Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
• • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/243—Two or more independent types of crosslinking for one or more polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• Another desirable feature for dual cure composition is to increase the rate and extent of the moisture cure step so as to more rapidly complete curing of the composition. For instance, it is desirable to achieve a moisture curing of a composition to a tack- free surface in less than 50 minutes. More importantly is to achieve such a moisture curing rate while also achieving a UV cure upon a 4 Joules per square centimeter (J/cm 2 ) UV exposure in air that is tack-free and cured to a depth of at least one millimeter. Even more desirable is such a dual cure composition that achieves these composition and performance characteristics using a thiol-ene UV cure chemistry so as to avoid problems with (meth)acrylate-based UV cure systems.
• the present invention provides a solution to the problem of simultaneously providing a dual cure composition that does not require a dual cure polymer and that achieves moisture cure to a tack-free surface in less than 50 minutes, a UV cure upon 4 J/cm 2 UV irradiation in air that is tack-free and cured to a depth of at least one millimeter and that utilized a thiol-ene UV cure chemistry.
• the present invention is a curable composition
• a curable composition comprising: (a) a first organopolysiloxane comprising at least two trialkoxysilyl groups per molecule and that is free of alkenyl groups and mercapto groups, the first organopolysiloxane present at a concentration in a range of 35 to 80 weight-percent based on a combined weight of first, second and third organopolysiloxanes; (b) a second organopolysiloxane containing at least one alkenyl group and that is free of mercapto groups and alkoxysilyl groups, where the second organopolysiloxane is present at a concentration in a range of 10 to 65 weight- percent and provides a concentration of double bonded carbon groups of more than 0.02 weight-percent, with weight-percent values based on a combined weight of first, second and third organopolysiloxanes; (c) a third organopolysiloxan
• Products identified by their tradename refer to the compositions available under those tradenames on the priority date of this document.
• Chemical structures and compositions for polymers indicate the average chemical composition for a polymer and, unless otherwise stated, include any configuration of the polymer units specified including random polymers, block copolymers and combinations thereof.
• the present invention is a curable composition. That means it is capable of undergoing a crosslinking reaction between components in the composition.
• the present invention is actually a dual cure curable composition that is capable of undergoing both ultraviolet (UV) light initiated curing as well as moisture curing.
• UV ultraviolet
• the first organopolysiloxane comprises at least two trialkoxysilyl groups per molecule and that is free of alkenyl groups and mercapto groups.
• the first organopolysiloxane can be free of (meth)acryl groups.
• the first organopolysiloxane can contain more than two trialkoxysilyl groups per molecule.
• the trialkoxy silyl groups are groups that contain an (RO)sSi- functionality where R is independently in each occurrence selected from hydrocarbon groups, preferably from hydrocarbon groups having an average of one to 8 carbon atoms, more preferably R is methyl.
• the first organopolysiloxane can be one or any combination of more than one organopolysiloxane having a chemical composition (I):
• X is independently in each occurrence selected from trialkoxy silyl containing groups such as -Si(OR) 3 and -R’-SiR 2 -OSiR 2 -R’-Si(OR) 3 ;
• Subscript d’ has an average value of zero or more, and can be one or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 15 or more, 20 or more, 30 or more, even 40 or more while at the same time is typically 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, or even 5 or less;
• Subscript t has an average value of zero or more, and can be one or more, 2 or more, 3 or more 4 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, even 90 or more while at the same time is typically 100 or less, and can be 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or even 10 or less; and
• Subscript q has an average value of zero or more, and can be one or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, even 9 or more, while at the same time is typically 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or even one or less.
• X and R are as defined herein above, ; subscript a has an average value of 20 or more and can be 40 or more, 50 or more, 55 or more, 60 or more, 80 or more 100 or more, 145 or more, 150 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 2000 or more, even 3000 or more while at the same time is typically 5000 or less, and can be 4000 or less, 3000 or less, 2000 or less, 1000 or less, 500 or less, 400 or less, 300 or less, 290 or less, 250 or less, 200 or less, 150 or less, 100 or less; 80 or less, 60 or less, even 57 or less; and subscript b has an average value of zero or more, one or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 20 or more, 30 or more, even 40 or more while at the same time typically has a value of 50 or less, and can be 40
• the concentration of first organopolysiloxane is 35 weight-percent (wt%) or more and can be 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, even 75 wt% or more while at the same time is typically 80 wt% or less, and can be 75 wt% or less, 70 wt% or less, 65 wt% or less, 60 wt% or less, 55 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, or even 35 wt% or less relative to the combined weight of first, second and third organopoly siloxanes.
• the second organopolysiloxane comprises at least one alkenyl group, preferably two or more alkenyl groups per molecule and is free of mercapto groups and alkoxysilyl groups.
• the second organopolysiloxane can be one or any combination of more than one organopolysiloxane having a chemical composition (II):
• Y is independently in each occurrence a terminal alkenyl group having from 2 to 8 carbon atoms and can have 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, even 7 or more while at the same time typically contains 8 or fewer, and can contain 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, even 3 or fewer carbon atoms; Y can be a vinyl group in each occurrence;
• R is independently in each occurrence selected from hydrocarbyl groups containing one or more, even 2 or more, 3 or more, 4 or more, even 5 or more while at the same time 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, even two or fewer carbon atoms; preferably R is methyl in each occurrence;
• Subscript m’ has an average value of 2 or more and can be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, even 9 or more and at the same time is typically 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less;
• Subscript d2 has an average value of 20 or more, and can be 40 or more, 60 or more, 80 or more, 100 or more, 150 or more, 250 or more, 500 or more, 1000 or more, 2000 or more, 3000 or more, even 4000 or more while at the same time is typically, 5000 or less, 400 or less, 3000 or less, 2000 or less, 1000 or less, 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 80 or less, 60 or less, 40 or less, even 30 or less;
• Subscript d2’ has an average value of zero or more, and can be one or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 15 or more, 20 or more, 30 or more, even 40 or more while at the same time is typically 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, or even 5 or less;
• Subscript t’ has an average value of zero or more, and can be one or more, 2 or more, 3 or more 4 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, even 90 or more while at the same time is typically 100 or less, and can be 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or even 10 or less; and
• Subscript q’ has an average value of zero or more, and can be one or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, even 9 or more, while at the same time is typically 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or even one or less.
• Y is independently in each occurrence a terminal alkenyl group having from 2 to 8 carbon atoms and can have 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, even 7 or more while at the same time typically contains 8 or fewer, and can contain
• Y can be a vinyl group in each occurrence
• the second organopolysiloxane can be selected from:
• the concentration of second organopolysiloxane is 10 wt% or more and can be 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, even 60 wt% or more while at the same time is typically 65 wt% or less, and can be 60 wt% or less, 55 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, or even 20 wt% or less relative to the combined weight of first, second and third organopolysiloxanes.
• the third organopolysiloxane can have an average chemical composition (III): [R3SiOi/2]2-j[R”R2SiOi/2]j[RR”SiO2/2]o[R2SiO 2 /2]p (III) where:
• R is independently in each occurrence selected from hydrocarbyl groups having one to 6 carbon atoms and can have one or more, 2 or more, 3 or more, 4 or more, even 5 or more while at the same time typically contains 6 or fewer, and can contain 5 or fewer, 4 or fewer, 3 or fewer, even 2 or fewer carbon atoms; R can be methyl in each occurrence;
• R” is HS(CH 2 ) t CH 2 - subscript t has an average value of one or more, and can be 2 or more, 3 or more, 4 or more, 5 or more, even 6 or more while at the same time is typically 7 or less, and can be 6 or less, 5 or less, 4 or less, 3 or less, even 2 or less; subscript j has an average value of 0 or more and can be one or more and at the same time is 2 or less, or even one or less provided that the sum of subscripts j and o have an average value of at least 2; subscripts o and p are desirably selected so as to provide a weight ratio of mercapto groups that is in a range of 0.5 to 15.0 weight-percent based on weight of the third organopolysiloxane.
• subscript o has an average value of zero or more, and can be one or more, 2 or more, and can be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, even 9 or more while at the same time is typically 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, and can be 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, even 2 or less; and
• subscript p has an average value of 3 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more and can be 41 or more, 42 or more, 43 or more, even 44 or more while at the same time is typically 500 or less, 250 or less, 100 or less, 75 or less, 50 or less, 45 or less, and can be 44 or less, 43 or less, 42 or less, even 41 or less; and
• the third organopolysiloxane can have an average chemical composition (Illa):
• R is methyl in each occurrence, R” is HS(CH2)2CH2-, subscript p has a value in a range of 40 to 45, and subscript o has an average value of 5.
• the concentration of third organopolysiloxane is typically 0.5 wt% or more, and can be 0.6 wt% or more, one wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, 5 wt% or more, 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, even 25 wt% or more while at the same time is typically 30 wt% or less, and can be 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, even 5 wt% or less relative to the combined weight of first, second and third organopolysiloxanes.
• the curable composition further comprises a photoinitiator.
• Photoinitiators are triggered by exposure to light, typically ultraviolet (UV) light, for form radicals that initiate chemical reactions.
• suitable photoinitiators include any one or any combination of more than one selected from a group consisting of benzophenone, substituted benzophenones, acetophenone, substituted acetophenone (such as diethoxyacetophenone (DEAP)), benzoin and its alkyl esters (such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether), xanthone, and substituted xanthone (such as diethoxyxanthone, chloro-thioxanthone), azo-bisisobutyronitrile, N- methyldiethanolaminebenzophenone, 2-hydroxy-2-methylpropiophenone and bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide.
• Photoinitiator is present at a concentration of 0.01 wt% or more, and can be present at a concentration of 0.05 wt% or more, 0.1 wt% or more, 0.5 wt% or more, 1.0 wt% or more, 1.25 wt% or more, 1.50 wt% or more, 2.0 wt% or more, even 2.5 wt% or more while at the same time is typically present at a concentration of 5 wt% or less, and can be 4 wt% or less, 3 wt% or less, 2 wt% or less, one wt% or less, or even 0.5 wt% or less relative to curable composition weight.
• the curable composition further comprises a condensation catalyst.
• Suitable moisture cure catalysts include any one or combination of more than one organo-metal catalysts selected from a group consisting of titanium compounds, tin compounds, and zirconium compounds.
• suitable titanium compounds include tetra-t-butyl titanate, tetraisopropylorthotitanate, tetrabutoxyorthotitanate, di(isopropoxy)bis(ethylacetoacetate)titanium, di(isopropoxy)bis(methylacetoacetate)titanium, di(isopropoxy)bis(acetylacetonate)titanium and titanium ethyl acetoacetate complex mixed with methyl-trimethoxy silane.
• Table 1 lists the components for the compositions that follow. Abbreviations are: First Polyorganosiloxane (“FP”), Second Polyorganosiloxane (“SP”), Third
• TP Polyorganosiloxane
• PI Photoinitiator
• MCC Moisture Cure Catalyst
• AS Alkoxy Silane
• Vi vinyl
• Me methyl
• Tyzor is a trademark of E.I.Du Pont De Nemours and Company.
• Darocur is a trademark of IGM group B.V.
• Irgacure is a trademark of BASF SE Company.
• DOWSIL is a trademark of The Dow Chemical Company.
• XIAMETER and SILASTIC are trademarks of Dow Corning Corporation.

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• 2022
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