WO2023035192A1 - Matériau polymère organosilicié auto-cicatrisant, son procédé de préparation et son utilisation - Google Patents

Matériau polymère organosilicié auto-cicatrisant, son procédé de préparation et son utilisation Download PDF

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WO2023035192A1
WO2023035192A1 PCT/CN2021/117480 CN2021117480W WO2023035192A1 WO 2023035192 A1 WO2023035192 A1 WO 2023035192A1 CN 2021117480 W CN2021117480 W CN 2021117480W WO 2023035192 A1 WO2023035192 A1 WO 2023035192A1
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polysiloxane
polymer material
modified polysiloxane
aminated
organosilicon polymer
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PCT/CN2021/117480
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Chinese (zh)
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王�华
周传健
卢海峰
张晨
梁艳
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山东大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the application relates to a self-healing organic silicon polymer material and its preparation method and application, belonging to the field of composite materials.
  • Silicone polymer materials are a special class of polymer materials, and their unique Si-O segments make them exhibit unique advantages in terms of thermal properties, flexibility, film-forming properties, and hydrophobicity.
  • organosilicon polymers can form a dense protective film on the surface of the substrate, which can still prevent corrosion of the substrate under the action of strong acids and alkalis, and have excellent hydrophobicity.
  • organosilicon polymers Can be used as a hydrophobic coating for slow release of fertilizers.
  • the Pt catalyst is often required in the preparation process of organosilicon polymers, and the cost is relatively high, which hinders the application of organosilicon polymers in the agricultural field.
  • the slow-release effect of existing slow-release fertilizers is poor due to the poor performance of the coating material, which causes the problems of waste of resources and indiscriminate application of fertilizers.
  • this application provides a self-healing silicone polymer material and its preparation method and application, using efficient and reversible Diels-Alder reaction, the silicone polymer with specific functional groups is cross-linked
  • a new type of self-healing silicone polymer material with high slow-release characteristics and good coating effect has been prepared, and its application in the slow-release of fertilizers and the reduction of the use of coating materials has significant advantages, and has a positive effect on environmental protection. It has good hydrophobic properties, permeability, film-forming property and reusability; the organosilicon polymer material produced by the preparation method of the organosilicon polymer material has high product purity, mild reaction conditions, high yield and low cost , in line with the various needs of coating materials in fertilizers.
  • a self-healing organosilicon polymer material undergoes Diels-Alder reaction with modified polysiloxane A and modified polysiloxane B to Prepared by cross-linking polymerization to form at least one reversible substituted cyclohexenyl group;
  • the modified polysiloxane A is a polysiloxane A having at least one maleimide group substitution in one molecule
  • the modified polysiloxane B is a polysiloxane A having at least one furoacetyl group in one molecule
  • the polysiloxane B substituted by the group, the structure of the reversibly substituted cyclohexenyl group is shown in formula I:
  • the multiple maleimide groups of the modified polysiloxane A are reversibly cross-linked and polymerized with the multiple furoacetyl groups of the modified polysiloxane B, so that the prepared organic Silicone polymeric materials are porous and can be used as sustained release coatings.
  • the modified polysiloxane B is a polysiloxane B having at least one furoacetylamino substitution in one molecule.
  • the grafting rate of the maleimide group in the modified polysiloxane A is X
  • the grafting rate of the furoacetyl group in the modified polysiloxane B is Y
  • the ratio of the grafting rate X to the grafting rate Y is 1:1.2-1.5.
  • the ratio of the grafting rate X to the grafting rate Y is 1:1.2-1.5; more preferably, the ratio of the grafting rate X to the grafting rate Y is 1:1.5, so that the grafted horse The imide group and furoacetyl can fully react to improve the utilization rate of grafting raw materials.
  • the grafting rate X is 8%-20%
  • the grafting rate Y is 5%-25%; preferably, the grafting rate X is 10%-20%, and the grafting rate Y is 12% -twenty four%.
  • the values of the grafting ratio X and the grafting ratio Y can ensure the slow-release effect of the prepared organosilicon polymer material, especially the slow-release effect as a fertilizer coating.
  • the calculation of the grafting ratio of X and Y is carried out according to the following method: Accurately weigh about 1.5g of modified polysiloxane in a conical flask with an analytical balance, add about 20mL of tetrahydrofuran and toluene to dissolve, and then add 0.1mol/ L of hydrochloric acid solution, shake well for 5 minutes, add phenolphthalein indicator, measure the excess acid with calibrated sodium hydroxide standard solution, until the solution changes color. In addition, do a blank sample again for the hydrochloric acid solution. Calculate amino group concentration and grafting rate according to the following formula:
  • V 0 the volume of sodium hydroxide consumed for titrating the blank sample (mL);
  • V the volume of sodium hydroxide consumed by the titration sample (mL);
  • the polysiloxane A and the polysiloxane B are independently selected from poly(diorganosiloxanes).
  • polysiloxane A has a structural formula as shown in Formula II:
  • R1, R2, R3 and R4 are independently selected from one of hydrocarbon groups, substituted hydrocarbon groups, heteroaryl groups, substituted heteroaryl groups and non-hydrocarbon substituents; m1 and n1 are respectively taken from integers>0, the formula
  • the weight-average molecular weight of the aminated polysiloxane A of II is 2000-20000, and the grafting rate of amino groups in the aminated polysiloxane A is 3%-30%;
  • the R 1 , R 2 , R At least one of 3 and R 4 is linked to the maleimide group of the reversibly substituted cyclohexenyl of formula I.
  • R5, R6, R7 and R8 are independently selected from one of hydrocarbon groups, substituted hydrocarbon groups, heteroaryl groups, substituted heteroaryl groups and non-hydrocarbon substituents; m2 and n2 are respectively taken from integers>0, the formula
  • the weight average molecular weight of the aminated polysiloxane B of III is 2,000 to 20,000, and the grafting rate of amino groups in the aminated polysiloxane B is 3%-30%; the R5, R6, R7 and R8
  • the imino group contained in is connected to the furoacetyl group of the reversibly substituted cyclohexenyl of formula I.
  • the R1, R2, R3 and R4 are independently selected from an alkyl group; one of the R1, R2, R3 and R4 is connected to the nitrogen atom of the reversibly substituted cyclohexenyl of formula I; preferably , the R5, R6, R7 and R8 are independently selected from imino substituted alkyl; the imino group of one of the R5, R6, R7 and R8 and the furoacetyl of the reversibly substituted cyclohexenyl of formula I connect.
  • the carbon chain parts in R1, R2, R3, R4 and R5, R6, R7 and R8 are independently selected from one of C1-C5 alkyl groups.
  • R2 and R6 are respectively propyl and imino substituted propyl or the molecular formula shown in formula VI, and the R3, R4, R5, R7 and R8 are respectively methyl;
  • n3 and n3 are respectively selected from integers not less than 1, specifically, m3 is 2, and n3 is 3.
  • aminated polysiloxane is based on aminodialkoxysilane coupling agent, dimethyldialkoxysilane and hexamethyldisiloxane hydrolysis, capping preparation, amino grafting
  • the calculation of the rate is according to the NMR method, by calculating the ratio of the amino peak area to the Si- CH3 peak area:
  • Grafting rate 3 ⁇ amino peak area/2 ⁇ Si-CH 3 peak area ⁇ 100%.
  • the ratio between the m1 value and the m2 value is 1:1.5, to ensure that the Diels-Alder reaction can be carried out completely.
  • the modified polysiloxane A and the modified polysiloxane B are linear polysiloxanes respectively, which increases the flexibility and film-forming properties of the obtained organosilicon polymer material.
  • a method for preparing a self-healing silicone polymer material includes the following steps:
  • modified polysiloxane A is polysiloxane A having at least one maleimide group substitution in one molecule;
  • modified polysiloxane B said modified polysiloxane B is polysiloxane B having at least one furoacetyl group substitution in one molecule;
  • modified polysiloxane A and modified polysiloxane B are dissolved and then heated to cause a Diels-Alder reaction to generate the organosilicon polymer material crosslinked by at least one reversibly substituted cyclohexene.
  • the preparation method of the modified polysiloxane A comprises the following steps:
  • Aminated polysiloxane A is provided;
  • the modified polysiloxane A is obtained by dissolving the aminated polysiloxane A and maleic anhydride in the organic solvent I and heating to reflux for at least 3 hours.
  • the weight-average molecular weight of the aminated polysiloxane A is 2,000 to 20,000; and the grafting rate of amino groups in the aminated polysiloxane A is 3%-30%, calculated by amino group
  • the molar ratio of the aminated polysiloxane A to the maleic anhydride is 1:1-3.
  • the weight-average molecular weight range of the aminated polysiloxane A is 2000-20000. Because the amino grafting rate is low, this molecular weight range can promote the free stretching of the molecular chain in a benign solvent, which is beneficial to the maleic anhydride and the side chain.
  • the amino group reacts to avoid the incomplete reaction caused by the inability of the molecular chain to stretch freely due to too large a molecular weight.
  • the grafting rate of amino groups in the aminated polysiloxane A is conducive to the grafting of maleimide functional groups with larger steric volumes, avoiding the steric hindrance between maleimide groups.
  • the response is incomplete.
  • the molar ratio of the amino group to the maleic anhydride is favorable for the sufficient reaction between the maleic anhydride and the amino group, avoiding the problem of incomplete reaction.
  • the upper and lower limits of the weight average molecular weight range of the aminated polysiloxane A can be selected from 3000, 5000, 8000, 11000, 14000, 17000 or 19000, respectively.
  • the weight average molecular weight may be 3000, 5000, 8000, 10000 or 15000.
  • the grafting rate of amino groups in the aminated polysiloxane A is 3%-30%. Furthermore, the grafting rate of amino groups in the aminated polysiloxane A is 10%-15%.
  • the molar ratio of the aminated polysiloxane A to the maleic anhydride in terms of amino groups is 1:1.5-2.5.
  • the organic solvent I is glacial acetic acid.
  • the heating reaction temperature is 140-180°C
  • the reflux reaction time is 4-8h, that is, the modified polysiloxane Alkane A.
  • the preparation method of the modified polysiloxane B comprises the following steps:
  • Aminated polysiloxane B is provided;
  • the weight average molecular weight of the aminated polysiloxane B is 2000-20000;
  • the grafting rate of the amino groups in the aminated polysiloxane B is 3%-30%, and the molar ratio of the amino groups to the furoacetyl chloride is 1:1-5; the acid-binding agent and the The mass ratio of aminated polysiloxane B is 3wt%-7wt%.
  • the weight-average molecular weight range of the aminated polysiloxane B is beneficial to the reaction between furoacetyl chloride and the amino side chain in the aminated polysiloxane, and avoids incomplete reaction.
  • the grafting ratio of amino groups in the aminated polysiloxane B is beneficial to the dispersed distribution of amino side chains on the polysiloxane main chain, and avoids the problem of incomplete reaction caused by too concentrated dispersion.
  • the molar ratio of the amino group to the furoyl chloride is conducive to the completeness of the reaction between the furoyl chloride and the side chain amino group, and avoids incomplete reaction.
  • the mass ratio of the acid-binding agent to the aminated polysiloxane B is conducive to the timely adsorption of hydrogen chloride produced by the reaction of acid chlorides and amino groups, and avoids the breakage of polysiloxane chains caused by excessive acidity.
  • the upper limit and the lower limit of the range of the weight average molecular weight of the aminated polysiloxane B can be selected from 3000, 5000, 8000, 11000, 14000, 17000 or 19000 respectively, the specific aminated polysiloxane B
  • the weight average molecular weight may be 3000, 5000, 8000, 10000 or 15000.
  • the grafting rate of amino groups in the aminated polysiloxane B is 3%-30%. Furthermore, the grafting rate of amino groups in the aminated polysiloxane B is 10%-15%.
  • the molar ratio of the aminated polysiloxane B to the furoacetyl chloride in terms of amino groups is 1:1-1.5.
  • the mass ratio of the acid-binding agent to the aminated polysiloxane B is 4wt%-6wt%.
  • the acid-binding agent is at least one selected from pyridine, triethylamine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate and cesium carbonate. More preferably, the acid-binding agent is pyridines.
  • the organic solvent II is at least one selected from anhydrous ether, tetrahydrofuran and dichloromethane.
  • the modified polysiloxane A and modified polysiloxane B are dissolved in the organic solvent III and reacted at a temperature of 150°C-200°C for at least 15h, preferably 24h-48h, to ensure the reaction yield It can reach more than 95%.
  • the molar ratio of modified polysiloxane A based on maleimide group to modified polysiloxane B based on furoacetyl group is 1:1-4.
  • the molar ratio of the modified polysiloxane A based on maleimide groups to the modified polysiloxane B based on furoacetyl groups is 1:2-3.
  • the organic solvent III is selected from one of dimethyl ether, xylene, benzyl alcohol, dicarboxylate and ethyl benzoate.
  • a porous coating material is provided, which is made of any one of the above-mentioned organosilicon polymer materials, or an organosilicon polymer material prepared by any of the above-mentioned methods.
  • an application of a porous film material as a fertilizer coating is provided, wherein the porous film material is selected from any one of the porous film materials described above.
  • any waste that can be granulated including but not limited to urea, NPK compound fertilizer, DAP, medium element fertilizer, biological fertilizer and organic fertilizer.
  • the self-healing organosilicon polymer material of the present application can realize the breaking and crosslinking of crosslinking bonds at a specific temperature, and when used as a coating material, for example, as a fertilizer coating material, the Diels-Alder reaction has Temperature reversibility, the bonding and dissociation characteristics of chemical bonds can be controlled by temperature. If the coating is uneven, the coating treatment can be repeated many times, reducing the defective rate, improving the coating yield, and avoiding the coating The problem of poor fertilizer slow release effect caused by uneven film.
  • the Si-O segment it has has extremely strong hydrophobic properties the reversible crosslinking of maleimide groups and furan acetylation groups is composite Holes are provided inside the material to ensure the slow-release effect of the coated fertilizer.
  • the preparation method of the self-healing silicone polymer material of the present application is constructed by using catalyst-free Diels-Alder reaction between maleimide functionalized and furan acetylated polysiloxane, and there is no catalyst Removal and residual problems, easy post-processing steps.
  • porous film material of the present application it can be industrialized as a coating material, especially as a fertilizer coating material, and has huge economic value and industry influence; it is environmentally friendly and can realize “recycling of polymer materials" ", with great potential for development.
  • Fig. 1 (A) and (B) are respectively the infrared spectrograms of maleimidated polysiloxane A1# and furan acetylated polysiloxane B1# involved in Example 1 of the present application;
  • Fig. 2 (A) and (B) are respectively embodiment 1 and maleimidated polysiloxane A1#, furan acetylated polysiloxane B1# GPC spectrogram;
  • Fig. 3 (A) is the thermogravimetric analysis figure of organosilicon polymer material 1# under nitrogen and air; (B) is the DSC spectrogram of organosilicon polymer material 1#;
  • Fig. 4 is the microstructure schematic diagram of the organosilicon polymer material 1# obtained in embodiment 1;
  • Fig. 5 is the optical performance spectrogram of the organosilicon polymer material 1# obtained in embodiment 1, (A) is the ultraviolet spectrum and (B) is the fluorescence spectrogram;
  • Fig. 6 (A) is the urea granule figure that embodiment 2 uses; (B) is the coated fertilizer 1# photograph behind the organosilicon polymeric material 1# coated urea granules;
  • Fig. 7 is the coated fertilizer 1#-3# slow-release property spectrogram that embodiment 2,4,6 makes respectively in 60d;
  • Fig. 8 is the self-repair diagram of the organosilicon compound fertilizer obtained in Example 2, (A) the 1# shell of the organosilicon polymer material after urea release; (B) the 2# shell of the organosilicon polymer material after the Diels-Alder reverse reaction repair occurred ;
  • Fig. 9 is a schematic diagram of the process and structure of the preparation of the organosilicon polymer material in the embodiment.
  • Hydrocharbyl includes alkyl, alkenyl, alkynyl and aryl.
  • Alkyl means a monovalent aliphatic hydrocarbon group.
  • An alkyl group can have any number of carbon atoms.
  • Many alkyl groups are C1 to C30.
  • Some alkyl groups can be C1 or larger, such as C2 or larger, C4 or larger, C6 or larger, or C8 or larger.
  • Some alkyl groups can be C22 or less, C16 or less, C12 or less, C8 or less, or C4 or less.
  • any alkyl groups may independently be linear, branched, cyclic, or combinations thereof (eg, cyclic alkyl groups may also have linear or branched components.)
  • Exemplary Alkyl includes methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, 2-ethylhexyl, isooctyl, dodecyl, hexadecane base, docosyl group and so on.
  • Aryl refers to a monovalent aromatic group.
  • Aryl groups may include only carbon and hydrogen, or may also include one or more heteroatoms, such as one or more of oxygen, nitrogen, and sulfur.
  • Aryl groups can have an aromatic ring with three or more atoms, four or more atoms, or five or more atoms.
  • Aryl groups can have rings with ten or fewer atoms, eight or fewer atoms, seven or fewer atoms, or six or fewer atoms.
  • Exemplary aryl groups include phenyl, furyl, naphthyl, anthracenyl, and the like. Phenyl is a common aryl substituent.
  • Amino means a group having the formula -Nc(H)p(R')q, wherein each R' is independently an alkyl, alkenyl, alkynyl, aryl, or alkaryl group, any of which One may be optionally substituted, p+q is 2 or 3, and c represents the charge on the nitrogen atom, which is 0 or 1+. Typically, each R' is an alkyl group. When p+q is 2, c is 0; when p+q is 3, c is 1+.
  • the amino group can be primary, secondary, tertiary or quaternary, depending on the value of q. Amino groups with q values of 0, 1, 2 and 3 are primary, secondary, tertiary and quaternary ammonia, respectively.
  • Polydiorganosiloxane refers to a polymer having the repeating unit -Si(G) 2O- , wherein each occurrence of G is independently an organic moiety.
  • G is typically independently alkyl, aryl, alkenyl or alkynyl. Alkyl and aryl are the most common, and alkyl is more common than aryl.
  • G is aryl, it may be any aryl group, for example any group referred to herein by the definition of "aryl”. Typical aryl groups include phenyl.
  • Typical alkyl groups include those discussed with reference to the definition of alkyl herein, and also include C1 to C22 alkyl, C1 to C16 alkyl, C1 to C12 alkyl, C1 to C8 alkyl, or C1 to C4 Alkyl groups such as methyl, ethyl, propyl, butyl (such as tert-butyl, isobutyl, n-butyl and sec-butyl), and C8 alkyl groups such as 2-ethylhexyl and isooctyl.
  • the end groups of polydiorganosiloxanes can vary; typical end groups include triorganosilyl groups and hydroxyl groups, as well as capping, quenching, and chain transfer groups .
  • the raw materials, reagents and fertilizers in the examples of the present application were purchased through commercial channels.
  • the raw material aminated polysiloxane is self-made in the laboratory, using aminopropylmethyldiethoxysilane or 3-(2-aminoethyl)-aminopropylmethyldiethoxysilane and dimethyl Side aminopolysiloxane prepared by hydrolysis of diethoxysilane, prepared by hydrolysis of aminopropyldimethylethoxysilane or 3-(2-aminoethyl)-aminopropyldimethylethoxysilane become.
  • the test method is the method of soaking in water, leaching the coating with water or a certain concentration of salt solution Controlled-release fertilizers to calculate the amount of nutrients dissolved within a certain period of time.
  • the figure shows the process of reversible reaction and thermal self-repair, and the structure diagram of the obtained organosilicon composite material, in which, 1 is the Si-O-Si segment in polysiloxane, and 2 is maleyl Imino group, 3 is furoacetyl, 4 is
  • the preparation method of self-healing silicone polymer material comprises the following steps:
  • Step 1 Preparation of modified polysiloxane A (maleimidated polysiloxane A): Dispersed in 30mL of glacial acetic acid with end aminated polysiloxane A or side amino group with different weight average molecular weight Polysiloxane A and maleic anhydride were placed in a 100mL round bottom flask equipped with an air duct, a constant pressure low liquid funnel and a spherical condenser, heated to 140-180°C under electromagnetic stirring and refluxed for 4-8h.
  • modified polysiloxane A maleimidated polysiloxane A
  • the weight-average molecular weight of aminated polysiloxane A includes but is not limited to 3000, 5000, 10000, and 15000, and the grafting ratio of amino groups in aminated polysiloxane A includes but is not limited to 3%-30%.
  • the molar ratio of maleic anhydride is 1:1-1:3;
  • Step 2 Preparation of modified polysiloxane B (furan acetylated polysiloxane B): Three extractions and three discharges were performed on a 50mL round bottom flask, and then nitrogen was introduced for protection. Terminal amino-modified polysiloxane B or pendant amino-modified polysiloxane B, dissolved in 20mL organic solvent II, and introduced acid-binding agent, the amount of acid-binding agent added is amino-modified polysiloxane B 3%-7% of the mass; after electromagnetic stirring for 15-30min, slowly drop the furoyl chloride dissolved in the organic solvent II into the round bottom flask, the molar ratio of amino group to furoyl chloride is 1:1-1:1.5 , and reacted for 1h-3h under reflux; vacuum distillation and purification were performed to remove the generated salt by suction filtration to obtain a light yellow oily liquid, which was to obtain modified polysiloxane B;
  • the weight-average molecular weight of amino-modified polysiloxane B includes but is not limited to 3000, 5000, 10000, and 15000, and the amino graft ratio of amino-modified polysiloxane B includes but is not limited to 3%-30%.
  • Solvent II includes but not limited to anhydrous ether, tetrahydrofuran, dichloromethane; acid-binding agents include but not limited to pyridine, triethylamine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, cesium carbonate, etc.; organic solvents
  • the volume of furoacetyl chloride in II: the volume (v:v) ratio is 1:5-1:10;
  • Step 3 preparation of silicone polymer material: Dissolve modified polysiloxane A (maleimidated polysiloxane A) and modified polysiloxane B (furan acetylated polysiloxane B) in After the organic solvent III, transfer to a round bottom flask, heat to 150°C-200°C under electromagnetic stirring and react for 24h-48h; after the reaction is completed, pour it into anhydrous methanol solution to obtain a light red precipitate, remove the organic solvent by suction filtration After III, repeatedly wash with anhydrous methanol for several times, and vacuum dry overnight to obtain the organosilicon polymer material;
  • organic solvent III includes but not limited to dimethyl ether, xylene, benzyl alcohol, diformic acid ester, ethyl benzoate Esters etc.
  • the application of the self-healing organosilicon polymer material as a fertilizer coating includes the following steps:
  • Organosilicon polymer material as fertilizer coating process After sieving the fertilizer with sieves of different meshes (10-40 mesh), divide the fertilizer into 50g portions;
  • reaction equations of modified polysiloxane A1# and modified polysiloxane B1# of the present embodiment are as follows respectively
  • the preparation method of self-healing organosilicon polymer material 1# comprises the following steps:
  • modified polysiloxane A1# maleimidated polysiloxane A1#: Aminopropyl-terminated polysiloxane with a weight-average molecular weight of 5000 dispersed in 30 mL of glacial acetic acid Alkanes and maleic anhydride are placed in a 100mL round-bottomed flask equipped with an airway tube, a constant pressure low liquid funnel and a spherical condenser at a molar ratio of amino to maleic anhydride of 1:1, and heated to 140°C under electromagnetic stirring After reflux for 4 hours, the glacial acetic acid was removed under reduced pressure and the residue was dissolved in chloroform, purified and washed several times with saturated aqueous sodium chloride solution, and the organic phase was separated.
  • Modified polysiloxane B1# furan acetylated polysiloxane B1#: the 50mL round-bottomed flask was pumped three times and vented three times, and then passed into nitrogen for protection.
  • the modified polysiloxane A and The Diels-Alder reaction between the modified polysiloxane B is more complete, and the performance of the obtained film is better, and the selected aminopropyl polysiloxane is the same as that selected in A1#.
  • thermogravimetric analysis of organosilicon polymer material 1# under nitrogen and air is shown in Figure 3(A)
  • DSC spectrum of organosilicon polymer material 1# is shown in Figure 3(B)
  • schematic diagram of the microstructure of organosilicon polymer material 1# is shown in Figure 4 .
  • the ultraviolet spectrum of organosilicon composite material 1# is shown in Figure 5(A) and the fluorescence spectrum is shown in Figure 5(B).
  • organosilicon polymeric material 1# of embodiment 1# as the fertilizer coating process: after sieving the urea with a 10-mesh sieve, pack it with 50g as a portion; get a portion of urea in a drum coating machine, adjust The angle of the coating machine is 35°, and the speed is controlled at 40r/m, so that the urea can form a continuous material curtain in the coating machine; preheat after 15 minutes, and the temperature is controlled at about 90°C, so that the surface of the urea particles is in a slightly molten state , spray into the organosilicon polymer material 1# dissolved in dichloromethane solution, the addition amount of the organosilicon polymer material 1# is selected as 1% of the fertilizer mass, and the rotation speed is adjusted during the coating process to prevent mutual adhesion, so that the organosilicon polymerizes Material 1# forms a uniform film on the surface of urea granules to obtain coated fertilizer 1#.
  • Fig. 6(A) is a photo of urea granules
  • Fig. 6(B) is a photo of coated fertilizer 1#.
  • the preparation method of self-repairing organosilicon polymer material 2# comprises the following steps:
  • modified polysiloxane A2# maleimidated polysiloxane A2#
  • the side aminopropyl modified polysiloxane with a weight average molecular weight of 5000 dispersed in 30mL of glacial acetic acid Alkanes and maleic anhydride are placed in the 100mL round-bottomed flask that airway is housed with amino group and maleic anhydride mol ratio as 1:3, amino graft rate 15%, constant pressure low liquid funnel and spherical condenser, in After heating to 160°C under electromagnetic stirring and reflux for 6 hours, the glacial acetic acid was removed under reduced pressure and the residue was dissolved with chloroform, purified and washed several times with saturated aqueous sodium chloride solution, and the organic phase was separated.
  • Modified polysiloxane B2# (furan acetylated polysiloxane B2#): the 50mL round-bottomed flask was pumped three times and discharged three times, and then passed through nitrogen for protection.
  • the side aminopropyl group with a weight average molecular weight of 5000 The modified polysiloxane was dissolved in 20mL of anhydrous ether, the grafting rate of amino group was 15%, and the acid-binding agent triethylamine was added, and the amount of triethylamine added was 5% of the mass of the side aminopropyl modified polysiloxane ; After electromagnetic stirring for 20min, the furoyl chloride dissolved in the organic solvent tetrahydrofuran was slowly dropped into the round-bottomed flask with a volume to mass ratio (mL:g) of 15:1, wherein the molar ratio of amino group to furoyl chloride was 1 :3, after reacting for 2h under the reflux state,
  • organosilicon polymer material 2# Maleimidated polysiloxane A2# and furanacetylated polysiloxane B2# were calculated by maleimide group and furanacetyl group in a molar ratio of 1:2.5 was dissolved in the organic solvent xylene, the volume-to-mass ratio (mL:g) between the solvent and the raw material was 25:1, and transferred into a round bottom flask, heated to 180°C under electromagnetic stirring and reacted for 36h, Then pour it into anhydrous methanol solution to obtain a light red precipitate, remove the solvent by suction filtration, wash with anhydrous methanol several times, and vacuum dry overnight to obtain organosilicon polymer material 2#.
  • mL:g volume-to-mass ratio
  • organosilicon polymeric material 2# of embodiment 3# as the fertilizer coating process: after the urea is sieved with a 39-purpose sieve, it is divided into parts with 50g; get a part of urea in a drum coating machine, adjust The angle of the coating machine is 40°, and the speed is controlled at 60r/m, so that the urea can form a continuous material curtain in the coating machine; preheat after 15 minutes, and the temperature is controlled at about 110°C, so that the surface of the urea particles is in a slightly molten state , spray into the organosilicon polymer material 2# dissolved in dichloromethane solution, the addition amount of the organosilicon polymer material 2# is selected as 1.5% of the fertilizer mass, and the rotation speed is adjusted during the coating process to prevent mutual adhesion, so that the organosilicon polymerizes Material 2# forms a uniform film on the surface of urea granules.
  • the preparation method of the organic silicon polymer material 3# of self-healing comprises the following steps:
  • modified polysiloxane A3# maleimidated polysiloxane A3#: The side aminopropyl modified polysiloxane with a weight average molecular weight of 15000 dispersed in 30mL of glacial acetic acid Alkane and maleic anhydride are placed in the 100mL round-bottomed flask of constant pressure low liquid funnel and spherical condenser with airway tube being housed in the amount of 1:2.5 with amino group and maleic anhydride mol ratio, amino grafting rate 30%.
  • Modified polysiloxane B3# (furan acetylated polysiloxane B3#): the 50mL round-bottomed flask was pumped three times and released three times, and then passed through nitrogen for protection.
  • the side aminopropyl group with a weight average molecular weight of 15000 The modified polysiloxane was dissolved in 20mL of anhydrous ether, the grafting rate of the amino group was 30%, and the acid-binding agent 4-dimethylaminopyridine was added, and the amount of 4-dimethylaminopyridine added was the 5% of the quality of oxane B3#; after electromagnetic stirring for 30min, the furoyl chloride dissolved in the organic solvent methylene chloride of 30:1 was slowly dropped into the round-bottomed flask with a volume to mass ratio (mL:g), The molar ratio of amino group to furoacetyl chloride is 1:5. After reacting under reflux for 3 hours, remove the generated salt
  • organosilicon polymer material 3# Maleimidated polysiloxane A3# and furanacetylated polysiloxane B3# were calculated by maleimide group and furanacetyl group in molar ratio of 1:3 dissolved in the organic solvent benzyl alcohol, the volume-to-mass ratio between the solvent and the raw material (mL:g) is 30:1, and transferred to a round bottom flask, heated to 200°C under electromagnetic stirring and reacted for 48h , and then poured into anhydrous methanol solution to obtain a light red precipitate. After the solvent was removed by suction filtration, it was repeatedly washed with anhydrous methanol several times, and vacuum-dried overnight to obtain organosilicon polymer material 3#.
  • organosilicon polymer material 3# of embodiment 5# as the fertilizer coating process: after the urea is sieved with a 40-mesh sieve, 50g is used as a portion to pack respectively; get a portion of urea in a drum coating machine, adjust The angle of the coating machine is 45°, and the speed is controlled at 80r/m, so that the urea can form a continuous material curtain in the coating machine; preheat after 15 minutes, and the temperature is controlled at about 110°C, so that the surface of the urea particles is in a slightly molten state , spray into the organosilicon polymer material 3# dissolved in dichloromethane solution, the addition amount of the organosilicon polymer material 3# is selected as 2% of the fertilizer mass, and the rotation speed is adjusted during the coating process to prevent mutual adhesion, so that the organosilicon polymerizes Material 3# forms a uniform film on the surface of urea granules.
  • Example 7 The slow-release performance test of coated fertilizer 1-3#
  • Example 3 has a better slow-release effect than 1 and 2, and the cumulative release rate within 28 days has not exceeded 80%, which has met the requirements of slow-release fertilizers.
  • the coated fertilizer prepared by the present application has a slow slow release rate, can maintain nutrients and can be fully absorbed by crops, has a low fertilizer loss rate, and greatly improves the fertilizer utilization rate, thereby avoiding excessive application of fertilizers.
  • the prepared coated fertilizers 1#, 2# and 3# did not exceed 80% of the cumulative nitrogen release rate in 28 days, which has reached the requirements of GB/T 23348-2009, and the coated fertilizer 3# accumulated nitrogen in 28 days
  • the release rate is lower than 1#, 2# and commercially available products, indicating that the slow-release effect of coated fertilizer 3# is better.
  • Fig. 8(A) is the shell surface of the organosilicon composite material after the nutrient release of the prepared coated fertilizer 1#. It can be seen from Fig. 8(A) that the organosilicon composite material can form a shell with holes on the surface of the fertilizer, but as the nutrients After release, the surface may collapse and create debris around it.
  • Figure 8(B) shows the 2# shell of the organic silicon composite material repaired by the Diels-Alder reverse reaction after the conditioned treatment of the coated fertilizer 3# material.
  • coated fertilizers 4#-10# and contrast coated materials D1#-D2# were respectively tested using the test method of Example 7
  • the 28-day cumulative nitrogen release rate and the repairable times of the coating material are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

L'invention concerne un matériau polymère organosilicié auto-cicatrisant, son procédé de préparation et son utilisation, se rapportant au domaine des matériaux composites. Le matériau polymère organosilicié auto-cicatrisant est obtenu par réticulation et polymérisation d'au moins un cyclohexène substitué de manière réversible généré après une réaction de Diels-Alder sur un polysiloxane modifié A et un polysiloxane modifié B, le polysiloxane modifié A étant un polysiloxane A substitué par au moins un groupe maléimide, et le polysiloxane modifié B étant un polysiloxane B substitué par au moins un groupe furane acétyle. Le matériau composite organosilicié présente de bonnes propriétés hydrophobes, une bonne perméabilité, de bonnes propriétés de formation de film et une bonne aptitude à la réutilisation ; le matériau composite organosilicié est bénéfique pour améliorer l'effet de libération lente d'un engrais lorsqu'il est appliqué à un matériau de revêtement de l'engrais chimique, a un avantage remarquable dans la réduction de la quantité d'utilisation du matériau de revêtement, et a un effet positif sur la protection de l'environnement.
PCT/CN2021/117480 2021-09-07 2021-09-09 Matériau polymère organosilicié auto-cicatrisant, son procédé de préparation et son utilisation WO2023035192A1 (fr)

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WO2024090189A1 (fr) * 2022-10-27 2024-05-02 信越化学工業株式会社 Composition de résine de silicone durcissable qui est recyclable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111470A (zh) * 2015-08-13 2015-12-02 四川大学 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用
CN109852241A (zh) * 2019-02-01 2019-06-07 哈尔滨工业大学 一种耐热自修复聚硅氧烷-环氧树脂复合材料涂层及其制备方法
CN110218330A (zh) * 2019-06-18 2019-09-10 刘涛 一种自修复改性硅橡胶及其制备方法
US20190315934A1 (en) * 2018-04-11 2019-10-17 Paul M. Zelisko Self-healing siloxane elastomers
CN113336604A (zh) * 2021-06-15 2021-09-03 山东农业大学 一种可回收的自修复弹性生物基包膜材料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19652544A1 (de) * 1996-12-17 1998-06-18 Wacker Chemie Gmbh Härtbare Organosiloxanmassen
CN110092911B (zh) * 2018-01-31 2021-01-19 天津大学 基于Diels-Alder反应的聚硅氧烷弹性体材料在自修复材料中的应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111470A (zh) * 2015-08-13 2015-12-02 四川大学 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用
US20190315934A1 (en) * 2018-04-11 2019-10-17 Paul M. Zelisko Self-healing siloxane elastomers
CN109852241A (zh) * 2019-02-01 2019-06-07 哈尔滨工业大学 一种耐热自修复聚硅氧烷-环氧树脂复合材料涂层及其制备方法
CN110218330A (zh) * 2019-06-18 2019-09-10 刘涛 一种自修复改性硅橡胶及其制备方法
CN113336604A (zh) * 2021-06-15 2021-09-03 山东农业大学 一种可回收的自修复弹性生物基包膜材料及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIU, YINGYING: "Design, Synthesis and Applications of Linear Polysiloxane Based Functional Silicone Materials", SCIENCE-ENGINEERING (A), CHINA DOCTOR’S THESES FULL-TEXT DATABASE, 15 August 2020 (2020-08-15), CN, pages 1 - 150, XP009544431, DOI: 10.27272/d.cnki.gshdu.2020.000005 *
YAN, QIAN: "Preparation and Properties of the Self-healing Silicone Polymer Based on Multiple Reaction", CHINESE MASTER'S THESES FULL-TEXT DATABASE, ENGINEERING TECHNOLOGY I, 15 February 2020 (2020-02-15), pages 1 - 85, XP009544411 *
ZHAO JIAN, XU RUI, LUO GAOXING, WU JUN, XIA HESHENG: "A self-healing, re-moldable and biocompatible crosslinked polysiloxane elastomer", JOURNAL OF MATERIALS CHEMISTRY. B, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 4, no. 5, 1 January 2016 (2016-01-01), GB , pages 982 - 989, XP093046965, ISSN: 2050-750X, DOI: 10.1039/C5TB02036K *

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