Disclosed is a polyurethane based composition for treating textiles to provide such treated textile with oil, water or oil and water repellency. The composition comprises a polyfunctional liquid polyurethane-containing adduct wherein the adduct contains as a first functional group at least one structo-terminal blocked isocyanate moiety per molecule, and at least one second structo-terminal functional group per molecule which is a perfluoro or siloxane moiety.

The present invention relates to textile treatment compositions to impart oil and water repellency to textiles, methods of treating textiles and to the resulting treated textiles.
Various processes exist for the treatment of textiles to impart some water and/or oil repellency. For example, the use of various fluorochemical compositions for such purposes on fibers and fibrous substrates, is known. See, for example, Banks, Ed., Organofluorine Chemicals and Their Industrial Applications, Ellis Horwood Ltd., Chichester, England, 1979, pp. 226-234. As the fluorochemicals are generally expensive, extenders are generally added to reduce the cost. Considerable effort has been put forth in finding suitable extenders for use with fluorochemicals to impart water and oil repellency to fibers.
U.S. Pat. No. 5,466,770 describes a fluorochemical oil- and water-repelling agent together with a polymer extender and a polymer extender having a saturated carbon-carbon backbone chain and at least one percent by weight, based on the weight of the extender, of interpolymerized units derived from ethylenically-unsaturated monomer containing at least one blocked or masked isocyanato group.
U.S. Pat. No. 3,849,521 (Kirimoto et al.) describes water- and oil-repellent compositions containing an oil- and water-repellent fluoroalkyl-containing polymer and an additive copolymer containing monomer units having the formula CR1R2xe2x95x90CR3COOR4, wherein R1, R2 and R3 represent hydrogen atoms or methyl groups, and R4 represents a C1-18 alkyl group; and monomer units having the formula CH2xe2x95x90CR5CONHCH2OH, wherein R5 represents a hydrogen atom or a methyl group.
U.S. Pat. No. 4,834,764 (Deiner et al.) describes the use of certain blocked isocyanate compounds in combination with reactive perfluoroalkyl containing (co)polymers. Such compounds are said to improve the oil and water repellency and also make possible a reduction in the amount of fluoroalkyl-containing compounds.
World patent publication W092/17636 (Dams et al.) describes certain compositions comprising a fluorochemical agent, a copolymer extender, and a blocked isocyanate extender.
The present invention provides for a tailored reactive molecule suitable for a chemically bonded thin textile coating that provides water and oil repellency without significantly impacting the feel of the fabric.
In a first aspect, this invention relates to a liquid polyurethane-based composition which comprises a polyfunctional liquid polyurethane-containing adduct wherein the adduct contains as a first functional group at least one structo-terminal blocked isocyanate moiety per molecule, and at least one second structo-terminal functional group per molecule which is a repellent moiety, preferably a perfluoro or siloxane moiety, or a combination thereof.
In a second aspect, this invention relates to a process for preparing a polyfunctional liquid polyurethane-containing composition as mentioned above, by a solvent-free multi-step process which comprises reacting in a first step a polyisocyanate with a polyol to provide an isocyanate-terminated intermediate, in a second step reacting the isocyanate-terminated intermediate with a blocking agent to block at least one isocyanate moiety and in a subsequent step, reacting at least one isocyanate moiety with a repellent compound. In a preferred method for the preparation of the polyfunctional polyurethane:
a) the polyisocyanate comprises at least two isocyanate moieties per molecule with mutually different reactivities to the polyol;
b) the polyol is an organic substance having a molecular weight of from 60 to 20,000 and containing per molecule from two or more isocyanate-reactive functional groups selected from the group consisting of xe2x80x94OH, xe2x80x94SH, xe2x80x94COOH, xe2x80x94NHR where R is hydrogen or alkyl, or epoxy; and
c) the repellent compound is a molecule containing one isocyanate-reactive functional group selected from the group consisting of xe2x80x94OH, xe2x80x94SH, xe2x80x94COOH, xe2x80x94NHR where R is hydrogen or alkyl, or epoxy and further containing a second functional group which is not an isocyanate or an isocyanate-reactive moiety,
characterized in that:
i) the first step is conducted in essentially anhydrous conditions and in the absence of a urethane-promoting catalyst, the polyol is added at a controlled rate to the polyisocyanate such that the reaction temperature does not exceed 100xc2x0 C. and the total amount of polyol added is less than a stoichiometric equivalent with respect to the polyisocyanate;
ii) for the second step, the blocking agent is added in a total amount of less than a stoichiometric equivalent with respect to the isocyanate content of the intermediate;
iii) and in one or more subsequent steps, a repellent compound is added such that the final polymer is substantially free of any isocyanate functionality or any isocyanate-reactive functionality.
In another aspect, the invention is to a process for preparation of a polyfunctional polyurethane as above where steps (ii) and (iii) are reversed. Thus in step (ii), a repellent compound is added at less than a stoichiometric equivalent with respect to the isocyanate content of the intermediate and in step (iii), the blocking agent is added.
In yet another aspect, this invention relates to a process for imparting water and oil repellent properties to a textile comprising applying to a surface of a textile an amount of the above disclosed composition sufficient to impart water and/or oil repellent properties thereto. Such treated fibers are preferably heated in a second step at a temperature and for a time sufficient to cure the treated substrate.
This invention also relates to a repellant textile resulting from the treatment of such textile by the above described method.
Treatment of fibers by the composition and method of the present invention is advantageous in that the fiber retains the touch, feeling, color shade and softness originally possessed by the fibers even after treatment and imparts a water and/or oil repellency to such fibers.
A further advantage of the compositions of the present invention for treating textiles is that the urethane compositions have self-emulsifyable behavior and due to the nature of the compounds, their architecture can be tailored to result in smaller r emulsion particles. This imparts the advantage of applying a thinner coating of the above composition versus conventional water repellency compounds.
An additional advantage of the present invention is when the repellent moiety is a perfluoropolyether, such compounds allow self-organization to take place at room temperature so that the textile does not need to undergo a heat treatment after washing.
The polyfunctional polyurethanes of the present invention provide an additional advantage in that when applied to a textile, they are chemically bonded to the textile so that the water and/or oil repellency of such treated textiles is maintained by the textile after repeated washings or extensive use.
When used herein, the term xe2x80x9ctextilexe2x80x9d refers to both textiles which are composed of natural fibers and/or synthetic fibers, for example wool, cotton, silk, nylon, cellulose and also blends of natural fibers and synthetic fibers, including synthetic fibers modified to react with an isocyanate functionality. The treated textile may be in the form of a fiber, a yarn, a woven fabric, a carpet, a knitted fabric, a nonwoven fabric which are formed from the fibers.
The term xe2x80x9crepellent moietyxe2x80x9d or xe2x80x9crepellent compoundxe2x80x9d, or variations thereof, means a moiety or compound which when added to a textile will give the textile the characteristics of repelling water, oil or oil and water. Preferred repellent moieties are perfluorocarbons and siloxanes. Perfluorocarbons are generally characterized in imparting to a textile the ability to repel water and oil and siloxanes are characterized in imparting to a textile the ability to repel water. The ability to repel oils is also associated with stain resistance.
The composition of this invention is characterized in that it comprises a polyfunctional liquid polyurethane adduct bearing a blocked isocyanate functional group and a second different functional group which is a repellent moiety. By the term xe2x80x9cliquidxe2x80x9d it is meant that the adduct is a liquid at a temperature of 50xc2x0 C. or less, and preferably is a liquid at a temperature of from 0xc2x0 C. to 50xc2x0 C. The composition advantageously comprises the adduct in an amount of from 1 to 99, preferably from 5 to 95, more preferably from 10 to 90, and yet more preferably from 50 to 90 weight percent, based on total parts by weight of the composition.
The polyfunctional liquid polyurethane-containing adduct has a polyol core which is chain extended with an isocyanate moiety and terminated with at least two functional groups. These functional groups are structo-terminal, that is, they are not pendent. At least one chain end bears a blocked isocyanate functional group, and at least one chain end bears a repellent functional group. In a preferred embodiment of this invention, the adduct has on average of from 2 to 8, more preferably from 3 to 8, and yet more preferably from greater than 3 to 6 chain ends per molecule, wherein each chain contains one or more urethane linkages. When the adduct contains from 2 to 8 chain ends per molecule; then from 1 to 7 blocked isocyanate moieties per molecule and from 7 to 1 perfluoro functional moieties are present. The optimum ratio of masked isocyanate moiety to second functional moiety will depend on the intended fabric to be treated and can vary within the ranges of from 1:7 to 7:1, and preferably from 1:2 to 2:1.
The polyfunctional liquid polyurethanes of the present invention can contain additional functional moieties such as an aryl, alkyl, ester, nitrile, alkene, alkyne, halogen, silyl or combinations thereof. The equivalents of repellent moieties, blocking agent and optionally additional functional groups is such that the polyfunctional polyurethane is substantially free of any isocyanate functionality or any isocyante-reactive functionality.
In general, repellent compounds useful in this invention include any of the known agents useful for the treatment of textiles to obtain oil, water or oil and water repellency. Preferred repellent compounds are the known fluoro-containing and siloxane-containing compounds useful for the treating of textiles to obtain water and/or oil repellency.
The fluoro-compounds, called RfX for brevity, are stable, inert, non-polar, and both oleophobic and hydrophobic. X refers to a isocyanate-reactive functional group where such functional groups include xe2x80x94OH, xe2x80x94SH, xe2x80x94COOH, xe2x80x94NHR, with R being hydrogen or an alkyl moiety, or epoxy. The Rf group preferably contains at least 3 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 6 to 14 carbon atoms. Rf can contain straight chain, branched chain, or cyclic aliphatic fluorinated groups, aromatic fluorinated groups or combinations thereof. Rf can optionally contain heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that Rf contains oxygen. It is preferred that Rf contains 40 percent to 80 percent fluorine by weight, more preferably 50 percent to 78 percent fluorine by weight. The terminal portion of the Rf group is fully fluorinated preferably containing at least 7 fluorine atoms, for example, CF3CF2CF2xe2x80x94, (CF3)2CFxe2x80x94, xe2x80x94CF2SF5, F(CF(CF3)CF2xe2x80x94O)4CF(CF3)CH2xe2x80x94. Perfluorinated aliphatic groups and perfluorinated ethers are the most preferred embodiments of RfX.
Examples of useful fluorochemical agents include, for example, Rf containing urethanes, ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, oxazolidinones, and other substances containing one or more Rf groups, as well as mixtures and blends thereof. Such agents are well known to those skilled in the art, see for example, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 24, pp. 448-451 and many are commercially available as ready-made formulations. Useful fluorochemical agents can be polymers containing multiple Rf groups such as copolymers of fluorochemical acrylate and/or methacrylate.
Preferred siloxane compounds useful in the present invention can be represented by the general formula
Xxe2x80x94(CH2)nxe2x80x94Oxe2x80x94[(SiO)(CH3)2]mxe2x80x94CH3
where
X is as previously defined;
n is an integer from 1 to 20; and
m is an integer from 1 to 12.
Preferably m is an integer from 2 to 15, and more preferably from 3-12. Preferably n is an integer from 1 to 10, and more preferably from 2 to 8. M and n are generally selected such that the molecular weight of the siloxane compound is 120 to 423,000.
Siloxane compound are commercially available, as from ABCR GmbH and Co., Karlsruhe, Germany.
The polyisocyanate used in the process to prepare the adduct product has at least two isocyanate moieties per molecule and which, with respect to the isocyanate-reactive group of the polyol, are distinguished by a difference in reactivity. The reactivity difference optimizes the manufacture of a product having a narrow molecular weight distribution and reduces the potential for formation of higher oligomers leading to gel-like or non-liquid products. When the polyisocyanate contains three or more isocyanate groups per molecule then the relative reactivity of the individual isocyanate moieties is such to minimize formation of higher oligomers. Suitable polyisocyanates can be aliphatic or preferably aromatic polyisocyanates and especially aromatic or aliphatic diisocyanates. An advantage to using diisocyanates, where the relative reactivity of the individual isocyanate groups are different, is that it permits the amounts of free, non-reacted, polyisocyanate that may be present in the isocyanate-terminated intermediate to be limited to the subsequent advantage of material requirements for the second process step, and further to the value of the adduct in end applications. Exemplary of suitable aromatic polyisocyanates include toluene diisocyanate, methylene diphenylisocyanate and polymethylene polyphenylisocyanates. Exemplary of suitable aliphatic polyisocyanates include isophorone diisocyanate, isopropylcyclohexyl diisocyanate and methylene dicyclohexylisocyanate. Preferred are polyisocyanates comprising isomers of toluene diisocyanate, of methylene diphenylisocyanate or mixtures thereof. Especially preferred, for reasons of relative isocyanate reactivity, is 2,4xe2x80x2-methylene diphenylisocyanate and notably 2,4-toluene diisocyanate, or mixtures comprising such diisocyanate.
The term polyol as used herein refers to a compound which has two or more isocyanate-reactive functional groups per molecule where such functional groups include xe2x80x94OH, xe2x80x94SH, xe2x80x94COOH, xe2x80x94NHR, with R being hydrogen or an alkyl moiety, or epoxy. Preferred is a polyol bearing xe2x80x94OH functionality. The polyol may contain up to 8 such functional groups per molecule, preferably from 2 to 8, more preferably from 3 to 8, and most preferably from greater than 3 to 6, functional groups per molecule.
The polyol used in the process of this invention has a molecular weight of from 60 to 20,000; preferably from 200, more preferably from 1000, and yet more preferably from 2000; and preferably up to 15,000, and more preferably up to 10,000. In a preferred embodiment the polyol is a polyester or particularly a polyoxyalkylene polyol where the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof, including especially oxypropylene-oxyethylene mixtures. Alternative polyols that may be used in the invention include polyalkylene carbonate-based polyols and polyphosphate based polyols. The nature of the polyol selected depends on whether or not to impart some water solubility to the adduct, which can be advantageous for certain applications and disadvantageous for other applications. Water solubility can be enhanced by selection of polyols having a lower molecular weight or an elevated oxyethylene content.
Suitable polyoxyalkylene polyols are exemplified by various commercially available polyols as used in polyurethane, lubricant, surfactancy applications and include polyoxypropylene glycols designated as VORANOL(trademark) P-2000 and P-4000 with respectively molecular weights of 2000 and 4000; polyoxypropylene-oxyethylene glycols such as DOWFAX(trademark) DM-30 understood to have a molecular weight of 600 and an oxyethylene content of 65 weight percent, and SYNALOX(trademark) 25D-700 understood to have a molecular weight of 5500 and an oxyethylene content of 65 weight percent, all available from The Dow Chemical Company; polyoxyethylene triols available under the trademark TERRALOX(trademark) and designated as product WG-98 and WG-116 understood to have a molecular weight of 700 and 980, respectively, polyoxypropylene-oxyethylene triols designated as VORANOL(trademark) CP 1000 and CP 3055 understood to have respectively a molecular weight of 1000 and 3000, and VORANOL(trademark) CP 3001 understood to have a molecular weight of 3000 and an oxyethylene content of 10 weight percent and VORANOL(trademark) CP 6001 understood to have a molecular weight of 6000 and an oxyethylene content of 15 weight percent, all available from The Dow Chemical Company; polyoxypropylene hexols including VORANOL(trademark) RN-482 understood to have a molecular weight of 700, and polyoxyethylene hexols including TERRALOX(trademark) HP-400 understood to have a molecular weight of 975, both available from The Dow Chemical Company; higher functionality polyether polyols including those based on carbohydrate initiators such as, for example, sucrose and exemplified by VORANOL(trademark) 370 available from The Dow Chemical Company.
The blocking group is a conventional blocking agent which is removable from the isocyanate under thermal conditions, such as those employed during cure of a fibrous substrate treated with a compound containing the blocked isocyanate group.
Conventional isocyanate blocking agents include alcohols such as 1,6-hexanediol, ethylene glycol, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol; aryl alcohols (for example, phenols, cresols, nitrophenols, o- and p-chlorophenol, naphthols, 4-hydroxybiphenyl); C2 to C8 alkanone oximes (for example, acetone oxime, butanone oxime); benzophenone oxime; aryl-thiols (for example, thiophenol); organic carbanion active hydrogen compounds (for example, diethyl malonate, acetylacetone, ethyl acetoacetate, ethyl cyanoacetate); epsilon-caprolactam; a primary or secondary amine (for example, butyl amine); hydroxylamine; and primary amino mercaptan and secondary amino mercaptans. Particularly preferred blocked isocyanates include those blocked with C2 to C8 alkanone oximes, for example, 2-butanone oxime, with a phenol, with a lactam, with 2-ethylhexanol, or with glycidol.
In a preferred embodiment of this invention the polyisocyanate is toluene diisocyanate comprising, substantially, the 2,4-isomer; the polyol is a polyoxyalkylene polyol, especially a polyoxyethylene-oxypropylene polyol containing from 3 to 6 hydroxyl groups; the blocking agent is 2-butanone oxime and the preferred fluorocarbons are CF3CF2CF2xe2x80x94, (CF3)2CFxe2x80x94, xe2x80x94CF2SF5, and F(CF(CF3)CF2xe2x80x94O)4CF(CF3)CH2xe2x80x94.
The method of preparing the polyurethane compositions of the present invention comprises a multi-step process.
The first step concerns the preparation of an isocyanate-terminated intermediate by reacting the polyisocyanate with the polyol at a reaction temperature that does not exceed 100xc2x0 C., in essentially anhydrous conditions. By xe2x80x9cessentially anhydrous conditionsxe2x80x9d it is meant that water is present in an amount of less than 1500, preferably less than 750, more preferably less than 350 ppm of total polyisocyanate and polyol reactants. The presence of water in an amount greater than this increases the risk of forming gel or solid products. The reaction temperature advantageously is from 20xc2x0 C., more preferably from 35xc2x0 C.; and preferably up to 80xc2x0 C., more preferably up to 70xc2x0 C. At higher reaction temperatures, the beneficial effect of the relative isocyanate reactivity rates can be substantially diminished, and additionally isocyanate may be consumed by an undesirable allophanate reaction. The polyol is added at a controlled rate to the polyisocyanate such that the reaction temperature does not exceed 100xc2x0 C., and the total amount of polyol added is a stoichiometric equivalent or less with respect to the polyisocyanate. The total amount of polyol advantageously does not exceed 0.99, preferably does not exceed 0.95 of an equivalent; and advantageously is at least 0.1, preferably at least 0.25, and more preferably from 0.5 of an equivalent per equivalent of isocyanate.
The first process step is conducted in the absence of a processing aid. By the term xe2x80x9cprocessing aidxe2x80x9d in the context of this invention, it is meant substances that promote the formation of urethane linkage by reaction of isocyanate with an active hydrogen atom. To minimize potential gel formation, solidification, it is advantageous to use polyols that do not contain any catalyst or catalyst finishing residues, for example, potassium acetate, which might promote urethane formation or isocyanate dimerization or trimerization. Additionally to minimize gel formation when preparing the intermediate it is advantageous to use polyols, especially polyols, that have an acid content.
The intermediate can be characterized in that it has an isocyanate content of from about 0.5 to about 5, preferably from about 1 to about 4 weight percent and is a composition which comprises structures (I), (II), and (III) represented by the structural formulae:
P (-A)bxe2x80x83xe2x80x83(I)
A or A-xe2x80x83xe2x80x83(II)
A-(P-A)c-P-Axe2x80x83xe2x80x83(III)
wherein:
cxe2x89xa71
A- is a residue from a polyisocyanate;
A is a free polyisocyanate
P is a residue from a polyol; and
b is the number of isocyanate reactive groups formally present on the polyol.
The proportions and amounts of (I), (II), and (III) based on total mole amount of said substances, in an amount of from: for (I), at least 65, preferably at least 75, more preferably at least 80, and up to 100 mole percent; for (II), less than 35, preferably less than 25, more preferably less than 15, and most preferably 0 mole percent; and for (III), less than 12, preferably less than about 10, more preferably less than about 7, yet more preferably less than 5, and most preferably 0 mole percent. In a preferred embodiment the adduct composition may comprises substances (I), (II), and (III) in the mole percent ranges of from 65 to 90: from 30 to 5: from about 6 to 1 respectively, wherein the total is to 100. By reference to purity, it is understood that the end product has a low content of free polyisocyanates and adducts represented by structures (II) and (III), respectively.
The proportion and amounts of (I), (II) and (III) are carried over in the formation of adducts of the present invention. By way of example, when all the isocyanate moieties of the intermediate contain a blocking group or repellent group, the final adduct can be represented by the general structure (IV)
(W-A)(b-d)-P-(A-M)dxe2x80x83xe2x80x83(IV)
where
P, A and b are as previously defined;
M represents a blocking moiety;
W represents a repellent moiety; and
d is the number of blocked isocyanate groups.
As per the description herein, b is greater than d.
The process minimizes the formation of structure (III) type substances, resulting in an adduct which has a liquid characteristic at room temperature, especially when the polyol used in the preparation of the adduct formally contained three or more isocyanate reactive groups/molecule. Adduct III is depicted with a linear structure although it can have a highly complex branched structure.
When the resulting isocyanate-terminated intermediate has a high free, unreacted, isocyanate content, and before proceeding with the second step of the process it can be advantageous to reduce such content by, for example, distillation or extraction techniques using suitable solvents including pentane or hexane. Free, unreacted isocyanate can participate in the second process step providing capped products, the presence of which in the final product may be detrimental to performance in certain end applications.
In the second step of the process, the isocyanate-terminated intermediate is reacted with less than a stoichiometric amount of a blocking agent. The stoichiometry is such to provide for the desired content of capped isocyanate moieties.
The process for blocking isocyanates can be carried out under conditions which are well know in the art. See for example, U.S. Pat. Nos., 4,008,247; 4,189,601; 4,190,582; 4,191,843; and 4,191,833, the disclosures of which are incorporated herein by reference, and Z. W. Wicks, Progress in Organic Coatings, volume 3, pages 73-99 (1975) and volume 9, pages 3-28 (1981). The process temperature is chosen for convenience of reaction time and can be greater than 80xc2x0 C. without noticeable detriment to the quality of the resulting product. Exposure to a temperature greater than 100xc2x0 C. should be minimized to avoid undesirable side reactions, such as reversal of the blocking reaction.
In a third or subsequent step of the process, the partially blocked isocyanate-terminated intermediate is reacted with a repellent compound. When the repellent compound is the final functional moiety to be added to a partially blocked isocyanate-terminated intermediate, the repellent compound is added in an amount sufficient to xe2x80x9ccapxe2x80x9d the remaining reactive isocyanate groups to provide for the final adduct.
For addition of a functional group to the blocked isocyanate-terminated intermediate, such as a repellent compound, the process temperature is chosen for convenience of reaction time and can be greater than 80xc2x0 C. In general, exposure to a temperature greater than 100xc2x0 C. should be minimized for the purpose of avoiding undesirable side reactions. The reaction of the blocked isocyanate-terminated intermediate with a polyfunctional substance can, if desired, be accelerated by use of a suitable urethane-promoting catalyst. Representative of such catalysts include tertiary amine compounds and organotin compounds as used when preparing, for example, polyurethane foam by reaction of a polyisocyanate with a polyol. It is to be noted that use of a catalyst in this step can lead to final adducts having a higher viscosity than those prepared in the absence of catalyst.
A third or subsequent step means at least one step in which a repellent compound is reacted with a partially blocked isocyanate-terminated intermediate. Thus the third step encompasses a process where one repellent compound, such as a fluorocarbon, is added in less than a stoichiometric amount with respect to the reactive isocyanate groups, and in a subsequent step another functional moiety is added. Thus the process encompasses the addition of multiple repellent molecules or other functional moieties.
The polyurethane compositions of the present invention can also be produced whereby the final step in the process is the addition of a blocking agent. Thus the isocyanate-terminated intermediate produced in the first step is reacted with one or more repellent compounds, and optionally with other functional moieties, in less than a stoichiometric amount with respect to the reactive isocyanate groups. In the final step sufficient blocking agent is then added to provide a polyfunctional polymer which contains substantially no free isocyanate functionality.
The polyfunctional polyurethanes of the present invention can be applied to the textile by common processes known to those skilled in the art. The polyfunctional polyurethane is generally applied using a solvent. Preferred solvents are ketones, ethers and esters or mixtures thereof. Alternatively, a composition can be prepared in the form of an aqueous dispersion or emulsion and the textile treated therewith. The polyfunctional polyurethanes of the present invention are particular advantageous when containing a perfluoroether in that these are capable of forming an emulsion in water. When water is used as a solvent, water is preferably present is an amount of 70 to 900 parts by weight based on 100 parts of weight of the composition of the invention.
A composition of the invention comprises the polyfunctional polyurethane, containing the repellent-functionality, in an amount sufficient to impart repellent properties to a fibrous substrate treated with the composition. The amount of the polyfunctional polyurethane that constitutes an effective amount can be easily determined to those skilled in the art and depends on the particular fluorocarbon agent used and textile to be treated.
When the composition of the invention is applied as a treatment to a fibrous substrate, such as a fabric intended for use in a garment, it is preferred that the treated substrate comprise the polyfunctional polyurethane in a amount of 0.01 percent to 5 percent by weight based on the weight of the untreated fiber. More preferred is an amount of 0.01 percent to 3 percent by weight of the untreated fiber.
Once the polyfunctional polyurethane has been applied to a textile, the textile is cured at a temperature and for a time sufficient to provide a cured treated substrate. This curing process can be carried out at temperatures between 110xc2x0 C. and 190xc2x0 C. depending on the particular composition used. In general, a temperature of 150xc2x0 C. for a period of 1 to 10 minutes, preferably 3 to 5 minutes, is suitable. The curing process breaks the bond between an isocyanate functional group and the blocking agent and allows the isocyanate to react and form a chemical bond with the treated textile. The cured treated substrate can be cooled to room temperature and used as desired, for example, incorporated or fashioned into a garment such as rainwear.
The need for a blocking agent on an isocyante moiety is to prevent the moiety from reacting with water if the composition is to be applied to a fiber in a solvent containing water. In another aspect of the invention, if it is desired to apply a polyurethane composition containing a repellent moiety without the use of a water solvent, the process step of adding a blocking agent to an isocyanate moiety can be omitted. This will then result in a polyfunctional liquid polyurethane-containing adduct wherein the adduct contains as a first functional group at least isocyanate moiety per molecule, and at least one second functional group per molecule which is a repellent moiety. Such compositions can then be applied to the fibers directly without the need of an aqueous solvent.
The invention is illustrated by the following examples in which all parts and percentages are by weight, unless otherwise stated.

Liquid urethane compositions for textile coatings


This invention relates to a process for the preparation of polyurethane encapsulated fertilizer particles. This process comprises applying an isocyanate-reactive component to fertilizer particles, and applying an aliphatic polyisocyanate to fertilizer particles in separate steps to form polyurethane encapsulated fertilizer particles. The two reactants may be applied in either order, with the polyisocyanate being first or last. These two steps may optionally be repeated as many times, as necessary to yield polyurethane encapsulated fertilizer particles which contain from 0.5 to 15% by weight of polyurethane, based on the total weight of the encapsulated fertilizer particles. It is also possible to mix the isocyanate-reactive component and the polyisocyanate together to form a mixture which is then applied to the fertilizer particles. These polyurethane coatings which encapsulates the fertilizer particles are biodegradable.

This invention relates to a process for producing encapsulated fertilizers which are biodegradable. This process comprises applying at least one coat of an isocyanate-reactive component comprising at least one polyester polyol or at least one polyether polyol to fertilizer particles, and applying at least one coat of an organic polyisocyanate to fertilizer particles, thus forming polyurethane encapsulated fertilizer particles. The present invention also relates to the encapsulated fertilizers produced by this process.
Commercial particulate fertilizers are produced and marketed in several different particle types, i.e., granular, pelletized, dusts, pilled, and prilled fertilizers. Also, they may be formed of inorganic substances, organic substances, or combinations thereof. The improvements of the present invention can be applied to any of these types of particulate fertilizers.
In order to be effective in promoting plant growth, fertilizers must contain some amount of water soluble plant nutrients. These are typically in the form of water soluble compounds of nitrogen, phosphorus and potassium, alone or in combination, and often in conjunction with other elements such as, for example, calcium, boron, magnesium, zinc, chlorine, etc. Such particular fertilizers can be made of a single component, e.g., urea, ammonium nitrate, potassium chloride, etc., or of multiple components often mixed with inert water soluble or water insoluble materials as in common fertilizers designated as 6-6-6, 4-6-4, 10-10-10, 20-20-5, 14-16-0, 5-20-20, and the like. In addition, specialized fertilizers may contain optional additives such as herbicides, insecticides, trace elements, iron salts, sulfur, etc. The improvements of the present invention can be applied to any of these fertilizers.
Historically, particulate fertilizers possessed a number of known defects, the most notable being the too rapid release of soluble plant food, causing phytotoxicity and the rapid depletion of the plant nutrients by leaching. Other problems included tendencies to cake and form dust. These problems are well documented in previous patents that professed solutions to one or more of the known defects, including U.S. Pat. Nos. 3,475,154, 3,259,482, 3,264,088, 3,264,089, 4,711,659, 4,772,490 and Japanese Patent 52-38361. The present invention provides additional improvements in the construction of particulate fertilizers which render them highly attrition resistant, biodegradable, and further extended release properties.
A number of slow release coatings for particular fertilizers have previously been proposed. The process of sulfur coating urea particles is described in U.S. Pat. No. 3,342,577 and was developed in the late 1960""s by the Tennessee Valley Authority (TVA) as an economical system for reducing the rate of dissolution when urea particles are applied to the soil as fertilizer. This process requires high levels of sulfur, which reduces the nutrient analysis of the fertilizer particles, and even then, imperfections remain in the coating making it necessary to apply a sealant coating, which is composed of a mixture of 30% polyethylene resin in a 70% bright stock mineral oil.
Coatings in which preformed polymer resins are applied from solvents have been described in, for example, U.S. Pat. Nos. 3,475,154 and 3,264,089. The use of solvents creates a vapor hazard as the products are dried and the solvent evaporation step can result in pinhole imperfections in the coatings when applied.
U.S. Pat. No. 4,369,055 tried to facilitate degradation of coating materials while maintaining the function for controlling the dissolving-out rate by dispersing inorganic powders such as sulfur and talc in a low molecular weight olefin polymer. However, the disclosed coating materials are not completely degraded and thus remain intact in the soil.
Polyurethane coatings as disclosed in U.S. Pat. No. 4,711,659 and 4,969,947 require that the substrate contains a minimum quantity of reactive xe2x80x94NH2 groups. Thus, these are not applicable to all fertilizer compositions for which slow release properties may be desirable.
Coating of fertilizer compositions with a biodegradable polymer was described in U.S. Pat. No. 5,176,734 and 5,206,341 and Japanese Patent Application No. 146492/1991. These references disclose coating the fertilizer composition with a biodegradable coating material in a single layer. The single layer coating has difficulties controlling the dissolving out rate of fertilizer nutrients while maintaining biodegradability simultaneously.
Japanese Patent Application No. 97561/1993 discloses a three layer coating which was prepared by using one type of biodegradable film and a water soluble resin. This coating also has difficulty in controlling both the dissolving-out rate and the biodegradability at the same time. The thickness of the coating material is disclosed as being from 500 to 2,000 xcexcm. Such a coating material requires increased cost, thus making it unsuitable for commercial use.
Canadian Patent Application No. 2,135,788 relates to coating fertilizer compositions with at least two types of coating materials wherein the two coating materials have different dissolving-out rates and moisture permeability in a multi-layer structure.
U.S. Pat. No. 5,538,531 also describes controlled release fertilizers and a method for their production. These controlled release fertilizers have a central mass of particulate fertilizer which contains at least one water soluble plant nutrient surrounded by a plurality of coatings. The inner coating comprises the reaction product of (A) an aromatic polyisocyanate or derivatives thereof which contain about 1.5 to 3 NCO groups per molecule and an NCO group content of 10 to 50% by weight, and (B) a polyol having from 2 to 6 hydroxyl moieties and at least one alkyl moiety containing from about 10 to 22 carbon atoms. An outer coating is also necessary. The outer coating consists essentially of an organic wax having a drop melting point of between 50 and 120xc2x0 C. These encapsulated fertilizers are not, however, biodegradable.
As used herein, the term biodegradable means a nearly quantitative biological degradation and conversion process (i.e., composting) of the coatings produced according to the present invention. Biodegradation is brought about mainly by bacteria such as, for example, actinomycetes and fungi such as, for example, members of the genera Aspergillus, Penicillium and Mucor and yeast. This requires an aerobic medium with sufficient moisture. Thus, the synthetic coating composition to be composted according to the present invention must satisfy several fundamental requirements. It must be completely mineralized without leaving a residue and converted into CO2 and water or into a biomass (i.e., a living cell). Both the material (i.e., coating composition) and all metabolites and degradation products must be toxicologically and ecotoxicologically harmless.
Advantages of the present invention include the fact that this process provides a more uniform coating on the fertilizer particles with good time release properties while the fertilizer is being absorbed into the soil. Additionally, the coating degrades, leaving no harmful residue in the soil.
This invention relates to a process for the production of biodegradable polyurethane encapsulated fertilizer particles. This process comprises 1) applying a) an isocyanate-reactive component comprising one or more polyester polyols or one or more polyether polyols to fertilizer particles coated with an isocyanate-reactive component, wherein said polyester polyols and polyether polyols have functionalities of from 1.5 to 4, preferably from 2 to 3, and a molecular weight of from 500 to 5,000, preferably from 1,000 to 3,000; and 2) applying b) a (cyclo)aliphatic polyisocyanate to the fertilizer particles from step 1) to form polyurethane encapsulated fertilizer particles. These two steps are optionally repeated (successively) as many times as necessary to form the desired thickness of the polyurethane coating which encapsulates the fertilizer particles. The encapsulated fertilizer compositions which are produced by this process contain from about 0.5 to 15%, preferably 1 to 10%, most preferably 3 to 7% by weight of polyurethane, based on the total weight of the encapsulated fertilizer composition.
In another embodiment, this process comprises 1) applying b) an organic (cyclo)aliphatic polyisocyanate to fertilizer particles to form isocyanate coated fertilizer particles, followed by 2) applying a) one or more polyester polyols or one or more polyether polyols to the isocyanate coated fertilizer particles from step 1), thereby forming a polyurethane encapsulated fertilizer composition. Suitable polyester polyols and polyether polyols have functionalities of from 1.5 to 4, preferably 2 to 3, and molecular weights of from 500 to 5,000, preferably from 1,000 to 3,000. These two steps are optionally repeated (successively) as many times as necessary to form the desired thickness of polyurethane coating which encapsulates the fertilizer particles. The encapsulated fertilizer compositions which are produced contain from about 0.5 to 15%, preferably 1 to 10%, most preferably 3 to 7% by weight of polyurethane, based on the total weight of the encapsulated fertilizer composition.
In a less preferred embodiment, this process comprises 1) mixing a) and b) either continuously or in a batch process in quantities such that the ratio of isocyanate groups contained in component b) to isocyanate-reactive groups contained in component a) is from about 0.8:1 to about 2.0:1, preferably about 0.9:1 to about 1.2:1 and most preferably about 0.93:1 to about 1.1:1; followed by 2) applying the mixture to the fertilizer particles; and, optionally, 3) repeating step 2) as often as necessary to form the desired thickness of polyurethane coating encapsulating the fertilizer particles. This embodiment is less preferred due to the possibility of air entrapment during the mixing stage which can result in bubbles forming in the coating leading to a less continuous film on the encapsulated particle. Another problem is since the viscosity of the reacting mixture increases as the reaction proceeds after combining a) and b), the result is that the thickness of the coating applied on the fertilizer particles may increase correspondingly as the viscosity of the reacting mixture does. Thus, the particles coated using the last portion of the mixture would have a thicker coating than particles coated using the first portion of the mixture.
The present invention also relates to encapsulated fertilizer compositions produced by these processes.
Suitable polyisocyanates for the present invention include aliphatic and/or cycloaliphatic diisocyanates or polyisocyanates derived therefrom. These are referred to herein as (cyclo)aliphatic polyisocyanates.
Suitable (cyclo)aliphatic polyisocyanates for the present invention have an NCO functionality of at least 2, and preferably a viscosity of less than about 20,000, preferably less than 10,000 mPaxc2x7s at 25xc2x0 C. It is preferred that the polyisocyanate component of the present invention contains, besides a multiplicity of isocyanate groups, at least one functional group which is selected from the group consisting of:
b1) isocyanurate groups (trimer),
b2) biuret groups,
b3) uretdione groups (dimer),
b4) urethane groups,
b5) allophanate groups,
b6) a combination of isocyanurate and allophanate groups,
b7) carbodiimide groups and/or uretonimines,
b8) oxadiazinetrione groups,
b9) urea groups, and
b10) blends thereof.
Suitable polyisocyanate components and adducts for the present invention include, for example, aliphatic diisocyanates and cycloaliphatic diisocyanates, such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 2,4xe2x80x2-dicyclo-hexylmethane diisocyanate, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclo-hexane, bis-(4-isocyanato-3-methylcyclohexyl)-methane, xcex1,xcex1,xcex1xe2x80x2,xcex1xe2x80x2-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate (TMXDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- and/or 6-hexahydro-toluylene diisocyanate, and mixtures thereof.
Polyisocyanate compounds wherein all the NCO groups are attached to tertiary carbon atoms are least preferred. These include compounds such as, for example, xcex1,xcex1,xcex1xe2x80x2,xcex1xe2x80x2-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate (TMXDI). It is less preferred to use polyisocyanate compounds wherein NCO groups are cycloaliphatically bound. Examples of such less preferred polyisocyanates are 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI) and bis-(4-isocyanatocyclohexyl)-methane.
It is preferred that the polyisocyanate be an alicyclic (or linear) aliphatic diisocyanate. Of the aliphatic diisocyanates, it is preferred that the NCO groups are attached to primary carbon atoms. Of these diisocyanates, hexamethylene diisocyanate is most preferred.
Suitable polyisocyanate adducts containing biuret groups include polyisocyanates such as those described, for example, in U.S. Pat. Nos. 3,124,605, 3,358,010, 3,644,490, 3,862,973, 3,906,126, 3,903,127, 4,051,165, 4,147,714, and 4,220,749, the disclosures of which are herein incorporated by reference. As set forth in these patents, these biuret group-containing polyisocyanates may be prepared by using co-reactants such as water, tertiary alcohols, primary and secondary monoamines, and primary and/or secondary diamines. These polyisocyanates preferably have an NCO content of 18 to 22% by weight and an average NCO functionality at least about 2, preferably of 3 to 3.8.
Suitable polyisocyanates containing isocyanurate groups include compounds such as those described, for example, in U.S. Pat. Nos. 4,288,586 and 4,324,879, the disclosures of which are herein incorporated by reference; European Patents 3,765, 10,589 and 47,452, the disclosures of which are herein incorporated by reference; and German Offenlegungsschriften 2,616,416, herein incorporated by reference. The isocyanato-isocyanurates generally have an average NCO functionality of at least about 2, preferably of 3 to 3.8, and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.
Uretdione diisocyanates may be prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the presence of a trialkyl phosphine catalyst, and may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates described hereinabove.
Urethane group-containing polyisocyanates which may be prepared in accordance with the process disclosed in U.S. Pat. No. 3,183,112, herein incorporated by reference, by reacting excess quantities of polyisocyanates, preferably diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof.
Allophanate group-containing polyisocyanates include, for example, those prepared according to the processes disclosed in U.S. Pat. Nos. 3,769,318, 4,160,080 and 4,177,342, the disclosures of which are herein incorporated by reference.
Isocyanurate and allophanate group-containing polyisocyanates include, for example, those which may be prepared in accordance with the processes set forth in U.S. Pat. Nos. 5,124,427, 5,208,334 and 5,235,018; the disclosures of which are herein incorporated by reference. These polyisocyanates containing isocyanurate and allophanate groups preferably have an NCO content of 16 to 22% by weight, most preferably of 18 to 21% by weight.
Suitable carbodiimide group-containing and uretone imine group-containing polyisocyanates for the present invention include, for example, those which may be prepared by oligomerizing di- or polyisocyanates in the presence of known carbodiimidization catalysts such as described in, for example, German Patentschrift 1,092,007, herein incorporated by reference, U.S. Pat. No. 3,152,162, herein incorporated by reference, and German Offenlegungschriften 2,504,400, 2,537,685 and 2,552,350, the disclosures of which are herein incorporated by reference.
It is also possible to use polyisocyanates containing oxadiazinetrione groups and containing the reaction product of two moles of a diisocyanate and one mole of carbon dioxide.
Preferred polyisocyanate adducts are the polyisocyanates containing isocyanurate groups b1), biuret groups b2), or polyisocyanates containing both isocyanurate and allophanate groups b6). Isocyanurate group-containing polyisocyanates suitable for the present invention generally have an average NCO functionality of at least about 2 and a viscosity of less than about 20,000 mPaxc2x7s at 25xc2x0 C. The biuret group-containing polyisocyanates generally have an average NCO functionality of at least about 2 and a viscosity of less than about 20,000 mPaxc2x7s at 25xc2x0 C. Polyisocyanates containing isocyanurate and allophanate groups generally have an average NCO functionality of at least about 2 and a viscosity of less than about 20,000 mPaxc2x7s at 25xc2x0 C.
It is more preferred to use isocyanurate group-containing polyisocyanates as component b1) which are prepared, for example, by trimerizing a portion of the isocyanate groups of 1,6-hexamethylene diisocyanate; containing tris-(6-isocyanatohexyl)-isocyanurate and higher homologs thereof; and having an NCO content of about 20-23% by weight, a monomeric diisocyanate content of  less than 2%, a viscosity at 25xc2x0 C. of less than 10,000 mPaxc2x7s and an average isocyanate (i.e., NCO) functionality of about 3 to 3.5. Suitable compounds include isocyanurate group-containing polyisocyanates such as those described, for example, in U.S. Pat. Nos. 4,288,586 and 4,324,879, the disclosures of which are herein incorporated by reference. Low monomer content polyisocyanates such as these significantly decrease health concerns and risks associated with handling polyisocyanates.
The more preferred polyisocyanates to be used as component b2) include, for example, tris-(6-isocyanatohexyl)-biuret or mixtures thereof with its higher homologs. These biuret group-containing polyisocyanates generally have an NCO content of about 18 to 25% by weight and an average NCO functionality of at least about 2. Suitable biuret group-containing polyisocyanates include polyisocyanates such as those described, for example, in U.S. Pat. No. 3,903,127, herein incorporated by reference. As mentioned hereinabove, low monomer content polyisocyanates such as these significantly decrease health concerns and risks associated with handling polyisocyanates.
Another more preferred group of polyisocyanate adduct includes the polyisocyanates containing isocyanurate and allophanate groups that are based on 1,6-hexamethylene diisocyanate. Suitable such compounds generally have an NCO content of from 16 to 25% by weight, and a viscosity of less than about 3000 mPaxc2x7s at 25xc2x0 C. Some examples of suitable isocyanates include, for example, those compounds described, for example, in U.S. Pat. Nos. 5,124,427, 5,208,334, and 5,235,018, the disclosures of which are herein incorporated by reference. These polyisocyanates also contain low quantities of monomeric isocyanates.
A most preferred isocyanurate group-containing polyisocyanate to be used as component bi) can be prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of about 21.6%, a content of monomeric diisocyanate of  less than 0.2%, and a viscosity at 25xc2x0 C. of about 3000 mPaxc2x7s.
A most preferred biuret group-containing polyisocyanate to be used as component b2) of the invention can be prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of about 23%, a content of monomeric diisocyanate of  less than 0.7% and a viscosity at 25xc2x0 C. of about 1300 to 2200.
A most preferred polyisocyanate containing isocyanurate and allophanate groups to be used as component b6) can be prepared from 1,6-hexamethylene diisocyanate and 1-butanol, and has an isocyanate content of about 18 to 21% by weight such as described, for example, in U.S. Pat. No. 5,124,427, herein incorporated by reference. This preferred polyisocyanate component has an isocyanate content of about 18 to 21% by weight, a viscosity at 25xc2x0 C. of less than about 1500 mPaxc2x7s, and a monomeric diisocyanate content of  less than 0.7%.
Suitable polyester polyols have functionalities of from 1.5 to 4, preferably from 2 to 3, and molecular weights of from 500 to 5,000, preferably from 1,000 to 3,000. Suitable polyester polyols may be prepared, for example, by polymerizing organic compounds containing both the alcohol and carboxylic acid functionalities. Examples of these compounds are the hydroxyacetic acids represented by the formula:
wherein:
Q and R can be the same or different, and each represents a linear or branched alkyl group (preferably a C1 to C18 alkyl group), a cycloaliphatic group, a substituted cycloaliphatic group or hydrogen.
Two particularly preferred polyester polyols which correspond to the above formula are lactic acid and hydroxyvaleric acid.
Suitable polyester polyols may also be prepared, for example, by reacting polyhydric, preferably a dihydric alcohol (optionally in the presence of trihydric alcohols), with polyvalent, preferably divalent carboxylic acids (optionally in the presence of trivalent carboxylic acids). These types of reactions are known, per se, in the field of polyurethane chemistry. The reaction may be by solvent-free condensation in the presence of catalysts such as, for example, titanium tetrabutylate. It is also possible that carboxylic acid chlorides, carboxylic acid anhydrides, or carboxylic acid esters of lower alcohols may be used instead of the corresponding free carboxylic acids in the preparation of these polyester polyols.
In one embodiment, the linked esterified alkoxylated polyol is obtainable by, for example, alkoxylation of a polyol having from 3 to 8 hydroxyl groups with from n to 10n equivalents of a C2-C6 aliphatic epoxide, wherein n is equal to the number of hydroxyl groups on the polyol, to form an alkoxylated polyol and (b) esterification of the alkoxylated polyol with both (i) at least one C6-C24 monocarboxylic acid entity and (ii) a polycarboxylic acid entity selected from dimer or trimer fatty acid entities and dicarboxylic acid entities having the general structure:
wherein X is an aliphatic moiety comprised of from 1 to 10 carbon atoms and up to 2 carbon-carbon double bonds and Y is hydroxy, halide, or alkoxy, wherein the amount of C6-C24 monocarboxylic acid entity is from 1 to nxe2x88x921 moles per mole of polyol and the amount of polycarboxylic acid entity is from 1/z to nxe2x88x921/z moles per mole of polyol, where z is equal to the number of carboxylate functionalities in the polycarboxylic acid entity.
Some examples of suitable polyhydric alcohols for preparing the polyester polyols include aliphatic or cycloaliphatic polyhydric, and preferably dihydric alcohols. These include compounds such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, 1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimethanol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, etc. It is also possible that mixtures of these polyhydric alcohols may be used. It is preferred that dihydric alcohols are used which contain from 2 to 5 carbon atoms and which are preferably linear compounds.
The polyol (or polyhydric alcohol) may be selected from C3-C12 aliphatic triols (e.g., glycerol, 1xe2x80x2-2xe2x80x2-4-butane triol, 2,3,4-pentane triol, 2-ethyl-2-(hydroxymethyl)-1,3-propane triol (trimethylol propane), 1,1,1-tris(hydroxymethyl)ethane, 1,2,6trihydroxyhexane, 1,2,3-hep-tanetriol, and the like), C4-C12 aliphatic tetrols (e.g., erthyritol, sorbitan, pentaerythritol), C5-C8 sugar alcohols [including those compounds corresponding to the formula HOCH2(CHOH)nxe2x80x94CH2OH wherein n is 3 to 6 such as xylitol, sorbitol, arabitol, mannitol, and the like], monosaccharides (e.g., erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, fructose, galactose, and the like), disaccharides (e.g., sucrose, lactose, maltose) and alkyl glycosides (e.g., methyl glycosides, ethyl glycosides, propyl glycosides, and other glycoside molecules wherein the alkyl glycoside is an acetal formed by interaction of a C1-C20 alcohol with a carbonyl group of a mono- or disaccharide such as glucose).
Some examples of suitable polyvalent carboxylic acids include those wherein the polycarboxylate linking segment corresponds to the general structure:
wherein X is an aliphatic moiety comprised of from 1 to 10 carbon atoms and up to 2 carbon-carbon double bonds, or a cycloaliphatic moiety comprised of the residue obtained by removing the carboxyl groups from the different isomers of hexahydrophthalic acids or their corresponding anhydrides. For example, X may be xe2x80x94(xe2x80x94CH2)m where m is an integer of from 1 to 10. Polycarboxylate linking segments of this type thus may be derived from dicarboxylic acids or their functional equivalents (halides, anhydrides, esters) such as, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, oxalic acid, and brassylic acid and mixtures or combinations thereof. Branched, substituted (including hydroxy-substituted), or unsaturated di- and tri-carboxylic acid entities may also be utilized, including, without limitation, carboxystearic acid, polycarboxystearic acid, tricarballylic acid, aconitic acid, maleic acid, tartaric acid, citric acid, maleic acid, citraconic acid, cyclohexane dicarboxylic acid, ethyl malonic acid, methyl succinic acid, 2,2-dimethyl succinic acid, methyl glutaric acid, fumaric acid, methyl adipic acid, 2-ethyl-2-methyl succinic acid, diethyl malonic acid, tartaric acid, thapsic acid, dimethyl glutaric acid, cyclohexane diacetic acid, C21 dicarboxylic acid (obtainable, for example, by reacting linoleic acid with acrylic acid), and their halides, anhydrides, esters and the like and mixtures thereof. Cyclodextrins are also suitable for the present invention. Of these, adipic acid is preferred.
Less preferred are the polyvalent aromatic carboxylic acids, including the isomers of phthalic acid. When these are used, they are used preferably in admixture with the aliphatic carboxylic acids.
In another desirable embodiment, the polycarboxylate linking segment is derived from a dimer fatty acid, a trimer fatty acid, or a mixture of dimer and trimer fatty acids or their equivalents (halide, ester, anhydride). Such substances are well-known and are described, for example, in Leonard, xe2x80x9cDimer Acidsxe2x80x9d, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7, pp. 768-782 (1979), Leonard, The Dimer Acids, Humko Sheffield Chemical (1975), Johnson, xe2x80x9cDimerization and Polymerizationxe2x80x9d, in E. H. Pryde, ed., Fatty Acids, American Oil Chemists"" Society, pp. 343-352, (1979), and Pryde et al., xe2x80x9cAliphatic Dibasic Acidsxe2x80x9d, in Condensation Monomers, Wiley-Interscience (1972). Especially preferred for use are the dimer and trimer fatty acids formed by the polymerization of C18 unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, elaidic acid and the like. The dimer fatty acid may have an acyclic, monocyclic, or bicyclic structure or comprise a mixture of compounds having different such structures. The use of a dimer or trimer fatty acid entity furnishes a polycarboxylate linking segment having the general structure:
wherein w is 2 (as in a dimer acid) or 3 (as in a trimer acid) and A is the hydrocarbyl portion of a dimerized or trimerized fatty acid.
Also suitable are fatty acids and their equivalents which are readily available at a low cost from natural sources such as edible triglycerides. Specific illustrative fatty acids suitable for use include, but are not limited to eicosanoic (arachidic) acid, heneicosanoic acid, docosanoic (behenic) acid, elaidic acid, tricosanoic acid, tetracosanoic (lignoceric) acid, caprylic acid, pelargonic acid, capric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, cetoleic acid, myristic acid, palmitoleic acid, gadoleic acid, erucic acid, rincinoleic acid, linoleic acid, linolenic acid, myristoleic acid, eleostearic acid, arachidonic acid, or mixtures or hydrogenated derivatives of these acids. The fatty acids may be derived synthetically or from natural sources such as triglyceride lipids. Mixtures of fatty acid entities, such as the mixtures of fatty acids typically obtained by hydrolysis (splitting) of a triglyceride such as corn oil or soybean oil, may advantageously be used.
The properties and characteristics of the linked esterified alkoxylated polyol may be varied or controlled as desired by adjusting the relative proportions of C6-C24 monocarboxylic fatty acid-esterified oxyalkylene segments to polycarboxylate linking segments.
The triglyceride lipid admixed with the linked esterified propoxylated glycerin composition may be any of the known edible fatty acid triglycerides available from natural or synthetic sources. These edible fatty acid triglycerides include, but are not limited to, fats and oils such as tallow, soybean oil, linseed oil, castor oil, cottonseed oil, coconut oil, palm kernel oil, corn oil, fish oil, lard, butterfat, olive oil, palm oil peanut oil, safflower seed oil, cocoa butter, sesame seed oil, rapeseed oil, sunflower seed oil, as well as fully or partially hydrogenated derivatives and mixtures of these triglycerides. While the linked esterified alkoxylated polyol composition may be combined in any proportion with the triglyceride lipid, weight ratios of from 5:95 to 95:5 are particularly advantageous. The triglyceride lipid may be selected so as to impart a desirable thermal stability, viscosity, rheology (Newtonian or non-Newtonian) or other property to the blend.
Suitable polyether polyols for the present invention are those having functionalities of from 1.5 to 4, preferably 2 to 3, and molecular weights of from 500 to 5,000, preferably 1,000 to 3,000. These polyethers may be obtained, for example, by polymerizing tetrahydrofuran or epoxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin in the presence of suitable catalysts, such as, for example, BF3 or KOH, or by chemically adding these epoxides, preferably ethylene oxide and propylene oxide, in admixture or successively to components containing reactive hydrogen atoms such as water, alcohols or amines. Examples of suitable alcohols and amines include the low molecular weight chain extenders set forth hereinafter, propylene glycol, glycerin, ethylene glycol, triethanolamine, water, trimethylolpropane, bisphenol A, sucrose, aniline, ammonia, ethanolamine and ethylene diamine. It is preferred to use polyethers which contain substantial amounts of primary hydroxyl groups in terminal positions (greater than 80% by weight, based on all of the terminal hydroxyl groups present in the polyether). It is also preferred to use polyether copolymers which contain a substantial amount (i.e., greater than about 25% by weight) of ethylene oxide in the internal blocks of the polyether.
It is also possible that the isocyanate-reactive component which comprises one or more polyester polyols or one polyether polyols additionally comprises a low molecular weight organic compound. Suitable low molecular weight organic compounds include, for example, those compounds having a molecular weight of less than 500, and an average functionality of from 1.0 to 3.0, preferably 1.5 to 2.5, and most preferably 1.8 to 2.2. These compounds are carefully selected from the group consisting of monoalcohols, diols, triols, and mixtures thereof. Some examples of suitable compounds include, for example, glycols such as, for example, those described above as suitable polyhydric alcohols for the preparation of the polyester polyols. Preferred are ethylene glycol, diethylene glycol, and triethylene glycol as well as 1,4-butylene glycol.
It is also possible to include other additives in either the isocyanate-reactive component or the polyisocyanate component prior to applying the component to the fertilizer particles. Possible additives include, for example, catalysts, preferably ones that are not toxic and do not contain heavy metals, flow aids, surfactants, defoamers and other additives known to those skilled in the art. Any additive which aids the formation of the polyurethane coating which encapsulates the fertilizer particles may be included in one or both of these components. It is, however, preferred that no additives are included in either of the two components. One concern is that these additives may not be biodegradable. Thus, it is most preferred that heavy metal catalysts are not used in the process of the present invention.
Suitable fertilizer particles for the present encapsulation process include any of the known chemical fertilizers. Some examples are ammonium sulfate, ammonium nitrate, urea, guanidine, melamine, sodium nitrate, ammonia phosphate, potassium phosphate, and combinations thereof. These fertilizer particles are obviously water soluble. In the present application, it is not necessary, but however acceptable, for the fertilizer particles to contain some reactive functional groups such as, for example, NH2 groups.
As used herein, the phrase xe2x80x9cfertilizer particlesxe2x80x9d refers to any of the commercially available particulate fertilizers which are produced and marketed in various particle types. Some examples include granular, pelletized, dusts, pilled and prilled fertilizers.
An attrition resistant, controlled release particulate fertilizer may be prepared by applying the isocyanate-reactive component and the polyisocyanate to fertilizer particles which are heated to a temperature of between about 60 and 105xc2x0 C. The fertilizer particles are kept in continuous low shear, low impact, motion relative to each other by mixing apparatus. Examples of suitable mixing apparatus include fluid bed, rotating drum, pan pelletizer, and any others which can provide a continuous, low shear motion of the fertilizer particles.
More specifically, attrition resistant, controlled release fertilizers may be produced by (i) providing a quantity of fertilizer particles and heating them to a temperature above the melting point of the isocyanate-reactive component, but no higher than about 120xc2x0 C., (ii) agitating the fertilizer particles such that a gentle mixing thereof is maintained, (iii) adding to the agitated fertilizer particles an isocyanate-reactive component comprising one or more polyester polyols and/or one or more polyether polyols as described above, (iv) after the isocyanate-reactive component has spread uniformly, adding to the agitated fertilizer particles a polyisocyanate component, in an amount such that the ratio of NCO groups to hydroxyl groups is from about 2.0 to about 0.8, more preferably 1.2 to 0.9, an most preferably 1.1 to 0.93, (v) allowing the polyisocyanate and the isocyanate-reactive materials to react, thus forming a solidified polyurethane coating on the fertilizer particles, and (vi) cooling the coated fertilizer particles to about or slightly above room temperature, with continuous agitation.
Metering of the streams of the polyisocyanate component and the isocyanate-reactive component onto the fertilizer particles can be continuous. It is may be, however, advantageously discontinuous, when only a portion of the total amount of each of the two reactants is added and allowed to react prior to applying additional portions.
Successful application of the coatings of the present invention to particulate fertilizers depends on factors such as i) fairly precise temperature control, ii) continuous non-shear movement of fertilizer particles during application of the optionally successive urethane coatings, and iii) followed by cooling.
In practicing the process of the present invention, the polyol component containing I or more alkyl moieties is preferably applied to the central mass of fertilizer prior to the addition of the first isocyanate component. The low interfacial tension between the hydroxyl moieties and the polar fertilizer particle surface and the low viscosity of the alkyl containing polyol component in the liquid state allows this component to spread on and adhere to the particle surface producing a cohesive film; this polyol film is then reacted with the isocyanate component. Adhesion which depends on surface activity of the polyol component is superior to that resulting from the chemical reaction of the isocyanate component since (1) it is not necessary for the fertilizer particles to contain reactive groups for adhesion of the coating material, and (2) only a very minute portion of the reactive groups in the fertilizer particles containing them are actually exposed on the surface, and these reactive groups are in a solid phase and thus do not readily react with the liquid isocyanate component. When fertilizers containing reactive groups (e.g., urea groups) are used, it is often necessary to heat the fertilizer close to its melting point to allow these reactive groups to combine with the isocyanate component.

Process for the production of biodegradable encapsulated fertilizers