• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a method for manufacturing a thermoset solid foam, comprising the following successive steps: (a) providing an expandable and thermosetting composition containing - a first reagent chosen from reducing sugars, - a second selected reagent among primary amines, acid addition salts of primary amines, secondary amines, secondary amine acid addition salts, ammonium salts of formula Rn- (NH4 +) n where n is an integer at least 1 and Rn- is the residue of an organic or inorganic acid, (b) introducing the expandable and thermosetting composition into a mold or applying the expandable composition to a support in a film of a thickness at least equal to 1 mm, (c) heating the expandable and thermosetting composition at a temperature of at least 140 ° C. so as to react the first reagent with the second reagent e to form, by polymerization and chemical foaming, a block of thermoset solid foam. It also relates to thermoset mousses based on melanoidines that can be manufactured by this process.
    公开号:FR3033326A1
    申请号:FR1551723
    申请日:2015-03-02
    公开日:2016-09-09
    发明作者:Marie Savonnet
    申请人:Saint Gobain Isover SA France；
    IPC主号:
    专利说明:

    [0001] The present invention relates to thermoset solid foams obtained by reaction and chemical foaming of an expandable composition containing Maillard reagents, namely reducing sugars and amines and amine salts. BACKGROUND OF THE INVENTION The manufacture of insulating products based on mineral wool generally comprises a step of manufacturing the glass or rock fibers by a centrifugation process. On their path between the centrifuge device and the fiber collection belt, the still hot fibers are sprayed with an aqueous sizing composition, also known as a binder, which is then subjected to thermosetting reaction at temperatures of about 200 ° C. . Phenolic resins used for several decades as binders have been replaced more and more by products from renewable sources and emitting little or no formaldehyde, a compound considered to be harmful to human health . Thus, application WO 2007/014236 discloses sizing compositions, or binders, based on reducing sugars and amines or ammonium salts which, inter alia by Maillard reaction, harden and bind the glass fibers. on which they are applied. Applications WO 2009/019232 and WO 2009/019235 similarly disclose binders for glass fibers containing at least one reducing sugar and phosphate, sulfate, nitrate or ammonium carbonate, these reactants being capable of reacting by reaction. of Maillard after application to the glass fibers directly after formation of these. The present invention is based on the surprising discovery that these sizing compositions, when heated in more concentrated form beyond a certain temperature (about 150 ° C), instead of spraying them on glass fibers hot, are highly foaming. Gaseous evolution occurs at the same time as the complex condensation reaction of the monomers (Maillard reaction). The liquid starting composition, introduced into an open container and exposed to sufficient heat, increases in size, thickens and eventually hardens, giving rise, after a few minutes, to a rigid, dark-colored foam. This foaming occurs in the absence of physical foaming agent other than the water possibly present in the starting composition. The presence of water in the mixture of reagents (reducing sugars and 10 amines / ammonium salt) is however not essential for foaming and does not explain the phenomenon observed. Indeed, as long as the composition contains liquid water its temperature does not exceed about 100 ° C and the Maillard reaction responsible for curing can not occur. In other words, when the Maillard reaction begins, all of the liquid water initially present has evaporated. It was therefore necessary to produce a phenomenon of chemical foaming. One or more of the starting ingredients were to undergo thermal decomposition or react with each other by releasing a gas in an amount sufficient for the production of foams.
    [0002] The present invention therefore relates to the use of a composition containing a first reagent selected from reducing sugars, a second reagent selected from primary amines, acid addition salts of primary amines, secondary amines, secondary amine acid addition salts, ammonium salts of the formula Rn- (NH4 +) n wherein n is an integer of at least 1 and Rn- is the residue of an organic or inorganic acid, as an expandable and thermosetting composition for the manufacture of a foam-type insulating product. More particularly, the subject of the present invention is a process for manufacturing a thermoset solid foam, usable as a thermal insulation product, comprising the following successive stages: (a) provision of an expandable composition and a thermosetting agent containing a first reagent selected from reducing sugars, a second reagent selected from primary amines, acid addition salts of primary amines, secondary amines, acid addition salts, and secondary amines, the ammonium salts of the formula Rn- (NH4) +, where n is an integer at least 1 and Rn- is the residue of an organic or mineral acid, (b) introduction of the expandable and thermosetting composition in a mold or application of the expandable composition on a carrier to a film of a thickness of at least 1 mm, (c) heating the expandable and thermosetting composition to a temperature at least 140 ° C so as to react the first reagent with the second reagent and to form, by polymerization and chemical foaming, a block of thermoset solid foam. By reducing sugars is meant carbohydrates of the formula C n (H 2 O) p having at least one aldehyde or ketone group (reducing group). Reducing sugars for use in the present invention include monosaccharides (monosaccharides) and osides (disaccharides, oligosaccharides, and polysaccharides). By way of examples of monosaccharides, mention may be made of those comprising from 3 to 8 carbon atoms, preferably the aldoses and advantageously the aldoses containing 5 to 7 carbon atoms. The particularly preferred aldoses are natural aldoses (belonging to the D series), in particular hexoses such as glucose, mannose and galactose. Lactose or maltose are examples of disaccharides useful as reducing sugars. It is also advantageous to use starch hydrolysates obtained by enzymatic hydrolysis or acid hydrolysis of starch. The degree of hydrolysis is generally characterized by the equivalent of dextrose (DE), defined by the following relation: / number of broken glycosidic bonds DE = 100 x number of glycosidic bonds in the initial starch The hydrolysates having a DE less than The foams are preferably relatively foamed and starch hydrolysates having an ED greater than 20, also known as glucose syrups, are preferably used. Hydrolysates having an ED ranging from 50 to 90 are particularly preferred.
    [0003] In general, any oligomer or precursor of a reducing sugar capable of releasing a reducing sugar under the reaction conditions is considered to be usable as the first reagent in the present invention. The second reagent may be a primary amine of formula R 1 NH 2 or a secondary amine of formula R 1 R 2 NH wherein R 1 and R 2 independently independently represent a linear alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl residue, optionally containing one or more heteroatoms. Examples of amines include ethylamine, diethylamine, dimethylamine, ethylpropylamine, aniline, 1-naphthylamine, 2-naphthylamine and para-aminophenol. The second reagent may also be an acid addition salt of such a primary or secondary amine. The acids used for the formation of such a salt are, for example, monocarboxylic or polycarboxylic acids, sulfuric acid, nitric acid, organosulfonic acids such as lignosulphonate, and phosphoric acid. The polycarboxylic acids are preferably dicarboxylic, tricarboxylic or tetracarboxylic acids. The dicarboxylic acids include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and the like. azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and its derivatives, especially those containing at least one boron or chlorine atom, tetrahydrophthalic acid and its derivatives, in particular those containing at least one chlorine atom such as chlorendic acid, isophthalic acid, terephthalic acid, mesaconic acid and citraconic acid; The tricarboxylic acids include, for example, citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid and trimesic acid. Tetracarboxylic acid, for example 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid, may be mentioned. Of the carboxylic acids, citric acid which degrades under the reaction conditions and liberates H2O, CO2 and reactive gaseous anhydride is preferably used. Finally, the second reagent may be an ammonium salt of the formula Rn- (N1-14-1) where n is an integer at least 1 and Rn- is the residue of an organic or inorganic acid. The organic or inorganic acid is preferably selected from those enumerated above.The expandable and thermosetting compositions used in the present invention for the formation of solid foams generally contain water, which essentially acts as a solvent for the former. and second reagent and not the role of physical foaming agent, as explained above, since the foaming composition used in the process of the present invention need not be finely dispersed in air, it is less crucial than in the case of a binder for mineral fibers, to ensure that its viscosity is sufficiently low, whereas an aqueous binder for mineral fibers comprises, at the time of spraying, the At 90% or even 95% water, the expandable compositions of the present invention are much more concentrated and viscous. They advantageously contain less than 50% by weight of water, in particular at most 35% by weight, preferably at most 25% by weight, more preferably at most 15% by weight and ideally at most 5% by weight of water. The solids content of the foamable composition before heating is therefore at least 50% by weight, in particular at least 65% by weight, preferably at least 75%, more preferably at least 85% by weight. % by weight and ideally at least 95% by weight. The first and second reagents represent in total at least 70%, preferably at least 80%, in particular at least 90% of the dry weight of the foamable composition.
    [0004] The first reagent preferably represents from 30 to 95% by weight, in particular from 60 to 90% by weight and the second reagent preferably represents from 5 to 70% by weight, preferably from 10 to 40% by weight of the weight. total of the first and second reagents. Although the first and second reagents are the major and essential components of the expandable composition, it may contain a number of other adjuvants and additives to improve the properties of the final thermoset foams or to reduce the cost of production. The total amount of these adjuvants and additives, however, preferably does not exceed 30% of the dry weight of the expandable composition.
    [0005] Thus, the expandable composition may contain, for example, one or more surfactants to reduce the average size and dispersion of the pore sizes of the final foam or to facilitate the incorporation of a filler. The expandable composition preferably contains from 1 to 15% by weight, preferably from 2 to 10% by weight, based on the dry weight of the total foamable composition, of one or more surfactants. The expandable composition used in the present invention may further contain up to 20% by weight, preferably up to 10% by weight, based on the dry weight of the total foamable composition, of one or more fillers. mineral or organic.
    [0006] Finally, the expandable composition may contain one or more other additives conventionally used in the polymer processing and processing industry such as dyes, pigments, antibacterial or antifungal agents, flame retardants, UV absorbers, hydrophobic agents. . These additives represent in total preferably at most 10% of the dry weight of the composition. The expandable composition is preferably substantially free of organic physical blowing agent. Its pH is generally between 5 and 9. In the process of the present invention, reactive compositions, known as such in highly diluted form, are therefore used in a totally different way from that described in the documents of the present state. the technique mentioned in the introduction. They are not sprayed as fine droplets on hot mineral fibers for the formation of a mat of fibers bonded together, but remain in compact, undispersed form. Their solids content is considerably higher than that of the compositions of the state of the art. When the expandable composition is spread as a continuous film on a support, the film thickness, before heating, i.e. before expansion and curing, is preferably at least 2 mm, in particular at least 5 mm, and more preferably at least 10 mm. The volume of the foam block formed can vary between very wide limits. When the expandable composition is used in a continuous process forming, for example, strips or profiles of insulating materials, it is potentially infinite. When the expandable composition is used to form discrete blocks, for example foams or foams, the amount thereof is preferably such that the volume of each block of thermoset solid foam is at least 500 cc. preferably at least 0.001 m3, in particular at least 0.01 m3.
    [0007] The foam block is preferably in the form of a plate. In order to react the first and second reagents it is necessary to heat the foamable composition to a temperature of at least 140 ° C. It is known that the Maillard reaction between a reducing sugar and an amine takes place only beyond this temperature. The reaction temperature will preferably be between 150 ° C and 180 ° C. This temperature is, of course, that measured at the heart of the reaction mixture. To heat the expandable composition in step (c), any conventional means known in the field of processing and processing of polymers, such as hot air, heat microwaves or placing in contact with a hot support (mold). Of course, the temperature of the heating means (oven, support, mold) may be higher than the reaction temperature mentioned above, for example between 160 and 210 ° C. Another subject of the present invention is a solid foam that can be obtained by the method that is the subject of the present invention.
    [0008] This foam is based on melanoidines, the complex reaction products of the Maillard reaction and can contain up to about 25% by weight of other components, including mineral fillers. It is important to note that the content of these other components, especially mineral fillers, of the cured foam may be higher than that of the expandable and thermosetting starting composition. Indeed the Maillard reaction between the first and second reagents is accompanied by a release of gaseous products such as CO2, NH3, SH2, SO2 and the melanoidin fraction in the final foam is therefore less than the fraction. , by dry weight, of the first and second reagents of the initial composition. The solid foams prepared by the process of the invention are of a dark brown to black color. Their density is between 30 and 60 kg / m3. They have a closed porosity with an average pore diameter, determined by X-ray tomography, between 100 and 800 nm.
    [0009] EXAMPLES Several thermosetting expansible compositions are prepared by adding an aqueous solution of the second reagent to a powder of the first reagent. The mixture is stirred at ambient temperature until the powder is dissolved. Table 1 shows the respective amounts of the first and second reagents, expressed as solids, as well as the total solids content of the compositions obtained. Each of the compositions is introduced into a flat-bottomed aluminum dish (5 cm in diameter) in a film having a thickness of about 1 mm. The cups are introduced into an oven heated to 200 ° C. After 20 minutes, they are removed, allowed to cool to room temperature and the thickness of the foam formed is observed: Table 1 Reagent 1 Reagent 2 Extract Thickness of dry foam 32.5 parts of D-glucose monohydrate 67.5 parts 63 `) / 0 +++ of ammonium citrate 85 parts of D-glucose monohydrate 15 parts 75`) / 0 +++++ of ammonium sulfate 85 parts 15 parts 3033326 - 10 - of ammonium sulfate maltodextrin 61% + (DE = 3 - 20) 85 parts of 15 parts D-glucose ammonium carbonate monohydrate 75 `) / 0 +++ -: less than 0.5 cm +: 0 , 5 to 1 cm ++: 1.1 to 2 cm 5 +++: 2.1 to 3 cm ++++: 3.1 to 4 cm +++++: more than 4 cm For comparison A series of compositions identical to those of Table 1 are prepared except that the first reagent (reducing sugar) is replaced by a polyol having no reducing group. They are cooked for 20 minutes in an oven at 200 ° C. The observed results are recorded in Table 2.
    [0010] Table 2 Polyglycerol Reagent 2 Dry Extract Foam 32.5 parts 67.5 parts 63 `) / 0 - Ammonium citrate black crust 85 parts 15 parts 75`) / 0 - Color transparent ammonium sulphate film beige 85 parts 15 parts 75 ') / 0 - Transparent colorless ammonium carbonate Only the sample containing ammonium citrate appears to have reacted. Its color has changed and its consistency is hard, but no foam formation is observed.
    [0011] For the other two samples containing, as the second reagent, ammonium sulfate and ammonium carbonate, the color of the reaction mixture remained almost unchanged. A very slightly transparent transparent film is observed, but no foam formation. 5
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A method of manufacturing a thermoset solid foam, comprising the following successive steps: (a) providing an expandable and thermosetting composition containing - a first reagent selected from reducing sugars, - a second reagent selected from primary amines, acid addition salts of primary amines, secondary amines, acid addition salts of secondary amines, ammonium salts of formula Rn (NH 4 +) n wherein n is an integer to less than 1 and Rn- represents the residue of an organic or inorganic acid, (b) introduction of the expandable and thermosetting composition into a mold or application of the expandable composition on a support to a film of at least a thickness at 1 mm, (c) heating the expandable and thermosetting composition to a temperature at least 140 ° C so as to react the first reagent with the second reagent and form, by polymerization and chemical foaming, a block of thermoset solid foam.
    [0002]
    2. Method according to claim 1, characterized in that the amount of expandable and thermosetting composition is such that the volume of the thermoset solid foam block obtained is at least 500 cm3, preferably at least 0.001 m3, in in particular not less than 0.01 m3.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the thickness of the film is at least 2 mm, preferably at least 5 mm, in particular at least 10 mm.
    [0004]
    4. Method according to any one of the preceding claims, characterized in that the thermoset solid foam block is a plate. 3033326 - 13 -
    [0005]
    5. Method according to any one of the preceding claims, characterized in that the expandable composition contains at most 35% by weight, preferably at most 25% by weight, more preferably at most 15% by weight and in particular at most 5% by weight of water. 5
    [0006]
    6. Method according to any one of the preceding claims, characterized in that the first and second reagents represent in total at least 70%, preferably at least 80%, in particular at least 90% of the dry weight of the expandable composition. .
    [0007]
    7. Process according to any one of the preceding claims, characterized in that the first reagent is chosen from glucose and starch hydrolysates, preferably starch hydrolysates having a dextrose equivalent (DE) greater than 20. , in particular between 50 and 90.
    [0008]
    8. Process according to any one of the preceding claims, characterized in that the expandable composition further contains one or more surfactants.
    [0009]
    9. Process according to any one of the preceding claims, characterized in that the expandable composition further contains up to 20% by weight, preferably up to 10% by weight, based on the dry weight of the expandable composition. total, of one or more mineral or organic fillers.
    [0010]
    10. Process according to any one of the preceding claims, characterized in that the first reagent represents from 30 to 95% by weight and the second reagent represents from 5 to 70% by weight of the total weight of the first and second reagents.
    [0011]
    Solid foam obtainable by the process according to any one of the preceding claims.
    [0012]
    12. Solid foam according to claim 11, characterized in that it has a density of between 30 and 60 kg / m3.
    [0013]
    13. Solid foam according to claim 11 or 12, characterized in that it has a closed porosity. 3033326 -
    [0014]
    14 - 14. Solid foam according to one of claims 11 to 13, characterized in that the average pore diameter determined by X-ray tomography is between 100 and 800 nm.
    [0015]
    15. Use of a composition containing a first reagent chosen from reducing sugars, a second reagent chosen from primary amines, acid addition salts of primary amines, secondary amines, sodium salts and the like. addition of secondary amine acid, ammonium salts of the formula Rn (NH 4 +) n wherein n is an integer of at least 1 and Rn represents the residue of an organic or inorganic acid, as that expandable and thermosetting composition for the manufacture of a foam-type insulating product.
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    同族专利:
    公开号 | 公开日
    JP2018507308A|2018-03-15|
    CN107257821B|2020-04-21|
    JP6726199B2|2020-07-22|
    FR3033326B1|2018-10-26|
    EP3265507B1|2019-11-27|
    BR112017017654B1|2022-01-25|
    US20180016356A1|2018-01-18|
    DK3265507T3|2020-03-02|
    RU2708203C2|2019-12-04|
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    CA2977166A1|2016-09-09|
    EP3265507A1|2018-01-10|
    BR112017017654A2|2018-05-08|
    WO2016139401A1|2016-09-09|
    KR20170126884A|2017-11-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20070027283A1|2005-07-26|2007-02-01|Swift Brian L|Binders and materials made therewith|
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    JP5977015B2|2010-11-30|2016-08-24|ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ|Stable reactive thermosetting formulations of reducing sugars and amines|FR3075208B1|2017-12-18|2019-12-20|Saint-Gobain Isover|PROCESS FOR PRODUCING THERMOSET POLYESTER FOAMS WITH PREOLIGOMERIZATION STEP|
    CN108535292B|2018-03-28|2020-08-11|东南大学|Method for determining upper limit of fine-grained soil mixing amount in high-speed railway base filler|
    FR3080850A1|2018-05-04|2019-11-08|Saint-Gobain Isover|THERMAL INSULATION MATERIAL|
    FR3089984B1|2018-12-18|2021-01-01|Saint Gobain Isover|Use of linear diols for the manufacture of bio-based polyester foams|
    法律状态:
    2016-03-22| PLFP| Fee payment|Year of fee payment: 2 |
    2016-09-09| PLSC| Publication of the preliminary search report|Effective date: 20160909 |
    2017-03-24| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-22| PLFP| Fee payment|Year of fee payment: 4 |
    2020-03-25| PLFP| Fee payment|Year of fee payment: 6 |
    2021-03-31| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1551723A|FR3033326B1|2015-03-02|2015-03-02|THERMODURCAL FOAMS AND METHOD OF MANUFACTURE|
    FR1551723|2015-03-02|FR1551723A| FR3033326B1|2015-03-02|2015-03-02|THERMODURCAL FOAMS AND METHOD OF MANUFACTURE|
    JP2017546074A| JP6726199B2|2015-03-02|2016-02-18|Thermosetting foam and manufacturing method|
    CN201680013234.7A| CN107257821B|2015-03-02|2016-02-18|Thermoset foam and method of manufacture using reducing sugars and amines|
    EP16714469.0A| EP3265507B1|2015-03-02|2016-02-18|Thermoset foams, and method for manufacturing same from reducing sugars and amines|
    CA2977166A| CA2977166A1|2015-03-02|2016-02-18|Thermoset foams, and method for manufacturing same from reducing sugars and amines|
    BR112017017654-8A| BR112017017654B1|2015-03-02|2016-02-18|Process of manufacturing thermosetting solid foams|
    RU2017133689A| RU2708203C2|2015-03-02|2016-02-18|Thermoset foamed products and method for production thereof|
    DK16714469.0T| DK3265507T3|2015-03-02|2016-02-18|THERMO-HEARDED FOAM AND PROCEDURE FOR PREPARING BASIS IN REDUCING SUGAR AND AMINES|
    PCT/FR2016/050372| WO2016139401A1|2015-03-02|2016-02-18|Thermoset foams, and method for manufacturing same from reducing sugars and amines|
    US15/553,615| US10457750B2|2015-03-02|2016-02-18|Thermoset foams, and method for manufacturing same from reducing sugars and amines|
    KR1020177024289A| KR20170126884A|2015-03-02|2016-02-18|Method for preparing the same from thermosetting foams and reducing sugars and amines|
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