WO2013142969A1 - Uréthanes et urées, et procédés associés - Google Patents

Uréthanes et urées, et procédés associés Download PDF

Info

Publication number
WO2013142969A1
WO2013142969A1 PCT/CA2013/000290 CA2013000290W WO2013142969A1 WO 2013142969 A1 WO2013142969 A1 WO 2013142969A1 CA 2013000290 W CA2013000290 W CA 2013000290W WO 2013142969 A1 WO2013142969 A1 WO 2013142969A1
Authority
WO
WIPO (PCT)
Prior art keywords
ldkp
lysine
acrylate
urea
compound
Prior art date
Application number
PCT/CA2013/000290
Other languages
English (en)
Inventor
Jian Ping Gao
Original Assignee
Jian Ping Gao
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jian Ping Gao filed Critical Jian Ping Gao
Priority to CN201380015332.0A priority Critical patent/CN104284918B/zh
Publication of WO2013142969A1 publication Critical patent/WO2013142969A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to novel lysine and lysine-based-diketopiperazine urethanes, ureas, and methods of preparing the same, and their uses.
  • polyurethanes are the types of polymers that contain urethane (-OCONH-) or urea (-HNCONH-) linkages in the backbone.
  • Polyurethanes are among the most versatile materials, which have found utility as foams, adhesives, elastomers and plastics. They are present in many of the products we use daily, from household items, sporting goods, and food packaging, to hardwood floors, carpet under layers, wall paints and so on. They are also widely employed as bio-medical and
  • Polyurethanes are typically made of diisocyanates, polyols and diamines, where typical diisocyanates include aromatic diisocyanates, e.g., 2, 4-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and aliphatic diisocyanates, e.g., isophore diisocyanate (IPDI) and hexamethylene diisocyanate (HDI).
  • TDI 2, 4-toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • aliphatic diisocyanates e.g., isophore diisocyanate (IPDI) and hexamethylene diisocyanate (HDI).
  • IPDI isophore diisocyanate
  • HDI hexamethylene diisocyanate
  • Urethane and urea linkages are known to undergo degradations, e.g., by hydrolysis, thermolysis or microbial ("Chemical degradation of Polyurethane", Vincent Gajewski, Rubber World Sept. 1 , 1990), to give either aromatic diamines that are potentially carcinogenic or aliphatic diamines that, to a less degree, are still toxic.
  • NOPs Natural oil polyols
  • Lysine is an amino acid produced from natural resources on a large scale.
  • LMI lysine diisocyanate
  • Early work includes U.S. Patent No. 3,281 ,378 and No. 3,358,005, which disclose the syntheses and usage of polyurethanes, polyureas, and polyurethane ureas obtained from lysine diisocyanate:
  • OCNCH 2 CH 2 CH 2 CH 2 CH(COOX)NCO Due to its non-toxic degradation nature, for decades, studies have been conducted in the field of synthesis and application of biodegradable polyurethane based on LDI.
  • WO 89/05830 describes biomedical and biodegradable polyurethanes based on lysine diisocyanate, and their potential applications as artificial skins, artificial veins, nerve grafts, etc.
  • U.S. 7,264,823 discloses medical adhesives containing a lysine-isocyanate terminated prepolymer. Rapid degradation of polyurethanes based on LDI and poly(lactic
  • Lysine based polyurethanes disclosed to date are typically made from lysine isocyanate (methyl or ethyl ester). Condensation of lysine ethyl ester and poly-succinimidyl carbonate to give lysine polyurethane is described by Nathan, (A. Nathan, D. Bolikal, N. Vyavahare, S. Zalipsky, and J. Kohn, Macromolecules, 25, 4476-4484, 1992.). In this process,
  • succinimidyl carbonate derivative which after purification is then condensed with lysine to give polyurethane.
  • polyurethanes made from lysine derivatives often have poor solvent and water resistance and poor mechanical properties compared with those made of conventional diamines and diisocyanates (P. C. Caracciolo, F. Buffa, G.A. Abraham, J Mater Sci: Mater Med (2009) 20: 145-155).
  • the drawbacks limit the practical applications of lysine
  • polyurethane especially for those where chemical and water resistance, toughness, durability, and cost are the crucial factors for commercial acceptance. It is known in the art of polyurethane that incorporation of segments, for example, crosslinked segments, polymerizable acrylyl moieties (urethane acrylate prepolymer), or copolymerization with acrylate (polyurethane/acrylate/acrylic hybrids-PUA), can improve chemical and water resistance, and other properties. It will be desirable to provide polyurethane hybrids made directly from lysine and its derivatives with improved properties suitable for a wide range of applications,
  • Unsymmetrical lysine-based-diketopiperazines can be obtained by heating lysine and another amino acid:
  • Diketopiperazines are naturally-occurring compounds which appear in a variety of natural products, foods and beverages, such as beer (M. Gautschi and J. P. Schmid, J. Agric. Food Chem., 45, 3183-3189, 1997).
  • PTMG polytetramethylene ether glycol
  • PEG polyethylene ether glycol
  • diketopiperazine-containing polyurethanes and ureas reported so far are formed by condensation of dihydroxyl diketopiperazine or diamine diketopiperazine with toxic diisocyanates, such as MDI.
  • polymeric urethane made from lysine-based-diketopiperazine with the following structure, in which the nitrogen (N ) atom of the urethane bond is originated from
  • LLKP-LDKP urea Neither the urea compounds made from lysine-based-diketopiperazines (LDKP-LDKP urea), nor the ureas based on lysine and lysine-based-diketopiperazine (LPKP- Lysine urea) have been reported:
  • lysine-based-diketopiperazine in which the nitrogen (W ) atom of the urethane bond is originated from lysine-based-diketopiperazine. It will be also desirable and novel to prepare LDKP-LDKP and LDKP-Lysine urea linkages from lysine-based-diketopiperazine and lysine.
  • LDKP/lysine based polyurethanes suitable for a wide range of commercial applications, such as adhesives, coatings, paints, films, inks, binders, fillers and elastomers for various substrates including woods, metals, plastics, concretes, textiles, glass, fibers, papers, leathers and skins.
  • the present invention relates to the novel compounds comprising the structural element derived from lysine and lysine-based-diketopiperazines (LDKP): LDKP urethane unit (I), or LDKP-LDKP urea unit (II), or LDKP-Lysine urea unit (III), LDKP-acryl unit (IV), or their repeat units, or their mixtures:
  • LDKP-acryl (IV)
  • the present invention also relates to the methods for preparation of LDKP urethane unit (I), or LDKP-LDKP urea unit (II), or LDKP-Lysine urea unit (III), LDKP-acryl unit (IV), or their repeat units, or their mixtures, and their use.
  • the present invention also relates to non-isocyanate methods for preparation of lysine polyurethane and urea directly from lysine and its derivatives, and their use:
  • the present invention also relates to non-isocyanate methods for preparation of lysine and/or LDKP based acrylyl containing urethane prepolymers and polyurethane hydrids from lysine and LDKP, and their use.
  • the invention also relates to methods employing carbonylation agents to produce the aforementioned products.
  • the carbonylation agents are more especially non-isocyanate compounds; particular carbonylation agents include chloro carbonylation agents such as phosgene, diphosgene, triphosgene and bischloroformates; particular bischloroformates are those of formula:
  • U is a linking group for example alkylene, optionally interrupted by O, and/or optionally substituted.
  • U is a group inert to the carbonylation reaction and which thus does not disadvantageously interfere with the carbonylation reaction.
  • the group U may be selected to introduce desired properties in the product.
  • the compounds of the invention may be dimers, oligomers, prepolymers, or polymers including homopolymers and copolymers.
  • the polymers will typically have a Molecular Weight (weight average) greater than 2,000, especially 5,000 to 200,000 and preferably 8,000 to 100,000. Dimers, oligomers and prepolymers will typically have a Molecular Weight (weight average) greater than 300 and preferably 500 to 10,000.
  • Polyurethane herein may refer to polyurethane, polyurethane urea, a mixture of
  • polyurethanes a mixture of polyurethane ureas and a mixture of one or more polyurethanes and one or more polyurethane ureas.
  • One aspect of the present invention is the novel compounds comprising the structural element of LDKP urethane unit (I), or LDKP-LDKP urea unit (II), or LDKP-Lysine urea unit (III), LDKP-acryl unit (IV), or their repeat units, or their mixtures: o
  • S-LDKP symmetrical lysine-based-diketopiperazine
  • R' is a linear or branched, saturated or unsaturated, or cyclic or heterocyclic , substituted or unsubstituted, alkyl radical or aryl radical, or the like and mixtures thereof;
  • Y can be H, or methyl
  • cyclic alkylene optionally interrupted by O (e.g., -(CH 2 CH 2 0) ( -CH 2 CH 2 -, -(CH 2 CH 2 CH 2
  • Compound comprising urethane (I) may have the following U-LDKP urethane (I) structure:
  • lysine-based-diketopiperazines made of lysine and an amino acid other than lysine.
  • compound comprising urethane (I) may have the following S-LDKP urethane (I) structure:
  • S-LDKP Urethane (I) in which diketopiperazine is a symmetrical lysine-based-diketopiperazines (S-LDKP), and both amines of S- LDKP form urethane linkages.
  • compound comprising urethane (I) may have the following S-LDKP urethane (I) structure:
  • S-LDKP Urethane (I) in which diketopiperazine is a symmetrical lysine-based-diketopiperazines (S-LDKP), and one amine of S-LKDP forms urethane bond and the other amine forms different bond, e.g., amide or urea linkage.
  • S-LDKP symmetrical lysine-based-diketopiperazines
  • Compound comprising LDKP-LDKP urea (II) may have the following urea structure:
  • LDKP-LDKP Urea (II) can be di(LDKP) urea, or poly(LDKP) urea, for example, tri(LDKP) tetra(LDKP) urea, in which diketopiperazine (DKP) is a symmetrical
  • S-LDKP lysine-based-diketopiperazines
  • Compound comprising LDKP-LYS urea (III) may have the following urea structure:
  • Urea (III) can be LDKP-lysine urea, or poly(LDKP-lysine) urea, for example, LDKP-di(lysine) urea, di(LDKP)-lysine urea, di(LDKP)-di(lysine) urea, tri(LDKP)-lysine urea
  • diketopiperazine is a symmetrical lysine-based-diketopiperazines (S-LDKP).
  • Compound comprising LDKP-acryl unit (IV) may have the following structures in which LDKP is symmetrical:
  • LDKP urethane unit I
  • LDKP-LDKP urea II
  • LDKP-Lysine urea unit III
  • LDKP-acryl unit IV
  • the method for making urethane linkages (I) of this invention comprises reacting
  • lysine-based-diketopiperazines for example S- LDKP, preferably its salt, or S-LDKP terminated compound or prepolymer, with a carbonylation agent for example chloroformates, such as bis-chloroformate.
  • chloroformates can be prepared through phosgenation of the corresponding hydroxyl compounds, e.g., butanediol and polymeric polyol.
  • Lysine polyurethane of this invention is prepared simply by mixing lysine, or its salt, lysine terminated compound or prepolymer, or the mixtures, with chloroformates, such as bis-chloroformate, in the presence of a base, e.g., sodium hydroxide.
  • a base e.g., sodium hydroxide.
  • Reaction may be conducted in a medium, such as in an organic solvent, or aqueous medium, preferably a mixture of water and an organic solvent, in the presence of an acid binding substance, such as sodium carbonate or sodium hydroxide.
  • an emulsifying agent may be employed.
  • Reaction may proceed in interfacial form, e.g. emulsion or suspension, or in a solution, at relatively low temperature, e.g., from -20 to 60 °C, preferably 0-30 °C.
  • Temperature may be raised towards the end of the reaction.
  • concentration of reaction solution and the ratio of chloroformate to amine may vary depending on the product required. High concentration of reaction solution may give a higher yield of urethane products.
  • chain extenders may be employed.
  • lysine-based-diketopiperazine polyurethane is synthesized by addition of sodium hydroxide aqueous solution to the mixture of S- LDKP salt aqueous solution and the chloroformates in acetone under vigorous agitation:
  • Lysine polyurethane is synthesized by the addition of sodium carbonate aqueous solution to the mixture of lysine methyl ester aqueous solution and bis-chloroformate of
  • LDKP-LDKP urea II
  • LDKP-lysine urea III
  • lysine-lysine urea linkages their repeat units, or their mixtures
  • S- LDKP preferably its salt
  • S-LDKP terminated compound or prepolymer or lysine, lysine terminated compound or prepolymer, or mixtures thereof
  • phosgene, diphosgene or triphosgene, or mixtures thereof in the present of an acid binding agent.
  • Reaction may be conducted in a medium, such as in an organic solvent, or aqueous medium, preferably a mixture of water and organic solvent, in the presence of an acid binding substance, such as sodium carbonate or sodium hydroxide.
  • Reaction may proceed in interfacial form, e.g., emulsion, or suspension, or in a solution, at relatively low temperature, e.g., from -20 to 60 °C, preferably 0-30 °C. Temperature may be raised towards the end of the reaction.
  • triphosgene in acetone reacts with S-LDKP salts in an aqueous medium by addition of sodium carbonate solution to produce symmetrical LDKP-LDKP urea (II).
  • triphosgene in acetone reacts with lysine and S-LDKP salts in an aqueous medium by addition of sodium carbonate solution to produce a mixture comprising S-LDKP/S-LDKP urea (II) (mass+H: 539), S-LDKP/LYS urea (III) (mass+H: 429), and other polyureas, for example, S-LDKP/di(LYS) urea (mass+H: 601.4), di(S-LDKP)/LYS urea (Mass+H: 71 1.4), tri(S-LDKP) urea (Mass+H: 821.5),
  • reaction may be carried out in different ways in order to obtain desired products, for example, by changing the order of addition of reactants, or adjusting the pH of reaction mixture.
  • Reaction may proceed by adding base to the mixtures of amine salts, chloroformates and/or phosgene; or chloroformates and/or phosgene may be added to the mixtures of amines and base. It is also possible that amines, base,
  • reaction solution may be adjusted ranging from 4 to 1 , preferably 6-9.
  • Inorganic or organic acid binding substances may be employed, but inorganic base is preferred.
  • Reaction may be conducted in water, or in an organic solvent, but preferably in a mixture of water and organic solvent.
  • the quantity of water and the quantity of organic solvent used during the reaction may vary largely, depending on the type of chloroformates employed and solubility of the product.
  • Soluble solution or dispersion may be formed during the reaction and may be used directly for the application of films, coatings, paints, inks, binders, adhesives, and the like. Gels or precipitant may be produced during the reaction, for example, if reaction is carried out in a concentrated solution.
  • the present invention it is possible to synthesize the polymers in which, all of the urethane and urea linkages are made of LDKP and lysine derivatives.
  • polyols such as natural oil polyols, or biodegradable polyols, e.g., castor oil polyols, polycarbonate polyols, or poly(lactic acid) (PLA) based polyols
  • the present invention teaches the art of the synthesis of low health hazard and environmentally friendly polyurethanes based on renewable materials, LDKP, LDKP/lysine and lysine.
  • polyurethanes can be formulated to fit specific applications by selecting appropriate polyols, varying content and distribution of hard segments, adjusting molecular weight or degree of branching or crosslinking.
  • LDKP low density polyethylene
  • LDKP/lysine and lysine based urethane and urea compounds of varied sizes, shapes, and forms may be designed and obtained. They may be small molecules, oligomers, polymers. They may be linear molecules, dendritic compound, branched, hyper-branched, or cross-linked, or they may contain crosslinkable or reactive groups. They may be employed alone, or be part of other compositions, or be blended with others.
  • They may be produced in liquid form, in solution or dispersion, or in solid state form as elastomers, plastics, or binders, fillers, films, pellets, foams, powders, etc. They may comprise additives, such as pigments, coloring agents, UV absorbing agents, stabilizers, anti-oxidants, silicones, flow agents and the like.
  • polyurethane systems Incorporation of segments, such as crosslinked segments, silicon-containing segments, fluorine-containing segments, the like and mixtures thereof, into polyurethane systems are known in the art to improve chemical and water resistance, abrasion, toughness, durability, and other properties. Accordingly, the polymers of the present invention with desired properties may be achieved by incorporating various segments.
  • chloroformate of caster oil has been employed to prepare crosslinked LDKP polyester polyurethane.
  • PUA polyurethane/acrylate/acrylic hybrids
  • PUAs have been prepared with various methods, e.g., blend, IPN, graft copolymerization, block copolymerization, emulsion or micro-emulsion polymerization.
  • PUA comprising LDKP urethane unit (I), or LDKP-LDKP urea unit (II) or LDKP-lysine urea unit (III), or LDKP-acryl unit (IV), or lysine urethane, or lysine-lysine urea linkages, their repeated units, or the mixtures can be obtained.
  • methacrylate-capped S-LDKP urethane (Unit IV: S-LDKP-mono- and double-Hema-capped) and methacrylate-capped lysine urethane (lysine-Hema-urethane) have been prepared by reacting chloroformate of 2-hydroxyethyl methacrylate (HEMA) with S-LDKP and lysine.
  • HEMA 2-hydroxyethyl methacrylate
  • unit (IV) includes N-LDKP -(meth)acrylamide
  • acrylyl group containing lysine compound and prepolymers for example, N-lysine-acrylamide and lysine-Hema-ester, may be prepared directly from lysine.
  • Any suitable chloroformate of acrylyl moiety containing polyol may be employed for the synthesis of PUA of the present invention.
  • the waterborne polyurethanes of the present invention comprising LDKP urethane unit (I), or LDKP-LDKP urea unit (II), or LDKP-lysine urea unit (III), or LDKP-acryl unit (IV), or lysine urethane, or lysine-lysine urea linkages, their repeated units, or the mixtures, can be designed and obtained.
  • Polyurethane comprising lysine urethane linkage formed directly from lysine can be water soluble or water dispersible.
  • Waterborne urethane copolymers based on S-LDKP, lysine and bis-chloroformates of polyester polyol and butanediol have been achieved through the presence of the carboxylic salt of lysine.
  • waterborne polyurethane can be formulated to obtain desired properties.
  • WPU coatings US 6359060; US 6239209; Z.S. Chen, W.P. Tu, and J.Q. HU; Thermosetting Resin Vol.22, No.2, 51 -54, 2007).
  • the waterborne polyurethane of the present invention comprising LDKP urethane unit (I), or LDKP-LDKP urea unit (II) or LDKP-lysine urea unit (III), or LDKP-acryl unit (IV), or lysine urethane, or lysine-lysine urea linkages, their repeated units, or the mixtures, with special properties
  • LDKP urethane unit (I), or LDKP-LDKP urea unit (II) or LDKP-lysine urea unit (III), or LDKP-acryl unit (IV), or lysine urethane, or lysine-lysine urea linkages, their repeated units, or the mixtures, with special properties may be achieved through crosslinking, grafting, incorporation of special segments and functional groups, such as acrylates, self-crosslinkable ethylenically unsaturated double bonds, epoxy, silicon-containing segments, flu
  • lysine-hema-PUA prepolymer is obtained by mixing lysine with the chloroformates of hema, caster oil and polyols, and sodium hydroxide solution.
  • the resulting PUA prepolymer can be dissolved in a green organic solvent, e.g., ethanol or isopropanol (alcohol lysine PUA), or be dispersed into water (waterborne lysine PUA), or water/alcohol mixture solvents.
  • a green organic solvent e.g., ethanol or isopropanol
  • water waterborne lysine PUA
  • water/alcohol mixture solvents water/alcohol mixture solvents.
  • Homopolymerization or copolymerization with other monomers, e.g. butyl mathacrylate by UV irradiation in the presence of photo-initiator yields a crosslinked PUA hybrid with improved water resistance:
  • amines other than LDKP or lysine may also be employed in order to obtain specific properties.
  • the ratio of components may vary depending upon the physical properties desired in the final polymers.
  • IPDA isophore diamine
  • bis-chloroformate of polyester polyol as a soft segment
  • lysine as an ionic compound
  • lysine/IPDA waterborne polyurethane dispersion is synthesized by addition of sodium hydroxide aqueous solution to the mixture of IPDA, lysine and chloroformates in acetone:
  • IPDA-lysine based polyurethane waterborne dispersion After distilling off the acetone.
  • Other polyamines, polyisocyanates and chain extenders may also be employed in the synthesis of lysine and lysine-based-diketopiperazine containing waterborne polyurethane of the present invention.
  • isophore diamine first reacts with methacrylol chloride to form
  • N-IPDA-methacrylamide N-IPDA-methacrylamide. It is then mixed with bis-chloreformates of polytetramethylene ether glycol (PTMG) and 1 ,4-butanediol, lysine and sodium hydroxide aqueous solution under vigorous agitation to give methacrylamide-IPDA/ lysine urethane prepolymers.
  • PTMG polytetramethylene ether glycol
  • 1 ,4-butanediol 1 ,4-butanediol
  • lysine and sodium hydroxide aqueous solution under vigorous agitation to give methacrylamide-IPDA/ lysine urethane prepolymers.
  • the resulting PUA prepolymer can be dissolved in ethanol or isopropanol, or dispersed into water/alcohol mixture solvents. Homopolymerization or copolymerization with other monomers, by UV irradiation,
  • the present invention provides a simple cost-effective method for preparing polyurethane prepolymer containing polymerizable ethylenically unsaturated group directly from amines, such as lysine and LDKP.
  • Acrylyly moiety is used in the present examples, but other types of polymerizable double bond containing moieties, for example, allyly group may be employed as well.
  • the PUA prepolymer can be used directly from reaction solution for further polymerization, or they can be isolated, and dissolved or dispersed in water, in ethanol or isopropanol, or in water/alcohol mixture for further applications.
  • the hydrophilic group employed in the present examples is the carboxylic acid of lysine. It is obvious that the solubility or dispersibility of the polyurethanes of the present invention in water or
  • water/alcohol mixtures, or alcohol can be achieved by attaching anionic groups, such as carboxylic, sulfonic, sulfate, phosphate or cationic group, such as tertiary amine, or by introducing non-ionic hydrophilic groups, such as polyethoxy chain, repeat unit of ethylene oxide and other alkylene oxides, into polymer chains.
  • anionic groups such as carboxylic, sulfonic, sulfate, phosphate or cationic group, such as tertiary amine
  • non-ionic hydrophilic groups such as polyethoxy chain, repeat unit of ethylene oxide and other alkylene oxides
  • the prepolymer of the present invention are capable of homopolymerization and
  • lysine-based-diketopiperazine may be employed as a salt, such as hydrochloric acid, acetic acid, or sulfate salt, the like, and mixtures thereof. It may be obtained according to various methods.
  • LDKP may be used as a crude product or aqueous solution, which may contain lysine, polypeptides, amino caprolactam, and other derivatives. Therefore, the resulting urethane and/or urea compounds of the present invention may have peptide and caprolactam segments.
  • Lysine derivatives may have the following formula:
  • Lysine diisocyanates may have the following formula:
  • R is a linear or branched, saturated or unsaturated, cyclo or heterocycio, substituted or unsubstituted, alkyl radical or aryl radical, the like and mixtures thereof.
  • Any suitable chloroformate may be used in the preparation of LDKP, LDKP/lysine and lysine based urethane and/or urea compounds of the present invention.
  • the chloroformates may be prepared in a known manner, such as by the phosgenation of the corresponding hydroxyl containing compound. It is also possible to use crude chloroformates, which may contain hydroxyl group, carbonate linkage, phosgene component, solvent, etc.
  • Hydroxyl containing compounds used to prepare chloroformates of the present invention may be monohydroxyl compounds, diols, triols, polyols, polymeric polyols, or mixtures thereof. They may contain other substituents, functional groups, unsaturated bonds, hetero elements, such as Si, F, S, N. They may be produced from renewable natural resources and such as to be biodegradable.
  • hydroxyl containing compounds include, but are not limited to: low molecular weight diols, triols and polyol, including aliphatic, aromatic, mixed aliphatic-aromatic, cycloaliphatic diols, such as ethylene glycol, di- and tri-ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,3- and 14-butanediol, various pentanediols, hexanediols, heptanediols, octanediols, neopentyl glycol, 2,2-dimethyl propanediol,
  • carboxylic acid such as adipic acid, succinic acid, fumaric acid, malonic acid, oxalic acid, methyl adipic acid, glutaric acid, tartaric acid, citric acid, phthalic acid, maleic acid, thiodipropionic acid, thiodibutyric acid, sulfonyl dibutyric acid, glutamic acid, suberic acid, pimeric acid, sebacic acid, terephthalic acid, isophthalic acid, the like and mixtures thereof, and those prepared by ring opening or other process, such as polyols of
  • poly(cycloalkylene carbonate) polyols e.g., WO Patent 201 1/129940 A1
  • polyether polycarbonate polyols e.g., PACAPOL tm , QUICKSTAR tm
  • those by various suppliers such as Bayer, Arch Chemicals INC, Daicel Chemical Industries Inc., and any linear and branched polycarbonate polyols or copolymers containing or modified with functional groups, e.g., double bond, crosslinkable moiety, the like and mixtures thereof; any suitable other polymeric polyols, various polyacrylic polyols and polyacetal polyols, hydroxyl-terminated butanediene polymers(HTBP), hydrogenated HTBP, hydroxyl-terminated polysiloxanes, dihydrooxypolydimethylsiloxane, polysulfide polyol, hydroxyl containing polythioethers, hydroxyl-containing epoxies, or any other suitable hydroxyl-
  • Any suitable (alkyl)acrylate, acrylate, methacrylate, acrylic, acrylamide or vinyl monomers can be employed for the preparation of PUA hybrids, waterborne PUA hybrids and alcohol PUA hybrids of the present invention.
  • suitable (alkyl)acrylate, acrylate, methacrylate, acrylic, acrylamide or vinyl monomers can be employed for the preparation of PUA hybrids, waterborne PUA hybrids and alcohol PUA hybrids of the present invention. Examples include, but are not limited to, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, (n-, t-)butyl (meth)crylate, hexyl
  • Chloroformates of acrylyly or methacrylyl moiety containing polyols may also be used.
  • polymerization initiators such as azoisobutylnitrile (AIBN), benzoylperoxide, potassium persulfate, photo initiators, e.g., those of Irgacure from Siba, and the like may be employed.
  • Any suitable compound which may contain anionic groups, such as carboxylic, sulfonic, sulfate, phosphate, or cationic group, such as tertiary amine, or non-ionic hydrophilic groups, such as polyethoxy chain, repeat unit of ethylene oxide and other alkylene oxides, e.g., polyethoxy diol, poly(ethoxy/-propoxy) diol, a diol containing a pendant ethoxy chain, etc., may be employed in the syntheses of waterborne or alcohol polyurethane of the present invention.
  • anionic groups such as carboxylic, sulfonic, sulfate, phosphate, or cationic group, such as tertiary amine
  • non-ionic hydrophilic groups such as polyethoxy chain, repeat unit of ethylene oxide and other alkylene oxides, e.g., polyethoxy diol, poly(ethoxy/-propoxy) diol, a di
  • Any suitable chain extender may be used in the preparation of urethane and/or urea compounds of the present invention. They can be selected from, but are not limited to, polyisocyanates, polyamines, polychloroformates, phosgene, diphosgene, triphosgene, the like, and mixtures thereof.
  • Any suitable acid binding agent, organic base, e.g., tertiary amine, or inorganic base, such as hydroxide, oxide, carbonate, hydrogen carbonates of the alkali metals and alkaline earth metals, or the mixtures, may be used in the preparation of urethane and/or urea compounds of the present invention.
  • suitable acid binding agent, organic base, e.g., tertiary amine, or inorganic base such as hydroxide, oxide, carbonate, hydrogen carbonates of the alkali metals and alkaline earth metals, or the mixtures, may be used in the preparation of urethane and/or urea compounds of the present invention.
  • suitable acid binding agent organic base, e.g., tertiary amine, or inorganic base, such as hydroxide, oxide, carbonate, hydrogen carbonates of the alkali metals and alkaline earth metals, or the mixtures
  • examples include, but are not limited to, sodium hydroxide, potassium hydroxide
  • amines such as lysine-based-diketopiperazine, or lysine
  • Any suitable amines may be employed in the preparation of urethane and /or urea compounds of the present invention.
  • Amines can be primary or secondary aliphatic, alicyclic, aromatic or heterocyclic polyamines, polymeric amines, or any suitable amine, their derivatives or mixtures.
  • Representatives include, but are not limited to, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, piperazine, 2,5-dimethylpiperazine, (m-.p-)xylene diamine, 1 ,4-diaminocyclohexane, p-phenylene diamine,
  • Polyisocyanates may react with amines or hydroxyl groups, LDKP, LDKP-terminated prepolymer, lysine, lysine-terminated prepolymer, or be used as chain extenders.
  • Isocyanates can be primary or secondary aliphatic, alicyclic, aromatic or heterocyclic polyisocyanates, or isocyanate-terminated prepolymers, or any suitable isocyanate, or their derivatives or mixtures.
  • IPDI isophore diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI methylene bis (p-cyclohexl) isocyanate
  • CHDI cyclohexyl diisocyanate
  • TDI 4-toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • PPDI p-phenylene diisocyanate
  • 1 ,5-naphthylene diisocyanate tolidine diisocyanate
  • m-.p-)xylene diisocyanate and more.
  • Triisocyanates such as lysine based triisocyanate, or tetraisocyanates or polyisocyanates or derivatives of the said isocyanates or mixtures of the said isocyanates may also be used.
  • Any suitable solvent or diluent may be used in the preparation of urethane and/or urea compounds of the present invention. It can be water, or organic solvent, preferably a mixture of water and organic solvent. It can be water miscible or immiscible, such as acetone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, isopropanol, dioxane, ethyl acetate, acetonitrile, diethyl ether, aromatic hydrocarbon such as toluene, chlorinated aromatic or aliphatic hydrocarbons and the like. Mixtures of such solvents may also be used.
  • water miscible or immiscible such as acetone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, isopropanol, dioxane, ethyl acetate, acetonitrile, diethyl ether,
  • LDKP urethanes of the present invention may be obtained by routes other than by the reaction of LDKP with chloroformates.
  • reaction of LDKP with carbonates, such as dimethyl carbonate or cyclic carbonates may lead to the formation of urethanes of the present invention.
  • chlorofomate first reacts with N-hydroxysuccinimide to yield the corresponding succinimidyl carbonate derivative, which is then condensed with lysine diketopiperazine to give diketopiperazine urethane.
  • LDKP-Lysine urea (III) may also be obtained by reaction of LDKP with lysine diisocyanate derivatives.
  • the present invention provides a simple non-isocyanate method to produce LDKP
  • LDKP/lysine and lysine based urethane and urea compounds from LDKP, lysine and its derivatives According to the method of the present invention, it will be apparent to those skilled in the art that a wide variety of combinations are possible to yield various LDKP and lysine products and copolymers according to the ultimate use without departing from the spirit of the invention.
  • Lysine polyurethanes are known in the art to be used as biomedical and biodegradable materials. They have been tailored to fit various usages, such as adhesives, artificial skins, wound dressings, artificial veins, gels, etc.
  • the present invention provides an alternative low-cost green method for the preparation of lysine urethane and urea compounds directly from more readily available lysine, instead of lysine diisocyanate. Therefore, they may have similar applications as those of lysine polyurethane prepared via the known conventional isocyanate process.
  • the novel LDKP and LDKP/lysine based urethane and urea polymers of the present invention provide the alternative polyurethanes of comparable performance based on raw materials deriving from natural renewable resources. They are intended to replace polyurethanes made of conventional isocyanates and may have as many applications as those of conventional polyurethanes, providing the advantages of the absence of health and environmental hazard. They may be utilized in preparing various polyurethane articles, such as coatings, paints, adhesives, inks, binders, fillers, castings, elastomers, fibers, gels and the like in the art, for packaging, toy, cosmetic, building materials, automobiles, biomedical, and other urethane related industries.
  • LDKP polyurethanes of the present invention exhibit excellent film-forming property and moisture resistance.
  • polyurethane made from polyester and castor oil polyols has less than 4% water uptake and displays a good resistance to scratch.
  • the thermal stability of LDKP polyurethane of the present invention has been found to be eminently higher (e.g., 5% weight loss at 310 °C) than that of lysine polyurethane ( ⁇ 260 °C).
  • LDKP/lysine based PUA copolymer (urethane/acrylate hybrids) displays an excellent water resistance.
  • LDKP and LDKP/lysine based polyurethane films, coatings and paints of varied properties suitable for a range of high performance applications on various substrates including woods, metals, plastics, concretes, textiles, glass, fibers, papers, leathers, artificial leathers, and skins.
  • LDKP , LDKP/lysine and lysine polyurethanes of the present invention may be used as adhesives for laminates, flexible packaging, multilayer films, leathers and artificial leathers, shoes, printing inks and other adhesive related applications.
  • LDKP, LDKP/lysine and lysine polyurethanes with various soft or melting points can be obtained. They display excellent hot-melt adhesive properties on surfaces such as glass, metals, woods, and papers.
  • LDKP, LDKP/lysine and lysine polyurethanes of the present invention may be especially useful as adhesives for food package, flexible package, medical package, e.g., glues for papers, labels, or glues for caps and closures of containers, bags, bottles, where adhesives may come in contact with the food products, medicines etc. They may also be useful as adhesives for plywood and furniture, providing good properties normally associated with polyurethane adhesives without releasing toxic chemicals such as formaldehyde fumes or diamines.
  • LDKP, LDKP/lysine and lysine polyurethanes of the present invention may be useful in preparing moldings, or casting articles of various kinds, and the like, such as toys, sporting goods, household items.
  • LDKP, LDKP/lysine and lysine polyurethanes of the present invention may be useful as biomedical materials for making various biomedical products and applications, such as artificial skin, wound dressings, artificial veins, medical devices, bandages, pads, tubings, gels, drug delivery, etc. They may be excellent biodegradable materials, especially when biodegradable polyols such as polycarbonate or PLA polyols are employed.
  • LDKP , LDKP/lysine and lysine based waterborne polyurethanes (WPU), waterborne or alcohol urethane-acryl prepolymers and PUA hybrids have the advantages including environmental friendliness, low cost and good water resistance. They may be utilized in preparing various polyurethane articles, such as coatings, paints, adhesives, inks, binders, castings, gels and the like in the art, Coatings, paints, adhesives, or films may be obtained from LDKP, LDKP/lysine and lysine polyurethanes of the present invention by any suitable known method, including spray, brush, roller coating, casting, dipping, or hot-melt.
  • 0.52 gram of symmetrical lysine-based-diketopiperazines dihydrochoride is dissolved in 15 ml of water cooled by ice water. To this are added with agitation a solution of 0.30 gram of sodium carbonate in 2 ml of water and a solution of 0.03 gram of triphosgene in 2 ml of acetone. The reaction mixture is stirred for 20 min at 10-15 ° C and then pH is adjusted to 6 with dilute hydrochloric acid aqueous solution.
  • 0.2 gram of symmetrical lysine-based-diketopiperazines dihydrochoride and 0.2 gram of lysine monohydrochoride are dissolved in 5 ml of water cooled by ice water. To this are added with agitation a solution of 0.16 gram of sodium carbonate in 1 ml of water and a solution of 0.04 gram of triphosgene in 1 ml of acetone. The reaction mixture is stirred for 20 min at 10-15 ° C and then pH is adjusted to 6 with dilute hydrochloric acid aqueous solution.
  • S-LDKP/S-LDKP urea (II) (Mass+H: 539), S-LDKP/LYS urea (III) (Mass+H: 429) and polyureas, e.g., S-LDKP/di(LYS) urea (mass+H: 601.4), di(S-LDKP)/LYS urea (Mass+H: 71 1.4), tri(S-LDKP) urea (Mass+H: 821.5), di(S-LDKP)/di(LYS) urea (mass+H:883.5), tri(S-LDKP)/LYS urea (mass+H: 993.6), tetra(S-LDKP) urea (mass+H: 1 103.8), tri(S-LDKP)/di(LYS) urea (mass+H: 1 165.8), tetra(S-LDKP/di(LYS) urea (mass
  • 0.33 gram of symmetrical lysine-based-diketopiperazines dihydrochoride and 0.23 gram of lysine monohydrochoride are dissolved in 1 ml of water cooled by ice water. To this are added with agitation a solution of 0.10 gram of sodium carbonate in 0.5 ml of water and a solution of 0.015 gram of triphosgene in 1 ml of acetone.
  • phosgenation product of polyester polyol, Mn 2000, made of hexanedioic acid, , 4-butanediol and 1 , 2-ethanediol
  • a solution of 0.70 gram of sodium carbonate in 2 ml of water while the temperature is held around 5-15 ° C and pH is around 6-8 during the addition. It is then allowed to stir at room temperature until solution becomes viscous.
  • HEMA 2-hydroxyethyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • urethane-acrylate solution yields a tough film with a water absorption of 3%.
  • lysine hydrochloride is dissolved in 2 ml of water cooled by ice water. To this are added with agitation a solution of 1.1 grams of chloroformate of 2-hydroxyethyl methacrylate (HE A) in 2 ml of cold acetone and sodium hydroxide solution. The temperature of reaction solution is held around 5-15 ° C and pH is around 6-8.
  • Part one is subjected to a strong agitation to give a lysine-urethane-methacrylate prepolymer waterborne dispersion after distilling off the acetone.
  • Irradiation (NOVACURE, 00 W Hg vapor short arc) of the coat of lysine-urethane-methacrylate prepolymer waterborne dispersion yields a crosslinked film with a water absorption large than 80 %.
  • Part two after removing solvent, yields the sticky lysine PUA prepolymer which is then dissolved in a water/alcohol mixture solvents to give an alcohol PUA prepolymer solution.
  • Copolymerization with butyl mathacrylate by UV irradiation the coat of mixtures in the presence of
  • photo-initiator yields a crosslinked PUA hybrid with a water absoption of 25 %.
  • reaction solution is held around 5-15 ° C and pH is controlled around 6-8 during the addition. It is then allowed to stir at room temperature until solution becomes viscous. Organic layer is then added into water under strong stirring to give an IPDA-Lysine based polyurethane waterborne dispersion after distilling off the acetone.
  • the film coat of resultant waterborne polyurethane displays an excellent adhesive property on paper.
  • the organic layer is separated to give the sticky PUA prepolymer after distilling off the solvent.
  • the resulting PUA prepolymer is soluble in ethanol and isopropanol, and can be dispersed into water/ethanol (2:1 ) mixture solvents.
  • Example 14 After the solution becomes very viscous, polymer is removed, washed with water and dried. The resultant polyurethane melts around 1 10 ° C and displays a good hot-melt adhesive property on surface of glass. The film has a water absorption of 60 %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne a) un composé comprenant un élément structural d'unité d'uréthane de dicétopipérazine dérivé de lysine (LDKP) (I), d'unité d'urée LDKP-LDKP (II), d'unité d'urée de lysine LDKP (III) ou d'unité LDKP-acnl (IV), ou de leurs mélanges ou unités répétés et; b) un procédé de préparation desdits composés à base de lysine et d'un agent de carbonylation, sans l'utilisation d'un isocyanate.
PCT/CA2013/000290 2012-03-28 2013-03-26 Uréthanes et urées, et procédés associés WO2013142969A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201380015332.0A CN104284918B (zh) 2012-03-28 2013-03-26 氨酯型和脲酯型化合物及其制备方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261616578P 2012-03-28 2012-03-28
US61/616,578 2012-03-28

Publications (1)

Publication Number Publication Date
WO2013142969A1 true WO2013142969A1 (fr) 2013-10-03

Family

ID=49258000

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2013/000290 WO2013142969A1 (fr) 2012-03-28 2013-03-26 Uréthanes et urées, et procédés associés

Country Status (2)

Country Link
CN (1) CN104284918B (fr)
WO (1) WO2013142969A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016050798A1 (fr) * 2014-10-02 2016-04-07 Solvay Specialty Polymers Usa, Llc (co)polymères, dont des diamides cycliques
WO2017173202A1 (fr) * 2016-03-31 2017-10-05 Lubrizol Advanced Materials, Inc. Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables
WO2017176671A1 (fr) * 2016-04-05 2017-10-12 Sun Chemical Corporation Systèmes hybrides de polyuréthane-polyacrylate pour des encres et des revêtements d'emballage
US10221309B2 (en) 2016-09-23 2019-03-05 Rohm And Haas Company Latex functionalized with structural units of an amino acid
WO2020142450A1 (fr) * 2018-12-31 2020-07-09 Zymergen Inc. Compositions polymères comprenant des composés dérivés de la biologie
US10751423B2 (en) 2016-05-02 2020-08-25 Massachusetts Institute Of Technology Nanoparticle conjugates of highly potent toxins and intraperitoneal administration of nanoparticles for treating or imaging cancer
KR102209962B1 (ko) * 2019-08-27 2021-02-01 한국화학연구원 폴리아미도아민 입자 및 이를 이용한 중금속 오염수의 처리방법
CN114591652A (zh) * 2014-04-15 2022-06-07 爱克发有限公司 水性树脂基喷墨油墨
CN115522275A (zh) * 2022-09-30 2022-12-27 连云港杜钟新奥神氨纶有限公司 一种高回弹氨纶纤维及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112018072006A2 (pt) * 2016-04-28 2019-04-02 The University Of Akron adesivo ósseo degradável à base de poli (éster ureia) fosforilada
CN106590304A (zh) * 2016-12-09 2017-04-26 佛山市顺德区数码彩涂料有限公司 一种水泥聚合物环保外墙涂料
CN114716635A (zh) * 2022-05-12 2022-07-08 四川大学 一种多功能聚脲基酸衍生物及其制备方法和应用
CN114907546B (zh) * 2022-05-12 2023-06-02 四川大学 一种多功能聚脲基酸酯衍生物及其制方法和应用
CN115160173B (zh) * 2022-09-01 2022-12-02 烟台海川化学制品有限公司 Nε-十二酰基赖氨酸的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018754A1 (fr) * 1992-03-11 1993-09-30 Pharmaceutical Discovery Corporation Systeme d'administration de medicaments a base de dicetopiperazine
WO1997017985A1 (fr) * 1995-11-13 1997-05-22 Smithkline Beecham Corporation Composes hematoregulateurs
CA2575692A1 (fr) * 2004-08-20 2006-03-02 Mannkind Corporation Catalyse de la synthese de dicetopiperazine
WO2009037642A1 (fr) * 2007-09-17 2009-03-26 Ariel - The University Company For Research And Development, Ltd Echafaudages hétérocycliques utiles pour la préparation de bibliothèques combinatoires, bibliothèques et leurs procédés de préparation
CA2748490A1 (fr) * 2008-12-29 2010-07-08 Mannkind Corporation Analogues substitues de dicetopiperazine pour une utilisation en tant qu'agents d'administration de medicaments
WO2012109256A2 (fr) * 2011-02-10 2012-08-16 Mannkind, Corp Formation de 3,6-bis(4-aminoalkyl)-2,5-dicétopipérazine n-protégée

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006046650A1 (de) * 2006-09-29 2008-04-03 Bayer Materialscience Ag Wässrige Beschichtungsmittel auf Basis von Polyurethan-Dispersionen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018754A1 (fr) * 1992-03-11 1993-09-30 Pharmaceutical Discovery Corporation Systeme d'administration de medicaments a base de dicetopiperazine
US5503852A (en) * 1992-03-11 1996-04-02 Pharmaceutical Discovery Corporation Method for making self-assembling diketopiperazine drug delivery system
WO1997017985A1 (fr) * 1995-11-13 1997-05-22 Smithkline Beecham Corporation Composes hematoregulateurs
CA2575692A1 (fr) * 2004-08-20 2006-03-02 Mannkind Corporation Catalyse de la synthese de dicetopiperazine
WO2009037642A1 (fr) * 2007-09-17 2009-03-26 Ariel - The University Company For Research And Development, Ltd Echafaudages hétérocycliques utiles pour la préparation de bibliothèques combinatoires, bibliothèques et leurs procédés de préparation
CA2748490A1 (fr) * 2008-12-29 2010-07-08 Mannkind Corporation Analogues substitues de dicetopiperazine pour une utilisation en tant qu'agents d'administration de medicaments
WO2012109256A2 (fr) * 2011-02-10 2012-08-16 Mannkind, Corp Formation de 3,6-bis(4-aminoalkyl)-2,5-dicétopipérazine n-protégée

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
AKERLUND, J ET AL.: "Dil.etopiperazine-Based polymers from Common Amino Acids", JOURNAL OF APPLIED POLYNZER SCIENCE, vol. 78, 2000, pages 2213 - 2218 *
DEL FRESNO, M ET AL.: "Solid-phase synthesis of Dil.etopiperazines, Useful Scaffolds for Combinatorial Chemistry", TETRAHEDRON LETTERS, vol. 39, 1998, pages 2639 - 2642 *
HAINO, T ET AL.: "on-beads screening of solid-attached diketopiperazines for cliz[5]arene-based receptor", TETRAHEDRON LETTERS, vol. 44, 2003, pages 3889 - 3892, XP004421868, DOI: doi:10.1016/S0040-4039(03)00825-6 *
HAN, SO-YEOP E ET AL.: "Recent development of peptide coupling reagents in organic synthesis", TETRAHEDRON, vol. 60, 2004, pages 2447 - 2467, XP004492575, DOI: doi:10.1016/j.tet.2004.01.020 *
KAUR, N ET AL.: "A Delineation of Diketopiperazine Self-Assembly Processes: Understanding the Molecular Events Involved in N-(Fumarovl)diketopiperazine of Lys (FDKP) Interactions. whole document", MOLECZRLAR PHARNZACEZRTICS, vol. 5, no. 2, 2008, pages 294 - 315 *
MAJO, MA ET AL.: "Polvcondensation of Lysine Diketopiperazine with Tartaric Acid -Evidence on the Formation of Cyclic Oligomers", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 207, 2006, pages 615 - 620 *
RODIONOV, I ET AL.: "Cyclic dipeptides as buidling blocks for combinatorial libraries. Part 2: synthesis of bifunctional diketopiperazines", TETRAHEDRON, vol. 58, 2002, pages 8515 - 8523 *
SCOTT, BO ET AL.: "Solid Phase Organic Synthesis (SPOS): A novel route to diketopiperazines and diketomorpholines", MOLECULARDIVERSITY, 1995, pages 125 - 134 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114591652A (zh) * 2014-04-15 2022-06-07 爱克发有限公司 水性树脂基喷墨油墨
WO2016050798A1 (fr) * 2014-10-02 2016-04-07 Solvay Specialty Polymers Usa, Llc (co)polymères, dont des diamides cycliques
CN109196012A (zh) * 2016-03-31 2019-01-11 路博润先进材料公司 可生物降解和/或生物可吸收的热塑性聚氨酯
WO2017173202A1 (fr) * 2016-03-31 2017-10-05 Lubrizol Advanced Materials, Inc. Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables
US11525028B2 (en) 2016-03-31 2022-12-13 Lubrizol Advanced Materials, Inc. Biodegradable and/or bioabsorbable thermoplastic polyurethanes
WO2017176671A1 (fr) * 2016-04-05 2017-10-12 Sun Chemical Corporation Systèmes hybrides de polyuréthane-polyacrylate pour des encres et des revêtements d'emballage
US11299649B2 (en) 2016-04-05 2022-04-12 Sun Chemical Corporation Polyurethane-polyacrylate hybrid systems for packaging inks and coatings
US10751423B2 (en) 2016-05-02 2020-08-25 Massachusetts Institute Of Technology Nanoparticle conjugates of highly potent toxins and intraperitoneal administration of nanoparticles for treating or imaging cancer
US11730826B2 (en) 2016-05-02 2023-08-22 Massachusetts Institute Of Technology Amphiphilic nanoparticles for delivery of CRISPR based therapy
US10221309B2 (en) 2016-09-23 2019-03-05 Rohm And Haas Company Latex functionalized with structural units of an amino acid
WO2020142450A1 (fr) * 2018-12-31 2020-07-09 Zymergen Inc. Compositions polymères comprenant des composés dérivés de la biologie
KR102209962B1 (ko) * 2019-08-27 2021-02-01 한국화학연구원 폴리아미도아민 입자 및 이를 이용한 중금속 오염수의 처리방법
CN115522275A (zh) * 2022-09-30 2022-12-27 连云港杜钟新奥神氨纶有限公司 一种高回弹氨纶纤维及其制备方法

Also Published As

Publication number Publication date
CN104284918A (zh) 2015-01-14
CN104284918B (zh) 2017-03-29

Similar Documents

Publication Publication Date Title
WO2013142969A1 (fr) Uréthanes et urées, et procédés associés
EP2956495B1 (fr) Dispersion uréthane-polyamide à base d'eau
Mehravar et al. Polyurethane/acrylic hybrid waterborne dispersions: synthesis, properties and applications
CA1125299A (fr) Triisocyanate aliphatique, methode de preparation, et composition de revetement a base de polyurethane et de ce produit
CA2957915C (fr) Compositions aqueuses de revetement de copolymere destinees a des applications de construction et industrielles
US10640616B2 (en) Waterborne polyamide and their chain extension with isocyanates to form cationic waterborne polyureas dispersions
JPH01168756A (ja) 水性重合体分散体
CA2034857A1 (fr) Production de polymeres de polyurethane, les polymeres ainsi produits et les compositions les renfermant
US5900457A (en) Aqueous polyurethane dispersions formed from polyisocyanates having a methylene bridge
US9988555B2 (en) Water-borne polyamide-urea dispersions
KR102628833B1 (ko) 매트한 폴리아미드-푸드
Wołosz et al. Environmentally friendly synthesis of urea-free poly (carbonate-urethane) elastomers
CA2435110A1 (fr) Procede de production de polyurethanes exempts d'isocyanate par polyesterification de carbamate
JPH06145289A (ja) 熱可塑性ポリウレタンポリ尿素及びその製造方法
US7314899B2 (en) Process for the preparation of poly (urethane-acrylic) copolymer dispersion for industrial applications
JP2023097364A (ja) ポリエステル

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13767606

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13767606

Country of ref document: EP

Kind code of ref document: A1