EP2817348A2 - Biosourced epoxide resins having improved reactivity - Google Patents
Biosourced epoxide resins having improved reactivityInfo
- Publication number
- EP2817348A2 EP2817348A2 EP13710476.6A EP13710476A EP2817348A2 EP 2817348 A2 EP2817348 A2 EP 2817348A2 EP 13710476 A EP13710476 A EP 13710476A EP 2817348 A2 EP2817348 A2 EP 2817348A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- biosourced
- epoxy resins
- epoxidized
- groups
- crosslinking agent
- 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.)
- Withdrawn
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 37
- 230000009257 reactivity Effects 0.000 title description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 35
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- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- -1 epoxide lipid Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 73
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 50
- 239000003822 epoxy resin Substances 0.000 claims description 34
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- 125000003700 epoxy group Chemical group 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 150000002632 lipids Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 23
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- TVQGDYNRXLTQAP-UHFFFAOYSA-N ethyl heptanoate Chemical compound CCCCCCC(=O)OCC TVQGDYNRXLTQAP-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000008169 grapeseed oil Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010460 hemp oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- CJYCVQJRVSAFKB-UHFFFAOYSA-N octadecane-1,18-diamine Chemical compound NCCCCCCCCCCCCCCCCCCN CJYCVQJRVSAFKB-UHFFFAOYSA-N 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C08G2150/00—Compositions for coatings
-
- 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
- C08G2170/00—Compositions for adhesives
Definitions
- the present invention relates to new biosourced epoxy resins with improved reactivity, their manufacturing process and their uses.
- epoxy resins are a class of thermosetting polymers widely used in the fields of electronics, building, paints or transport.
- the vast majority of those currently marketed are of petrochemical origin and are sometimes considered toxic when they are based on the use of bisphenol A, such as DGEBA type resins (bisphenol A di-glycidyl ether). ).
- a first commercial solution consisted in proposing mixed formulations based on the mixture of petrochemical epoxy resins with biosourced epoxies. But these mixtures, if they lead to reactive formulations capable of meeting the requirements of an industrial production rate (Miyagawa H. et al., Macromol, Mater Eng (2004), 289, 629-635 and 636-641 ), can not claim the benefits of biosourced resins, whether in terms of renewable carbon content, toxicity or dependence on oil.
- the most commonly used petroleum-based matrices are DGEBA and DGEBF (di-glycidyl ether of biphenol F).
- ESO epoxidized soybean oil
- TETA triethylenetetramine
- Ratna D. et al. Polymer Int (2001), 50, 179-184.
- the same petrochemical resin has It has also been declined by adding epoxidized crambe oil, epoxidized grape oil (ERO), or epoxidized linseed oil (ELO).
- a vegetable oil is, as its name suggests, derived from biomass. It can be defined as a statistical product consisting mainly of triglycerides but also to a lesser extent, diglycerides and monoglycerides.
- the associated fatty acids are naturally present in the vegetable oils of flax, sunflower, rapeseed, soya, olive, grape seeds, Tung wood, cotton, corn, hazelnut, walnuts, coconut, palm, castor, cashew nut and peanut. Unsaturated fatty acids are also found in animal oils, such as lard, beef tallow and fish oils (salmon, sardines, anchovies, mackerel, tuna, herring, etc.).
- the presence of unsaturations in the fatty chains is particularly interesting because they can be converted into oxirane groups by use of peracids or peroxide hydrogen. This step is also referred to as epoxidation.
- Tan S. G. et al. discloses a thermosetting resin formulated by reacting soybean oil epoxidized with methylhexahydronaphthalic anhydride (MHHPA) as a hardener and in the presence of tetraethylammonium bromide as a catalyst. The mixture is placed in a mold and then crosslinked at 140 ° C. The polymerization is complete only after 3 hours.
- MHHPA methylhexahydronaphthalic anhydride
- Gerbase A. E. et al. report the mechanical properties of soy oil-based epoxy resins obtained by reaction of said soybean oil with different cyclic acid anhydrides in presence of tertiary amines. The mixtures are heated in general for 14 hours at 150 ° C.
- Boquillon N. et al. Polymer (2000) 41, 8603-8613 describe the properties of epoxy resins obtained by reaction of epoxidized linseed oil with different anhydride hardeners in the presence of different catalysts. The treatment cycle is 15 hours at 150 ° C. then 1 hour at 170 ° C.
- the formulation of the mixture linseed oil / tetrahydrophthalic anhydride (THPA) / 2-methylimidazole leads to resins having after crosslinking the best mechanical properties.
- Chrysanthos M. et al. (Polymer (2011) 52, 8603-8613, describe biosourced resins derived from diglycidyl ether of epoxidized isosorbide of plant origin to replace DGEBA
- the hardener used is isophorone diamine and the treatment cycle is 1 hour at 80 ° C followed by 2 hours at 180 ° C.
- the international application WO 2008/147473 relates to biobased polymers obtained by the reaction of a resin based on glycidyl ethers of anhydrosugars of vegetable origin, for example isosorbide, isomannide or isoiodide with a hardener of biosourced origin or not.
- a resin based on glycidyl ethers of anhydrosugars of vegetable origin for example isosorbide, isomannide or isoiodide
- a hardener of biosourced origin or not for example isosorbide, isomannide or isoiodide
- the object of the present invention is to provide a wide range of resins based on natural oils and having a very high reactivity so able to crosslink at room temperature and short polymerization times while providing additional mechanical properties.
- Another objective of the present invention is to be able to control the crosslinking of these resins in terms of time and temperature.
- An additional goal is to be able to adjust the final properties of these resins against a targeted application.
- the inventors have used biosourced structures with epoxy terminations which are more easily accessible than those carried by the triglyceride units and yet capable of participating directly in the formation of the polymer network or even of forming a polymer network, even in the absence of epoxidized natural oils.
- the mixtures thus formulated have much lower freezing times than the formulation free of co-reagent, even in the absence of catalyst. They are also able to cross-link at room temperature.
- Formulations prepared from co-reactant alone are also capable of displaying low gel times, even when working at room temperature or in the absence of catalyst.
- the subject of the invention is biosourced epoxy resins comprising the reaction product:
- the ratio of the number of reactive chemical groups of the crosslinking agent to the total number of epoxy groups present in the epoxidized / co-reactive oil mixture is equal to the ratio of the number of chemical groups.
- the co-reagent may be used in addition or substitution of the epoxy groups of the epoxidized lipid derivative.
- Q the ratio
- Epoxy resins or “epoxy resins” means the product of the reaction of an epoxidized compound with a crosslinking agent. Epoxy resins are examples of resins thermosets. "Epoxidized compound” is understood to mean a compound in which one or more epoxide groups has been introduced. An epoxidized compound may also be called an epoxide or "oxirane” or “epoxy”.
- Oxirane function or "oxirane group” means a three-membered cyclic function having two carbons and one oxygen atom.
- reactive chemical groups of the crosslinking agent any group or chemical function capable of reacting by establishing covalent bonds with the epoxy groups of lipid derivatives or co-reactive.
- biomass refers to a product derived from biomass.
- Biomass describes the total mass of living organisms of plant or animal origin in a defined environment, called a biotope, and the resources derived from it through direct, indirect or potential use for civilization.
- the number of reactive groups and epoxy groups can be measured by any method known to those skilled in the art, in particular by chemical methods (chemical determination in the presence of acid halide) or by NMR spectroscopy or FTIR (Lee, H., Neville, K., Handbook of Epoxy Resins, McGraw-Hill: New York, (1967)).
- crosslinking agent or "hardener” means a compound that reacts with epoxides to allow the creation of a three-dimensional polymer network. This is called crosslinking.
- the hardeners are either of biosourced origin, or those usually used for the preparation of petrocoured resins and are selected from the group comprising compounds bearing acidic functions such as acid anhydrides, carrier compounds and primary or secondary amines such as diamines, polyamines and mixtures thereof, diacids and polyacids, alcohols including phenols and polymercaptans and mixtures of two or more of these agents.
- acid anhydrides are succinic anhydride, maleic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl tetrahydrophthalic acid and methyl-en-o-methylenetetrahydrophthalic anhydride.
- amines examples include:
- Ra is an aliphatic chain, especially ethylenediamine, hexamethylenediamine, bis (3-aminopropyl) amine, 1,10-decanediamine.
- cycloaliphatic diamines of generic form H 2 N-Rb-NH 2 where Rb is an aliphatic cyclic unit, in particular isophorone diamine also designated by the abbreviation IPDA the aromatic diamines of generic form H 2 N-Rc-NH 2 wherein Rc is an aromatic ring, especially phenylenediamine in its ortho, meta, para forms, xylylenediamine in its ortho, meta, para forms, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 4,4 ' diaminodiphenylmethane.
- polyamines carrying at least 5 N-H groups especially diethylenetriamine, triethylenetetramine, tetraethylenepentamine, poly (oxypropylene) triamine and polyetheramines or polyoxyalkyleneamines.
- Some biobased examples natural polypeptides.
- diacids examples include the following molecules: heptanedioic acid HOOC- (CH 2 ) 5 -COOH; phthalic acid; isophthalic acid; fumaric acid, maleic acid, terephthalic acid, succinic acid, itaconic acid, hexahydrophthalic acid, methyl hexahydrophthalic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, and pyromellitic acid.
- polymercaptans or polythiols the following molecules may be mentioned: 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethyl - 1,5-Dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto
- biosourced epoxidized lipid derivatives means unsaturated fatty acids naturally present in epoxidized form in natural vegetable or animal oils, or compounds obtained by epoxidation of unsaturated fatty acids, unsaturated fatty acid esters, said unsaturated fatty acids comprising one or more carbon-carbon double bonds and being derived from natural, vegetable or animal oils.
- unsaturated fatty acids comprise at least 12 carbon atoms, more advantageously between 12 and 20 carbon atoms, especially 12, 14, 16, 18 or 20 carbon atoms.
- the natural vegetable oil in which the epoxidized lipid derivatives are naturally present is vernonia oil.
- the epoxidized lipid derivative (s) are obtained by epoxidation of lipids extracted from natural vegetable or animal oils.
- vegetable oil mention may be made of linseed oil, hemp seed, sunflower oil, rapeseed oil, soya oil, olive oil, grape seed oil, Tung wood, cotton oil, corn oil , hazelnut, walnut, coconut, palm, castor, cashew, peanut, calabash, margarine and pipangaille and the mixture thereof.
- animal oils include lard, beef tallow and fish oils such as salmon, sardine, anchovy, mackerel, tuna or herring oil.
- the linseed or hemp oil will be chosen. Indeed, the oil extracted from the seeds of these plants is very rich in unsaturated fatty acids (> 90%) with in particular a high proportion of linoleic and linolenic fatty acids (see table 2 for linseed oil).
- Table 2 Typical composition of a linseed oil
- flaxseed oil does not come into conflict with any food-oriented production that favors sunflower, soybean, rapeseed, peanut or olive oils.
- Linseed oil is already commercially available in epoxidized form. Its epoxidation thus makes it possible to form a model molecule carrying 1 to 6 epoxide groups which will be as many functions that can react with reactive groups of the crosslinking agent to form macromolecular networks.
- epoxidized lipid derivatives are commercially available or are prepared by epoxidation according to any method known to those skilled in the art, for example by reaction with hydrogen peroxide.
- the oxirane groups present on the fatty acid ester chains are arranged along the main skeleton and therefore have limited accessibility with respect to the reactive groups of the agent. crosslinking (see Figure 1).
- the glycidyl ether derivatives of biosourced polyols used in accordance with the invention either as co-reagents or as sole epoxy group carriers, comprise oxirane groups that are very accessible because they are located at the end of linear aliphatic molecular segments. and whose size is smaller than that of fatty acids present in vegetable oils as defined above. In other words, these molecular segments have less than 12 atoms.
- the preferred arrangement of the oxirane groups in the co-reagent gives the latter an increased reactivity with respect to the reactive groups of the crosslinking agent in comparison with the vegetable oil. This feature then induces a step of crosslinking easier and faster.
- These co-reactants thus participate directly in the polymer network and even if their increased reactivity makes it possible to shorten the gel times, they must not be confused with "simple" catalysts which do not intervene as structural elements of the polymer network. When these molecules of low molecular weight are used alone, they allow, by their increased reactivity, an easy and rapid crosslinking step, even in the absence of oil.
- the amount of crosslinking agent is advantageously chosen so as to consume all the epoxy functions of the oil and the co-reactant, which makes it possible to have a continuous macromolecular network whose mesh has a lower average size. than that characteristic of the network obtained by the only reaction of the epoxidized vegetable oil with the crosslinking agent.
- the thermomechanical properties of the resins according to the invention are then better than those obtained by crosslinking the epoxidized lipid derivative alone.
- the person skilled in the art is able, in the light of his knowledge, to determine the necessary quantities of each compound with respect to the final mechanical rigidity of the material.
- the amount of crosslinking agent is advantageously chosen so as to consume all of said epoxy functions.
- polyols means aliphatic compounds comprising at least two hydroxyl groups. They are biobased and are chosen either from glycerols and polyglycerols derived from natural oils, in particular plant oils, or from sugar derivatives which are sufficiently hydrophobic for them to be soluble in lipids. By way of example, mention may be made of sorbitol, xylitol and mannitol.
- the polyol glycidyl ether derivative used as a co-reagent or alone, is obtained by epoxidation of glycerol or a polyglycerol derived from vegetable oils and corresponds to formula (I)
- n is an integer between 1 and 20, in particular the glycidyl ether derivative of glycerol of formula (Ia)
- polyol glycidyl ether derivative used as co-reactant or alone is obtained by epoxidation of a sugar, and is in particular the glycidyl ether derivative of sorbitol of formula (II)
- each molecular segment bearing an oxirane function comprises, in addition to the said function, 2 or 3 atoms, namely respectively an oxygen atom and a carbon atom or an oxygen atom and two carbon atoms.
- the at least one crosslinking agent is chosen
- the at least one crosslinking agent is a compound bearing NH groups, belonging to primary or secondary amine functions
- the lipid derivatives + the at least one co-reagent) or by the glycidyl ether derivatives of polyols when they are used alone is advantageously such that each epoxy group corresponds to 1 group N-H. This is equivalent to saying that the ratio of the number of N-H groups to the number of epoxy groups is equal to unity.
- the Qanhydnde ratio when the at least one crosslinking agent is a compound carrying acid anhydride groups, the Qanhydnde ratio
- lipid derivatives + the at least one co-reagent) or by the glycidyl ether derivatives of polyols when they are used alone is advantageously such that each epoxy group corresponds to 1 anhydride group of acid. That is tantamount to saying that the report of the number of acid anhydride groups on the number of epoxy groups is equal to unity.
- the resins according to the invention may also contain additives that are customary in the field, such as, for example, diluents, solvents, pigments, fillers, plasticizers, antioxidants, stabilizers. These additives may or may not be biobased.
- the subject of the invention is also a process for the formulation of biosourced epoxy resins comprising a step of mixing one or more epoxidized biosourced lipid derivatives with at least one crosslinking agent, in the presence of at least one selected co-reactant. among the glycidyl ether derivatives of biosourced polyols.
- the process for preparing biosourced epoxy resins comprises the following steps:
- the stirring in steps b) and c) can be performed by any technique known to those skilled in the art, especially by mechanical stirring.
- the duration of the stirring in step b) is of the order of 1 to 5 minutes and is easily determined by those skilled in the art.
- the duration of the stirring in step c) is of the order of one minute.
- Step d) is carried out under the conditions of time and temperature determined by the prior conduct of experiments conventionally assigned to the optimization of the crosslinking of a thermosetting polymer (measurements differential calorimetric or DSC, steady state or oscillatory rheometry, dielectric techniques ).
- the crosslinking agent and the co-reactant may be in solid or liquid form.
- the crosslinking agent and / or the co-reactant used are in solid form, it is preferable to preheat each component of the formulation separately at a temperature permitting the melting of all the compounds. This precaution guarantees the homogeneity of the future mixture. Once this temperature is reached, the co-reagent can be added to the oil, followed by the crosslinking agent by following the steps b) to d) described above.
- the gains in terms of temperature and / or time required for the crosslinking operation are very important compared to commonly used methods.
- the resin can be cured in less than 10 minutes at 80 ° C, preferably in less than 5 minutes.
- the process can also be carried out in the presence of a catalyst if this proves necessary.
- the catalysts are those usually used with epoxy formulations such as tertiary amines, imidazoles.
- the epoxy resins according to the invention are derived from biobased materials and meet the expectations of the new environmental rules in particular enacted by the Reach constraints.
- the resins according to the invention have a renewable carbon content of at least 50%, advantageously at least 85%, even more advantageously at least 95%; they can therefore be used as a substitute for petrochemical resins as products derived from Green Chemistry.
- the resins according to the invention do not exhibit the toxicity of certain petrochemical derivatives, in particular those derived from bisphenol A, which is the subject of much criticism.
- the resins according to the invention are provided with a very fast crosslinking kinetics (which can be less than 5 minutes at a temperature of 80 ° C.) compared to conventional biobased productions. Even in the presence of initiator and / or catalyst, they therefore meet the requirements of industrial productivity, particularly in the composites sector. In the latter field, their reactivity is comparable to that of unsaturated polyesters.
- the biosourced epoxy resins according to the invention can be used as a substitute for resins derived from petrochemicals, in particular for the manufacture of composite materials for mechanical engineering or for construction and in structural parts.
- examples include: construction (sections, beams, tools), transportation (molded parts, body panels), aerospace (internal or structural elements of aircraft), boating (parts resistant to corrosion: hulls, appendages such as drifts, rudders ...), recreation and sports (skis, skates, canoes, racket frames, snowboards ..). They can also be used for applications involving structural parts exposed to fatigue or parts subjected to thermal variations or as adhesives, preferably as structural adhesives or as surface coatings.
- FIG. 1 illustrates the crosslinking reaction of an epoxidized oil with a diamine as known from the state of the prior art.
- FIG. 2 illustrates the viscosimetric monitoring of formulations based on epoxidized linseed oil and hexamethylene diamine and formulations based on epoxidized glycerol and hexamethylenediamine in accordance with FIG. Example 1.
- ELO-C6 mixture of epoxidized linseed oil and hexamethylenediamine
- GE-C6 epoxidized glycerol mixture and hexamethylenediamine.
- the ratio of the number of NH groups to the number of epoxy groups is constant and equal to 1.
- FIG. 3 illustrates the comparison of reactivities of epoxy glycerol co-reactant (CR) and epoxidized linseed oil (ELO) with respect to hexamethylenediamine (C6) measured by the effect of temperature on the frost time.
- FIG. 4 illustrates the gel times measured at various temperatures of a mixture comprising 1 mole of epoxidized linseed oil per 1.5 moles of isophorone diamine (ELO-IPDA) compared with those of a mixture in accordance with invention comprising a mixture of epoxidized linseed oil and co-reactant in an 80/20 proportion (80% of the number of epoxy groups are provided by the ELO oil and 20% by the co-reactant) with isophorone diamine (IPDA), keeping equal to the previous case the ratio of the number of NH group on the number of epoxy function (ie equal to 1).
- ELO-IPDA isophorone diamine
- FIG. 5 illustrates the effect of the addition of epoxidized glycerol co-reactant on the thermomechanical performances of mixtures based on epoxidized linseed oil (ELO) and isophorone diamine (IPDA).
- ELO epoxidized linseed oil
- IPDA isophorone diamine
- the component G denotes the” loss modulus "characteristic of the mechanical energy dissipated because of the molecular movements occurring within the material.
- the mixture does not contain a co-reactant; (80:20) represents a mixture in which the epoxy groups are provided at 80% of the total number by the ELO, the remaining 20% being provided by the co-reactant; (50:50) represents a mixture in which the epoxy groups are provided in equal proportion by the ELO and the co-reactant; (20:80) represents a mixture in which the epoxy groups are provided at 20% of the total number by the ELO, the remaining 80% being provided by the co-reactant.
- Example 1 Properties of the mixture linseed oil and hexamethylenediamine and the mixture of epoxidized glycerol and hexamethylenediamine
- the hexamethylenediamine diamine is solid at room temperature.
- Each component of the formulations namely epoxidized linseed oil (ELO), diamine (C6) or epoxidized glycerol (GE) is heated separately at a temperature of 45 ° C for example in a water bath.
- ELO epoxidized linseed oil
- C6 diamine
- GE epoxidized glycerol
- the molten diamine is then added to the linseed oil to form the mixture ELO-C6 advantageously defined by a molar ratio of 1: 1.5.
- the number of epoxy functions is then equal to the number of N-H functions.
- Example 1 This latter mixture is then stirred at a temperature of 45 ° C. for one minute and is then heated to the desired crosslinking temperature.
- Example 1 two cases are described namely 120 ° C and 140 ° C.
- the GE-C6 mixture is obtained by pouring the molten diamine into the epoxidized glycerol preheated to 45 ° C to prevent any risk of crystallization of the crosslinking agent.
- the polymerization can be carried out as early as 25 ° C. in the image of the case shown in FIG.
- the technique used for the measurement of the gel time is the steady-state viscometry.
- the experiment consists of recording the evolution of the viscosity of the mixture at constant temperature (that chosen for the crosslinking) by means of a rotary rheometer equipped for example with a "parallel trays" geometry.
- the gel point associated with the critical formation of the macromolecular network is then defined by the time at which the viscosity of the mixture diverges. Practically, this time is raised by taking the point of intersection of the asymptote with the curve of the viscosity in the region of divergence with the time axis.
- Figure 2 shows that the direct reaction of epoxidized glycerol (GE or CR) with C6 diamine is possible even at 25 ° C.
- GE or CR epoxidized glycerol
- C6 diamine epoxidized glycerol
- the co-reactant participates directly in the formation of the macromolecular network, by itself reacting directly with the C6 diamine units.
- the CR-C6 mixture displays a 100-minute gel time intermediate to that observed with the ELO-C6 couple at 140 ° C (49 minutes) and 120 ° C (249 minutes) ( Figure 2).
- FIG. 3 illustrates that the evolution of the gel time of the ELO-C6 mixture with the temperature can be described by an Arrhenius law. This same figure specifies that the value of the freezing time of the CR-C6 pair at 25 ° C is equivalent to that of the ELO-C6 mixture at 130 ° C.
- the increased reactivity of the CR compared to the ELO makes it possible to set the mass at low temperature, which allows the declination of the formulations in contact with thermosensitive substrates.
- Example 2 Epoxy resin prepared from epoxidized linseed oil, epoxidized glycerol as a co-reactant and isophorone diamine (IPDA).
- the ELO-IPDA mixture is prepared by pouring the liquid diamine into the oil at ambient temperature.
- the temperature of the ELO-CR mixture is maintained at ambient temperature and the stirring is carried out for 5 minutes before crosslinking.
- the stoichiometry of the ELO-CR-IPDA mixture is calculated so as to give the medium a ratio of the number of epoxy groups by the number of amino groups equal to that chosen for the ELO-IPDA binary mixture. Moreover, in this example, 80% of the number of epoxy groups present in the medium are carried by the ELO oil and 20% by the co-reactant. The ratio (N-H / epoxy) is still equal to 1.
- the mass composition of the formulation is 68.1% ELO, 9.6% CR, 22.3% IPDA. In terms of molar composition, the ELO-CR-IPDA stoichiometry is 1: 0.5: 1.9.
- the interest of the co-reagent is therefore especially marked in the field of low temperatures because it makes it possible to overcome the low reactivity of the epoxidized oils.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1251539A FR2987049B1 (en) | 2012-02-20 | 2012-02-20 | BIOSOURCE EPOXY RESINS WITH IMPROVED REACTIVITY. |
PCT/FR2013/050331 WO2013124574A2 (en) | 2012-02-20 | 2013-02-18 | Biosourced epoxide resins having improved reactivity |
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EP2817348A2 true EP2817348A2 (en) | 2014-12-31 |
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EP13710476.6A Withdrawn EP2817348A2 (en) | 2012-02-20 | 2013-02-18 | Biosourced epoxide resins having improved reactivity |
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US (1) | US20150011680A1 (en) |
EP (1) | EP2817348A2 (en) |
JP (1) | JP2015508122A (en) |
CN (1) | CN104144963B (en) |
FR (1) | FR2987049B1 (en) |
WO (1) | WO2013124574A2 (en) |
Families Citing this family (12)
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FR2997401B1 (en) * | 2012-10-25 | 2016-01-29 | Univ Montpellier Ii | RETICULABLE EPOXY RESINS AT AMBIENT TEMPERATURE |
FR3024981B1 (en) | 2014-08-22 | 2016-09-09 | Univ Montpellier 2 Sciences Et Techniques | POLYESTER DERIVATIVES OF FATTY ACIDS OF POLYGLYCOSIDES |
FR3025203B1 (en) * | 2014-08-26 | 2016-12-09 | Renfortech | EPOXY FOAMS DERIVED FROM REACTIVE FORMULATIONS BIOSOURCEES |
AU2015334010B2 (en) | 2014-09-12 | 2019-03-28 | Drexel University | Toughening of epoxy thermosets |
US9828508B2 (en) * | 2015-04-21 | 2017-11-28 | The United States Of America, As Represented By The Secretary Of The Navy | Rapid cure polysulfide coatings for cavitation resistance, erosion resistance, and sound damping |
CN104892858B (en) * | 2015-05-13 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of high Bio-based content composition epoxy resin and its curing and application |
AU2017285476A1 (en) * | 2016-06-15 | 2019-01-31 | Steed Mifsud Pty Ltd | Glycerol-based epoxy resins |
CN108715631B (en) * | 2018-07-02 | 2020-05-26 | 扬州市文祺材料有限公司 | Xylitol-based multifunctional epoxy resin and preparation method thereof |
CN109021902B (en) * | 2018-07-02 | 2021-03-19 | 扬州市文祺材料有限公司 | Bio-based degradable epoxy resin adhesive and preparation method thereof |
CN113667434B (en) * | 2021-07-29 | 2023-02-28 | 北京林业大学 | Adhesive based on mercapto-epoxy reaction, and preparation method and application thereof |
JP2023177577A (en) * | 2022-06-02 | 2023-12-14 | 住友化学株式会社 | Agent containing asymmetric diamine, resin and use of the same |
CN115433342B (en) * | 2022-10-08 | 2023-11-14 | 南京先进生物材料与过程装备研究院有限公司 | Bio-based epoxy resin based on sorbitol glycidyl ether and preparation method thereof |
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US3351574A (en) * | 1965-02-24 | 1967-11-07 | Celanese Coatings Co | Castor oil polyglycidyl ether |
US4962179A (en) * | 1989-08-31 | 1990-10-09 | Shell Oil Company | Epoxidized fatty acid ester compositions |
US5728779A (en) * | 1992-12-01 | 1998-03-17 | Dsm N.V. | Powder paint of epoxy-reactive polymer and aliphatic chain-containing polyepoxide |
DE69403959T2 (en) * | 1993-03-30 | 1997-11-20 | Shell Int Research | THE MODIFICATION OF EPOXYESTERS WITH EPOXIZED PLANT OIL |
DE4410785A1 (en) * | 1994-03-28 | 1995-10-05 | Hoechst Ag | Amine modified epoxy resin composition |
US5569733A (en) * | 1994-03-31 | 1996-10-29 | Ppg Industries, Inc. | Tertiary aminourea compositions and their use as catalysts in curable compositions |
US6194490B1 (en) * | 1998-02-27 | 2001-02-27 | Vantico, Inc. | Curable composition comprising epoxidized natural oils |
DE19914183C2 (en) * | 1999-03-29 | 2001-03-15 | Dlw Ag | Materials containing polyreaction products based on renewable raw materials, manufacturing processes and fabrics |
AU2003225176A1 (en) * | 2002-04-25 | 2003-11-10 | Ashland Inc. | Surface improver for reinforced composite compositions |
DE10224275B4 (en) * | 2002-05-31 | 2007-08-02 | Clariant Produkte (Deutschland) Gmbh | demulsifiers |
JP2004059812A (en) * | 2002-07-30 | 2004-02-26 | Dainichiseika Color & Chem Mfg Co Ltd | Coating agent composition |
DE102005046642B4 (en) * | 2005-09-29 | 2019-08-22 | Tib Chemicals Ag | Method for protecting the inner surfaces of metallic components against corrosion |
US7619056B2 (en) * | 2006-06-02 | 2009-11-17 | New Jersey Institute Of Technology | Thermoset epoxy polymers from renewable resources |
WO2008147473A1 (en) * | 2007-05-31 | 2008-12-04 | New Jersey Institute Of Technology | Thermoset epoxy polymers from renewable resources |
JP5532562B2 (en) * | 2008-09-02 | 2014-06-25 | 株式会社明電舎 | Insulating polymer material composition |
FR2946049B1 (en) | 2009-05-27 | 2013-01-18 | Chaire Europ De Chimie Nouvelle Pour Un Dev Durable | NATURAL PHENOLIC COMPOUNDS AND THEIR ACTIVATION MODE FOR THE FORMULATION OF THERMOSETTING RESINS |
JP5437929B2 (en) * | 2010-06-24 | 2014-03-12 | パナソニック株式会社 | Epoxy resin composition and molded article using the same |
-
2012
- 2012-02-20 FR FR1251539A patent/FR2987049B1/en not_active Expired - Fee Related
-
2013
- 2013-02-18 WO PCT/FR2013/050331 patent/WO2013124574A2/en active Application Filing
- 2013-02-18 CN CN201380010198.5A patent/CN104144963B/en not_active Expired - Fee Related
- 2013-02-18 US US14/379,582 patent/US20150011680A1/en not_active Abandoned
- 2013-02-18 EP EP13710476.6A patent/EP2817348A2/en not_active Withdrawn
- 2013-02-18 JP JP2014558180A patent/JP2015508122A/en active Pending
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FR2987049B1 (en) | 2014-03-07 |
FR2987049A1 (en) | 2013-08-23 |
JP2015508122A (en) | 2015-03-16 |
CN104144963A (en) | 2014-11-12 |
WO2013124574A3 (en) | 2014-07-03 |
WO2013124574A2 (en) | 2013-08-29 |
CN104144963B (en) | 2016-10-26 |
US20150011680A1 (en) | 2015-01-08 |
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