based on the surprising discovery that the thermal treatment to activate the thixotropic agent can be replaced by the long storage according to the invention. This saves the time and energy-consuming work step of a separate thermal treatment. Since the material according to the invention can of course also be packaged, transported and delivered to intermediaries, even to the end user, during the long storage according to the invention, as long as it is not used, the method according to the invention with the long storage periods according to the invention is suitable for the manufacturer of an adhesive or sealant is often much cheaper than the conventional process, which involves thermal activation of the thixotropic agent.
  • radicals R are alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, iso-octyl radicals and the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as
  • substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl radical.
  • the radical R is preferably an optionally halogen-substituted, monovalent hydrocarbon radical having 1 to 6 carbon atoms, particularly preferably an alkyl radical having 1 or 2 carbon atoms, in particular the methyl radical.
  • radicals R 1 are hydrogen, the radicals specified for R and optionally substituted hydrocarbon radicals bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or a carbonyl group.
  • radical R 1 is preferably a hydrogen atom or a hydrocarbon radical having 1 to 20 carbon atoms, in particular a hydrogen atom.
  • radical R 2 are hydrogen atom and the examples given for radical R.
  • the radical R 2 is preferably a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is unsubstituted or substituted by halogen atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical.
  • polymers on which the polymer radical Y is based are to be understood as meaning all polymers in which at least 50%, preferably at least 70%, particularly preferably at least 90%, of all bonds in the main chain are carbon-carbon, carbon- are nitrogen or carbon-oxygen bonds.
  • polymer radicals Y are polyester, polyether, polyurethane, polyalkylene and polyacrylate radicals.
  • the radical R' is preferably one
  • radicals R' are cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl radical, the various stereoisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical.
  • the radicals R" are preferably alkyl groups having 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl radicals.
  • Component (A) can have the groups -[(CR 12 )b _ SiR a (OR 2 ) 3- a ] attached in the manner described, at any desired positions in the polymer, such as in the chain and/or at the ends.
  • the radical Y in formula (I) is particularly preferably x-valent organic polymer radicals bonded via nitrogen, oxygen, sulfur or carbon and containing polyurethanes or polyoxyalkylenes as the polymer chain, in particular polyurethane radicals with terminally attached groups -[( CR 1 2 ) b- SiR a (OR 2 ) 3- a ] or polyoxyalkylene radicals with terminally bonded groups - [(CR 1 2 b) _ SiR a (OR 2 ) 3-a ], the radicals and indices being the have the meanings mentioned above.
  • the residues Y are preferably linear or have 1 to 3 branching points. They are particularly preferably linear.
  • the polyurethane radicals Y can preferably be prepared from linear or branched polyoxyalkylenes, in particular from polypropylene glycols, and di- or polyisocyanates.
  • the radicals Y preferably have average molar masses M n (number average) of 400 to 30,000 g/mol, preferably of 4,000 to 20,000 g/mol.
  • Suitable processes for preparing a corresponding component (A) and also examples of component (A) itself are, inter alia, in EP 1093 482 B1 (paragraphs [0014]-[0023], [0039]-[0055] and example 1 and comparative example 1) or EP 1 641 854 B1 (paragraphs [0014]-[0035], examples 4 and 6 and comparative examples 1 and 2), which are included in the disclosure content of the present application.
  • the number-average molar mass M n is determined by means of size exclusion chromatography (SEC) against a polystyrene standard, in THE, at 60° C., flow rate 1.2 ml/min and detection with RI (refractive index detector ) on a Waters Corp. Styragel HR3-HR4-HR5-HR5 column set. USA determined with an injection volume of 100 ⁇ l.
  • SEC size exclusion chromatography
  • the polyoxyalkylene radicals Y preferably have average molar masses M n of from 4000 to 30,000 g/mol, preferably from 8000 to 20,000 g/mol.
  • Suitable processes for preparing a corresponding component (A) and also examples of component (A) itself are, inter alia, in EP 1535 940 B1 (paragraphs [0005]-[0025] and examples 1-3 and comparative example 1-4) or EP 1896 523 B1 (paragraphs [0008]-[0047]), which are part of the disclosure of the present application.
  • the end groups of the compounds (A) used according to the invention are preferably those of the general formulas
  • the compounds (A) are polyurethanes, which is preferred, they preferably have one or more end groups
  • the compounds (A) are polypropylene glycols, which is particularly preferred, they preferably have one or more of the end groups -o-(CH 2 ) 3 -si(CH 3 )(OCH 3 ) 2 , -O-( CH2 ) 3 -Si(OCH3 )3 ,
  • the average molecular weights Mn of the compounds (A) are preferably at least 400 g/mol, particularly preferably at least 4000 g/mol, in particular at least 10000 g/mol, and preferably at most 30000 g/mol, particularly preferably at most 20000 g/mol. mol, in particular at most 19000 g/mol.
  • the viscosity of the compounds (A) is preferably at least 0.2 Pas, preferably at least 1 Pas, particularly preferably at least 5 Pas, and preferably at most 700 Pas, preferably at most 100 Pas, measured at 20° C. in each case.
  • the viscosity of the polymers (A) used according to the invention is, in the context of the present invention, after heating to 23° C. with a DV 3 P rotational viscometer from A. Paar (Brookfield system), using spindle 5 at 2.5 RPM determined according to ISO 2555.
  • the compounds (A) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • the polymers (A) can be prepared by known methods, such as addition reactions, such as hydrosilylation, Michael addition, Diels-Alder addition, or reactions between isocyanate-functional compounds and compounds containing isocyanate-reactive groups.
  • the component (A) used according to the invention can contain only one type of compound of the formula (I) as well as mixtures of different types of compounds of the formula (I).
  • Component (A) can contain exclusively compounds of the formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98% of all the silyl groups bonded to the radical Y are identical.
  • a component (A) which at least partly contains compounds of the formula (I) in which different silyl groups are bonded to a radical Y can also be used as component (A) in which at least 2 different types of silyl groups bonded to radicals Y are present, but all silyl groups bonded to a radical Y are identical.
  • metal soaps (B) are calcium and aluminum stearates.
  • Heat-activatable thixotropic agents selected from fatty acid amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil and hydrogenated castor oil derivatives are preferred as component (B), fatty acid amides, polyamide waxes and polyamide wax derivatives being particularly preferred.
  • Component (B) is particularly preferably polyamide waxes or polyamide wax derivatives, very particularly preferably polyamide waxes.
  • the melting points of the thixotropic agents (B) are preferably between 40° C. and 200° C., particularly preferably between 50° C. and 150° C., particularly preferably between 60 and 150° C., in each case at 1013 mbar.
  • all process steps preferably start with the mixing of components (A) and (B), the simultaneous or subsequent mixing in of further components, if appropriate, and further process steps, if appropriate, and the storage of the finished composition
  • thixotropic agents are those with the trade name Disparlon® 6500 (polyamide wax with a melting point of approx. 123° C. from Kusumoto Chemicals Ltd), Crayvallac® SLT (polyamide wax with a melting point of 117-127 °C from Arkema) or Crayvallac® SLX (polyamide wax with a melting point of 117-127 °C from Arkema).
  • Component (B) is preferably used in amounts of 1 to 50 parts by weight, particularly preferably in amounts of 3 to 40 parts by weight. parts by weight based on 100 parts by weight of component (A).
  • compositions (M) produced according to the invention can contain all other substances which have also previously been used in crosslinkable compositions and which are different from components (A) and (B), such as e.g. those selected from the group of nitrogen-containing organosilicon compounds (C), non-reactive plasticizers (D), fillers (E), silicone resins (F), catalysts (G), adhesion promoters (H), water scavengers (I), additives ( J) and aggregates (K).
  • Any component (C) used is preferably an organosilicon compound containing units of the formula
  • R 3 can be the same or different and is a monovalent, optionally substituted SiC-bonded, nitrogen-free organic radical,
  • R 4 can be the same or different and is a hydrogen atom or optionally substituted hydrocarbon radicals
  • c is 0, 1, 2 or 3, preferably 0 or 1
  • d is 0, 1, 2 or 3, preferably 1, 2 or 3, particularly preferably 2 or 3
  • e is 0, 1, 2, 3 or 4, preferably 1 , is, with the proviso that the sum of c+d+e is less than or equal to 4 and at least one radical D is present per molecule.
  • radical R 3 examples of radical R 3 are the examples given for R.
  • the radical R 3 is preferably an optionally halogen-substituted hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably a hydrocarbon radical having 1 to 5 carbon atoms, in particular the methyl radical.
  • the radicals R 4 are preferably hydrogen atom or hydrocarbon radicals optionally substituted with halogen atoms having 1 to 18 carbon atoms, particularly preferably hydrogen atom or hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl or ethyl radical.
  • radicals D are radicals of the formulas H2N(CH 2 ) 3 -, H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -, H 2 N (CH 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 3 -, H 3 CNH (CH 2 ) 3 -, C 2 H 5 NH (CH 2 ) 3 -, C 3 H 7 NH (CH 2 ) 3 -, C 4 H 9 NH (CH 2 ) 3 -, C5H11NH( CH2 ) 3- , C6H13NH ( CH2 ) 3- , C7H15NH ( CH2 ) 3- , H2N ( CH2 ) 4- , H2N- CH 2 -CH (CH 3 )-CH 2 -, H 2 N(CH 2 ) 5 -, cyclo-C 5 H 9 NH (CH 2 ) 3 -, cyclo-C 6 H 11 NH (CH 2 ) 3 - , phenyl
  • the radical D is preferably the H2N( CH2 ) 3 , H2N ( CH2 ) 2NH ( CH2 )3 or cyclo- C6H11NH ( CH2 ) 3 radical.
  • silanes of the formula (II) optionally used according to the invention are H 2 N (CH 2 ) 3 -Si (OCH 3 ) 3 , H 2 N (CH 2 ) 3 -Si (OC 2 H 5 ) 3 , H 2 N ( CH2 ) 3 -Si( OCH3 ) 2CH3 ,
  • organosilicon compounds (C) optionally used according to the invention can also assume the function of a curing catalyst or cocatalyst in the compositions (M) prepared according to the invention.
  • organosilicon compounds (C) optionally used according to the invention can act as adhesion promoters and/or as water scavengers.
  • organosilicon compounds (C) optionally used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • compositions (M) according to the invention contain component (C), the amounts involved are preferably from 0.1 to 25 parts by weight, particularly preferably from 0.2 to 20 parts by weight, in particular from 0.5 to 15 parts by weight, in each case based on 100 parts by weight component (A).
  • Component (C) is preferably used in the process according to the invention.
  • Non-reactive plasticizers (D) used can be any non-reactive plasticizers which have hitherto also been used in crosslinkable organopolysiloxane compositions.
  • the non-reactive plasticizers (D) are preferably organic compounds selected from the groups of substances consisting of
  • the non-reactive plasticizers (D) optionally used according to the invention are preferably those which react neither with water nor with components (A) and (B) at temperatures ⁇ 80.degree. C. and at 20.degree 1013 hPa are liquid and have a boiling point >250°C at 1013 hPa.
  • carboxylic acid ester (D) examples include phthalic acid esters such as dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate; perhydrogenated phthalic acid esters such as diisononyl 1,2-cyclohexanedicarboxylate and dioctyl 1,2-cyclohexanedicarboxylate; adipic acid esters such as dioctyl adipate; benzoic acid esters; esters of trimellitic acid, glycol esters; Esters of saturated alkanediols, e.g.
  • polyethers (D) are polyethylene glycols, poly-THF and polypropylene glycols with molar masses of preferably 200 to 20,000 g/mol.
  • Plasticizers (D) are preferably those with molar masses, or in the case of polymeric plasticizers average molar masses M n , of at least 200 g/mol, particularly preferably greater than 500 g/mol, in particular greater than 900 g/mol , inserted. They preferably have molar masses or average molar masses M n of not more than 20000 g/mol, particularly preferably not more than 10000 g/mol, in particular not more than 8000 g/mol.
  • phthalic acid ester-free plasticizers such as perhydrogenated phthalic acid esters, esters of trimellitic acid, polyesters or polyethers, are used as component (D).
  • Plasticizers (D) are particularly preferably polyethers, in particular polyethylene glycols, poly-THF and polypropylene glycols, very particularly preferably polypropylene glycols.
  • the preferred polyethers (D) have molar masses preferably between 400 and 20,000 g/mol, particularly preferably between 800 and 12,000 g/mol, in particular between 1000 and 8000 g/mol.
  • non-reactive plasticizers (D) are used according to the invention, the amounts involved are preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, in particular 20 to 150 parts by weight, based in each case on 100 parts by weight of component (A). Plasticizers (D) are preferably used in the process according to the invention.
  • fillers (E) it can be any previously known fillers.
  • examples of fillers (E) are non-reinforcing fillers, ie fillers with a BET surface area of preferably up to 50 m 2 /g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powders such as aluminum , Titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powder, such as polyacrylonitrile powder; reinforcing fillers, ie fillers with a BET surface area of more than 50 m 2 /g, such as pyrogenic silica, precipitated silica, precipitated chalk and silicon-aluminum mixed oxides, carbon black, such as furnace and acetylene black with a large BET surface area; Aluminum trihydrate, hollow
  • the optionally used fillers (E) are preferably calcium carbonate, magnesium carbonate and/or calcium-magnesium mixed carbonates, talc, aluminum trihydroxide and silica.
  • Preferred types of calcium carbonate are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or salts thereof.
  • the preferred silicic acid is preferably pyrogenic silicic acid.
  • Any fillers (E) used have a moisture content of preferably less than 1% by weight, particularly preferably less than 0.5% by weight.
  • fillers (E) are used according to the invention, the amounts involved are preferably from 10 to 1000 parts by weight, particularly preferably 40 to 500 parts by weight, in particular 80 to 300 parts by weight, based in each case on 100 parts by weight of component (A). Fillers (E) are preferably used in the process according to the invention.
  • filler (El) calcium carbonate, magnesium carbonate and/or calcium-magnesium mixed carbonates are used as filler (El) in amounts of 10 to 900 parts by weight, particularly preferably 40 to 450 parts by weight, in particular 80 to 280 parts by weight used per 100 parts by weight of component (A).
  • other fillers (E2) other than (E1) may also be present.
  • the same materials that have already been described above as fillers (E) can be used as fillers (E2), provided these do not fall under the definition of (E1).
  • the preferred total amounts of fillers (E1) and (E2) correspond to the preferred amounts for fillers (E) given above.
  • the silicone resins (F) optionally used in the compositions (M) of the invention are preferably phenyl silicone resins.
  • the silicone resins (F) optionally used according to the invention are particularly preferably those which contain at least 50% by weight, preferably at least 70% by weight, in particular at least 90% by weight, of T units of the For - meln PhSiO 3 / 2 , PhSi(OR 5 )O 2 /2, PhSi(OR 5 ) 2 0i /2 ,MeSiO 3 / 2 , MeSi(OR 5 )O2/2 and/or MeSi(OR 5 )2O1/ 2, where Ph is phenyl, Me is methyl and R 5 is hydrogen or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms, each based on the total number of units.
  • These resins preferably consist of at least 30% by weight, particularly preferably at least 40% by weight, of the three abovementioned units with a PhSi function.
  • the silicone resins (F) optionally used according to the invention are particularly preferably those which contain at least 50% by weight, preferably at least 70% by weight, in particular at least 90% by weight, of T units of the formula PhSiO 3/2 , PhSi(OR 5 )O 2/2 and/or PhSi(OR 5 ) 2 O 1/2 , where all variables have the meaning given above.
  • the silicone resins (F) optionally used according to the invention preferably have an average molar mass (number average) M n of at least 400 g/mol and particularly preferably of at least 600 g/mol.
  • the average molar mass M n of the silicone resins (F) is preferably not more than 400,000 g/mol, particularly preferably not more than 10,000 g/mol, in particular not more than 3000 g/mol.
  • the silicone resins (F) optionally used according to the invention can be both solid and liquid at 23° C. and 1000 hPa, silicone resins (F) being preferably liquid.
  • the silicone resins (F) preferably have a viscosity of from 10 to 100,000 mPas, preferably from 50 to 50,000 mPas, in particular from 100 to 20,000 mPas, in each case at 25.degree.
  • the silicone resins (F) can be used either in pure form or in the form of a mixture in a suitable solvent, although use in pure form is preferred.
  • phenyl silicone resins that can be used as component (F) are commercially available products, for example various SILRES® Types from Wacker Chemie AG, such as SILRES® IC 368, SILRES® IC 678 or SILRES® IC 231 and SILRES® SY231.
  • the amounts are preferably at least 1 part by weight, particularly preferably at least 5 parts by weight, in particular at least 10 parts by weight and preferably at most 1000 parts by weight, particularly preferably at most 500 parts by weight, in particular at most 300 parts by weight, in each case based on 100 parts by weight of component (A).
  • the catalysts (G) optionally used in the compositions (M) according to the invention can be any previously known catalysts for compositions which cure by silane condensation.
  • metal-containing curing catalysts (G) are organic titanium and tin compounds, for example titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; Tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxides, and corresponding dioctyltin compounds.
  • titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate
  • Tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutylt
  • metal-free curing catalysts (G) are basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,1,2,2-tetramethylguanidine, 1,1,2,3-tetramethylguanidine, N,N-bis-(N,N-dimethyl -2-aminoethyl)-methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine and N-ethylmorpholinine.
  • basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]unde
  • Acidic compounds can likewise be used as catalyst (G), such as phosphoric acid and its partially esterified derivatives, toluenesulfonic acid, sulfuric acid, nitric acid or else organic carboxylic acids, for example acetic acid and benzoic acid.
  • G catalyst
  • phosphoric acid and its partially esterified derivatives toluenesulfonic acid
  • sulfuric acid sulfuric acid
  • nitric acid or else organic carboxylic acids, for example acetic acid and benzoic acid.
  • organic carboxylic acids for example acetic acid and benzoic acid.
  • catalysts (G) are used according to the invention, the amounts involved are preferably from 0.01 to 20 parts by weight, more preferably from 0.05 to 5 parts by weight, based in each case on 100 parts by weight of component (A).
  • any catalysts (G) used are metal-containing curing catalysts, preferably tin-containing catalysts.
  • This embodiment of the invention is particularly preferred when component (A) consists entirely or at least partially, i.e. to an extent of at least 90% by weight, preferably to an extent of at least 95% by weight, of compounds of the formula (I) in which b is not equal to 1.
  • metal-containing catalysts (G), and in particular tin-containing catalysts can preferably be dispensed with if component (A) is completely or at least partially, ie at least 10% by weight, preferably to an extent of at least 20% by weight, of compounds of the formula (I) in which b is 1 and R 1 is a hydrogen atom.
  • component (A) is completely or at least partially, ie at least 10% by weight, preferably to an extent of at least 20% by weight, of compounds of the formula (I) in which b is 1 and R 1 is a hydrogen atom.
  • adhesion promoters (H) optionally used according to the invention can be any adhesion promoters previously described for systems curing by silane condensation.
  • adhesion promoters (H) are epoxysilanes, such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmethyldiethoxysilane, 2-(3-triethoxysilylpropyl)maleic anhydride, N-(3-trimethoxysilylpropyl)urea, N- (3-Triethoxysilylpropyl) urea, N-(Trimethoxysilylmethyl) urea, N-(Methyldimethoxysilymethyl) urea, N-(3-Triethoxysilylmethyl) urea, N-(3-Methyldiethoxysilylmethyl) urea,
  • adhesion promoters (H) are used in the process of the invention, the amounts involved are preferably from 0.5 to 30 parts by weight, particularly preferably from 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition (M).
  • the water scavengers (I) optionally used in the process according to the invention can be any water scavengers described for systems curing by silane condensation.
  • water scavengers (I) are silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimeth- oxysilane, tetraethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, and/or their partial condensates and orthoesters, such as 1,1,1-trimethoxyethane, 1,1 ,1-triethoxyethane, trimethoxymethane and triethoxymethane, with vinyltrimethoxysilane being preferred.
  • silanes such as vinyltrimethoxysilane, vinyltrie
  • (I) are present in amounts of preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition (M).
  • Water scavengers (I) are preferably used in the process according to the invention.
  • (J) can be any additives typical of silane-crosslinking systems known to date.
  • the additives (J) optionally used according to the invention are compounds other than the components mentioned above, preferably antioxidants, UV stabilizers such as HALS compounds, fungicides, commercial defoamers, e.g BYK (D-Wesel), commercial wetting agents, e.g. from BYK (D-Wesel) or pigments.
  • additives (J) are used for the preparation of the compositions (M) according to the invention, which is preferred, they are
  • the additives (K) optionally used according to the invention are preferably tetraalkoxysilanes, for example tetraethoxysilane, and/or their partial condensates, reactive plasticizers, rheology additives different from component (B), flame retardants or organic solvents.
  • Preferred reactive plasticizers (K) are compounds which contain alkyl chains having 6 to 40 carbon atoms and have a group which is reactive toward the compounds (A). Examples are isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane and hexadecyltriethoxysilane.
  • flame retardants preferably halogenated compounds and (partial) esters of phosphoric acid and derivatives thereof, in particular (partial) esters of phosphoric acid.
  • organic solvents (K) are low molecular weight ethers, esters, ketones, aromatic and aliphatic and optionally halogen-containing hydrocarbons and alcohols, preference being given to the latter.
  • organic solvents (K) are added to the compositions (M) according to the invention.
  • the amounts involved are preferably from 0.5 to 200 parts by weight, particularly preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, based in each case on 100 parts by weight of component (A).
  • Fillers optionally (F) silicone resins, optionally (G) catalysts, optionally (H) adhesion promoters, optionally (I) water scavengers, optionally (J) additives and optionally (K) aggregates are mixed with one another and then the resulting mixture is mixed for at least 7 days stored, with all process steps being carried out at temperatures below 80°C.
  • the components used according to the invention can each be one type of such a component or a mixture of at least two types of a respective component.
  • the masses (M) produced according to the invention are preferably pasty masses. After storage for 21 days at 23° C., these preferably have a viscosity determined according to DIN 54458 at 25° C. and a 0.1% deformation of 100 to 100,000 Pas, particularly preferably 1,000 to 50,000 Pas. in particular from 2,000 to 30,000 Pas.
  • filling preferably takes place at a time when the mass (M) is at 25.degree has a viscosity value, measured according to DIN 54458 with a deformation of 100%, which is at least a factor of 1.5, preferably at least a factor of 2, particularly preferably at least a factor of 3, below the viscosity value measured under identical conditions , which the same mass (M) has reached after a storage of 21 days at 23°C after its production.
  • the filling takes place at a point in time at which the mass (M) at 25° C. has a viscosity, measured according to DIN 54458 with a deformation of 0.1%, which is at least by a factor of 2 , preferably at least a factor of 3, particularly preferably at least a factor of 4, particularly preferably at least a factor of 5 below the amount of viscosity measured under identical conditions, which the same mass (M) after storage for 21 days at 23 ° C reached after its manufacture.
  • the crosslinkable composition (M) is preferably heated to temperatures below 69°C at most, particularly preferably to temperatures below 59°C at most, particularly preferably to temperatures below 49°C at most.
  • the crosslinkable mass (M) is not heated to temperatures above 45.degree. C., particularly preferably to temperatures above 35.degree. C., in particular to temperatures above 25.degree. C., after being filled into the container (GB). , heated.
  • storage temperatures above the limits mentioned can occur if these are stored without a heating device, for example due to high outside temperatures and/or ambient temperatures are reached during storage and/or transport.
  • the process according to the invention can be carried out continuously or batchwise.
  • compositions (M) produced according to the invention are preferably one-component crosslinkable compositions.
  • the compositions (M) produced according to the invention can also be part of two-component crosslinking systems in which OH-containing compounds, such as water, are added in a second component.
  • compositions (M) produced according to the invention can be stored if water is excluded and can be crosslinked if water is present.
  • compositions (M) produced according to the invention can be used for all purposes for which crosslinkable compositions based on organosilicon compounds have also been used to date, such as, for example, for the production of shaped bodies by crosslinking and for the production of material composites.
  • the usual water content of air is sufficient for crosslinking the compositions (M) prepared according to the invention.
  • the compositions (M) of the invention are preferably crosslinked at room temperature. If desired, it can also be carried out at temperatures higher or lower than room temperature, for example at ⁇ 5° C. to 15° C. or at 30° C. to 50° C. and/or using water concentrations exceeding the normal water content of air will.
  • the moldings produced according to the invention preferably have a tear strength of at least 1.0 MPa, particularly preferably at least 1.5 MPa, measured in each case according to DIN EN 53504-S1.
  • the moldings produced according to the invention preferably have an elongation at break of at least 100%, particularly preferably at least 200%, measured in each case according to DIN EN 53504-S1.
  • the moldings produced according to the invention can be any moldings, such as seals, pressed articles, extruded profiles, coatings, impregnations, encapsulation, lenses, prisms, polygonal structures, laminate or adhesive layers.
  • Composite molded parts are to be understood here as meaning a uniform molded article made from a composite material which is composed of a crosslinked product of the compositions (M) according to the invention and at least one substrate such that there is a firm, permanent bond between the two parts.
  • composition (M) produced according to the invention can also be vulcanized between at least two identical or different substrates, for example in the case of adhesive bonds, laminates or encapsulations.
  • compositions (M) produced according to the invention can be used for all purposes for which compositions which can be stored in the absence of water and which crosslink to form elastomers when exposed to water at room temperature can be used.
  • the process according to the invention has the advantage that the compositions (M) according to the invention can be produced easily and, because the heating step is no longer necessary, also particularly quickly and with low energy consumption.
  • the method according to the invention also has the advantage that the masses (M) can be filled quickly into the respective containers for end use, since this filling can take place at viscosities that are significantly lower than at the time of the respective end use. This is particularly advantageous when highly viscous and/or highly thixotropic masses are required or at least desired for the final application.
  • crosslinkable compositions (M) produced according to the invention have the advantage that they are notable for very high storage stability and a high crosslinking rate.
  • crosslinkable compositions (M) produced according to the invention have the advantage that they have an excellent adhesion profile.
  • crosslinkable materials (M) produced according to the invention have the advantage that they are easy to process.
  • compositions (M) are carried out at a pressure of the surrounding Atmosphere, ie at 1013 hPa, and at room temperature, ie at 23 ° C, or at a temperature that occurs when the reactants come together at room temperature without additional heating or cooling.
  • the crosslinking of the compositions (M) is carried out at a relative humidity of 50%.
  • all parts and percentages are by weight.
  • M n average molar mass
  • a stabilizer mixture containing a Hindered Amine Light Stabilizer (HALS) and a UV absorber commercially available under the name GENIOSIL® Stabilizer F from Wacker Chemie AG, D-Munich
  • 20 g of vinyltrimethoxysilane commercially available at of the designation GENIOSIL® XL 10 from Wacker Chemie AG, D-Munich
  • 2 g of dioctyltin dilaurate commercially available under the name TIB Kat 216 from TIB Chemicals AG, D-Mannheim
  • N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF 9 from Wacker Chemie AG, D-Munich) are mixed for 2 minutes with a bar mixer at 600 rpm min and 1000 rpm stirred in with the dissolver.
  • GENIOSIL® GF 9 from Wacker Chemie AG, D-Munich
  • the mixture is homogenized for 1 minute at 600 rpm with the bar mixer and for 1 minute at 200 rpm with the bar mixer at a pressure of about 100 mbar and stirred without bubbles.
  • the mass obtained in this way is filled into 310 ml PE cartridges, sealed airtight and stored for 3 weeks at 23° C. before the examination.
  • Example 2 The procedure is as described in Example 1, except that the material obtained, which has been stirred without bubbles, is used directly in the investigations described in Example 3 without any storage.
  • Example 2 The procedure is as described in Example 1, except that the finished cartridge is first stored at 80° C. for 3 h and then at 23° C. for 3 weeks before the examination.
  • Example 2 The procedure is as described in Example 1, except that the finished cartridge is first stored at 110° C. for 3 h and then at 23° C. for 3 weeks before the examination.
  • Example 3 Determination of the Properties of the Samples from Examples 1 and 2 and Comparative Examples (VI) to (V4) skin formation time (HTO)
  • the crosslinkable compositions obtained in the examples are applied to PE film in a layer 2 mm thick and stored under standard conditions (23° C. and 50% relative atmospheric humidity). During curing, the formation of a skin is tested every 5 minutes. To do this, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to your finger, a skin has not yet formed. If no more sample sticks to the finger, a skin has formed and the time is noted. The results are in Table 1.
  • the Shore A hardness is determined according to DIN EN 53505.
  • the tear strength is determined according to DIN EN 53504-S1.
  • the elongation at break is determined according to DIN EN 53504-S1.
  • the 100% module is determined according to DIN EN 53504-S1.
  • the results are in Table 1.
  • the amount of viscosity at 0.1% deformation is determined according to DIN 54458 at 25.degree.
  • the amount of viscosity at 100% deformation is determined according to DIN 54458 at 25.degree.
  • compositions according to the invention even without thermal treatment, develop thixotropic properties during the length of storage according to the invention, which are in no way inferior to the properties of thermally treated compositions and in some cases are even superior.
  • Comparative Examples VI and V2 show that the material according to the invention, if it is filled into a container for the final application, e.g. a cartridge, within 24 hours of its production, at the time of filling both at high and has a significantly lower viscosity at low shear than at the time of its application, which takes place only after the storage period according to the invention.
  • cyclohexane -1,2-dicarboxylic acid diisononyl ester commercially available under the name "Hexamoll DINCH” from BASF SE; D-Ludwigshafen
  • a plasticizer 261 g of a stearic acid-coated calcium carbonate with an average particle diameter (D50%) of about 2, 0 ⁇ m (commercially available under the name Omyabond 520 from Omya, D-Cologne), 261 g of an ultra-fine, fatty acid-coated calcium carbonate with a primary particle size of approx.
  • the mixture is homogenized for 1 minute at 600 rpm with the bar mixer and for 1 minute at 200 rpm with the bar mixer at a pressure of about 100 mbar and stirred without bubbles.
  • the mass obtained in this way is filled into 310 ml PE cartridges, sealed airtight and stored for 3 weeks at 23° C. before the examination.
  • Example 5 Determination of the properties of the samples from example 4.
  • composition according to the invention from example 3 develops thixotropic properties even without thermal treatment during the length of storage according to the invention, which are in no way inferior to the properties of thermally treated composition in comparative example V6.

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Abstract

L'invention se rapporte à un procédé de production de matériaux réticulables (M) par mélange de (A) 100 % en poids de composés de formule Y-[(CR1 2)b-SiRa(OR2)3-a]x, dans laquelle les groupes et les indices ont les significations indiquées dans la revendication 1 ; (B) 0,1 à 75 % en poids d'au moins un agent thixotrope choisi parmi les amides d'acides gras, les cires de polyamide, les dérivés de cire de polyamide, l'huile de ricin hydratée, les dérivés d'huile de ricin hydratée, les amides de polyester, les polyurées, les polyéthylènes oxydés et les savons métalliques, et éventuellement des constituant supplémentaires ; éventuellement, par mise en œuvre d'étapes de traitement successives supplémentaires ; et par stockage ultérieur du mélange (M) obtenu de cette manière. L'invention est caractérisée en ce que la période allant du début de l'étape de mélange pour (A) et (B) à la fin du processus de stockage du matériau réticulable (M) est d'au moins 7 jours, et en ce que toutes les étapes de procédé sont mises en œuvre à des températures inférieures à 80 °C pendant la période susmentionnée.
EP20838918.9A 2020-12-15 2020-12-15 Procédé de production de matériaux réticulables à base de polymères à terminaison organyloxysilane Pending EP4263717A1 (fr)

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DE19908562A1 (de) 1998-03-25 1999-10-07 Henkel Kgaa Polyurethan und polyurethanhaltige Zubereitung
DE10330288A1 (de) 2003-07-04 2005-02-03 Consortium für elektrochemische Industrie GmbH Alkoxysilanterminierte Prepolymere
DE10355318A1 (de) 2003-11-27 2005-06-23 Wacker-Chemie Gmbh Verfahren zur Herstellung von organyloxysilylterminierten Polymeren
WO2006006620A1 (fr) 2004-07-14 2006-01-19 Kaneka Corporation Processus de production d’une composition résineuse curable
DE102005029169A1 (de) 2005-06-23 2006-12-28 Wacker Chemie Ag Kontinuierliche polymeranaloge Umsetzung von reaktiven Silanmonomeren mit funktionalisierten Polymeren
US20120225983A1 (en) * 2009-11-05 2012-09-06 Jochen Wagner Adhesives and sealants comprising esters based on 2-propylheptanol
DE102011081264A1 (de) 2011-08-19 2013-02-21 Wacker Chemie Ag Vernetzbare Massen auf Basis von organyloxysilanterminierten Polymeren
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CN116802234A (zh) 2023-09-22

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