WO1998008903A1 - Modified lignins - Google Patents
Modified lignins Download PDFInfo
- Publication number
- WO1998008903A1 WO1998008903A1 PCT/US1997/015039 US9715039W WO9808903A1 WO 1998008903 A1 WO1998008903 A1 WO 1998008903A1 US 9715039 W US9715039 W US 9715039W WO 9808903 A1 WO9808903 A1 WO 9808903A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- melt
- composition
- flow characteristics
- polyether
- Prior art date
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 47
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000000155 melt Substances 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 229920000728 polyester Polymers 0.000 claims 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 229920001225 polyester resin Polymers 0.000 claims 1
- 239000004645 polyester resin Substances 0.000 claims 1
- 239000005011 phenolic resin Substances 0.000 abstract description 16
- 229920001568 phenolic resin Polymers 0.000 abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229930014626 natural product Natural products 0.000 description 3
- 230000002860 competitive effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920002176 Pluracol® Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
- C07G99/002—Compounds of unknown constitution containing sulfur
- C07G99/0022—Compounds of unknown constitution containing sulfur derived from hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
Definitions
- lignins There are substantial markets available to lignins if they can achieve the same melt and flow characteristics as a phenolic resin. There are at least two major factors of this present invention which allow these new modified lignins to be able to totally replace phenolic resins.
- the first factor that has been that a lignin which does not have any distinct melt point or flow characteristics can be modified with a certain amount of polyether glycol to achieve a certain desired melt point. So, what occurs is a certain ratio of lignin to a polyether compound (such as polyether glycol) produces a product which has a distinct melt point and melt viscosity. This effect can be thought of as a type of plasticizing effect wherein the lignin can be thought of as the hard resin.
- lignin is derived from wood, which is a natural product. As in all natural products there will exist a certain amount of variation depending on the exact type of wood, age and other conditions. These variations are another major reason why lignins have not been extensively utilized as replacements for phenolic resins, whereas a synthetic phenolic resin can be made to exact and reproducible specifications, and the lignin molecule may have wide variations. Therefore, if there is a variation in the lignin this can be adjusted by changing the ratio of lignin to a polyether compound (such as polyether glycol) in order to achieve the desired melt and flow characteristics.
- a polyether compound such as polyether glycol
- lignins are a natural product and as such there may be natural chemical variations in the lignin molecule. These variations may include different functional groups or different concentrations of these functional groups. These variations become rather significant when you are trying to formulate a product that must have, in addition to certain physical properties such as melt and flow, certain curing characteristics in order to produce a consistent product day in and day out.
- lignins can be used as either partial or total replacement of phenolic resins in phenolic production.
- One major advantage is that lignins can offer significant economic advantages. Since most phenolic resins are made from phenol and phenol is a petrochemical product, cost of phenol is very dependent on the cost of oil. So, as the cost of oil increases, the cost of phenol and phenolic resins will also increase. These price increases could make phenolic resins less competitive and thereby make it possible for these phenolic products to be replaced by other products.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
Ligning and polyether glycol produces a product which has a distinct melt point and melt viscosity. This has a plasticizing effect wherein the polyether glycol can be thought of as the hard resin. When 20 parts of polyether glycol are processed with 80 parts of lignin a new material which has a melt point and a viscosity is created whereas lignin itself has no melt and flow characteristics. The new modified lignin can be cured with hexamine like a phenolic resin.
Description
MODIFIED LIGNINS
There are substantial markets available to lignins if they can achieve the same melt and flow characteristics as a phenolic resin. There are at least two major factors of this present invention which allow these new modified lignins to be able to totally replace phenolic resins. The first factor that has been that a lignin which does not have any distinct melt point or flow characteristics can be modified with a certain amount of polyether glycol to achieve a certain desired melt point. So, what occurs is a certain ratio of lignin to a polyether compound (such as polyether glycol) produces a product which has a distinct melt point and melt viscosity. This effect can be thought of as a type of plasticizing effect wherein the lignin can be thought of as the hard resin. For example, when 20- parts of a polyether glycol is properly processed with 80 parts of lignin what results is a new material which now has melt and flow characteristics, whereas lignin by itself has no melt and flow characteristics. Because these melt and flow characteristics are similar to a phenolic resin these new modified lignins can be cured with hexamine just like a phenolic resin. This is because the lignin molecule contains phenolic groups which are reactive to hexamine just as in a phenolic resin. This is significant because although lignin itself does contain phenolic groups that are reactive to hexamine the fact that the lignin molecule does not melt and flow means that it would be almost impossible to obtain a commercially moldable part from a press with heat and pressure.
.Another major advantage of this present invention is that lignin is derived from wood, which is a natural product. As in all natural products there will exist a certain amount of variation depending on the exact type of wood, age and other conditions. These variations are another major reason why lignins have not been extensively utilized as replacements for phenolic resins, whereas a synthetic phenolic resin can be made to exact and
reproducible specifications, and the lignin molecule may have wide variations. Therefore, if there is a variation in the lignin this can be adjusted by changing the ratio of lignin to a polyether compound (such as polyether glycol) in order to achieve the desired melt and flow characteristics. Mother important aspect of this invention that has a synergisric effect on the melt and flow characteristics is the sodium level of the lignin. It was discovered that if the sodium level is too high the modified lignin will not have melt and flow characteristics which can be utilized as a commercial product. It was found that the same lignin, but with different sodium levels, will produce modified lignins with wide variations in melt and flow characteristics. Therefore, it was discovered that there is a certain critical level for the presence of sodium and other ionic materials above which no useful products could be obtained. This critical level may vary depending on the specific nature or chemical composition of the lignins. .Another major invention is the fact that lignins are a natural product and as such there may be natural chemical variations in the lignin molecule. These variations may include different functional groups or different concentrations of these functional groups. These variations become rather significant when you are trying to formulate a product that must have, in addition to certain physical properties such as melt and flow, certain curing characteristics in order to produce a consistent product day in and day out.
These curing characteristics are very important because in addition to the physical properties of the product they also determine the productivity, which directly affects how profitable the product will be. One major market for lignins is to either partially or totally replace phenolic resins in many products that currently use all phenolic resins. There are at least two major advantages why lignins can be used as either partial or total replacement of phenolic resins in phenolic production. One major advantage is that lignins can offer significant economic advantages. Since most phenolic
resins are made from phenol and phenol is a petrochemical product, cost of phenol is very dependent on the cost of oil. So, as the cost of oil increases, the cost of phenol and phenolic resins will also increase. These price increases could make phenolic resins less competitive and thereby make it possible for these phenolic products to be replaced by other products.
Therefore, when more lignin can be incorporated into a phenolic product, this could offset price increases and make these lignin modified phenolic products more profitable and more competitive, thus increasing their market share.
EXAMPLE 1 In a suitable vessel 20 parts of Pluracol P-410 is heated to
200 °F and 80 parts of lignin is slowly added while adequate agitation is maintained and the heat slowly increased to 270 °F. The viscosity of this mixture will increase significantly but it still is able to be mixed. Then once all of the lignin is added, the mixture is continued to be mixed until everything is homogeneous. Then this mixture is poured out on to a surface which allows this mixture to cool and form a hard brittle material. This lignin is now in a form which is very similar to phenolic resins. This modification of the lignin now makes it possible for it to have melt and flow characteristics.
Claims
1. A composition comprising lignin blended with a polyether compound to improve the melt and flow characteristics of the lignin.
2. A composition as claimed in claim 1 wherein the ratio of said polyether compound to lignin is from 1% to 70%.
3. A composition comprising lignin blended with a polyester compound to improve the melt and flow characteristics of the lignin.
4. A composition as claimed in claim 3 wherein the ratio of said polyester compound to lignin is from 1% to 70%.
5. A composition as claimed in claim 1 wherein said polyether compound is produced by the reaction product of ethylene oxide and propylene oxide.
6. A composition comprising a combination of polyester resins and polyether glycols are blended to improve the melt and flow characteristics of the lignin.
7. A composition comprising a polyether derivative (reaction product of ethylene oxide and propylene oxide) selected from the group of nonylphenol, phenol or a substituted phenol blended with lignin to improve the melt and flow characteristics of lignin.
8. A composition as claimed in claim 1 wherein the sodium level of the ligrun in claim 1 is preferably below 22% by weight of sodium.
9. A composition as claimed in claim 1 wherein the modified lignin is reacted with hexamine to produce a cured product.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10511863A JP2000517362A (en) | 1996-08-26 | 1997-08-26 | Modified lignin |
| CA002262940A CA2262940C (en) | 1996-08-26 | 1997-08-26 | Modified lignins |
| AU40924/97A AU4092497A (en) | 1996-08-26 | 1997-08-26 | Modified lignins |
| EP97938638A EP0920477A4 (en) | 1996-08-26 | 1997-08-26 | Modified lignins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2455896P | 1996-08-26 | 1996-08-26 | |
| US60/024,558 | 1996-08-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998008903A1 true WO1998008903A1 (en) | 1998-03-05 |
Family
ID=21821209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1997/015039 WO1998008903A1 (en) | 1996-08-26 | 1997-08-26 | Modified lignins |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0920477A4 (en) |
| JP (1) | JP2000517362A (en) |
| AU (1) | AU4092497A (en) |
| CA (1) | CA2262940C (en) |
| WO (1) | WO1998008903A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075153A3 (en) * | 1999-06-04 | 2001-04-19 | Univ Minnesota | Compositions based on lignin derivatives |
| CN101265364B (en) * | 2007-07-27 | 2010-08-11 | 张国栋 | Thermoset plastics infiltration strengthened powdery plant fiber material and preparation method thereof |
| JP2015519452A (en) * | 2012-06-01 | 2015-07-09 | ストラ エンソ オーワイジェイ | Dispersed composition containing lignin, process for its production and use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200131318A1 (en) * | 2016-08-23 | 2020-04-30 | National Research Council Of Canada | Lignin pellets and process for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2156160A (en) * | 1938-05-17 | 1939-04-25 | Northwood Chemical Company | Lignin molding compound |
| US2192030A (en) * | 1935-12-12 | 1940-02-27 | Gen Electric | Process for the manufacture of a lignin-containing press mass |
| US3355400A (en) * | 1960-09-26 | 1967-11-28 | Union Carbide Corp | Polyether-lignin compositions |
| US4833182A (en) * | 1986-09-29 | 1989-05-23 | Jim Walter Research Corp. | Isocyanate-polyester polyol binder for manufacture of cellulosic composites |
| US5025046A (en) * | 1989-12-15 | 1991-06-18 | Kimberly-Clark Corporation | Creping adhesive composition |
| US5300593A (en) * | 1991-11-07 | 1994-04-05 | Rutgerswerke Aktiengesellschaft Ag | Lignin modified binding agents |
| US5614564A (en) * | 1993-07-28 | 1997-03-25 | Samsung General Chemicals Co., Ltd. | Degradable foam and the method for its production |
-
1997
- 1997-08-26 CA CA002262940A patent/CA2262940C/en not_active Expired - Fee Related
- 1997-08-26 JP JP10511863A patent/JP2000517362A/en active Pending
- 1997-08-26 AU AU40924/97A patent/AU4092497A/en not_active Abandoned
- 1997-08-26 WO PCT/US1997/015039 patent/WO1998008903A1/en not_active Application Discontinuation
- 1997-08-26 EP EP97938638A patent/EP0920477A4/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2192030A (en) * | 1935-12-12 | 1940-02-27 | Gen Electric | Process for the manufacture of a lignin-containing press mass |
| US2156160A (en) * | 1938-05-17 | 1939-04-25 | Northwood Chemical Company | Lignin molding compound |
| US3355400A (en) * | 1960-09-26 | 1967-11-28 | Union Carbide Corp | Polyether-lignin compositions |
| US4833182A (en) * | 1986-09-29 | 1989-05-23 | Jim Walter Research Corp. | Isocyanate-polyester polyol binder for manufacture of cellulosic composites |
| US5025046A (en) * | 1989-12-15 | 1991-06-18 | Kimberly-Clark Corporation | Creping adhesive composition |
| US5300593A (en) * | 1991-11-07 | 1994-04-05 | Rutgerswerke Aktiengesellschaft Ag | Lignin modified binding agents |
| US5614564A (en) * | 1993-07-28 | 1997-03-25 | Samsung General Chemicals Co., Ltd. | Degradable foam and the method for its production |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0920477A4 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075153A3 (en) * | 1999-06-04 | 2001-04-19 | Univ Minnesota | Compositions based on lignin derivatives |
| CN101265364B (en) * | 2007-07-27 | 2010-08-11 | 张国栋 | Thermoset plastics infiltration strengthened powdery plant fiber material and preparation method thereof |
| JP2015519452A (en) * | 2012-06-01 | 2015-07-09 | ストラ エンソ オーワイジェイ | Dispersed composition containing lignin, process for its production and use thereof |
| JP2018021211A (en) * | 2012-06-01 | 2018-02-08 | ストラ エンソ オーワイジェイ | Composition in the form of dispersion comprising lignin, method for producing the same and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2262940C (en) | 2003-11-04 |
| AU4092497A (en) | 1998-03-19 |
| CA2262940A1 (en) | 1998-03-05 |
| EP0920477A4 (en) | 1999-10-06 |
| JP2000517362A (en) | 2000-12-26 |
| EP0920477A1 (en) | 1999-06-09 |
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