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WO1986007070A1 - Utilisation de lignine comme composant de reaction dans la production de polyurethanes - Google Patents

Utilisation de lignine comme composant de reaction dans la production de polyurethanes Download PDF

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Publication number
WO1986007070A1
WO1986007070A1 PCT/SE1986/000237 SE8600237W WO8607070A1 WO 1986007070 A1 WO1986007070 A1 WO 1986007070A1 SE 8600237 W SE8600237 W SE 8600237W WO 8607070 A1 WO8607070 A1 WO 8607070A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
polyurethanes
polyurethane
molecular weight
producing polyurethanes
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/SE1986/000237
Other languages
English (en)
Inventor
Hirohiza Yoshida
Knut Kringstad
Roland MÖRCK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Svenska Traforskningsinstitutet
Original Assignee
Svenska Traforskningsinstitutet
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 Svenska Traforskningsinstitutet filed Critical Svenska Traforskningsinstitutet
Publication of WO1986007070A1 publication Critical patent/WO1986007070A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof

Definitions

  • the present invention relates to the production of polyurethanes, and more particularly to the production of polyurethanes in which lignin is used as a reaction component.
  • lignin as a filler in rubber used in the manufacture of motor-vehicle tires.
  • lignin as a substitute for phenol in phenolic resins, or as a polyol component in polyurethanes. In this latter case, however, the lignin has a low reactivity and the resultant material is brittle, this brittleness increas ⁇ ing with increasing lignin contents. Attempts have been made to overcome these drawbacks, by chemically modify ⁇ ing the lignin. These attempts have met with no success, however.
  • This low reactivity of lignin is not solely due to the steric hindrance of the methoxy group in the proximity of the reactive phenolic hydroxy group, but also to the configuration of the lignin in the solid phase of the reaction system in the' production of phenolic resins and polyurethanes.
  • Polyurethanes are polymers which contain the group
  • a cross-linked polyurethane is obtained by carry- ing out the reaction in the presence of an exessive quantity of isocyanate (NCO/OH > 1.0).
  • isocyanate NCO/OH > 1.0
  • the reaction takes a complex course. This is due to subsidiary reactions which, inter alia, may result in the formation of allophanate and biuret structures. Allophanate-formation:
  • the tri- functional allophanate and biuret-bonds are able to contribute to the genesis of the network structure.
  • the degree of cross-linking, or cross-linking density increases generally with an increasing NCO/OH-ratio.
  • the mechanical properties of the polymers are highly dependent on the cross-linking density. An increase in cross-link ⁇ ing density results in a higher Young's modulus and increased maximum strength. The polymers also become brittle, however, as a result hereof.
  • diisocyanates have been replaced to a large extent with polymeric isocyanate. This change from diisocyanates to polymeric isocyanate was made for reasons of an economic and environmentally technical nature.
  • polymeric isocyanate incorporates aromatic rings in its principal chain, there is normally obtained a rigid polyurethane.
  • a soft polyurethane can be obtained by using a linear polyol or a polyester polyol. Another method of obtaining soft polyurethanes is to reduce the NCO/OH-ratio. However, it is difficult to produce strong polyurethanes under such conditions, because the mechanical properties of the polyurethanes depend to a large extent on the NCO/OH-ratio.
  • the high molecular fraction of the lignin is separated by fractionation or in some other way
  • the present invention relates to a method for producing polyurethanes by polymerizing polymeric isocyanate, polyol and lignin, " characterized by using as a lignin reactant lignin which has been substantially freed from fractions of high molecular ⁇ weight.
  • high molecular weight is meant in accordance with the invention primarily molecular weights above 10,000, determined in a manner herein ⁇ after described.
  • Molecular weight fractionation of lignins can be effected in differing ways. Examples of such methods are solvent fractionation, ultra-filtration, fractionated precipitates of spent kraft liquor (black liquor) , and preparative GPC.
  • solvent fractionation can be effected in two different ways, firstly by successive extraction with differing organic solvents or combinations thereof, and secondly by successive precipitation from a solution. Fractionation by successive extraction can be carried out with solvents or solvent combinations other than those used in the working example of this specification. Successive extraction can either be carried out in a Soxhlet apparatus or by applying the type of technique described in the following example.
  • the molecular weight fractionation of kraft lignin by successive extraction with an organic solvent can be carried out, for example, in the follow ⁇ ing manner.
  • fractionation is effected in four separate extraction stages: The lignin is first extracted with dichloromethane (fraction 1), then with n-propanol (fraction 2) , methanol (fraction 3) and dichloromethane/methanol 3/7 (fraction 4) .
  • Fraction 5 consisted of the undissolved residue obtained from these four extraction stages.
  • the yields obtained in the various extraction stages and the molecular-weight data relating to the fractions obtained are set forth in Table 1. Table 1
  • fractions 1-3 have low molecular weights with relatively narrow molecular weight distributions ( M w / M n 2).
  • the fractions 4 and 5 of higher molecular weights have considerably broader molecular weight distributions, encompassing molecular weights from some thousands to several millions.
  • fraction 5 about 15 - 20 % of the material has molecular weights above 100,000.
  • the molecular weight data recited in Table 1 was obtained with the aid of GPC (Gel Permeation Chromotography) .
  • the GPC-columns were calibrated with p r oly - styrene standards .
  • Mn and Mw were calculated with the aid of a computer program.
  • polyurethane are produced in solution by polymerizing polymeric isocyanate, polyol and fractions of kraft lignin.
  • the solvent used may be, for example, tetrahydrofuran, acetone, dimethylfofmamide, or dimethylacetamide.
  • the amount of lignin charged to the system varied from zero to about 40 % by weight, and the NCO/OH-ratio varied from about 0.5 to about 2.5 (in moles).
  • films were produced by evaporating the solvent ("solvent casting") and curing at elevated temperature.
  • the polyurethane films which contain lignin from the fractions 1 to 3 are optically homo ⁇ geneous, whereas the films containing lignin from the fractions 4 and 5 and non-fractionated lignin are hetero ⁇ geneous. Films were also produced for the purpose of testing the mechanical and thermal properties of the polyurethanes. In the following Examples 1 to 3, rigid, flexible and soft polyurethane films, respectively., have been produced.
  • Table 2 illustrates the mechanical properties • of these polyurethanes.
  • the samples listed within each section of the table have mutually different NC0/0H- ratios.
  • Example 1 refers to rigid polyurethane.
  • Example 2 to flexible polyurethane and Exa ⁇ ple 3 to soft polyurethane, respectively.
  • the thermal decomposition temperature of the lignin- containing polyurethane is approximately 10 - 15 C higher than the corresponding temperature of the lignin-free polyurethane.
  • the rate of pyrolysis of the lignin-containing polyurethane is markedly lower than that of the lignin-free polyurethane.
  • the increased thermal stability of the lignin-containing polyurethane may be due to the anti-oxidation properties of the lignin.
  • the lignin-containing polyurethane exhibits a broad temperature band with respect to glass transition temperatures, as is normally also the case for inter ⁇ penetrating polymer networks.
  • Such material is able, among other things, to absorb vibrations over a wide frequency band, and can be used effectively as a material for damping sound and vibrations.
  • the physical properties of these materials are also stable over a wide range of temperatures.
  • the cross-linking density of lignin-containing poly ⁇ urethanes is much higher than that of lignin-free poly ⁇ urethanes for a given isocyanate/hydroxy (NCO/OH) ratio. This indicates that the lignin has reacted with isocyanate and contributed to the formation of the network structure.
  • An increase in cross-linking density results in an increase in the Young's modulus and maximum strength of the lignin-containing polyurethane. The maximum strength obtains a constant level independent of the NCO/OH-ratio and the kraft-lignin content.
  • the lignin-containing polyurethane can be used within all areas in which polyurethane is normally used, e.g. polyurethane foam, binders, etc.
  • New usages of interest with regard to the properties of the material may also include
  • the resultant film had a density and cross- linking density of 1.194 g/cm 3 and 1.32 x 10—3 moles/cm3, respectively.
  • the Young's modulus, maximum strength and breaking energy were 1.07 GPa, 47 MPa and 0.812 J, respectively.
  • the resultant film had a density and a cross- linking density of 1.185 g/cm 3 and 0.89 x 10—3 moles/cm3 respectively.
  • the Young's modulus, maximum strength and breaking energy were 0.44 GPa, 35.9 MPa and 1.88 J, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Production de polyuréthanes par polymérisation d'isocyanate polymère de polyol et de lignine kraft ou d'un autre type de lignine technique, dans laquele la lignine utilisée a été substantiellement libérée de ses fractions à poids moléculaire élevé au moyen d'une méthode appropriée à cet effet. Le polyuréthane produit présente de bonnes propriétés mécaniques et une stabilité thermique élevée.
PCT/SE1986/000237 1985-05-29 1986-05-21 Utilisation de lignine comme composant de reaction dans la production de polyurethanes Ceased WO1986007070A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8502651-6 1985-05-29
SE8502651A SE8502651L (sv) 1985-05-29 1985-05-29 Forfarande for framstellning av polyuretaner med lignin, som en reaktionskomponent

Publications (1)

Publication Number Publication Date
WO1986007070A1 true WO1986007070A1 (fr) 1986-12-04

Family

ID=20360377

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1986/000237 Ceased WO1986007070A1 (fr) 1985-05-29 1986-05-21 Utilisation de lignine comme composant de reaction dans la production de polyurethanes

Country Status (2)

Country Link
SE (1) SE8502651L (fr)
WO (1) WO1986007070A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342781A3 (en) * 1988-05-16 1990-11-07 Director-General Of Agency Of Industrial Science And Technology New polyurethane and process for preparing same
WO2014029918A1 (fr) * 2012-08-24 2014-02-27 Upm-Kymmene Corporation Procédé permettant de récupérer de la lignine à faible poids moléculaire à partir d'un filtrat
EP2860210A1 (fr) 2013-10-14 2015-04-15 Solvay SA Compositions de biopolymères phénoliques
EP2860209A1 (fr) 2013-10-14 2015-04-15 Solvay SA Procédé pour la préparation de compositions biopolymères
WO2015178771A1 (fr) * 2014-05-20 2015-11-26 Stichting Dienst Landbouwkundig Onderzoek Fractionnement de lignine technique
US9598529B2 (en) 2013-08-13 2017-03-21 Enerlab 2000 Inc. Process for the preparation of lignin based polyurethane products
CN109206589A (zh) * 2017-07-03 2019-01-15 北京化工大学 裂解木质素及木质素基聚氨酯硬质泡沫的制备方法
CN115746241A (zh) * 2022-11-17 2023-03-07 大连工业大学 一种分子量可控分级工业碱木质素制备聚氨酯泡沫材料的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3519581A (en) * 1967-01-13 1970-07-07 Westvaco Corp Method of producing synthetic lignin-polyisocyanate resin
US3654194A (en) * 1967-02-06 1972-04-04 Kaiser Aluminium Chem Corp Process for producing polyoxyalkylene ether-polyols from lignin and tannin and products so made

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3519581A (en) * 1967-01-13 1970-07-07 Westvaco Corp Method of producing synthetic lignin-polyisocyanate resin
US3654194A (en) * 1967-02-06 1972-04-04 Kaiser Aluminium Chem Corp Process for producing polyoxyalkylene ether-polyols from lignin and tannin and products so made

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 101 (1984), Abstract No. 153 097. *
CHEMICAL ABSTRACTS, Vol. 101 (1984), Abstract No. 153 669. *
CHEMICAL ABSTRACTS, Vol. 101 (1984), Abstract No. 25 196. *
CHEMICAL ABSTRACTS, Vol. 102 (1985), Abstract No. 221 556. *
CHEMICAL ABSTRACTS, Vol. 84 (1976), Abstract No. 123 661. *
CHEMICAL ABSTRACTS, Vol. 85 (1976), Abstract No. 144 139. *
CHEMICAL ABSTRACTS, Vol. 98 (1983), Abstract No. 217 426. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342781A3 (en) * 1988-05-16 1990-11-07 Director-General Of Agency Of Industrial Science And Technology New polyurethane and process for preparing same
US9982004B2 (en) 2012-08-24 2018-05-29 Upm-Kymmene Corporation Method for recovering low molecular weight lignin from a filtrate
WO2014029918A1 (fr) * 2012-08-24 2014-02-27 Upm-Kymmene Corporation Procédé permettant de récupérer de la lignine à faible poids moléculaire à partir d'un filtrat
US9598529B2 (en) 2013-08-13 2017-03-21 Enerlab 2000 Inc. Process for the preparation of lignin based polyurethane products
EP2860210A1 (fr) 2013-10-14 2015-04-15 Solvay SA Compositions de biopolymères phénoliques
EP2860209A1 (fr) 2013-10-14 2015-04-15 Solvay SA Procédé pour la préparation de compositions biopolymères
WO2015055662A1 (fr) 2013-10-14 2015-04-23 Solvay Sa Compositions de biopolymères phénoliques
WO2015055648A1 (fr) 2013-10-14 2015-04-23 Solvay Sa Procédé de préparation de compositions de biopolymères
WO2015178771A1 (fr) * 2014-05-20 2015-11-26 Stichting Dienst Landbouwkundig Onderzoek Fractionnement de lignine technique
CN109206589A (zh) * 2017-07-03 2019-01-15 北京化工大学 裂解木质素及木质素基聚氨酯硬质泡沫的制备方法
CN109206589B (zh) * 2017-07-03 2021-08-06 北京化工大学 裂解木质素及木质素基聚氨酯硬质泡沫的制备方法
CN115746241A (zh) * 2022-11-17 2023-03-07 大连工业大学 一种分子量可控分级工业碱木质素制备聚氨酯泡沫材料的方法
CN115746241B (zh) * 2022-11-17 2024-06-07 大连工业大学 一种分子量可控分级工业碱木质素制备聚氨酯泡沫材料的方法

Also Published As

Publication number Publication date
SE8502651D0 (sv) 1985-05-29
SE8502651L (sv) 1986-11-30

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