WO2020150227A1 - Compositions durcissables pour la production d'élastomères de silicone renforcés comprenant des domaines de silicone réticulés élevés - Google Patents

Compositions durcissables pour la production d'élastomères de silicone renforcés comprenant des domaines de silicone réticulés élevés Download PDF

Info

Publication number
WO2020150227A1
WO2020150227A1 PCT/US2020/013499 US2020013499W WO2020150227A1 WO 2020150227 A1 WO2020150227 A1 WO 2020150227A1 US 2020013499 W US2020013499 W US 2020013499W WO 2020150227 A1 WO2020150227 A1 WO 2020150227A1
Authority
WO
WIPO (PCT)
Prior art keywords
siloxane
curable composition
siloxane component
curable
component
Prior art date
Application number
PCT/US2020/013499
Other languages
English (en)
Inventor
Robert P. Cross
Michael Paul LEVANDOSKI
Christina Despotopoulou
Tianzhi ZHANG
Darel GUSTAFSON
Bahram Issari
Original Assignee
Henkel IP & Holding GmbH
Henkel Ag & Co. Kgaa
Henkel (China) Co. Ltd.
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 Henkel IP & Holding GmbH, Henkel Ag & Co. Kgaa, Henkel (China) Co. Ltd. filed Critical Henkel IP & Holding GmbH
Publication of WO2020150227A1 publication Critical patent/WO2020150227A1/fr

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences

Definitions

  • the present invention relates to curable compositions that form silicone polymer domains within a continuous silicone polymer matrix upon curing and provide beneficial physical and chemical properties the cured composition and methods of use of such curable compositions. More particularly, the present invention relates to curable compositions that form a continuous silicone polymer matrix in response to a first set of curing conditions and forms domains of silicone polymer domains within the continuous silicone polymer matrix in response to a second set of curing conditions to improve the physical properties of the domains and the cured composition, such as improvements in glass transition temperature and thermal degradation.
  • Both domain forming composition and the continuous matrix forming composition include polymerizable moieties that cure under similar
  • This combination of the domain forming composition and the continuous matrix forming composition is subjected to conditions that promote polymerization. While the continuous matrix forming composition begins to cure into a continuous matrix, the domain forming composition simultaneously begins to agglomerate into domains and cure. When fully cured the final product is a cured matrix containing cured domains.
  • the domains resulting from the phase separation provide for a toughening of the cured matrix, such as increase in tensile strength and elongation at break, as compared to a polymer of the cured matrix alone.
  • the phase separated domains are organic and exhibit the associated glass transition temperatures (T g ) and decomposition temperatures. Accordingly, the domains are susceptible to the impact of temperature and warming to the T g of the organic domain, and elevated temperature can greatly diminished the toughening contribution provided by the domains .
  • the present invention provides a means of satisfying the above-mentioned need.
  • the present invention provides curable compositions that form silicone polymer domains within a continuous silicone polymer matrix upon curing and provide beneficial physical and chemical properties the cured
  • compositions and methods of use of such curable compositions exhibit better physical characteristics
  • T g glass transition temperatures
  • the present invention provides curable
  • compositions that form a continuous silicone polymer matrix in response to a first set of curing conditions and forms silicone polymer domains within the continuous silicone polymer matrix in response to a second set of curing conditions to improve the physical properties of the domains and the cured composition, such as improvements in glass transition temperature and thermal degradation.
  • the physical properties of the domains leads to improvements in the physical properties of the cured composition
  • composition such as increased resistance to softening at elevated temperatures.
  • a curable composition including an admixture of: a) a siloxane polymer with at least two methacrylate moieties, b) a first siloxane component comprising from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and c) a second siloxane component comprising from 2 to 10 silicon atoms and at least three reactive hydride moieties .
  • a method of producing a dual-phase, cured composition including the steps of: a) providing curable composition including an admixture of: i) a siloxane polymer with at least two
  • methacrylate moieties ii) a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and iii) a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties, b) exposing the curable composition to a first set of curing conditions to induce curing of the siloxane polymer to form a continuous matrix, c) exposing the cured siloxane polymer to a second set of curing conditions to promote curing of the first siloxane component and the second siloxane component to produce the dual-phase, cured composition.
  • a dual-phase, cured composition produced by a method comprising: a) providing curable composition including an admixture of: i) a siloxane polymer with at least two methacrylate moieties, ii) a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and iii) a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties, b) exposing the curable composition to a first set of curing conditions to induce curing of the siloxane polymer to form a continuous matrix, c) exposing the cured siloxane polymer to a second set of curing conditions to promote curing of the first siloxane component and the second siloxane component to produce the dual-phase, cured composition
  • a curable dual-phase composition having a continuous silicone polymer matrix containing a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties and a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties.
  • the first siloxane component is a cyclic siloxane having at least three reactive vinyl moieties.
  • the second siloxane component is a cyclic siloxane having at least three reactive hydride moieties.
  • Figure 1 is a graph of plots of the photorheometry and heat cure testing of Compositions C-F.
  • the present invention is directed to curable
  • compositions and methods of use of such curable compositions.
  • the present invention is directed to curable compositions that form a continuous silicone polymer matrix in response to a first set of curing conditions and forms domains of silicone polymer within the continuous silicone polymer matrix in response to a second set of curing conditions to improve the physical properties of the domains and the cured composition, such as improvements in glass transition
  • Tg of the domains close to or below room temperature means that the physical properties obtained at room temperature will be preserved as temperature is increased .
  • a curable composition including an admixture of: a) a siloxane polymer with at least two methacrylate moieties, b) a first siloxane component comprising from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and c) a second siloxane component comprising from 2 to 10 silicon atoms and at least three reactive hydride moieties.
  • the siloxane polymer with at least two methacrylate moieties is capable of being cured into a continuous matrix upon exposure to the appropriate conditions.
  • the siloxane polymer with at least two methacrylate moieties is telechelic.
  • the siloxane polymer with at least two methacrylate moieties is a diemethoxy endcapped polydimethyl siloxane.
  • the siloxane polymer with at least two methacrylate moieties has a molecular weight of about 500 daltons or greater.
  • the siloxane polymer with at least two methacrylate moieties has a molecular weight between about 500 daltons and about 1 million daltons, between about 1,000 daltons and about 500,000 daltons, between about 2,500 daltons and about 250,000 daltons, or between about 5,000 daltons and about 100,000 daltons.
  • the siloxane polymer is present in the curable composition in an amount of about 60% to about 95% by weight based on the total weight of the curable composition.
  • the siloxane polymer is present in the curable composition in an amount of about 65% to about 90% by weight based on the total weight of the curable composition OR about 70% to about 80% by weight based on the total weight of the curable composition.
  • the first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties is 1, 3, 5, 7-tetravinyl-
  • the first siloxane component has a molecular weight of about 1,000 daltons or less.
  • the second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties is 1, 3,5,7- tetramethylcyclotetracylosiloxane,
  • the second siloxane component has a molecular weight of about 1,000 daltons or less.
  • the combination of the first siloxane component and the second siloxane component is present in the curable composition in an amount of about 10% to about 35% by weight based on the total weight of the curable composition or about 20% to about 30% by weight based on the total weight of the curable composition.
  • the molar ratio of the first siloxane component to the second siloxane component is in the range of from about 2:1 to about 1:2. In another aspect of the present invention the molar ratio of the first siloxane component to the second siloxane component is about 1:1.
  • the average diameter of the domains increases or forms an interpenetrating polymer network, which may not be desired.
  • the domains formed in the continuous matrix have an average diameter between about 10 nanometers and about 100 nanometers, between about 15 nanometers and about 75 nanometers, or about 20 nanometers and about 50 nanometers. If the size of the domains is too great they will interfere with light penetration through the cured composition.
  • method of producing a dual-phase, cured composition including the steps of: a) providing curable composition including an admixture of: i) a siloxane polymer with at least two
  • methacrylate moieties ii) a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and iii) a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties, b) exposing the curable composition to a first set of curing conditions to induce curing of the siloxane polymer to form a continuous matrix, c) exposing the cured siloxane polymer to a second set of curing conditions to promote curing of the first siloxane component and the second siloxane component to produce the dual-phase, cured composition.
  • a dual-phase, cured composition produced by a method comprising: a) providing curable composition including an admixture of: i) a siloxane polymer with at least two methacrylate moieties, ii) a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties, and iii) a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties, b) exposing the curable composition to a first set of curing conditions to induce curing of the siloxane polymer to form a continuous matrix, c) exposing the cured siloxane polymer to a second set of curing conditions to promote curing of the first siloxane component and the second siloxane component to produce the dual-phase, cured composition
  • the curable composition is a solution of the first siloxane component and the second siloxane component in the siloxane polymer.
  • the combination of the first siloxane component and the second siloxane component can be considered a liquid filler.
  • the domains act as a filler in the cured composition to impart strength to the final composition, but prior to curing the low viscosity of the domain forming component lowers the viscosity of the curable composition. This allows for the optimization of viscosity and allows the curable composition to be spread and worked easily.
  • avoiding solid filler avoids imparting thixotropic properties to the curable composition. Such thixotropic properties are
  • all of the siloxane polymer, the first siloxane component, and the second siloxane component are liquids at room at room
  • all of the siloxane polymer, the first siloxane component, and the second siloxane component have a viscosity of about 10,000 or less at room temperature, about 5,000 cps or less at room temperature, or about 1,000 cps or less at room temperature.
  • the admixture of the siloxane polymer, the first siloxane component, and the second siloxane component is a liquid at room at room
  • the admixture of the siloxane polymer, the first siloxane component, and the second siloxane component has a viscosity of about
  • the "first set of curing conditions” are conditions that promote the curing of the acrylate moieties in the siloxane polymer.
  • the siloxane polymer is curable by radiation. As used herein, “radiation” means any energy in the electromagnetic spectrum.
  • the siloxane polymer is photocurable or light
  • curable i.e., curable using light such as visible or
  • the siloxane polymer may be cured using a light source, such a bulb or LED that produces visible or UV light.
  • the siloxane polymer after the completion of the first curing step (i.e., after exposure to the first set of curing conditions) , the siloxane polymer has cured to form a continuous silicone matrix in which the first and second siloxane components are dispersed and remain unreacted.
  • this intermediate cured continuous silicone matrix is exposed to the second set of curing conditions the first and second siloxane components react to form silicone polymer domains within the cured continuous silicone matrix resulting a the dual phase, cured composition.
  • continuous silicone matrix containing a first siloxane component having from 2 to 10 silicon atoms and at least three reactive vinyl moieties and a second siloxane component having from 2 to 10 silicon atoms and at least three reactive hydride moieties.
  • the first and second siloxane components react to form silicone polymer domains within the cured continuous silicone matrix resulting in a dual phase, cured composition.
  • the curable composition includes a first cure catalyst.
  • first cure catalyst means a composition or compound that initiates or promotes polymerization or curing of the acrylate moieties in the siloxane polymer.
  • the first cure catalyst is a photoinitiator.
  • the photoinitiator may be a UV initiator, a visible initiator, or a combination of UV and visible initiators.
  • UV initiators may be employed.
  • initiators are generally effective in the 200 to 400 nm range, and particularly in the portion of the spectrum that borders on the invisible light and the visible portion just beyond this, e.g. >200 nm to about 390 nm.
  • Initiators that will respond to UV radiation to initiate and induce curing of the (meth)acryl functionalized curable component include, but are not limited to, benzophenone and substituted benzophenones , acetophenone and substituted acetophenones, benzoin and its alkyl esters, xanthone and substituted
  • xanthones phosphine oxides, diethoxy-acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thio-xanthone, N-methyl diethanol- amine-benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2- benzyl-2- (dimethylamino) -1- [4- ( 4-morpholinyl ) phenyl] -1-butanone and mixtures thereof.
  • UV initiators examples include initiators available commercially from IGM Resins under the "IRGACURE” and “DAROCUR” tradenames, specifically "IRGACURE” 184 (1- hydroxycyclohexyl phenyl ketone), 907 (2-methyl-l- [4- (methylthio) phenyl] -2-morpholino propan-l-one) , 369 (2-benzyl-2- N, N-dimethylamino-1- ( 4-morpholinophenyl ) -1-butanone) , 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and
  • benzophenone 651 (2 , 2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis (2 , 6-dimethoxybenzoyl-2 , 4 , 4-trimethyl pentyl) phosphine oxide and 2-hydroxy-2-methyl-l-phenyl-propan- 1-one) , and 819 [bis (2 , 4 , 6-trimethyl benzoyl) phenyl phosphine oxide], and "DAROCUR" 1173 (2-hydroxy-2-methyl-l-phenyl-l- propane) and 4265 (the combination of 2,4,6- trimethylbenzoyldiphenyl-phosphine oxide and 2-hydroxy-2-methyl- 1-phenyl-propan-l-one) ; and 2,4,6- trimethylbenzoyldiphenylphosphine oxide (commercially available as LUCIRIN TPO from BASF Corp.) ⁇ Of course, combinations of these materials may also be employed herein.
  • UV photoinitiators categorized herein as UV photoinitiators have a tailing absorption into the visible range, and thus straddle the line between UV and visible light cure initiators, but nonetheless are included herein as part of the invention.
  • Initiators suitable for use in the present invention that will respond to visible light to initiate and induce curing include, but are not limited to, camphorquinone peroxyester initiators, 9-fluorene carboxylic acid peroxyesters , visible light [blue] photoinitiators, dl-camphorquinone, "IRGACURE"
  • EP 0 369 645 Al discloses a three-part photoinitiator system which includes a trihalomethyl substituted-s-triazine, a sensitizing compound capable of absorbing radiation in the range of about 300-1000 nm and an electron donor.
  • Exemplary sensitizing compounds are disclosed, including: ketones; coumarin dyes; xanthene dyes; 3H-xanthen-3- one dyes; acridine dyes; thiazole dyes; thiazine dyes; oxazine dyes; azine dyes; aminoketone dyes; methane and polymethine dyes; porphyrins; aromatic polycyclic hydrocarbons; p- substituted aminostyryl ketone compounds; aminotriaryl methanes; merocyanines ; squarylium dyes; and pyridinium dyes.
  • Exemplary donors also are disclosed, including: amines; amides; ethers; ureas; ferrocene; sulfinic acids and their salts; salts of ferrocyanide; ascorbic acid and its salts; dithiocarbamic acid and its salts; salts of xanthates; salts of ethylene diamine tetraacetic acid; and salts of tetraphenylboronic acid.
  • Such initiators are sensitive to both UV and visible light.
  • EP 0 563 925 Al discloses photopolymerization initiators including a sensitizing compound that is capable of absorbing radiation in the range of about 250-1000 nm and 2-aryl-4 , 6-bis (trichloromethyl) -1 , 3 , 5-triazine .
  • exemplary sensitizing compounds that are disclosed include:
  • cyanine dye merocyanine dye, coumarin dye, ketocoumarin dye, (thio) xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, squarylium dye, pyridinium dye, (thia) pyrylium dye, porphyrin dye, triaryl methane dye, (poly) methane dye, amino styryl compounds and aromatic polycyclic hydrocarbons.
  • photopolymerization initiators are sensitive to UV and visible light.
  • Such fluorone initiator systems also include a coinitiator, which is capable of accepting an electron from the excited fluorone species.
  • exemplary coinitiators are disclosed, including: onium salts, nitrohalomethanes and diazosulfones .
  • the three-part system includes an arylidonium salt, a
  • sensitizing compound and an electron donor exemplary iodonium salts include diphenyliodonium salts. Exemplary sensitizers and electron donors for use in the three-part system also are disclosed. Additionally, the sensitizer is capable of absorbing light in the range of about 300-1000 nm.
  • the first cure catalyst may be employed in amounts of about 0.05% to about 8% by weight of the total composition. In another aspect of the invention, the first cure catalyst is present in amounts of 0.1% to about 3% by weight of the total composition.
  • the "second set of curing conditions" are conditions that promote the curing of vinyl moieties of the first siloxane component and the hydride moieties of the second siloxane component.
  • the combination of the first and second siloxane components is curable via hydrosilylation and the second set of curing conditions promotes hydrosilylation.
  • the second set of curing conditions includes heat.
  • the curable composition includes a second cure catalyst.
  • second cure catalyst means a composition or compound that initiates or promotes hydrosilylation.
  • the second cure catalyst is Karstedt's catalyst, Speier's catalyst, an alkene-stabilized platinum catalyst, or a combination thereof.
  • the catalyst may be employed in amounts of about 0.05% to about 8% by weight of the total composition.
  • the second cure catalyst is present in amounts of 0.1% to about 3% by weight of the total composition.
  • the curable composition may include a hydrosilylation stabilizer or
  • hydrosilylation inhibitor As used herein, the terms
  • hydrosilylation stabilizer or “hydrosilylation inhibitor” means a compound or composition that prevents or slows
  • the hydrosilylation stabilizer or hydrosilylation inhibitor prevents the hydride vinyl reaction at room temperature, but at elevated temperatures, such as 100°C, will either evaporate off or react with the hydrides and bind into the matrix.
  • the hydrosilylation stabilizer or hydrosilylation inhibitor has double or triple bonds that reversibly coordinate with the platinum in the hydrosilylation catalyst to modify its
  • hydrosilylation inhibitors include dimethyl fumarate, dimethyl maleate, 1, 3-divinyltetramethyldisiloxanae, 1,3, 5, 7 tetravinyl- 1, 3, 5, 7-tetramethylcyclotetrasiloxane, and 2-hexyn-l-ol (
  • Optional additives such as, but not limited to, stabilizers, inhibitors, oxygen scavenging agents, fillers, dyes, colors, pigments, adhesion promoters, plasticizers, toughening agents, reinforcing agents, fluorescing agents, wetting agents, antioxidants, rheology modifying agents, and combinations thereof also may be included in the compositions of the present invention.
  • DMA Dynamic mechanical analysis
  • Measurement tool 3-point bending tool
  • Formulation A showed two glass transitions during the first run, which merged into one T g during the second run.
  • Formulation B showed only one glass transition during the first and second runs. This indicates that the glass transitions at room temperature are so weak that increasing the temperature should have a negligible impact on the physical properties of the domains as compared to those that were initially measured at room temperature. All glass transitions observed are very weak. The glass transition states are close to that of the expected silicone polymer.
  • Temperature program equilibrate to 30 °C, then heat to 300 °C at 10°C/min and hold at 300°C for 30 minutes
  • vinyl/hydride monomers afford very low thermal decomposition temperatures .
  • 12DMA is a 12,000 raw dimethoxy acrylate terminated polydimethyl siloxane.
  • 4DMA is a 4,000 mw dimethoxy acrylate terminated polydimethyl siloxane.
  • the photoinitiator was 1% Irgacure 891 in Diethoxyacetophenone (DEAP) .
  • Formulations C-F were subjected to photorheometry cure testing under the following conditions:
  • UV light source shutter 5%
  • UVA 111 mW/cm 2
  • UVB 0 mW/cm 2
  • UVC 0 mW/cm 2
  • UVV 0 mW/cm 2 measured by EIT UV Power Puck SN2560
  • Formulations G-J. 12DMA is a 12,000 mw dimethoxy acrylate terminated polydimethyl siloxane. 4DMA is a 4,000 mw dimethoxy acrylate terminated polydimethyl siloxane.
  • the photoinitiator was 1% Irgacure 891 in Diethoxyacetophenone (DEAP) .
  • Formulations H-J were cured by a UV cure at 365 nm (30 Mw/cm 2 ) for 30 seconds per side followed by a heat cure for 15 minutes at 150 °C.
  • Formulation G was cured only by a UV cure at 365 nm (30 Mw/cm 2 ) for 30 seconds per side. 5 replicates
  • Formulations become harder with the secondary cure component as seen by the hardness of the cured formulation and the modulus obtained by photorheometry followed by heat cure.

Landscapes

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

Abstract

L'invention concerne des compositions durcissables qui forment des domaines de polymère de silicone dans une matrice polymère de silicone continue lors du durcissement et fournissent des propriétés physiques et chimiques bénéfiques, la composition durcie et des procédés d'utilisation de telles compositions durcissables. Plus particulièrement, l'invention concerne des compositions durcissables qui forment une matrice polymère de silicone continue en réponse à un premier ensemble de conditions de durcissement et formant des domaines de domaines polymères de silicone à l'intérieur de la matrice polymère de silicone continue en réponse à un second ensemble de conditions de durcissement pour améliorer les propriétés physiques des domaines et de la composition durcie, telles que des améliorations de la température de transition vitreuse et de la dégradation thermique.
PCT/US2020/013499 2019-01-16 2020-01-14 Compositions durcissables pour la production d'élastomères de silicone renforcés comprenant des domaines de silicone réticulés élevés WO2020150227A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962792934P 2019-01-16 2019-01-16
US62/792,934 2019-01-16

Publications (1)

Publication Number Publication Date
WO2020150227A1 true WO2020150227A1 (fr) 2020-07-23

Family

ID=71614021

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/013499 WO2020150227A1 (fr) 2019-01-16 2020-01-14 Compositions durcissables pour la production d'élastomères de silicone renforcés comprenant des domaines de silicone réticulés élevés

Country Status (1)

Country Link
WO (1) WO2020150227A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023101220A1 (fr) * 2021-12-02 2023-06-08 주식회사 엘지화학 Composition durcissable, film protecteur, élément optique et dispositif d'affichage à cristaux liquides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996039458A1 (fr) * 1995-06-05 1996-12-12 Loctite Corporation Compositions adhesives/d'obturation, durcissables a base de silicone
US5585035A (en) * 1993-08-06 1996-12-17 Minnesota Mining And Manufacturing Company Light modulating device having a silicon-containing matrix
WO2014123906A1 (fr) * 2013-02-05 2014-08-14 Medarray, Inc. Fibres creuses à base de siloxane
US20160068720A1 (en) * 2013-07-03 2016-03-10 Henkel IP & Holding GmbH High temperature debondable adhesive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585035A (en) * 1993-08-06 1996-12-17 Minnesota Mining And Manufacturing Company Light modulating device having a silicon-containing matrix
WO1996039458A1 (fr) * 1995-06-05 1996-12-12 Loctite Corporation Compositions adhesives/d'obturation, durcissables a base de silicone
WO2014123906A1 (fr) * 2013-02-05 2014-08-14 Medarray, Inc. Fibres creuses à base de siloxane
US20160068720A1 (en) * 2013-07-03 2016-03-10 Henkel IP & Holding GmbH High temperature debondable adhesive

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AMIT S KULKARNI , GREGORY BEAUCAGE: "Reaction induced phase-separation controlled by molecular topology", POLYMER, 8 March 2005 (2005-03-08), pages 4454 - 4464, XP027727561, ISSN: 0032-3861, DOI: 10.1016/j.polymer.2005.02.028 *
SHENG-SHU HOU , YEN-PIN CHUNG , CHENG-KUANG CHAN , PING-LIN KUO: "Function and performance of silicone copolymer. Part IV. Curing behavior and characterization of epoxy-siloxane copolymers blended with diglycidyl ether of bisphenol-A", POLYMER, vol. 41, no. 9, 30 April 2000 (2000-04-30), pages 3263 - 3272, XP004184972, ISSN: 0032-3861, DOI: 10.1016/S0032-3861(99)00525-X *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023101220A1 (fr) * 2021-12-02 2023-06-08 주식회사 엘지화학 Composition durcissable, film protecteur, élément optique et dispositif d'affichage à cristaux liquides

Similar Documents

Publication Publication Date Title
JP5818879B2 (ja) 芳香族カルボキシレートアニオンを含む重合性イオン液体
JP6177126B2 (ja) 重合性イオン液体組成物
JP6914238B2 (ja) 単官能性アクリレートを含む硬化性組成物
US8404758B2 (en) Stress relaxation in crosslinked polymers
JP2005521764A5 (fr)
JP7203056B2 (ja) 印刷可能な硬化性混合物及び硬化組成物
US9931280B2 (en) Dental composite compositions for reduced shrinkage stress
US9682018B2 (en) Denture tooth and material
KR20080024209A (ko) 광경화성 엘라스토머 조성물
Hasa et al. Manipulation of crosslinking in photo-induced phase separated polymers to control morphology and thermo-mechanical properties
US8877830B2 (en) Stress relief for crosslinked polymers
WO2021055862A1 (fr) Compositions photodurcissables de (méth)acrylate
JP7130561B2 (ja) ナノゲルによるポリマーネットワーク構造の制御
JP6962745B2 (ja) Ｌｅｄ硬化型防湿絶縁コート剤組成物
WO2020150227A1 (fr) Compositions durcissables pour la production d'élastomères de silicone renforcés comprenant des domaines de silicone réticulés élevés
JP2022544012A (ja) ３ｄ印刷用チオールアクリレートエラストマー
Abbasi et al. Modified POSS nano-structures as novel co-initiator-crosslinker: Synthesis and characterization
JPH11322818A (ja) 光硬化性組成物
Sideridou et al. Copolymerization kinetics of dental dimethacrylate resins initiated by a benzoyl peroxide/amine redox system
JP2000072854A (ja) 光硬化性組成物、光硬化性組成物の製造方法、光硬化型粘接着シート、光硬化型粘接着シートの製造方法及び接合方法
Shi et al. Investigation of 3, 4‐methylenedioxybenzene methoxyl methacrylate as coinitiator and comonomer for dental application
JP4215119B2 (ja) アクリル系のホットメルト型粘着剤樹脂組成物及びそれを用いる粘着シート
US20210332176A1 (en) Curable compositions for production of reaction induced phase separated compositions with improved properties
CN115286508A (zh) 一种含光引发剂基团的树脂单体及其制备方法和可光聚合组合物
Czech et al. Polymerization shrinkage of UV curable dental composites containing multifunctional methacrylates

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20741022

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20741022

Country of ref document: EP

Kind code of ref document: A1