EP0812326A1 - Lignin based polyols - Google Patents

Lignin based polyols

Info

Publication number
EP0812326A1
EP0812326A1 EP96944852A EP96944852A EP0812326A1 EP 0812326 A1 EP0812326 A1 EP 0812326A1 EP 96944852 A EP96944852 A EP 96944852A EP 96944852 A EP96944852 A EP 96944852A EP 0812326 A1 EP0812326 A1 EP 0812326A1
Authority
EP
European Patent Office
Prior art keywords
lignin
composition
polyol
foam
pulping process
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
EP96944852A
Other languages
German (de)
French (fr)
Other versions
EP0812326A4 (en
Inventor
Kenneth R. Kurple
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP0812326A1 publication Critical patent/EP0812326A1/en
Publication of EP0812326A4 publication Critical patent/EP0812326A4/en
Ceased legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • foams and urethane plastics are made by reacting a polyol with an isocyanate with a functionality of at least 2 (two) or greater.
  • the polyol can be a polyester molecule which has at least a functionality of at least 2 (two) or greater.
  • the polyol can also be a polyether polyol which is made by reacting propylene oxide or ethylene oxide with a molecule such as ethylene glycol or glycerine to produce molecules with various molecule weights, which have pendant hydroxyl groups which will react with difunctional or multifunctional isocyanates to produce a solid plastic or foam.
  • a polyether polyol which is made by reacting propylene oxide or ethylene oxide with a molecule such as ethylene glycol or glycerine to produce molecules with various molecule weights, which have pendant hydroxyl groups which will react with difunctional or multifunctional isocyanates to produce a solid plastic or foam.
  • a rigid foam or a urethane plastic it is necessary to react one part polyol with one part isocyanate. This is because the isocyanate generally contains aromatic rings and this is what makes the foam rigid, as well as having a high cross
  • a major disadvantage of these high levels of isocyanate is that when the foam is burned, high levels of toxic gases are produced which are generally derived from the isocyanate part of the molecule. It would be a tremendous advantage to be able to reduce the toxic fumes. It has been discovered that by using the lignin molecule as part of the polyol portion the significant advantages result. One is that by using the lignin molecule in the polyol portion of the system the amount of isocyanate can be reduced 40% or more and still produce rigid foam. This reduces the amount of toxic gases that are derived from the isocyanate portion of the system.
  • the lignin molecule is a natural phenolic type molecule that occurs in wood, straw, sugar cane and other natural materials.
  • lignin that is produced as a byproduct of the pulping process to make paper is just burned to recover heat value. In the United States alone over 50 billion pounds lignin are burned annually just for its heat value. Any lignin from the Kraft pulping process, sulfite pulping process, semi mechanical pulping process, thermomechanical pulping process, semi-chemical pulping process, solvent process, steam explosion pulping process and biomass pulping process can be used.
  • lignins can function quite well as a polyol component for an isocyanate system, these lignins can be used at different levels in the system depending on what fmal properties of the system are desired.
  • the use of the lignin molecule also significantly improves the moisture resistance of a foam, in fact when the proper level of lignin is used in a urethane foam the urethane foam will be almost impervious to moisture even when in direct contact with moisture.
  • Commercial foams made with the present polyols literally absorb moisture like a sponge.
  • Another major advantage of using lignin as a part of the polyol system is the flame resistance of the finished foam or urethane foam of urethane plastic part.
  • lignin acts as a natural flame retardant.
  • polyether polyol that is made from ethylene oxide. This is very important because when a regular polyether polyol is made from just propylene oxide the resulting polyol does not readily solubilize the lignin molecule and in many cases phase separation results and does not produce a quality urethane foam or plastic product.
  • ethylene oxide as a part of the polyol makes it possible to make these blends with lignin.
  • one of the major aspects of this invention is that in order to make high quality urethane foams and plastic materials the amount of sodium or other caustic ions such as potassium that are present in the lignin can have a dramatic affect on the properties of the final urethane product. This is because it is a well known fact that materials that produce a basic PH in water can perform as very strong catalysts for the isocyanate hydroxyl reaction that produces the urethane linkage. Therefore if the sodium level is too high it will cause the reaction between the hydroxyl groups and isocyanates go too fast which can produce a very poor quality product.
  • a suitable vessel use heat and or pressure to blend 300 parts of a lignin produced from a solvent pulping process and 700 parts of WL-440 (a polyether polyol that is made from a combination of propylene oxide and ethylene oxide) with agitation by using a suitable mixer and heat and higher pressure if necessary.
  • This mixture can be heated to 200° F. to improve the rate of solution, the mixing is continued until a dark solution results.
  • What results is a liquid material that has the following physical viscosity: 1532 centistrokes at 100° F. whose viscosity will depend on the particular lignin that is used.
  • thermosetting urethane part 1.5 parts of the resin solution of Example I is mixed with 1 part of Rubinate R1840 (an ICI product) and poured into a mold and allowed to harden. The mold can be heated as in a compression mold and this will produce a very hard tough plastic. The hardness of the product will depend on the particular lignin used.
  • Example III In order to produce a foam, 2 parts of the lignin based polyol of
  • Example I is premixed with 0.05 parts of water and 1 part Rubinate R1840 and then poured into a suitable container and a free rising foam will result.
  • Example IV is premixed with 0.05 parts of water and 1 part Rubinate R1840 and then poured into a suitable container and a free rising foam will result.
  • a blowing agent can be mixed with this lignin based polyol in example I. Therefore 2 parts of lignin based polyol of example I is premixed with 0.6 parts of Forane 141 b (1.1 dichloro- 1-fluroethane), then this mixture is mixed with 1 part of Rubinate R-1840 and then poured into a suitable container and a free rising foam low density will result.
  • Forane 141 b 1.1 dichloro- 1-fluroethane
  • one part of the lignin based polyol of example I is mixed with 1 part of suitable coating solvent depending on the coating application. Then this premix is mixed with 1 part Rubinate R-1840 and the resulting mixture is used to coat a variety of substances. The viscosity of this resulting mixture can be adjusted with suitable solvents depending on the final coating application.
  • Kraft lignin or other type lignin may be employed.

Landscapes

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

Abstract

Certain lignins which are readily available from pulping processes function as a polyol component of an isocyanate system to make foams and urethane plastics. Use of the lignin in this manner provides moisture and flame resistance and produces products having sufficient rigidity. The sodium level must be controlled so that the reaction between the hydroxyl groups and the isocyanates produces products with the optimal properties.

Description

LIGNIN BASED POLYOLS
BACKGROUND OF THE INVENTION
At the present time foams and urethane plastics are made by reacting a polyol with an isocyanate with a functionality of at least 2 (two) or greater.
The polyol can be a polyester molecule which has at least a functionality of at least 2 (two) or greater. The polyol can also be a polyether polyol which is made by reacting propylene oxide or ethylene oxide with a molecule such as ethylene glycol or glycerine to produce molecules with various molecule weights, which have pendant hydroxyl groups which will react with difunctional or multifunctional isocyanates to produce a solid plastic or foam. However at present time in order to produce a rigid foam or a urethane plastic it is necessary to react one part polyol with one part isocyanate. This is because the isocyanate generally contains aromatic rings and this is what makes the foam rigid, as well as having a high crosslink density.
Also, a major disadvantage of these high levels of isocyanate is that when the foam is burned, high levels of toxic gases are produced which are generally derived from the isocyanate part of the molecule. It would be a tremendous advantage to be able to reduce the toxic fumes. It has been discovered that by using the lignin molecule as part of the polyol portion the significant advantages result. One is that by using the lignin molecule in the polyol portion of the system the amount of isocyanate can be reduced 40% or more and still produce rigid foam. This reduces the amount of toxic gases that are derived from the isocyanate portion of the system. The lignin molecule is a natural phenolic type molecule that occurs in wood, straw, sugar cane and other natural materials. Generally the majority of the lignin that is produced as a byproduct of the pulping process to make paper is just burned to recover heat value. In the United States alone over 50 billion pounds lignin are burned annually just for its heat value. Any lignin from the Kraft pulping process, sulfite pulping process, semi mechanical pulping process, thermomechanical pulping process, semi-chemical pulping process, solvent process, steam explosion pulping process and biomass pulping process can be used.
As part of this present invention it was discovered that certain lignins can function quite well as a polyol component for an isocyanate system, these lignins can be used at different levels in the system depending on what fmal properties of the system are desired. The use of the lignin molecule also significantly improves the moisture resistance of a foam, in fact when the proper level of lignin is used in a urethane foam the urethane foam will be almost impervious to moisture even when in direct contact with moisture. Commercial foams made with the present polyols literally absorb moisture like a sponge. Another major advantage of using lignin as a part of the polyol system is the flame resistance of the finished foam or urethane foam of urethane plastic part. This is because lignin acts as a natural flame retardant. However one of the major aspects of this invention is that the lignin molecule becomes readily soluble in polyether polyol that is made from ethylene oxide. This is very important because when a regular polyether polyol is made from just propylene oxide the resulting polyol does not readily solubilize the lignin molecule and in many cases phase separation results and does not produce a quality urethane foam or plastic product. We have found that ethylene oxide as a part of the polyol makes it possible to make these blends with lignin.
What has been discovered is that where current polyether polyols only have marginal solubility for various lignins this fact makes it very difficult to produce a high quality foam or urethane plastic part because the lignin will tend to phase separate when the isocyanate is added to the lignin polyol blend and this makes it very difficult to make consistent physical products.
Also one of the major aspects of this invention is that in order to make high quality urethane foams and plastic materials the amount of sodium or other caustic ions such as potassium that are present in the lignin can have a dramatic affect on the properties of the final urethane product. This is because it is a well known fact that materials that produce a basic PH in water can perform as very strong catalysts for the isocyanate hydroxyl reaction that produces the urethane linkage. Therefore if the sodium level is too high it will cause the reaction between the hydroxyl groups and isocyanates go too fast which can produce a very poor quality product. It was discovered and it is one of the major aspects of this invention to reduce the sodium level to levels that are low enough to make it possible to produce a useful product once the lignin based polyol has reacted with the isocyanate. Also high levels of sodium ions or other inorganic ions such as potassium will actually degrade the foam in time.
Example I
In a suitable vessel use heat and or pressure to blend 300 parts of a lignin produced from a solvent pulping process and 700 parts of WL-440 (a polyether polyol that is made from a combination of propylene oxide and ethylene oxide) with agitation by using a suitable mixer and heat and higher pressure if necessary. This mixture can be heated to 200° F. to improve the rate of solution, the mixing is continued until a dark solution results. What results is a liquid material that has the following physical viscosity: 1532 centistrokes at 100° F. whose viscosity will depend on the particular lignin that is used.
Example II
In order to make a thermosetting urethane part, 1.5 parts of the resin solution of Example I is mixed with 1 part of Rubinate R1840 (an ICI product) and poured into a mold and allowed to harden. The mold can be heated as in a compression mold and this will produce a very hard tough plastic. The hardness of the product will depend on the particular lignin used. Example III In order to produce a foam, 2 parts of the lignin based polyol of
Example I is premixed with 0.05 parts of water and 1 part Rubinate R1840 and then poured into a suitable container and a free rising foam will result. Example IV
In order to produce a low density foam, a blowing agent can be mixed with this lignin based polyol in example I. Therefore 2 parts of lignin based polyol of example I is premixed with 0.6 parts of Forane 141 b (1.1 dichloro- 1-fluroethane), then this mixture is mixed with 1 part of Rubinate R-1840 and then poured into a suitable container and a free rising foam low density will result. Example V
In order to make a urethane coating based on the lignin based polyol of example I, one part of the lignin based polyol of example I is mixed with 1 part of suitable coating solvent depending on the coating application. Then this premix is mixed with 1 part Rubinate R-1840 and the resulting mixture is used to coat a variety of substances. The viscosity of this resulting mixture can be adjusted with suitable solvents depending on the final coating application.
It is understood to those skilled in the art that Kraft lignin or other type lignin may be employed.

Claims

What is claimed is:
1. A composition wherein lignin is blended with a polyol to produce a lignin polyol which is a mixture that can be readily reacted with isocyanates to produce a foam, plastic or other useable material.
2. A composition as in claim(l) wherein the polyether polyol that is used to blend with lignin contains between 1% and 100% ethylene oxide as one of its reactive materials.
3. A composition as in claim (1) wherein mixtures of polyether polyols are used to blend with lignin.
4. A composition as in claim (1) wherein mixtures of polyether and polyester polyols are used to blend with lignin.
5. A composition as in claim (1) wherein mixtures of polyether polyols that contain amino groups are used to blend with lignin.
6. A composition as in claim (1) wherein the lignin that is used is from a solvent pulping process.
7. A composition as in claim (1) wherein the lignin that is used is from the kraft paper pulping process.
8. A composition as in claim (1) wherein the lignin is from a biomass process.
9. A composition as in claim (1) wherein the lignin is from a mechanical pulping process.
10. A composition as in claim (1) wherein the lignin is a lignosulfonate from the sulfite paper pulping process.
11. A composition as in claim (1) wherein the polyol is WL-440 (a polyol produced from ethylene oxide and propylene oxide).
12. A composition as in claim (1) wherein the polyol is WL-1590 ( a polyol produced from ethylene oxide and propylene oxide by Huntsman Chemical).
13. A composition as in claim (1) wherein the lignin is a lignosulfonate from the sulfite paper pulping process.
14. A composition as in claim (1) wherein the polyol is WL-400 ( a polyol produced from ethylene oxide and propylene oxide).
15. A composition as in claim (1) wherein the lignin is a lignin from a semi-mechanical pulp.
16. A composition as in claim (1) wherein the lignin mat is used has preferably less than 2% ash level.
17. A Composition as in claim (1) wherein the lignin that is used has preferably less than 1% sodium.
18. A composition as in claim (1) wherein the lignin that is used has preferably less than 500 parts per million of sodium.
19. A composition as in claim (1) wherein the lignin preferably contains less than 2% water soluble ions.
20. A composition wherein lignin is added to a polyol to improve the moisture resistance of the resulting foam or urethane product.
21. A composition wherein lignin is added to the polyol system to improve the flame resistance of the urethane foam or urethane product.
22. A composition as in claim (1) wherein the sodium level is low enough so that the reaction rate of the isocyanate and hydroxyls group of the lignin based polyol is controllable enough to produce a useful product such as foam, plastic and coating.
23. A composition as in claim (1) wherein this lignin based polyol is blended with suitable solvents and mixed with the appropriate isocyanates to produce a urethane coating for a variety of substrates.
EP96944852A 1995-12-29 1996-12-27 Lignin based polyols Ceased EP0812326A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US952995P 1995-12-29 1995-12-29
US952P 1995-12-29
PCT/US1996/020140 WO1997024362A1 (en) 1995-12-29 1996-12-27 Lignin based polyols

Publications (2)

Publication Number Publication Date
EP0812326A1 true EP0812326A1 (en) 1997-12-17
EP0812326A4 EP0812326A4 (en) 1998-05-06

Family

ID=21738217

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96944852A Ceased EP0812326A4 (en) 1995-12-29 1996-12-27 Lignin based polyols

Country Status (13)

Country Link
EP (1) EP0812326A4 (en)
JP (1) JPH11501946A (en)
KR (1) KR19980702567A (en)
CN (1) CN1176643A (en)
AU (1) AU1336497A (en)
BR (1) BR9607058A (en)
CA (1) CA2214013C (en)
EA (1) EA199700204A1 (en)
MX (1) MX9706348A (en)
NO (1) NO973988L (en)
PL (1) PL322023A1 (en)
SE (1) SE9703037D0 (en)
WO (1) WO1997024362A1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100469810C (en) * 2001-06-15 2009-03-18 独立行政法人产业技术综合研究所 Lignin-containing polyurethane and process for producing the same
ITTO20090351A1 (en) * 2009-05-04 2010-11-05 Univ Pisa PROCEDURE FOR THE PRODUCTION OF POLYURETHANE / POLYUREIC FOAMS FROM LIGNINA-BASED MATERIALS
WO2010135832A1 (en) * 2009-05-28 2010-12-02 Lignol Innovations Ltd. Resin compositions comprising lignin derivatives
EP2435453B1 (en) 2009-05-28 2022-03-02 Suzano Canada Inc. Derivatives of native lignin
JP2011219715A (en) * 2010-02-10 2011-11-04 Hitachi Chem Co Ltd Resin compound material for molding
CA2824446C (en) 2010-02-15 2018-09-18 Lignol Innovations Ltd. Binder compositions comprising lignin derivatives
JP5909840B2 (en) 2010-02-15 2016-04-27 フィブリア イノヴェイションズ インコーポレイテッド Carbon fiber composition containing lignin derivative
CN103459511A (en) 2011-03-24 2013-12-18 丽格诺创新有限公司 Compositions comprising lignocellulosic biomass and organic solvent
CA2832563C (en) * 2011-04-06 2023-06-13 Harold E. Thompson Multi-purpose lignin-carbohydrate binding system
WO2013113462A1 (en) * 2012-02-02 2013-08-08 Annikki Gmbh Process for the production of polyols
JP2013170245A (en) * 2012-02-22 2013-09-02 Hitachi Chemical Co Ltd Novel polyurethane
EP2644758B1 (en) * 2012-03-29 2014-12-10 Honda R&D Europe (Deutschland) GmbH Stabilization of lignin carbon fibers with crosslinkers
US20150144829A1 (en) * 2012-06-01 2015-05-28 Stora Enso Oyj Composition in the form of a dispersion comprising a lignin, a method for the manufacturing thereof and use thereof
RU2652183C2 (en) * 2012-12-18 2018-04-25 Акцо Нобель Коатингс Интернэшнл Б.В. Lignin-based coating compositions
WO2015021541A1 (en) 2013-08-13 2015-02-19 Enerlab 2000 Inc. Process for the preparation of lignin based polyurethane products
CN105622957B (en) * 2014-11-05 2018-05-04 中国石油化工集团公司 A kind of preparation method of lignin polyether polyalcohol
CN107207713A (en) 2015-01-21 2017-09-26 瑞森内特材料集团有限公司 The high recovery content polyols obtained by thermoplastic polyester and lignin or tannin
CN105175682B (en) * 2015-09-25 2017-11-14 南京工业大学 A kind of technique for preparing polyurethane foam using the new liquifying method of lignin
CN106283642B (en) * 2016-08-09 2018-12-18 李挺晖 A method of fire retardant is prepared using black liquid
BR112019003599A2 (en) * 2016-08-23 2019-05-21 National Research Council Of Canada. lignin pellets and process for their production
CN111454465B (en) * 2020-04-15 2022-05-24 黎明化工研究设计院有限责任公司 Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof
CN111607062B (en) * 2020-05-29 2022-04-08 河南恒泰源新材料有限公司 Biomass polyurethane foam material and preparation method thereof
CN113142184A (en) * 2021-04-08 2021-07-23 浙江海洋大学 Method for manufacturing marine organism specimen for teaching

Family Cites Families (3)

* 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
US4851457A (en) * 1988-02-16 1989-07-25 Kurple Kenneth R Foundry resins
JP2675997B2 (en) * 1988-05-16 1997-11-12 工業技術院長 Novel polyurethane manufacturing method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9724362A1 *

Also Published As

Publication number Publication date
PL322023A1 (en) 1998-01-05
EP0812326A4 (en) 1998-05-06
AU1336497A (en) 1997-07-28
MX9706348A (en) 1997-11-29
SE9703037L (en) 1997-08-22
KR19980702567A (en) 1998-07-15
SE9703037D0 (en) 1997-08-22
NO973988L (en) 1997-10-28
CA2214013A1 (en) 1997-07-10
JPH11501946A (en) 1999-02-16
CN1176643A (en) 1998-03-18
WO1997024362A1 (en) 1997-07-10
EA199700204A1 (en) 1998-02-26
BR9607058A (en) 1998-12-15
CA2214013C (en) 2011-05-10
NO973988D0 (en) 1997-08-29

Similar Documents

Publication Publication Date Title
US6025452A (en) Lignin based polyols
CA2214013C (en) Lignin based polyols
CA1335311C (en) Polyurethane and process for preparing same
Mahmood et al. Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: A review
Wang et al. Synthetic polymer-lignin copolymers and blends
US4017474A (en) Polyurethane intermediates and products and methods of producing same from lignin
Pan et al. Effect of replacing polyol by organosolv and kraft lignin on the property and structure of rigid polyurethane foam
EP0038677B1 (en) A process for producing a wood composition using a liquid adhesive comprising a solution of lignin
Yao et al. Water‐absorbing polyurethane foams from liquefied starch
US3519581A (en) Method of producing synthetic lignin-polyisocyanate resin
de Oliveira et al. Lignopolyurethanic materials based on oxypropylated sodium lignosulfonate and castor oil blends
DE60031290T2 (en) Thermoplastic polyurethanes
Gandini et al. Lignins as components of macromolecular materials
Feldman Lignin and its polyblends—a review
Bernardini et al. Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents
Feldman et al. Lignin-polymer systems and some applications
Gandini et al. Lignins as macromonomers for polyesters and polyurethanes
CA1102481A (en) Dissolution of polyurethane foams and re-use of the products therefrom
US4297456A (en) Process for working up isocyanate distillation residues
US4156759A (en) Polyurethane foams containing stabilized amylaceous materials
EP0745627B1 (en) A process for preparing open-cellular polyurethane modified polyisocyanurate foam
Sternberg et al. Structure-property relationships in flexible and rigid lignin-derived polyurethane foams: A review
JP3101701B2 (en) New polyurethane and its manufacturing method
KR20020034654A (en) Process for preparing depolymerized polyol
CA2284460A1 (en) New polyols and their use in polyurethane preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17P Request for examination filed

Effective date: 19970822

A4 Supplementary search report drawn up and despatched

Effective date: 19980320

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20001025

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20030306