WO2020202125A1 - Rubber compound for an innerliner - Google Patents

Rubber compound for an innerliner Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
lignin
htc
innerliner
innerliner layer
phr
Prior art date
Application number
PCT/IB2020/053270
Other languages
French (fr)
Inventor
Alessandra CALZETTA
Claudia AURISICCHIO
Original Assignee
Bridgestone Europe Nv/Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Europe Nv/Sa filed Critical Bridgestone Europe Nv/Sa
Publication of WO2020202125A1 publication Critical patent/WO2020202125A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008Compositions of the inner liner
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00Compositions of rubber derivatives
    • C08L15/02Rubber derivatives containing halogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions 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
    • C08L23/28Compositions 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
    • C08L23/283Halogenated homo- or copolymers of iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00Compositions of lignin-containing materials
    • C08L97/005Lignin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/006Additives 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
Figure imgf000009_0001
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.
TABLE II
Figure imgf000010_0001
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.
PCT/IB2020/053270 2019-04-05 2020-04-06 Rubber compound for an innerliner WO2020202125A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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EP3053929A1 (en) * 2015-02-06 2016-08-10 Valmet Technologies Oy Method for treating lignin-based material
EP3243877A1 (en) * 2016-05-09 2017-11-15 Nokian Renkaat Oyj A tyre comprising hydrothermally carbonized lignin
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US9205704B2 (en) * 2007-09-27 2015-12-08 The Goodyear Tire & Rubber Company Tire having tread with repellent groove surface
EP2433813A1 (en) * 2010-09-28 2012-03-28 The Goodyear Tire & Rubber Company Wire coat compositions for rubber articles
US20150321173A1 (en) * 2012-12-19 2015-11-12 Teknologian Tutkimuskeskus Vtt Oy Process for the hydrothermal treatment of high molar mass biomaterials
EP3053929A1 (en) * 2015-02-06 2016-08-10 Valmet Technologies Oy Method for treating lignin-based material
US20180141290A1 (en) * 2015-05-15 2018-05-24 Bridgestone Corporation Tyre sealant layer
EP3243877A1 (en) * 2016-05-09 2017-11-15 Nokian Renkaat Oyj A tyre comprising hydrothermally carbonized lignin

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Title
HANNE WIKBERG ET AL: "Structural and Morphological Changes in Kraft Lignin during Hydrothermal Carbonization", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 3, no. 11, 6 October 2015 (2015-10-06), US, pages 2737 - 2745, XP055542953, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.5b00925 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2022195159A1 (en) * 2021-03-19 2022-09-22 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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