WO2020202125A1 - Rubber compound for an innerliner - Google Patents
Rubber compound for an innerliner Download PDFInfo
- Publication number
- WO2020202125A1 WO2020202125A1 PCT/IB2020/053270 IB2020053270W WO2020202125A1 WO 2020202125 A1 WO2020202125 A1 WO 2020202125A1 IB 2020053270 W IB2020053270 W IB 2020053270W WO 2020202125 A1 WO2020202125 A1 WO 2020202125A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- htc
- innerliner
- innerliner layer
- phr
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 229920001971 elastomer Polymers 0.000 title claims abstract description 12
- 229920005610 lignin Polymers 0.000 claims abstract description 34
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 229920005555 halobutyl Polymers 0.000 claims abstract description 4
- 125000004968 halobutyl group Chemical group 0.000 claims abstract description 4
- 239000006229 carbon black Substances 0.000 claims description 13
- 229920005611 kraft lignin Polymers 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 bromobutyl Chemical group 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- JMFRWRFFLBVWSI-UHFFFAOYSA-N cis-coniferyl alcohol Natural products COC1=CC(C=CCO)=CC=C1O JMFRWRFFLBVWSI-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229930015763 p-coumaryl alcohol Natural products 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 125000001474 phenylpropanoid group Chemical group 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- PTNLHDGQWUGONS-UHFFFAOYSA-N trans-p-coumaric alcohol Natural products OCC=CC1=CC=C(O)C=C1 PTNLHDGQWUGONS-UHFFFAOYSA-N 0.000 description 1
- PTNLHDGQWUGONS-OWOJBTEDSA-N trans-p-coumaryl alcohol Chemical compound OC\C=C\C1=CC=C(O)C=C1 PTNLHDGQWUGONS-OWOJBTEDSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Definitions
- the present invention is in relation to a rubber compound for the preparation of an innerliner layer.
- the innerliner consists of a rubber inner layer used in tubeless pneumatic tyres, i.e., pneumatic tyres that are devoid of an air chamber, in order to ensure the sealing thereof under the pressure of the air contained within the cavity of the pneumatic tyre.
- the innerliner must ensure that oxygen remains, as much as possible, confined within the cavity and does not spread into portions of the pneumatic tyre thereby leading to degradation phenomena.
- increasing the thickness of the innerliner layer if on the one hand ensures an improvement in terms of impermeability, on the other hand involves a series of disadvantages in relation to the increase in weight and to a compromise in relation to rolling resistance.
- one of the needs for the pneumatic tyre industry is that of conferring them an increasingly lower rolling resistance, and a contribution to this need is sought precisely in decreasing the thickness of the innerliner.
- a reduced thickness of the innerliner layer necessarily translates into a lower quantity of material used and therefore, a lower weight for the pneumatic tyre, with positive effects on the overall energy consumption of the vehicle and on the rolling resistance. From the foregoing, it would immediately appear that a decrease in the thickness of the innerliner might only be possible if a high degree of impermeability were to be imparted to it.
- Carbon black is known to be used as a filler within the compounds of the innerliner.
- the carbon black of the N660 series is used. This carbon black ensures the required levels of reinforcement for the innerliner layers.
- the innerliner must meet those mechanical characteristics that ensure the effective implementation thereof. If the integrity of the innerliner were to be compromised then the functionality of the entire pneumatic tyre would be lost.
- Lignin is an organic substance that binds the cells and fibers that constitute wood and the lignified elements of plants.
- lignin After cellulose, it is the most abundant renewable source of carbon on earth. Although it is not possible to define the precise structure of lignin as a chemical molecule, it is however possible to identify lignin as a polymer comprising the following three phenylpropanoids : p-coumaryl alcohol; coniferyl alcohol ( 4-hydroxy-3-methoxycinnamyl alcohol); sinapyl alcohol ( 4-hydroxy-3 , 5-dimethoxycinnamyl alcohol). There are different types of lignin that are commercially available and that differ therebetween as a function of the different extraction process by which the different raw material used were obtained. The Kraft process and the Sulfonation process are two examples of processes dedicated to the extraction of lignin.
- Kraft Lignin is a byproduct of the Kraft process that is utilized to chemically extract cellulose from wood. This is obtained by means of precipitation, lowering the pH of spent liquor from the Kraft process. Phenol, alcohol and carboxyl hydroxyls are the main identifiable functional groups within Kraft lignin, whilst thiol groups are present to a lesser extent.
- lignin represents a significant advantage in terms of sustainability.
- lignin is a natural product that constitutes a byproduct of wood in the production of paper.
- disposal of lignin is a limiting step within the paper production chain.
- lignin if properly treated, can be used for the partial replacement of carbon black within innerliner compounds, ensuring both that the levels of the mechanical properties are maintained and an unexpectedly large improvement in terms of impermeability.
- the object of the present invention is a rubber compound for the preparation of an innerliner layer, said compound comprising a cross linkable unsaturated chain polymer base comprising at least one halobutyl rubber, a reinforcing filler and a vulcanization system; said compound being characterized in that said reinforcing filler comprises from 15 to 45 phr of HTC lignin.
- vulcanization system means a complex of ingredients comprising at least sulfur and some accelerating compositions that, during the preparation of the compound, are added in a final mixing step and are aimed at promoting the vulcanization of the polymer base once the compound is subjected to a vulcanization temperature.
- HTC lignin refers to lignin that has been subjected to a hydrothermal carbonization process.
- Hydrothermal carbonization (Hydro Thermal Carbonization - HTC) is a thermochemical process for converting biomass under relatively low conditions of temperature and pressure in the presence of water.
- the temperature of the hydrothermal carbonization reaction is generally of between 150 and 250°C, whilst the pressure is generally of between 10 and 40 bar. It has been found that as a result of the hydrothermal carbonization process, the structure of lignin is modified and that the principal changes concern demethylation and dealkylation, as well as the splitting of the b-O-4 links.
- HTC Lignin has, therefore, a thermally more stable and complex cross linked structure than the original lignin.
- HTC Lignin has a surface area of between 30 and 55 m 2 /g; a distribution of D50 particles of between 1 and 4 pm; a distribution of D90 particles of between 5 and 8 pm; a pH of between 7.5 and 10.
- the surface areas were measured by means of nitrogen absorption according to the ASTM D6556 standard.
- the D50 and D90 values were obtained by means of the LLS technique (Malvern Mastersizer 2000).
- said lignin is HTC Kraft lignin.
- said reinforcing filler comprises from 15 to 40 phr of carbon black having a specific surface area of between 30 and 50 m 2 /gr.
- a further object of the present invention is an innerliner layer obtained using the compound of the present invention.
- a further object of the present invention is a pneumatic tyre comprising the innerliner according to the present invention .
- a further object of the present invention is the use of HTC Lignin within a compound for the implementation of an innerliner layer, in an amount of between 15 and 45 phr.
- the comparison compound A represents a compound commonly used for the manufacture of the innerliner; the comparison compound B differs from comparison compound A in that part of the carbon black was replaced with untreated Kraft lignin; the compound of the invention C differs from the comparison compound A in that part of the carbon black was replaced with
- HTC lignin Herebelow, the procedure is given for the preparation of the compounds described in the examples. This procedure does not represent a limitation for the present invention.
- the mixer was operated at a speed of 40-60 revolutions/minute, and the mixture thus formed was discharged once a temperature of 140-160°C had been reached.
- the mixture thus obtained was processed once again in a mixer operated at a speed of between 40-60 revolutions/minute. Subsequently, the compound is discharged once a temperature of between 130-150°C had been reached.
- the vulcanization (sulfur, stearic acid and vulcanization accelerator) system was added to the mixture obtained from the previous step, reaching a filling factor of 63-67%.
- the mixer was operated at a speed of 20-40 revolutions/minute, and the mixture thus formed was discharged once a temperature of between 100-110°C had been reached.
- Table I shows the compositions in phr of the compounds according to the invention.
- Halobutyl rubber is a bromobutyl rubber.
- CB refers to the carbon black of the N660 series.
- the Kraft lignin used in the examples is marketed under the trade name "Kraft Lignin” by the StoraEnso company.
- the HTC Kraft Lignin is marketed under the name "SQ-243" by the SUN COAL company.
- HTC Kraft Lignin has a surface area of 55.0 m 2 /g; a distribution of D50 particles of 2.7 pm; a distribution of D90 particles of 9.0 pm; a pH of 8.6.
- MBTS is the English acronym for the mercaptobenzothiazole disulfide () and is used as a vulcanization accelerant.
- the oxygen impermeability test was performed on materials with a thickness of 0.7 mm and using a conventional apparatus as MOCON® OX-TRA® (model 2/61) . The measurements were performed at a temperature of 25°C.
- Table II lists the results obtained from the tests described above.
- the present invention offers the great advantage of replacing, within the compounds for the innerliner, a fossil-derived material with a material from renewable sources, and of ensuring, at the same time, an improvement in terms of impermeability to oxygen without compromising, in any way, the mechanical properties.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A rubber compound for the preparation of an innerliner layer, comprising a cross linkable unsaturated chain polymer base, having at least one halobutyl rubber, a reinforcing filler and a vulcanization system. The reinforcing filler comprises from 15 to 45 phr of HTC lignin.
Description
"RUBBER COMPOUND FOR AN INNERLINER"
DESCRIPTION
The present invention is in relation to a rubber compound for the preparation of an innerliner layer.
The innerliner consists of a rubber inner layer used in tubeless pneumatic tyres, i.e., pneumatic tyres that are devoid of an air chamber, in order to ensure the sealing thereof under the pressure of the air contained within the cavity of the pneumatic tyre.
Moreover, the innerliner must ensure that oxygen remains, as much as possible, confined within the cavity and does not spread into portions of the pneumatic tyre thereby leading to degradation phenomena. As is known to a person skilled in the art, increasing the thickness of the innerliner layer, if on the one hand ensures an improvement in terms of impermeability, on the other hand involves a series of disadvantages in relation to the increase in weight and to a compromise in relation to rolling resistance.
In this respect, one of the needs for the pneumatic tyre industry is that of conferring them an increasingly lower rolling resistance, and a contribution to this need is sought precisely in decreasing the thickness of the innerliner. In fact, a reduced thickness of the innerliner layer necessarily translates into a lower quantity of material used and therefore, a lower weight for the pneumatic tyre, with
positive effects on the overall energy consumption of the vehicle and on the rolling resistance. From the foregoing, it would immediately appear that a decrease in the thickness of the innerliner might only be possible if a high degree of impermeability were to be imparted to it.
Carbon black is known to be used as a filler within the compounds of the innerliner. In particular, the carbon black of the N660 series is used. This carbon black ensures the required levels of reinforcement for the innerliner layers. In fact, as is known to a person skilled in the art, the innerliner must meet those mechanical characteristics that ensure the effective implementation thereof. If the integrity of the innerliner were to be compromised then the functionality of the entire pneumatic tyre would be lost.
For a more complete understanding of the scope of the present invention, it must be considered that for reasons of environmental sustainability, within the pneumatic tyre industry there is an increasing need to be able to replace part of the materials of fossil origin, such as the carbon black, with materials from renewable sources.
The need was therefore felt to have a solution that would make it possible to improve the impermeability of the innerliner layer, in order to be able to reduce the thickness thereof and, at the same time, be able to replace the carbon black (a fossil material) with a material from a renewable source .
In this respect, the use of lignin has long been known in the pneumatic tyre industry. Lignin is an organic substance that binds the cells and fibers that constitute wood and the lignified elements of plants.
After cellulose, it is the most abundant renewable source of carbon on earth. Although it is not possible to define the precise structure of lignin as a chemical molecule, it is however possible to identify lignin as a polymer comprising the following three phenylpropanoids : p-coumaryl alcohol; coniferyl alcohol ( 4-hydroxy-3-methoxycinnamyl alcohol); sinapyl alcohol ( 4-hydroxy-3 , 5-dimethoxycinnamyl alcohol). There are different types of lignin that are commercially available and that differ therebetween as a function of the different extraction process by which the different raw material used were obtained. The Kraft process and the Sulfonation process are two examples of processes dedicated to the extraction of lignin.
In particular, Kraft Lignin is a byproduct of the Kraft process that is utilized to chemically extract cellulose from wood. This is obtained by means of precipitation, lowering the pH of spent liquor from the Kraft process. Phenol, alcohol and carboxyl hydroxyls are the main identifiable functional groups within Kraft lignin, whilst thiol groups are present to a lesser extent.
In contrast the Sulfonation process leads to lignin being obtained that is characterized by the presence of hydroxyls
and high concentrations of sulfonic groups.
As it may immediately seem to a person skilled in the art, the use of lignin represents a significant advantage in terms of sustainability. In fact, lignin is a natural product that constitutes a byproduct of wood in the production of paper. In this respect, it should also be specified that the disposal of lignin is a limiting step within the paper production chain.
Although the partial replacement of carbon black using lignin leads to advantages in terms of impermeability, it does however turn out to be extremely disadvantageous in terms of mechanical properties.
The inventors of the present invention have surprisingly found that lignin, if properly treated, can be used for the partial replacement of carbon black within innerliner compounds, ensuring both that the levels of the mechanical properties are maintained and an unexpectedly large improvement in terms of impermeability.
The object of the present invention is a rubber compound for the preparation of an innerliner layer, said compound comprising a cross linkable unsaturated chain polymer base comprising at least one halobutyl rubber, a reinforcing filler and a vulcanization system; said compound being characterized in that said reinforcing filler comprises from 15 to 45 phr of HTC lignin.
Preferably, said reinforcing filler comprises from 25 to
Here and hereinafter, vulcanization system means a complex of ingredients comprising at least sulfur and some accelerating compositions that, during the preparation of the compound, are added in a final mixing step and are aimed at promoting the vulcanization of the polymer base once the compound is subjected to a vulcanization temperature.
Here and hereinafter, HTC lignin refers to lignin that has been subjected to a hydrothermal carbonization process.
Hydrothermal carbonization (Hydro Thermal Carbonization - HTC) is a thermochemical process for converting biomass under relatively low conditions of temperature and pressure in the presence of water. The temperature of the hydrothermal carbonization reaction is generally of between 150 and 250°C, whilst the pressure is generally of between 10 and 40 bar. It has been found that as a result of the hydrothermal carbonization process, the structure of lignin is modified and that the principal changes concern demethylation and dealkylation, as well as the splitting of the b-O-4 links. HTC Lignin has, therefore, a thermally more stable and complex cross linked structure than the original lignin.
Preferably, HTC Lignin has a surface area of between 30 and 55 m2/g; a distribution of D50 particles of between 1 and 4 pm; a distribution of D90 particles of between 5 and 8 pm; a pH of between 7.5 and 10.
The surface areas were measured by means of nitrogen absorption according to the ASTM D6556 standard. The D50 and
D90 values were obtained by means of the LLS technique (Malvern Mastersizer 2000).
Preferably, said lignin is HTC Kraft lignin.
Preferably, said reinforcing filler comprises from 15 to 40 phr of carbon black having a specific surface area of between 30 and 50 m2/gr.
A further object of the present invention is an innerliner layer obtained using the compound of the present invention.
A further object of the present invention is a pneumatic tyre comprising the innerliner according to the present invention .
A further object of the present invention is the use of HTC Lignin within a compound for the implementation of an innerliner layer, in an amount of between 15 and 45 phr.
The following are non-limiting examples given purely by way of illustration.
Three compounds were produced wherein two thereof are comparison compounds (A and B) and one is a compound according to the invention (C) .
The comparison compound A represents a compound commonly used for the manufacture of the innerliner; the comparison compound B differs from comparison compound A in that part of the carbon black was replaced with untreated Kraft lignin; the compound of the invention C differs from the comparison compound A in that part of the carbon black was replaced with
HTC lignin.
Herebelow, the procedure is given for the preparation of the compounds described in the examples. This procedure does not represent a limitation for the present invention.
- preparation of the compounds -
(1st mixing step)
Before the start of the mixing, a mixer with tangential rotors and an internal volume of between 230 and 270 liters was loaded with the ingredients listed in Table I, excluding the vulcanization system (sulfur, stearic acid and vulcanization accelerator), reaching a fill factor of between 66-72%.
The mixer was operated at a speed of 40-60 revolutions/minute, and the mixture thus formed was discharged once a temperature of 140-160°C had been reached.
(2nd mixing step)
The mixture thus obtained was processed once again in a mixer operated at a speed of between 40-60 revolutions/minute. Subsequently, the compound is discharged once a temperature of between 130-150°C had been reached.
(final mixing step)
The vulcanization (sulfur, stearic acid and vulcanization accelerator) system was added to the mixture obtained from the previous step, reaching a filling factor of 63-67%.
The mixer was operated at a speed of 20-40 revolutions/minute, and the mixture thus formed was discharged once a temperature of between 100-110°C had been reached.
Table I shows the compositions in phr of the compounds according to the invention.
TABLE I
Halobutyl rubber is a bromobutyl rubber.
CB refers to the carbon black of the N660 series.
The Kraft lignin used in the examples is marketed under the trade name "Kraft Lignin" by the StoraEnso company.
The HTC Kraft Lignin is marketed under the name "SQ-243" by the SUN COAL company.
HTC Kraft Lignin has a surface area of 55.0 m2/g; a distribution of D50 particles of 2.7 pm; a distribution of D90 particles of 9.0 pm; a pH of 8.6.
Here and hereinbelow the pH values for the HTC Kraft lignin were measured in accordance with the ISO 787/9 standard .
MBTS is the English acronym for the mercaptobenzothiazole disulfide () and is used as a vulcanization accelerant.
Using the compounds of Table I respective samples were produced that represent the innerliner layers. The samples were subjected to mechanical tests and oxygen impermeability tests .
The mechanical properties were measured in accordance with the ISO 37 standard.
The oxygen impermeability test was performed on materials with a thickness of 0.7 mm and using a conventional apparatus as MOCON® OX-TRA® (model 2/61) . The measurements were performed at a temperature of 25°C.
Table II lists the results obtained from the tests described above.
In order to more immediately highlight the advantages deriving from the present invention, the values were indexed to the respective values for the comparison compound A.
In particular, in Table II the higher the values, the better the relevant characteristics.
The values reported in Table II show that the replacement of carbon black with HTC Lignin, not only ensures that the levels of the mechanical properties are maintained but gives the resulting innerliner layer better impermeability to oxygen than the one that might have been expected. In fact, in a completely unexpected manner, it was found that the compound comprising HTC lignin has considerably greater impermeability to oxygen than the compound comprising the lignin that has not been subjected to the hydrothermal carbonization treatment.
In summary, the present invention offers the great
advantage of replacing, within the compounds for the innerliner, a fossil-derived material with a material from renewable sources, and of ensuring, at the same time, an improvement in terms of impermeability to oxygen without compromising, in any way, the mechanical properties.
Claims
1. Innerliner layer made of a rubber compound comprising a cross linkable unsaturated chain polymer base comprising at least one halobutyl rubber, a reinforcing filler and a vulcanization system; said innerliner layer being characterized in that said reinforcing filler comprises from 15 to 45 phr of HTC lignin.
2. Innerliner layer according to claim 1, characterized in that said reinforcing filler comprises from 25 to 35 phr of HTC Lignin.
3. Innerliner layer according to claim 1 or 2, characterized in that the HTC Lignin has a surface area of between 30 and 55 m2/g; a distribution of D50 particles of between 1 and 4 pm; a distribution of D90 particles of between 5 and 8 pm; a pH of between 7.5 and 10.
4. Innerliner layer according to one of the preceding claims, characterized in that said lignin is HTC Kraft lignin.
5. Innerliner layer according to one of the preceding claims, characterized in that said reinforcing filler comprises from 15 to 40 phr of carbon black having a specific surface area of between 30 and 50 m2/gr.
6. Pneumatic tyre characterized in that it comprises an innerliner layer according to one of the preceding claims.
7. Use of HTC Lignin within a compound for the implementation of an innerliner layer, in an amount of between
15 and 45 phr .
8. Use according to claim 7, characterized in that said HTC Lignin is used in an amount of between 25 and 35 phr .
9. Use according to claim 7 or 8, characterized in that the HTC Lignin has a surface area of between 30 and 55 m2/g; a distribution of D50 particles of between 1 and 4 pm; a distribution of D90 particles of between 5 and 8 pm; a pH of between 7.5 and 10.
10. Use according to one of claims 7 to 9, characterized in that said lignin is HTC Kraft lignin.
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EP3974470A1 (en) * | 2020-09-23 | 2022-03-30 | SunCoal Industries GmbH | Rubber composition for an inner liner for pneumatic vehicle tyres |
EP4059996A1 (en) * | 2021-03-19 | 2022-09-21 | Nokian Renkaat Oyj | A rubber-based article with low fluid permeability |
EP4059997A1 (en) * | 2021-03-19 | 2022-09-21 | Nokian Renkaat Oyj | A pneumatic tyre with low gas permeability |
WO2023180405A1 (en) | 2022-03-22 | 2023-09-28 | Suncoal Industries Gmbh | Rubber composition for an inner liner for pneumatic vehicle tyres |
FR3137917A1 (en) | 2022-07-18 | 2024-01-19 | Upm-Kymmene Corporation | Elastomeric composition and articles comprising the composition |
WO2024017455A1 (en) | 2022-07-18 | 2024-01-25 | Upm-Kymmene Corporation | Elastomeric composition and articles comprising the composition |
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EP3974470A1 (en) * | 2020-09-23 | 2022-03-30 | SunCoal Industries GmbH | Rubber composition for an inner liner for pneumatic vehicle tyres |
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WO2024017455A1 (en) | 2022-07-18 | 2024-01-25 | Upm-Kymmene Corporation | Elastomeric composition and articles comprising the composition |
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