EP3976691A1 - Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels - Google Patents

Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels

Info

Publication number
EP3976691A1
EP3976691A1 EP21716452.4A EP21716452A EP3976691A1 EP 3976691 A1 EP3976691 A1 EP 3976691A1 EP 21716452 A EP21716452 A EP 21716452A EP 3976691 A1 EP3976691 A1 EP 3976691A1
Authority
EP
European Patent Office
Prior art keywords
optionally substituted
group
polyols
methyl
butyl
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
EP21716452.4A
Other languages
German (de)
English (en)
Inventor
Klaus Langerbeins
Michael Senzlober
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.)
Nitrochemie Aschau GmbH
PolyU GmbH
Original Assignee
PolyU GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PolyU GmbH filed Critical PolyU GmbH
Publication of EP3976691A1 publication Critical patent/EP3976691A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

Definitions

  • the invention relates to a process for the production of polymeric, organosilane-containing compounds by reacting isocyanate-reactive compounds (P) with special silane compounds (S), the polymeric compounds (V) obtainable therefrom, and their use in the production of unfoamed polymers, flexible foams and / or two-component (2K) systems as well as their use in the CASE area (coatings, adhesives, seals and elastomers), furniture, mattresses, car seats, sealing or REst R acoustic materials, for the insulation of district heating pipes, tanks and pipelines as well as for Manufacture of all types of cooling devices.
  • P isocyanate-reactive compounds
  • S special silane compounds
  • V polymeric compounds
  • urethane reaction of isocyanates with hydroxy-functionalized compounds has long been known.
  • hydroxy-functionalized compounds e.g. polyols
  • long-chain polyurethanes chain extension
  • crosslinked polyurethanes crosslinking
  • Polyurethanes can have different properties depending on the choice of isocyanate and polyol.
  • the later properties are essentially determined by the polyol component, since in order to achieve the desired properties it is usually not the isocyanate component that is adapted (chemically changed), but the polyol component.
  • Mechanical properties can be influenced depending on the chain length and number of branches in the polyol.
  • polyester polyols in addition to the usual polyether polyols leads to better stability. The reason for this is that polyester polyols have a higher melting point and thus solidify when the polyurethane is applied. Polyurethane formation requires at least two different monomers, in the simplest case a diol and a diisocyanate.
  • isocyanates are harmful to the environment and health. They can trigger allergies and are suspected of causing cancer. Respiratory diseases caused by isocyanates can be recognized as occupational diseases (BK1315). Employees who are regularly exposed to isocyanates must take part in preventive occupational health examinations. In order to avoid inhalation exposure, the low molecular weight representatives are often replaced by low-volatility derivatives in many applications.
  • silanes are known as adhesion promoters and crosslinkers. Different functional silanes were mainly used for this in silicone chemistry.
  • Tri-alkoxy-functional silanes are also used under the name Dynasylan ® (Evonik) for crosslinking polymers such as silicones, polyethers, epoxy resins, polyethylene, polyacrylate or polyurethane. The networking takes place in Presence of moisture instead.
  • the tri-alkoxy-functional vinyl silane vinyltrimethoxysilane is available, for example, for cross-linking and chain extension of OH-functional compounds under the name Silquest A- 171 ® (Momentive).
  • EP 3309 187 A1 also describes a moisture-curing composition, alkoxysilanes being used.
  • EP 1 509 533 A1 discloses a method for producing organic polyol silanes by combining an alkoxysilane with one or more organic polyols.
  • alkoxy-functional silanes alkoxysilanes
  • hydroxy-functional compounds such as polyols
  • reaction temperatures > 100 ° C.
  • the task is to link isocyanate-reactive compounds, such as hydroxy-functional compounds, isocyanate-free, either in a chain extension and / or in the crosslinking of these compounds.
  • the invention thus provides a process for the production of polymeric compounds (V) with the formation of Si-OC bonds by reacting isocyanate-reactive compounds (P) with at least one silane compound (S) of the general formula Si (R) m (R a ) 4-m characterized in that
  • R a is selected independently of one another from the group consisting of • a hydroxycarboxylic acid ester residue with the general structural formula
  • R b independently of one another is H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group or an optionally substituted C4 to C14 aryl group,
  • R c independently of one another, denotes H or an optionally substituted, straight-chain or branched C1- to C16-alkyl group or an optionally substituted C4- to C14-aryl group,
  • R d denotes H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group, an optionally substituted C5 to C15 aralkyl group or an optionally substituted C4 to C14 aryl group,
  • R e is a carbon atom or an optionally substituted saturated or partially unsaturated cyclic ring system with 4 to 14 carbon atoms or an optionally substituted aromatic group with 4 to 14 carbon atoms, and n is an integer from 1 to 10,
  • R n independently of one another is H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group or an optionally substituted C4 to C14 aryl group,
  • R ° independently of one another, denotes H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group or an optionally substituted C4 to C14 aryl group,
  • R p and R q independently of one another are H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group, an optionally substituted C5 to C15 aralkyl group or an optionally substituted C4 to C14 - aryl group, means
  • R r is a carbon atom or an optionally substituted saturated or partially unsaturated cyclic ring system with 4 to 14 carbon atoms or an optionally substituted aromatic group with 4 to 14 carbon atoms, and p is an integer from 1 to 10, an oxime radical with the general structural formula (C),
  • R 9 and R h independently of one another are H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group or an optionally substituted C5 to C15 -Aralkyl distr, mean, a carboxamide radical -N (R ') - C (0) -R j , where
  • R j H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14
  • Aryl group or an optionally substituted C5 to C15 aralkyl group is optionally substituted
  • R f H or an optionally substituted, straight-chain or branched C1- to C16-alkyl group, an optionally substituted C4- to C14-
  • Aryl group or an optionally substituted C5 to C15 aralkyl group is optionally substituted.
  • the silane compound (S) is oligomeric or polymeric in nature. This means that such a silane compound (S) is bound to an oligomeric or polymeric backbone. This happens preferably by splitting off at least one of the radicals R a and / or R via the silicon atom or via an oxygen atom on the silicon atom.
  • the oligomeric or polymeric silane compounds (S) also contain at least one radical R a , preferably at least two radicals R a .
  • the radicals R and R a are defined as above.
  • the silane compound (S), whether taken by itself or incorporated in oligomers or polymers, can also have radicals R a , where R a is independently selected from the group consisting of a hydroxycarboxylic acid ester radical with the general structural formula (A '),
  • R b and R c do not mean H
  • R b is not H and R c is not methyl
  • R b is not methyl and R c is not H
  • R e represents a carbon atom.
  • the present invention relates to the polymeric compounds (V) obtainable by the process according to the invention.
  • the chain-extended polymeric compounds (V) can optionally be reacted in a subsequent step in a further reaction with silane compounds (S) or by means of isocyanates to form crosslinked polymeric compounds (V).
  • Suitable isocyanates are diisocyanates, triisocyanates or mixtures thereof, in particular IPDI, MDI, HDI, TDI, isocyanates derived therefrom, or mixtures thereof.
  • chain-extended polymeric compounds (V) likewise prepared beforehand in a process according to the invention, can be reacted with isocyanatosilanes to give silylated polymeric compounds (SiV).
  • the properties of polymeric compounds (V) can thus be further advantageously influenced and / or improved.
  • the invention therefore allows a process for the production of polymeric compounds (V), for example for use in the area of non-foamed materials Providing polymers or flexible foams as well as for the CASE area (coatings, adhesives, seals and elastomers), whereby the use of isocyanates can be dispensed with.
  • reaction temperature can advantageously be lowered while still ensuring good reactivity.
  • an advantageous conversion can already be recorded at 80 ° C. or even at room temperature.
  • the mechanical properties of the resulting polymer materials can also be influenced by using polymeric compounds (V) obtainable by the process according to the invention.
  • the non-foamed polymer materials produced with the polymeric compounds (V) obtainable according to the invention are softer compared to isocyanate-crosslinked polymer materials and therefore have a lower Shore A hardness.
  • the invention thus also relates to the use of polymeric compounds, obtainable by the process according to the invention, for providing polymer materials - non-foamed polymer materials with
  • the silane compound (S), as defined above is preferably used in a deficit relative to (P), based on the amounts used in moles.
  • isocyanate-reactive compound (P) For chain extension of the isocyanate-reactive compound (P), preference is given to the compounds (S) and (P) in a molar ratio (mol) of at least 1: 1.1, preferably of at least 1: 2, particularly preferably of at least 1: 3, very particularly preferably from 1: 2.2 or 1: 3.3 and in particular from 1: 4.2. Also in particular in the range from 1: 1.2 to 1: 2.5.
  • the silane compound (S), as defined above is preferably used in equal parts as (P) or in excess to (P), based on the amounts used in moles.
  • the isocyanate-reactive compound (P) For crosslinking the isocyanate-reactive compound (P), preference is given to the compounds (S) and (P) in a molar ratio (mol) of at least 1: 1 or 1.1: 1, preferably of at least 1.4: 1, particularly preferably of at least 1.5: 1 to 3: 1 are used and very particularly preferably used in a molar ratio range of 1.5: 1 to 6: 1.
  • an acetoxy-silane to (P) is used in a molar ratio of 1: 3 or if an oxime-silane to (P) is present in a molar ratio range of 1.5: 1 to 3: 1.
  • silane compounds (S) are functionalized silanes (silanes for short) which have at least two groups which can be split off by hydrolysis. Due to their reactivity, they can alternatively be referred to as “crosslinkers”, “hardeners” or “silane crosslinkers”. Depending on the chemical nature of the silane compound (S), it can be further specified with a prefix, e.g. "Oxime-Silane".
  • polymeric compounds are any reaction products which can be obtained by the process according to the invention.
  • the generic term includes both chain-extended isocyanate-reactive compounds and crosslinked isocyanate-reactive compounds.
  • Chain extension generally means a process or a reaction, whereby monomers, oligomers and / or polymers either connect directly to one another and thus become “longer” or are connected to one another through a linking connection and also become “longer”.
  • a chain extension of a compound for example a hydroxy-functionalized compound (P) such as a polyol, increases the molecular weight. Furthermore, this can also lead to an increase in the viscosity of these compounds.
  • Oxime silanes or “oxime crosslinkers” are crosslinkers with the general formula
  • a mixture of at least two different silane compounds can also be used and reacted.
  • a combination of an acetate-silane and an oxime-silane or a combination of two different oxime-silanes can be used.
  • the use of mixtures of silane compounds in the crosslinking of hydroxy-functionalized polymers (polyols) can have advantageous properties. For example, the proportion of a toxicologically questionable, malodorous and / or expensive silane compound can be reduced.
  • the combination of different silane compounds can influence the properties of the resulting polymeric compounds (V). Because of the different Reactivities of the silane compounds can thus be controlled accordingly, the material properties of the resulting polymer materials.
  • Suitable silane compounds (S) for the purposes of the invention are silanes of the general formula Si (R) m (R a ) 4-m , where each R and R a are as defined above.
  • silane compounds (S) are oxime silanes, acetoxy silanes or lactatosilanes or mixtures thereof:
  • the oxime residue is bonded to the silicon atom via the oxygen atom of the flydroxy group.
  • R is independently selected from the group consisting of vinyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, isobutyl -, 2-ethylhexyl or phenyl and
  • R a independently selected from an oxime radical of the general structure (C), where
  • R independently selected from the group consisting of vinyl, methyl, ethyl or n-propyl and
  • R a independently selected from an oxime radical of the general structure (C), where
  • R 9 and R h are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl and phenyl
  • R 9 and R h are preferably selected, independently of one another, from the group consisting of methyl, ethyl and n-propyl.
  • R 9 is n-propyl- and R h is methyl-;
  • R 9 is ethyl- and R h is methyl-;
  • R 9 is methyl and R h is isobutyl
  • R 9 and R h are each methyl or R 9 and R h are each ethyl.
  • silane compounds (S) tetra (2-pentanonoximojsilane, tetra (2-butanonoximo) silane, tetra (2-propanonoximo) silane, tetra (3-pentanonoximo) silane or tetra (4-methyl-2-pentanonoximo) silane are very particularly preferred .
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl, phenyl, Methoxy or ethoxy,
  • R 9 and R h are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, vinyl and phenyl
  • R is preferably selected from the group consisting of methyl, ethyl, vinyl, phenyl and methoxy, particularly preferably from vinyl, methyl, phenyl and / or methoxy as well
  • R 9 and R h are particularly preferably independently selected from the group consisting of methyl, ethyl, n-propyl, and isobutyl
  • R is vinyl, R 9 is n-propyl and R h is methyl are very particularly preferred;
  • R is methyl-, R 9 is n-propyl- and R h is methyl-;
  • R is ethyl-, R 9 is n-propyl- and R h is methyl-;
  • R is ethyl-, R 9 is n-propyl- and R h is methyl-;
  • R is n-propyl-, R 9 is n-propyl- and R h is methyl-;
  • R is phenyl-, R 9 is n-propyl- and R h is methyl-;
  • R is vinyl-, R 9 and R h are each methyl-;
  • R is methyl-, R 9 and R h are each methyl-;
  • R is ethyl-, R 9 and R h are each methyl-;
  • R is n-propyl-, R 9 and R h are each methyl-;
  • R is phenyl-, R 9 and R h are each methyl-;
  • R is vinyl-, R 9 is ethyl- and R h is methyl-;
  • R is methyl-, R 9 is ethyl- and R h is methyl-;
  • R is ethyl-, R 9 is ethyl- and R h is methyl-;
  • R is n-propyl-, R 9 is ethyl- and R h is methyl-;
  • R is phenyl-, R 9 is ethyl- and R h is methyl-; R is vinyl-, R 9 and R h are each ethyl-;
  • R is methyl-, R 9 and R h are each ethyl-;
  • R is ethyl-, R 9 and R h are each ethyl-;
  • R is n-propyl-, R 9 and R h are each ethyl-;
  • R is phenyl-, R 9 and R h are each ethyl-;
  • R is vinyl-, R 9 is methyl- and R h is isobutyl-;
  • R is methyl-, R 9 is methyl- and R h is isobutyl-;
  • R is ethyl-, R 9 is methyl- and R h is isobutyl-;
  • R is n-propyl-, R 9 is methyl- and R h is isobutyl- or
  • R is phenyl-, R 9 is methyl- and R h is isobutyl-.
  • silane compounds of structure (C2) have positive properties for sealant formulations.
  • the resulting cured sealants have improved mechanical properties - Shore A hardnesses of at least 3 and an elongation at break of at least 40%. Sealants with these silane compounds also have a colorless and transparent appearance.
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl, phenyl, Methoxy or ethoxy and
  • R 9 and R h are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, vinyl and phenyl
  • R is preferably selected from the group consisting of methyl, ethyl, vinyl, phenyl and methoxy, particularly preferably from vinyl, methyl, phenyl and / or methoxy and
  • R 9 and R h are preferably selected independently of one another from the group consisting of methyl, ethyl, n-propyl, and isobutyl, particularly preferably from the group consisting of methyl, ethyl and n-propyl
  • R is independently vinyl or methyl, R 9 and R h are each methyl;
  • R is independently vinyl or methyl, R 9 is ethyl and R h is methyl;
  • R is independently vinyl or methyl, R 9 is n-propyl and R h is methyl;
  • R is independently vinyl or methyl, R 9 and R h are each ethyl;
  • R is independently vinyl or methoxy, R 9 and R h are each methyl;
  • R is independently vinyl or methoxy, R 9 is ethyl and R h is methyl;
  • R is independently vinyl or methoxy, R 9 is n-propyl and R h is methyl;
  • R is independently vinyl or methoxy, R 9 and R h are each ethyl;
  • R is independently vinyl or phenyl, R 9 and R h are each methyl;
  • R is independently vinyl or phenyl, R 9 is ethyl and R h is methyl;
  • R is independently vinyl or phenyl, R 9 is n-propyl and R h is methyl or
  • R is independently vinyl or phenyl, R 9 and R h are each ethyl.
  • silane compounds (S) methylvinyl-di- (2-propanonoximojsilane, methylvinyl-di- (2-butanonoximo) silane, methylvinyl-di- (2- pentanonoximojsilane, methylvinyl-di- (3-pentanonoximo) silane, methoxyvinyl- di- (2-propanonoximojsilane, methoxyvinyl-di- (2-butanonoximo) silane, methoxyvinyl-di- (2-pentanonoximojsilane, methoxyvinyl-di- (3-pentanonoximo) silane, phenylvinyl-di- (2-propanonoximojsilane, phenylvinyl-di - (2-butanonoximo) silane, phenylvinyl-di- (2-pentanonoximoj
  • Silane compounds (S) with the general structural formula (C2) are very particularly preferred in the process according to the invention for preparing crosslinked polymeric compounds (V).
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl, phenyl, Methoxy or ethoxy,
  • R f is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, vinyl or phenyl and m is an integer from 0 to 2 is.
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, phenyl or vinyl, as well as
  • silane compounds (S) vinyltriacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane or phenyltriacetoxysilane are particularly preferred. It is known that such acetoxy-silanes can have particularly positive properties for sealant formulations, in particular with regard to the toxicological harmlessness.
  • the method comprises a combination of the silane compounds (S) and vinyltriacetoxysilane
  • the method comprises a combination of the silane compounds (S) methyltriacetoxysilane and ethyltriacetoxysilane.
  • the method comprises a combination of the silane compounds (S) and ethyltriacetoxysilane
  • the process comprises only vinyltriacetoxysilane as the silane compound (S).
  • this comprises
  • this comprises
  • this comprises
  • acetoxysilanes as the silane compound (S) in the process according to the invention for producing chain-extended polymeric compounds (V) is very particularly preferred.
  • R a stands for a hydroxycarboxylic acid ester radical with the general structural formula ( A) and as defined herein in which the oxygen atom of the hydroxy group is bonded to the silicon atom and R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl, phenyl, Methoxy or ethoxy,
  • R d H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group, an optionally substituted C5 to C15 aralkyl group or an optionally substituted C4 to C14 aryl group,
  • R e is a carbon atom and m is an integer from 0-2.
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, phenyl or vinyl, as well as
  • lactatosilanes as the silane compound (S) in the process according to the invention for the production of chain-extended polymeric compounds (V) produces stable products.
  • the reaction in the process according to the invention using lactatosilanes is slowed down (e.g. in comparison with the use of oxime silanes) and therefore requires higher reaction temperatures (> 90 ° C., preferably> 100 ° C. and longer reaction times (> 4h, preferably between 4 and 60 hours).
  • the silane compound (S) is selected from the group consisting of oxime crosslinkers such as vinyl-tris (2-pentanonoximo) silane, methyl-tris (2-pentanonoximo) silane, vinyl-tris (2 - propanonoximo) silane, methoxyvinyl-di- (2-propanonoximo) silane and dimethoxyvinyl- (2-propanonoximo) silane or mixtures thereof or from acetate crosslinkers such as methyltriacetoxysilane or ethyltriacetoxysilane or from lactatosilanes such as vinyltris (ethyllactato) silane or mixtures thereof .
  • oxime crosslinkers such as vinyl-tris (2-pentanonoximo) silane, methyl-tris (2-pentanonoximo) silane, vinyl-tris (2 - propanonoximo) silane, methoxyvinyl-d
  • the silane compound (S) is selected from the group consisting of vinyl-tris (2-pentanonoximo) silane, methyl-tris (2-pentanonoximo) silane, vinyl-tris (2-propanonoximo) silane, methoxyvinyl -di (2-propanonoximo) silane, dimethoxyvinyl- (2-propanonoximo) silane and
  • alkyl group it is meant a saturated hydrocarbon chain.
  • alkyl groups have the general formula —C n H 2n + i .
  • the term “C1 to C16 alkyl group” refers in particular to a saturated hydrocarbon chain with 1 to 16 carbon atoms in the chain. Examples of C1 to C16 alkyl groups are methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and ethylhexyl.
  • a “C1 to C8 alkyl group” denotes in particular a saturated hydrocarbon chain with 1 to 8 carbon atoms in the chain. In particular, alkyl groups can also be substituted, even if this is not specifically stated.
  • Straight chain alkyl groups refer to alkyl groups that contain no branches. Examples of straight-chain alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
  • Branched alkyl groups denote alkyl groups that are not straight-chain, that is to say in which the hydrocarbon chain in particular has a fork.
  • Examples of branched alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl, 2-methylbut -2-yl-, neopentyl-, ethylhexyl-, and 2-ethylhexyl.
  • alkenyl groups refer to hydrocarbon chains that contain at least one double bond along the chain.
  • an alkenyl group with a double bond has in particular the general formula -C n H 2n -i.
  • alkenyl groups can also have more than one double bond.
  • C2 to C16 alkenyl group refers in particular to a hydrocarbon chain with 2 to 16 carbon atoms in the chain.
  • the number of hydrogen atoms varies depending on the number of double bonds in the alkenyl group. Examples of alkenyl groups are vinyl, allyl, 2-butenyl and 2-flexenyl
  • Straight-chain alkenyl groups refer to alkenyl groups that do not contain any branches. Examples of straight-chain alkenyl groups are vinyl, allyl, n-2-butenyl and n-2-flexenyl.
  • Branched alkenyl groups denote alkenyl groups which are not straight-chain, in which the hydrocarbon chain in particular has a fork. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl and 2-ethyl-2-pentenyl
  • 'Aryl groups' denote monocyclic (e.g. phenyl), bicyclic (e.g. indenyl, naphthalenyl, tetrahydronapthyl, or tetrahydroindenyl) and tricyclic (e.g. fluorenyl, tetrahydrofluorenyl, anthracenyl, or tetrahydroanthracenyl) Ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.
  • a C4 to C14 aryl group refers to an aryl group having 4 to 14 carbon atoms.
  • Aryl groups can in particular also be substituted, even if this is not specifically stated.
  • aromatic group denotes cyclic, planar hydrocarbons with an aromatic system.
  • An aromatic group with 4 to 14 carbon atoms denotes in particular an aromatic group which contains 4 to 14 carbon atoms.
  • the aromatic group can in particular be monocyclic, bicyclic or tricyclic.
  • An aromatic group can also contain 1 to 5 heteroatoms selected from the group consisting of N, O and S. Examples of aromatic groups are benzene, naphthalene, anthracene, phenanthrene, furan, pyrrole, thiophene, isoxazole, pyridine and quinoline, the necessary number of hydrogen atoms being removed in each of the above examples to enable inclusion in the corresponding structural formula.
  • a "cycloalkyl group” refers to a hydrocarbon ring that is not aromatic.
  • a cycloalkyl group with 4 to 14 carbon atoms denotes a non-aromatic hydrocarbon ring with 4 to 14 carbon atoms.
  • Cycloalkyl groups can be saturated or partially unsaturated. Saturated cycloalkyl groups are not aromatic and also have no double or triple bonds. In contrast to saturated cycloalkyl groups, partially unsaturated cycloalkyl groups have at least one double or triple bond, although the cycloalkyl group is not aromatic. Cycloalkyl groups can in particular also be substituted, even if this is not specifically stated.
  • aralkyl group means an alkyl group substituted by an aryl group.
  • a “C5 to C15 aralkyl group” refers in particular to an aralkyl group having 5 to 15 carbon atoms, both the carbon atoms of the alkyl group and the aryl group being contained therein. Examples of aralkyl groups are benzyl and phenylethyl. Aralkyl groups can in particular also be substituted, even if this is not specifically stated.
  • a "cyclic ring system” refers to a hydrocarbon ring that is not aromatic.
  • a cyclic ring system with 4 to 14 carbon atoms denotes a non-aromatic hydrocarbon ring system with 4 to 14 carbon atoms.
  • a cyclic ring system can consist of a single hydrocarbon ring (monocyclic), two hydrocarbon rings (bicyclic) or of three hydrocarbon rings (tricyclic).
  • can cyclic ring systems also contain 1 to 5 heteroatoms, preferably selected from the group consisting of N, O, and S.
  • saturated cyclic ring systems are not aromatic and also have no double or triple bonds.
  • saturated cyclic ring systems are cyclopentane, cyclohexane, decalin, norbornane and 4H-pyran, the necessary number of hydrogen atoms being removed in each of the aforementioned examples to enable inclusion in the corresponding structural formula.
  • R * is a cyclic ring system with 6 carbon atoms, in particular cyclohexane
  • two hydrogen atoms would be removed from the cyclic ring system, in particular from cyclohexane, in order to allow inclusion in the structural formula.
  • N denotes in particular nitrogen.
  • O denotes in particular oxygen, unless otherwise stated.
  • S denotes sulfur, unless otherwise stated.
  • “Optionally substituted” means that hydrogen atoms in the corresponding group or in the corresponding radical can be replaced by substituents.
  • Substituents can in particular be selected from the group consisting of C1 to C4 alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen, fluorine, chlorine, bromine, iodine and hydroxy -, Amino, alkylamino, dialkylamino, C1 to C4 alkoxy, phenoxy, benzyloxy, cyano, nitro and thio If a group is designated as optionally substituted, 0 to 50, especially 0 to 20 hydrogen atoms of the group may be replaced by substituents. When a group is substituted, at least one hydrogen atom is replaced by a substituent.
  • Alkoxy refers to an alkyl group attached to the main carbon chain through an oxygen atom.
  • “Tear strength” is one of the mechanical properties of polymers that can be determined using various test methods. It is the quotient (o R ) of the force FR measured at the moment of tearing and the initial cross-section A 0 of the test specimen.
  • the "elongation at break” is the ratio of the change in length to the initial length after the test specimen has broken. It expresses the ability of a material to withstand changes in shape without cracking. It is the quotient (s R ) of the change L R - L 0 measured at the moment of tearing, the measured length L R and the initial measured length L 0 of the test specimen.
  • the "tension value” is the quotient (s,) of the tensile force F, which is present when a certain elongation is reached, and the initial cross-section A 0
  • the tensile strength, elongation at break and stress values in the tensile test are determined in accordance with DIN 53504: 2017-03.
  • “Shore hardness” is a common indication of the hardness of an elastic material. It is tested using a Shore hardness tester (durometer) comprising a spring-loaded pin made of hardened steel. Its depth of penetration into the material to be tested is a measure of the Shore hardness, which is measured on a scale from 0 Shore (2.5 millimeter penetration depth) to 100 Shore (0 millimeter penetration depth). So a high number means great hardship. Depending on the truncated cone used for the measurement, which presses into the sample, a distinction is made between Shore A, Shore B, Shore C and Shore D hardness.
  • the “Shore A” value is given for elastomers after measurement with a needle with a blunt tip.
  • the end face of the truncated cone has a diameter of 0.79 millimeters, the opening angle is 35 °.
  • the value 0 for the Shore A hardness corresponds roughly to the strength of gelatine, the value 10 to the strength of a gummy bear. Values of 50-70 correspond to the strength of car tires and the Shore A value of 100 describes the hardness of hard plastic.
  • the Shore A hardness is determined according to ASTM D2240-15.
  • “Sealants” or “sealing compounds” denote elastic substances, applied in liquid to viscous form or as flexible profiles or strips, for sealing a surface, in particular against water, gases or other media.
  • adheresive refers to materials that connect wing parts through surface adhesion and / or internal strength (cohesion). from This term includes in particular glue, paste, dispersion, solvent, reaction and contact adhesives.
  • Coating agents are all means for coating a surface.
  • potting compounds or also “cable potting compounds” are compounds to be processed hot or cold for potting cables and / or cable accessories.
  • room temperature is understood to mean a temperature range of 20-25 ° C.
  • the process takes place at temperatures from 20 to 100.degree. C. or from 20 to 40.degree. C., preferably at temperatures from 75 to 85.degree. C. or from 20 to 35.degree.
  • catalyst refers to a substance that lowers the activation energy of a certain reaction and thereby increases the rate of the reaction or enables a reaction at all.
  • Catalysts can optionally be used in the process according to the invention.
  • the following group represents suitable catalysts, consisting of metal silsesquioxanes such as heptaisobutyl POSS titanium (IV) ethoxide (TiPOSS), heptaisobutyl POSS tin (IV) ethoxide (SnPOSS) or mixtures thereof, tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate Tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyltitanat, tetra-sec-butyl titanate, tetraoctyl titanate, tetra- (2-ethylhexyl) titanate, Dialkyltitanate ((R # 0) 2 Ti0 2, wherein R # is, for example
  • Aluminum trisalkylates such as aluminum triisopropoxide, aluminum sec-butyate;
  • Aluminum acetylacetonate chelates such as aluminum tris (acetylacetonate) and
  • organotin compounds such as dibutyltin dilaurate (
  • Metal-silsesquioxanes are chain-like metal-siloxane-silanol (-at) compounds which are linear, branched and / or form a cage.
  • a “cage” or an oligomeric or polymeric “cage structure” is understood in the context of the invention as a three-dimensional arrangement of the chain-like metal-siloxane-silanol (-at) compound, with individual atoms of the chain forming the corner points of a polyhedral basic structure of the connection. At least two surfaces are spanned by the atoms that are linked to one another, creating a common intersection.
  • a cube-shaped basic structure of the connection is formed.
  • a single cage structure or a singular cage structure that is, a connection that is defined by an isolated cage.
  • nuclear describes the nuclear nature of a compound, how many metal atoms it contains.
  • a mononuclear compound has one metal atom, whereas a polynuclear or binuclear compound has two metal atoms within a compound.
  • the metals can be linked directly to one another or linked via their substituents.
  • the metal siloxane silanol (-ate) compound (I) represents a single-core single-cage structure, whereby
  • X 4 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th , 8th, 10th and 11th subgroups and metals of the 1st, 2nd, 3rd, 4th and 5th main group, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V , Fe, Pt, Cu, Ga, Sn and Bi; is particularly preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, very particularly preferably Ti or Sn.
  • hydroxy-functional compound or "hydroxy-functionalized compound” describes a chemical compound which one or more OH- Identifies groups.
  • the term includes hydroxy-functionalized polymers, hydroxy-functionalized oligomers and hydroxy-functionalized monomers.
  • isocyanate-reactive compounds are those which can react with an isocyanate. These compounds can have one or more NH, OH or SH functions.
  • the isocyanate-reactive compounds include, in particular, the class of hydroxy-functional compounds.
  • Polyols are hydroxy-functional compounds, especially hydroxy-functional polymers.
  • Suitable polyols for the production of polyurethane polymers are in particular polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
  • Polyethers represent a class of polymers. They are long-chain compounds comprising at least two identical or different ether groups. According to the invention, the term polyethers is also used when the polymeric ether groups are interrupted by other groups (for example by polymerized / built-in isocyanates or further polymer or oligomer units of other monomer origins).
  • polyether polyols also called polyoxyalkylene polyols or oligoetherols
  • polyoxyalkylene polyols or oligoetherols are those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule with two or more active hydrogen atoms such as water, ammonia or compounds with several OH or NH groups such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and Tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octaned
  • polyoxyalkylene polyols which have a low degree of unsaturation (measured according to ASTM D-2849-69: 1980 and stated in milliequivalents of unsaturation per gram of polyol (mEq / g)), produced for example with the help of so-called double metal cyanide complex catalysts ( DMC catalysts), as well as polyoxyalkylene polyols with a higher degree of unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates.
  • DMC catalysts double metal cyanide complex catalysts
  • anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates.
  • Polyoxyethylene polyols and polyoxypropylene polyols in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols, are particularly suitable.
  • polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation lower than 0.02 mEq / g and with a molecular weight in the range from 1000 to 30,000 g / mol, as well as polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols and polyoxypropylene triols with a molecular weight of 200 to 20,000 g / mol.
  • So-called ethylene oxide-terminated (“EOendcapped”, ethylene oxide-endcapped) polyoxypropylene polyols are also particularly suitable.
  • polyoxypropylene polyoxyethylene polyols that are obtained, for example, by further alkoxylating pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, after the polypropoxylation reaction has ended with ethylene oxide and thus have primary hydroxyl groups.
  • polyoxypropylene polyoxyethylene diols and polyoxypropylene polyoxyethylene triols are preferred.
  • hydroxyl-terminated polybutadiene polyols such as, for example, those which are prepared by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and their hydrogenation products.
  • styrene-acrylonitrile-grafted polyether polyols such as are commercially available, for example, under the trade name Lupranol® from Elastogran GmbH, Germany.
  • polyester polyols are polyesters which carry at least two hydroxyl groups and are produced by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • Polyester polyols which are produced from dihydric to trihydric alcohols such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol are particularly suitable , Glycerine, 1,1,1-trimethylolpropane or mixtures of the the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid,
  • dihydric to trihydric alcohols such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentan
  • Dodecanedicarboxylic acid maleic acid, fumaric acid, dimeric fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride or mixtures of the aforementioned acids, as well as polyester polyols from caprolactones such as, for example, e-lactones.
  • Polyester diols are particularly suitable, especially those made from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid or from lactones such as e-caprolactone and from ethylene glycol, diethylene glycol, neopentylene glycol, and neopentylene glycol , 1,6-hexanediol, dimer fatty acid diol and 1,4-cyclohexanedimethanol as dihydric alcohol.
  • polycarbonate polyols are those obtainable by reacting, for example, the abovementioned alcohols used to synthesize the polyester polyols with dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate or phosgene.
  • dialkyl carbonates such as dimethyl carbonate
  • diaryl carbonates such as diphenyl carbonate or phosgene.
  • Polycarbonate diols, in particular amorphous polycarbonate diols are particularly suitable.
  • polycarbonate diols or polyether-polycarbonate diols can be obtained by polymerizing propylene oxide with CO 2.
  • polystyrene resins are poly (meth) acrylate polyols.
  • polyhydroxy-functional fats and oils for example natural fats and oils, in particular castor oil, or so-called oleochemical polyols obtained by chemical modification of natural fats and oils, the epoxy polyesters obtained, for example, by epoxidizing unsaturated oils and subsequent ring opening with carboxylic acids or alcohols or epoxy polyethers, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils.
  • polyols which are obtained from natural fats and oils through degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example through transesterification or dimerization, of the degradation products obtained in this way or derivatives thereof.
  • Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized, for example, by hydroformylation and hydrogenation to give hydroxy fatty acid esters.
  • FAME methyl esters
  • polyhydrocarbon polyols also called oligohydrocarbonols
  • polyhydroxy-functional ethylene Propylene, ethylene-butylene or ethylene-propylene-diene copolymers such as those produced by Kraton Polymers, USA, for example, or polyhydroxy-functional copolymers made from dienes such as 1, 3-butanediene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or Isobutylene, or polyhydroxy-functional polybutadiene polyols, for example those which are produced by copolymerization of 1,3-butadiene and allyl alcohol and can also be hydrogenated.
  • polyhydroxy-functional acrylonitrile / butadiene copolymers such as those produced, for example, from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers, which are commercially available under the name Hypro® CTBN from Emerald Performance Materials, LLC, USA.
  • These likewise particularly preferred polyols have an average molecular weight of 250 to 40,000 g / mol, in particular 1,000 to 30,000 g / mol, and an average OFI functionality in the range from 1.6 to 3.
  • polyols are polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and
  • Polyoxypropylene polyoxyethylene polyol preferably polyoxyethylene diol
  • Polyoxypropylene diol polyoxyethylene triol
  • polyoxypropylene triol polyoxypropylene triol
  • Polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol are Polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol.
  • geeigenete polyols (68082-28- 0 CAS No .:) available ethylene glycol dimers available from the company Oleon under the Flandelsnamen Radialube ® 7662, fatty diol dimers (CAS No .: 147853-32-5) in from Oleon under the trade name Radianol ® 1990 and / or natural oil-based polyester polyols with an OFI number of ⁇ 40-55 mgKOFI / g available from Oleon under the trade name Radia ® 7294.
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, Pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerine, Pentaerythritol, sugar alcohols such as xylito
  • all of the above processes or compositions in the embodiments preferably have POSS-titanium (IV) -ethoxide (TiPOSS) in the production of polymeric compounds (V) instead of heptaisobutyl, but heptaisobutyl POSS-tin (IV) -ethoxide (SnPOSS) on or a mixture of both catalysts.
  • the process according to the invention or the composition according to the invention of all of the above combinations has a further catalyst selected from among metal-siloxane-silanol (ate) compounds, in particular heptaisobutyl POSS-titanium (IV) -ethoxide (TiPOSS) or heptaisobutyl POSS tin (IV) ethoxide (SnPOSS), dibutyl tin dilaurate (DBTL), or mixtures thereof.
  • a further catalyst selected from among metal-siloxane-silanol (ate) compounds, in particular heptaisobutyl POSS-titanium (IV) -ethoxide (TiPOSS) or heptaisobutyl POSS tin (IV) ethoxide (SnPOSS), dibutyl tin dilaurate (DBTL), or mixtures thereof.
  • Dibutyltin dilaurate can preferably be used as a second catalyst in the process according to the invention or in the composition according to the invention.
  • DBTL dibutyltin dilaurate
  • this / s includes additives from the group comprising one or more fillers selected from the group of inorganic and organic fillers, in particular natural, ground or precipitated calcium carbonates, which may optionally be mixed with fatty acids, in particular stearic acid, are coated, barite (barite), talc, quartz flour, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminum silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicas including highly dispersed silicas from pyrolysis processes, industrially produced soot , Graphite, metal powder such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres, one or more foaming agents from the group comprising citric acid with chalk, sodium hydrogen carbonate with disodium hydrogen carbonate, poly (methylhydrosiloxane), azodicarboxamide, gas-
  • Unicell ® MS 140 DS one or more water repellants from the group of carnauba wax, zinc stearate, castor oil, paraffin, Teflon powder or natural oil-based polyesters, one or more adhesion promoters from the group of silanes, in particular aminosilanes such as 3-aminopropyl-trimethoxysilane, 3- Aminopropyl-dimethoxy-methylsilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, N- (2-amino-ethyl) -3-aminopropyl-methyldimethoxysilane, N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine and their analogs with ethoxy or isopropoxy instead of methoxy groups on silicon, aminosilanes with secondary amino groups, such as in particular N-phenyl
  • the method according to the invention and / or the composition according to the invention additionally contains a water scavenger, preferably a vinylalkoxysilane, particularly preferably vinyltrimethoxysilane (VTMO).
  • VTMO vinyltrimethoxysilane
  • (crosslinked) polymeric compounds (V) are prepared by reacting oxime-silanes with polypropylene glycol-based diols or triols.
  • (crosslinked) polymeric compounds (V) are prepared by reacting oxime-silanes with higher-functionality polyether polyols with an OH functionality> 3, preferably> 4.
  • (crosslinked) polymeric compounds (V) are prepared by reacting oxime silanes with polyester polyols with an OH functionality> 2.
  • cross-linked polymeric compounds (V) is prepared by oxime silanes with natural oil based polyester polyols, preferably castor oil, Radialube ® 76, Radianol ® 1990 Radia ® 7294, an OH functionality of> 2 are implemented.
  • (crosslinked) polymeric compounds (V) are prepared by reacting oxime silanes with polyether carbonate polyols with an OH functionality> 2.
  • a mixture of oxime-silanes is reacted with polypropylene glycol-based diols or triols.
  • foamed polymeric compounds (V) are produced by using one or more blowing agents.
  • EO-typed polypropylene glycol-based diol
  • EO-typed polypropylene glycol-based diol or
  • EO-typed polypropylene glycol-based diols or triols
  • (chain-extended) polymeric compounds (V) are prepared by reacting an acetoxy-silane, in particular triacetoxymethylsilane or diacetoxydimethylsilane, with a polyol, in particular with a diol.
  • (chain-extended) polymeric compounds (V) are prepared by reacting an acetoxy-silane, in particular triacetoxymethylsilane or diacetoxydimethylsilane, with a polypropylene glycol-based diol, the diol having a molecular weight between 3900 and 4300 g / mol and an OH number between 24 and 30.
  • Diacetoxydimethylsilane is reacted with a polypropylene glycol-based diol, the diol having a molecular weight between 7900 and 9300 g / mol and an OH number between 10 and 18.
  • Diacetoxydimethylsilane is reacted with a polypropylene glycol-based diol, the diol having a molecular weight between 11800 and 12500 g / mol and an OH number between 17 and 14.
  • Diacetoxydimethylsilane is reacted with a polypropylene glycol-based diol, the diol having a molecular weight between 17800 and 19500 g / mol and an OH number between 3 and 10.
  • (crosslinked) polymeric compounds (V) are prepared by first reacting an acetoxysilane, in particular triacetoxymethylsilane or diacetoxydimethylsilane, with a polyol, in particular with a diol, and then reacting the reaction product obtained with a further silane Compound (S) of the general formula Si (R) m (R a ) 4-m as defined herein, preferably an oxime-silane or an isocyanate or isocyanatosilane is reacted.
  • Particularly preferred embodiments of the present invention Process for the production of polymeric compounds (V) with the formation of Si-OC bonds by reacting isocyanate-reactive compounds (P) with at least one silane compound (S) of the general formula Si (R) m (R a ) 4-m , characterized in that
  • R - R a is selected independently of one another from the group consisting of
  • R b independently of one another is H or an optionally substituted, straight-chain or branched C1- to C16- alkyl group or an optionally substituted C4- to C14-aryl group,
  • R c independently of one another, denotes H or an optionally substituted, straight-chain or branched C1- to C16-alkyl group or an optionally substituted C4- to C14-aryl group,
  • R d denotes H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group, an optionally substituted C5 to C15 aralkyl group or an optionally substituted C4 to C14 aryl group,
  • R e is a carbon atom or an optionally substituted saturated or partially unsaturated cyclic ring system with 4 to 14 carbon atoms or an optionally substituted aromatic group with 4 to 14 carbon atoms, and n is an integer from 1 to 10,
  • R n independently of one another is H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group or an optionally substituted C4 to C14 aryl group,
  • R ° independently of one another, denotes H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group or an optionally substituted C4 to C14 aryl group,
  • R p and R q independently of one another are H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group, an optionally substituted C5 to C15 aralkyl group or an optionally substituted C4 to C14 -Aryl group, means
  • R r is a carbon atom or an optionally substituted saturated or partially unsaturated cyclic ring system with 4 to 14 carbon atoms or an optionally substituted aromatic group with 4 to 14 carbon atoms, and p is an integer from 1 to 10,
  • R 9 and R h independently of one another are H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group or an optionally substituted C5 to C15 -Aralkyl group, mean
  • R j H is an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14
  • Aryl group or an optionally substituted C5 to C15 aralkyl group is optionally substituted
  • R f H or an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14
  • the silane compound (S) is bound to an oligomeric or polymeric backbone.
  • the silane compound (S) has at least one radical R a , preferably at least two radicals R a , on the oligomeric or polymeric backbone.
  • R a is independently selected from the group consisting of a hydroxycarboxylic acid ester radical with the general structural formula (A '), whereby
  • R b and R c do not mean H
  • R e represents a carbon atom.
  • the isocyanate-reactive compound (P) is a hydroxy-functionalized polymer which is selected from the group consisting of polyalkylene polyols, polybutadiene polyols, polyisoprene polyols, higher functionality polyols, ethylene oxide (EO) -terminated polyoxypropylene polyols
  • Polyether polyols polyester polyols, styrene-acrylonitrile, acrylic methacrylate, (poly) urea-grafted or containing polyether polyols, polycarbonate polyols, polyether carbonate polyols (CCV polyols), glycerine, polyhydroxy-functional fats and oils, natural oil-based polyester polyols, polyhydrocarbon-based polyols (POHP, polytetrafluoroethylene) ), OFl-terminated prepolymers based on the reaction of a poly
  • hydroxy-functionalized polymer is selected from the group consisting of polypropylene glycol-based di- and / or triols, (higher functional)
  • Polyether polyols polyester polyols, natural oil-based polyester polyols, polyether carbonate polyols (CCV polyols), hydroxyalkyl-functionalized
  • Catalyst is selected from the group consisting of metal silsesquioxanes such as heptaisobutyl POSS titanium (IV) ethoxide (TiPOSS), heptaisobutyl POSS tin (IV) ethoxide (SnPOSS) or mixtures thereof, tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetra n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra (2-ethylhexyl) titanate,
  • metal silsesquioxanes such as heptaisobutyl POSS titanium (IV) ethoxide (TiPOSS), heptaisobut
  • Dialkyl titanates ((R # 0) 2 Ti0 2 , where R # stands for isopropyl, n-butyl, isobutyl), such as isopropyl-n-butyl titanate; Titanium acetylacetonate chelates, such as di-isopropoxy-bis (acetylacetonate) titanate, di-isopropoxy-bis (ethylacetylacetonate) titanate,
  • Aluminum trisalkylates such as aluminum triisopropoxide, aluminum sec-butyate;
  • Aluminum acetylacetonate chelates such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetylacetonate), organotin compounds such as
  • Dibutyltin dilaurate DBTL
  • dibutyltin maleate dibutyltin diacetate
  • tin (II) -2- ethylhexanoate tin octoate
  • tin naphthenate dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dileate
  • Tris dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo (5.4.0) undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] non-5 -en (DBN), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-en, salts of these compounds with carboxylic acids or other acids or mixtures thereof.
  • additives are used, the additives being selected from the group comprising one or more fillers selected from the group of inorganic and organic fillers, one or more Foaming agents, one or more water repellants, one or more adhesion promoters, one or more moisture scavengers, one or more plasticizers, one or more UV Stabilizers and antioxidants, one or more thixotropic agents, or mixtures thereof.
  • Method according to one or more of embodiments 1 to 13 characterized in that
  • R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, vinyl, phenyl, Methoxy or ethoxy;
  • R a stands for a carboxylic acid radical -0-C (0) -R f , in which the oxygen atom of the hydroxyl group is bonded to the silicon atom and
  • R f is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, vinyl or phenyl and m is an integer from 0 to 2 is.
  • Method according to embodiment 15 the deficiency being a ratio represents the silane compound (S) to the isocyanate-reactive compound (P) of at least 1: 1.1, based on the amounts used in moles.
  • R is independently selected from the group consisting of vinyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, isobutyl, 2-ethylhexyl or Phenyl and
  • R a is independently selected from an oxime radical of the general structure (C), where
  • the method according to one or more of embodiments 1 to 13 or 17, wherein the crosslinking of isocyanate-reactive compounds (P), (S) and (P) is present in equal parts 1: 1 or (S) in excess of (P), is based on the amounts used in moles.
  • step (ii) in a second step the components from step (i) are brought together and mixed and worked up using mechanical and / or thermal energy,
  • a silane compound (S) of the general formula Si (R) m (R a ) 4-m according to one of embodiments 17 to 19 is added and optionally at least one catalyst according to embodiment 12 and optionally at least one Additive according to embodiment 13 is added to the mixture from step (i) or (ii),
  • step (iv) in a fourth step the components from step (iii) are mixed using mechanical and / or thermal energy.
  • step (ii) in a second step optionally at least one catalyst according to embodiment 10 and / or at least one additive according to embodiment 13 is added to the components from step (i), and
  • a propellant is added which is selected from the group consisting of water, air, nitrogen, carbon dioxide, pentane, cyclopentane, fluorocarbons or mixtures thereof.
  • polymeric compounds according to embodiment 26 the flexible foam having a Shore A hardness according to ASTM D2240-15 in the range from 0-100.
  • Part A Isocyanate-free crosslinking of hydroxy-functionalized polymers (P) with silane compounds (S)
  • Part A1 Manufacture of non-foamed elastomers by reacting silane compounds with polyols
  • hydroxy-functionalized polymers used were the polyols given in Table 2 below, which can be divided into different groups with regard to their chemical structure:
  • Table 8 Hydroxyalkyl-functionalized polydimethylsiloxane (OH-alkyl-PDMS) The curing or reaction process of the reaction of the abovementioned silane compounds (Table 1) with the OH groups of the polyols (Table 3 to Table 8) with elimination of the leaving groups (oxime, acetate) on the silane compounds was investigated.
  • the reaction rate for the formation of EPs depends largely on the substitution pattern (vinyl vs. methyl) of the silane compound S.
  • the vinyl-substituted silane compound S A reacts significantly faster under considerably milder temperature conditions than the methyl-substituted silane compound S B.
  • the stability of the compounds obtained, which were obtained with the methyl-substituted silane compound S B increases significantly (see Examples EP 1, EP 8, EP 12 and EP 15).
  • the stability and reactivity are generally also influenced by the functionality and, in particular, by the molecular weight of the polyols used. It was found that polyols with a low molecular weight and at the same time high functionality (example EP 15 and EP 16) react at high reaction rates, even at room temperature, to form stable products.
  • EO-typed polyols e.g. PolyU-Pol DE4020, PolyU-Pol M5020
  • S silane compounds
  • non-EO-typed polyols e.g. PolyU L 4000, PolyU-Pol G1000
  • EP elastomer products
  • SAN polyols styrene-acrylonitrile copolymers
  • EP 20 and EP 26 •
  • the novel polyether carbonate polyols that are obtained by incorporating CO2 into the polymer chain (CCV polyols) can also be converted into particularly stable elastomer products by means of the silane compound S in analogy to examples EP 19, EP 20 and EP 26 ( EP 23, EP 24 and EP 25).
  • the type of silane influences the rate at which the elastomer products are formed.
  • the following levels of reactivity can be derived:
  • Table 12 below lists different elastomer products (EP 27 to EP 36) based on the reaction of PolyU-Pol M5020 and the silane compound S B (Wasox), EP 9, with the hydrophobizing agents mentioned. Since the stability of the EP 9 / S B is reduced compared to the elastomer EP 12 / S B formed on the basis of PolyU-Pol MS5240, a more significant observation about the change in the stability behavior could be made. Reaction conditions for all reactions: 60 min at 100 ° C., molar ratio 1: 1.5 (P: S).
  • Part A2 Production of foamed elastomers by reacting silane compounds with polyols
  • the polyol PolyU-Pol MS5240 was used to determine suitable reactions for the formation of the elastomeric foam products SP, as this has a particularly advantageous ratio between reactivity and stability.
  • the results of the reactions of PolyU-Pol MS5240 with the blowing agents mentioned in Table 13 are listed in Table 14 below.
  • Table 14 Foam reactions (A - E) of Polyll-Pol MS5240 with different blowing agents
  • a stabilizer (Tegostab® B 8863z) was added to the polyol (component A). Then, in a 100 ml disposable cup, 20 g of component A, the corresponding amount of the silane compound S (which can be found in the lines MV of the tables below 15 and 16 results) and the amount of propellant (5% or 10%) weighed and mixed with a propeller stirrer for 15 s at 2500 rpm. About 15 g of the mixture were transferred to another 100 ml disposable beaker and reacted under the reaction conditions (temperature, time) given in Tables 15 and 16.
  • a stabilizer Tetrade® B 8863z
  • the fine cell structure of the foams depends on the diameter of the hollow plastic balls.
  • the pore size depends to a large extent on the foaming method used. Physical foaming principally leads to fine-celled foams, while chemical foaming only forms fine-celled foams with increasing solids content (SAN).
  • SAN solids content
  • the density of the foams obtained from the chemical blowing process is determined by the amount of poly (methylhydrosiloxane) (SP 4C to SP 5C) and controllable by temperature (SP 4C to SP 7C). Larger amounts of the blowing agent and / or a higher temperature lead to lower densities.
  • tests with hydrophobizing additives or hydrophobic polyols were carried out analogously to the elastomer products (EP, Part A1) (Table 17). For this purpose, the silane compound S (Wasox) and the reaction conditions (100 ° C., 60 min) were kept constant.
  • Part A3 Comparison of non-foamed elastomer products (EP) and foamed elastomer products (SP) with reference materials based on polyurethane
  • the PolyU-Pol MS5240 served as the polyol.
  • the silane compound S B (Wasox) was used for the isocyanate-free crosslinking and polymeric diphenylmethane diisocyanate (PMDI, Desmodur 44V20 L) was used for the isocyanate-containing crosslinking.
  • the higher molecular weight polyols obtained in this way are used in recipes for the production of coatings, adhesives, seals and elastomers (CASE).
  • DPG dipropylene glycol
  • DADMS di- (diacetoxydimethylsilane
  • TAMS trifunctional acetoxysilane
  • the molecular weights calculated from the OH numbers show that the reaction of the diacetoxydimethylsilane with the diols used leads to a doubling of the molecular weight, in the case of the reaction of triacetoxymethylsilane with PolyU L 4000 leads to a tripling of the molecular weight.
  • the structure of the polymer chain is also underpinned by the increase in viscosity of the reaction products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne : un procédé de préparation de composés contenant un organosilane polymère par réaction de composés réactifs avec les isocyanates (P) avec un composé silane spécifique (S) ; les composés polymères qui peuvent être obtenus à l'aide dudit procédé ; et l'utilisation desdits composés polymères dans la préparation de polymères non expansés, de mousses souples et/ou de systèmes à deux composants (2K), ainsi que l'utilisation desdits composés polymères dans le domaine CASE (revêtements, adhésifs, agents d'étanchéité et élastomères), des meubles, des matelas, des sièges de voiture, des matériaux d'étanchéité ou acoustiques, pour l'isolation de tuyaux de chauffage urbain, de réservoirs et de conduites, ainsi que pour la production de tous types de dispositifs de refroidissement.
EP21716452.4A 2020-04-07 2021-04-07 Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels Pending EP3976691A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20168560.9A EP3892669A1 (fr) 2020-04-07 2020-04-07 Extension de chaîne sans isocyanate et réticulation au moyen des silanes fonctionnels
PCT/EP2021/059056 WO2021204874A1 (fr) 2020-04-07 2021-04-07 Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels

Publications (1)

Publication Number Publication Date
EP3976691A1 true EP3976691A1 (fr) 2022-04-06

Family

ID=70227902

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20168560.9A Ceased EP3892669A1 (fr) 2020-04-07 2020-04-07 Extension de chaîne sans isocyanate et réticulation au moyen des silanes fonctionnels
EP21716452.4A Pending EP3976691A1 (fr) 2020-04-07 2021-04-07 Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20168560.9A Ceased EP3892669A1 (fr) 2020-04-07 2020-04-07 Extension de chaîne sans isocyanate et réticulation au moyen des silanes fonctionnels

Country Status (2)

Country Link
EP (2) EP3892669A1 (fr)
WO (1) WO2021204874A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114507329A (zh) * 2021-12-27 2022-05-17 中国人民大学 一种pH响应可控降解的聚氨酯及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003229206A1 (en) 2002-05-31 2003-12-19 Mcmaster University Polyol-modified silanes as precursors for silica
EP2030976B1 (fr) * 2007-08-31 2013-06-19 Nitrochemie Aschau GmbH Durcisseur pour masses en caoutchouc silicone
DE102008041097A1 (de) * 2008-08-07 2010-02-11 Wacker Chemie Ag Verfahren zur Herstellung von siliconbasierten Schäumen
EP2742085B1 (fr) * 2011-08-10 2021-12-01 University of Virginia Patent Foundation Compositions de caoutchouc silicone viscoélastiques
EP3276417B1 (fr) * 2015-03-27 2019-07-17 Toray Industries, Inc. Composition de silicone pour plaques d'impression, original de plaque d'impression lithographique, plaque d'impression lithographique et procédé de fabrication de d'imprimés
EP3309187B1 (fr) 2016-10-17 2020-08-05 Sika Tech Ag Plastifiant réactif pour compositions durcissant à l'humidité comprenant des polymères à fonction silane
WO2020000387A1 (fr) * 2018-06-29 2020-01-02 Dow Silicones Corporation Additif d'ancrage et ses procédés de préparation et d'utilisation
EP3613803B1 (fr) * 2018-08-20 2022-02-23 Nitrochemie Aschau GmbH Compositions pour masses en caoutchouc silicone

Also Published As

Publication number Publication date
WO2021204874A1 (fr) 2021-10-14
EP3892669A1 (fr) 2021-10-13

Similar Documents

Publication Publication Date Title
EP3224294B1 (fr) Composition contenant des groupes de silanes à durcissement rapide
EP3224295B1 (fr) Composition contenant des groupes de silanes à durcissement rapide
EP2076568B1 (fr) Compositions constituées de polymères partiellement terminés par des groupes silyle
EP2167562B1 (fr) Procédé de fabrication de mousses de polyuréthanne à base de polymères spéciaux à fonction alcoxysilane
WO2020193435A1 (fr) Composé métal-siloxane-silanol(ate) utilisé en tant que catalyseur pour l'obtention d'un gel
DE102008020979A1 (de) Härtbare Zusammensetzungen enthaltend silylierte Polyurethane
WO2009087228A1 (fr) Compositions durcissables contenant des polyuréthannes silylés souples
EP3743454A1 (fr) Composition durcissable renfermant un plastifiant de type acétal
EP3976691A1 (fr) Extension de chaîne sans isocyanate et réticulation au moyen de silanes fonctionnels
DE102013022173B4 (de) Polyurethan-Elastomere auf der Basis von Polyetheralkoholgemischen und trimerisierten Diisocyanaten
WO2010010128A2 (fr) Mélanges expansibles à faible viscosité
WO2004056905A1 (fr) Polymere contenant des groupes de 3-(n-silylalkyle)-amino-propenoate et son utilisation
EP2108669B1 (fr) Composition de matériau d'étanchéité durcissant à l'humidité ayant une bonne stabilité de stockage et une adhérence de surface réduite
DE102008038399A1 (de) Härtbare Zusammensetzungen auf Basis silylierter Polyurethane
WO2022268895A1 (fr) Réduction de la concentration de polyisocyanates monomères dans des compositions de polyuréthane
WO2020038804A1 (fr) Déshydratant pour compositions durcissant à l'humidité
DE102008003155A1 (de) Härtbare Zusammensetzungen enthaltend wässrige Dispersionen von Organopolysiloxanen
DE102007060919A1 (de) Härtbare Zusammensetzungen enthaltend wässrige Dispersionen von Organopolysiloxanen
DE102009027332A1 (de) Schäumbare Mischungen mit niedriger Viskosität

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20211227

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NITROCHEMIE ASCHAU GMBH

Owner name: POLYU GMBH

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LIPPSTREU, JOERG

Inventor name: KNOTT, THOMAS

Inventor name: SCHUCK, RUEDIGER

Inventor name: PICHL, ULRICH

Inventor name: KRUPP, ALEXIS

Inventor name: SENZLOBER, MICHAEL

Inventor name: LANGERBEINS, KLAUS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20231121

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NITROCHEMIE ASCHAU GMBH

Owner name: POLYU GMBH