Coated agrochemical compositions
阅读说明：本技术 包衣农业化学品组合物 (Coated agrochemical compositions ) 是由 E·特卡利亚 R·P·J·戈森斯 S·T·K·西斯特曼斯 M·E·J·亨德里克斯 M·A·F 于 2018-10-30 设计创作，主要内容包括：本发明涉及一种包衣组合物,其包含通过含有聚硫醇的单体与含有一个或多个不饱和碳-碳键的单体的化学反应形成的加合物；更具体地涉及用所述包衣组合物包衣的农业化学品组合物。(The present invention relates to a coating composition comprising an adduct formed by a chemical reaction of a polythiol-containing monomer and a monomer containing one or more unsaturated carbon-carbon bonds; more particularly, to agrochemical compositions coated with said coating compositions.)
1. A biodegradable controlled release agrochemical composition comprising an agriculturally active material encapsulated with a coating composition, wherein the coating composition comprises an adduct formed by a chemical reaction of a monomer a containing a component having at least two mercaptoalkanoate groups with a monomer B containing a component having an ester moiety and an unsaturated carbon-carbon bond.
2. The biodegradable controlled release agrochemical composition according to claim 1 wherein said coating composition exhibits a controlled material release rate wherein greater than 75% by weight of the initial weight of said material is released from said coating agrochemical composition 30 days or more from the date of initial exposure of said material to moisture or water.
3. The biodegradable controlled release agrochemical composition according to claim 1 or 2, wherein said coating composition has a biodegradation of at least about 16% over a period of about 10 to 24 months.
4. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the coating composition is adapted such that, after the initial contact of the coated agrochemical composition with water, at ambient temperature, preferably 25 ℃, no more than 15 wt.% of the agriculturally active material is released in the first 24 hours, no more than 75 wt.% of the material is released in 28 days, and at least 75 wt.% of the material is released in 30 days or longer.
5. The biodegradable, controlled release agrochemical composition according to any of the preceding claims, wherein monomer a comprises a compound having 2 to 8 mercaptoalkanoate groups and having a molecular weight of 200 to 2000g/mol and a melting point below 60 ℃.
6. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the monomer a comprises a component represented by the following structural formula:
D—R1d or
Wherein D is represented by the structure:
X1is a straight or branched aliphatic carbon chain of 1 to 20 carbon atoms;
R1represented by the following structure:
wherein Z is selected from the group consisting of: o, S, NH, N-methyl, N-ethyl, N-propyl and N-isopropyl, and wherein the wavy line is indicated by the symbols
7. The biodegradable, controlled release agrochemical composition according to any of the preceding claims, wherein the monomer a comprises a component selected from the group consisting of: GDMA, TMPTMA, PETMA, PETMP, TMPTMP, GDMP, and any combination thereof.
8. The biodegradable, controlled-release agrochemical composition according to any of the preceding claims, wherein the monomer a comprises PETMA.
9. The biodegradable, controlled release agrochemical composition according to any of the preceding claims, wherein the monomer B comprises a component having 2 to 50 ester groups and 2 to 8 unsaturated carbon-carbon double bonds and having a molecular weight of 200 to 5000g/mol, a melting point below 60 ℃.
10. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the monomer B comprises a component represented by the following structure:
F-R2or F-R2-F or
Wherein F is represented by the structure:
X2is a polyester and a polyester resin, and the polyester resin,
y is H or CH3；
R2Represented by the following structure:
wherein Z is selected from the group consisting of: o, S, NH, N-methyl, N-ethyl, N-propyl and N-isopropyl, and wherein the wavy line is indicated by the symbols
11. The biodegradable, controlled release agrochemical composition according to any of the preceding claims, wherein the monomer B further comprises a cyclopentane and/or cyclohexane moiety.
12. The biodegradable, controlled-release agrochemical composition according to any of the preceding claims, wherein the monomer B has a general structure represented by:
X-R2or X-R2-X or
Wherein X is represented by the formula:
y ═ H or CH3，
m is 0 to 20, optionally 1-10;
R3represented by the following structure:
n is an integer of 0 to 20,
R4represented by the following structure:
or HC ═ CH or
p is an integer of 0 to 20,
q is an integer of 0 to 34,
R2represented by the following structure:
wherein Z is selected from the group consisting of: o, S, NH, N-methyl, N-ethyl, N-propyl and N-isopropyl, and wherein the wavy line is indicated by the symbolsRepresents a bond to X.
13. The biodegradable, controlled release agrochemical composition according to any of the preceding claims, wherein the monomer B comprises a 5 or 6 membered cycloalkyl moiety having at least 2 (meth) acrylate end groups, or a 5 or 6 membered cycloalkyl moiety separated by 1 to 9 ester linkages, and having at least 2 acrylate or methacrylate end groups.
14. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the monomer B comprises a component represented by the following structure:
wherein r is an integer from 0 to 20, optionally an integer from 1 to 10;
y is H or CH3；
And/or a component represented by the structure:
wherein m is an integer from 0 to 20, optionally an integer from 1-10;
q is an integer from 0 to 34, optionally an integer from 1-4,
y ═ H or CH3。
15. The biodegradable, controlled-release agrochemical composition according to any of the preceding claims, wherein the adduct is formed by a chemical reaction of PETMA with monomer B comprising a component represented by the following structure:
wherein
r is an integer from 0 to 20, optionally an integer from 0 to 10;
y is H or CH3；
And/or a component represented by the structure:
wherein m is an integer from 0 to 20, optionally an integer from 1-10;
q is an integer from 0 to 34, optionally an integer from 1-4,
y ═ H or CH3。
16. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the adduct is formed by a chemical reaction of monomer a with monomer B, wherein the monomer B comprises a component having a structure represented by:
R2-G or G-R2-G or
Wherein G is represented by the formula:
y ═ H or CH3；
R5Is thatOr (CH)2)s；
n is an integer of 0 to 20;
s is an integer from 2 to 36;
t is an integer of 0 to 20;
X3＝O、NH、S、CH2；
R6represented by the following structure:
R6sign of wavy line
R2represented by the following structure:
wherein Z is selected fromIn the following group: o, S, NH, N-methyl, N-ethyl, N-propyl and N-isopropyl, and wherein the wavy line is indicated by the symbolsRepresents a bond to G.
17. The biodegradable controlled release agrochemical composition according to any of the preceding claims, wherein the core material is selected from the group consisting of: fertilizers, nitrification inhibitors, denitrification inhibitors, urease inhibitors, pesticides, herbicides, bactericides, pheromones, biostimulants, growth regulators, and mixtures thereof.
Technical Field
The present invention generally relates to a coating composition comprising an adduct formed by a chemical reaction of a polythiol-containing monomer and a monomer containing one or more unsaturated carbon-carbon bonds; more particularly, the present invention relates to agrochemical compositions coated with said coating composition.
Background
The use of controlled release fertilizer compositions to provide nutrients in a culture substrate is well known. Controlled Release Fertilizers (CRF) are generally defined as fertilizer granules with a coating, usually a polymer coating, to control the penetration of moisture into the fertilizer and its release. It is well known that CRF is a very effective source of nutrients to growing plants because the nutrients are released at a controlled rate, thereby achieving sustained feeding of the plant. One application of CRF can provide the necessary nutrients that can be provided using an uncoated fertilizer requiring multiple uses.
Recent developments in european legislation require fertilizer coating compositions with controlled release properties in order to additionally have biodegradability properties. For example, the EU Committee has set forth a requirement in its EU regulatory draft (2016. 3.month) for CE-tagged fertilizer products that the polymer coating be capable of physical, biological decomposition such that most of it is ultimately decomposed to carbon dioxide (CO)2) Biomass, and water.
Currently available CRFs on the market have polymeric coating compositions based on alkyd chemistry, crosslinked vegetable oils (GB954555A, US3223518A, US4657576A), polyolefins (US4019890A), or polymeric coating compositions based on reactive monomers like polyurethanes (US4772490A, US 5538531A). Biodegradation of such coating compositions is very slow (Terlingen et al, Proceedings International Fertizer Society 781,1-24(2016)) and does not comply with European Union regulations.
US7989655B2 and US7713326B2 describe mercaptide compositions and methods of making and using them on controlled release fertilizers. It describes the preparation of thiol ester compositions from synthetic unsaturated esters and thiols by free radical initiation. The thiol ester composition reacts with the isocyanate to form a polythiourethane coated controlled release fertilizer. It is known to those skilled in the art that the resulting polythiourethane coating is not biodegradable due to the resistance of the thiourethane linkages to hydrolysis.
US5645624A describes applying a first layer of polylactic acid (PLA) from a solvent, followed by a top coating of a water insoluble slow degrading material (e.g. wax). After 4.5 months of soil burial, hardly any visual biodegradation of the 2-layer coating was visible.
US 9266787B2 follows a similar process, coating fertilizer granules with PLA oligomers obtained from a melt and wax top layer. However, a nutrient release test in water at 20-25 ℃ for 2 hours showed that urea release at the coating level of 2.3% PLA and 1% polyvinyl acetate was between 5% and 80%, and urea release at the coating level of 4.7% PLA and 2% paraffin was between 7% and 70%, with a wide variation. Furthermore, no biodegradation is shown.
EP931036 describes polyester dispersions in water based on aliphatic and aromatic units (e.g. 1, 4-butanediol with adipic acid and terephthalic acid) for coating fertilizer granules. The examples show 25-35% fertilizer release over 7 days, but the amount of coating is not disclosed. Furthermore, no information is given about biodegradation, but it is expected that such polyester-based coatings are comparable to the alkyd coatings described above.
US6503288B1 discloses a method for biodegradable polyurethane encapsulated fertilizer granules. However, biodegradability is not described. Furthermore, it is well known that polyurethane coatings are difficult to biodegrade by microorganisms (see, for example, N.Mahajan, P.Gupta: "New insights into the microbial degradation of polyurethanes", RSC adv.,2015,5, 41839). In addition, the barrier properties of the coating were poor and 11% of the fertilizer was released from the fertilizer with 12% coating after 20 hours of standing in water at room temperature.
Accordingly, there is a need in the agrochemical industry for a biodegradable coating composition for application to fertilizer granules that provides sufficient moisture protection to achieve the desired controlled release nutrient characteristics.
In particular, it is desirable to produce coated agrochemical compositions wherein their coating or the entire coated agrochemical composition has the desired biodegradation properties and at the same time the desired mechanical properties to provide a controlled release over a desired period of time.
More specifically, it is desirable to produce coated particulate fertilizer compositions to have desirable biodegradation properties and controlled nutrient release properties over a desired period of time.
The present invention provides such coating compositions, coated agrochemical compositions, CRFs, and methods of making the same that address one or more of the problems set forth above. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
Drawings
The features and advantages of the present invention will be understood with reference to the following drawings, in which:
FIG. 1 shows the controlled release of nutrients at 21 ℃ for fertilizer granules coated with the reaction product of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) and polyester-acrylate-1 (coating according to the present invention).
Figure 2a shows the pH of the polymer film used in the product of figure 1 as a function of time. The polymer film was immersed in water at 58 ℃ and the pH of the surrounding water was measured periodically over 15 days.
Fig. 2b shows the change in conductivity over time. The polymer film was immersed in water at 58 ℃ and the conductivity of the surrounding water was measured periodically over 15 days.
FIG. 3 shows the biodegradation curves of the reaction product of ethylene glycol bis (2-mercaptoacetate) (GDMA) and polyester-acrylate-1 (polymer according to the invention) and of the reaction product of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) and polyester-acrylate-1 (coating according to the invention). Biodegradation was measured according to ISO 14855 under domestic composting conditions at 28 ℃.
Detailed Description
In one aspect of the invention, there is provided a biodegradable coating composition having a controlled release rate. The coating composition of the present invention comprises an adduct formed by the chemical reaction of monomer a comprising a component having at least two mercaptoalkanoate groups with monomer B comprising a component having one or more ester moieties and an unsaturated carbon-carbon bond.
In a preferred embodiment, the coating composition exhibits a biodegradation of at least about 16% over a period of about 10 to 24 months, preferably measured according to ISO 14855 (which is part of CEN method EN 13432), ASTM D-5338.98, ISO17556, ASTM D5988, UNI 11462 or NF U52-001 at an ambient temperature of 20-28 ℃, and wherein the coating composition is adapted to have a controlled release rate. The thickness and dosage form of the coating composition of the present invention is sufficient to act as a controlled release protective layer for the fertilizer.
As used herein, the term "adduct" is a chemical reaction product formed from reactants (e.g., components of monomer a and monomer B). The adducts are novel compounds having different entities from the reactants. The chemical reaction may be carried out, for example, by a michael addition reaction or a radical polymerization reaction.
As used herein, the term "monomer" generally includes monomers that are capable of covalently attaching to a growing polymer chain in a chemical process such as a michael addition reaction or a free radical polymerization reaction. The term also includes monomers that can affect polymer chain growth, as well as monomers that can affect chain growth and branching. The term "monomer" also includes mixtures of different specific monomer species. Such mixtures are well known to those skilled in the art and the specific proportions of monomers having functional groups are routinely employed depending on the degree of branching desired.
As used herein, the terms "biodegradable," "biodegradability," and the like refer to the decomposition of a coating composition by a microorganism in the presence of oxygen into carbon dioxide, water, and mineral salts of any other elements present (mineralization) and new biomass. For certain polymer systems, biodegradation begins with hydrolysis of the polymeric chain, wherein carboxylic acids and alcohols are formed.
The biodegradation rate can be measured by various known methods according to various standards. For example, the biodegradation rate of the coating compositions of the invention is determined according to ISO 14855-, ASTM D5988-12 (method for determining aerobic biodegradation of plastic materials in soil), UNI 11462-. All of the above standardization methods are incorporated herein by reference in their entirety.
For example, the coating composition or coated agrochemical composition (e.g., coated granular fertilizer composition) is mixed with soil. The mixture was allowed to stand in the flask for a period of time during which the amount of oxygen consumed (biological oxygen demand (BOD)) or the amount of carbon dioxide released was determined. If CO is released2Absorbed, BOD can then be determined by: for example, measuring the amount of oxygen required to maintain a constant volume of gas in a spirometer flask, or automatically or manually measuring changes in volume or pressure (or a combination of both methods). The amount of carbon dioxide released is measured in terms of the time interval of the biodegradation kinetics of the substance to be measured by flowing carbon dioxide-free air through the soil and then determining the carbon dioxide content of the air by known methods. BOD is compared to the theoretical oxygen demand (ThOD: maximum theoretical amount of oxygen required to fully oxidize the chemical compound, calculated from the molecular formula), or the amount of carbon dioxide released is compared to the theoretical amount (ThCO 2: maximum theoretical amount of carbon dioxide released after fully oxidizing the chemical compound, calculated from Total Organic Carbon (TOC)Quantitative calculations) were compared and the level of biodegradation (expressed as a percentage) was determined. The test was terminated when a constant level of biodegradation was reached within a certain number of months.
The coating composition prepared with the monomer of the present invention exhibits "biodegradability", and the like, which terms refer to biodegradability under specified conditions satisfying at least the following criteria: at least about 16% biodegradation of the coating composition and/or agrochemical composition coated with the coating composition is achieved over a period of about 10 to 24 months. Such biodegradation can be measured at ambient temperatures of 20 ℃ to 28 ℃ according to test methods such as ISO 14855, ISO17556, ASTM D5988, UNI 11462 or NF U52-001.
Preferably, the present invention provides a coating composition and/or an agrochemical composition having the coating composition, which biodegrades at least about 16%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% within a period of about 10 to 24 months, optionally about 10 months, about 11 months, about 12 months, about 13 months, about 14 months, about 15 months, about 16 months, about 17 months, about 18 months, about 19 months, about 20 months, about 21 months, about 22 months, about 23 months or about 24 months, optionally obtained at an ambient temperature of 20 ℃ to 28 ℃.
Preferably, the coating composition and/or agrochemical composition with the coating composition exhibits at least about 40% minimal biodegradation over 10-24 months, even more preferably about 90% biodegradation over 10-24 months.
As used herein, the term "about" refers to any value within a range defined by a variation of up to ± 10% of the value.
As used herein, the term "release" according to the present invention refers to the transfer of material (e.g., nutrients, fertilizers) from the coated agrochemical composition to a receiving medium (e.g., soil or water). Coatings prepared with the monomers of the present invention exhibit "controlled release rate", "controlled release characteristics", comply with "controlled release standards", and the like, which terms refer to release under specified conditions that satisfy at least the following conditions:
(1) no more than 15 weight percent (wt.%) of core material is released from the coated agrochemical composition within the first 24 hours after initial contact of the coated agrochemical composition with moisture or water at ambient temperature (temperature between 20 ℃ and 28 ℃); and
(2) no more than 75 weight percent (wt.%) of the core material is released from the coated agrochemical composition within 28 days after initial contact of the coated agrochemical composition with moisture or water at ambient temperature; and
(3) at least 75 weight percent (wt.%), optionally at least 80 wt.% or at least 90 wt.% of the core material is released from the coated agrochemical composition at a predetermined time, preferably at 30 days or more, after initial contact of the coated agrochemical composition with moisture or water at ambient temperature.
As used herein, the term "longevity" defines the time between 30 days of initial contact of a material with moisture or water and the time of release of about 75 weight percent (wt.%) of a material such as a fertilizer, insecticide, herbicide, fungicide, pheromone, biostimulant, growth regulator, and the like, and mixtures thereof. The method of determining the release of materials such as fertilizers from the coated agrochemical compositions of the present invention is preferably performed according to NEN-EN 13266, month 11 2001, the entire contents of which are incorporated herein by reference.
Preferably, monomer a comprises a compound having at least two mercaptoalkanoate groups. Preferably, the monomer A includes a compound having a linear or branched alkyl polythioalkanoate, a linear or branched alkylene oxide polythioalkanoate, or a polyester polythioalkanoate.
Typically, the number of mercaptoalkanoate groups of monomer A is from 2 to 8, preferably from 2 to 6, even more preferably from 2 to 4. It is to be understood that commercially available monomers may be a mixture of compounds and the average number of mercaptoalkanoate groups in the monomer mixture may be about 3, meaning that about half of the molecules in the mixture have 2 mercaptoalkanoate groups and half have 4 mercaptoalkanoate groups.
The molecular weight of the monomers A is preferably from 200 to 2000g/mol, preferably from 200 to 1000 g/mol. Preferably, the melting point of monomer A is below 60 degrees Celsius (. degree. C.), preferably below 50 degrees Celsius.
Preferably, the monomer a of the present invention comprises a component represented by the following structure:
D-R1-D or
Wherein the content of the first and second substances,
d is represented by the following structure:
X1is a straight or branched aliphatic carbon chain of 1 to 20 carbon atoms;
R1represented by the following structure:
wherein, Z is O, S, NH, N-methyl, N-ethyl, N-propyl, N-isopropyl.
Wavy line symbol
R1Typically containing from 2 to 36 carbon atoms and from 0 to 5 oxygen, from 0 to 3 nitrogen or alkylated nitrogen, or from 0 to 3 sulfur atoms. Preferably, R1Containing 2 to 10 carbon atoms and 0 to 1 oxygen or nitrogen atom.
Preferably, monomer a comprises commercially available ethylene glycol bis (2-mercaptoacetate) (GDMA) represented by the structure:
preferably, monomer a comprises commercially available trimethylolpropane tris (2-mercaptoacetate) (TMPTMA) represented by the following structure:
preferably, monomer a comprises commercially available pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) represented by the following structure:
preferably, monomer a comprises commercially available pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) represented by the structure:
preferably, monomer a comprises commercially available trimethylolpropane tris (3-mercaptopropionate) (tmptmptmptm) represented by the structure:
preferably, monomer a comprises commercially available ethylene glycol bis (3-mercaptopropionate) (GDMP) represented by the structure:
preferably, the monomer B of the present invention comprises a component having an ester moiety and an unsaturated carbon-carbon bond. Preferably, the monomers B of the present invention comprise a component having at least two ester moieties. Typically, monomer B comprises a component having at least two unsaturated carbon-carbon double bonds to provide a polymer with monomer a. Alternatively, the unsaturated carbon-carbon bond of the monomer B component comprises a (meth) acrylate and/or maleate functionality.
Generally, the number of unsaturated groups of monomer B is from 2 to 8, preferably from 2 to 6, even more preferably from 2 to 4. It is to be understood that commercially available monomers may be a mixture of compounds and the average number of unsaturated groups in the monomer mixture may be about 2.5, meaning that about half of the molecules in the mixture have 2 unsaturated groups and half have 3 unsaturated groups.
Generally, the number of ester groups of monomer B is from 2 to 50, preferably from 2 to 20, even more preferably from 2 to 8. The molecular weight of the monomers B is preferably from 200 to 5000g/mol, preferably from 200 to 2000 g/mol. Preferably, the melting point of monomer B is less than 60 ℃, preferably less than 50 ℃.
Preferably, monomer B of the present invention comprises a component having a general structure represented by:
F-R2or F-R2-F or
Wherein the content of the first and second substances,
f is represented by the following structure:
X2is an oligomer or polyester, optionally formed by the following chemical reaction of 1) with 2): 1) c2To C36A linear, branched or cycloaliphatic polyacid which may contain one or more unsaturated carbon-carbon bonds, amide bonds, urea bonds, urethane bonds, ester bonds, carbonate bonds, ether bonds or mixtures thereof, and 2) C2To C36The linear, branched or cycloaliphatic polyols of (a), which may contain one or more unsaturated carbon-carbon bonds, amide bonds, urea bonds, urethane bonds, carbonate bonds, ether bonds; or by lactones having 4 to 8 carbon atomsOr by the chemical reaction of a straight or branched chain hydroxyalkanoic acid having from 2 to 8 carbon atoms.
Y is H or CH3；
R2Represented by the following structure:
wherein Z is O, S, NH, N-methyl, N-ethyl, N-propyl, N-isopropyl
Wavy line symbol
Preferably, monomer B comprises a component having a functionalized caprolactone represented by the following structure:
wherein the content of the first and second substances,
n is an integer greater than 1, optionally an integer between 1 and 50;
y is H or CH3；
R1Represented by the following structure:
wherein Z is O, S, NH, N-methyl, N-ethyl, N-propyl, N-isopropyl
Wavy line symbol
Preferably, monomer B comprises a component having an ester moiety, a cyclopentane and/or cyclohexane moiety, and an unsaturated carbon-carbon bond.
Preferably, monomer B comprises a component having a 5-or 6-membered cycloalkyl moiety with at least 2 (meth) acrylate end groups, or a component having a 5-or 6-membered cycloalkyl moiety separated by 1-9 ester linkages, and having at least 2 acrylate or methacrylate end groups.
Preferably, monomer B of the present invention comprises a component having a general structure represented by:
X-R2or X-R2-X or
Wherein X is represented by the following formula
Y ═ H or CH3；
m is an integer from 0 to 20, preferably from 1 to 10;
R3represented by the following structure:
n is an integer from 0 to 20, preferably from 1 to 4;
R4represented by the following structure:
or HC = CH or C ≡ C or (CH)2)q
p is an integer from 0 to 20, preferably from 1 to 4;
q is an integer of 0 to 34,
R2by being provided withThe following structure represents:
wherein Z is O, S, NH, N-methyl, N-ethyl, N-propyl, N-isopropyl
R2Sign of wavy line
In one embodiment, monomer B comprises a component represented by the following structure:
wherein the content of the first and second substances,
r is an integer from 0 to 20, preferably from 1 to 10;
y ═ H or CH3。
In one embodiment, monomer B comprises a component represented by the following structure:
m is an integer of 0 to 20, preferably 1 to 10;
q is an integer from 0 to 34, preferably from 1 to 4,
y ═ H or CH3。
In one embodiment, the present invention provides a coating composition comprising an adduct formed by a chemical reaction of PETMA with monomer B, as shown in the following structure:
wherein the content of the first and second substances,
r is an integer from 0 to 20, optionally from 1 to 10;
y ═ H or CH3，
Wavy line symbolIndicating the bond formed between the thioglycolate group in PETMA and the unsaturation in monomer B.
In another embodiment, the present invention provides a coating composition comprising an adduct formed by a chemical reaction of PETMA and monomer B, said monomer B being represented by the structure:
m is an integer from 0 to 20, optionally from 1 to 10;
q is an integer from 0 to 34, optionally from 1 to 4;
y ═ H or CH3，
Wavy line symbolIndicating the bond formed between the thioglycolate group in PETMA and the unsaturation in monomer B.
In one embodiment, the molar ratio of the mercaptoalkanoate groups in monomer A to the unsaturated groups in monomer B is from 0.5:1.5 to 1.5:0.5, preferably from 0.9:1.1 to 1.1:0.9, for example, about 1: 1. In the nonstoichiometric case, an excess of unsaturated groups, for example, 0.9:1.1, is preferred.
Preferably, monomer B of the present invention comprises a component having a general structure represented by:
R2-G or G-R2-G or
Wherein G is represented by the formula:
y ═ H or CH3；
R5Is thatOr (CH)2)s；
n is an integer of 0 to 20;
s is an integer from 2 to 36;
t is an integer of 0 to 20; alternatively an integer from 1 to 10;
X3＝O、NH、S、CH2；
R6represented by the following structure:
R6sign of wavy line
R2represented by the following structure:
wherein Z is O, S, NH, N-methyl, N-ethyl, N-propyl, N-isopropyl
R2Sign of wavy line
Preferably, the adduct of the present invention is formed by chemical reaction of monomer a with monomer B, monomer a comprising a component selected from the group consisting of: GDMA, TMPTMA, PETMA, PETMP, TMPTMP, GDMP, and any combination thereof. For example, the adduct may be formed by the reaction of monomer a comprising PETMA with monomer B according to any one of the embodiments of the present invention.
Preferably, monomer B comprises a mixture of monomer species. For example, monomer B includes a mixture of monomer B comprising a 5-or 6-membered cycloalkyl moiety and another monomer B not comprising a 5-or 6-membered cycloalkyl moiety, i.e., monomer B may be a mixture of two or more monomers having the same or different substituents as described above.
The composition used for preparing the coating comprising monomers A and B may comprise further unsaturated compounds which typically have 1-5 unsaturated groups and have a molecular weight of about 100-2000g/mol, preferably 150-1000 g/mol. The other monomer may act as a plasticizer, lowering the melting point of one of the monomers.
Examples of other monomers include unsaturated or modified unsaturated vegetable oils (e.g., soybean oil, linseed oil, castor oil, olive oil, peanut oil, safflower seed oil, fish oil, tung oil, cottonseed oil, canola oil, rapeseed oil, sunflower oil, etc.), alkenes and polyalkenes, alkynes and polyacetenes, linear or branched alkyl di (meth) acrylates, linear or branched alkyl tri (meth) acrylates or linear or branched alkyl tetra (meth) acrylates, cycloalkyl-di (meth) acrylates, cycloalkyl-tri (meth) acrylates or cycloalkyl-tetra (meth) acrylates, linear or branched alkylene oxide-di (meth) acrylates, linear or branched alkylene oxide-tri (meth) acrylates or linear or branched alkylene oxide-tetra (meth) acrylates, dialkyl acetylenedicarboxylates, castor oil modified with one, two, three or more (meth) acrylate groups, castor oil modified with one, two, three or more vinyl or allyl groups, aliphatic polyesters having 2 or more (meth) acrylate, vinyl or allyl groups, aliphatic copolyesters having 2 or more (meth) acrylate, vinyl or allyl groups, aliphatic polyethers having 2 or more (meth) acrylate, vinyl or allyl groups, polyesters containing unsaturated monomers such as maleic acid, fumaric acid, citraconic acid, itaconic acid, acetylenic acid, optionally with acetate, propionate, butyrate, valerate, hexanoate, octanoate, decanoate, 1-undecanoate, dodecanoate, tetradecanoate, oleate, palmitate, stearate, Behenate (behenate), (meth) acrylate, vinyl or allyl groups.
In another aspect of the invention, there is provided a process for preparing the adduct according to any of the preceding embodiments.
The term "polymerization" refers to a process of chemically reacting a monomer compound according to any of the preceding embodiments to form a polymer chain. The type of polymerization process may be selected from a variety of processes. Such methods include, but are not limited to, free radical polymerization methods and reaction methods by Michael Addition.
"Polymer" resulting from the polymerization process includes homopolymers and/or non-homopolymers. The term "non-homopolymer" refers to a polymer formed from two or more polymerizable monomers and includes substantially all polymers that are not homopolymers.
In one embodiment, monomer a reacts with monomer B according to any one of the embodiments by free radical polymerization to form a linear polymer or a crosslinked network. The term "free radical polymerization" or the like means that the monomers of the present invention can be polymerized in a chemical process such as free radical polymerization initiated by thermal or photo initiators. Such chemistry is known to those skilled in the art, and the monomers of the present invention can be free-radically polymerized conventionally by free-radical polymerization methods. See, for example, Thiol-Ene Click Chemistry; charles e.hoyleand Christopher n.bowman; int. ed.,2010,49, 1540-assistance 1573, which is incorporated herein by reference in its entirety.
A "free radical initiator" is a compound that is capable of generating free radical species and thereby promoting free radical reactions. Free radical initiators generally have bonds with low bond dissociation energy. Free radical initiators are particularly suitable for polymer synthesis.
The free radical initiator of the present invention includes thermal initiators such as bislauroyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile (azobisisobutyronitrile), t-amyl peroxybenzoate, 4 '-azobis (4-cyanovaleric acid), 1' -azobis (cyclohexanecarbonitrile), 2-bis (t-butylperoxy) butane, 1-bis (t-butylperoxy) cyclohexane, 2, 5-bis (t-butylperoxy) -2, 5-dimethyl-hexane, 2, 5-bis- (t-butylperoxy) -2, 5-dimethyl-3-hexane, bis [1- (t-butylperoxy) -1-methylethyl ] benzene, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, T-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxide, t-butyl perbenzoate, t-butyl peroxyisopropyl formate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, 2, 4-pentanedione peroxide, peracetic acid, potassium persulfate, and the like.
The radical initiator of the present invention also includes photoinitiators such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), Benzophenone (BP), Thioxanthone (TX), Camphorquinone (CQ), trienone (benzophenone), alpha-hydroxy ketone, phenylglyoxylate, acylphosphine oxide, oxime ester, alpha amino ketone, benzoin dimethyl ether (benzyl dimethyl ketone), and the like.
The term "michael addition" or "michael reaction" generally refers to the nucleophilic addition of a carbanion or another nucleophile to an α, β unsaturated carbonyl compound (electrophile). For example, the term refers to a thio-michael addition, wherein a compound having an — SH functional group is added to a carbon-carbon double bond.
Preferably, the adducts of the present invention are formed in the presence of a catalyst, wherein compound a reacts with compound B by michael addition to form a linear polymer or a crosslinked network. The skilled person is aware of the michael addition reaction and can routinely polymerize the monomers of the invention by this method. For example, see "The thio-Michael Addition click reaction A Powerfull and Widely Used Tool in Materials Chemistry"; nair et al, American Chemical Society, 2013, which is incorporated herein by reference in its entirety.
The adduct according to any of the preceding embodiments formed by the chemical reaction of monomer a with monomer B via michael addition is advantageous because it avoids the risk of homopolymerization of the unsaturated carbon-carbon bonds into a carbon backbone polymer rather than polyvinyl alcohol. As is known to those skilled in the art, carbon backbone polymers, other than polyvinyl alcohol, are difficult to biodegrade. Furthermore, the michael addition reaction avoids the risk of disulfide bond formation, which is difficult to biodegrade under oxidative conditions, as is known to those skilled in the art. Alternatively, the michael addition reaction occurs in the presence of a catalyst. Optionally, the catalyst comprises any one of the following: 1, 5-diazabicyclo [4.3.0] non-5-ene, triethylamine, diethylamine, ethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1-aminopentane, 1-aminohexane, N-diisopropylethylamine, N-dimethylisopropylamine, 4- (dimethylamino) pyridine, imidazole, dimethylphenylphosphine, tris (2-carboxyethyl) phosphine.
In another aspect of the present invention, there is provided a coated agrochemical composition.
As used herein, the term "agrochemical composition" includes biologically active ingredients or plant protection products, including insecticides, herbicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, nematicides, bactericides and the like. They are commonly used to control pests and to promote plant growth in agriculture.
As used herein, the term "coated agrochemical composition" or the like refers to an agrochemical composition that is encapsulated by being covered with a coating composition according to any embodiment of the present invention to reduce the release rate of its ingredients or materials (such as fertilizer) when it is contacted with moisture or water (i.e., to exhibit a controlled release rate).
In one embodiment, the bioactive ingredient or plant protection product may be active only after the coating is sufficiently biodegradable.
The coated agrochemical composition of the present invention may have various shaped formulations, such as granules, tablets or other forms, for targeted application of the coated agrochemical composition (e.g., plant growth nutrients) to plants in a defined area. Preferably, the coated agrochemical composition of the present invention may be a mixture of the same or different formulations.
Preferably, the invention is applied to granular products of fertilizers.
In one embodiment, the coated agrochemical composition comprises a material encapsulated with a coating composition, wherein the coating composition comprises an adduct formed by a chemical reaction of a monomer a comprising a component having at least two mercaptoalkanoate groups and a monomer B comprising a component having one or more ester moieties and an unsaturated carbon-carbon bond. The coating composition encapsulating the material has a thickness and formulation sufficient to act as a controlled release protective layer and sufficient to have biodegradability properties according to the invention.
In one embodiment, the coated agrochemical composition comprises a material encapsulated with a coating composition, wherein the coating composition comprises an adduct formed by a chemical reaction of a monomer a comprising a component having at least two mercaptoalkanoate groups and a monomer B comprising a component having one or more ester moieties and an unsaturated carbon-carbon bond. Alternatively, monomer B comprises a component having a) one or more ester moieties, B) cyclopentane and/or cyclohexane moieties, and c) unsaturated carbon-carbon bonds. For example, according to any embodiment of the present invention, the adduct is formed by reacting monomer a with monomer B. Alternatively, monomer a is reacted with monomer B by free radical polymerization or by michael addition.
In one embodiment, the coated agrochemical composition comprises an agriculturally active material and a coating composition, wherein the coating composition encapsulates the agriculturally active material, wherein the coating composition comprises an adduct formed by a chemical reaction of a monomer a comprising a component having at least two mercaptoalkanoic acid esters and a monomer B comprising a component having an ester moiety and an unsaturated carbon-carbon bond, wherein the coating composition and/or the coated agrochemical composition exhibits a controlled material release rate over 30 days or more from the day of initial exposure of the material to moisture or water, wherein at least 75 wt.% of the initial weight of the material is released from the coated agrochemical composition.
In one embodiment, the coating composition and/or the coated agrochemical composition of the present invention exhibits a controlled material release rate, wherein no more than 15 wt.% of the material is released within the first 24 hours after the agrochemical composition is first contacted with moisture or water at an ambient temperature of 20 ℃ to 28 ℃ (preferably 25 ℃), no more than 75 wt.% of the material is released within 28 days, at least 75 wt.% of the material is released for 30 days or longer (preferably according to NEN-EN 13266), and wherein the coating composition is biodegraded by at least about 16% over a period of about 10 to 24 months, as measured by test methods ISO 14855, ISO17556, ASTM D5988, UNI 11462 or NF U52-001 at an ambient temperature of 20 ℃ to 28 ℃ (preferably 28 ℃).
Optionally, the coated composition and/or the coated agrochemical composition has a minimum of about 16%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% biodegradation over a period of about 10 to 24 months, optionally about 10 months, about 11 months, about 12 months, about 13 months, about 14 months, about 15 months, about 16 months, about 17 months, about 18 months, about 19 months, about 20 months, about 21 months, about 22 months, about 23 months or about 24 months, optionally obtained at an ambient temperature of 20 ℃ to 28 ℃.
In one embodiment, the agriculturally active material is at least partially water soluble, ensuring transport of a medium, such as water, to the material via permeation through the composition layer. The "osmotic" transport of the material is the result of a net movement of water through the composition towards higher solute concentrations, which results in an increase in osmotic pressure. Osmotic pressure allows for controlled release of the solution from the coated agrochemical composition and continues until all material is released. Thus, once dissolved, the water soluble material is transported out of the coated agrochemical composition.
As used herein, the term "soluble" refers to a material that can be substantially dissolved in a given amount of fluid at a given temperature and has a solubility greater than 2 g/L. In one embodiment, the fluid of the invention is selected from the group comprising water or any liquid solvent capable of substantially dissolving said material.
Examples of materials suitable for use in the present invention are fertilizers such as ammonium sulfate, potassium nitrate, potassium sulfate, urea, ammonium nitrate, monopotassium sulfate, ammonium phosphate, superphosphate, calcium phosphate, potassium chloride, magnesium oxide, magnesium sulfate, dolomite, and the like, or any fertilizer obtained from a mixture of these fertilizers. Alternatively, the material of the present invention includes a variety of well known standard NPK or other fertilizer granules, such as those described in European Community code (EC) No. 2003/2003. Alternatively, the material may be a water soluble salt or other such material, for example, a sodium or calcium salt. In addition, inactive materials such as sugars and other particulate materials may be used as core materials herein, if desired.
In one embodiment, the material comprises at least one secondary nutrient and/or micronutrient. Suitable secondary nutrients include calcium, magnesium, sulfur, sodium and mixtures thereof. Suitable micronutrients in chelated or non-chelated form include iron, copper, zinc, manganese, boron, cobalt, chlorine, molybdenum and mixtures thereof.
In one embodiment, the material comprises one or more nitrification inhibitors, denitrification inhibitors, urease inhibitors, biostimulants, herbicides, insecticides, bactericides, plant growth regulators, pheromones, animal repellents, insect repellents or mixtures thereof.
Typically, the solubility of the material is from about 2 to about 1200g/L, preferably about 120 and 450 g/L. Optionally, the material is formed into granules having a diameter of about 0.35 to about 6mm, preferably about 0.72-4mm, for better dispensing of the product.
As used herein, the term "solubility" refers to the maximum amount of the material of the present invention that can be dissolved in a given amount of fluid, such as water, at a given temperature. For example, a measure of the solubility of a material at a given temperature is the number of grams dissolved in 1 liter of fluid to form a saturated solution.
The coating composition according to any one of the embodiments may be applied to the material (e.g. granular fertilizer) by a variety of methods. For example, in one embodiment, such as in the Wurster process, the coating process is carried out in a blender, a coating drum, or a fluidized bed.
The (total) thickness of the coating applied on the material, such as fertilizer granules, is typically between about 5 and 110 μm; preferably between about 25 and 90 μm. Typically, these values correspond to an amount of applied coating material of about 1 to about 20 parts per hundred parts (pph) by weight and about 4-15pph by weight, respectively.
In another embodiment, a method for preparing a coated agrochemical composition is provided. The method comprises the following steps: a) providing a material, optionally comprising at least one water-soluble fertilizer compound, b) coating the material with a coating composition according to any embodiment of the present invention, preferably such that the material coats a layer of the coating composition that forms a uniform, substantially continuous polymeric film on the core material, and optionally at least about 90% of all material (e.g., granular fertilizer) is coated with the film; wherein the coating composition and/or agrochemical composition exhibits controlled material release and is biodegradable according to the defined criteria of the invention.
In one embodiment, the present invention provides a coated agrochemical product comprising two or more coated agrochemical compositions according to any one of the preceding embodiments (e.g., a coated granular fertilizer composition) and a thermoplastic polymer binder comprising C1-C4 polyethylene oxide (having a melting temperature of from about 50 ℃ to about 160 ℃); wherein the coated agrochemical composition is held (bound) together by a binder in a mechanically stable shaped controlled release product which is dispersed into separate multiple particles upon contact with water.
In one embodiment, the C1-C4 polyethylene oxide is a C1-C4 homopolymer, a C1-C4 polyethylene oxide block copolymer or terpolymer, or a polyolefin-C1-C4 polyethylene oxide block copolymer.
Optionally, the product comprises about 0.1 to 40 wt% binder. Optionally, the adhesive has a melting temperature of about 50 ℃ to 100 ℃.
In one embodiment, the adhesive comprises a polyethylene oxide homopolymer, a polyethylene oxide-block-polypropylene oxide copolymer, a polyethylene oxide-block-polypropylene oxide-block-polyethylene oxide terpolymer, a polypropylene oxide-block-polyethylene oxide-block-polypropylene oxide terpolymer, a polyethylene-block-polyethylene oxide copolymer, a polyethylene-block-polypropylene oxide copolymer, a polypropylene-block-polyethylene oxide copolymer, a polypropylene-block-polypropylene oxide copolymer, or a mixture thereof. The block copolymer has the additional advantage of exhibiting wetting properties relative to the homopolymer, which increases water absorption in soil.
In one embodiment, at least one additional component is mixed with the coated agrochemical composition (e.g., coated fertilizer granule) and the binder, the additional component comprising a water-absorbing gel, nitrification inhibitor, urease inhibitor, herbicide, insecticide, fungicide, pheromone, animal repellent, insect repellent, or mixtures thereof.
The shaped nutritional products of the present invention may be prepared by various methods. For example, the method comprises: providing a coated agrochemical composition (e.g., a coated granular fertilizer) according to any embodiment of the present invention; preheating the agrochemical composition to a temperature of about 50-100 ℃; mixing the agrochemical composition with a thermoplastic polymer binder comprising C1-C4-polyethylene oxide, wherein the thermoplastic polymer binder has a melting temperature of about 50 ℃ to about 160 ℃, which has been heated to form a melt, wherein the mixture comprises about 0.1 to 40 weight percent binder; and introducing the mixture into a mold and cooling in the mold to form a shaped plant growth nutrient product, wherein the coated plant growth nutrient particles are held in the mechanically stable shaped controlled release plant growth nutrient product by a binder, and upon contact with water, the shaped biodegradable controlled release plant growth nutrient product is rapidly dispersed into individual particles, as described in US8399020B2,
the monomers A and B of the present invention are commercially available or can be prepared conventionally by those skilled in the art. The following examples will serve to further illustrate the invention but are not meant to be limiting thereto.
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