• 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 subject of the invention is a crosslinked biosourced poly (itaconate) obtained by polymerization of an itaconate and a biosourced crosslinking agent. The invention also relates to a process for obtaining this crosslinked poly (itaconate), as well as a composition including it and its uses as a superabsorbent polymer.
    公开号:FR3029525A1
    申请号:FR1461905
    申请日:2014-12-04
    公开日:2016-06-10
    发明作者:Cedric Dever
    申请人:VALAGRO CARBONE RENOUVELABLE POITOU-CHARENTES；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a biobased superabsorbent polymer and to a process for obtaining it. BACKGROUND OF THE INVENTION The invention also relates to the compositions including it and its uses. Superabsorbent polymers are polymers that can absorb and retain very large quantities of liquids relative to their own mass without dissolving. Because of their absorbency and retention, superabsorbent polymers are ideally suited for organic fluid absorbent applications in personal care products such as diapers and incontinence pads. Superabsorbent polymers are generally obtained by polymerization of a monomer in the presence of a crosslinking agent. The three-dimensional network created makes it possible to absorb a liquid by an osmosis phenomenon by storing it in its empty spaces while avoiding its dissolution. The most used superabsorbent polymer is a crosslinked polyacrylic acid having partially neutralized hydroxyl functions. It is synthesized by radical polymerization of acrylic acid in the presence of a crosslinking agent (of the bisacrylamide type) and then partially neutralized with sodium hydroxide, dried and milled. When the ground material is then placed in the presence of water, it swells and forms a gel which can contain up to 100 times its weight in water. Despite its very good performance in terms of absorption, polyacrylic acid and all current superabsorbent polymers are completely petrochemical origin. There is therefore a need for fully biobased superabsorbent polymers. In order to meet them, the present invention proposes a totally biosourced superabsorbent polymer obtained by polymerization of an itaconate and a biosourced crosslinking agent. In particular, the invention relates to a crosslinked biosourced poly (itaconate) obtained by polymerization of an itaconate, preferably a sodium itaconate, and a biosourced crosslinking agent, said crosslinking agent having the following formula: CH 2 = C (-COOH) -CH 2 -C (= O) -O-ROC (= O) -CH 2 -C (-COOH) = CH 2 with: R = (CH 2) n, n = 2 to 6, or R = CH 2 The use of itaconic polymer for its absorption properties has already been described, but the known itaconic acid polymers are obtained with a crosslinking agent of petrochemical origin. The invention has the advantage of being entirely biobased. The invention also relates to a composition comprising a crosslinked poly (itaconate) according to the invention, a process for obtaining and uses as a superabsorbent polymer. Other features and advantages will become apparent from the detailed description of the invention which follows. DEFINITIONS "Itaconic acid" within the meaning of the invention means the molecule represented by the following formula: For the purposes of the invention, the term "initiator" means a chemical molecule capable of generating radicals by thermal activation, photochemical or redox. For the purposes of the invention, the term "biobased" means a molecule (or a set of 20 molecules) obtained by extraction of the biomass (for example: cellulose) or obtained by reactions applied to the biomass (for example: glycerol derived from the esterification of triglycerides). By "acid number" within the meaning of the invention is meant the mass of potash (expressed in mg) necessary to neutralize the free acidity contained in 1 g of material. By "itaconate" within the meaning of the invention is meant the molecule represented by the following formula: M + -O-C (= O) -C (= CH2) -CH2-C (= O) -O- - + M with M = Na, K or NH4. For the purposes of the invention, the term "sodium itaconate" means the molecule represented by the following formula: Nat-OC (= O) -C (= CH 2) -CH 2 -C (= O) -O-Na + may be The term "poly (itaconate)" within the meaning of the invention is understood to mean a polymer obtained by polymerization of itaconate. For the purposes of the invention, the term "crosslinked poly (itaconate)" means a polymer obtained by copolymerization of itaconate and a divinyl monomer. By "radical polymerization" within the meaning of the invention is meant a chain polymerization involving radical active species during priming, propagation, termination and chain transfer reactions. By "biosourced polyol" within the meaning of the invention is meant a biosourced molecule having at least 2 hydroxyl functions. It may be preferentially a bisolated diol such as propane-diol, butanediol or a triol such as glycerol. For the purposes of the invention, the term "crosslinking agent" or "crosslinking agent" means a molecule having at least two vinyl functions. It may be preferentially an itaconate diester obtained by esterification of a biosourced polyol and itaconic acid. DETAILED DESCRIPTION OF THE INVENTION The invention therefore relates to a crosslinked biosourced poly (itaconate) obtained by polymerization of an itaconate and a biosourced crosslinking agent, said crosslinking agent having the following formula: CH 2 = C (-COOH) -CH 2 C (= O) -O-ROC (= O) -CH 2 -C (-COOH) = CH 2 with: R = (CH 2) n, n = 2 to 6, or R = CH 2 -CH (OH) -CH 2 3029525 The crosslinked poly (itaconate) according to the invention is a three-dimensional molecule. Itaconate can be obtained by neutralizing itaconic acid with a base. It is preferably neutralized with sodium hydroxide. This is called sodium itaconate. The crosslinking agent has at least two vinyl functions. It preferably has an acid number of between 300 and 450 mgKOH / g, preferably between 350 and 400 mgKOH / g. Preferably, the crosslinking agent is a crosslinking agent obtained by esterification of itaconic acid and of a biopolymer polyol, preferably of a 1,3-propanediol type biosourced diol. By way of example, the condensation reaction by esterification of itaconic acid and 1,3-propanediol is schematized hereafter: 2 HO-C (= O) -C (= CH 2) -CH 2 -C (= 0) -OH + HO- (CH2) 3-OH CH2 = C (-COOH) -CH2-C (= O) -O- (CH2) 3-O-C (= O) -CH2-C (-COOH ) = CH 2 + 2H 2 O Itaconic acid can be obtained by fermentation of sugars using varieties of Aspergillus terreus. 1,3-Propanediol can be obtained by biochemical conversion of sugars by a modified E. coli. The polymer according to the invention can be obtained by a process comprising at least the following succession of steps: - obtaining a crosslinking agent by esterification of a biosourced polyol and itaconic acid, - obtaining itaconate, preferentially from a sodium itaconate, by neutralization of itaconic acid with a soda-based base, - radical polymerization of a mixture in water of itaconate and of a crosslinking agent in the presence of an initiator, - obtaining a gel of crosslinked poly (itaconate), - drying of the gel to obtain a crosslinked poly (itaconate) in dry form. Preferably, the biosourced polyol is a diol.
    [0002] The step of obtaining the crosslinking agent preferably comprises the following steps: a catalyst (preferably sulfuric acid) is added dropwise to a mixture of itaconic acid and of polyol (with an acid mole ratio itaconic / diol greater than 2), the mixture is refluxed until complete consumption of the diol.
    [0003] Itaconate is obtained by neutralization of itaconic acid with a sodium base, preferentially sodium hydroxide. The step of obtaining itaconate preferably comprises the following steps: - cold addition and drip of a sodium salt, preferably sodium hydroxide, on itaconic acid in water up to obtaining a molar ratio of sodic base on itaconic acid of 2, - stirring for 1h. The itaconate and the crosslinker are then mixed in water in the presence of an initiator. The initiator may be chosen from redox, thermal or photochemical initiators. It is preferably potassium persulfate.
    [0004] Radical polymerization of the mixture occurs. Preferentially, the crosslinker / itaconate molar ratio is between 0.001 and 0.1, more preferably between 0.002 and 0.05. The radical polymerization of the mixture in water leads to the production of a crosslinked poly (itaconate) gel, which is then dried to obtain a crosslinked poly (itaconate) in dry form, preferably in the form of a powder. The drying can be carried out by washing with a solvent followed by a stoving step. Preferably the drying is carried out by washing with acetone and by drying at 50 ° C. for 24 hours. The crosslinked poly (itaconate) according to the invention can be used in a composition. The invention is particularly directed to a composition comprising between 30 and 100% by weight of a crosslinked poly (itaconate). The composition may also comprise, in particular, vegetable or mineral fillers, additives (dye, etc.) and polymers (of the polylactic acid type, polyolefins). It is preferably in the form of powders or granules.
    [0005] The crosslinked poly (itaconate) according to the invention has the characteristics of a superabsorbent polymer, in particular: a good capacity for absorbing liquids; a good absorption kinetics; a good desorption kinetics; therefore be used as super absorbent polymer. Advantageously, it is a superabsorbent polymer fully biobased.
    [0006] In particular, it can be used in superabsorbent compositions. Preferentially, the poly (itaconate) according to the invention is used to absorb water and / or aqueous solutions and / or alcoholic solutions. In particular, it may be used in diapers, absorbent papers, cooling textile fibers, artificial snow, sanitary napkins, moisturizing burn gels, temporary flood protection, disposable urinals, lighter gels. fire, nutrient solutions of soils or plants. The invention is now illustrated by examples of crosslinked poly (itaconate) and compositions, as well as by test results demonstrating the absorbent effectiveness of the crosslinked poly (itaconate) according to the invention, these examples and tests not being not being limiting.
    [0007] EXAMPLES OF POLY (ITACONATES) RETICULATED ACCORDING TO THE INVENTION Raw materials used: - 99% itaconic acid (Alfa Aesar): C8H604 / M = 130.1 g / mol - sodium ltaconate: C8H404Na2 / M = 174.06 g / mol - Potassium persulfate 97% (Alfa Aesar): K 2 S 2 O 8 / M = 270.33 g / mol 20-Tert-butyl-hydro 70% solution in Water (Sigma Aldrich): (CH 3) 3COOH / M = 90.12 g / mol - Propane-1,3- diol: C 3 H 8 O 2 / M = 76.09 g / mol - 99% Hydroquinone (Alfa Aesar): C 6 H 60 2 / M = 110.11 g / mol - Sodium hydroxide (Sigma Aldrich): NaOH / M = 40 g / mol Synthesis of the crosslinking agent itaconic acid, propane-1,3-diol, catalyst and hydroquinone are introduced into a flask and evacuated under vacuum (10 mbar) with an oil bath at 140 ° C. The reaction time varied depending on the catalyst, for the catalyst H2504, SnOt2 and PTSA it took 2 hours of reaction, for the MSA 1 hour and 30 minutes and without catalyst 2 hours and 45 minutes. Hydroquinone serves to prevent the polymerization of itaconic acid on itself.
    [0008] In each case, a translucent liquid is obtained which solidifies and turns white on cooling with a mass of about 45 g. The crosslinking agent is represented by the following formula: Homopolymerization of itaconic acid to obtain sodium itaconate In a flask, 26.5 g of itaconic acid (0.20 mol) are premixed with 35 g of demineralized water. 16 g of 50% NaOH (0.4 mol) are added very slowly and keeping cold, with stirring. The mixture is bubbled with nitrogen for 30 minutes while heating at 90 ° C, 2 g of K2S208 (7.40x10-3 mol) dissolved in 7.5 g of demineralized water are then added. The reaction is stirred magnetically at 90 ° C for 2 hours. Hydroquinone (1 ml) is then added to the mixture in order to stop the polymerization. The sodium itaconate obtained is referred to as PIA030314. Polymerization synthesis of itaconic acid with the biosourced crosslinking agent: Polymerizations of itaconic acid in the presence of a biosourced crosslinking agent were carried out with the following procedure: In the first step, sodium itaconate with 50% is prepared in a flask by mixing 50 g of itaconic acid (0.38 mol), 25 g of demineralized water and 15.4 g of sodium hydroxide pellets (0.38 mol) which are added very slowly and keeping the flask at 20 ° C. cold. Once sodium itaconate is obtained, the flask is put under nitrogen and heated to 60 ° C. Once the temperature at 60 ° C, the addition of tert-butyl hydroperoxide (0.5 mL or 5.2 mol) and the cross-linking agent biosourced (2 g is 6.6x10-3 mol) is carried out. Heat for 2h30 and allow to cool.
    [0009] The gel obtained is then washed with acetone (3 times 20 ml) to extract the trapped water and is placed in an oven at 50 ° C. for 24 hours. The same protocol was carried out with 4 g, 6 g and 10 g of crosslinking agent.
    [0010] The references of the samples obtained are PRIA + SRH2s04300414, PRIA + SR 060514, PRIA + SRsnot2060514, PRIA + SRpTsA070514 and PRIA + SRMsA070514. The synthesis conditions and the acid number of the molecules obtained are given below: Reference Acid Propane-1,3-diol Catalyst Hydroquinone Itaconic acid number (mgKOH / g) SRH2so4150414 2 moles 1 mole 9.51 g H2SO4 1mL 363 32.5 g (1% by mass of IA) 0.325 g SRsnot2160414 2 moles 1 mole 9.51 g SnOt2 1mL 415 32.5 g (1% by mass of IA) 0.325 g SRprsA160414 2 moles 1 mole 9.51 g PTSA 1mL 360 32.5 g (1% by mass of IA) 0.325 g SRmsA170414 2 moles 1 mole 9.51 g MSA (0.1% 1mL 358 32.5 g total mass) 0.042 g SR 280414 2 moles 1 mole 9.51 g Catalyst-free 1mL 424 32.5 g 5 acid number of the cross-linking agent biobased L acid number (Ia) is the number of mg of potassium hydroxide (KOH) required to neutralize the free acids contained in 1 g of sample. The free fatty acids present in the fatty substance are dosed by a solution of potash. R - COOH + KOH -> R - COOK + H20 The procedure is described below.
    [0011] Weigh accurately a mass of material (0.1 - 0.2 g) in a 250 ml beaker, dissolve the fat with 50 ml of the 95% (v / v) diethyl ether / ethanol mixture, add a few drops of colored indicator, titrate with the KOH solution (previously verified) until the indicator turns. A blank is made by dosing only the mixture of the two solvents (with the same volumes). Expression of the results: m: the mass of the fat test sample (g), CKOH: the concentration of the KOH solution (mol / L), - the equivalent volume of the blank (ml), - Test: the equivalent volume of the test portion (mL), - 56.1: the molar mass of KOH (g / mol). The acid number, expressed in mg of KOH per gram of fat, is then: = 56.1 X CKOH X (Vessel - Vblanc) m The theoretical acid number of the crosslinking agent has been determined in order to compare with the results obtained. The method of calculation of I'la is detailed below: The crosslinker has a theoretical molecular weight = 301 g / mol The crosslinking agent has two free acids.
    [0012] Demonstration of calculation of the theoretical acid number: 2 x M (KOH) × 1000 IA = 301 IA = 372 The crosslinkers obtained have an acid number close to the theoretical index. The structure of the crosslinkers was analyzed by NMR. NMR spectra show the presence of free propanediol and propanediol reacted with itaconic acid. By comparing the integral of the peaks, it is possible to determine the condensation rate: C Condensation rate = - x 100 C + C 'Here are the results of each crosslinking agent: Reference Rate of condensation acid number (mgKOH / g SRH2so4150414 99% 363 SRsnot2160414 70% 415 SRmsA170414 98% 358 SR 280414 67% 424 IA = M (molecule) 2 x 56.1 x 1000 3029525 The condensation rate is found to be well identified with the acid number, since each acid number which is close to the theoretical acid number (372) has a very good rate of condensation. EVALUATION OF THE ABORBENT EFFICIENCY OF THE POLY (ITACONATES) ACCORDING TO THE INVENTION The WAC is the water absorption capacity of a material and is expressed in gram H 2 O per gram sample. To perform these WAC tests, it is necessary to introduce a known mass (m1) of dry polymer in 500 times m1 volume of water and leave for 24 hours the product to absorb the water. Then, the gel obtained is filtered and weighed (m2).
    [0013] The WAC is calculated as follows: m2 - m1 WAC = m1 Molar ratio WAC lirticulantinitaconate gH20 / sample 0 0 0.02 0 0.04 5 0.08 18 0.12 23 0.2 24
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. A crosslinked biosourced poly (itaconate) obtained by polymerizing an itaconate and a biosourced crosslinking agent, said crosslinking agent having the following formula: CH 2 = C (-COOH) -CH 2 -C (= O) -O-ROC (= O) ) -CH 2 -C (-COOH) = CH 2 with R = (CH 1, n = 2 to 6, or R = CH 2 -CH (OH) -CH 2.
    [0002]
    2. Crosslinked poly (itaconate) according to claim 1, characterized in that the itaconate is an itaconate previously neutralized with a base.
    [0003]
    3. Crosslinked poly (itaconate) according to claim 1 or 2, characterized in that the itaconate is sodium itaconate.
    [0004]
    4. Crosslinked poly (itaconate) according to claim 3, characterized in that the sodium itaconate is an itaconate previously neutralized with sodium hydroxide.
    [0005]
    5. Crosslinked poly (itaconate) according to one of the preceding claims, characterized in that the crosslinking agent has an acid number of between 350 and 400 mgKOH / g.
    [0006]
    6. Crosslinked poly (itaconate) according to one of the preceding claims, characterized in that the crosslinking agent is obtained by esterification of itaconic acid and a biosourced polyol.
    [0007]
    7. Crosslinked poly (itaconate) according to one of the preceding claims, characterized in that the crosslinking agent is obtained by esterification of itaconic acid and a biosourced diol.
    [0008]
    8. Crosslinked poly (itaconate) according to one of the preceding claims, characterized in that it has at least two vinyl functions.
    [0009]
    9. Crosslinked poly (itaconate) according to one of the preceding claims, characterized in that the crosslinker / itaconate molar ratio is between 0.001 and 0.1.
    [0010]
    10. Use of a crosslinked poly (itaconate) according to one of the preceding claims, as superabsorbent polymer.
    [0011]
    11. Use according to claim 10 in superabsorbent compositions.
    [0012]
    12. Use according to one of claims 10 or 11 for absorbing water and / or aqueous solutions and / or alcoholic solutions. 3029525 12
    [0013]
    13. Use according to one of claims 10 to 12, in diapers, absorbent papers, cooling textile fibers, artificial snow, sanitary napkins, moisturizing gels burns, temporary protection against flooding, disposable urinals, fire starters, soil or plant nutrient solutions.
    [0014]
    14. Composition comprising between 30 and 100% by weight of a crosslinked poly (itaconate) according to one of claims 1 to 9.
    [0015]
    15. Process for obtaining a crosslinked poly (itaconate) according to one of claims 1 to 9, characterized in that it comprises the following succession of steps: 10 - obtaining a crosslinking agent by esterification of a polyol biosourced and itaconic acid, - obtaining itaconate by neutralization of itaconic acid with a soda-based base, - radical polymerization of a mixture in water of itaconate and a crosslinking agent in the presence of an initiator, - Obtaining a crosslinked poly (itaconate) gel, - drying the gel to obtain a crosslinked poly (itaconate) in dry form.
    [0016]
    16. The method of claim 15, characterized in that the biosourced polyol is a diol.
    [0017]
    17. Process according to claim 15 or 16, characterized in that the itaconate is a sodium itaconate.
    [0018]
    18. The method of claim 17, characterized in that the soda base used to neutralize itaconic acid and obtain sodium itaconate is sodium hydroxide.
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    同族专利:
    公开号 | 公开日
    FR3029525B1|2017-01-06|
    WO2016087795A1|2016-06-09|
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    US11090255B2|2018-12-04|2021-08-17|Momentive Performance Materials Inc.|Use of polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair|
    CN111647107B|2020-05-14|2021-11-30|陕西科技大学|Performance-adjustable castor oil-based vinyl ester thermosetting material and preparation method thereof|
    法律状态:
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    2018-07-13| TP| Transmission of property|Owner name: BIOMANITY, FR Effective date: 20180604 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1461905A|FR3029525B1|2014-12-04|2014-12-04|POLYRETICLE BIOSOURCE, INCLUDING COMPOSITIONS AND USES AS SUPER ABSORBENT POLYMER|FR1461905A| FR3029525B1|2014-12-04|2014-12-04|POLYRETICLE BIOSOURCE, INCLUDING COMPOSITIONS AND USES AS SUPER ABSORBENT POLYMER|
    PCT/FR2015/053322| WO2016087795A1|2014-12-04|2015-12-04|Biosourced cross-linked poly, compositions including same and uses thereof as a superabsorbent polymer|
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