WO2001030913A1 - Composition d'asphalte comprenant un prepolymere a base de mdi polymerique - Google Patents

Composition d'asphalte comprenant un prepolymere a base de mdi polymerique Download PDF

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Publication number
WO2001030913A1
WO2001030913A1 PCT/EP2000/009557 EP0009557W WO0130913A1 WO 2001030913 A1 WO2001030913 A1 WO 2001030913A1 EP 0009557 W EP0009557 W EP 0009557W WO 0130913 A1 WO0130913 A1 WO 0130913A1
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WO
WIPO (PCT)
Prior art keywords
asphalt
polymeric mdi
prepolymer
asphalt composition
based prepolymer
Prior art date
Application number
PCT/EP2000/009557
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English (en)
Inventor
Berend Eling
Norman Washington Keane
Original Assignee
Huntsman International Llc
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 Huntsman International Llc filed Critical Huntsman International Llc
Priority to AU77853/00A priority Critical patent/AU7785300A/en
Publication of WO2001030913A1 publication Critical patent/WO2001030913A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the instant invention provides an asphalt composition comprising polymeric MDI based prepolymer as asphalt modifier.
  • Asphalts that are modified by added polymers are known for years.
  • Polyurethane modifiers, especially prepolymers, are known for this use.
  • US-P-3179610 discloses asphalt compositions comprising from 5 to 25% by weight of a polyurethane prepolymer.
  • US-P-4871792 discloses asphalt compositions where the ratio prepolymer/bitumen is from 30/70 to 70/30.
  • the invention is based on the surprising effect that the amount of a specific polymeric MDI based prepolymer can be below 5% by weight, while still imparting improved properties to the final asphalt composition.
  • the instant invention provides an asphalt composition comprising, by weight based on the total weight of the composition, about 1 to 5%, preferably about 2 to 5%, especially about or less then the stoichiometric amount, of a polymeric MDI based prepolymer, where the polymeric MDI has a functionality of at least 2.5, preferably at least
  • the polymeric MDI is known in the art. It is polymethylene-polyphenylene polyisocyanate, and is also referred to as polyarylene polyisocyanate or polyphenylmethane polyisocyanate, PAPI. It can comprise varying amounts of the standard isomers, i.e. the 4,4'-, 2,4'- and 2,2'-isomers. It can also comprise modified variants containing carbodiimide, uretonimine, isocyanurate, urethane, aliphanate, urea or biuret groups. This will be referred to in the following as pMDI.
  • the isocyanate functionality of the pMDI is one key feature of the invention. This functionality is to be at least 2.5, preferably at least 2.6.
  • the polyol that is used to prepare the prepolymer is any polyol that can be used in the instant field, provided it is compatible with the asphalt.
  • One can use any high molecular weight polyol used in the invention may be any of the polyols, or mixtures thereof, used in the manufacture of polyurethanes, having an average hydroxyl equivalent weight of at least 500, preferably from 500 to 5000.
  • polyols can be polyether polyols, polyester polyols, polyesteramides polyols, polythioether polyols, polycarbonate polyols, polyacetal polyols, polyolefin polyols, and the like.
  • Preferred polyols are polyether (especially polypropyleneglycol), polyester (especially aromatic polyesters), and polyolefin (especially polybutadiene) polyols.
  • the functionality of the polyol can be 2-4, especially 2-3 and most preferably 2.
  • PPG notably PPG2000
  • the NCO value of the prepolymer can vary within broad limits. It can be from about 6 to
  • the ratio polyol/pMDI can in fact vary from 65/35 to
  • the pMDI-based prepolymer can react with the phenolic, carboxylic, anhydride and pyrrolic groups of the asphalt, which are NCO-reactive groups. What is formed is a covalently linked polymer gel/network that was found to reduce the plastic flow of the asphalt at elevated temperatures, i.e. about 60°C or more. It is in fact possible to determine an "equivalent weight" of NCO-reactive in the asphalt. Experimentally this can be determined by preparing asphalt-polymeric MDI blends with increasing amounts of polymeric MDI.
  • the stoichiometric amount of MDI for the selected asphalt could be defined as that amount MDI that is present in the sample that contains the highest concentration of MDI and in which all the NCO groups have reacted.
  • the presence of unreacted isocyanate (NCO) groups in the asphalt could, for instance, be detected by Infra Red measurements. From this amount the equivalent weight of the asphalt can be calculated. This equivalent weight varies as a function of the kind and nature of the asphalt; examples of asphalt equivalent weight are about 2000-10,000.
  • the "stoichiometric" amount of pMDI based prepolymer with, for instance, an NCO value of 13 amounts to about 8.5 weight %, this leads to an estimated equivalent weight of about 3800.
  • This value for the "stoichiometric" amount however varies as a function of the equivalent weight of the asphalt (which itself varies as a function of the asphalt).
  • the advantage that the use of a prepolymer of polymeric MDI has over the use of straight polymeric MDI in modifying asphalt is two-fold. Firstly it is more effective in improving the rheological properties of the asphalt then straight polymeric MDI when the result is expressed in the weight amount of MDI added. Without wishing to be bound by any theory, the applicant believes that this is the result of the increased average molecular weight of the polymeric MDI based polymer as opposed to that of polymeric MDI. This allows the use of the prepolymer in quantities less then the stoichiometric amount, whilst still giving improved mechanical properties.
  • the formation of the product MDI-asphalt of the present invention can be measured by an increase in the product's viscosity, but more preferably dynamic mechanical analysis
  • DMA Dynamic mechanical analysis properties are determined using a dynamic mechanical analyzer (DMA), for example, a RDA II Dynamic Analyzer (from
  • DMA Dynamic Microwave Access
  • G* complex modulus
  • G' storage modulus
  • G" loss modulus
  • G' describes the amount of energy stored and released elastically in each oscillation
  • G" describes the average energy dissipation rate that is associated with viscous effects.
  • phase angle (delta) The difference between the stress and strain in an oscillatory deformation is defined as phase angle (delta).
  • Delta is a measure of the viscoelastic character of the material. If delta equals 90°, then the binder can be considered to be purely viscous in nature and, vice versa, a delta of 0° represents an ideal elastic solid.
  • SHRP strategic highway research program, USA
  • G*/sin delta at 10 rad sec has been selected to measure the contribution of a binder to rutting performance. High G*/sin delta values were found to correlate with high rutting resistance (L.H. Lewandowski, Rubber Chem. Techn., 67, 447 (1994)).
  • a minimum value of rheological G*/sin delta should be 1 kPa at 60°C for the binder to be considered as pavement mix.
  • the criterion suggests that the binder should have both high complex modulus and elasticity at the maximum pavement temperatures.
  • the pMDI-based prepolymer When added to the asphalt (the continuous, non-asphaltene, phase thereof), the pMDI-based prepolymer will act as a modifier.
  • the G* value will increase by about a factor 2 to 5, when compared to an unmodified asphalt.
  • the delta value will decrease from about 85° to about 55°, when compared to an unmodified asphalt, evidencing a change in the rheological behavior from liquid-like to visco-elastic.
  • the rheological and mechanical properties are similar to those obtained with a 3% SBS modified asphalt.
  • the instant invention thus allows not using high processing temperature and refusion that are mandatory in case of SBS.
  • the NCO groups of the pMDI-based prepolymer When added to the asphalt, the NCO groups of the pMDI-based prepolymer will react relatively quickly, in about less than 60 minutes, at the temperature of about 135°C. Thus, since the storage temperature for hot asphalt is 120-150°C, i.e. around this value of 135°C, it makes it possible to mix the pMDI-based prepolymer just before use. Thus, at the time the composition is applied to the desired site, the pMDI-based prepolymer will have completely reacted.
  • the present invention allows in-line blending and affords improved adhesion to substrates.
  • the stoichiometric value (of about 5 weight % on the asphalt) brings the additional benefit that substantially all the NCO groups will be consumed by the reaction, thus avoiding any release of NCO in the atmosphere, thereby avoiding any risk to the safety, health and environment of the workers.
  • Another part of the invention is to produce the prepolymer in situ in the asphalt.
  • This process is especially advantageous when asphalt is applied of which the number of reactive groups per unit mass is relatively low.
  • a further advantage is that the prepolymer does not have to be produced, thus avoiding production costs.
  • the asphalt used in the instant invention is any asphalt known and generally covers any bituminous compound. It can be any of the materials referred to as bitumen or asphalt, e.g. distillate, blown, high vacuum and cut-back bitumen, and also e.g. asphalt concrete, cast asphalt, asphalt mastic and natural asphalt. For example, a directly distilled asphalt can be used, having, for example, a penetration of 80/100 or 180/220. For example, the asphalt can be free of fly ash.
  • the asphalt compositions of the invention will be used as any classical asphalt compositions of the prior art. The asphalt compositions of the invention will notably be useful for the production of:
  • compositions may also be used as the asphalt part of emulsions, the water reacting with the NCO groups that could have remained, thus rendering the final emulsion completely free of NCO group, and thus fully meets the safety, health and environment requirements.
  • the present invention also provides a process for making the composition, which comprises mixing the asphalt and the pMDI-based prepolymer at a temperature comprised between 120 and 150°C, for a sufficient time, for example between 1 and 120 minutes, preferably between 10 and 60 minutes.
  • a temperature comprised between 120 and 150°C, for a sufficient time, for example between 1 and 120 minutes, preferably between 10 and 60 minutes.
  • the following examples illustrate the invention without limiting it. Examples Prepolymer synthesis.
  • a prepolymer was prepared from polypropylene glycol with a molecular weight of 2000, in the text referred to as PPG-2000, and polymeric MDI with an NCO value of 30.7% by weight and a functionality of 2.7.
  • PPG-2000 polypropylene glycol with a molecular weight of 2000
  • polymeric MDI with an NCO value of 30.7% by weight and a functionality of 2.7.
  • 500 g of polymeric MDI and 500g PPG-2000 were weighed into a 1L jar. The two products were mixed in the jar with a mechanical stirrer for 10 minutes at room temperature after which the jar was closed with a lid. The closed jar was put in an oven at 80 °C for 4 hours. After the prepolymer had cooled down to room temperature a sample was taken for NCO value determination using standard titration techniques. The NCO value amounted to 13.4, which is close to the calculated value of 13.2.
  • the prepolymer was labeled isocyanate A.
  • the dynamic viscoelastic properties of asphalts and isocyanate modified asphalts were measured using a RDA II Dynamic Analyzer (from Rheometrics, Inc) at a frequency of 10 radians per second and 10% stain. The measurements were carried out in the temperature range from 25 to 90°C with a temperature ramp of 1°C per minute. A sample was placed between parallel plates with a diameter of 25 mm and a gap of approximately 1.7 mm. The values of G*, delta and G*/sin delta given in the Tables 1, 2 and 4 are measured at 60°C.
  • the DMA results of the unmodified asphalt (sample l)and that of the prepolymer modified asphalts (samples 2 and 3) are given in Table 1.
  • Nr. lymer (wt%) mmol/lOOg 60°C 60°C 60°C (kPa) asphalt) (kPa)
  • Comparative examples modified with polymeric MDI Preparation of the samples: The asphalt was modified with a given amount of polymeric MDI with an average functionality of 2.7 and an NCO value of 30.6 in the same way as described for the preparation of polymeric MDI based prepolymers. Using polymeric MDI sample 4 and 5 have been prepared. The DMA results of these modified asphalts are given in Table 2.
  • Samples 4 and 5 have been submitted to infra red measurement. In none of the samples an adsorption at 2270 cm “1 , assigned to isocyanate (e.g. NCO), was detected. A sample prepared from the asphalt and 4 weight % polymeric MDI, however, showed a clear absorption at 2270 cm “1 , indicating the presence of unreacted isocyanate in the sample.
  • isocyanate e.g. NCO
  • the asphalt was modified with SBS block-copolymer (Vector 241 Ip, from 'DEXCO POLYMERS', styrene/butadiene ratio 30/70). This modifier was added at a 3.0 weight % addition.
  • the additive was added to the asphalt in a similar manner as described above for the preparation of the MDI modified asphalts with this difference that the temperature was raised, according to the suppliers recommendation, to 160°C. This raise is intended to melt the crystalline polymer. Using the above amounts and conditions, sample 6 was prepared.
  • Nr. 60°C 60°C 60°C (kPa) (kPa)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Road Paving Structures (AREA)

Abstract

La présente invention concerne une composition d'asphalte comprenant, en poids par rapport au poids total de la composition, environ de 1 à 5 % d'un prépolymère à base de MDI polymérique, le MDI polymérique possédant une fonctionnalité d'au moins 2,5. Elle concerne aussi un procédé destiné à préparer cette composition d'asphalte.
PCT/EP2000/009557 1999-10-25 2000-09-29 Composition d'asphalte comprenant un prepolymere a base de mdi polymerique WO2001030913A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU77853/00A AU7785300A (en) 1999-10-25 2000-09-29 Asphalt composition comprising polymeric mdi based prepolymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99121281.2 1999-10-25
EP99121281 1999-10-25

Publications (1)

Publication Number Publication Date
WO2001030913A1 true WO2001030913A1 (fr) 2001-05-03

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018228840A1 (fr) 2017-06-14 2018-12-20 Basf Se Composition d'asphalte comprenant des composés réactifs thermodurcissables
WO2020035403A1 (fr) 2018-08-15 2020-02-20 Basf Se Composition d'asphalte comprenant un mélange d'un isocyanate et d'un polymère en tant qu'additifs de performance
WO2020126585A1 (fr) 2018-12-18 2020-06-25 Basf Se Composition d'asphalte comprenant un mdi monomère en tant que composé réactif thermodurcissable
WO2021053101A1 (fr) 2019-09-18 2021-03-25 Basf Se Procédé de préparation d'une composition de mélange d'asphalte
WO2021148313A1 (fr) 2020-01-23 2021-07-29 Basf Se Procédé à basse température pour la préparation d'une composition de mélange d'asphalte
WO2021148418A1 (fr) 2020-01-21 2021-07-29 Basf Se Composition d'asphalte comprenant un composé réactif thermodurcissable
WO2021254815A1 (fr) 2020-06-19 2021-12-23 Basf Se Composition d'asphalte comprenant un mélange d'un isocyanate et d'un plastifiant en tant qu'additifs de performance

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2064750A5 (fr) * 1969-10-29 1971-07-23 Naphtachimie Sa

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
FR2064750A5 (fr) * 1969-10-29 1971-07-23 Naphtachimie Sa

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. SENDIJAREVIC ET AL: "Urethane-modified asphalt for pavement overlays/wearing courses for road applications.", POLYURETHANES 95, 26 September 1995 (1995-09-26) - 29 September 1995 (1995-09-29), pages 418 - 426, XP000909053 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110719940A (zh) * 2017-06-14 2020-01-21 巴斯夫欧洲公司 包含热固性反应性化合物的沥青组合物
JP2020523463A (ja) * 2017-06-14 2020-08-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 熱硬化性反応性化合物を含むアスファルト組成物
US11059749B2 (en) 2017-06-14 2021-07-13 Basf Se Asphalt composition comprising thermosetting reactive compounds
WO2018228840A1 (fr) 2017-06-14 2018-12-20 Basf Se Composition d'asphalte comprenant des composés réactifs thermodurcissables
JP7242566B2 (ja) 2017-06-14 2023-03-20 ビーエーエスエフ ソシエタス・ヨーロピア 熱硬化性反応性化合物を含むアスファルト組成物
RU2770600C2 (ru) * 2017-06-14 2022-04-18 Басф Се Асфальтовая композиция, содержащая термореактивные соединения
WO2020035403A1 (fr) 2018-08-15 2020-02-20 Basf Se Composition d'asphalte comprenant un mélange d'un isocyanate et d'un polymère en tant qu'additifs de performance
WO2020126585A1 (fr) 2018-12-18 2020-06-25 Basf Se Composition d'asphalte comprenant un mdi monomère en tant que composé réactif thermodurcissable
CN114423826A (zh) * 2019-09-18 2022-04-29 巴斯夫欧洲公司 制备沥青混合料组合物的方法
WO2021053101A1 (fr) 2019-09-18 2021-03-25 Basf Se Procédé de préparation d'une composition de mélange d'asphalte
CN114423826B (zh) * 2019-09-18 2023-08-11 巴斯夫欧洲公司 制备沥青混合料组合物的方法
WO2021148418A1 (fr) 2020-01-21 2021-07-29 Basf Se Composition d'asphalte comprenant un composé réactif thermodurcissable
CN114981362A (zh) * 2020-01-23 2022-08-30 巴斯夫欧洲公司 制备沥青混合料组合物的低温方法
WO2021148313A1 (fr) 2020-01-23 2021-07-29 Basf Se Procédé à basse température pour la préparation d'une composition de mélange d'asphalte
CN114981362B (zh) * 2020-01-23 2024-04-16 巴斯夫欧洲公司 制备沥青混合料组合物的低温方法
WO2021254815A1 (fr) 2020-06-19 2021-12-23 Basf Se Composition d'asphalte comprenant un mélange d'un isocyanate et d'un plastifiant en tant qu'additifs de performance

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