CN104284918A - Urethanes and ureas and processes - Google Patents

Urethanes and ureas and processes Download PDF

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CN104284918A
CN104284918A CN201380015332.0A CN201380015332A CN104284918A CN 104284918 A CN104284918 A CN 104284918A CN 201380015332 A CN201380015332 A CN 201380015332A CN 104284918 A CN104284918 A CN 104284918A
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ldkp
urea
methionin
compound
acrylate
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CN104284918B (en
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高剑萍
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Liaoning Tiancai Materials Co ltd
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    • 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

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  • 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

The present invention relates to a) a compound comprising a structural element of lysine-derived diketopiperazine (LDKP) urethane unit (I), LDKP-LDKP urea unit (II), LDKP-Lysine urea unit (III), or LDKP-acnl unit (IV), or their repeated units or mixtures, and to b) a process for preparing the compounds based on lysine and a carbonylation agent without the use of an isocyanate.

Description

Ammonia ester type and urea ester type compound and preparation method thereof
Technical field
The present invention relates to ammonia ester type and urea ester type compound, the preparation method and application of Methionin and Methionin diketopiperazine.
Background technology
Urethane and polyurethane-urea (being referred to as urethane here) refer to and main chain contain carbamate (-OCONH-) or/and the macromolecular material of carboxylamine urea (-HNCONH-) structural unit.
Urethane is one of synthetic materials be most widely used, and major domain comprises foam, tackiness agent, elastomerics and plastics etc.Such as household articles in daily daily necessities, sports equipment, food product pack, wood floors, substrate, wall coating etc., be also seen everywhere polyurethane material.Nowadays, also widespread use urethane in bio-medical and biodegradable material.Because the whole world consumes a large amount of polyurethane materials every year, its impact of bringing to the health of people and environment is also taken seriously day by day.
One of reason is the isocyanic ester using toxicity relatively large in production process.Urethane is by vulcabond, polyvalent alcohol and the synthesis of the raw material reaction such as small molecules glycol or diamines, and applying more vulcabond has aromatic diisocyanate, as toluene 2,4-vulcabond (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI); Aliphatic diisocyanate, comprises isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) etc.Although polyurethane products itself are considered to nontoxic, these di-isocyanate reactions are high, toxicity large, can cause serious respiratory system infection and other people body health problem.
Another potential harm is that polyurethane material may discharge objectionable impurities (Delilah Lithner, Jeanette Damberg, Goran Dave, Ake Larsson, Chemosphere74 (2009) 1195-1200).Research shows that ammonia ester bond (-OCONH-) in urethane and urea key (-HNCONH-) can be degraded, as passed through hydrolysis, pyrolysis or microbiological deterioration etc. (" Chemical degradation of Polyurethane ", Vincent Gajewski, Rubber World Sept.1,1990), carcinogenic aromatic diamine of degrading out lentamente, or lower but still there is the aliphatie diamine of certain toxicity.As slowly released carcinogenic 4 from MDI type polyurethane material, 4 '-methylene dianiline (MDA), directly have influence on surrounding environment (Maurizio Tosin, Francesco Degli-Innocenti, and Catia Bastioti, Journal of Environmental Polymer Degradation (1998), 6 (2), 79-90).
In addition, the problem involved by urethane also comprises carbon emission and the dependence to petroleum sources.Along with the regulation of increasingly stringent and the appearance of low-carbon (LC) row policy, require will become more urgent from renewable resources synthesis of polyurethane material.At present, many natural base vegetable oil polyols (NOPs) have been developed, as castor oil polyhydric alcohol and soybean oil polyol, and for the synthesis of polyurethane material.
Methionin is can mass-produced natural amino acid.Substituting as a kind of petrochemicals, lysinediisocyanate (LDI) is developed (French Patent 1351368) by people.Early stage United States Patent (USP) (US3281378, US3358005) also describes uses lysinediisocyanate synthesis of polyurethane, polyureas and polyurethane-urea and application thereof.
OCNCH2CH2CH2CH2CH(COOX)NCO (LDI).
Based on advantages such as its non-toxic degradables, existing a large amount of about the urethane of LDI synthesized degradable and the report of potential application thereof in recent decades.As, WO 89/05830 just describes how to prepare biodegradation type medical polyurethane with LDI, and has looked forward to it at artificial skin, artificial blood vessel, the application prospect of the medical fields such as neural transplantation; The base polyurethane prepolymer for use as that United States Patent (USP) (US7264823) also discloses a kind of LDI end-blocking can be used as medical adhesive; Also bibliographical information is had recently with LDI and poly-(lactic acid), PEG-poly-(lactic acid) (PLA-PEG-PLA) polyvalent alcohol etc. is Material synthesis fast degradation type polyurethane (Z.Wang, L.Yu, M.Ding, H.Tan, J.Li, and Q.Fu, Polym.Chem., 2,601-607,2011).
But current reported Methionin type polyurethane all mainly uses lysinediisocyanate (formicester or second fat) to be Material synthesis.And document (A.Nathan, D.Bolikal, N.Vyavahare, S.Zalipsky, and J.Kohn, Macromolecules, 25,4476-4484,1992) describe and prepare Methionin type polyurethane polycondensate with Methionin second fat and polysuccinimide carbonate reaction.This method first the chloro-formic ester of two functional polyesters and N-hydroxy-succinamide is reacted, the product of the succinimdyl carbonate that the main chain of gained contains purified again with Methionin Reactive Synthesis polyurethane high molecule.
As a kind of environment-friendly materials, if by succinct low-consumption process, and directly preparing Methionin type polyurethane material by Methionin cheap and easy to get and chloro-formic ester, will be ideal and advantageously.
But on the other hand, compare with the polyurethane material synthesized by isocyanic ester with traditional diamines with those, by the polyurethane material obtained by Methionin and derivative thereof, its good solubility-resistence, all more poor (the P.C.Caracciolo of the performance such as water tolerance and physical strength, F.Buffa, G.A.Abraham, J Mater Sci:Mater Med (2009) 20:145-155).And these defects strongly limit the application of Methionin type polyurethane, particularly in chemical resistance and water tolerance, weather resistance and cost etc. require harsher field.Knownly in polyurethane material field to address these problems; shape modification must be entered to its molecular structure; as introduced crosslinking structure; import polymerisable acryl (polyurethane acrylate prepolymer); or with acrylic ester copolymer (polyurethane/acrylate/acrylic acid hybridisation-PUA) etc., improve the water tolerance and resistance to chemical attack etc. of its polyurethane material thus.So, if directly prepared the polyurethane hybrid body of modification by Methionin and derivative thereof, the range of application of the polyurethane material prepared by it itself will be expanded.
In addition, as everyone knows, amino acid self can carry out two polycondensation reaction, generates the amino acid dipolymer with ring-type, i.e. Diketopiperazine derivative:
Such as, through heating, bimolecular Methionin is condensed into symmetrical Methionin diketopiperazine (S-LDKP):
And asymmetric Methionin diketopiperazine (U-LDKP) can be formed by Methionin and other amino acid heat condensation:
U-LDKP
Diketopiperazine is naturalization compound, and many products, food, beverage all contain diketopiperazine, as (M.Gautschi and J.P.Schmid, J.Agric.Food Chem., 45,3183-3189,1997) in the beverages such as beer.
Report the multiple Diketopiperazine derivative of synthesis at present, main as medical carrier and other medical substances (M.del Fresno, D.Fernandez-Forner, M.Miralpeix, V.Segarra, H.Ryder, M.Royo and F.Albericio, Bioorganic & Medicinal Chemistry Letters, 15,1659-1664,2005; N.Kaur, B.Zhou, F.Breitbeil, K.Hardy, K.S.Kraft, I.Trantcheva, and O.Phanstiel IV, Molecular Pharmaceutics, Vol.5, No.2,294-315,2008; G.Gellerman, E.AZAN, t.Brider, T.Traube, A.Albeck, Int.J.Pept.Res.Ther., 14,183-192,2008).
About the macromolecular material of diketopiperazine also has many bibliographical informations.As prepared polyamine (V.Crescenzi, V.Giancotti, and F.Quadrifogilo, Die Makromolekulare Chemie, 120 (1968), 220-224) with Adipoyl Chloride and Methionin diketopiperazine interfacial condensation.How US Patent No. 3763091 uses dual functional diketopiperazine, the diketopiperazine of two hydroxyl or two amino structure if also illustrating, and di-isocyanate reaction synthesis of polyurethane and carbamide resin:
Recently research is had to point out, with the polytetrahydrofuran of MDI end-blocking (PTMG) and polyvinyl ether glycol (PEG) performed polymer, by dihydroxy-dione piperazine (cyclic dimer Serine) chain extending reaction, the polyurethane material of gained has certain biocompatible property.Research also finds that the main chain resin that contains diketopiperazine structure has good thermal property, shows its potential application in high performance material.
But up to the present, the urethane containing diketopiperazine structure of most report and polyureas are all by the diketopiperazine of two hydroxyl or two amino structure and larger other di-isocyanate reaction gained of toxicity, as with MDI.
For the ammoniacum compound of Methionin diketopiperazine, as following multiple Methionin type diketopiperazine compound, have been reported (M.del Fresno, D.Fernandez-Forner, M.Miralpeix, V.Segarra, H.Ryder, M.royo and F.Albericio, Bioorganic & Medicinal Chemistry Letters, 15,1659-1664,2005; N.Kaur, B.Zhou, F.Breitbeil, K.Hardy, K.S.Kraft, I.Trantcheva, and O.Phanstiel IV, Molecular Pharmaceutics, Vol.5, No.2,294-315,2008):
But for the urethane containing Methionin diketopiperazine structure of macromole type, the nitrogen-atoms (N) being showed no ammonia ester bond in its structure comes from Methionin diketopiperazine molecule itself:
Macromolecular Methionin diketopiperazine type polyurethane
Equally, the structure of following Methionin diketopiperazine type urea ester and Methionin and Methionin diketopiperazine urea ester is not all reported:
Methionin diketopiperazine type urea ester LDKP-LDKP Urea linkage
Methionin diketopiperazine and Methionin urea ester LDKP-Lysine Urea linkage
In sum, even more ideal and novel, the polyurethane structural containing Methionin diketopiperazine formed, wherein the nitrogen-atoms (N) of ammonia ester bond comes from Methionin diketopiperazine itself.
Even more ideal too and novelty, utilizes Methionin diketopiperazine and Methionin synthesis with the urea ester of LDKP-LDKP urea key and LDKP-Lysine urea bond structure.
More preferably, by succinct low consumption polymerization means, directly from Methionin synthetic lysine type polyurethane and Methionin type urea ester.
More preferably, directly from Methionin or Methionin diketopiperazine (LDKP synthesis containing the Methionin of acryl and/or Methionin diketopiperazine ammonia ester performed polymer, or directly synthetic lysine and/or Methionin diketopiperazine polyurethane hybridization material.
Too more preferably, provide asepsis environment-protecting, based on the polyurethane material of Methionin diketopiperazine (LDKP) and/or Methionin diketopiperazine (LDKP)/Methionin, and material can be widely used in different fields, as sizing agent, coating, paint, film, ink, mixture, filler and elastomerics etc., be applied on different materials, as timber, metal, plastics, cement, glass, weaving, fiber, paper, leather, skin etc.
Invention discloses
Involved by patent of the present invention is compounds; it is characterized in that containing the structural unit of following any one based on Methionin and Methionin diketopiperazine (LDKP): ammonia ester type structural unit LDKP Urethane (I); or urea ester type structural unit LDKP-LDKP urea unit (II); or urea ester type structural unit LDKP-Lysine urea unit (III); or acryl type structural unit LDKP-acryl unit (IV); or their repeating unit, or their mixture:
LDKP Urethane(I)
LDKP-LDKP Urea(II)
LDKP-Lysine Urea(III)
LDKP-acryl(IV)
The preparation method of patent of the present invention also involved following structural unit: ammonia ester type structural unit LDKP urethane (I); or urea ester type structural unit LDKP-LDKP urea (II); or urea ester type structural unit LDKP-Lysine urea (III); acryl type structural unit LDKP-acryl (IV); or their repeating unit; or their mixture, and their application.
The preparation method of patent of the present invention also involved following structural unit: ammonia ester type structural unit LDKP urethane (I); or urea ester type structural unit LDKP – LDKP urea (II); or urea ester type structural unit LDKP-Lysine urea (III); acryl type structural unit LDKP-acryl (IV); or their repeating unit; or their mixture, and their application.
Lysine Urethane Methionin ammonia ester bond
Lysine urea Methionin urea ester bond
Non-isocyanate method is also comprised, directly from Methionin and LDKP synthetic lysine and/or LDKP acryl ammonia ester performed polymer and polyurethane hybridization material and their purposes involved by patent of the present invention.
The carbonylation method that what patent of the present invention related to further comprises about polyvalent alcohol, wherein involved carbonylation agent is not isocyanic ester, but comes from carbonyl chlorine compounds as phosgene, trichloromethylchloroformate, triphosgene and bischloroformates etc.; Wherein bischloroformates class compound matter represents as follows: ClCO-U-OCCl; Shown in U is linking group, can be alkylidene group, also can be that Sauerstoffatom O inserts, and/or can containing replace.In general, U should react with carbonyl reagent, so also do not disturb carbonylation reaction.And according to the requirement of material property, suitable U structure can be selected.
Compound involved in the present invention can be dipolymer, oligopolymer, prepolymer, or superpolymer, can be that homopolymer also can multipolymer.Polymericular weight (on average) is greater than 2000 usually, and preferably 5000 ~ 200000, more preferably 8000 to 100000.Dipolymer, oligopolymer and prepolymer usually have a molecular weight (on average) and are greater than 300, and preferably 500 to 10000.
In this patent, the urethane of indication can comprise urethane, polyurethane-urea, the mixture of urethane, the mixture of polyurethane-urea, the mixture of one or more urethane and the mixture of one or more polyurethane-ureas.
Summary of the invention
Involved by patent of the present invention is compounds; it is characterized in that containing following any one structural unit: ammonia ester type structural unit LDKP urethane (I); or urea ester type structural unit LDKP-LDKP urea (II); or urea ester type structural unit LDKP-Lysine urea (III); or acryl type structural unit LDKP-acryl (IV); or their repeating unit, or their mixture:
LDKP Urethane(I)
LDKP-LDKP Urea(II)
LDKP-Lysine Urea(III)
-------DKP-NH-R
LDKP-acryl(IV)
Wherein:----be free valence bond;
The structure of DKP represents as follows:
Or n=4 is that preferably its structure is:
It is a part of structure of symmetrical Methionin diketopiperazine (S-LDKP) (structure is as follows):
The structural formula of LYS in urea ester bond structure (III) can be represented by the formula:
---CH 2CH 2CH 2CH 2CH(X)---
It is lysine derivative (structure is shown below) a part of structure wherein:
H 2N-CH 2CH 2CH 2CH 2CH(X)-NH 2
In formula, X can be COOH or COOM, and wherein M is metal ion, as Li +, Na +, K +, Ca 2+, Zn 2+and Mg 2+, or amine ion, as, H+NR ' 3, tertiary amine, ammonium salt, analogue and mixture, or X also can be COOR ', CONHR ', CONR ' 2, COSR ', or their analogue and mixture, wherein the structure of R ' can be straight chain, also can be with branched structure, both can be saturated, also can be undersaturated, both can be ring-type, also can be heterocycle shape, can be replace, also can not replace, can be aliphatic, also can be aromatic, or their analogue and mixture;
R is
Wherein Y can be H or methyl, and Z is linking group, if alkylidene group is (as-(CH 2) m-, m=2-10), ring alkylidene group, or also can be that Sauerstoffatom O inserts (as-(CH 2cH 2o) i-CH 2cH 2-,-(CH 2cH 2cH 2cH 2o) i-CH 2cH 2cH 2cH 2-, i=1-20), and/or can have substituent;
At this, the described compound containing ammonia ester bond LDKP urethane (I) is the macromole that molecular weight is greater than 2000, if it is not containing unit urea (II), also not containing unit urea (III), also not containing unit (IV), also not containing structural unit---LYS---HNCOO---lysine urethane linkage (Methionin ammonia ester bond), also not containing structural unit---LYS---HNCONH---LYS---lysine urea linkage (Methionin urea ester bond).
In this patent, the described compound containing ammonia ester bond (I) can comprise following U-LDKP ammoniacum (I) structure:
U-LDKP Urethane(I)
Wherein n is 1-4, and diketopiperazine is asymmetric Methionin diketopiperazine (U-LDKP), is formed by the amino acid condensation of Methionin and other non-Methionins.
Or the structure that the described compound containing ammonia ester bond (I) can comprise S-LDKP ammoniacum (I) is as follows:
S-LDKP Urethane(I)
In formula, diketopiperazine is a symmetrical Methionin diketopiperazine (S-LDKP), and wherein the amino at S-LDKP two ends all generates ammoniacum key.
Or the described compound containing ammonia ester bond (I) can comprise S-LDKP ammoniacum (I), can be following structure:
S-LDKP Urethane(I)
In formula, diketopiperazine compound is a symmetrical Methionin diketopiperazine (S-LDKP), but S-LDKP end amido generates ammonia ester bond, and another end amido generates different keys, as acid amides or urea ester bond.
Above-mentioned urea ester type can be following structure containing LDKP-LDKP (II) compound:
LDKP-LDKP Urea(II)
Wherein urea (II) can be two (LDKP) type ureas, or poly (LDKP) type urea, as trimerization tri (LDKP) urea or four poly-tetra (LDKP) ureas etc., wherein diketopiperazine (DKP) is a symmetrical Methionin diketopiperazine (S-LDKP):
Poly(LDKP)urea(II)
The above-mentioned structure containing urea ester group compound LDKP-LYS (III) can be as follows:
LDKP-Lysine Urea(III)
Wherein urea ester cpds (III) can be LDKP-LYS type urea, or poly (LDKP-LYS) type urea, (LYS) urea as two in LDKP-, two (LDKP)-LYS urea, two (LDKP)-bis-(LYS) urea, three (LDKP)-LYS urea, three (LDKP)-bis-(LYS) urea, four (LDKP)-LYS ureas etc., wherein diketopiperazine is a symmetrical Methionin diketopiperazine (S-LDKP).
Above-claimed cpd can have structure as follows containing LDKP-acryl (IV), and LDKP is symmetrical:
Or R in formula 1for a part for urethane.
The synthetic method also comprising following a series of structural unit involved in the present invention: ammonia ester type structural unit LDKP (I); or urea ester type structural unit LDKP-LDKP (II); or urea ester type structural unit LDKP-Lysine (III); or acryl type structural unit LDKP-acryl (IV); or their repeating unit; or their mixture, and be that raw material is through non-isocyanate method synthetic lysine urethane and urea with Methionin.
The synthetic method of ammonia ester (I) involved in the present invention, specifically by Methionin diketopiperazine, as S-LDKP, its salt is preferably, or the compound of S-LDKP end-blocking or performed polymer, and with carbonylation agent, as chloro-formic ester, bischloroformates reaction is obtained.Wherein chloro-formic ester compounds can by phosgene and corresponding oxy-compound, and as butyleneglycol, polyvalent alcohol etc. are obtained by reacting.
The preparation method of Methionin type polyurethane involved in the present invention, by lysine compound, as Methionin, or its salt, or the compound of Methionin end-blocking or prepolymer, or its mixture, with chloro-formic ester, as mixed with bischloroformates, in the presence of a basic, as sodium hydroxide, reaction is obtained.The succinct environment-protection low-consumption of the method provided, the reaction times is short, and temperature is low, is priorly the use of raw material cheap and easy to get.
This reaction can be carried out in a solvent, as organic solvent, or water, be wherein preferably the mixed solvent of water and organic solvent, except under the existence of acid substance, as sodium carbonate or sodium hydroxide.Necessary change, can add emulsifying agent.Reaction can be undertaken by the form of surface reaction, such as, carry out in emulsion or suspension or solution.Reaction is generally carried out at low temperatures, such as from-20 to 60 DEG C, preferred 0-30 DEG C.Along with the carrying out of reaction, the temperature of system also can increase.The concentration of reaction, and the ratio of chloro-formic ester and amine etc. can change with the characteristic requirements of product itself.Generally react in higher concentration, the recovery rate of urethane is also relatively high.Necessary change, can add chainextender.
Such as, preparing in Methionin diketopiperazine polyurethane reaction, first by the acetone soln of butyleneglycol chloro-formic ester and polyester chloro-formic ester and S-LDKP aqueous solution, then dripping aqueous sodium hydroxide solution under vigorous stirring, forming urethane:
ClCO-O-(CH 2) 4-O-OCCl+S-LDKP(HCl)+ClCO-O--polyester--O-OCCl
↓
-[-CONH--DKP--HN-CO-O-(CH 2) 4-O--]--[--CONH--DKP--HN-CO-O-polyester--O-]-
Methionin type polyurethane can drip aqueous sodium carbonate by under vigorous stirring simply, in and the mixture of the Methionin formicester aqueous solution and polytetrahydrofuran chloro-formic ester acetone solution obtain:
Lysine(HCl)+ClCO-O--PTMG--O-OCCl
↓
-[--CONH--LYS--HN-CO-O--PTMG-O--]-
LDKP-LDKP (II) in this patent, LDKP-lysine (III) or lysine – lysine urea type structure, their repeating unit, or their mixture, can except acid substance existence under, by Methionin diketopiperazine, as S-LDKP, preferably its salt, or with the compound of S-LDKP end-blocking or prepolymer, or Methionin, with the compound of Methionin end-blocking or prepolymer, or mixture, with phosgene, trichloromethylchloroformate, or triphosgene, or mixture, reaction gained.
Under the material except disacidify exists, as sodium carbonate or sodium hydroxide, this reaction can be carried out in a solvent, as organic solvent or water, is wherein preferably the mixed solvent of water and organic solvent.Reaction can be undertaken by the form of surface reaction, such as, carry out in emulsion or suspension or solution.Reaction is generally carried out at low temperatures, such as from-20 to 60 DEG C, preferred 0-30 DEG C.Along with the carrying out of reaction, the temperature of system also can increase.
Such as, in this patent example, symmetrical LDKP-LDKP (II) urea ester can be obtained by being added to by aqueous sodium carbonate in triphosgene acetone soln and the S-LDKP aqueous solution.For another example, aqueous sodium carbonate is added to triphosgene acetone soln, in the mixed solution of Methionin and the S-LDKP aqueous solution, mix products can be prepared: S-LDKP/S-LDKP type urea ester (II) (mass+H:539), S-LDKP/LYS type urea ester (III) (mass+H:429), and other many ureas ester type materials: comprise S-LDKP/di (LYS) type urea ester cpds (mass+H:601.4), di (S-LDKP)/LYS type urea ester cpds (Mass+H:711.4), tri (S-LDKP) type urea ester cpds (Mass+H:821.5), di (S-LDKP)/di (LYS) type urea ester cpds (mass+H:883.5), tri (S-LDKP)/LYS type urea ester cpds (mass+H:993.6), tetra (S-LDKP) type urea ester cpds (mass+H:1103.8), tri (S-LDKP)/di (LYS) type urea ester cpds (mass+H:1165.8), tetra (S-LDKP)/LYS type urea ester cpds (mass+H:1276) etc.Above-mentioned resultant is reacted with the chloro-formic ester of polyester polyol further, S-LDKP/lysine type polyurethane urea copolymer can be synthesized.
According to the present invention, different technique can being adopted to obtain the product of different performance, as by changing reactant order of addition, regulating the means such as the pH value of reaction mixture.As alkali being added to ammonium salt, in the mixture of chloro-formic ester and/or phosgene; Or chloro-formic ester and/or phosgene join in the solution of amine salt and alkali.These materials can certainly be joined in solvent simultaneously react.General pH value can from 4 to 11, wherein preferably between 6-9.Inorganic or organic acid scavenger all can be used to the pH value of conciliation system, is wherein preferably mineral alkali.Reaction can be carried out in water, in organic solvent, can also wherein be preferably the mixture at water and organic solvent.In reaction process, the consumption of water and the consumption of organic solvent can alter a great deal, and depend on the chloro-formic ester of use and the solubleness of product itself.Reaction can produce soluble material and form solution or dispersion, and it can directly be used in the fields such as film, coating, paint, ink, tackiness agent.Reaction also can produce insoluble substance, as formed gel or precipitation in strong solution.
According to the present invention, can the wherein all ammonia ester bond of synthesizing polymeric material or urea ester bond be all obtained by LDKP and Methionin and derivative thereof.So present invention is disclosed, by selecting suitable polyvalent alcohol, comprise biodegradable natural oil polyols, as castor oil polyhydric alcohol, polycarbonate polyol, poly-(lactic acid) (PLA) polylol etc., then add those renewable resourcess above-mentioned as LDKP, LDKP/ Methionin and Methionin etc., just can synthesize green environmentally friendly polyurethane material.
As everyone knows, by selecting suitable polyvalent alcohol, change the hard section ratio distribution in molecular chain, Molecular regulator amount size and chain thereof form as side chain or the parameter such as crosslinked, the polyurethane material that performance differs can be prepared.Therefore, around this principle, in this patent, the polyvalent alcohol different by choice structure and functional compound, can obtain different volumes, shape and kenel etc., based on the polyurethane material of LDKP, LDKP/ Methionin.And these different polyurethane materials can be small molecules, oligopolymer, polymer can be linear, dendroid, side chain, crosslinked, or containing crosslinkable or reactive group.They can be used alone, or a part for other compositions, or blended with other materials.They can exist in a variety of forms, as all multi-form in liquid, solution or dispersion etc.; Also can be with solid, as elastomerics, plastics, or tackiness agent, filler, film, microballoon, foam materials, the forms such as powder exist.Further, different additive can be added, as auxiliary agents such as different pigment, tinting material, uv-absorbing agent, stablizer, oxidation inhibitor, organosilicon, liquid agents according to application.
As everyone knows, improve polyurethane molecular chain by introducing certain segment, as crosslinked segment, siliceous segment, fluorine-containing groups, and analogue and mixture, can improve the water tolerance of material itself, chemical resistance, wear resistance, snappiness etc.In like manner, also improve to obtain excellent performance to macromolecular chain of the present invention by introducing certain segment.As imported castor-oil plant grease, cross-linking type LDKP polyester-polyurethane can be prepared.
Same well-known, acrylic acid modified polyurethane hybridization material (PUA) not only low in raw material price, and there is excellent chemical resistant properties, water tolerance and wear resistance, snappiness and weather resistance.The synthetic method of conventional PUA has, blended, IPN (interpenetrating net polymer), graft copolymerization, block copolymerization, letex polymerization or micro-emulsion polymerization etc.Therefore according to same principle, can obtain a series of containing LDKP urethane unit (I), or LDKP-LDKP urea unit (II), or LDKP-lysine urea unit (III), or LDKP-acry unit (IV), or lysine ammonia ester, or the structural unit of lysine-lysine urea ester, their repeating unit, or the polyurethane hybrid body PUA of mixture structure.
As follows, be several with Methionin type ammonia ester (Lysine-Hema-urethane) of the S-LDKP type ammonia ester of methacrylic ester hydroxyl ethylester end-cap (unit IV:S-LDKP-mono-Hema mono-end-blocking ammonia ester and S-LDKP-double-Hema two end-blocking ammonia ester) and methacrylic ester hydroxyl ethylester end-cap.They react gained by the chloro-formic ester of S-LDKP and Methionin and corresponding hydroxyethyl methylacrylate.The S-LDKP-Hema-urethane performed polymer that can obtain corresponding Hydroxyethyl acrylate end-blocking and Lysine-Hema-urethane performed polymer is reacted further to bischloroformate.These materials, under UV-light initiation, thermal initiation or other radical initiators etc. cause, the Acrylic Acid Monomers such as itself and butyl acrylate are copolymerized into the acrylic acid modified polyurethane material (LDKP-Lysine-methacrylate PUA hybrid) having and improve water absorbing properties.
The mono-end-blocking of unit IV:S-LDKP-mono-Hema-capped
The two end-blocking of unit IV:S-LDKP-double-Hema-capped
Unit IV:S-LDKP-Hema-urethane performed polymer
Lysine-Hema-urethane performed polymer
LDKP-Lysine-methacrylate PUA hybrid
The example of other (IV) structure comprises following N-LDKP-(methyl) acrylamide:
In like manner, other Methionin or derivatives thereof performed polymer etc. through the compound of acryl blocking modification, as following N-lysine-acrylamide and lysine-Hema-ester directly can be obtained by Methionin and derivative thereof.If suitable, the polyvalent alcohol chloro-formic ester containing acryl may be used to synthesize PUA material of the present invention.
As everyone knows, aqueous polyurethane (WPU) obtains by introducing hydrophilic radical (US3479310) in urethane segment as environmental friendliness shaped material.The water-soluble modified method of urethane has a lot of example, specifically comprises anion-modified, as introduced carboxylic acid in molecular chain, and sulfonic acid, sulfuric acid, the anionic groups such as phosphoric acid; Or cation group, as introduced tertiary amine; Or by introducing non-ionic hydrophilic group, as polyethoxye alkane, the repeating unit of alkoxyvinyl chain and other alkoxyalkyl chains.Therefore according to same principle, in patent of the present invention, can obtain a series of containing LDKP (I), or LDKP-LDKP (II), or LDKP-lysine (III), or LDKP-acryl (IV), or lysine ammonia ester, or the structural unit of lysine-lysine urea ester, their repeating unit, or the aqueous polyurethane of mixture structural unit etc.
The Methionin type polyurethane obtained with water miscible Methionin inherently has certain water-soluble or water dispersible property.Therefore, by S-LDKP, the aqueous polyurethane that Methionin and polyester diol chloro-formic ester and butyleneglycol chloro-formic ester are polymerized is carboxylate salt through Methionin and is formed.
As everyone knows, according to demand by combining the aqueous polyurethane that can obtain a series of performance and differ.Such as, by introducing polymerisable acryl (vinylformic acid urethane prepolymer), with acrylic ester copolymer (PUA hybrid), or introduce in polyurethane chain can atmospheric oxidation and self-crosslinking the lipid structures containing unsaturated double-bond (such as, unsaturated fatty acids modification WPU) etc. means, all can improve the over-all properties (US6359060 of water-base polyurethane material; US6239209; Z.S.Chen, W.P.Tu and J.Q.Hu, Thermosetting Resin Vol.22, No.2,51-54,2007).Introduce the performance (WO2006/124035A1 that structure that is siliceous or fluorine also effectively can strengthen water-base polyurethane material; S.H.Park, S.K.Lee, H.Y.Choi, E.M.Lee, E.Y.Kim, C.H.Lim, D.W.Lee and B.K.Kim; Journal of Applied Polymer Science, 2009,111,1828-1834).Therefore according to same principle, in the present invention, can to comprising containing ammonia ester type structural unit LDKP urethane unit (I), or urea ester type structural unit LDKP-LDKP urea unit (II), or urea ester type structural unit LDKP-Lysine urea unit (III), or LDKP-acryl (IV), or lysine ammonia ester, or the structural unit of lysine-lysine urea ester, or their repeating unit, or the aqueous polyurethane of their mixture carries out modification, by crosslinked, graft modification, introduce special element and functional group, as acrylate, the unsaturated double-bond of self-crosslinkable, epoxy group(ing), the unit of siliceous or fluorine, or analogue etc., obtain the water-base polyurethane material with certain performance.These functional groups can introduce high molecular any position.
Such as, in one example, the performed polymer PUA of Methionin-Hydroxyethyl acrylate is by the chloro-formic ester by Methionin and Hydroxyethyl acrylate, Viscotrol C and polyvalent alcohol, and sodium hydroxide solution is mixed to get mutually.This PUA performed polymer can be dissolved in green organic solvent further, as ethanol or Virahol (alcohol type Methionin PUA), or is dispersed in (water-based Methionin PUA) in middle water, or in water/alcohol mixed solvent.Through the mode such as homopolymerization or copolymerization, by itself and other monomer, as butyl acrylate, UV illumination causes in the presence of photoinitiators, obtains the cross-linking type PUA hybrid material of water tolerance modification:
In this patent except using LDKP or Methionin, in actually operating, the amine substance of other types also can add, and obtaining certain character, wherein the ratio etc. of amine can be adjusted according to the final performance requriements of polymkeric substance.
Such as, with isophorone diamine (IPDA) for diamines, polyester bischloroformate is soft section, lysine salt does ionization reagent, when butyleneglycol bischloroformate is chainextender, Lysine/IPDI type polyurethane aqueous liquid dispersion, by past IPDA, Methionin and dichloro formic acid acetone mixing solutions drip aqueous sodium hydroxide solution and obtain:
IPDA+ClCO-O-(CH 2) 4-O-OCCl+Lysine(HCl)+ClCO-O--polyester--O-OCCl
↓
-[-OCONH-IPDA--HN-CO-O-(CH 2) 4-O-]-[-OCONH--LYS-HN-CO-O--polyester-O-]-
Again gained organic solution is distributed in water with vigorous stirring, after distilling out acetone, makes Methionin IPDA-lysine type aqueous polyurethane dispersing liquid.With reference to the method, also can add and use other polyamines, polyisocyanates and chainextender etc. are to obtain the aqurous ployurethane dispersion liquid containing the constitutional features such as Methionin and Methionin diketopiperazine in the present invention.
For another example, isophorone diamine and methacrylic chloride are reacted obtained N-isophorone methyl propanamide, again it is mixed mutually with two (polytetramethylene ether PTMG) chloro-formic ester and butyleneglycol chloro-formic ester, add Methionin and sodium hydroxide solution under vigorous stirring, finally obtain the Methionin base polyurethane prepolymer for use as of methyl propanamide-IPDI modification.This PUA performed polymer may be dissolved in ethanol or Virahol, also can in water/alcohol mixed solvent dispersion.By uviolizing, thermal initiation, or the means such as radical initiator, can carry out copolymerization by its homopolymerization or with other monomer, obtain cross-linking type PUA material.
The invention provides a kind of simple effective method directly from amine, as Methionin, LDKP, preparation is containing the polyurethane prepolymer of polymerisable unsaturated group.It can also use the polymerisable unsaturated group of other types, as allyl group except the unsaturated modified method of modal polyacryl.Further polymerization can be directly used in through unsaturated modified polyurethane prepolymer (PUA) reaction solution, also can isolate, then be dissolved or dispersed in water, or ethanol, or Virahol, or use in the mixture of water/alcohol.In this instance, be use the carboxylic acid of Methionin as ion modification agent.Certainly for making urethane of the present invention have better consistency or dispersiveness in the mixed solution of water or water/alcohol, also can introduce other ionogens, as can carboxylic acid be introduced, sulfonic acid, sulfuric acid, phosphoric acid etc. carry out anion-modified, or introduce tertiary amine etc. and carry out cation-modified, or by introducing non-ionic hydrophilic group, as polyethoxye alkane, repeating unit of alkoxyvinyl chain and other alkoxyalkyl chains etc.In synthesis of the present invention, can also be introduced other and contain hydrophilic radical acryloyl-oxy based compound, as PEG (methyl) acrylate, 2-(diethylamino) ethyl (methyl) acrylate, 3 acrylic acid (methyl) sulphur propionic acid (Na +, K +) salt etc.
Performed polymer of the present invention namely can homopolymerization also can with other monomers or oligomer copolymerization.So, from numerous monomers, in oligopolymer and polyvalent alcohol, select corresponding raw material, a series of low cost can be prepared, there is the Methionin type polyurethane hybrid material of different structure composition and performance, be suitable for different ranges of application.
According to of the present invention, Methionin diketopiperazine can be salt, example hydrochloric acid, acetic acid, or vitriol, analogue, or the mixture of these salt.Different Preparation gained can be adopted.On the other hand, owing to adopting the factor such as preparation technology and purity, the LDKP produced may be crude product or its aqueous solution, may contain other materials, as Methionin, and polypeptide, hexanolactam and other derivatives etc.Therefore, the segment such as peptide and hexanolactam may be contained in the ammonia ester that obtains of the present invention and/or carbamide compound.
Wherein the structure of lysine derivative can represent by following formula:
H 2N-CH 2CH 2CH 2CH 2CH(X)-NH 2(or its salt)
Wherein X definition is as front.
The structure of lysinediisocyanate can represent by following formula:
OCN-CH 2CH 2CH 2CH 2CH(X’)-NCO
X ' can be COOR ', or analogue, or mixture, wherein the structure of R ' can be straight chain, also can be with branched structure, both can be saturated, also can be undersaturated, both can be ring-type, also can be heterocycle shape, can be to replace, also can not replace, can be aliphatic, also can be aromatic, or their analogue or mixture.
In the present invention, optional a kind of suitable chloro-formic ester all may be used for preparation containing LDKP, LDKP-Methionin, the ammonia ester of Methionin and/or urea ester cpds.Chloro-formic ester is wherein by the known compound containing hydroxyl through phosgenation reaction gained, and also can use chloro-formic ester crude product, it may contain oxy-compound, carbonic ether, phosgene, solvent etc.
In the present invention, the hydroxy-containing compounds for the preparation of chloro-formic ester can be monohydroxy compound, also can be polyol as glycol, triol, polyvalent alcohol, polymer polyatomic alcohol, or the mixture of these alcohol.In these alcohol, can also other substituting groups be contained, functional group, unsaturated link(age) or mix element etc. containing other, as containing the element such as Si, F, S, N.They come from renewable natural resources, biodegradable in this way.
Wherein comparatively representational oxy-compound is as follows, certainly following substances is not limited only to: low molecular weight diols, triol and polyvalent alcohol, can be aliphatics, also aromatic series can be used, or aliphatic aromatic mixture, ring-shaped fat alcohol, as ethylene glycol, glycol ether and triglycol, 1, 2-propylene glycol, 1, ammediol, 1, 3 – and 1, 4-butyleneglycol, all kinds of pentanediol, hexylene glycol, heptanediol, ethohexadiol, neopentyl glycol, 2, 2-dimethyl propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1, 3-hexylene glycol, ring pentanediol, two (methylol) pentamethylene, cyclohexanediol, 1, 4-cyclohexanediol, two (methylol) hexanaphthene, 1, 4-pair-(methylol) hexanaphthene, thiodiglycol, Resorcinol, cresorcinol, dihydroxyphenyl propane, two (2-hydroxyethyl) dihydroxyphenyl propane, two (2-hydroxypropyl) dihydroxyphenyl propane, 4, 4 '-dihydroxy-benzene propane, 4, 4 '-dihydroxy-benzene methane, methylresorcinol, terephthalyl alcohol, Resorcinol, Resorcinol di-hydroxyethylether, glycerol, TriMethylolPropane(TMP), trihydroxybutane, penta triol, hexanetriol, tetramethylolmethane, 2-methyl glucoside, hexitol, Sorbitol Powder, sorbyl alcohol, or contain the glycol of other specific groups, triol and polyvalent alcohol, as introduced double bond in the molecule, crosslinkable groups, analogue and mixture,
Involved polymer polyatomic alcohol, mainly refers to that those are generally used for preparing polyurethane polyol and composition thereof, and its middle-molecular-weihydroxyethyl, 300 ~ 15000, is preferably 500 to 5000;
Optional a kind of suitable polyether glycol, as polyoxyethylene glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether diol (PTMG), poly-hexamethylene ether glycol, poly-1, 2-dimethylether glycol, polyoxytrimethylene triol, polyalkylene phenylate glycol, with any linear and branch polyether polyatomic alcohol or multipolymer, functional group containing functional group or modification is as double bond, crosslinkable groups etc., as poly-(glycidyl allyl ether-oxyethane copolymerization) polyvalent alcohol, poly-(glycidyl allyl ether-propylene oxide copolymer) polyvalent alcohol, and analogue and mixture,
Optional a kind of suitable polyester polyol, comprise by dibasic alcohol and polyvalent alcohol and diprotic acid (or polyprotonic acid, or acid anhydrides) polycondensation synthesis, these acid and alcohol both can be aliphatics also can be aromatic structure, wherein selected dibasic alcohol comprises ethylene glycol, glycol ether, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexanediol, hexamethylene dimethyl glycol, glycerine, ring pentanediol, 1, 4-pair-methylol hexanaphthene, two (2-hydroxyethyl) dihydroxyphenyl propane, two (propyl group of 2-hydroxyl) dihydroxyphenyl propane, 4, 4 '-dihydroxy-benzene propane, cresorcinol, Resorcinol, Resorcinol di-hydroxyethylether etc. and their mixture, selected carboxylic acid comprises hexanodioic acid, succsinic acid, fumaric acid, propanedioic acid, oxalic acid, pentanedioic acid, tartrate, citric acid, phthalic acid, toxilic acid, thio-2 acid, Thiobutyric acid, sulphonyl two butenoic acid, L-glutamic acid, suberic acid, pimelic acid, sebacic acid, m-phthalic acid, terephthalic acid etc. and their mixture.The polyester polyol selected also comprises those polyesterols produced by ring-opening reaction or additive method, as polycaprolactone, and poly-propiolactone, poly-valerolactone, poly(lactic acid), PGA etc. and their multipolymer and analogue;
Optional a kind of suitable polycarbonate polyol, comprise poly-(alkylene carbonate) polyvalent alcohol, poly-(propylene carbonate) polyvalent alcohol, poly-(NSC 11801) polyvalent alcohol, poly-(butylene carbonate) polyvalent alcohol, poly-(hexylene carbonate) polyvalent alcohol, poly-(alkylene carbonate) polyvalent alcohol of branching, poly-(cycloalkylidene carbonic ether) polyvalent alcohol (as WO PATENT 2011/129940A1), polyether polycarbonate polyvalent alcohol, PACAPOL tm, QUICKSTAR tmand by different suppliers, as Bayer, Arch Chemicals INC, the special carbonate polyol that Daicel Chemical Industries Inc etc. provides, and linear and branching, or through the polycarbonate polyol and composition thereof of modification, such as, containing polycarbonate polyol etc. and their analogue and the mixture of double bond, crosslinkable groups modification;
Optional other a kind of suitable polymer polyatomic alcohols, comprise various polyacrylate polyol and end Polyacetal polyols, terminal hydroxy group butene rubber (HTBP), hydrogenation HTBP, hydroxy-terminated polysiloxane, polydimethylsiloxane polyol, the polythioether of hydroxyl, the epoxy resin of hydroxyl, and the polymkeric substance of other suitable hydroxyls, multipolymer, grafting polymer, containing the polymkeric substance of the hydroxyl of functional group, and their analogue and mixture;
Optional a kind of suitable polyvalent alcohol also comprises those polyvalent alcohols coming from renewable resources, as levels of natural oil-based polyols (NOP), castor oil polyhydric alcohol, soya-based polyvalent alcohol, Mierocrystalline cellulose or biopolyol, comprise company as Cargill (BiOH polyols), BASF, Hensel steps, BioBased Technologoes (Agrol), DOW CORNING (RENUVA), the natural polyols that Bayer etc. are produced.Selected polyvalent alcohol also comprises the polyhydroxycarboxyliacid acid (PLA-BASED POLYOL) of modification, as poly(lactic acid)-ethylene oxide ethoxylated polyhydric alcohol PLA-PEG-PLAPOLYOL, (LACTIDE) is come from lactide polyester polyvalent alcohol, or lactic acid and Viscotrol C polyester polyol, epoxidised fat and oily epoxidized fat and oil (as described in US2010/0016628 A1), lactide/myo-inositol rac-Lactide/inositol, or other suitable natural polyols, polymkeric substance, multipolymer, graftomer, polymer polyatomic alcohol containing functional group, analogue and their mixture,
Optional a kind of suitable polyol is the suitable polyvalent alcohol comprising block copolymerization, such as, and PCL-PEG-PCL glycol, poly-(ether-ether) polyvalent alcohol, poly-(carbonic ether ethoxylated polyhydric alcohol) etc. and analogue;
Optional a kind of suitable polyvalent alcohol also comprises those and contains oxy-compound or contain other groups, as oxidable, the polyvalent alcohol of the unsaturated double-bond of self-crosslinking, as, unsaturated fatty acids polyvalent alcohol is (as at patent US2008/0236449A1, US2006/0089453A1, US6620893B1, describe in US6359060B1, US6239209B1);
Optional a kind of suitable for the acrylate of polymerisable unsaturated double-bond or the hydroxyl of methacrylic ester ((methyl) acrylate) or polyol, hydroxyl second-2-ester as acrylic acid in (methyl), (methyl) vinylformic acid-hydroxypropyl (2 or 3) ester, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) glycidyl acrylate, ACE tmclass hydroxy-acrylate monomer etc., analogue and their mixture;
Also comprise the compound of other hydroxyls, as vinyl alcohol, fluoroalkyl alcohol, ZONYL, polyvalent alcohol contains fluoro-alkyl, and analogue etc.
Optional a kind of suitable acrylate comprises vinylformic acid (alkyl) ester class, methyl acrylate, vinylformic acid, and acrylamide or vinyl monomer can be used for preparing PUA Hybrids of the present invention, waterborne PUA Hybrids and alcoholic PUA Hybrids.Specifically include but not limited to, methyl methacrylate, methyl acrylate, β-dimethyl-aminoethylmethacrylate, ethyl propenoate, (n-, t-) (methyl) vinylformic acid butyl, (methyl) vinylformic acid polyhexamethylene, cyclohexyl acrylate, methacrylic acid, vinylformic acid, Ethylene Glycol Methyl ether (methyl) acrylate, two (ethylene glycol) ethyl ester ether (methyl) acrylate, PEG ethyl ether (methyl) acrylate, glycol ether alcohol two (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, PEG two (methyl) acrylate, the isomer of glycerine two (methyl) acrylate mixture, triethylene glycol methyl ether (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexanediyl ester, polyethyleneglycol diacrylate, acrylic polyester, polycarbonate acrylic, diallylcarbonate, allyl ethers, fluoroalkyl (methyl) acrylate, as perfluoro capryl (ethyl) acrylate, vinylformic acid hexafluoro butyl ester, 2, 2, 2-trifluoroethyl (methyl) acrylate, 1H, 1H, 2H, 1H, 2H-perfluorodecyl acrylate, 1H, 1H-perfluoro capryl (methyl) acrylate.And Zony TM FLUORO MONOMER, glycidyl acrylate, acrylated epoxidized soybean oil ester, 2-(diethylamino) ethyl (methyl) acrylate, 2-(dimethylamino) ethyl (methyl) acrylate, 3-(dimethylamino) propyl acrylate, N-[3-(dimethylamino) propyl group] methyl propanamide, sulphur third (methyl) acrylic acid (sodium, potassium) salt, and patent US4241202, US4250322, the monomer that US5512205, DE2365631, JP277308 introduce.In addition the chloro-formic ester of (methyl) acrylic acid hydroxy ester of hydroxyl is applicable to this system too.Those are with the monomer of multiple and/or different polymerisable unsaturated groups, prepolymer or linking agent, as disclosed in US5512205 (styryl or mixture are containing monomer or linking agent for propenyl, vinyl), are all applicable to above-mentioned system.
All kinds of polymerization starter, as Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), Potassium Persulphate, analogue and their mixtures such as light trigger (the Irgacure initiator as SIBA).
Optional a kind of suitable compound, containing anionic group as carboxyl, sulfonic acid, sulfuric acid, the groups such as phosphoric acid; Or cation is as groups such as tertiary amines; Or containing non-ionic hydrophilic group as polyethoxye chain, oxyethane and other alkylene oxide segment or repeating segments, as polyoxyethylene glycol, poly-(oxyethyl group/propoxy-) dibasic alcohol, glycol contains the compound of side oxyethyl chain etc., all likely for the synthesis of water-based of the present invention or alcoholic Polyurethane.
Optional a kind of suitable chainextender can be used for the compound preparing ammonia ester of the present invention and/or urea, and wherein available chainextender includes but not limited to, multicomponent isocyanate, polyamine, polynary chloro-formic esters etc., also can comprise phosgene, trichloromethylchloroformate, triphosgene, analogue and their mixture etc.
Optional a kind of suitable acid scavenger (acid binding agent), can be that organic bases is as tertiary amine, also mineral alkali can be selected, as oxyhydroxide, oxide compound, the carbonate of basic metal or alkaline-earth metal, or mixture etc., can be used for the compound preparing ammonia ester of the present invention and/or urea.Specifically include but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, calcium hydroxide, ammonia, ammoniacal liquor etc. and analogue.In addition, amine substance excessive in reaction, as Methionin diketopiperazine or Methionin etc., also can be used as acid scavenger.
Optional a kind of suitable amine can be used for the compound preparing ammonia ester of the present invention and/or urea.Be applicable to the diamines of the preparation of polyurethane/urea compound of the present invention, both can be primary amine also can be secondary amine, both can be aliphatic also can be aromatic series or heterocycle, also can be the materials such as polymer amine, or suitable amine, their derivative and mixture.Specifically include but not limited to, quadrol, propylene diamine, tetramethylene-diamine, pentamethylene diamine, hexanediamine, heptyl diamines, octamethylenediamine, piperazine, 2,5-lupetazin, (m-, p-) xylidene(s), Isosorbide-5-Nitrae-diamino-cyclohexane, Ursol D, 1,5-naphthylene diamine, isophorone diamine, 4,4 '-methylenedianiline, two (p-aminocyclohexyl) methane, 1,3-bis-(4-piperidyl) propane.In addition, also comprise with the polymkeric substance of amido end-blocking as, the Jeffamine amine that Hensel is graceful, various sulfanilic acid is as (2,4 or 2,5-)-diamino benzene sulfonic acid, (2.5-or 2.6-) diamino-4-Phenylsulfonic acid, and hydrazine etc., and other tertiary amine, quaternary amine, polyamine etc., and their mixture.
In addition, in actually operating, how different polycyanate ester also may be used for the preparation of this patent.Polyisocyanates can with amine or hydroxyl reaction, can with the substance reactions such as the prepolymer of LDKP, LDKP end-blocking, Methionin, the prepolymer of Methionin end-blocking, also can be used as chain propagation agent.Isocyanic ester wherein used can be one-level or secondary fatty race, cycloaliphatic ring, also can be aromatic series or heterocyclic polyisocyanates, also can be with isocyanate-terminated prepolymer etc., or these are containing the analogue of isocyanic acid, and composition thereof.Example comprises, but be not limited to, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methylene-bis is to cyclohexane isocyanic ester (H12MDI), to cyclohexyl vulcabond (CHDI), 2,4 toluene diisocyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI), PPDI (PPDI), 1,5-naphthalene diisocyanate, tolidine diisocyanate, (m-, p-) Xylene Diisocyanate etc.Poly isocyanate comprises isocyanuric acid ester, as Lysine triisocyanate, and four polymeric polyisocyanates or other polyisocyanates, its analogue and their mixture etc.
Optional a kind of suitable solvent can be used for the compound preparing ammonia ester of the present invention and/or urea.Comprise water, or organic solvent, or the mixture of preferably water and organic solvent.It also can be immiscible that organic solvent wherein and water both can dissolve each other, as acetone, and methyl ethyl ketone, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol, dioxane, ethyl acetate, acetonitrile, diethyl ether, aromatic hydrocarbon, as toluene, chloro fat race hydrocarbon or aromatic hydrocarbons, analogue and their mixture etc.
LDKP ammonia ester involved in the present invention, except LDKP and chloro-formic ester can form its ammonia ester, may also have other preparation method.Such as, LDKP and carbonic ether, perhaps methylcarbonate or cyclic carbonate, can form compound of the present invention.Also likely chloro-formic ester is first reacted to N-hydroxy-succinamide and generate corresponding succinimdyl carbonate derivative, be then obtained by reacting Methionin diketopiperazine type polyurethane with Methionin diketopiperazine.In addition LDKP-LYS type urea ester (III) also can be generated by Methionin diketopiperazine and LDI derivative.
Involved by this patent is with Methionin diketopiperazine (LDKP), and Methionin and derivative are raw material, provides the synthesis of simple non-isocyanate method based on LDKP, LDKP/ Methionin, the ammonia ester of Methionin and urea compound.For person skilled in the art obviously, according to method provided by the present invention, and according to product service requirements, do not departing under spirit of the present invention, LDKP and LDKP/ Methionin product and the multipolymer of various combination can obtained.
Methionin type polyurethane is known can be used as biomedicine and biodegradable material.They have been applied to the many aspects of medical science, as tackiness agent, and artificial skin, wound dressings, artificial blood vessel, high-molecular gel.The invention provides a kind of directly application to be more easy to get Methionin, replace Methionin isocyanic ester, synthetic lysine ammonia ester and urea compound, and this preparation method environmental protection more, inexpensive.The urethane of gained in this way have similar use properties by Methionin urethane out prepared by traditional isocyanic ester.
Novel LDKP and LDKP/ Methionin type ammonia ester/urea ester polymer in patent of the present invention is that application natural reproducible thing makes Material synthesis, these have similar performance Polyurethane to replace the urethane of those traditional isocyanic ester synthesis to its objective is application, make it have similar range of application also to have the advantages such as environmental protection low toxicity simultaneously.They can be used on the various polyurethane material of preparation, and as coating, paint, tackiness agent, ink, tackiness agent, filler, foundry goods, rubber, fiber, gel etc., for such as packing, toy, makeup, building materials, automobile, medical treatment waits urethane association area.
Have been found that the LDKP type polyurethane that this patent is invented has excellent film-forming properties and wet fastness.Such as, the layer that the LDKP type polyurethane synthesized by polyester chloroformic acid fat and castor-oil plant wet goods polyvalent alcohol chloroformic acid fat is coated with has good scratch resistance, and its water-intake rate is less than 4%.In addition, the LDKP type polyurethane in the present invention has excellent thermostability (such as, the temperature of 5% rate of weight loss is 310 DEG C), and it is much larger than pure Methionin urethane (LYS type) (< 260 DEG C).The copolymer p UA (polyurethane/acrylate mixing) of acrylic acid modified LDKP-Methionin has excellent water tolerance.Therefore, by selecting different polyvalent alcohols, functional body and additive, LDKP and the LDKP/ Methionin type polyurethane film that a series of structure is different can be prepared, coating and ink etc., and can adapt on various base material, comprise timber, metal, plastics, glass, concrete, fiber, textiles, paper, leather, leatheroid and skin etc.
LDKP and the LDKP/ Methionin that this patent is invented and Methionin type polyurethane can be used as caking agent material, are applied to adhesive sheet, soft packaging, multilayer film, leather and imitation leather, footwear, printing-ink and other association areas.The LDKP of a series of different softening temperature or fusing point can be obtained, LDKP/ Methionin and Methionin type polyurethane according to patent of the present invention.And these materials have shown good hot melt adhesive character on the base materials such as glass, metal, timber and paper.LDKP and the LDKP/ Methionin that this patent is invented, Methionin type polyurethane is suitable for food product pack, soft packaging, medical packaging, such as, and paper glue, label, or lid glue and container glue, as sealing bag glue, air-tight bottle glue etc.Also may apply to and food, medicine etc. has the packaging field of contact.They also can be used as the tackiness agent of glued board and furniture, and these sizing agents in use can not discharge amine, the objectionable impuritiess such as aldehydes.
LDKP and the LDKP/ Methionin that this patent is invented and Methionin type polyurethane can also cast the object of various form, as toy, and sports goods, household articles etc.
LDKP and the LDKP/ Methionin that this patent is invented, Methionin type polyurethane can also make various biomedical products etc. as medical material, as artificial skin, wound dressings, artificial blood vessel, medicine equipment, bandage, pad, conduit, gel, drug conveying etc.They can be the biodegradable materials of superior performance, if especially with the material of biodegradable polyvalent alcohol prepared by polycarbonate or polylactic acid PLA.
LDKP, LDKP/ Methionin, and the aqueous polyurethane of Methionin type (WPU), water-based or alcoholic ammoniacum acrylic acid performed polymer and PUA hybrid, have and comprise environmental protection, the advantages such as the water tolerance that cost is low and good.Thus, they have and may be used for goods, as coating, and paint, tackiness agent, ink, tackiness agent, foundry goods, gel etc.
This patent is invented and is applied to coating, paint, tackiness agent, or LDKP and the LDKP/ Methionin of film, and the urethane of Methionin type is constructed by various method, comprises spraying, brushes, roller coat, casting, dipping or hot melt.
Help is understood the present invention by the following examples better.Certainly be readily appreciated that for person skilled in the art, according to method provided by the present invention and the final service requirements of product, do not departing under key concept of the present invention and spirit, the product with suitable different structure and character can prepared by various combination.
Example
Example 1: by 1 gram of polyester chloro-formic ester containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1,4-butyleneglycol and 1, synthesized by 2-ethylene glycol, Mn=2000) and 0.15 gram of BDO chloro-formic ester, is dissolved in the acetone of 10 milliliters of ice-water bath coolings.Under agitation, drip the aqueous solution 1 milliliter being dissolved with 0.48 gram of symmetrical Methionin diketopiperazine hydrochloride inward, drip the aqueous solution 1 milliliter being dissolved with 0.24 gram of sodium hydroxide, then add 30 milligrams of triphosgene.Reaction system insulation is at 5-15 DEG C.Then after stirring at room temperature for some time, polymkeric substance is isolated, washing and drying.Gained S-LDKP type polyurethane shows good hot melt adhesive character on glass, paper, and film water-absorbent is 6%, and hardness is F-H.
Example 2: 1.16 grams of polytetramethylene ether diol chloro-formic esters (PTMG, Mn=1000) containing double functional group are dissolved in the acetone of 15 milliliters of ice-water bath coolings.Drip the hydrochloride aqueous solution 1 milliliter being dissolved with 0.33 gram of lysine methyl ester under stirring inward, afterwards, then drip the aqueous solution 2 milliliters being dissolved with 0.49 gram of sodium carbonate to system, and this system temperature is controlled between 5-15 DEG C always.Then stirring at room temperature for some time is until reaction solution becomes sticky, and system pH is adjusted to 7.Isolate gained urethane, washing, dry.Its film water-absorbent is 60.4%, and has excellent adhesion property at glass, timber, metal and paper.
Example 3: in the water that 0.52 gram of symmetrical Methionin diketopiperazine hydrochloride salt is cooled at 15 milliliters of ice-water baths, drip inward under stirring containing 0.30 gram of sodium carbonate water liquid 2 milliliters and be dissolved with the acetone soln 2 milliliters of 0.03 gram of triphosgene.Stir after 20 minutes at 10-15 DEG C, with dilute hydrochloric acid, system pH is adjusted to 6.Except desolventizing, obtain mixture: Methionin diketopiperazine (S-LDKP, Mass+H:257) and Methionin diketopiperazine urea S-LDKP/S-LDKP urea (II) (Mass+H:539).
Example 4: 0.2 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.2 gram of lysine hydrochloride are dissolved in the water of 5 milliliters of ice-water baths coolings.The aqueous solution 1 milliliter being dissolved with 0.16 gram of sodium carbonate and the acetone soln 1 milliliter being dissolved with 0.04 gram of triphosgene is added inward under stirring.Stir after 20 minutes at 10-15 DEG C, with dilute hydrochloric acid, system pH value is adjusted to 6.Except desolventizing obtains mixture: S-LDKP/S-LDKP type urea (II) (Mass+H:539), S-LDKP/LYS type urea (III) (Mass+H:429) and polyureas ester: S-LDKP/di (LYS) urea (mass+H:601.4), di (S-LDKP)/LYS urea (Mass+H:711.4), 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:1103.8), tri (S-LDKP)/di (LYS) urea (mass+H:1165.8), tetra (S-LDKP)/LYS urea (mass+H:1276).
Example 5: 0.33 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.23 gram of lysine hydrochloride are dissolved in the water of 1 milliliter of ice-water bath cooling.The aqueous solution 0.5 milliliter being dissolved with 0.10 gram of sodium carbonate and the acetone soln 1 milliliter containing 0.015 gram of triphosgene is added inward under stirring.Stirring reaction, system temperature controls at 5-15 DEG C.Afterwards, the acetone soln 10 milliliters containing 3.5 grams of polyester chloro-formic esters containing double functional group (phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, synthesized by BDO and 1，2-ethandiol, Mn=2000) is added.Add the aqueous solution 2 milliliters containing 0.70 gram of sodium carbonate under stirring more inward, now temperature remains on 5-15 DEG C, and pH value is 6-8.Then stirring at room temperature for some time is until reaction solution becomes sticky, is separated, and washing and drying obtain polyurethane-urea.
Example 6: by 4.9 grams of polyester chloro-formic esters containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1,4-butyleneglycol and 1, synthesized by 2-ethylene glycol, Mn=2000), 0.92 gram of BDO chloro-formic ester and 1.0 grams of Viscotrol C chloro-formic esters are dissolved in the acetone of 20 milliliters of ice-water bath coolings.Under agitation, dropping is dissolved with 3.2 grams of symmetrical Methionin diketopiperazine hydrochloride aqueous solution 3 milliliters, and contains the aqueous solution 2 milliliters of 1.4 grams of sodium hydroxide, and by this architecture heat preservation at 5-15 DEG C.Then stirring at room temperature for some time is until reaction solution becomes sticky.Isolate resulting polymers, washing, dry.Its water-intake rate of the film coating of gained Polyurethane is 4%, hardness F-H, the scratch resistance had.
Example 7: the chloro-formic ester of 0.13 gram of hydroxyethyl methylacrylate (HEMA) is dissolved in the acetone of 1 milliliter of ice-water bath cooling.Under agitation, add the aqueous solution 2 milliliters being dissolved with 0.3 gram of symmetrical Methionin diketopiperazine hydrochloride, and containing the aqueous solution 1 milliliter of 0.12 gram of sodium carbonate, and by this architecture heat preservation at 5-15 DEG C.After stirring at room temperature for some time, with diluted hydrochloric acid aqueous solution, pH value is adjusted to about 6.Except desolventizing obtains mixture, be mainly: S-LDKP-mono-Hema urethane (IV) (Mass+H:413), and subsidiary a small amount of HEMA-S-LDKP-double-Hema urethane (Mass+H:569).
Example 8: under ice-water bath, is dissolved in the chloro-formic ester of 0.31 gram of hydroxyethyl methylacrylate (HEMA) in the tetrahydrofuran (THF) of 3 milliliters.Add the aqueous solution 1 milliliter containing 0.25 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.25 gram of lysine hydrochloride to this solution under stirring, and then drip aqueous sodium hydroxide solution.Add the tetrahydrofuran (THF) cold soln 8 milliliters being dissolved with 1.12 grams of polytetramethylene ether diol chloro-formic esters (PTMG, Mn=1000) and 0.12 gram of BDO chloro-formic ester afterwards, then drip aqueous sodium hydroxide solution.In reaction process, system temperature remains on 5-15 DEG C and pH value remains on 4-9.At room temperature stir after 1 hour, obtain organic phase with after aqueous phase separation, and it is mixed with 0.5 gram of butyl methacrylate and 0.06 gram of light trigger Irgacure2959 (SIBA).Gained ammonia ester-acrylic acid solution, through film, obtain firmly solid film after illumination (NOVACURE, 100W mercury lamp arc of lighting), its water-intake rate is 3%.
Example 9: 1.1 grams of lysine hydrochlorides are dissolved in the water of 2 milliliters of ice-water bath coolings.The acetone cold soln 2 milliliters and the aqueous sodium hydroxide solution that are dissolved with 1.1 grams of hydroxyethyl methylacrylate chloro-formic esters (HEMA) is dripped inward under stirring.In reaction process, system temperature remains on 5-15 DEG C and pH value remains on 6-8.Add the polytetramethylene ether diol chloro-formic ester (PTMG, Mn=1000) being dissolved with 1.0 grams afterwards, the acetone cold soln of 0.12 gram of BDO chloro-formic ester and 0.03 gram of Viscotrol C chloro-formic ester 8 milliliters, then drip aqueous sodium hydroxide solution.In reaction process, system temperature remains on 5-15 DEG C and pH value remains on 6-9.After further stirring, solution ph is adjusted to about 7, and adds the light trigger Irgacure2959 (SIBA) of 0.08 gram inward.Gained solution is divided into two parts.
First part of solution is through violent stirring and boil off the aqueous dispersions that acetone obtains Methionin-ammoniacum-methacrylate performed polymer.The aqueous dispersions of gained Methionin-ammoniacum-methacrylate performed polymer is through film, and obtain the film be cross-linked after illumination (NOVACURE, 100W mercury lamp arc of lighting), its water-intake rate is greater than 80%.Second part of solution is except obtaining sticky Methionin ammoniacum methacrylate (PUA) performed polymer after desolventizing again in water-soluble/alcohol mixed solvent, the alcoholic solution of obtained PUA performed polymer.It mixed with methacrylic acid fourth fat, in the presence of photoinitiators, its coating of UV illumination obtains the PUA hybrid be cross-linked, and its water-intake rate is 25% again.
Example 10: under ice-water bath, by 2.1 grams of polyester chloro-formic esters containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1, synthesized by 4-butyleneglycol and 1，2-ethandiol, Mn=2000) and 0.4 gram 1,4-butyleneglycol chloro-formic ester, is dissolved in 20 milliliters of acetone.Under agitation, drip the aqueous solution 1.5 milliliters being dissolved with acetone soln 1 milliliter and the 0.45 gram lysine hydrochloride of 0.18 gram of isophorone diamine IPDA, then drip the aqueous solution 2 milliliters containing 0.3 gram of sodium hydroxide to system.In reaction process, controlled between 5-15 DEG C by system temperature, pH value controls at 6-8.After stirring at room temperature certain hour, system viscosity increases gradually.Be added in water by this organic liquor under violent stirring, removing acetone obtains the Polyurethane aqueous dispersions of the IPDA-Methionin of water-based.The film prepared by gained Polyurethane aqueous dispersions has good sticking power on paper.
Example 11: under ice-water bath, stirs the 1 milliliter of tetrahydrofuran solution being dissolved with 0.2 gram of methyl-prop acyl chlorides and is added to 10 milliliters containing in the tetrahydrofuran solution of 0.34 gram of isophorone diamine.Afterwards, the aqueous solution that 2 milliliters are dissolved with 0.26 gram of Methionin is added again, 5 milliliters of tetrahydrofuran solutions being dissolved with 1 gram of polytetramethylene ether diol chloro-formic ester (PTMG, Mn=1000) and 0.3 gram of butyleneglycol chloro-formic ester to it, afterwards, sodium hydroxide solution is dripped.And keeping the temperature of system at 5-15 DEG C, system PH is between 7-9.After stirring at room temperature for some time, separate organic phase, and the solvent removed in system obtains sticky shape PUA performed polymer.This PUA performed polymer can be dissolved in ethanol, Virahol, can be distributed in the mixed solvent of second alcohol and water (water: ethanol=2:1).It mixed with methacrylic acid fourth fat, under light trigger Irgacure2959 (CIBA) exists, UV illumination coating obtains cross-linking type PUA film again.
2.23 grams of polytetramethylene ether diol chloro-formic esters (PTMG, Mn=1000) containing double functional group are added to 20 milliliters containing in the aqueous solution of 0.49 gram of lysine hydrochloride by example 12: in ice-water bath with vigorous stirring.Slowly drip the aqueous solution 3 milliliters containing about 0.3 gram of sodium hydroxide to system again, and in dropping process, controlled between 10-20 DEG C by system temperature, pH value controls between 7-9.Then, solution room temperature for overnight.The elastic property that the polyurethane coating film of gained has shown.
Example 13: 1.08 grams of polytetrahydrofuran chloro-formic esters (PTMG, Mn=1000) containing double functional group and 0.11 gram of butyleneglycol chloro-formic ester are dissolved in the acetone of 10 milliliters of ice-water bath coolings.Then add to this solution the aqueous solution that 1 milliliter is dissolved with 0.24 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.24 gram of Methionin under stirring, drip afterwards 1 milliliter be dissolved with 0.24 can the aqueous solution of sodium hydroxide.Add in alkali process, controlled by system temperature between 5-15 DEG C, pH value controls between 6-8, and along with the carrying out of reaction, system viscosity becomes large gradually, is then separated polymer, and through washing, dry.Its fusing point of gained Polyurethane is about 110 DEG C, the hot melt adhesive character that glass-based has had, and the water-intake rate of its film is 60%.
Example 14: by 2.6 grams of polyester chloro-formic esters containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1,4-butyleneglycol and 1, synthesized by 2-ethylene glycol, Mn=2000) and 0.30 gram of Viscotrol C chloro-formic ester be dissolved in the acetone of 20 milliliters of ice-water baths coolings.Under agitation add to this solution and be dissolved with 0.29 gram of Methionin and 0.25 gram of aqueous sodium hydroxide solution 2.5 milliliters, add triphosgene again until about system pH to 7.5 afterwards.In the process, system temperature is controlled between 5-15 DEG C.Stirring at room temperature is until system viscosity increases.Isolate organic phase wherein, be dispersed in water under strong stirring, form the polyurethane aqueous dispersions (particle diameter is about 60nm) of slightly blue light.The film hardness that gained urethane is made is 6B.
Example 15: by 2.05 grams of polyester chloro-formic esters containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1,4-butyleneglycol and 1, synthesized by 2-ethylene glycol, Mn=2000) and 0.40 gram of BDO chloro-formic ester is dissolved in the acetone of 20 milliliters of ice-water bath coolings.Under agitation, drip inward and be dissolved with 0.21 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.50 gram of lysine solution aqueous solution 2 milliliters, drip the aqueous solution 1.5 milliliters being dissolved with 0.4 gram of sodium hydroxide afterwards.In the process, controlled by system temperature between 5-15 DEG C, pH value is 6-8.Stirring at room temperature is until system viscosity increases.Under strong stirring, organic phase is wherein dispersed in water afterwards, then forms aqueous polyurethane dispersion after boiling off acetone.The film softening temperature prepared by this aqueous polyurethane is about 70 DEG C, and at glass, timber, metal, the base materials such as paper shows excellent hot melt adhesive character.
Example 16: by 5.2 grams of polyester chloro-formic esters containing double functional group (by phosgenation polyester polyol gained, wherein polyester polyol is by hexanodioic acid, 1,4-butyleneglycol and 1, synthesized by 2-ethylene glycol, Mn=2000) and 0.75 gram of BDO chloro-formic ester is dissolved in the acetone of 30 milliliters of ice-water bath coolings.Under agitation, add the aqueous solution 3 milliliters being dissolved with 0.81 gram of symmetrical Methionin diketopiperazine hydrochloride and 0.38 gram of piperazine (HCl neutralization) inward, drip the aqueous solution 1.5 milliliters being dissolved with 1.2 grams of sodium hydroxide afterwards.In the process, system temperature is controlled between 5-15 DEG C.Stirring at room temperature is until system viscosity increases.Isolate polymkeric substance and obtain S-LDKP-piperazine urethane after washing, drying.

Claims (35)

1. a compound contains following structural unit: LDKP Urethane (I), or LDKP-LDKP Urea (II), or LDKP-Lysine Urea (III), or LDKP-acryl (IV), or their repeating unit, or mixture:
LDKP Urethane(I)
LDKP-LDKP Urea(II)
LDKP-Lysine Urea(III)
-------DKP-NH-R
LDKP-acryl(IV)
Wherein----be free valence bond;
The structural formula of DKP is as follows:
In LDKP-Lysine Urea (III), the structural formula of LYS is as follows:
---CH 2CH 2CH 2CH 2CH(X)---
It is the part in the lysine derivative that is shown below of structure:
H 2N-CH 2CH 2CH 2CH 2CH(X)-NH 2
Wherein X can be COOH, or COOM, and wherein M is metal ion, ammonium positive ion, or mixture, and/or X can be COOR ', CONHR ', CONR ' 2, COSR ', or analogue and mixture, R ' can be straight chain or side chain, saturated or unsaturated, ring-type or heterocycle shape, replacement or non-substituted, alkyl or aryl, its analogue and mixture;
R in LDKP-acryl (IV) is:
Wherein Y is H, methyl; Z is alkylidene group, cyclic alkylidene, optionally inserts Sauerstoffatom O and/or optionally with substituting group;
Wherein, the described compound containing ammonia ester bond LDKP urethane (I) is the macromole that molecular weight is greater than 2000, if not containing unit urea (II), also not containing unit urea (III), also not containing unit (IV), also containing Methionin ammoniacum (---LYS---HNCOO---), also containing Methionin urea (---LYS---HNCONH---LYS---).
2. compound as claimed in claim 1, comprises described repeating unit LDKP urethane (I).
3. compound as claimed in claim 1, comprises described structural unit LDKP-LDKP urea (II).
4. compound as claimed in claim 1, comprises described structural unit LDKP-Lysine urea (III).
5. compound as claimed in claim 1, comprises described structural unit LDKP-acryl (IV).
6., in the compound as described in any one claim 1-5, wherein n is that the structural formula of 4, DKP is as follows:
It is a part for symmetrical Methionin diketopiperazine (S-LDKP) (following structural formula):
7. the compound as described in any one right 1 and 4, M is a metal ion, can from Li +, Na +, K +, Ca 2+, Zn 2+and Mg 2+middle selection, or ammonium positive ion, from H +nR ' 3, tertiary ammonium salt, ammonium salt is selected, or from analogue, or their mixture is selected.
8. the compound as described in claim 1 or 5, the structural formula of LDKP-acryl (IV) is:
Or R 1it is a part for a urethane; Y is H, methyl; Z is alkylidene group, a cyclic alkylidene, optionally inserts Sauerstoffatom O and/or optionally with substituting group.
9. the compound as described in any one claim 1,3 and 6, wherein LDKP-LDKP urea (II) is di (S-LDKP) type urea, or tri (S-LDKP) type urea, or tetra (S-LDKP) type urea.
10. as any one claim 1, compound described in 4 and 6, wherein LDKP-Lysine urea (III) is S-LDKP/Lysine type urea, or S-LDKP)/di (Lysine) type urea, or di (S-LDKP)/Lysine type urea, or di (S-LDKP)/di (Lysine) type urea, or tri (S-LDKP)/Lysine type urea, or tri (S-LDKP)/di (Lysine) type urea, or tetra (S-LDKP)/Lysine type urea.
11. 1 kinds of compounds contain structural unit urethane unit (I), or urea unit (II), or urea unit (III), or LDKP-acryl unit (IV), or their repeating unit, or their mixture, as described in any one claim 1-10, be the product being reacted gained by following compound:
Methionin diketopiperazine, or with the compound of Methionin diketopiperazine end-blocking or prepolymer, or Methionin, or with the compound of Methionin end-blocking or prepolymer, or its salt, or mixture,
With chloro-formic ester, comprise one or more chloroformate group, or the compound of chloro-formic ester end-blocking or prepolymer, or phosgene, or trichloromethylchloroformate, or triphosgene, or mixture,
React under the existence of acid scavenger (acidbinding agent).
12. 1 kinds of macromolecular compounds contain Methionin ammonia ester bond or Methionin urea ester bond or their repeating unit or mixture:---LYS---HNCOO---Methionin ammonia ester bond,---LYS---HNCONH---LYS---Methionin urea ester bond, reacts products therefrom containing by following compound:
Methionin, its structural formula is (HCl) H 2n-CH 2cH 2cH 2cH2CH (X)-NH 2, in formula, X can be COOH, or COOM, and wherein M is metal from, or amine positive ion, or analogue or mixture, and/or X can be COOR ', CONHR ', CONR ' 2, COSR ', or analogue or mixture, wherein R ' can be saturated or unsaturated, straight chain or side chain, ring-type or heterocycle shape, replacement or non-substituted, alkyl or aryl, its analogue and mixture; Or the compound of Methionin end-blocking or prepolymer or its salt or mixture;
With chloro-formic ester, containing one or more chloroformate group, or the compound of chloro-formic ester end-blocking or prepolymer or phosgene or trichloromethylchloroformate or triphosgene or mixture,
React under the existence of acid scavenger (acid binding agent).
13. compounds as described in claim 12, wherein M is a metal ion, can from Li +, Na +, K +, Ca 2+, Zn 2+, and Mg 2+middle selection, or ammonium positive ion, from H +nR ' 3, tertiary ammonium salt, ammonium salt is selected, or from analogue, or their mixture is selected.
14. compounds described by any one claim 1-13 are polymers.
15. compounds described by any one claim 1-13 are crosslinkable or crosslinked compounds.
16. compounds described by any one claim 1-13 are aqueous polyurethane dispersion.
17., from the compound described by any one claim 1-13, prepare film.
18., from the compound described by any one claim 1-13, prepare coating.
19., from the compound described by any one claim 1-13, prepare paint.
20., from the compound described by any one claim 1-13, prepare sizing agent.
21., from the compound described by any one claim 1-13, prepare ink.
22., from the compound described by any one claim 1-13, prepare colloidal sol.
23., from the compound described by any one claim 1-13, prepare Polyurethane Thermoplastic Elastomer.
24. 1 kinds of synthetic methods are used for preparing the compound containing following structural unit: LDKP Urethane (I), or LDKP-LDKP Urea (II), or LDKP-Lysine Urea (III), or LDKP-acryl (IV), or their repeating unit, or mixture:
LDKP Urethane(I)
LDKP-LDKP Urea(II)
LDKP-Lysine Urea(III)
-------DKP-NH-R
LDKP-acryl(IV)
Wherein----be free valence bond;
The structural formula of DKP is as follows:
In urea (III), the structural formula of LYS is as follows:
---CH 2CH 2CH 2CH 2CH(X)---
It is the part in the lysine derivative that is shown below of structure: H 2n-CH 2cH 2cH 2cH 2cH (X)-NH 2wherein X can be COOH, or COOM, and wherein M is metal ion, ammonium positive ion, or mixture, and/or X can be COOR ', CONHR ', CONR ' 2, COSR ', or analogue and mixture, wherein R ' can be straight chain or side chain, saturated or unsaturated, ring-type or heterocycle shape, replace or non-substituted, alkyl or aryl, its analogue and mixture;
R in LDKP-acryl (IV) is:
Wherein Y is H, methyl; Z is alkylidene group, cyclic alkylidene, optionally inserts Sauerstoffatom O, and/or optionally with substituting group;
Wherein, the described compound containing ammonia ester bond LDKP urethane (I) is the macromole that molecular weight is greater than 2000, if not containing unit urea (II), also not containing unit urea (III), also not containing unit (IV), also containing Methionin ammoniacum (---LYS---HNCOO---), also containing Methionin urea (---LYS---HNCONH---LYS---);
Comprise and react products therefrom by following compound:
By the compound of Methionin diketopiperazine or Methionin diketopiperazine end-blocking or performed polymer, or Methionin, or the compound of Methionin end-blocking or performed polymer or its salt or mixture, with carbonylation agent, containing one or more chloroformate group, or the compound of chloro-formic ester end-blocking or performed polymer, or phosgene, or two phosgene, or triphosgene, or mixture, react under the existence of acid scavenger (acid binding agent).
25. reaction process as claimed in claim 24, wherein carbonylation reaction reagent is selected from chloro-formic ester compounds, containing one or more chloroformate group, the compound of chloro-formic ester end-blocking or performed polymer, or phosgene, or two phosgene, or triphosgene, or mixture.
26. reaction process as claimed in claim 25, to be wherein a bischloroformate structural formula be carbonylation reaction reagent: ClCO-U-OCCl, wherein U is spacer group.
27. reaction process as claimed in claim 26, wherein U is alkylidene group, containing Sauerstoffatom and/or can contain substituting group; U can not react with carbonyl reagent, so also do not disturb carbonylation reaction.
28. 1 kinds of acrylic or methacrylic acid compounds, it includes the product by following substance reaction gained:
Methionin diketopiperazine, or the compound of Methionin diketopiperazine end-blocking or performed polymer, or Methionin, or the compound of Methionin end-blocking or performed polymer or its salt or mixture,
A kind of carbonylation agent, containing one or more chloroformate group, or the compound of chloro-formic ester end-blocking or performed polymer, or phosgene, or two phosgene, or triphosgene, or mixture,
A kind of compound containing acrylic or methacrylic acid groups.
29. compounds as claimed in claim 28, its carbonylation agent is as claim 26 and 27 li of carbonylation agents defined.
30. compounds as claimed in claim 28, compound wherein containing acrylic or methacrylic acid groups is from selecting below: methyl-prop acyl chlorides, propionyl chloride, 2-monoethanolamine acrylate, 2-monoethanolamine methacrylic ester, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, (2 or 3)-Propylene glycol monoacrylate, (2 or 3)-Rocryl 410,4-hydroxyl butyl propyleneglycol acid esters, 4-hydroxybutyl methacrylate, acrylate glycidyl ester, glycidyl methacrylate, ACE tmclass hydroxy-acrylate monomer, (methyl) polyalkylene glycol acrylate ester, the chloro-formic ester of following monomer: Hydroxyethyl acrylate, hydroxyethyl methylacrylate, (2 or 3)-Propylene glycol monoacrylate, (2 or 3)-Rocryl 410,4-hydroxyl butyl propyleneglycol acid esters, 4-hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, ACE tmclass hydroxy-acrylate monomer, (methyl) polyalkylene glycol acrylate ester, and their mixture.
31. 1 kinds of macromolecular compounds are obtained by the compound described in polymerization claim 28.
32. 1 kinds of high-molecular copolymers are by the compound described in claim 28 and the copolymerization of acrylic or methacrylic acid mono being obtained.
33. as claimed in claim 32, wherein selected acrylic or methacrylic acid mono comes from, methyl methacrylate, methyl acrylate, β-dimethyl-aminoethylmethacrylate, ethyl propenoate, (n-, t-) (methyl) butyl acrylate, (methyl) Ethyl acrylate, cyclohexylacrylic ester, methacrylic acid, vinylformic acid, Ethylene Glycol Methyl ether (methyl) acrylate, two (ethylene glycol) ethyl ether (methyl) acrylate, PEG ethyl ether (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, two (ethylene glycol) two (methyl) acrylate, three (ethylene glycol) two (methyl) acrylate, four (ethylene glycol) two (methyl) acrylate, PEG two (methyl) acrylate, the isomer of glycerine two (methyl) acrylate mixture, three (ethylene glycol) methyl ether (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexanediyl ester, polyethyleneglycol diacrylate, acrylic polyester, polycarbonate acrylic, fluoroalkyl (methyl) acrylate, perfluorooctylethyl group acrylate, R 1216 acid butyl ester, 2, 2, 2-trifluoroethyl (methyl) acrylate, 1H, 1H, 2H, 1H, 2-perfluoro decyl acrylate, 1H, 1H-perfluoro decyl (methyl) acrylate.The fluorine class monomer of Zony TM, (methyl) glycidyl acrylate, acrylated epoxidized soybean oil ester, 2-(diethylamino) ethyl (methyl) acrylate, 2-(dimethylamino) ethyl (methyl) acrylate, 3-(dimethylamino) propyl group base acrylate, N-[3-(dimethylamino) propyl group] methyl propanamide, 3-sulphur third (methyl) vinylformic acid (sodium, potassium) salt, (methyl) acrylamide, N-alkyl (methyl) acrylamide, 2-Hydroxyethyl acrylate, 2-hydroxyethyl methylacrylate, (2 or 3)-Propylene glycol monoacrylate, (2 or 3)-Rocryl 410, 4-hydroxyl butyl propyleneglycol acid esters, 4-hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, ACE tmclass hydroxy-acrylate monomer.
34. compounds as described in claim 28,31 or 32 are aqueous polyurethane dispersion.
35. as claim 28, and 31, or the compound described in 32, be alcohol type, or alcohol/water mixed type solution or dispersion liquid.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101153192A (en) * 2006-09-29 2008-04-02 拜尔材料科学股份公司 Aqueous coating composition based on polyurethane dispersions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352461A (en) * 1992-03-11 1994-10-04 Pharmaceutical Discovery Corporation Self assembling diketopiperazine drug delivery system
JP2000500461A (en) * 1995-11-13 2000-01-18 スミスクライン・ビーチャム・コーポレイション Blood regulatory compounds
ATE486064T1 (en) * 2004-08-20 2010-11-15 Mannkind Corp CATALYSIS OF DIKETOPIPERAZINE SYNTHESIS
IL186004A0 (en) * 2007-09-17 2008-01-20 Ariel University Res And Dev C Piperzine-based scaffolds for solid phase synthesis of combinatorial libraries and method for their preparation
ES2531009T3 (en) * 2008-12-29 2015-03-09 Mannkind Corp Dicetopiperazine substituted analogs for use as agents for drug administration
SG10201802008TA (en) * 2011-02-10 2018-04-27 Mannkind Corp Formation of n-protected bis-3,6-(4-aminoalkyl) -2,5,diketopiperazine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101153192A (en) * 2006-09-29 2008-04-02 拜尔材料科学股份公司 Aqueous coating composition based on polyurethane dispersions

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