WO2014070036A1 - Lignin composite material - Google Patents
Lignin composite material Download PDFInfo
- Publication number
- WO2014070036A1 WO2014070036A1 PCT/RU2012/000901 RU2012000901W WO2014070036A1 WO 2014070036 A1 WO2014070036 A1 WO 2014070036A1 RU 2012000901 W RU2012000901 W RU 2012000901W WO 2014070036 A1 WO2014070036 A1 WO 2014070036A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite material
- lignin
- carboxylic anhydride
- binder
- linking agent
- Prior art date
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 17
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 125000003700 epoxy group Chemical group 0.000 claims 3
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000004990 dihydroxyalkyl group Chemical group 0.000 claims 1
- 239000012634 fragment Substances 0.000 claims 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 125000000879 imine group Chemical group 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 125000003636 chemical group Chemical group 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 229920000768 polyamine Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229920002732 Polyanhydride Polymers 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 125000002348 vinylic group Chemical group 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920005611 kraft lignin Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 0 CNC(C(C1)C(*)I)NC1O Chemical compound CNC(C(C1)C(*)I)NC1O 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
- C08L73/02—Polyanhydrides
-
- 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
Definitions
- polymerizable vinyl group like methacyloyl group, on lignin followed by free radical copolymerization with methacrylate, acrylamide and other vinylic monomers (US Pat. 5, 138,007; 5,121,801 ; 5,037,931 ; 4,931 ,527).
- This approach requires two steps for making lignin composites. First step, grafting reactive group on lignin, utilizes reagents dissolved in organic solvents. Removal of these solvents after the grafting is complete creates fire hazards and is expensive.
- Lignin can be treated with formaldehyde and/or added to phenol-formaldehyde resins to form a polymeric material (US 4,769,434; 4,221,708). In both cases formaldehyde should be utilized for the synthesis of polymeric material.
- Formaldehyde is known carcinogen and its usage is supposed to be avoided as much as possible, especially in consumer product.
- Lignin was converted into a polymeric material by heating with sulfur (US 4, 107, 1 1 1). The material has unpleasant odor.
- the present invention have endeavored to solve the problem of converting lignin into a structural material by reaction with polyanhydrides of carboxylic acids.
- polyanhydrides of carboxylic acids like maleinized vegetable oils, essentially natural binders can be applied.
- a composites with more than 90% natural components can be obtained.
- lignin forms a composite material with polymers containing carboxylic anhydride groups and a cross-linking agent (hardener).
- Lignin is not very reactive polymer so that chemical bonding with other polymers is problematic.
- polymers with carboxylic anhydride groups form with lignin a composite with sound mechanical properties.
- anhydrides react with hydroxyl groups of lignin.
- Solvent are capable to extract a polymer with broad range of molecular weights, from few hundred to several thousand Daltons from lignin matrix after this free radical polymerization.
- Second method of making mixtures of lignin with polyanhydrides is to use liquid, low molecular weight polyanhydrides.
- Maleinized vegetable oils are the example of such low molecular weight polyanhydrides, with average number of maleic anhydride moieties in the 2-4 range per molecule (Chakrabarty, M. M. Chemistry And Technology Of Oils And Fats. Allied Publishers. 2003).
- Oligomeric anhydrides can be synthesized by catalytic chain transfer polymerization (Sanders G.C. et al.. Macromolecules, 2012, 45 (15), pp 5923- 5933). We found, also, that polyanhydrides, especially low molecular weight one, do not form composites with lignin with acceptable mechanical properties when heated and pressed together at high level of lignin in such composites. A cross- linking agent (hardeher) is required. Such hardeners can be reagents that react with anhydrides.
- polyols examples 4-6
- polyepoxides examples 1 and 2
- imines examples 8 and 9
- polyanhydrides examples 1 and 2
- hydroxyl group can be introduced into a polyanhydride polymer during copolymerization.
- Polyols are chemical compounds bearing hydroxyl (OH) groups.
- Cured lignin compositions were tested and reasonable shear strength, from 3 to 12 MPa was determined. These values of tensile strength are comparable with shear strength of standard MDF (http://www.spanogroup.be/upload/docs/MDF- manual%20ENG%20LOW%20RES.pdf).
- Shear strength of invented lignin composite materials can be increases even further by mixing with fillers (Example 10 and 1 1). There is no doubt that fillers other than glass fiber or wood particles, described in the example 10 and 1 1 , can be applied the invented lignin composite due to high adhering properties of polyanhydrides to various surfaces.
- content of lignin in the composite can be reduced to less than 30% if technological, esthetical or other reasons require less amount of lignin in the invented composite.
- the lignin composites of the present invention have relatively low swelling in water (Example 7), less then 20% after 24 h immersion in water. Most important, after drying the composite restored its dimensions and shear strength. The higher is the content of binder, the less is swelling of the lignin composite in water.
- Curing rate of the present lignin composites depends on chemical origin of lignin, type of carboxylic anhydride, the hardener, temperature and catalyst. Reaction of hydroxy groups of polyols with anhydrides, acids and other reactive groups is known to be catalyzed by different catalyst including but not limited to acids, amines, phosphines and metallochelates. Examples 3-6 utilized only few of such catalysts. Examples 1-2 and 8-9 employed no catalysts.
- Preferred curing catalysts in this invention are tertiary amines due to good solubility of such amines in the invented composition, low cost and no leaching of the amine catalyst from the cured material. Especially, acidic groups that are formed during reaction of polyanhydrides with the hardeners hold the amine catalyst by forming a salt.
- ED20 resin consists of diglycidyl ether of bisphenol A by 90 wt % with the rest 10% of a corresponding dimer bearing hydroxyl groups.
- Sulfolignin lignin sulfate
- Svetogorsk Russian Federation
- Example 1 Maleinized oil.
- Example 2 Different maleinized oil, different epoxide.
- Example 3 Anhydride and hardener are in the same polymer.
- Example 4 Different hardener are in the same polymer.
- a composite material was made similar to the Example 4 but toluenesulfonic acid was taken instead of 2,4,6-tris(dimethylaminomethyl)phenol. Shear strength of the cured composite - 8.9 MPa.
- Example 9 Different imine hardener.
- Example 11 Wood reinforced lignin composite.
- Example 12 Low content of lignin.
Landscapes
- 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)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a composite material comprising lignin, carboxylic anhydride binder and cross-linking agent (hardener). Carboxylic anhydride binder is a polymeric material with amount of carboxylic anhydride 2 or more carboxylic anhydride fragments per molecule of the binder. The binder can be synthesized by copolymerization of different anhydrides with ethylenically unsaturated monomers in the presence of lignin. The hardener comprises chemical groups that are capable to react with carboxylic anhydride moieties, like polyols, polyepoxides or polyamines with amount of such groups 2 or more. Neither the binder, not the hardener contains solvents or water. The composite is obtained by cure of all ingredients together on heating and, optionally, pressing, and with optional catalyst. Catalysts can be applied to reduce process temperature or to improve properties of the composite material. Fillers can be introduced into the lignin composite to improve mechanical strength.
Description
LIGNIN COMPOSITE MATERIAL.
DESCRIPTION OF THE INVENTION
BACKGROUND OF THE INVENTION
The most common approach of making copolymers with lignin is, first, to graft a reactive group onto a lignin molecule. Then, this reactive group reacts with other reagents to form a polymer with lignin. ( T. Q. Hu (edd.). Chemical
Modifications, Properties and Usage of Lignin. Kluwer Publishers, New York, (2002) p. 57). Thus, cross-linked polymer was obtained by grafting
polymerizable vinyl group, like methacyloyl group, on lignin followed by free radical copolymerization with methacrylate, acrylamide and other vinylic monomers (US Pat. 5, 138,007; 5,121,801 ; 5,037,931 ; 4,931 ,527). This approach requires two steps for making lignin composites. First step, grafting reactive group on lignin, utilizes reagents dissolved in organic solvents. Removal of these solvents after the grafting is complete creates fire hazards and is expensive.
Lignin can be treated with formaldehyde and/or added to phenol-formaldehyde resins to form a polymeric material (US 4,769,434; 4,221,708). In both cases formaldehyde should be utilized for the synthesis of polymeric material.
Formaldehyde is known carcinogen and its usage is supposed to be avoided as much as possible, especially in consumer product.
Lignin was converted into a polymeric material by heating with sulfur (US 4, 107, 1 1 1). The material has unpleasant odor.
Each of the sited above methods of producing polymeric material from lignin has its own disadvantages preventing noticeable production of lignin-based polymers and composites.
]
The present invention have endeavored to solve the problem of converting lignin into a structural material by reaction with polyanhydrides of carboxylic acids. In some cases, like maleinized vegetable oils, essentially natural binders can be applied. Taking into consideration that lignin itself is naturally occurring material, a composites with more than 90% natural components can be obtained.
STATEMENT OF THE INVENTION
In accordance with the present invention, lignin forms a composite material with polymers containing carboxylic anhydride groups and a cross-linking agent (hardener).
Lignin is not very reactive polymer so that chemical bonding with other polymers is problematic. We found that polymers with carboxylic anhydride groups form with lignin a composite with sound mechanical properties. Most likely, anhydrides react with hydroxyl groups of lignin.
Polymers with anhydride groups are known. Mostly, these polymers are solid materials due to high polarity of anhydrides. Lignin is, laso, a solid material. Making composite material using two solid polymers requires good mixing of these two polymers. Such mixing can be made only with special blenders that have relatively low productivity and high energy consumption. The other approach, usage of polymer solutions, as it was mentioned above, requires removal of solvents that creates additional technological problems. Most likely, these problems of compatabilization of lignin with polymeric anhydride prevented discovery of corresponding composites earlier.
The solution was found in the present invention. First method utilizes concept of synthesis of a polymeric anhydride in lignin by methods or radical
polymerization of monomeric anhydride with vinylic monomers. This method is considered impossible due to presence of phenolic group in lignin. Phenols are considered inhibitors of radical polymerization (Dyumaev K. M. et al. Izv. Akad. Nauk SSSR (1961) 167). Leading experts in lignin believe that no polymers can be formed by radical polymerization of vinylic monomers in the presence of lignin ( Gandini A. Polymers from renewable resources in: Comprehensive Polymer Science, edited by Aggrawal S. L. and Russo S. Pergamon Press; Oxford 1992. Supplement V. l, pp. 527-573). This is why chemical blocking of phenolic hydroxyl is considered essential for making copolymers of lignin by free radical polymerization (i.g. grafting a vinylic monomer onto them as described on the first page).
However, we found that this is not true. In our experiments, polyanhydrides were obtained when various anhydrides, i.g. ithaconic, maleic, methacrylate, with different ethylenically unsaturated compounds were radically
copolymerized in lignin matrix (Examples 3-5). Solvent are capable to extract a polymer with broad range of molecular weights, from few hundred to several thousand Daltons from lignin matrix after this free radical polymerization.
Second method of making mixtures of lignin with polyanhydrides is to use liquid, low molecular weight polyanhydrides. Maleinized vegetable oils are the example of such low molecular weight polyanhydrides, with average number of maleic anhydride moieties in the 2-4 range per molecule (Chakrabarty, M. M. Chemistry And Technology Of Oils And Fats. Allied Publishers. 2003).
Oligomeric anhydrides, also, can be synthesized by catalytic chain transfer polymerization (Sanders G.C. et al.. Macromolecules, 2012, 45 (15), pp 5923- 5933).
We found, also, that polyanhydrides, especially low molecular weight one, do not form composites with lignin with acceptable mechanical properties when heated and pressed together at high level of lignin in such composites. A cross- linking agent (hardeher) is required. Such hardeners can be reagents that react with anhydrides. For example, polyols (examples 4-6), polyepoxides (examples 1 and 2) or imines (Examples 8 and 9) react with polyanhydrides to form a cross- linked composite materials with polymeric anhydride/lignin mixture with sound mechanical properties. In some cases (example 3) hydroxyl group can be introduced into a polyanhydride polymer during copolymerization.
Polyols are chemical compounds bearing hydroxyl (OH) groups. Imines are chemical compouds bearing RtR2C=NR3 group, wherein R,, R2, and R3 are independently H or hydrocarbon substituents.
Cured lignin compositions were tested and reasonable shear strength, from 3 to 12 MPa was determined. These values of tensile strength are comparable with shear strength of standard MDF (http://www.spanogroup.be/upload/docs/MDF- manual%20ENG%20LOW%20RES.pdf).
Shear strength of invented lignin composite materials can be increases even further by mixing with fillers (Example 10 and 1 1). There is no doubt that fillers other than glass fiber or wood particles, described in the example 10 and 1 1 , can be applied the invented lignin composite due to high adhering properties of polyanhydrides to various surfaces.
In the provided examples content of lignin in the invented lignin composites was used above 30 wt. % of the final material to keep composite cost low.
Apparently, content of lignin in the composite can be reduced to less than 30% if
technological, esthetical or other reasons require less amount of lignin in the invented composite.
The lignin composites of the present invention have relatively low swelling in water (Example 7), less then 20% after 24 h immersion in water. Most important, after drying the composite restored its dimensions and shear strength. The higher is the content of binder, the less is swelling of the lignin composite in water.
Curing rate of the present lignin composites depends on chemical origin of lignin, type of carboxylic anhydride, the hardener, temperature and catalyst. Reaction of hydroxy groups of polyols with anhydrides, acids and other reactive groups is known to be catalyzed by different catalyst including but not limited to acids, amines, phosphines and metallochelates. Examples 3-6 utilized only few of such catalysts. Examples 1-2 and 8-9 employed no catalysts.
Preferred curing catalysts in this invention are tertiary amines due to good solubility of such amines in the invented composition, low cost and no leaching of the amine catalyst from the cured material. Apparently, acidic groups that are formed during reaction of polyanhydrides with the hardeners hold the amine catalyst by forming a salt.
EXAMPLES
Maleic anhydride, methacrylic anhydride, ithaconic anhydride, DABCO, tetraethyleneglycol, hexanal, 2-(aminomethyl)-2-methyl-l,3-propanediamine (Aldrich, USA) were used as received. All oils were purchased in local grocery stores. Maleinization of oils was performed according to Tran P., Seybold ., Grayver D., Narayan R. J. Amer, Oil. Chem. Soc. 82(2005)169.
Epoxide resins ED20 (Karbokhim, Russian Federation) were used as received. ED20 resin consists of diglycidyl ether of bisphenol A by 90 wt % with the rest 10% of a corresponding dimer bearing hydroxyl groups. Sulfolignin (lignin sulfate) was received from Segezh and kraft-lignin from Svetogorsk (Russian Federation) paper mills.
(2,4,6-tris(dimethylaminomethyl)phenol), toluenesulfonic acid, diethylene glycol, hexamethylenediamine, azo-bis(isobutironiril), benzoyl peroxide ( Reakhim, Russian Federation) were used as received. Glycidyl methacrylate (Reakhim) was vacuum distilled prior the use.
Example 1. Maleinized oil.
0.8 g of maleinized sunflower oil (20% content of maleic anhydride) and 0.15 g of ED20 bisphenol A diglycidyl ether were mixed with 9 g of sulfolignin.
Obtained brown powder was pressed at 10 kg/cm2 and heated at 210°C for 10 min. Shear strength of the cured composite - 3.2 MPa.
Example 2. Different maleinized oil, different epoxide.
Glycidyl methacrylate was oligomerized to low oligomers (Mn=540) according to Polymer Journal, 24 ( 1992) 613. 0.3 g of this oligo glycidylmethacryiate and 1.7 g of maleinized soybean oil (17% content of maleic anhydride) were mixed with 8 g of sulfolignin. Obtained brown powder was pressed at 10 kg/cm2 and heated at 170°C for 20 min. Shear strength of the cured composite - 5.3 MPa.
Example 3. Anhydride and hardener are in the same polymer.
1.2 g of methacrylic anhydride, 2.2 g of butyl aery late, 0.2 g of benzoyl peroxide and 0.6 g of hydroxy ethylmethacrylate were mixed with 6 g of sulfolignin and heated under nitrogen lh at 70 C, then 30 min at 80 °C and, finally 20 min at
100°C. Obtained brown powder was mixed with 0.03 g of 2,4,6-2,4,6- tris(dimethylaminomethyl)phenol, pressed at 10 kg/cm2 and heated at 130°C for 1 h. Shear strength of the cured composite - 12.0 MPa.
Example 4. Different hardener are in the same polymer.
0.8 g of maleic anhydride, 2.5 g of butyl acrylate, 0.2 g of benzoyl peroxide and 1.1 g of tetraethylene glycol were mixed together and 3.5 g of obtained solution were with 6. 5 g of sulfolignin and heated under nitrogen lh at 70 C, then 30 min at 80 °C and, finally 20 min at 100°C. Obtained brown powder was mixed with 0.03 g of 2,4,6-tris(dimethylaminomethyl)phenol, pressed at 10 kg/cm and heated at 170°C for 1 min. Shear strength of the cured composite - 1 1.6 MPa.
Example 5. Different anhydride, different hardener
0.8 g of ithaconic anhydride, 2 g of styrene, 0.12 g of azo-bis(isobutironiril) , 0.02 g of DABCO and 0.25 g of 1,4-hexanediol, were mixed with 7 g of hydro lytic (kraft) lignin and heated under nitrogen 1 h at 70 C, then 30 min at 80 °C and, finally 10 min at 100°C. Obtained brown powder was pressed at 10 kg/cm2 and heated at 1 10° C for 50 min. Shear strength of the cured composite - 8.6 MPa.
Example 6. Different catalyst.
A composite material was made similar to the Example 4 but toluenesulfonic acid was taken instead of 2,4,6-tris(dimethylaminomethyl)phenol. Shear strength of the cured composite - 8.9 MPa.
Example 7. Water swelling.
3 g sample of cured lignin composite from example 2 was immersed in water for 24 h. Weight of the sample increased by 38% while volume of it increased by
19%. After drying in air both the weight and the volume of the sample returned to the initial numbers. Shear strength of dry sample was found to be 4.7 MPa. Swelling ration for sample from example 4 was found 10% and 3% for sample from example 3.
Example 8. Imine hardener.
100 g of toluene, 50 g of cyclohexanone and 30 g of hexamethylenediamine were refluxed under nitrogen with Dean-Stark trap. When all water was collected in the Dean-Stark trap, all volatiles were distilled off to yield diimine as colorless liquid.
2 g of maleic anhydride, 2.1 g of styrene and 0.1 g of benzoyl peroxide were mixed together and 3 g of obtained solution was mixed with 7 g of
SLilfolignin and heated under nitrogen lh at 80 C, then 30 min at 90 °C and, finally 20 min at 100°C. Then 2 g of diimine hardener were added and after mixing the mixture was kept at 170°C for 40 min under 10 kg/cm2 pressure. Shear strength of the cured composite - 7.0 MPa.
Example 9. Different imine hardener.
10 g of toluene, 3 g of hexanal and 3 g of 2-(aminomethyl)-2-methy 1- 1 ,3- propanediamine were refluxed under nitrogen with Dean-Stark trap. When all water was collected in the Dean-Stark trap, all volatiles were distilled off to yield triimine as colorless liquid.
2 g of maleic anhydride, 1.9 g of vinylacetate and 0.05 g of azo- bis(isobutironiril) were mixed together and 2 g of obtained sojution was mixed with 8 g of sulfolignin and heated under nitrogen 2 h at 70°C, then 30 min at 75 °C and, finally 10 min at 100°C. Then 1.2 g of triimine hardener were added and after mixing the mixture was kept at 170°C for 30 min under 10 kg/cm2 pressure. Shear strength of the cured composite - 5.2 MPa.
Example 10. Fiber reinforced lignin composite.
7 g lignin composite according example 1 was mixed with 3 g of chopped glass fibers and cured similar to the example 2. Shear strength of this 3-component cured composite - 12.3 MPa.
Example 11. Wood reinforced lignin composite.
7 g lignin composite according example 2 was mixed with 2 g of wood chips (<5 mm length) fibers and cured similar to the example 2. Shear strength of this 3- component cured composite - 7. 1 MPa.
Example 12. Low content of lignin.
Glycidyl methacrylate was oligomerized to low oligomers (Mn=540) according to Polymer Journal, 24 ( 1992) 613. 0.9 g of this oligo glycidylmethacrylate and 5.1 g of maleinized soybean oil ( 17% content of maleic anhydride) were mixed with 4 g of sulfolignin. Obtained brown powder was compacted and heated at 170°C for 20 min. Shear strength of the cured composite - 9.3 MPa.
Claims
1. A composite material comprising lignin, carboxylic anhydride binder and cross-linking agent (hardener).
2. Composite material of claim 1, wherein carboxylic anhydride binder comprises 2 or more than 2 carboxylic anhydride fragments.
3. Carboxylic anhydride binder of claim 2, wherein fragments of carboxylic anhydride binder are of the following structure
and/or
and/or wherein Ri, R2, R3, R4 , R5 , Re and R7 are independently H, alkyl, alkenyl, ethylenically polyunsaturated alkenyl, OOC-Alk, OOC-Alkenyl, OAlk, CI, CN, phehyl, substituted phenyl, aryl, substituted aryl, COOZ, wherein Z is indepedently H, alkyl, substituted alkyl, hydroxy alkyl, dihydroxyalkyl, glycidyl, ethylenically unsaturated alkyl, CO(NR8R9) wherein R8 and R9 are independently H, alkyl, substituted alkyl, hydroxyl
4. Composite material of claim 1, wherein carboxylic anhydride binder
obtained by copolymerization of maleic anhydride with ethylenically unsaturated compounds.
5. Composite material of claim 1, wherein carboxylic anhydride binder obtained by copolymerization of ithaconic anhydride with ethylenically unsaturated compounds.
6. Composite material of claim 1 , wherein carboxylic anhydride binder
obtained by copolymerization of methacrylic anhydride with ethylenically unsaturated compounds.
7. Composite material of claim 1 , wherein cross-linking agent comprises a polyol with number of hydroxy 1 groups is 2 or more than 2 per molecule of cross-linking agent.
1. Composite material of claim 1, wherein cross-linking agent comprises a polyepoxide with number of epoxy groups per molecule in the range of 1 to 8, preferably, 2 or 3.
8. Composite material of claim 1, wherein cross-linking agent comprises a polyimine compound with number of imine groups is 2 or more than 2 per molecule of cross-linking agent.
9. Composite material of claim 1, wherein cross-linking agent comprises a compound bearing both hydroxyl and epoxy groups with number of hydroxyl groups and epoxide groups combined is 2 or more than 2 per molecule of cross-linking agent.
10. Composite material of claim 1 , wherein cross-linking agent and
carboxylic anhydride binder are chemically bound together.
1 1. A process of making lignin composite material of claim 1, where lignin, the binder and the hardener are heated together at temperatures from 30 to 2500 C, preferably, 60-2000 C with or without a catalyst.
12. A process of making lignin composite material of claim 12, wherein the catalyst is a tertiary amine.
13. A process of making lignin composite material of claim 12, wherein the catalyst is a mineral acid.
14. A composite formed from the adhesive composition of claim 1 and one or more filler, wherein the weight ratio of the filler and the adhesive ranges from 250: 1 to 1 :250.
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WO2002068507A1 (en) * | 2001-02-27 | 2002-09-06 | Schneider Marc H | Furfuryl alcohol and lignin adhesive composition |
EP1359197A1 (en) * | 2002-05-03 | 2003-11-05 | SigmaKalon Group B.V. | Epoxy-polysiloxane resin based compositions useful for coatings |
US20040034154A1 (en) * | 2002-06-06 | 2004-02-19 | Georgia-Pacific Resins Corporation | Epoxide-type formaldehyde free insulation binder |
WO2011099544A1 (en) * | 2010-02-10 | 2011-08-18 | 日立化成工業株式会社 | Resin composition, molded body and composite molded body |
RU2448126C2 (en) * | 2006-08-24 | 2012-04-20 | Геркулес Инкорпорейтед | Adhesive composition of low-molecular weight polyamidoamine-epihalohydrin (pae) resin and protein |
US20120148740A1 (en) * | 2010-12-14 | 2012-06-14 | Yang Chia-Wei | Raw materials and methods of manufacturing bio-based epoxy resins |
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WO2002068507A1 (en) * | 2001-02-27 | 2002-09-06 | Schneider Marc H | Furfuryl alcohol and lignin adhesive composition |
EP1359197A1 (en) * | 2002-05-03 | 2003-11-05 | SigmaKalon Group B.V. | Epoxy-polysiloxane resin based compositions useful for coatings |
US20040034154A1 (en) * | 2002-06-06 | 2004-02-19 | Georgia-Pacific Resins Corporation | Epoxide-type formaldehyde free insulation binder |
RU2448126C2 (en) * | 2006-08-24 | 2012-04-20 | Геркулес Инкорпорейтед | Adhesive composition of low-molecular weight polyamidoamine-epihalohydrin (pae) resin and protein |
WO2011099544A1 (en) * | 2010-02-10 | 2011-08-18 | 日立化成工業株式会社 | Resin composition, molded body and composite molded body |
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