Hydrosilylation cure of elastomers

Abstract

To provide new curing processes and related compositions that reduce VOC and odor associated with cured rubber formulations and that maintain or improve cure properties.SOLUTION: A process to form a crosslinked composition is provided, the process comprising thermally treating a composition comprising the following: a) an elastomer; b) a siloxy-modified silica; and c) a hydrosilylation catalyst.SELECTED DRAWING: None

Description

BACKGROUND ART

[0001] Cured rubbers such as EPDM are used in automotive applications. Sulfur-cured EPDM generates high levels of VOC (Volatile Organic Compound), which in turn causes odors in end-use applications. Government regulations to reduce VOC levels are becoming more stringent. Therefore, there is a need for new curing processes and related compositions that reduce VOC and odor associated with cured rubber formulations and maintain or improve curing properties.

[0002] U.S. Patent No. 7,741,394 discloses a rubber composition containing a specific ethylene / alpha-olefin / non-conjugated polyene copolymer in which the non-conjugated polyene is a norbornene-based compound, a "SiH group-containing" compound, and optionally an organopolysiloxane (see the abstract). Fumed silica and precipitated silica may each be used as a rubber reinforcing agent. The silica is surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, alkoxysilane, or low molecular weight siloxane (see column 17, lines 40-46).

[0003] U.S. Patent Application Publication No. 2009 / 0234057 discloses a rubber composition containing a rubber having at least two functional groups capable of crosslinking by hydrosilylation, a crosslinking agent, a hydrosilylation catalyst system, at least one filler, and an auxiliary agent capable of crosslinking by hydrosilylation (see the abstract). The crosslinking agent has a center ​​​​​​​​​​​​​A hydrosiloxane or hydrosiloxane derivative containing at least two SiH groups per molecule, or a mixture of several hydro-siloxanes or derivatives (see the abstract). Examples of crosslinking agents are shown below: including, or a mixture of several hydro-siloxanes or derivatives (see the abstract). Examples of crosslinking agents are shown below: (See).

[0004]

Chemical formula

[0028] ). The filler includes a surface-modified silicate (see paragraph

[0035] ). wherein R 2 is a divalent organic group having 1 to 30 carbon atoms or oxygen atoms (see paragraph

[0028] ). The filler includes a surface-modified silicate (see paragraph

[0035] ). (See).

[0005] U.S. Patent No. 6,251,998 discloses the vulcanization of an elastomeric polymer blend in the presence of a hydrosilylation agent and a hydrosilylation catalyst, wherein the elastomer contains about 40 to about 9 0 weight percent of ethylene and at least about 0.25 weight percent of vinyl norbornene and has a Mooney viscosity of 45 to 100 (see claim 1). 0 weight percent of ethylene and at least about 0.25 weight percent of vinyl norbornene and has a Mooney viscosity of 45 to 100 (see claim 1). contains and has a Mooney viscosity of 45 to 100 (see claim 1). The hydrosilylation agent is a hydrogenated silicon compound having at least two SiH groups. Useful compounds include methylhydrogenpolysiloxane, methylhydrogen dimethyldimethyl siloxane copolymer, methylhydrogenalkylmethylpolysiloxane, bis(dimethylsilyl)alkane, and bis(dimethylsilyl)benzene. See column 5, lines 23 to 35 siloxane copolymer, methylhydrogenalkylmethylpolysiloxane, bis(dimethylsilyl)alkane, and bis(dimethylsilyl)benzene. See column 5, lines 23 to 35 siloxane copolymer, methylhydrogenalkylmethylpolysiloxane, bis(dimethylsilyl)alkane, and bis(dimethylsilyl)benzene. See column 5, lines 23 to 35 l)alkane, and bis(dimethylsilyl)benzene. See column 5, lines 23 to 35 (See).

[0006] U.S. Patent No. 5,936,028 relates to a process for the hydrosilylation crosslinking of "diene-containing" elastomers by dynamic vulcanization in the presence of an olefinic thermoplastic resin, a hydrosilylation agent, a platinum-containing hydrosilylation catalyst, and a filler or processing oil (see Claim 1). Preferred hydrosilylation agents are silicon hydride compounds represented by the following formula: : wherein D represents -(Si(R)(R)-O)-, D' represents

[0007]

Chem.

[0008]

Chem.

[0009] U.S. Patent No. 6,864,315 relates to an ethylene / alpha-olefin / non-conjugated polyene random copolymer containing a specific vinyl end group-containing norbornene compound, and one molecule A SiH group-containing compound having at least two SiH groups in it, and optionally, an addition reaction catalyst containing a platinum group element, and a reaction inhibitor, are disclosed in a crosslinkable rubber composition (see the abstract). The SiH group-containing compound and the resin produced can be linear, cyclic, branched, and three-dimensional network structures (see lines 38-49, column 33). The rubber reinforcing agent includes silica surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, alkoxysilane, or low molecular weight siloxane (see lines 9-22, column 44). Additional hydrosilylation reactions and polymer formulations are disclosed below: U.S. Patent Application Publication No. 2003 / 0127239, European Patent No. 0310129 (A2), British Patent No. 1118327 (A) (abstract), Japanese Unexamined Patent Application Publication No. 10212389 (A) (machine translation ), and Japanese Patent No. 8003324 (A) (abstract), Journal of Poly mer (Kobunshi Ronbunshu), 2007, 64(4), 204-2 14, Journal of Polymer (Kobunshi Ronbunshu ), 2007, 64(4), 215-222, Journal of Polymer(

[0010] Kobunshi Ronbunshu), 2006, 63(4), 257-265. However, as considered, there is still a need for new curing processes and related compositions that reduce VOCs and odors associated with cured rubber formulations and maintain or improve curing characteristics. These needs are met by the following invention.

Summary of the Invention

[0011] ​​​​​​​​​

[0012] In a first aspect, a process for forming a crosslinked composition, the process comprising a) an elastomer, and b) a siloxy-modified silica, and c) a hydrosilylation catalyst, heat treating a composition comprising the same.

[0013] In a second aspect, a) an elastomer, and b) a siloxy-modified silica, and c) a hydrosilylation catalyst, a composition comprising the same.

DETAILED DESCRIPTION OF THE INVENTION

[0014] A hydrosilylation process has been discovered that effectively crosslinks a composition comprising an elastomer, a siloxy-modified silica, and a hydrosilylation catalyst, resulting in a reduction in odor compared to conventional sulfur-cured compositions. Generally, the composition exhibits an increase in the level of crosslinking as indicated by the "MH-ML" difference compared to compositions containing other types of silane or siloxane compounds and compared to conventional sulfur-cured compositions. Also, the addition of a specific polybutadiene has been found to assist in increasing the "MH-ML" difference indicating the occurrence of additional reactions.

[0015] A process for forming a crosslinked composition as described in the first aspect of the invention discussed above is provided. Also, a composition as described in the second aspect of the invention discussed above is provided. The above process (first aspect) may include a combination of two or more embodiments as described herein. The above composition (second aspect) may include a combination of two or more embodiments as described herein. Each of components a, b, and c is as described in this ​​​​It may include combinations of two or more embodiments as described in the specification. The following embodiments are applicable to both the first and second aspects of the present invention.

[0016] In each embodiment described herein or a combination of two or more embodiments, the elastomer is selected from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii ) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, or ix) halogenated nitrile rubber, and further from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene , iv) styrene-butadiene rubber, v) nitrile rubber, and further from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers.

[0017] In each embodiment described herein or a combination of two or more embodiments, component b has a viscosity of ≦500 cSt, or ≦400 cSt, or ≦300 cSt, or ≦200 c St, or ≦100 cSt, or ≦50 cSt, or ≦40 cSt at 25°C. In each embodiment described herein or a combination of two or more embodiments, component b has a viscosity of ≧0.5 cSt, or ≧1.0 cSt, or ≧1.5 cSt, or ≧2.0 cSt at 25°C, or ≧2.5 cSt, or ≧3.0 cSt, or ≧3.5 cSt, or ≧4.0 cSt , or ≧4.5 cSt, or ≧5.0 cSt, or ≧6.0 cSt, or ≧8.0 cSt , or ≧10 cSt, or ≧12 cSt, or ≧14 cSt, or ≧16 cSt, or ≧1 8 cSt, or ≧20 cSt, or ≧25 cSt, or ≧30 cSt, or ≧35 cSt, or ≧40 cSt, or ≧45 cSt, or ≧50 cSt at 25°C. It has a viscosity of 8 cSt or ≥ 20 cSt.

[0018] In each embodiment described herein or a combination of two or more embodiments, the siloxy portion of the modified silica (component b) has the following Structure 1 of ≥ 4 units, or ≥ 6 units, or ≥ 8 units, or ≥ 10 units, or ≥ 15 units, or ≥ 20 units:

[0019]

Chemical formula

[0020]

Chemical formula

[0021] In each embodiment described herein or a combination of two or more embodiments, the siloxy portion of the modified silica is derived from a silica Q resin.

[0022] In each embodiment described herein or a combination of two or more embodiments, the hydrosilylation catalyst includes Pt, Pd, Rh, Re, Ir, Ru, or a mixture thereof, and further includes Pt .

[0023] ​In each embodiment described herein or in a combination of two or more embodiments, the composition further comprises polybutadiene, and more particularly liquid polybutadiene (at 25 °C, ambient atmosphere). This polybutadiene is different from the polybutadiene elastomer of component a (for example, having a lower Mn ).

[0024] In each embodiment described herein or in a combination of two or more embodiments, the polybuta diene comprises a 1,2-vinyl content of ≧5.0 mol%, or ≧10 mol%, or ≧15 mol%, or ≧20 mol%, or ≧22 mo l%, or ≧24 mol%, or ≧26 mol% based on the total moles of carbon-carbon double bond groups in the polybutadiene. In each embodiment described herein or in a combination of two or more embodiments, the polybutadiene comprises a 1,2-vinyl content of ≦50 mol%, or ≦45 mol%, or ≦40 mol%, or ≦38 mol%, or ≦36 mol%, or ≦34 mol%, or ≦32 mol%, or ≦30 mol% based on the total moles of carbon-carbon double bond groups in the polybutadiene. The 1,2-vinyl content can be determined using 1H NMR. For example, dissolve the polymer in tetrachloroethane-d2 in an 8 mm NMR tube using a BRUKER AVANCE 6 00 MHz spectrometer equipped with a 10 mm C / H DUAL cryoprobe. One skilled in the art can determine the total C-C double bond content and the 1,2-vinyl content from the NMR profile. 00 MHz spectrometer using an 8 mm NMR tube and dissolving the polymer in tetrachloroethane -d2. One skilled in the art can determine the total amount of C-C double bond content and the 1,2-vinyl content from the NMR profile. quantity and the 1,2-vinyl content.

[0025] In each embodiment described herein or in a combination of two or more embodiments, the polybuta diene has a molecular weight of ≧500 g / mol, or ≧600 g / mol, or ≧700 g / mol, or is ≥ 800 g / mol, or ≥ 900 g / mol, or ≥ 1,000 g / mol, or ≥ 1,200 g / mol, or ≥ 1,400 g / mol, or ≥ 1,600 g / mol, or is ≥ 1,800 g / mol, or ≥ 2,000 g / mol in number average molecular weight (Mn). In each embodiment described herein or a combination of two or more embodiments, polybutadiene has a number average molecular weight (Mn) of ≤ 10,000 g / mol, or ≤ 8 ,000 g / mol, or ≤ 6,000 g / mol, or ≤ 4,000 g / mol, or ≤ 3,000 g / mol.

[0026] In each embodiment described herein or a combination of two or more embodiments, the elastomer of component a is an ethylene / alpha-olefin / non-conjugated polyene interpolymer, more specifically EPDM. In each embodiment described herein or a combination of two or more embodiments combined, the non-conjugated polyene of the ethylene / alpha-olefin / non-conjugated polyene interpolymer, more specifically EPDM, is ENB.

[0027] In each embodiment described herein or a combination of two or more embodiments, the composition is heat-treated at a temperature of ≥ 90 °C, or ≥ 100 °C, or ≥ 110 °C, or ≥ 120 °C. In each embodiment described herein or a combination of two or more embodiments, the composition is heat-treated at a temperature of ≤ 220 °C, or ≤ 210 °C, or ≤ 200 °C, or ≤ 190 °C, or ≤ 180 °C, or ≤ 170 °C, or ≤ 160 °C, or ≤ 150 °C.

[0028] Also provided are crosslinked compositions formed from a process or composition of any one or combination of two or more of the embodiments described herein. Also provided are articles formed from a composition of any one or combination of two or more of the embodiments described herein. An elastomer is a polymer having viscoelastic (i.e., both viscous and elastic) properties. As discussed above, elastomers include, but are not limited to, i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, and ix) halogenated nitrile rubber.

[0029] Elastomer An elastomer is a polymer having viscoelastic (i.e., both viscous and elastic) properties. As discussed above, elastomers include, but are not limited to, i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, and ix) halogenated nitrile rubber. The ethylene / alpha-olefin / non-conjugated polyene interpolymers described herein include, in polymeric form, ethylene, an alpha-olefin, and a non-conjugated polyene. The alpha-olefin can be either an aliphatic or aromatic compound. The alpha-olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, more preferably a C3-C10 aliphatic compound. In one embodiment, the interpolymer is an ethylene / polyethylene / non-conjugated diene interpolymer, and even more preferably a terpolymer. Suitable examples of non-conjugated polyenes include C4-C40 non-conjugated dienes. In one embodiment, the polyene is a non-conjugated diene, and even more preferably 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, 1,4

[0030] The ethylene / alpha-olefin / non-conjugated polyene interpolymers described herein include, in polymeric form, ethylene, an alpha-olefin, and a non-conjugated polyene. The alpha-olefin can be either an aliphatic or aromatic compound. The alpha-olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, more preferably a C3-C10 aliphatic compound. In one embodiment, the interpolymer is an ethylene / polyethylene / non-conjugated diene interpolymer, and even more preferably a terpolymer. The alpha-olefin can be either an aliphatic or aromatic compound. The alpha-olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, more preferably a C3-C10 aliphatic compound. In one embodiment, the interpolymer is an ethylene / polyethylene / non-conjugated diene interpolymer, and even more preferably a terpolymer. Suitable examples of non-conjugated polyenes include C4-C40 non-conjugated dienes. In one embodiment, the polyene is a non-conjugated diene, and even more preferably 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, 1,4 The ethylene / alpha-olefin / non-conjugated polyene interpolymers described herein include, in polymeric form, ethylene, an alpha-olefin, and a non-conjugated polyene. The alpha-olefin can be either an aliphatic or aromatic compound. The alpha-olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, more preferably a C3-C10 aliphatic compound. In one embodiment, the interpolymer is an ethylene / polyethylene / non-conjugated diene interpolymer, and even more preferably a terpolymer. Suitable examples of non-conjugated polyenes include C4-C40 non-conjugated dienes. In one embodiment, the polyene is a non-conjugated diene, and even more preferably 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, 1,4 (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, 1,4 - hexadiene, or 7 - methyl - 1,6 - octadiene, and further ENB, VNB, dicyclopentadiene, or 1,4 - hexadiene, and further selected from ENB or VNB and more preferably ENB.

[0031] Examples of polyisoprene include natural polyisoprenes such as cis - 1,4 - polyisoprene (natural rubber (NR)) and trans - 1,4 - polyisoprene (gutta - percha), as well as synthetic polyisoprene (IR (isoprene rubber) representing isoprene rubber). Examples of polybutadiene (or BR (butadiene rubber) representing butadiene rubber) include polymers of 1,3 - butadiene. Examples of polychloroprene include polymers of chloroprene. Examples of butyl rubber include copolymers of isobutylene and isoprene (IIR). Examples of halogenated butyl rubber include chlorobutyl rubber (CIIR) and bromobutyl rubber (BIIR). Examples of styrene - butadiene rubber include copolymers of styrene and butadiene (Styrene - butadiene rubbers, SBR). Examples of nitrile rubber include copolymers of butadiene and acrylonitrile (NBR).

[0032] Siloxy - modified silica Siloxy - modified silica contains a Q structure (see the following examples) and at least three silane (Si - H) groups. Siloxy - modified silica has a Q n M H mrepresented by the formula as can be (see, for example, Scheme 1 below (here a dimethylsilane group)) ), where n ≥ 2, or n ≥ 3, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 15, or m ≥ 20. This modified silica can also be referred to as an MQ resin The Q n portion of this modified silica is a highly cross-linked structure where oxygen atoms are shared between each Q unit and, when Q and M are bonded, also shared between the Q unit and the M unit In one embodiment, Q and M are bonded

[0033]

Chemical formula

[0034]

Chemical formula

[0035] Another representation of the siloxy-modified silica is shown in the following structure S6, which shows some silane groups bonded to the Q-resin, and the Q-resin shown in structure S7 is a condensed tetraoxysiloxane

[0036] ​​

Chem.

[0037] Structure S6 can be prepared by the condensation of tetramethoxysilane (also known as tetramethyl orthosilicate, CAS: 681-84-5) and 1,1,3,3-tetramethyldisiloxane (also known as [(dimethylsilyl)oxy]dimethylsilane, CAS: 3277-26-7) under acidic aqueous conditions. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20. -26-7) can be used. Other methods for preparing Structure S6 include the condensation between tetraalkoxysilane (or tetrachlorosilane or sodium silicate) and dimethylalkoxysilane (or dimethylchlorosilane). In Structure S7), n ≥ 2, or n ≥ 4, or n ≥ 6, or n ≥ 8, or n ≥ 10, or n ≥ 15, or n ≥ 20, and in Structure S6, m ≥ 3, or m ≥ 4, or m ≥ 6, or m ≥ 8, or m ≥ 10, or m ≥ 20.

[0038] Examples of siloxy-modified silica include dimethylhydrogensiloxy-modified silica (CAS: 102262-28-2) from Dow Chemical Company, as well as HQM-105 and HQM-107 from Gelest. Examples of siloxy-modified silica include dimethylhydrogensiloxy-modified silica (CAS: 102262-28-2) from Dow Chemical Company, as well as HQM-105 and HQM-107 from Gelest. Examples of siloxy-modified silica include dimethylhydrogensiloxy-modified silica (CAS: 102262-28-2) from Dow Chemical Company, as well as HQM-105 and HQM-107 from Gelest.

[0039] Hydrosilylation Catalyst As used herein, a hydrosilylation catalyst is a compound that promotes the reaction between siloxy-modified silica and an alkene group on an elastomer. Suitable catalysts include those based on platinum (Pt), or other metals such as Pd, Rh, Re, Ir, or Ru. In one embodiment, the metal, and more particularly Pt, is used with vinyl-terminated PDMS. As used herein, a hydrosilylation catalyst is a compound that promotes the reaction between siloxy-modified silica and an alkene group on an elastomer. Suitable catalysts include those based on platinum (Pt), or other metals such as Pd, Rh, Re, Ir, or Ru. In one embodiment, the metal, and more particularly Pt, is used with vinyl-terminated PDMS. As used herein, a hydrosilylation catalyst is a compound that promotes the reaction between siloxy-modified silica and an alkene group on an elastomer. Suitable catalysts include those based on platinum (Pt), or other metals such as Pd, Rh, Re, Ir, or Ru. In one embodiment, the metal, and more particularly Pt, is used with vinyl-terminated PDMS. As used herein, a hydrosilylation catalyst is a compound that promotes the reaction between siloxy-modified silica and an alkene group on an elastomer. Suitable catalysts include those based on platinum (Pt), or other metals such as Pd, Rh, Re, Ir, or Ru. In one embodiment, the metal, and more particularly Pt, is used with vinyl-terminated PDMS. It is dissolved. In one embodiment, the catalyst is a Karstedt catalyst (i.e., platinum(0)- 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complex solution). K arstedt catalyst is commercially available (Sigma Aldrich) as a Pt solution in xylene with 2 wt% Pt based on the weight of the solution. In one embodiment, the catalyst comprises platinum, 1,3-diethenyl-1,1,3,3-tetramethyl-disiloxane complex.

[0040] Additives The inventive composition may include one or more additional additives. Suitable additives include, but are not limited to, fillers, oils, processing aids, stabilizers (e.g., antioxidants, anti-ozone agents, UV stabilizers), flame retardants, colorants, or pigments, and combinations thereof. Fillers include, but are not limited to, carbon black; calcium carbonate; silicon oxide; aluminum oxide; kaolinite; montmorillonite; aluminosilicates of aluminum, magnesium, calcium; titanium dioxide; natural fibers; synthetic fibers, etc. Oils include, but are not limited to, paraffin oil, naphthenic oil, and polyalkylbenzene oil. In one embodiment, the oil is selected from paraffin oil, naphthenic oil, and combinations thereof. Stabilizers include, but are not limited to, hindered phenols, bisphenols, thiobis-phenols, and substituted hydroquinones. Typically, amounts of one or more stabilizers in the "ppm" range are added to the polymer or polymer composition. Processing aids include PEG 4000 or PEGs with various molecular weights, fatty acids, fatty acids without Zn / Ca and Zn. Calcium oxide may be used as a desiccant.

[0041] ​​​​​​​​​ Definition Unless otherwise indicated, implied by context, or customary in the art, all parts and percentages are by weight, and all test methods are current as of the filing date of the present disclosure. As used herein, the term "composition" includes a composition and a mixture of materials including reaction products and decomposition products formed from the materials of the composition. Any reaction products or decomposition products are typically present in trace or residual amounts. Unless otherwise indicated, implied by context, or customary in the art, all parts and percentages are by weight, and all test methods are current as of the filing date of the present disclosure.

[0042] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same type or different types. Thus, the term "polymer" encompasses the term "homopolymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace impurities may be incorporated into the polymer structure), and the term "interpolymer" as defined hereinbelow. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers.

[0043] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term "interpolymer" encompasses the term "copolymer" (used to refer to a polymer prepared from two different types of monomers), and polymers formed from more than two different types of monomers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers.

[0044] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term "interpolymer" encompasses the term "copolymer" (used to refer to a polymer prepared from two different types of monomers), and polymers formed from more than two different types of monomers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers. including a polymer prepared therefrom.

[0045] As used herein, the term "olefin polymer" refers to a polymer in polymerized form that contains, based on the weight of the polymer, 50 weight percent or a majority weight percent of ethylene or an olefin such as propylene, and optionally may contain one or more comonomers. (based on the weight of the polymer) 50 weight percent or a majority weight percent of ethylene or an olefin such as propylene, and optionally may contain one or more comonomers. refers to a polymer.

[0046] As used herein, the term "propylene polymer" refers to a polymer in polymerized form that contains, based on the weight of the polymer, a majority weight percent of propylene, and optionally may contain one or more comonomers. (based on the weight of the polymer) a majority weight percent of propylene, and optionally may contain one or more comonomers. refers to a polymer.

[0047] As used herein, the term "ethylene polymer" refers to a polymer in polymerized form that contains, based on the weight of the polymer, 50 weight percent or a majority weight percent of ethylene, and optionally may contain one or more comonomers. (based on the weight of the polymer) 50 weight percent or a majority weight percent of ethylene, and optionally may contain one or more comonomers. refers to a polymer.

[0048] As used herein, the term "ethylene / alpha-olefin interpolymer" refers to a random interpolymer in polymerized form that contains, based on the weight of the interpolymer, 50 weight percent or a majority weight percent of ethylene and an alpha-olefin. (based on the weight of the interpolymer) 50 weight percent or a majority weight percent of ethylene and an alpha-olefin. refers to a random interpolymer.

[0049] As used herein, the term "ethylene / alpha-olefin / non-conjugated polyene interpolymer" refers to an interpolymer in polymerized form that contains ethylene, an alpha-olefin, and a non-conjugated polyene. In one embodiment, the "ethylene / alpha-olefin / non-conjugated polyene interpolymer" in polymerized form contains, based on the weight of the interpolymer, 50 weight percent or a majority weight percent of ethylene, an alpha-olefin, and a non-conjugated polyene. refers to an interpolymer. (based on the weight of the interpolymer) 50 weight percent or a majority weight percent of ethylene, an alpha-olefin, and a non-conjugated polyene. ​​contains ethylene (based on the weight of the interpolymer). As used herein the term "ethylene / alpha-olefin / non-conjugated diene interpolymer" refers to an interpolymer containing ethylene, an alpha-olefin, and a non-conjugated diene in polymerized form In one embodiment, the "ethylene / alpha-olefin / non-conjugated diene interpolymer" contains 50 weight percent or a majority weight percentage of ethylene (based on the weight of the interpolymer) in polymerized form The terms "ethylene / alpha-olefin / non-conjugated polyene terpolymer" and "ethylene / alpha-olefin / non-conjugated diene terpolymer" are similarly defined, but note that for each, the terpolymer contains ethylene, an alpha-olefin, and a polyene (or diene in polymerized form) as only three monomer types As used herein, the term "ethylene / alpha-olefin copolymer" refers to a random copolymer containing, in polymerized form, as only two monomer types, (based on the weight of the copolymer) 5 0 weight percent or a majority amount of ethylene monomer and an alpha-olefin

[0050] As used herein, the term "crosslinked composition" refers to a composition having a network structure resulting from the formation of chemical bonds between polymer chains The formation of this network structure can be indicated by an increase in the "MH-ML" difference discussed herein As used herein with respect to compositions containing elastomers, "heat treating" refers to

[0051] As used herein with respect to compositions containing elastomers, "heat treating" refers to a composition having a network structure resulting from the formation of chemical bonds between polymer chains The formation of this network structure can be indicated by an increase in the "MH-ML" difference discussed herein

[0052] As used herein with respect to compositions containing elastomers, "heat treating" The term "heat treatment", and like terms, refer to the application of heat to a composition. Heat can be applied by conduction (e.g., a heating coil), by convection (e.g., heat transfer through a fluid such as water or air), and / or by radiation (e.g., heat transfer using electromagnetic waves). Preferably, heat is applied by conduction or convection. The temperature at which the heat treatment is performed refers to the internal temperature of an oven or other device such as an MDR device (or tormer) used to cure (or crosslink) the elastomer. It should be noted that typically, the composition equilibrates readily (in less than 30 seconds) to the temperature of the oven or device.

[0053] With respect to a polymer (or interpolymer or terpolymer or copolymer), as used herein, the phrase "major weight percent" refers to the amount of the monomer that is present in the greatest amount in the polymer.

[0054] The terms "hydrocarbon group", "hydrocarbyl group", and like terms, as used herein, refer to a chemical group that contains only carbon atoms and hydrogen atoms.

[0055] The terms "comprising", "including", "having", and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid doubt, all compositions claimed through the use of the term "comprising" may contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless specifically stated to the contrary. In contrast, "consisting essentially of" ​ The term "comprising" excludes any following detailed description range or any other component, step, or procedure, except those essential for practicability. The term "consisting of" excludes any component, step, or procedure not specifically defined or enumerated.

[0056] Enumeration of characteristics of some processes and compositions A] A process for forming a crosslinked composition, the process comprising heat-treating a composition comprising a) an elastomer, b) a siloxy-modified silica, c) a hydrosilylation catalyst. B] The elastomer is selected from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, or ix) halogenated nitrile rubber, or further from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, or further from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, the process according to A] above. The process according to A] above. C] The siloxy moiety of the siloxy-modified silica (component b) has the following Structure 1 with ≧4 units, or ≧6 units, or ≧8 units, or ≧10 units, or ≧15 units, or ≧20 units:

[0057]

Chemical formula

[0058]

Chemical formula

[0059] Test method Gel permeation chromatography The chromatography system is a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with a built-in IR5 infrared detector (IR5) ​It consists of rough. Set the autosampler oven compartment to 160 degrees Celsius and the color compartment to 150 °C. The column is a 4-piece AGILENT "Mi xed A" 30 cm, 20 micron linear mixed-bed column. The chromatography eluent is 1,2,4-trichlorobenzene containing 200 ppm of butylated hydrox ytoluene (BHT). Inject nitrogen into the solvent source. The injection volume is 200 microliters and the flow rate is 1.0 milli liter / minute.

[0060] Calibrate the GPC column set using 2 1 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580 to 8,400,000 and place them in 6 "cocktail" mixtures having at least a 10-fold interval between individual molecular weights. The standards are purchased from Ag ilent Technologies. Prepare the polystyrene standards at "0.025 grams in 50 milliliters" of solvent for molecular weights above 1,000,000 and at "0.05 grams in 50 milliliters" of solvent for molecular weights below 1,000,000. Dissolve the polystyrene standards at 80 degrees Celsius with gentle stirring for 30 minutes. Convert the polystyrene standard peak molecular weights to polyethylene molecular weights using Equation 1 (Wi lliams and Ward, J. Polym. Sci., Polym. Let., as described in 6,621 (1968)). M = A × (M )B (Equation 1) (where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0). M ポリエチレン =A×(M ポリスチレン )B (Equation 1) (where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0).

[0061] Use a fifth-degree polynomial to fit each polyethylene equivalent calibration point. For A Make minor adjustments (approximately 0.375 - 0.445) to achieve column resolution and band broadening such that the linear homopolymer polyethylene standard gives a value of 120,000 Mw for calibration.

[0062] Measure the total plate count of the GPC column set using decane prepared with (T of "0.04 g in 50 milliliters" CB), dissolved for 20 minutes with gentle stirring. Perform the plate rate count (Equation 2) and symmetry (Equation 3) measurements with an injection of 200 microliters as follows.

[0063]

Equation

[0064]

Equation

[0065] Samples were prepared semi - automatically using PolymerChar "Instrument Control" software, where the target weight of the sample was set at 2 mg / ml, and through a PolymerChar high - temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a septum - capped vial pre - injected with nitrogen. The sample was dissolved at 160 °C for 2 hours under "low - speed" shaking. and through a PolymerChar high - temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a septum - capped vial pre - injected with nitrogen. The sample was dissolved at 160 °C for 2 hours under "low - speed" shaking. and through a PolymerChar high - temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a septum - capped vial pre - injected with nitrogen. The sample was dissolved at 160 °C for 2 hours under "low - speed" shaking. and through a PolymerChar high - temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a septum - capped vial pre - injected with nitrogen. The sample was dissolved at 160 °C for 2 hours under "low - speed" shaking.

[0066] Mn (GPC) 、Mw (GPC) 、and Mz (GPC) The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows: The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows: The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows: The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows: The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows: The calculations of are based on PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally - spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC - IR chromatograph to obtain the GPC results according to Equations 4 - 6. Equations 4 - 6 are as follows:

[0067]

Number

[0068] To monitor the deviation over time, a flow - rate marker (decane) was introduced into each sample through a micropump controlled by a PolymerChar GPC - IR system. Using this flow - rate marker (FM), each decane peak (RV(FM sample)) in the sample was compared with the decane peak in the narrow standard calibration (RV(FM calibrated)) To monitor the deviation over time, a flow - rate marker (decane) was introduced into each sample through a micropump controlled by a PolymerChar GPC - IR system. Using this flow - rate marker (FM), each decane peak (RV(FM sample)) in the sample was compared with the decane peak in the narrow standard calibration (RV(FM calibrated)) To monitor the deviation over time, a flow - rate marker (decane) was introduced into each sample through a micropump controlled by a PolymerChar GPC - IR system. Using this flow - rate marker (FM), each decane peak (RV(FM sample)) in the sample was compared with the decane peak in the narrow standard calibration (RV(FM calibrated)) To monitor the deviation over time, a flow - rate marker (decane) was introduced into each sample through a micropump controlled by a PolymerChar GPC - IR system. Using this flow - rate marker (FM), each decane peak (RV(FM sample)) in the sample was compared with the decane peak in the narrow standard calibration (RV(FM calibrated)) By matching with the -clause and RV, the pump flow rate (apparent flow rate) of each sample is linearly corrected. Then, any change in the time of the decanter marker peak is presumed to be related to a linear shift in the flow rate (effective flow rate) over the entire execution. To facilitate the highest accuracy of RV measurement of the flow marker peak, a least-squares fitting routine that fits the peak of the flow marker concentration chromatogram to a quadratic equation is used. Then, the first derivative of the quadratic equation is used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (for narrow standard calibration) is * calculated as in Equation 7: Flow (actual) = Flow (apparent) (RV (FM calibrated) / RV (FM sample)) (Equation 7). The processing of the flow marker peak is performed via PolymerChar GPCOne (trademark)

[0069] software. The acceptable flow correction is such that the effective flow rate is within + / - 0. 7% of the apparent flow rate. The melt index of the ethylene-based polymer was measured according to ASTM D-1238, condition

[0070] 190 °C / 2.16 kg. The melt flow rate of the propylene-based polymer was measured according to ASTM D-1238, condition 230 °C / 2.16 kg

[0071] The Mooney viscosity of the polymer (without oil, without filler) The Mooney viscosity (ML1+4 at 125 °C) was measured with a preheating time of 1 minute and a rotor The operating time was measured in accordance with ASTM 1646. This equipment was the Alpha Technologies Mooney Viscometer 2000. The sample was about 25 grams in size.

[0072] Mooney viscosity of the composition The Mooney viscosity (ML1+4) and stress relaxation (ML1+4+2 minutes) of each composition were recorded at 100 °C (large rotor) using an Alpha Technologies MV2000 E viscometer in accordance with ASTM D1646-19. The preheating time was 1 minute. The viscosity of each compounded composition was measured using an uncured sheet of about 25 grams (see the experimental section).

[0073] Curing kinetics - MDR The curing characteristics were measured at 185 °C or 180 °C at 0.5 degrees using a Priscott Rheo-Line Moving Die Rhe ometer in accordance with ASTM-D5289-15. The test period was 20 minutes at 185 °C or 15 minutes at 180 °C. Each sample (4 - 5 grams) was cut from its respective uncured sheet (see the experimental section). The following data from each MDR run were used: MH (dN m), i.e., the maximum torque applied by the MDR during the test interval (this usually corresponds to the torque applied at the end of the test interval or the maximum torque reached during the MDR test), ML (dN * m), i.e., the minimum torque applied by the MDR during the test interval (this usually corresponds to the lowest torque during the MDR test). Further reported values were ts1 and * m), i.e., the minimum torque applied by the MDR during the test interval (this usually corresponds to the lowest torque during the MDR test). Further reported values were ts1 and ts2 (time to reach an increase of "1 unit" and "2 units" of torque from ML, respectively) ), T10% (or tc10), T20%, T50% (or tc50), and T90% (or tc90) (time to reach 10%, 20%, 50%, and 90% of the maximum cure or MH value, respectively) ). It should be noted that the composition easily equilibrates to the set temperature of the MDR device (in less than 3 0 minutes).

[0074] Tensile strength Tensile properties were measured in accordance with ASTM D4 12 using a Zwick Roell Z010 device. Each dumbbell sample (Type 5A) was punched from a compression molded (cured) plaque (T90% + 5 minutes, 185 °C, 10 MPa, 2 mm thick plaque) - see the experimental section. Here, "T90%" is the time at which the sample reaches 90% of its maximum cure value (MH value) as determined by MDR. Tensile properties (tensile strength and elongation at break (or tensile elongation), modulus of elasticity) were measured in accordance with Method ASTM D - 412 at room temperature, in the machine direction, and at a travel speed of 500 mm / min.

[0075] FTIR method for EPDM composition analysis An EPDM polymer containing ethylene, propylene, and 5 - ethylidene - 2 - norbornene was analyzed for ethylene content using ASTM D3900 and for ethylidene - norbornene content using ASTM D6047. Similar analyses can be used to measure the monomer content of other interpolymers and terpolymers (e.g., C2, alpha - olefin, or diene).

[0076] Compression set ​​Compression set was measured according to ASTM D395 for 24 hours at 70 °C. The diameter "29 mm" and thickness "12 mm" disks were punched from compression molded plaques (185 °C, 10 MPa a, T90% + 10 minutes, 12 mm thick). See the experimental section. Each sample disk was inspected for dents, non-uniform thickness, and inhomogeneity, and the selected disks (without these defects) were tested. Compression set was performed on two specimens for each composition, and the average results were reported. A compression device having two metal plates that can be pressed together and fixed at a position 25% of the original height of the button sample was used to place the disks. The disks were placed in a compression device having two metal plates that can be pressed together and fixed at a position 25% of the original height of the button sample. Then, together with the disks to be compressed, the compression device was placed in an oven and equilibrated at the appropriate temperature for a specified time (24 hours at 70 °C or 168 hours at 70 °C). In this test, the stress was released at the test temperature, and after a "30-minute" equilibration period at room temperature, the thickness of the sample disk was measured. Compression set is a measure of the degree of recovery of the sample after compression and is calculated according to the equation CS=(H0 - H2) / (H0 - H1). Wherein, H 0 is the original thickness of the disk, H1 is the thickness of the spacer bar used, and H2 is the final thickness of the disk after removal of the compressive force. 0 is the original thickness of the disk, H1 is the thickness of the spacer bar used, and H2 is the final thickness of the disk after removal of the compressive force.

[0077] Shore A hardness Shore A hardness was measured according to ASTM D2240 using three-layer tensile strength samples (T90% + 10 minutes, 185 °C, 100 MPa a) total thickness of three layers 6 mm). The Shore A hardness was measured with an INSTRO N Shore A Durometer Model 2000 equipped with a Durometer Stand Model 902. This method Hardness measurement can be based on either the initial dent or the dent after a specific time, or both. Here, the dent was measured after a specified time of 3 seconds. Here, the dent was measured after a specified time of 3 seconds.

[0078] Odor test Sample preparation - Square pieces of "3.8 cm × 3.8 cm × 2 mm" of compression - molded plaque ( see the experimental section) were placed in 100 mL glass vials for testing. The vials were fixed with lids. The sample vials were labeled with random numbers. The order of the samples presented to the panelists was also random. The sealed glass vials were heated in an oven at 80 °C for 2 hours and then cooled to 60 °C. The trained human panel consisted of in - house employees certified by SGS.Co.Ltd. for odor intensity and hedonic training. A total of 15 panelists participated in this sensory test. certified by SGS.Co.Ltd. for odor intensity and hedonic training. A total of 15 panelists participated in this sensory test. A total of 15 panelists participated in this sensory test.

[0079] Paired - comparison method - Two sets of samples (sealed glass vials) were prepared for each panelist, and each set was placed on one sample tray so that the panelist could evaluate them in the same test. For odor intensity and hedonic (pleasant or unpleasant) odor, each panelist evaluated each sample. After evaluating the first sample set, the panelist evaluated each sample regarding odor characteristics. Then, each panelist evaluated only the second sample set regarding odor intensity. The paired - comparison method has traditionally been regarded as the simplest discrimination test. The panelist was asked to choose which of the two samples had the weakest (more favorable) odor. This method determined whether there was a difference between the two samples, and if there was a difference, which one was more favorable. Two sets of samples were evaluated to obtain a measure of the reproducibility of the test. to choose which of the two samples had the weakest (more favorable) odor. This method determined whether there was a difference between the two samples, and if there was a difference, which one was more favorable. Two sets of samples were evaluated to obtain a measure of the reproducibility of the test. which one was more favorable. Two sets of samples were evaluated to obtain a measure of the reproducibility of the test. Provided.

[0080] Die T tear strength The tear strength was measured according to ASTM D624 Type-T (Trouser Tear sample) Therefore, it was measured with a Zwick Roell Z010 device at a moving speed of 100 mm / min Determined. Test samples were cut out from compression-molded (cured) plaques (T90% + 5 minutes, 185 °C, 10 MPa, 2 mm thick ).

[0081] Kinematic viscosity The kinematic viscosity (cSt) was determined according to ASTM D-445, for example, using a Cannon-Fenske (No. 150) viscometer at a constant bath (e.g., water) temperature of 25 °C + / - 0.2 °C .

[0082] Experiment Commercially available polymers and additives NORDEL4760P, EPDM, MV = 60 (ML1+4, 125 °C), density = 0 .88 g / cc, crystallinity % = 10%, 4.9 wt% ENB, 67 wt% ethylene, available from Dow Chemical Company. NORDEL4770P, EPD M, MV = 70 (ML1+4, 125 °C), density = 0.88 g / cc, crystallinity % = 13 %, 4.9 wt% ENB, 70 wt% ethylene, available from Dow Chemical Compa ny. VISTALON1705, EPDM, MV = 35~51 (ML1+ 4, 125 °C), 0.70~0.90 wt% VNB, 62~77 wt% ethylene, available from Exxon Mobil . Available.

[0083] Natural rubber SVR3L, density = 0.92 g / cc, available from Vietnam. Zhe Polybutadiene rubber available from Jiang Transfar Chemicals BR9000. Styrene-butadiene rubber SBR1502, specific gravity = 0.94 g / cc (based on water) ), available from Sinopec Yangzi Petrochemical Compan y LTD. Nitrile rubber NBR3370c available from Lanxess .

[0084] Hydrosilylation catalyst: Platinum in a vinyl-terminated polydimethylsiloxane solution, 1,3-diene nyl-1,1,3,3-tetramethyldisiloxane complex (CAS: 68478-92- 2) (about 5200 ppm of Pt). Such a catalyst complex is available from the Dow Chemi cal Company.

[0085] Carbon black N-550 available from Cabot. Calcium carbonate (CaCO3) filler available from Omya . Silicate - VN-3 (SiO2) available from Evonik .

[0086] 2,4,6,8-Tetramethyltetravinylcyclotetrasiloxane (vi-d4) (CAS: 2554-06-5 ) available from the Dow Chemical Company. Multi-vinylsiloxane: A dimethylcyclic compound containing tetrakis(vinyldimethylsiloxy)silane (CAS: 316374-82-0) . Such a mixture is available from the Do w Chemical Company.

[0087] RICON130 (CAS: 9003-17-2), 28 mol% of 1,2-vinyl content , and polybutadiene having Mn = 2500 g / mol, Total Cray ​Available from Valley. NISSO PB B-1000 (CAS: 9003-17 -2), having a 1,2-vinyl content of 85 mol%, and Mn = 1200 g / mol Polybutadiene, available from Nippon Soda Co., Ltd.

[0088] Available from Sinopharm Chemical Reagent Co., Ltd. Possible TAIC (triallyl isocyanurate, triallyl isocyanurate rate). Sinopharm Chemical Reagent Co., Ltd. Available from TRIM (trimethylolpropane trimethac rylate, trimethylolpropane trimethacrylate) from Sinopharm Chemical Reagent Co., Ltd. SUNPAR2280- Plasticizer / paraffin oil, available from R.E. Carroll, Inc. RHENOG RAN ZnO-80 - Curing activator, available from Rhein Chemie. Stearic acid - Curing activator and processing aid, available from Loxiol. RHENOGRAN Ca O-80 - Desiccant, available from Rhein Chemie. PEG4000 - Processing aid (Polyethylene glycol), available from Sinoreagent, China

[0089] RHENOGRAN MBTS-75 - Curing accelerator, available from Rhein Chemie RHENOGRAN MBTS-80 - Curing accelerator, available from Rhein Chemie RHENOGRAN ZDEC-80 - Curing accelerator, available from Rhein Che mie. RHENOGRAN C BS-80 - Delayed action accelerator, available from Rhein Chemie. RHENOGRAN S-80 - Curing agent, Rhein C Available from Hemie. DTDM-80 - Curing accelerator, available from Rhein Chemie Available from Rhein Chemie. TETD-75 - Curing accelerator, available from Rhein Chemie. TE TD-80 - Curing accelerator, available from Rhein Chemie. ZDBC-80 - Har dening accelerator, available from Rhein Chemie. ZDEC-80 - Curing accelerator, Rh ein Chemie. Available from

[0090] Si-H-1: Dimethylhydrogen siloxy modified silica (CAS: 102262-28-2) , viscosity = 25 cSt (25 °C), available from the Dow Chemical Company or.

[0091] Si-H-2: DOWSIL 6-3570 polymer (linear siloxane) (CAS: 68 037-59-2), fluid, viscosity = 5 cSt (25 °C), available from the Dow Chemic al Company. It is not siloxy modified silica.

[0092] Si-H-3: HQM-105 (CAS: 68988-57-8), hydrogenated modified silica Q resin (siloxy - modified silica), viscosity = 3 - 5 cSt (25 °C), available from Gelest.

[0093] Si-H-4: Tris(dimethylsilyloxy)phenylsilane (CAS: 18027-45-7) available from TCI Shanghai .

[0094] Si-H-5: Methyltris(dimethylsilyl)silane (CAS: 17082-46-1) available from TCI Shanghai .

[0095] Si-H-6: 1,3,5,7-Tetramethylcyclotetrasiloxane (CAS: 2370-88-9) available from TCI Shanghai.

[0096] Si-H-7: Tetrakis(dimethylsiloxy)silane (CAS: 17082-47-2) available from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0097] Si-H-8: 1,1,3,3,5,5-Hexamethyltrisiloxane (CAS: 1189-93-1) available from Alfa Aesar.

[0098] Si-H-9: 1,1,3,3-Tetramethyldisiloxane (CAS: 3277-26-7) available from Alfa Aesar.

[0099] Si-H-10: Phenylsilsesquioxane, hydrogen-terminated (CAS: 68952-30-7) available from the Dow Chemical Company.

[0100] Compounding process - Studies 1 to 3 and 5 The filler (CaCO3, carbon black N550), oil (SUNPAR2280), and liquid additives (hydrosilicone (「Si-H-」 compounds), hydrosilylation catalyst) and the remaining additives were weighed into a container and mixed by hand until the mixture changed to black solid particles. Next, the solid particles were charged into a closed mixer (HAAKE Polylab OS) and mixed at 40 °C and 45 RPM. After 1 minute, the elastomer was added to the mixer, and then the mixer was covered and mixing was continued for about 1 minute until the torque of the mixed composition became balanced (about 38 - 40 Nm). Steps. Next, the RPM of the HAAKE mixer was increased to 70 RPM, and mixing was continued for 6 minutes. . Then, mixing was stopped (when the mixing composition reached about 100 °C). Then, the resulting composition was taken out of the mixer and pressed into plaques (about 5 mm thick) using a hydraulic press at 2.5 MPa and room temperature. For MDR measurement, a small piece of plaque with a square area (about 30 mm × 30 mm , 6 - 8 grams) was cut out. MDR was measured at 185 °C for 20 minutes using a Priscott Rheo - Line Moving Die Rheometer according to ASTM - D528 9 - 15.

[0101] Compositions for physical and mechanical properties, and odor tests were prepared by the above - described closed - mixing method. Each resulting composition was compression - molded at 185 °C, 10 MPa, for a time of "T90% + 5 minutes". The mold was "2 mm thick", and the area of the plaque was "15 cm × 15 cm". Each dumbbell (type 5A) test sample was punched out from the plaque. Plaques for compression set were prepared by compression - molding at 185 °C, 10 MPa, T90% + 10 minutes. Each test sample was a circular disk with a diameter of "12 mm thick × 29 mm" punched out from the compression - molded plaque.

[0102] Study 1 - Effect of different "Si - H" compounds on hydrosilylation curing Table 1 lists the MDR curing characteristics for six inventive compositions (Inv.1 - Inv.6) and eight comparative compositions (Comp A - Comp.H). As can be seen from Table 1, compositions containing two siloxy - modified silica compounds (Si - H - 1 and Si - H - 3) , as indicated by the high "MH-ML" value, had a high level of curing. Optimal results were obtained with compositions containing the "Si-H-1" compound (Inv.1, and Inv.3 - Inv.6). Refer to the results of "MH-ML" and "[(MH-ML) / T90%]".

[0103] The curing characteristics, mechanical characteristics, and odor ratings of the inventive composition (Inv.1) and the comparative industrial composition (Comp.I) are shown in Table 2. The inventive composition had good curing characteristics and good mechanical characteristics with respect to tensile strength, elongation, hardness, and tear. The inventive composition had excellent compression set. Most importantly, the odor test showed that the odor characteristics of the "hydrosilylation-cured EPDM" of the inventive composition were significantly better than those of the "sulfur-cured EPDM" of the industrial composition. Note that the degradation of the samples was carried out in a hot air circulation (convection) oven.

[0104] Study 2 - Filling amounts of filler, oil, and / or curing agent with respect to mechanical characteristics The mechanical characteristics of different formulations containing the siloxy-modified silica compound (Si-H-1) are shown in Tables 3A and 3B. As can be seen in these tables, the elastomer filling amount was varied from 21 to 30 wt%, the weight ratio of filler to oil was varied from about 2.0 to 2.5, the hydrosilylation catalyst filling amount was varied from 0.8 to 2.5 phr, and the Si-H-1 compound was varied from 3.0 to 8.0 phr. All the elastomer formulations gave reasonable mechanical characteristics such as a tensile strength (TS) varying from 5.6 to 8.8 MPa and a tensile elongation (TE) varying from 126 to 488%. Containing 28 - 30 wt% of EPDM Inventive Examples 12 to 18 had optimal properties for weatherstrip products.

[0105] Study 3 - Hydrosilylation Curing of Different Elastomers Table 4 demonstrates that hydrosilylation crosslinking is achievable not only with EPDM (NORDEL 4760P), but also applicable to other elastomers such as natural rubber (SVR 3L), polybutadiene rubber (BR 9000), styrene butadiene rubber (SBR 1502), and nitrile rubber (NBR 3370c).

[0106]

Table 1

[0107]

Table 2

[0108]

Table 3

[0109]

Table 4

[0110]

Table 5

[0111] Study on Continuous Vulcanization of 4 - Elastomer Mixing of Compounds Carbon black (N550) and calcium carbonate were dried in a vacuum oven at 120 °C for 12 hours before use. Using a typical "top - bottom reverse" mixing procedure, all compositions were mixed. For the inventive compositions (Inv.24 and Inv.25), for better dispersion, the Si - H - 1 compound and the hydrosilylation catalyst were premixed with the fillers (carbon black and CaCO3 ) and the oil. The initial mixing temperature was 40 °C, and this premix was slowly mixed at 10 RPM for 120 seconds, then the polymer and all other chemical components were added, and the mixing was continued at 30 RPM for another 5 minutes. For the comparative composition (Comp.J), the initial mixing temperature was 40 °C, the fillers and the oil were slowly mixed at 10 RPM for 120 seconds, then all other chemical components except the polymer and sulfur were added. Mixing was continued at 30 RPM for another 5 minutes, then sulfur was added, and mixing was continued at 30 RPM for another 5 minutes. For each of the inventive compositions and the comparative composition, mixing was continued for another 5 minutes, then the composition was put on a tray at about 90 °C. The motor current and the composition temperature were recorded every 30 seconds. The filling ratio was For each of the inventive compositions and the comparative composition, mixing was continued for another 5 minutes, then the composition was put on a tray at about 90 °C. The motor current and the composition temperature were recorded every 30 seconds. The filling ratio was For each of the inventive compositions and the comparative composition, mixing was continued for another 5 minutes, then the composition was put on a tray at about 90 °C. The motor current and the composition temperature were recorded every 30 seconds. The filling ratio was

[0112] For each of the inventive compositions and the comparative composition, mixing was continued for another 5 minutes, then the composition was put on a tray at about 90 °C. The motor current and the composition temperature were recorded every 30 seconds. The filling ratio was was 0.80. Mixing was completed using a 6-inch two-roll mill, and a thick sheet of "0.2" uncured material was formed into a sheet for rheological and mechanical tests. Refer to ASTM D3182-5 (Standard Practice for Rubber-Materials, Equipment, and Procedures for Mixing Standard Compounds and Preparing Standard Vulcanized Sheets). The composition is shown in Table 5. Compression Molding and Curing Plaques (for tensile tests, compression set, odor tests, and density) were compression molded from each composition (uncured sheet) and cured on a hot press at 185 °C, 10 MPa for T90% + 5 minutes. Test specimens were punched out from the plaques. Profiled Extrusion and Continuous Vulcanization To produce weather strips, the hydrosilylation curing of EPDM was tested on a continuous vulcanization (CV) line. Each profiled extrusion and continuous vulcanization (CV) test was conducted on a LabStar line consisting of an extruder for profiled extrusion, a shock oven for skin formation of sponge profiles, a microwave channel and a hot air system for rubber vulcanization, and a cooling channel. The conditions of the extrusion and CV lines are shown in Table 6. Uncured sheets (see above) were manually cut into smaller pieces (approx. 2 cm × 5 mm) and placed in the LabS

[0113]

[0114]

[0115] [Table 6] ​​​​​​​​​​​​Note that it has been supplied to the extruder part of the tar line.

[0116] The Mooney results and MDR results are shown in Tables 7 and 8, respectively. The MDR results show that the hydrosilylation-cured composition has a slightly higher curing level than the S-cured composition.

[0117] [Table 7]

[0118] [Table 8]

[0119] [Table 9]

[0120] The mechanical properties are shown in Table 9. As can be seen in Table 9, for the compression-molded samples, the S-cured EP DM composition has higher tensile strength (TS) and elongation at break (EB) properties than the hydrosilylation-cured EPDM composition. However, the mechanical results of the hydrosilylation-cured composition for the CV samples were comparable to those of the S-cured composition. For the CV cure profile in Table 9, note that the mechanical properties were determined using a microtensile test in the machine direction at a moving speed of 500 mm / min according to ASTM D1708-18. Miniature extrusion microtensile test samples with a thickness of 1.8 - 2.8 mm were used.

[0121] [Table 10] * ​​​​​​​​​The density was measured on a Mettler Toledo Balance using the buoyancy method The sample was weighed in air (A) and then again in an auxiliary liquid (water) of known density (B) The density ρ of the sample was calculated as follows: ρ = A(ρ0 - ρ L ) / (A - B ) + ρ L , where ρ = density of the sample, A = weight of the sample in air, B = weight of the sample in the auxiliary liquid , ρ0 = density of the auxiliary liquid, ρ L = density of air

[0122] The degradation characteristics are shown in Table 10. Table 10 demonstrates that at high temperatures, the hydrosilylation-cured EPDM compositions (Inv.24 and Inv.25) have better degradation performance than the S-cured EPDM composition (Comp.J). Overall, the inventive compositions have a smaller degree of change during degradation with respect to hardness, 100% modulus , TS, EB, and density. The test samples were degraded in an air circulation (convection) oven and equilibrated at the temperatures and days listed in Table 10 respectively .

[0123]

Table 11

[0124] The compression set values are shown in Table 11. As can be seen, the inventive compositions have lower compression set values at higher temperatures, which is a favorable characteristic for weatherstrip applications .

[0125]

Table 12

[0126] The odor characteristics are shown in Table 12. The hydrosilylation-cured EPDM composition (Inv.24) has an S ​Compared with the cured EPDM composition (Comp. J), a remarkable improvement in odor characteristics was shown. Odor This improvement was shown by both the odor intensity score and the pleasantness score. The hydrosilylation reaction was found not to produce a significant amount of undesirable by-products that increase the odor. In addition, the silicone-hydride species and the hydrosilylation catalyst are odorless.

[0127]

Table 13

[0128] Study 5 - Polybutadiene and Curing Aids for Hydrosilylation Curing In Study 5, two low molecular weight polybutadienes were added to several compositions to examine the curing characteristics. The results are shown in Table 13. As can be seen in Table 13, the compositions containing polybutadiene showed T10%, T20%, T50%, and T90% As shown by the decrease as a whole, it had an improved curing rate. The curing level ( MH-ML) was high in the inventive composition containing RICON130 polybutadiene all the way up.

[0129] Table 14 shows the curing characteristics of the inventive composition (Inv.27) containing RICON130 and the comparative industrial composition (Comp.I). As can be seen from this table, the inventive composition had a higher curing level (indicated by a higher "MH-ML" value) and a faster curing rate (indicated by, for example, lower T10%, T20%, T50%, and T90% values) compared to the comparative industrial composition.

[0130]

Table 14

[0131]

Table 15

Claims

1. A process for forming a crosslinked composition, the process comprising a) an elastomer, b) a siloxy-modified silica, and c) a hydrosilylation catalyst, by heat-treating a composition containing the same.

2. The process according to claim 1, wherein the elastomer is selected from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, or ix) halogenated nitrile rubber.

3. The process according to claim 1 or 2, wherein component b has a viscosity of ≤500 cSt at 25°C.

4. The process according to any one of claims 1 to 3, wherein the siloxy moiety of the siloxy-modified silica (component b) has the following structure 1 with ≥4 units: The process according to any one of claims 1 to 3.

5. 。 The process according to any one of claims 1 to 4, wherein component b has a viscosity of 0.5 cSt to 200 cSt at 25°C. The process according to any one of claims 1 to 4. 【Chemical 1】 O—Si(R １ )(R ２ )H (Structure 1), wherein R １ is a hydrocarbyl group , R ２ is a hydrocarbyl group, and R １ and R ２ may be the same or different

6. The process according to any one of claims 1 to 5, wherein the silica moiety of the siloxy-modified silica (component b) is derived from silica Q resin. The process according to any one of claims 1 to 5.

7. The process according to any one of claims 1 to 6, wherein the hydrosilylation catalyst contains Pt, Pd, Rh, Re, Ir, Ru, or a mixture thereof. The process according to any one of claims 1 to 6.

8. The process according to any one of claims 1 to 7, wherein the composition further contains polybutadiene. The process according to any one of claims 1 to 7.

9. The process according to claim 8, wherein the polybutadiene contains a 1,2-vinyl content of ≤50 mol% based on the total moles of carbon-carbon double bond groups in the polybutadiene. The process according to claim 8.

10. The process according to any one of claims 1 to 9, wherein the elastomer of component a is an ethylene / alpha-olefin / non-conjugated polyene interpolymer. The process according to any one of claims 1 to 9.

11. The process according to claim 10, wherein the non-conjugated polyene of the interpolymer is ENB. The process according to claim 10.

12. The process according to any one of claims 1 to 11, wherein the composition is heat-treated at a temperature of 90°C to 220°C. The process according to any one of claims 1 to 11.

13. A composition comprising a) an elastomer, b) a siloxy-modified silica, and c) a hydrosilylation catalyst.

14. The elastomer is selected from i) ethylene / alpha-olefin / non-conjugated polyene interpolymers, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) halogenated butyl rubber, or ix) halogenated nitrile rubber. ​ ​ ​ ​ a polymer, ii) polyisoprene, iii) polybutadiene, iv) styrene-butadiene rubber, v) nitrile rubber, vi) polychloroprene, vii) butyl rubber, viii) ha logenated butyl rubber, or ix) halogenated nitrile rubber, selected from the group consisting of: according to claim 13 The composition described.

15. The composition according to claim 13 or 14, wherein component b has a viscosity of ≦ 500 cSt at 25°C thing.

16. The siloxy part of the siloxy-modified silica (component b) has the following structure 1 of ≧ 4 units: 【Chemical 2】 O—Si(R １ )(R ２ )H (Structure 1), wherein R １ is a hydrocarbyl group wherein R ２ is a hydrocarbyl group, and R １ and R ２ may be the same or different Yes, the composition according to any one of claims 13 to 15.

17. The composition according to any one of claims 13 to 16, wherein component b has a viscosity of 0.5 cSt to 200 cSt at 25°C thing.

18. The silica part of the siloxy-modified silica (component b) is derived from silica Q resin, according to claim The composition according to any one of 13 to 17.

19. The hydrosilylation catalyst contains Pt, Pd, Rh, Re, Ir, Ru, or a mixture thereof The composition according to any one of claims 13 to 18.

20. The composition according to any one of claims 13 to 19, wherein the composition further comprises polybutadiene thing.

21. Based on the total moles of carbon-carbon double bond groups in the polybutadiene, the polybutadiene The composition according to claim 20, comprising a 1,2-vinyl content of ≦ 50 mol%.

22. The elastomer of component a is an ethylene / alpha-olefin / non-conjugated polyene in The composition according to any one of claims 13 to 21, which is a terpolymer.

23. The non-conjugated polyene of the interpolymer is ENB, according to claim 22 composition.

24. A crosslinked composition formed from the composition according to any one of claims 13 to 23.

25. At least one component formed from the composition according to any one of claims 13 to 24 An article comprising.

Images