CN104284918B - urethane type and urea ester type compound and preparation method thereof - Google Patents

urethane type and urea ester type compound and preparation method thereof Download PDF

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CN104284918B
CN104284918B CN201380015332.0A CN201380015332A CN104284918B CN 104284918 B CN104284918 B CN 104284918B CN 201380015332 A CN201380015332 A CN 201380015332A CN 104284918 B CN104284918 B CN 104284918B
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lysine
ldkp
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acrylate
methyl
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CN104284918A (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

Abstract

The present invention relates to a) a kind of compound contains lysine diketopiperazine ammoniacum unit (I); or lysine diketopiperazine lysine diketopiperazine urea ester units (II); or lysine diketopiperazine lysine urea ester units (III); or lysine diketopiperazine acyl unit (IV); or their repetitive; or mixed cell thing, and a kind of b) non-isocyanate process by lysine and carbonylation agent prepare compound.

Description

Urethane type and urea ester type compound and preparation method thereof
Technical field
The present invention relates to the urethane type of lysine and lysine diketopiperazine and urea ester type compound, preparation method and should With.
Background technology
Polyurethane and polyurethane-urea (being referred to as polyurethane here) refer on main chain containing carbamate (- OCONH-) or/ With the macromolecular material of carbamic acid urea (- HNCONH-) construction unit.
Polyurethane is one of synthetic material for being most widely used, and major domain includes foam, adhesive, elastomer and modeling Material etc..The such as household articles in daily daily necessities, sports equipment, packaging for foodstuff, wood floors, substrate, wall are applied Material etc., be also seen everywhere polyurethane material.Nowadays, polyurethane is also widely used in bio-medical and biodegradation material.By Substantial amounts of polyurethane material is consumed every year in the whole world, and the impact brought by its health for giving people and environment is also increasingly weighed Depending on.
One of reason is the relatively large isocyanates of toxicity used in production process.Polyurethane be by diisocyanate, The raw material reaction such as polyalcohol and small molecule glycol or diamines synthesizes, and has aromatic diisocyanates using more diisocyanate Ester, such as toluene 2,4- diisocyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI)；Aliphatic diisocyanate, bag Include IPDI (IPDI) and hexamethylene diisocyanate (HDI) etc..Although polyurethane products itself are recognized For nontoxic, but these di-isocyanate reactions are high, toxicity are big, can cause that serious respiratory system infects and other people bodies are good for Kang Wenti.
Another is potentially hazardous be polyurethane material may discharge harmful substance (Delilah Lithner, Jeanette Damberg,Goran Dave,Ake Larsson,Chemosphere74(2009)1195-1200).Research table Ammonia ester bond (- OCONH-) and urea bond (- HNCONH-) in bright polyurethane can occur degraded, such as by hydrolysis, be pyrolyzed or microorganism (" Chemical degradation of Polyurethane ", the Vincent Gajewski, Rubber World such as degraded Sept.1,1990), carcinogenic aromatic diamine of lentamente degrading out, or the lower but still aliphatic two with certain toxicity Amine.Carcinogenic 4 are slowly released from MDI type polyurethane materials such as, 4 '-methylene dianiline (MDA) directly influences surrounding Environment (Maurizio Tosin, Francesco Degli-Innocenti, and Catia Bastioti, Journal of Environmental Polymer Degradation(1998),6(2),79-90)。
Additionally, the problem involved by polyurethane also includes carbon emission and the dependence to petroleum sources.With increasingly strict Regulation and low-carbon (LC) arrange policy appearance, it is desirable to will become more urgent from renewable resource synthesis of polyurethane material.At present, Many natural base vegetable oil polyols (NOPs), such as castor oil polyhydric alcohol and soybean oil polyol are developed, and has been used for poly- ammonia The synthesis of ester material.
Lysine can be the natural amino acid of a large amount of productions.As a kind of replacement of petrochemicals, lysine two Isocyanates (LDI) is developed (French Patent (FRP) 1351368) by people.Early stage United States Patent (USP) (US3281378, US3358005) also describe and use LDI synthesis of polyurethane, polyureas and polyurethane-urea and its application.
OCNCH2CH2CH2CH2CH(COOX)NCO (LDI).
The advantages of based on its non-toxic degradable, polyurethane with regard to LDI synthesized degradables existing a large amount of in recent decades and The report of its potential application.Such as, WO 89/05830 just describes how to prepare Biodegradable medical polyurethane with LDI, and Its application prospect in medical domains such as artificial skin, artificial blood vessel, nerve-graftings is looked forward to；United States Patent (USP) (US7264823) Also disclose that a kind of base polyurethane prepolymer for use as of LDI end-blockings can be used as medical adhesive；Also there is document report recently with LDI and gather (lactic acid), (PLA-PEG-PLA) polyalcohol etc. is Material synthesis fast degradation type polyurethane to PEG-poly- (lactic acid) (Z.Wang,L.Yu,M.Ding,H.Tan,J.Li,and Q.Fu,Polym.Chem.,2,601-607,2011)。
But, the lysine type polyurethane reported at present is mainly with LDI (formicester or second fat) For Material synthesis.And document (A.Nathan, D.Bolikal, N.Vyavahare, S.Zalipsky, and J.Kohn, Macromolecules, 25,4476-4484,1992) describe with lysine second fat and polysuccinimide carbonate reaction system Standby lysine type polyurethane condensation polymer.The method is first will be the chloro-formate of two functional polyesters and N-hydroxy-succinamide anti- Should, the product of the succinimdyl carbonate that the main chain of gained contains is purified to be synthesized polyurethane high score again with lysine Son.
For as a kind of environment-friendly materials, if succinct low-consumption process can be passed through, and by lysine cheap and easy to get and chlorine Formic acid esters directly prepares lysine type polyurethane material, will be ideal and advantageously.
But on the other hand, compared with the polyurethane material synthesized by isocyanates with traditional diamines with those, by relying Polyurethane material obtained by propylhomoserin and its derivative, its solvent resistance, the performance such as resistance to water and mechanical strength are all more poor (P.C.Caracciolo,F.Buffa,G.A.Abraham,J Mater Sci:Mater Med(2009)20:145-155).And These defects strongly limit the application of lysine type polyurethane, particularly in chemical resistance and resistance to water, durability Harsher field is required with cost etc..These problems will be being solved known to polyurethane material field, must be to its molecular structure Enter shape to be modified, such as introduce cross-linked structure, import polymerisable acryloyl group (polyurethane acrylate prepolymer), or and acrylic acid Ester copolymerization (polyurethane/acrylate/acrylic acid hybridisation-PUA) etc., thus improving the resistance to water of its polyurethane material and resistance to Chemical attack etc..So, if directly preparing modified polyurethane hybrid body by lysine and its derivative, can expand by which The prepared polyurethane material range of application of itself.
Additionally, it is well known that being, amino acid itself can carry out two polycondensation reactions, generate the amino acid two with ring-type Polymers, i.e. Diketopiperazine derivative：
For example, heated, the lysine of two molecules is condensed into symmetrical lysine diketopiperazine (S-LDKP)：
And asymmetric lysine diketopiperazine (U-LDKP) can be formed with other amino acid heat condensations by lysine：
U-LDKP
Diketopiperazine is nature compound, and many products, food, beverage all contain diketopiperazine, such as in the beverage such as beer (M.Gautschi and J.P.Schmid,J.Agric.Food Chem.,45,3183-3189,1997)。
The various Diketopiperazine derivatives of synthesis are reported at present, are mainly used 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)。
Also there are many document reports about the macromolecular material of diketopiperazine.Adipoyl Chloride and lysine diketopiperazine are used such as Interfacial condensation prepares polyamide (V.Crescenzi, V.Giancotti, and F.Quadrifogilo, Die Makromolekulare Chemie,120(1968),220-224).United States Patent (USP) US3763091 is also described how with double officials The diketopiperazine of the diketopiperazine of energy, double hydroxyls or double amino structures, with di-isocyanate reaction synthesis of polyurethane and polyureas tree Fat：
Recently research points out, with the PolyTHF (PTMG) and polyvinylether glycol (PEG) performed polymer of MDI end-blockings, By dihydroxy-dione piperazine (cyclic dimer Serine) chain extending reaction, the polyurethane material of gained has certain biological doctor Learn performance.Research also finds that the resin that main chain contains diketopiperazine structure has preferable thermal property, shows which in high-performance material Potential application in terms of material.
However, up to the present, the polyurethane containing diketopiperazine structure and polyureas of most reports, are by double The diketopiperazine of hydroxyl or double amino structures such as uses MDI with obtained by other larger di-isocyanate reactions of toxicity.
For the ammoniacum compound of lysine diketopiperazine, such as following various lysine type diketopiperazine compounds, have Report (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 polyurethane of the structure of diketopiperazine containing lysine of macromolecular type, it is showed no urethane in its structure The nitrogen-atoms (N) of key comes from lysine diketopiperazine molecule itself：
The lysine diketopiperazine type polyurethane of macromolecular
Equally, following lysine diketopiperazine type urea esters and lysine are not reported with the structure of lysine diketopiperazine urea ester Road：
Lysine diketopiperazine type urea ester LDKP-LDKP Urea linkage
Lysine diketopiperazine and lysine urea ester LDKP-Lysine Urea linkage
In sum, the polyurethane structural containing lysine diketopiperazine that is even more ideal and novel, being formed, its The nitrogen-atoms (N) of middle ammonia ester bond comes from lysine diketopiperazine itself.
It is similarly even more ideal and novel, using lysine diketopiperazine and lysine synthesis with LDKP- The urea ester of LDKP urea bonds and LDKP-Lysine urea bond structures.
More preferably, by succinct low consumption polymerization means, directly from lysine synthetic lysine type polyurethane and rely Propylhomoserin type urea ester.
More preferably, directly from lysine or lysine diketopiperazine (LDKP lysines of the synthesis containing acryloyl group And/or lysine diketopiperazine urethane performed polymer, or it is directly synthesized lysine and/or lysine diketopiperazine polyurethane hybrid material Material.
Asepsis environment-protecting is more preferably to provide similarly, based on lysine diketopiperazine (LDKP) and/or lysine two The polyurethane material of ketone piperazine (LDKP)/lysine, and material can be widely applied to different fields, such as adhesive, apply Material, paint, film, ink, intermixture, filler and elastomer etc. are applied on different materials, such as timber, metal, plastics, Cement, glass, weaving, fiber, paper, leather, skin etc..
Invention is disclosed
Involved by patent of the present invention is compounds, it is characterised in that containing it is following it is any based on lysine and The construction unit of lysine diketopiperazine (LDKP)：Urethane type construction unit LDKP Urethane (I), or urea ester type structure list First LDKP-LDKP urea unit (II), or urea ester type construction unit LDKP-Lysine urea unit (III), or acryloyl Fundamental mode construction unit LDKP-acryl unit (IV), or their repetitive, or their mixture：
LDKP Urethane(I)
LDKP-LDKP Urea(II)
LDKP-Lysine Urea(III)
LDKP-acryl(IV)
The preparation method of the also involved following construction unit of patent of the present invention：Urethane type construction unit LDKP urethane (I), or urea ester type construction unit LDKP-LDKP urea (II), or urea ester type construction unit LDKP-Lysine urea (III), Acryl type construction unit LDKP-acryl (IV), or their repetitive, or their mixture, and they should With.
The preparation method of the also involved following construction unit of patent of the present invention：Urethane type construction unit LDKP urethane (I), or urea ester type construction unit LDKP-LDKP urea (II), or urea ester type construction unit LDKP-Lysine urea (III), Acryl type construction unit LDKP-acryl (IV), or their repetitive, or their mixture, and they should With.
Lysine Urethane lysine ammonia ester bonds
Lysine urea lysine urea ester bonds
Also include non-isocyanate method involved by patent of the present invention, directly from lysine and LDKP synthetic lysines and/ Or LDKP acryloyl group urethane performed polymers and polyurethane hybridization material and their purposes.
What patent of the present invention was related to further comprises the carbonylation method with regard to polyalcohol, wherein involved carbonylation agent It is not isocyanates, and comes from carbonyl chlorine class compound such as phosgene, surpalite, triphosgene and bischloroformates etc.；Wherein Bischloroformates class compound matter is expressed as below：ClCO-U-OCCl；Shown in U is linking group, can be alkylidene, it is also possible to It is oxygen atom O insertions, and/or can contains substituted.In general, U should be reacted with carbonyl reagent, so Carbonylation is not disturbed.And suitable U structures can be selected according to the requirement of material property.
Compound involved in the present invention can be dimer, oligomer, prepolymer, or high polymer, can be homopolymers Can also copolymer.Polymer molecular weight it is (average) be typically larger than 2000, preferably 5000～200000, more preferably 8000 to 100000.Dimer, oligomer and prepolymer generally have a molecular weight (average) more than 300, and preferably 500 to 10000.
In this patent the polyurethane of indication can include polyurethane, polyurethane-urea, the mixture of polyurethane, polyurethane-urea Mixture, the mixture of the mixture and one or more polyurethane-urea of one or more polyurethane.
The content of the invention
Involved by patent of the present invention is compounds, it is characterised in that containing following any construction unit：Ammonia Ester type construction unit LDKP urethane (I), or urea ester type construction unit LDKP-LDKP urea (II), or urea ester type structure Unit LDKP-Lysine urea (III), or acryl type construction unit LDKP-acryl (IV), or their repetition list 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 is expressed as below：
Or n=4 is preferred, its structure is：
It is a part of structure of symmetrical lysine diketopiperazine (S-LDKP) (structure is as follows)：
Structural formulas of the LYS in urea ester bond structure (III) can be represented by the formula：
---CH2CH2CH2CH2CH(X)---
It is lysine derivative (structure is shown below) a part of structure therein：
H2N-CH2CH2CH2CH2CH(X)-NH2
In formula X can be COOH or COOM, wherein M be metal ion, such as Li+,Na+,K+,Ca2+,Zn2+And Mg2+, or Amine ion, e.g., H+NR ' 3, tertiary amine, ammonium salt, analog and mixture, or X can also be COOR ', CONHR ', CONR ' 2, COSR ', or their analog and mixture, the wherein structure of R ' can be straight chains, or with branched structure, Can both be saturation, or undersaturated, can both be ring-type, or heterocycle shape, can replace, Can not also replace, can be aliphatic, or aromatic, or their analog and mixture；
R is
Wherein Y can be H or methyl, and Z is linking group, and such as alkylidene is (such as-(CH2)m-, m=2-10), ring alkylidene, Or can also be oxygen atom O insertion (such as-(CH2CH2O)i-CH2CH2-,-(CH2CH2CH2CH2O)i-CH2CH2CH2CH2-,i =1-20), and/or can substituted base；
Here, the compound containing ammonia ester bond LDKP urethane (I) is macromolecular of the molecular weight more than 2000, If which does not contain unit urea (II), also without unit urea (III), also without unit (IV), also without construction unit --- LYS---HNCOO---lysine urethane linkage (lysine ammonia ester bond), also without construction unit --- LYS--- HNCONH---LYS---lysine urea linkage (lysine urea ester bond).
In this patent, the compound containing ammonia ester bond (I) can include following U-LDKP ammoniacums (I) structure：
U-LDKP Urethane(I)
Wherein n be 1-4, and diketopiperazine be asymmetric lysine diketopiperazine (U-LDKP), be by lysine and its He forms the amino acid condensation of non-lysine.
Or, the compound containing ammonia ester bond (I) can include that the structure of S-LDKP ammoniacums (I) is as follows：
S-LDKP Urethane(I)
In formula, diketopiperazine is a symmetrical lysine diketopiperazine (S-LDKP), and the amino at wherein S-LDKP two ends is given birth to Into ammoniacum key.
Or, the compound containing ammonia ester bond (I) can include S-LDKP ammoniacums (I), can be following structure：
S-LDKP Urethane(I)
In formula, diketopiperazine compound is a symmetrical lysine diketopiperazine (S-LDKP), but of S-LDKP holds amine Base generates ammonia ester bond, and another end amido generates different keys, such 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 double (LDKP) type urea, or poly (LDKP) type urea, such as trimerization tri (LDKP) ureas or four poly- Tetra (LDKP) urea etc., wherein diketopiperazine (DKP) are a symmetrical lysine diketopiperazines (S-LDKP)：
Poly(LDKP)urea(II)
The structure of the above-mentioned LDKP-LYS of ester group compound containing urea (III) can be as follows：
LDKP-Lysine Urea(III)
Wherein urea ester compounds (III) can be LDKP-LYS type ureas, or poly (LDKP-LYS) type urea, and such as LDKP- is double (LYS) urea, double (LDKP)-LYS ureas, double (LDKP)-bis- (LYS) ureas, three (LDKP)-LYS ureas, three (LDKP)-bis- (LYS) ureas, Four (LDKP)-LYS ureas etc., wherein diketopiperazine are a symmetrical lysine diketopiperazines (S-LDKP).
Above-claimed cpd (IV) containing LDKP-acryl can have structure shown below, and LDKP is symmetrical：
Or R in formula1For a part for polyurethane.
Synthetic method also including a series of construction unit involved in the present invention：Urethane type construction unit LDKP (I), Or urea ester type construction unit LDKP-LDKP (II), or urea ester type construction unit LDKP-Lysine (III), or acryl type knot Structure unit LDKP-acryl (IV), or their repetitive, or their mixture, and with lysine as the non-isocyanides of raw material Jing Acid esters method synthetic lysine polyurethane and urea.
The synthetic method of urethane (I) involved in the present invention, specifically by lysine diketopiperazine, such as S-LDKP, its salt For preferred, or the compound or performed polymer of S-LDKP end-blockings, with carbonylation agent, such as chloro-formate, bischloroformates reaction It is obtained.Wherein chloro-carbonic acid ester type compound can be reacted by phosgene and corresponding hydroxy compounds, such as butanediol, polyvalent alcohol etc. Arrive.
The preparation method of lysine type polyurethane involved in the present invention, be by lysine compound, such as lysine, or its Salt, or the compound or prepolymer of lysine end-blocking, or its mixture, with chloro-formate, are such as mixed with bischloroformates, in alkali Property material in the presence of, such as NaOH, reaction are obtained.The succinct environment-protection low-consumption of method for being provided, reaction time are short, and temperature is low, It is prior to be the use of raw material cheap and easy to get.
The reaction can be carried out in a solvent, such as organic solvent, or water, wherein the mixing of preferably water and organic solvent is molten Agent, in the presence of except acid substance, such as sodium carbonate or NaOH.Necessaryization, can add emulsifying agent.Reaction can pass through boundary Face reaction form carry out, for example emulsion or suspend, or solution in carry out.Reaction typically carry out at low temperature, for example from- 20 to 60 DEG C, preferred 0-30 DEG C.With the carrying out of reaction, the temperature of system can also be increased.The concentration of reaction, and chloro-carbonic acid Ratio of ester and amine etc. can change with the characteristic requirements of product itself.Typically reacted in higher concentration, polyurethane Recovery rate it is also of a relatively high.Necessaryization, can add chain extender.
For example, in lysine diketopiperazine polyurethane reaction is prepared, first by butanediol chloro-formate and polyester chloro-carbonic acid The acetone soln of ester is mixed with the S-LDKP aqueous solution, is then stirred vigorously lower dropwise addition sodium hydrate aqueous solution, forms polyurethane：
ClCO-O-(CH2)4-O-OCCl+S-LDKP(HCl)+ClCO-O--polyester--O-OCCl
↓
-[-CONH--DKP--HN-CO-O-(CH2)4-O--]--[--CONH--DKP--HN-CO-O-polyester--O-]-
Lysine type polyurethane simply by lower dropwise addition aqueous sodium carbonate is stirred vigorously can neutralize lysine formicester water Solution is obtained with the mixture of PolyTHF chloro-formate acetone solution：
Lysine(HCl)+ClCO-O--PTMG--O-OCCl
↓
-[--CONH--LYS--HN-CO-O--PTMG-O--]-
LDKP-LDKP (II), LDKP-lysine (III) or lysine-lysine urea type structures in this patent, they Repetitive, or their mixture can be in the presence of except acid substance, by lysine diketopiperazine, such as S-LDKP, preferably Its salt, or the compound that blocked with S-LDKP or prepolymer, or lysine, the compound blocked with lysine or prepolymer, or Mixture, with phosgene, surpalite, or triphosgene, or mixture, reaction gained.
In the presence of the material for removing acid, such as sodium carbonate or NaOH, the reaction can be carried out in a solvent, such as organic Solvent or water, wherein the preferably mixed solvent of water and organic solvent.Reaction can be carried out by the form of interfacial reaction, for example Carry out in emulsion or suspension or solution.Reaction is typically carried out at low temperature, such as from -20 to 60 DEG C, preferred 0-30 DEG C.With The carrying out of reaction, the temperature of system can also be increased.
For example, in one example of this patent, by aqueous sodium carbonate is added to triphosgene acetone soln and S-LDKP Symmetrical LDKP-LDKP (II) urea ester is can be prepared by the aqueous solution.For another example, aqueous sodium carbonate is added to into triphosgene acetone molten In the mixed liquor of liquid, lysine 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 types urea ester (III) (mass+H:, and other many urea ester type materials 429)：Including S-LDKP/di (LYS) type urea ester compounds (mass+H:601.4), di (S-LDKP)/LYS type urea ester compounds (Mass+H:711.4), tri (S-LDKP) type urea ester compounds (Mass+H:821.5), di (S-LDKP)/di (LYS) type urea ester compounds (mass+H: 883.5), tri (S-LDKP)/LYS type urea ester compounds (mass+H:993.6), tetra (S-LDKP) type urea ester compounds (mass+H:1103.8), tri (S-LDKP)/di (LYS) type urea ester compounds (mass+H:1165.8),tetra(S-LDKP)/ LYS type urea ester compounds (mass+H:1276) etc..Above-mentioned product is further reacted with the chloro-formate of PEPA, S-LDKP/lysine type polyurethane urea copolymers can be synthesized.
According to the present invention, different techniques can be adopted to obtain the product of different performance, such as by changing reactant addition Sequentially, the means such as the pH value of reactant mixture are adjusted.Alkali can be such as added to the mixture of ammonium salt, chloro-formate and/or phosgene In；Or chloro-formate and/or phosgene are added in the solution of amine salt and alkali.These materials can certainly be added to simultaneously molten React in agent.General pH value can be from 4 to 11, wherein it is preferred that between 6-9.Inorganic or organic plumper can be adopted to mediation body The pH value of system, wherein preferably inorganic base.Reaction can be carried out in water, can also in organic solvent, wherein preferably in water With the mixture of organic solvent.During the course of the reaction, the consumption of the consumption and organic solvent of water can change very big, depending on making The solubility of chloro-formate and product itself.Reaction can produce soluble material and form solution or dispersion, and which can It is used directly in the fields such as film, coating, paint, ink, adhesive.Reaction can also produce insoluble substance, such as in concentrated solution Form gel or precipitation.
According to the present invention it is possible to the wherein all of ammonia ester bond of synthesizing polymeric material or urea ester bond are all by LDKP and bad ammonia Acid and its derivative are obtained.So present invention is disclosed, it is by selecting suitable polyalcohol including biodegradable natural Oil polyalcohol, such as castor oil polyhydric alcohol, polycarbonate polyol, poly- (lactic acid) (PLA) polylol etc. add those described above Renewable resource such as LDKP, LDKP/ lysines and lysine etc., it is possible to synthesize the environmentally friendly polyurethane material of green Material.
It is well known that by selecting suitable polyalcohol, the hard section ratio distribution in change strand, Molecular regulator amount are big The parameters such as the form of little and its chain such as side chain or crosslinking, can prepare the polyurethane material that performance differs.Therefore, according to this Principle, in this patent, by selecting the different polyalcohol of structure and functional compound, can obtain different volumes, shape and Kenel etc., based on LDKP, the polyurethane material of LDKP/ lysines.It is and these different polyurethane materials can be small molecule, low Polymers, macromolecule can be linear, dendroid, side chain, crosslinking, or contain cross-linking or reactive group.They can be with It is used alone, or a part for other compositions, or be blended with other materials.They can be present in a variety of forms, such as liquid, molten Liquid or dispersion etc. are all multi-form；Can also be or the adhesive with solid, such as elastomer, plastics, filler, film, microballoon, bubble The forms such as foam material, powder are present.Further, different additive can be added according to application, such as different pigment, colouring agent, purple The auxiliary agents such as outer absorbent, stabilizer, antioxidant, organosilicon, fluidizing reagent.
It is well known that being improved to polyurethane molecular chain by introducing certain segment, segment, siliceous chain are such as crosslinked Section, fluorine-containing groupses, and the like and mixture, the resistance to water of material itself can be improved, chemical resistance, wearability are flexible Property etc..In the same manner, also the macromolecular chain of the present invention can be improved to obtain excellent performance by introducing certain segment.Such as Castor oil ester is imported, cross-linking type LDKP polyester-polyurethanes can be prepared.
It is also well known that acrylic acid modified polyurethane hybridization material (PUA) not only low in raw material price, and have Excellent chemical resistance, resistance to water and wearability, pliability and durability.The synthetic method of conventional PUA has, blending, IPN (interpenetrating net polymer), graft copolymerization, block copolymerization, emulsion 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 urethanes, or the structure list of lysine-lysine urea esters The polyurethane hybrid body PUA of unit, their repetitive, or mixture structure.
It is as follows, it is several S-LDKP type urethane (unit IV blocked with methacrylate hydroxyl ethyl ester：S-LDKP- The mono- end-blocking urethanes of mono-Hema and the double end-blocking urethanes of S-LDKP-double-Hema) and methacrylate hydroxyl ethyl ester end-blocking Lysine type urethane (Lysine-Hema-urethane).They are by S-LDKP and lysine and corresponding hydroxyethyl methacrylate second The chloro-formate reaction gained of ester.The S- of corresponding hydroxy-ethyl acrylate end-blocking is obtained with bischloroformate reaction further LDKP-Hema-urethane performed polymers and Lysine-Hema-urethane performed polymers.These materials, ultraviolet light-initiated, hot Cause or under other radical initiators etc. cause, by which, acrylic monomers is copolymerized into improving water suction with butyl acrylate etc. The acrylic acid modified polyurethane material (LDKP-Lysine-methacrylate PUA hybrid) of performance.
Unit IV:The mono- end-blockings of S-LDKP-mono-Hema-capped
Unit IV:The double end-blockings of S-LDKP-double-Hema-capped
Unit IV:S-LDKP-Hema-urethane performed polymers
Lysine-Hema-urethane performed polymers
LDKP-Lysine-methacrylate PUA hybrid
The example of other (IV) structures includes following N-LDKP- (methyl) acrylamide：
In the same manner, the compound of the Jing such as other lysines or derivatives thereof performed polymer acryloyl group blocking modifications, as following N-lysine-acrylamide and lysine-Hema-ester can be directly obtained by lysine and its derivative.If closed Suitable, the polyalcohol chloro-formate containing acryloyl group may be used to the PUA materials for synthesizing the present invention.
It is well known that aqueous polyurethane (WPU) can be by introducing parent in polyurethane segment as environmentally friendly material Water base group (US3479310) and obtain.The existing many examples of the water-soluble modified method of polyurethane, specifically include anion and change Property, such as introduces carboxylic acid in strand, sulfonic acid, sulfuric acid, the anionic group such as phosphoric acid；Or cation group, such as introduce tertiary amine；Or By introducing non-ionic hydrophilic group, the such as repetitive of polyethoxy alkane, alkoxyvinyl chain and other alkoxyalkyl chains.Cause This can obtain a series of containing LDKP (I) according to same principle in patent of the present invention, or LDKP-LDKP (II), or LDKP- Lysine (III), or LDKP-acryl (IV), or lysine urethanes, or the construction unit of lysine-lysine urea esters, they Repetitive, or the aqueous polyurethane of mixture construction unit etc..
Inherently have come obtained lysine type polyurethane with water miscible lysine certain water-soluble or can moisture Scattered property.Therefore, by S-LDKP, it is aqueous poly- that lysine and polyester diol chloro-formate and butanediol chloro-formate are polymerized Urethane is the carboxylate of Jing lysines and is formed.
It is well known that a series of aqueous polyurethane that performances differ can be obtained by combination according to demand.For example, by drawing Enter polymerisable acryloyl group (acrylic acid urethane prepolymer), and acrylic ester copolymer (PUA hybrid), or in polyurethane chain Upper introducing can air oxidation and self-crosslinking lipid structures containing unsaturated double-bond (for example, the modified WPU of unrighted acid) etc. Etc. means, the combination property (US6359060 of water-base polyurethane material can be improved；US6239209；Z.S.Chen, W.P.Tu and J.Q.Hu,Thermosetting Resin Vol.22,No.2,51-54,2007).The structure for introducing siliceous or fluorine also can Effectively strengthen the performance (WO2006/124035A1 of 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 be to including tying containing urethane type Structure unit LDKP urethane unit (I), or urea ester type construction unit LDKP-LDKP urea unit (II), or urea ester type Construction unit LDKP-Lysine urea unit (III), or LDKP-acryl (IV), or lysine urethanes, or lysine- The construction unit of lysine urea esters, or their repetitive, or the aqueous polyurethane of their mixture is modified, and passes through Crosslinking, graft modification introduce special element and functional group, such as acrylate, and the unsaturated double-bond of self-crosslinkable, epoxy radicals contain The unit of silicon or fluorine, or the like etc., obtain the water-base polyurethane material with certain performance.These functional groups can introduce height Any position of molecule.
For example, in one example, the performed polymer PUA of lysine-hydroxy-ethyl acrylate can be by by lysine and acrylic acid The chloro-formate of hydroxyl ethyl ester, castor oil and polyalcohol, and sodium hydroxide solution is mutually mixed and obtains.The PUA performed polymers can enter one Step is dissolved in the organic solvent of green, such as ethanol or isopropanol (alcohol type lysine PUA), or is dispersed in middle water (aqueous bad ammonia Sour PUA), or in water/alcohol mixed solvent.Through the mode such as homopolymerization or copolymerization, by itself and other monomers, such as butyl acrylate, UV illumination in the presence of photoinitiators causes, and obtains the modified cross-linking type PUA hybrid materials of resistance to water：
In this patent in addition to using LDKP or lysine, in practical operation, other kinds of amine substance also may be used Add, can obtain certain property, wherein ratio of amine etc. can be required according to the final performance of polymer and be adjusted.
For example, with IPD (IPDA) as diamines, polyester bischloroformate is soft section, and lysine salt ionizes Reagent, when butanediol bischloroformate is chain extender, Lysine/IPDI type polyurethane aqueous liquid dispersions can be by toward IPDA, relying Propylhomoserin and dichloro formic acid acetone mixed solution are added dropwise sodium hydrate aqueous solution and obtain：
IPDA+ClCO-O-(CH2)4-O-OCCl+Lysine(HCl)+ClCO-O--polyester--O-OCCl
↓
-[-OCONH-IPDA--HN-CO-O-(CH2)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 lysine IPDA- Lysine type aqueous polyurethane dispersing liquids.With reference to the method, also can plus using other polyamines, polyisocyanates and chain extender etc. with Obtain the soluble polyurethane dispersion liquid containing the architectural feature such as lysine and lysine diketopiperazine in the present invention.
For another example, the reaction of IPD and methacrylic chloride is obtained into N- isophorone methyl propanamides, then by its Mix with double (polytetramethylene ether PTMG) chloro-formates and butanediol chloro-formate, be stirred vigorously down plus lysine and hydrogen Sodium hydroxide solution, finally gives the modified lysine base polyurethane prepolymer for use as of methyl propanamide-IPDI.The PUA performed polymers can dissolve In ethanol or isopropanol, also can be in water/alcohol mixed solvent dispersion.Irradiated by ultraviolet, thermal initiation, or radical initiator Etc. means, copolymerization can be carried out by its homopolymerization or with other monomers, obtain cross-linking type PUA materials.
The invention provides a kind of simple effective method is directly from amine, such as lysine, LDKP, prepare containing it is polymerisable not The polyurethane prepolymer of saturated group.Which can also use which in addition to modal polyacryl unsaturation modified method The polymerisable unsaturated group of his type, such as pi-allyl.Unsaturated modified polyurethane prepolymer (PUA) reactant liquors of Jing can be with It is directly used in and is further polymerized, it is also possible to isolate, re-dissolved or be dispersed in water, or ethanol, or isopropanol, or water/alcohol is mixed Use in compound.In this instance, it is as ion modification agent using the carboxylic acid of lysine.Certainly it is the polyurethane for making the present invention There are more preferable compatibility or dispersiveness in the mixed liquor of water or water/alcohol, can also introduce other ionogens, can such as introduce carboxylic Acid, sulfonic acid, sulfuric acid, phosphoric acid etc. carry out it is anion-modified, or introduce tertiary amine etc. carry out it is cation-modified, or by introducing nonionic Repetitive of hydrophilic radical, such as polyethoxy alkane, alkoxyvinyl chain and other alkoxyalkyl chains etc..In the conjunction of the present invention Cheng Zhong, may be incorporated into other and contains hydrophilic radical acryloyl-oxy based compound, such 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 i.e. can also be with other monomers or oligomer copolymerization with homopolymerization.So, from numerous Monomer, corresponding raw material is selected in oligomer and polyalcohol, is possible to prepare a series of low costs, with different structure group Into the lysine type polyurethane hybrid material with performance, it is suitable for different ranges of application.
According to of the present invention, lysine diketopiperazine can be salt, such as hydrochloric acid, acetic acid, or sulfate, analog, or The mixture of these salt.Can be using obtained by Different Preparation.On the other hand, due to using factors such as preparation technology and purity, Produced LDKP is probably crude product or its aqueous solution, may contain other materials, such as lysine, polypeptide, caprolactam and Other derivatives etc..Therefore, the chain such as peptide and caprolactam may be contained in the urethane and/or carbamide compound obtained by the present invention Section.
Wherein the structure of lysine derivative can be represented with following formula：
H2N-CH2CH2CH2CH2CH(X)-NH2(or its salt)
Wherein X is as defined above.
The structure of LDI can be represented with following formula：
OCN-CH2CH2CH2CH2CH(X’)-NCO
X ' can be COOR ', or the like, or mixture, the wherein structure of R ' can be straight chain, or with Chain structure, can both be saturation, or undersaturated, can both be ring-type, or heterocycle shape, Ke Yishi It is replacing, or do not replace, can be it is aliphatic, or aromatic, or they analog or Mixture.
In the present invention, optional a kind of suitable chloro-formate may be incorporated for preparation and contain LDKP, LDKP- lysines, The urethane and/or urea ester compounds of lysine.Chloro-formate therein can pass through the known compound Jing phosgene containing hydroxyl Change reaction gained, it is also possible to which, using chloro-formate crude product, which may contain hydroxy compounds, carbonic ester, phosgene, solvent etc..
In the present invention, the hydroxy-containing compounds for preparing chloro-formate can be monohydroxy compound, or many Hydroxy compounds such as glycol, triol, polyalcohol, polymer polyatomic alcohol, or the mixture of these alcohol.In these alcohol, can be with Mix element etc. containing other substituents, functional group, unsaturated bond or containing other, such as contain the elements such as Si, F, S, N.They can It is to come from renewable natural resources, biodegradable in this way.
Wherein more representational hydroxy compounds is as follows, is not limited only to certainly following substances：Low molecular weight diols, three Alcohol and polyalcohol, can be aliphatic, it is also possible to use aromatic series, or aliphatic aromatic mixture, such as ring-shaped fat alcohol, second two Alcohol, diethylene glycol (DEG) and triethylene glycol, 1,2-PD, 1,3-PD, 1,3-and BDO, all kinds of pentanediols, hexylene glycol, heptan Glycol, ethohexadiol, neopentyl glycol, 2,2- dimethyl propylene glycol, 3- methyl isophthalic acids, 5- pentanediols, 2- ethyl -1,3- hexylene glycols, ring Pentanediol, two (methylol) pentamethylene, cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, two (methylol) hexamethylene, Isosorbide-5-Nitrae-bis--(hydroxyl first Base) hexamethylene, thiodiglycol, resorcinol, cresorcinol, bisphenol-A, double (2- hydroxyethyls) bisphenol-As, double (2- hydroxyls Propyl group) bisphenol-A, 4,4 '-dihydroxy benzenes propane, 4,4 '-dihydroxy benzenes methane, methylresorcinol, terephthalyl alcohol, to benzene two Phenol, hydroquinones di-hydroxyethylether, glycerine, trimethylolpropane, butantriol, penta triol, hexanetriol, pentaerythrite, 2- first Base glucoside, hexitol, D-sorbite, sorbierite, or the glycol containing other specific groups, triol and polyalcohol, are such as dividing Double bond, crosslinkable groups, analog and mixture are introduced in son；
Involved polymer polyatomic alcohol, is primarily referred to as those and is commonly used for preparing polyurethane polyol and its mixture, Its middle-molecular-weihydroxyethyl is 300～15000, preferably 500 to 5000；
Optional a kind of suitable PPG, such as polyethylene glycol (PEG), polypropylene ether glycol (PPG), poly- four methylene Base ether glycol (PTMG), poly- hexamethylene ether glycol, poly- 1,2- dimethylethers glycol, PPOX triol, polyalkylene phenylate Glycol, and any linear and branch polyether polyatomic alcohol or copolymer, containing functional group or modified functional group such as double bond, cross-linking Group etc., such as poly- (allyl glycidyl ether-oxirane copolymerization) polyalcohol, poly- (allyl glycidyl ether-epoxy third Alkane copolymerization) polyalcohol, and the like and mixture；
Optional a kind of suitable PEPA, including by dihydroxylic alcohols and polyalcohol and binary acid (or polyacid, or acid Acid anhydride) polycondensation synthesis, it can also be aromatic structure that these acid and alcohol can both be aliphatic, wherein selected dihydroxylic alcohols bag Include ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol, cyclohexanediol, hexamethylene dimethyl glycol, glycerine, ring penta Glycol, Isosorbide-5-Nitrae-bis--methylol hexamethylene, double (2- hydroxyethyls) bisphenol-As, double (propyl group of 2- hydroxyls) bisphenol-As, 4,4 '-dihydroxy Phenylpropyl alcohol alkane, cresorcinol, hydroquinones, hydroquinones di-hydroxyethylether etc. and their mixture；Selected carboxylic Acid includes adipic acid, butanedioic acid, fumaric acid, malonic acid, oxalic acid, glutaric acid, tartaric acid, citric acid, phthalic acid, Malaysia Acid, thio-2 acid, Thiobutyric acid, two butenoic acid of sulphonyl, glutamic acid, suberic acid, pimelic acid, decanedioic acid, M-phthalic acid are right Phthalic acid etc. and their mixture.From PEPA also include that those pass through ring-opening reaction or additive method and produce Polyesterols, such as polycaprolactone, poly- propiolactone, poly- valerolactone, PLA, PGA etc. and their copolymer with it is similar Thing；
Optional a kind of suitable polycarbonate polyol, including poly- (alkylene carbonate) polyalcohol, poly- (propylene carbonic acid Ester) polyalcohol, poly- (ethylene carbonate) polyalcohol, poly- (butylene carbonate) polyalcohol, poly- (hexylene carbonate) polyalcohol are branched Poly- (alkylene carbonate) polyalcohol, poly- (cycloalkylidene carbonic ester) polyalcohol (such as WO PATENT 2011/129940A1), gather Ether polycarbonate polyol, PACAPOLtm,QUICKSTARtm, and by different suppliers, such as Bayer, Arch The special carbonate polyol provided by Chemicals INC, Daicel Chemical Industries Inc etc., and line Property and it is branched, or through modified polycarbonate polyol and its mixture, for example, containing modified poly- of double bond, crosslinkable groups Carbonate polyol etc. and their analog and mixture；
Optional a kind of suitable other polymers polyalcohol, including various polyacrylate polyols and end polyacetals it is many First alcohol, terminal hydroxy group butene rubber (HTBP) hydrogenate HTBP, hydroxy-terminated polysiloxane, polydimethylsiloxane polyol, hydroxyl Polythiaether, the epoxy resin of hydroxyl, and the polymer of other suitable hydroxyls, copolymer, grafting polymer, containing sense The polymer of the hydroxyl of group, and their analog and mixture；
Optional a kind of suitable polyalcohol also comes from the polyalcohol of renewable resource, such as natural oil Quito including those First alcohol (NOP), castor oil polyhydric alcohol, soybean polylol, cellulose or biopolyol, including company such as Cargill (BiOH polyols), BASF, Hensel are stepped, BioBased Technologoes (Agrol), DOW CORNING (RENUVA), Bayer Deng the natural polyols of production.Selected polyalcohol also includes modified polyhydroxycarboxyliacid acid (PLA-BASED POLYOL), such as poly- breast Acid-ethylene oxide ethoxylated polyhydric alcohol PLA-PEG-PLAPOLYOL, comes (LACTIDE) from lactide polyester polyalcohol, or lactic acid and castor Sesame oil PEPA, epoxidised fat and oil epoxidized fat and oil are (as retouched in US2010/0016628 A1 State), lactide/myo-inositol lactides/inositol, or other suitable natural polyols, polymer, copolymer connect Branch polymer, the polymer polyatomic alcohol containing functional group, analog and their mixture；
Optional a kind of suitable polyol is including the suitable polyalcohol including block copolymerization, for example, PCL- PEG-PCL glycol, poly- (ether-ether) polyalcohol, poly- (carbonic ester ethoxylated polyhydric alcohol) etc. and the like；
Optional a kind of suitable polyalcohol also contains hydroxy compounds including those or contains other groups, such as can oxygen Change, the polyalcohol of the unsaturated double-bond of self-crosslinking, e.g., unrighted acid polyalcohol (such as in patent US2008/0236449A1, Described in US2006/0089453A1, US6620893B1, US6359060B1, US6239209B1)；
The optional a kind of suitably acrylate containing polymerisable unsaturated double-bond or methacrylate ((methyl) Acrylate) hydroxyl or polyol, such as (methyl) acrylic acid hydroxyl second -2- esters, (methyl) acrylic acid-hydroxypropyl (2 Or 3) ester, (methyl) acrylic acid 4- hydroxybutyls, (methyl) glycidyl acrylate, ACEtmClass hydroxy-acrylate monomer In, analog and they mixture；
Also including the compound of other hydroxyls, such as vinyl alcohol, fluoroalkyl alcohol, ZONYL, polyalcohol contain fluoro-alkyl, and Analog etc..
Optional a kind of suitable acrylate includes acrylic acid (alkyl) esters, methyl acrylate, acrylic acid, acryloyl Amine or vinyl monomer can be used for the PUA Hybrids, waterborne PUA Hybrids and alcohol PUA for preparing the present invention Hybrids.It is specifically including but not limited to, methyl methacrylate, methyl acrylate, EMA, ethyl acrylate, (n-, t-) (methyl) propylene acid butyl, (methyl) acrylic acid hexyl ester, cyclohexyl acrylate, methacrylic acid, acrylic acid, Ethylene glycol methyl ether (methyl) acrylate, two (ethylene glycol) ethyl ester ether (methyl) acrylate, PEG ethylether (first Base) acrylate, diethylene glycol (DEG) alcohol two (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, two (methyl) third of triethylene glycol Olefin(e) acid ester, tetraethylene glycol two (methyl) acrylate, PEG two (methyl) acrylate, glycerine two (methyl) acrylate The isomers of mixture, triethylene glycol methyl ether (methyl) acrylate, BDO two (methyl) acrylate, 1,6- oneself two Alcohol diacrylate, polyethyleneglycol diacrylate, acrylic polyester, polycarbonate acrylic, diallylcarbonate, allyl Base ether, such as fluoroalkyl (methyl) acrylate, perfluoro capryl (ethyl) acrylate, hexafluorobutyl acrylate, 2,2,2- trifluoros Ethyl (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- (two Ethylamino) ethyl (methyl) acrylate, 2- (dimethylamino) ethyl (methyl) acrylate, 3- (dimethylamino) third Base acrylate, N- [3- (dimethylamino) propyl group] methyl propanamide, acrylic acid (sodium, the potassium) salt of sulphur third (methyl), and specially The monomer introduced by sharp US4241202, US4250322, US5512205, DE2365631, JP277308.In addition hydroxyl The chloro-formate of (methyl) acrylic acid hydroxy ester is applied equally to the system.Those gather with multiple and/or different The monomer of the unsaturated group of conjunction, prepolymer or crosslinking agent, such as (acrylic, vinyl, styrene disclosed in US5512205 Base or mixture contain monomer or crosslinking agent), suitable for above-mentioned system.
All kinds of polymerization initiators, such as azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO), potassium peroxydisulfate are light-initiated Analog and their mixtures such as agent (the Irgacure initiators of such as SIBA).
Optional a kind of suitable compound, containing groups such as anionic group such as carboxyl, sulfonic acid, sulfuric acid, phosphoric acid；Or fellatio The groups such as ion such as tertiary amine；Or containing non-ionic hydrophilic group such as polyethoxy chain, oxirane and other alkylene oxides The change of segment or repeating unit, such as polyoxyethylene glycol, poly- (ethyoxyl/propoxyl group) dihydroxylic alcohols, glycol oxyethyl chain containing side etc. Compound, is likely to for synthesizing aqueous or alcohol polyurethane of the invention.
Optional a kind of suitable chain extender can be used to prepare the compound of urethane of the present invention and/or urea, wherein can select Chain extender include but is not limited to, multicomponent isocyanate, polyamine, polynary chloro-formate etc., it is also possible to including phosgene, double light Gas, triphosgene, analog and their mixture etc..
Optional a kind of suitable plumper (acid binding agent), can be organic base such as tertiary amine, it is also possible to From inorganic base, the such as hydroxide of alkali metal or alkaline-earth metal, oxide, carbonate, or mixture etc., can be used to prepare this The compound of invention urethane and/or urea.It is specifically including but not limited to, NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, carbon Sour potassium, saleratus, calcium hydroxide, ammonia, ammoniacal liquor etc. and the like.Additionally, amine substance excessive in reaction, such as lysine two Ketone piperazine or lysine etc., it is also possible to as plumper.
Optional a kind of suitable amine can be used to prepare the compound of urethane of the present invention and/or urea.Suitable for the present invention's The diamines of the preparation of polyurethane/urea compound, can both be primary amine can also be secondary amine, can both be aliphatic can also to be Aromatic series or the material such as heterocycle, or macromolecule amine, or suitable amine, their derivative and mixture.Specifically Including but not limited to, ethylenediamine, propane diamine, tetra-methylenedimine, pentanediamine, hexamethylene diamine, heptyl diamines, octamethylenediamine, piperazine, 2, 5- lupetazins, (m-, p-) dimethylaniline, Isosorbide-5-Nitrae-DACH, p-phenylenediamine, 1,5- naphthylenediamine, isophorone two Amine, 4,4 '-methylene dianiline, double (p- aminocyclohexyl) methane, 1,3- bis- (4- piperidyls) propane.Additionally, also include with The polymer of amido end-blocking such as, the graceful Jeffamine amine of Hensel, various sulfanilic acids such as (2,4 or 2,5-)-diamino benzene sulfonic acid, (2.5- or 2.6-) diaminourea -4- benzene sulfonic acids, and hydrazine etc., and other tertiary amines, quaternary amine, polyamine etc., and they Mixture.
Additionally, in practical operation, polyisocyanate polycyanate ester can be used for the preparation of this patent.Polyisocyanates can be with amine Or hydroxyl reaction, can also may be used with LDKP, the prepolymer of LDKP end-blockings, lysine, the substance reaction such as prepolymer of lysine end-blocking For use as chain extender.Isocyanates wherein used can be one-level or secondary fatty race, cycloaliphatic ring, or aromatic series Or heterocyclic polyisocyanates, or with isocyanate-terminated prepolymer etc., or these are similar containing isocyanic acid Thing, and its mixture.Example includes, but not limited to IPDI (IPDI), hexamethylene diisocyanate (HDI), to thiacyclohexane isocyanates (H12MDI), to cyclohexyl diisocyanate (CHDI), 2,4- toluene two are different for di-2-ethylhexylphosphine oxide Cyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI), PPDI (PPDI), 1,5- naphthyl, two isocyanide Acid esters, tolidine diisocyanate, (m-, p-) XDI etc..Poly isocyanate includes trimerization isocyanide Acid esters, such as LTI, four PICs or other polyisocyanates, its analog and their mixture Deng.
Optional a kind of suitable solvent can be used for the compound of the urethane and/or urea for preparing the present invention.Including water, or have Machine solvent, or the preferably mixture of water and organic solvent.Organic solvent therein and water can both be that to dissolve each other can also be not phase Molten, such as acetone, methyl ethyl ketone, tetrahydrofuran, methyl alcohol, ethanol, isopropanol, dioxane, ethyl acetate, acetonitrile, diethyl Ether, such as aromatic hydrocarbon, toluene, chloro fat race hydrocarbon or aromatic hydrocarbon, analog and their mixture etc..
LDKP urethanes involved in the present invention may also have other system in addition to LDKP can form its urethane with chloro-formate Preparation Method.For example, perhaps LDKP and carbonic ester, dimethyl carbonate or cyclic carbonate, can form the compound of the present invention. It is possible to chloro-formate is first reacted with N-hydroxy-succinamide the corresponding succinimdyl carbonate derivative of generation, then Lysine diketopiperazine type polyurethane is obtained with the reaction of lysine diketopiperazine.In addition LDKP-LYS types urea ester (III) also can be by Lysine diketopiperazine and LDI derivatives are generated.
Involved by this patent is that with lysine diketopiperazine (LDKP), lysine and derivative are raw material, there is provided letter Single non-isocyanate method synthesis is based on LDKP, LDKP/ lysines, the urethane and urea compound of lysine.For affiliated technology It will be apparent that according to method provided by the present invention for the professional in field, and according to product use requirement, without departing from this Under the spirit of invention, LDKP the and LDKP/ lysines product and copolymer of various combinations can be obtained.
Lysine type polyurethane is known as biomedicine and biodegradation material.They have application to many sides of medical science Face, such as adhesive, artificial skin, wound dressing, artificial blood vessel, high-molecular gel.The invention provides a kind of directly application is more Be easy to get lysine, replaces lysine isocyanates, synthetic lysine urethane and urea compound, and the preparation method is more It is environmental protection, inexpensive.In this way gained polyurethane by with the lysine polyurethane prepared by traditional isocyanates out There is similar performance.
New LDKP and LDKP/ lysines type urethane/urea ester polymer in patent of the present invention is to apply natural reproducible Thing makees Material synthesis, its objective is what the isocyanates for having similar performance polyurethane to replace those traditional using these synthesized Polyurethane so as to have similar range of application while also having the advantage such as be environment-friendly and low-toxicity.They can be used on and prepare various polyurethane Material, such as coating, paint, adhesive, ink, adhesive, filler, foundry goods, rubber, fiber, gel etc., for such as packing, The polyurethane association area such as toy, cosmetics, building materials, automobile, medical treatment.
It has been found that the LDKP type polyurethanes invented by this patent have excellent film forming and moisture-proof.For example, by gathering The layer that LDKP type polyurethanes synthesized by the polyalcohol chloro-carbonic acid fat such as ester chloro-carbonic acid fat and castor oil are applied has good scratch resistance, and Its water absorption rate is less than 4%.Additionally, the LDKP type polyurethanes in the present invention have excellent heat endurance (for example, 5% weight-loss ratio Temperature be 310 DEG C), which is much larger than pure lysine polyurethane (LYS types) (260 DEG C of ＜).Acrylic acid modified LDKP- lysines Copolymer p UA (polyurethane/acrylate mixing) with excellent resistance to water.Therefore, by selecting different polyalcohols, work( Energy group and additive, can prepare a series of different LDKP and LDKP/ lysine type polyurethane films of structures, coating and oil Ink etc., and adapt on various base materials, including timber, metal, plastics, glass, concrete, fiber, textile, paper, skin Leather, artificial leather and skin etc..
LDKP the and LDKP/ lysines and lysine type polyurethane invented by this patent can serve as bonding agent material, application In bonding sheet, flexible package, multilayer film, leather and dermatine, footwear, printing-ink and other association areas.According to of the invention special Profit can obtain a series of LDKP of different softening temperatures or fusing point, LDKP/ lysines and lysine type polyurethane.And these materials Good PUR property has been shown on the base materials such as glass, metal, timber and paper.LDKP that this patent is invented and LDKP/ lysines, lysine type polyurethane are suitable for packaging for foodstuff, flexible package, medical packaging, for example, paper glue, label, or Lid glue and container glue, such as hermetic bag glue, air-tight bottle glue etc..It is also possible to apply to and food, medicine etc. has the packaging field of contact. They also are used as the adhesive of glued board and furniture, and these adhesives will not discharge amine, aldehyde in use The harmful substances such as class.
LDKP and LDKP/ lysines and lysine type polyurethane that this patent is invented can also cast the thing of various forms Body, such as toy, sports goods, household articles etc..
LDKP the and LDKP/ lysines invented by this patent, lysine type polyurethane are also used as medical material making Various biomedical products etc., such as artificial skin, wound dressing, artificial blood vessel, medicine equipment, bandage, pad, conduit, gel, Drug delivery etc..They can be the biodegradation material of superior performance, if especially with biodegradable polyalcohol such as Material prepared by Merlon or polylactic acid PLA.
LDKP, LDKP/ lysine, and the aqueous polyurethane (WPU) of lysine type, aqueous or alcohol ammoniacum acrylic acid pre-polymerization Body and PUA hybrids, with including environmental protection, the advantage such as low cost and good resistance to water.Thus, they have can be used for system Product, such as coating, paint, adhesive, ink, adhesive, foundry goods, gel etc..
This patent is invented to be applied to coating, paint, adhesive, or LDKP the and LDKP/ lysines of film, lysine type Polyurethane can be constructed by various methods, including spraying, brush, roller coat, casting, dipping or heat.
The following examples will facilitate a better understanding of the present invention.Come certainly for person skilled in the art Say and be readily appreciated that, according to the use requirement that method provided by the present invention and product are final, without departing from the present invention's Under basic conception and spirit, the product with suitable different structure and property can be prepared by various combinations.
Example
Example 1：By 1 gram of polyester chloro-formate containing double functional group (by obtained by phosgenation PEPA, wherein polyester Polyalcohol by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000) and 0.15 gram of BDO chloro-carbonic acid Ester, is dissolved in the acetone of 10 milliliters of ice-water bath coolings.Under agitation, it is added dropwise inward dissolved with 0.48 gram of symmetrical lysine diketone 1 milliliter of the aqueous solution of piperazine hydrochloride, is added dropwise 1 milliliter of the aqueous solution dissolved with 0.24 gram of NaOH, adds 30 milligram of three light Gas.Reaction system is incubated at 5-15 DEG C.Then, Jing after a period of time is stirred at room temperature, polymer, washing and drying are isolated.Gained S- LDKP type polyurethanes show good PUR property on glass, paper, and film water imbibition is 6%, and hardness is F-H.
Example 2：Will be 1.16 grams of polytetramethylene ether diol chloro-formates (PTMG, Mn=1000) containing double functional group molten Solution is in the acetone that 15 milliliters of ice-water baths are cooled down.The hydrochloric acid saline solution dissolved with 0.33 gram of lysine methyl ester is added dropwise under stirring inward 1 milliliter, afterwards, then 2 milliliters of the aqueous solution dissolved with 0.49 gram of sodium carbonate is added dropwise to system, and the system temperature is controlled always Between 5-15 DEG C.Then a period of time is stirred at room temperature until reactant liquor becomes sticky, system pH is adjusted to 7.Isolate gained poly- Urethane, washing are dried.Its film water imbibition is 60.4%, and has excellent tack in glass, timber, metal and paper Energy.
Example 3：By 0.52 gram of symmetrical lysine diketopiperazine hydrochloride salt in the water that 15 milliliters of ice-water baths are cooled down, 2 milliliters of the aqueous containing 0.30 gram of sodium carbonate and 2 milliliters of the acetone soln dissolved with 0.03 gram of triphosgene is added dropwise under stirring inward. After stirring 20 minutes at 10-15 DEG C, system pH is adjusted to into 6 with watery hydrochloric acid.Solvent is removed, mixture is obtained：Lysine diketone piperazine Piperazine (S-LDKP, Mass+H:257) with lysine diketopiperazine urea S-LDKP/S-LDKP urea (II) (Mass+H:539).
Example 4：0.2 gram of symmetrical lysine diketopiperazine hydrochloride and 0.2 gram of FE-5 are dissolved in into 5 milliliters In the water of ice-water bath cooling.Solubilization inward under stirring has 1 milliliter of the aqueous solution of 0.16 gram of sodium carbonate and dissolved with 0.04 gram of triphosgene 1 milliliter of acetone soln.After stirring 20 minutes at 10-15 DEG C, system pH value is adjusted to into 6 with watery hydrochloric acid.Remove solvent to mix Compound：S-LDKP/S-LDKP type urea (II) (Mass+H:539), S-LDKP/LYS types urea (III) (Mass+H:And polyureas 429) 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 lysine diketopiperazine hydrochloride and 0.23 gram of FE-5 are dissolved in into 1 milli Rise in the water of ice-water bath cooling.Solubilization inward under stirring has 0.5 milliliter of the aqueous solution of 0.10 gram of sodium carbonate and containing 0.015 gram of three light 1 milliliter of the acetone soln of gas.Stirring reaction, system temperature are controlled at 5-15 DEG C.Afterwards, add and contain double functional group containing 3.5 grams Polyester chloro-formate (obtained by phosgenation PEPA, wherein PEPA is by adipic acid, BDO and 1,2- second Synthesized by glycol, Mn=2000) 10 milliliters of acetone soln.Add the aqueous solution 2 containing 0.70 gram of sodium carbonate under stirring again inward Milliliter, now temperature is maintained at 5-15 DEG C, and pH value is 6-8.Then a period of time is stirred at room temperature until reactant liquor becomes sticky, point From washing and be dried to obtain polyurethane-urea.
Example 6：By 4.9 grams of polyester chloro-formates containing double functional group (by obtained by phosgenation PEPA, wherein gathering Ester polyol by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000), 0.92 gram of BDO chloromethane Acid esters and 1.0 grams of castor oil chloro-formates are dissolved in the acetone of 20 milliliters of ice-water bath coolings.Under agitation, it is added dropwise dissolved with 3.2 Gram 3 milliliters symmetrical of lysine diketopiperazine hydrochloric acid saline solution, and 2 milliliters of the aqueous solution containing 1.4 grams of NaOH, and should Architecture heat preservation is at 5-15 DEG C.Then a period of time is stirred at room temperature until reactant liquor becomes sticky.Isolate resulting polymers, water Wash, be dried.Its water absorption rate of film coating of gained polyurethane is 4%, hardness F-H, the scratch resistance having had.
Example 7：The chloro-formate of 0.13 gram of hydroxyethyl methacrylate (HEMA) is dissolved in into 1 milliliter of ice-water bath cooling In acetone.Under agitation, 2 milliliters of the aqueous solution dissolved with 0.3 gram of symmetrical lysine diketopiperazine hydrochloride is added, and contains 0.12 1 milliliter of the aqueous solution of gram sodium carbonate, and by the architecture heat preservation at 5-15 DEG C.It is after a period of time is stirred at room temperature, water-soluble with watery hydrochloric acid PH value is adjusted to 6 or so by liquid.Remove solvent and obtain mixture, predominantly：S-LDKP-mono-Hema urethane(IV)(Mass+ H:, and subsidiary a small amount of HEMA-S-LDKP-double-Hema urethane (Mass+H 413):569).
Example 8：Under ice-water bath, the chloro-formate of 0.31 gram of hydroxyethyl methacrylate (HEMA) is dissolved in into 3 milliliters Tetrahydrofuran in.Add containing 0.25 gram of symmetrical lysine diketopiperazine hydrochloride and 0.25 gram of lysine salt to the solution under stirring 1 milliliter of the aqueous solution of hydrochlorate, is then added dropwise sodium hydrate aqueous solution again.Add dissolved with 1.12 grams of polytetramethylene ether diols afterwards 8 milliliters of the tetrahydrofuran cold soln of chloro-formate (PTMG, Mn=1000) and 0.12 gram of BDO chloro-formate, then be added dropwise Sodium hydrate aqueous solution.In course of reaction, system temperature is maintained at 5-15 DEG C and pH value is maintained at 4-9.It is stirred at room temperature 1 little Shi Hou, it is separated from the water after obtain organic phase, and by itself and 0.5 gram of butyl methacrylate and 0.06 gram of light trigger Irgacure2959 (SIBA) mixes.Gained urethane-acrylic acid solution, Jing films, illumination (NOVACURE, 100W mercury lamp light Arc) after obtain hard solid film, its water absorption rate is 3%.
Example 9：1.1 grams of FE-5s are dissolved in the water of 2 milliliters of ice-water bath coolings.It is added dropwise under stirring inward molten There are 2 milliliters of the acetone cold soln and sodium hydrate aqueous solution of 1.1 grams of hydroxyethyl methacrylate chloro-formates (HEMA).Reacted Cheng Zhong, system temperature is maintained at 5-15 DEG C and pH value is maintained at 6-8.Add the polytetramethylene ether diol dissolved with 1.0 grams afterwards The acetone of chloro-formate (PTMG, Mn=1000), 0.12 gram of BDO chloro-formate and 0.03 gram of castor oil chloro-formate 8 milliliters of cold soln, then sodium hydrate aqueous solution is added dropwise.In course of reaction, system temperature is maintained at 5-15 DEG C and pH value is maintained at 6-9.After further stirring, solution ph is adjusted to into 7 or so, and adds 0.08 gram of light trigger Irgacure2959 inward (SIBA).Resulting solution is divided into into two parts.
First part of solution Jing strong agitation simultaneously boils off acetone and obtains lysine-ammoniacum-methacrylate performed polymer Aqueous dispersions.The aqueous dispersions Jing films of gained lysine-ammoniacum-methacrylate performed polymer, illumination (NOVACURE, 100W mercury lamp arc of lightings) after obtain be crosslinked film, its water absorption rate be more than 80%.Second part of solution obtains sticky relying after removing solvent Propylhomoserin ammoniacum methacrylate (PUA) performed polymer is re-dissolved in water/alcohol mixed solvent, and the alcoholic solution of PUA performed polymers is obtained. Again which is mixed with methacrylic acid fourth fat, in the presence of photoinitiators, UV illumination its coating obtains the PUA hybrids being crosslinked, Its water absorption rate is 25%.
Example 10：Under ice-water bath, by 2.1 grams of polyester chloro-formates containing double functional group (by phosgenation polyester polyols Obtained by alcohol, wherein PEPA by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000) and 0.4 gram 1, 4- butanediol chloro-formates, are dissolved in 20 milliliters of acetone.Under agitation, it is added dropwise dissolved with 0.18 gram of IPD IPDA's 1.5 milliliters of the aqueous solution of 1 milliliter and 0.45 gram FE-5 of acetone soln, then be added dropwise containing 0.3 gram of NaOH to system 2 milliliters of the aqueous solution.During the course of the reaction, system temperature is controlled between 5-15 DEG C, pH value is controlled in 6-8.It is stirred at room temperature After certain hour, system viscosity gradually increases.The organic liquor is added in water under strong agitation, removes acetone and obtain aqueous The polyurethane aqueous dispersions of IPDA- lysines.The film prepared by gained polyurethane aqueous dispersions has attached well on paper Put forth effort.
Example 11：Under ice-water bath, 1 milliliter of tetrahydrofuran solution stirring dissolved with 0.2 gram of methyl propionyl chloride is added to into 10 In tetrahydrofuran solution of the milliliter containing 0.34 gram of IPD.Afterwards, then to which 2 milliliters are added dissolved with 0.26 gram of lysine The aqueous solution, 5 milliliters dissolved with 1 gram of polytetramethylene ether diol chloro-formate (PTMG, Mn=1000) and 0.3 gram of butanediol chloro-carbonic acid The tetrahydrofuran solution of ester, afterwards, is added dropwise sodium hydroxide solution.And keep the temperature of system at 5-15 DEG C, system PH 7-9 it Between.Jing after a period of time is stirred at room temperature, separates the solvent in organic phase, and removing system and obtain sticky shape PUA performed polymers.The PUA Performed polymer can be dissolved in ethanol, and isopropanol can be distributed to second alcohol and water (water：Ethanol=2:1) in mixed solvent.Again by its with Methacrylic acid fourth fat mixes, and in the presence of light trigger Irgacure2959 (CIBA), UV illumination coatings obtain cross-linking type PUA Film.
Example 12：In ice-water bath, by 2.23 grams of polytetramethylene ether diol chloro-formates containing double functional group (PTMG, Mn=1000) is added in 20 milliliters of aqueous solution containing 0.49 gram of FE-5 with vigorous stirring.Again to system 3 milliliters of the aqueous solution containing about 0.3 gram of NaOH is slowly added dropwise, and during dropwise addition, system temperature is controlled at 10-20 DEG C Between, pH value is controlled between 7-9.Then, it is stirred overnight under solution room temperature.The elasticity that the polyurethane coating film of gained shows Matter.
Example 13：By 1.08 grams of PolyTHF chloro-formates (PTMG, Mn=1000) and 0.11 containing double functional group Gram butanediol chloro-formate is dissolved in the acetone of 10 milliliters of ice-water baths coolings.Then stir under to the solution add 1 milliliter dissolved with The aqueous solution of 0.24 gram of symmetrical lysine diketopiperazine hydrochloride and 0.24 gram of lysine, is added dropwise 1 milliliter afterwards dissolved with 0.24 Can NaOH the aqueous solution.Plus during alkali, system temperature is controlled between 5-15 DEG C, pH value is controlled between 6-8, with The carrying out of reaction, system viscosity becomes larger, then separate macromolecule, and Jing washings, be dried.Gained polyurethane its fusing point is about For 110 DEG C, the PUR property having had on glass base, the water absorption rate of its film is 60%.
Example 14：By 2.6 grams containing double functional group polyester chloro-formates (by obtained by phosgenation PEPA, wherein PEPA by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000) and 0.30 gram of castor oil chloro-carbonic acid Ester is dissolved in the acetone of 20 milliliters of ice-water bath coolings.There are 0.29 gram of lysine and 0.25 gram of hydrogen to the solution solubilization under agitation 2.5 milliliters of aqueous solution of sodium oxide, afterwards again plus triphosgene is until system pH is to 7.5 or so.In the process, by system temperature Control is between 5-15 DEG C.It is stirred at room temperature until system viscosity increases.Organic phase therein is isolated, will under strong stirring Which is dispersed in water, and forms the polyurethane aqueous dispersions (particle diameter about 60nm) of slightly blue light.Film made by gained polyurethane is hard Spend for 6B.
Example 15：By 2.05 grams containing double functional group polyester chloro-formates (by obtained by phosgenation PEPA, wherein PEPA by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000) and 0.40 gram of BDO chlorine Formic acid esters is dissolved in the acetone of 20 milliliters of ice-water bath coolings.Under agitation, it is added dropwise inward dissolved with 0.21 gram of symmetrical lysine 2 milliliters of diketopiperazine hydrochloride and 0.50 gram of lysine solution aqueous solution, are added dropwise the aqueous solution dissolved with 0.4 gram of NaOH afterwards 1.5 milliliter.In the process, system temperature is controlled between 5-15 DEG C, pH value is 6-8.It is stirred at room temperature until system viscosity Increase.Organic phase therein is dispersed in water under strong stirring afterwards, then aqueous polyurethane point is formed after boiling off acetone A prose style free from parallelism.About 70 DEG C of the film softening point prepared by the aqueous polyurethane, shows excellent on the base materials such as glass, timber, metal, paper Different PUR property.
Example 16：By 5.2 grams containing double functional group polyester chloro-formates (by obtained by phosgenation PEPA, wherein PEPA by adipic acid, synthesized by BDO and 1,2- ethylene glycol, Mn=2000) and 0.75 gram of BDO chlorine Formic acid esters is dissolved in the acetone of 30 milliliters of ice-water bath coolings.Under agitation, solubilization inward has 0.81 gram of symmetrical lysine two Ketone piperazine hydrochloride and 3 milliliters of the aqueous solution of 0.38 gram of piperazine (HCl neutralizations), are added dropwise the water dissolved with 1.2 grams of NaOH afterwards 1.5 milliliters of solution.In the process, system temperature is controlled between 5-15 DEG C.It is stirred at room temperature until system viscosity increases.Point Separate out polymer S-LDKP- piperazine type polyurethanes are obtained Jing washing, after being dried.

Claims (34)

1. a kind of compound, it is characterised in that containing repetitive Urethane Unit (I),
Or a kind of compound contains following construction unit：LDKP-LDKP Urea (II), or LDKP-Lysine Urea (III), Or LDKP-acryl (IV), or their repetitive, or mixture：
-------DKP-NH-R
LDKP-acryl(IV)
Wherein ----it is free valence bond；
The structural formula of DKP is as follows：
In LDKP-Lysine Urea (III), the structural formula of LYS is as follows：
---CH2CH2CH2CH2CH(X)---
It is the part in the lysine derivative that structure is shown below：
H2N-CH2CH2CH2CH2CH(X)-NH2
Wherein X is COOH, or COOM, wherein M are metal ion, ammonium cation, or mixture, and/or X is COOR ', CONHR ', CONR '2, COSR ', or mixture, R ' are straight chain or side chain,
It is saturated or unsaturated, ring-type or heterocycle shape, substituted or non-substituted, alkyl or aryl, or mixing Thing；R in LDKP-acryl (IV) is：
Wherein Y is H, methyl；Z is alkylidene, cyclic alkylidene, is selectively inserted into oxygen atom O and/or optionally with taking Dai Ji；
Wherein, if compound does not contain LDKP-LDKP Urea (II), without LDKP-Lysine Urea (III), do not contain yet yet LDKP-acryl (IV), also without lysine ammonia ester bond, also without lysine urea ester bond, the molecular weight of the compound is more than 2000。
2. compound according to claim 1, it is characterised in that comprising the repetitive Urethane Unit (I).
3. compound according to claim 1, it is characterised in that comprising the construction unit LDKP-LDKP Urea (II)。
4. compound according to claim 1, it is characterised in that comprising the construction unit LDKP-Lysine Urea (III)。
5. compound according to claim 1, it is characterised in that comprising the construction unit LDKP-acryl (IV).
6. compound according to claim 1, it is characterised in that wherein n is that the structural formula of 4, DKP is as follows：
It is a part for the following symmetrical lysine diketopiperazine of structural formula：
7. compound according to claim 1, it is characterised in that M is a metal ion, from Li+,Na+,K+,Ca2+,Zn2+ And Mg2+Middle selection.
8. compound according to claim 1, it is characterised in that the structural formula of LDKP-acryl (IV) is：
Or R1It is a part for a polyurethane；Y is H, methyl；Z is alkylidene, a cyclic alkylidene, is selectively inserted into oxygen former Sub- O and/or optionally carry substituent.
9. according to the compound described in claim 1, it is characterised in that wherein LDKP-LDKP urea (II) are double (S- LDKP) type urea, or three (S-LDKP) type urea, or four (S-LDKP) type urea.
10. according to the compound described in claim 1, it is characterised in that wherein LDKP-Lysine urea (III) are S- LDKP/Lysine type ureas, or double (Lysine) the type ureas of S-LDKP/, or double (S-LDKP)/Lysine type ureas, or double (S-LDKP)/ Double (Lysine) type ureas, or three (S-LDKP)/Lysine type ureas, or three (S-LDKP)/bis- (Lysine) type urea, or four (S- LDKP)/Lysine type ureas.
11. according to the compound described in claim 1, it is characterised in that by lysine diketopiperazine, or with lysine two The compound or prepolymer of ketone piperazine end-blocking, or lysine, or the compound that blocked with lysine or prepolymer, or lysine two The salt or lysine salt of ketone piperazine, or mixture,
With containing one or more chloroformate group chloro-formates, or the compound or prepolymer of chloro-formate end-blocking, or light Gas, or surpalite, or triphosgene, or mixture；
React in the presence of plumper and obtain.
A kind of 12. compounds containing lysine ammonia ester bond or lysine urea ester bond or their repetitive or mixture, Characterized in that, being prepared by the reaction of following compound：
Lysine, its structural formula are (HCl) H2N-CH2CH2CH2CH2CH(X)-NH2, in formula, X is COOH, or COOM, wherein M be Metal ion, or ammonium cation, or mixture, and/or X is COOR ', CONHR ', CONR '2, COSR ', or mixture, wherein R ' is saturated or unsaturated, straight chain or side chain, or ring-type or heterocycle shape, substituted or non-substituted, alkane Base or aryl, or mixture；Or the salt or bad ammonia of the compound or prepolymer or lysine diketopiperazine of lysine end-blocking Hydrochlorate or mixture,
With the chloro-formate containing one or more chloroformate groups, chloro-formate end-blocking compound or prepolymer or Phosgene or surpalite or triphosgene or mixture,
React in the presence of plumper.
13. compounds according to claim 12, it is characterised in that wherein M is a metal ion, from Li+,Na+,K+,Ca2 +,Zn2+, and Mg2+Middle selection.
14. compounds according to any one of claim 1-10,12,13, it is characterised in that be macromolecule.
15. compounds according to any one of claim 1-10,12,13, it is characterised in that be crosslinkable or friendship The compound of connection.
16. compounds according to any one of claim 1-10,12,13, it is characterised in that be aqueous polyurethane point A prose style free from parallelism.
The application of 17. claims 1-10, the compound any one of 12,13 in film is prepared.
The application of 18. claims 1-10, the compound any one of 12,13 in coating is prepared.
The application of 19. claims 1-10, the compound any one of 12,13 in paint is prepared.
The application of 20. claims 1-10, the compound any one of 12,13 in adhesive is prepared.
The application of 21. claims 1-10, the compound any one of 12,13 in ink is prepared.
The application of 22. claims 1-10, the compound any one of 12,13 in colloidal sol is prepared.
23. claims 1-10, the compound any one of 12,13 in TPUE is prepared should With.
A kind of 24. synthetic methods are used for preparing the compound containing following construction unit：Urethane unit (I), or LDKP- LDKP Urea (II), or LDKP-Lysine Urea (III), or LDKP-acryl (IV), or their repetitive, or it is mixed Compound：
-------DKP-NH-R
LDKP-acryl(IV)
Wherein ----it is free valence bond；
The structural formula of DKP is as follows：
In urea (III), the structural formula of LYS is as follows：
---CH2CH2CH2CH2CH(X)---
It is the part in the lysine derivative that structure is shown below：
H2N-CH2CH2CH2CH2CH(X)-NH2
Wherein X is COOH, or COOM, wherein M are metal ion, ammonium cation, or mixture, and/or X is COOR ', CONHR ', CONR '2, COSR ', or mixture, wherein R ' be it is straight chain or side chain, saturated or unsaturated, ring-type or Heterocycle shape, replace or non-substituted, alkyl or aryl, or mixture；
R in LDKP-acryl (IV) is：
Wherein Y is H, methyl；Z is alkylidene, cyclic alkylidene, is selectively inserted into oxygen atom O, and/or optionally carries Substituent；
Wherein, if compound does not contain LDKP-LDKP Urea (II), without LDKP-Lysine Urea (III), do not contain yet yet LDKP-acryl (IV), also without lysine ammonia ester bond, also without lysine urea ester bond, the molecular weight of the compound is more than 2000；Characterized in that, being the compound or performed polymer for blocking lysine diketopiperazine or lysine diketopiperazine, or rely Propylhomoserin, or the salt or lysine salt or mixture of the compound or performed polymer or lysine diketopiperazine of lysine end-blocking, with Carbonylation agent, or phosgene, or two phosgene, or triphosgene, or mixture, react in the presence of plumper.
25. synthetic methods according to claim 24, it is characterised in that wherein carbonylation agent is selected from containing one Or the chloro-carbonic acid ester type compound of multiple chloroformate groups, the compound or performed polymer of chloro-formate end-blocking.
26. synthetic methods according to claim 25, it is characterised in that wherein carbonylation agent is a bischloroformate knot Structure formula is：ClCO-U-OCCl, wherein U are spacer group.
27. synthetic methods according to claim 26, it is characterised in that wherein U is alkylidene, containing oxygen atom and/or contain Substituent；U will not be reacted with carbonyl reagent, so also not disturbing carbonylation.
28. a kind of acrylic or methacrylic acid compounds, it is characterised in that by obtained by following substance reaction：
Lysine diketopiperazine, or the compound or performed polymer of lysine diketopiperazine end-blocking, or lysine, or lysine end-blocking Compound or performed polymer or lysine diketopiperazine salt or lysine salt or mixture,
A kind of carbonylation agent, or phosgene, or two phosgene, or triphosgene, or mixture,
A kind of compound A；
The compound A is：Methyl propionyl chloride, propionyl chloride, 2- ethylaminoethanol acrylate, 2- ethylaminoethanol methacrylic acids Ester, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, (2 or 3)-hydroxypropyl acrylate, (2 or 3)-hydroxy propyl methacrylate, 4- hydroxyl butyl propyleneglycol acid esters, 4- hydroxybutyl methacrylates, acrylate ethylene oxidic ester, methyl propenoic acid glycidyl Ester, ACEtmClass hydroxy-acrylate monomer, (methyl) polyalkylene glycol acrylate ester, the chloro-formate of following monomer：Acrylic acid hydroxyl Ethyl ester, hydroxyethyl methacrylate, (2 or 3)-hydroxypropyl acrylate, (2 or 3)-hydroxy propyl methacrylate, 4- hydroxyls butyl third Olefin(e) acid ester, 4- hydroxybutyl methacrylates, glycidyl acrylate, GMA, ACEtmClass hydroxyl Base acrylate monomer, (methyl) polyalkylene glycol acrylate ester, and their mixture.
29. compounds according to claim 28, it is characterised in that its carbonylation agent is such as claim 26 and 27 In defined carbonylation agent.
30. a kind of high-molecular copolymer, it is characterised in that be by by the compound described in claim 28 and compound B Copolymerization and obtain；
The compound B is：Methyl methacrylate, methyl acrylate, EMA, ethyl acrylate, (methyl) N-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, cyclohexylacrylic ester, methacrylic acid, third Olefin(e) acid, Ethylene glycol methyl ether (methyl) acrylate, two (ethylene glycol) ethylether (methyl) acrylate, PEG ethyl Ether (methyl) acrylate, ethylene glycol two (methyl) acrylate, two (ethylene glycol) two (methyl) acrylate, three (ethylene glycol) Two (methyl) acrylate, four (ethylene glycol) two (methyl) acrylate, PEG two (methyl) acrylate, glycerine two The isomers of (methyl) acrylate mixture, three (ethylene glycol) methyl ether (methyl) acrylate, two (first of BDO Base) acrylate, 1,6- hexanediyl ester, polyethyleneglycol diacrylate, acrylic polyester, the poly- carbonic acid of acrylic acid Ester, fluoroalkyl (methyl) acrylate, perfluorooctylethyl group acrylate, hexafluoropropene acid butyl ester, 2,2,2- trifluoroethyl (first Base) acrylate, 1H, 1H, 2H, 2H- perfluoro decyl acrylate, 1H, 1H- perfluoro decyl (methyl) acrylate, Zony TM Fluorine class monomer, (methyl) glycidyl acrylate, acrylated epoxidized soybean oil ester, 2- (diethylamino) ethyl (methyl) Acrylate, 2- (dimethylamino) ethyl (methyl) acrylate, 3- (dimethylamino) propyl acrylate, N- [3- (two Methylamino) propyl group] methyl propanamide, 3- sulphurs third (methyl) acrylic acid (sodium, potassium) salt, (methyl) acrylamide, N- alkyl (first Base) acrylamide, 2- hydroxy-ethyl acrylates, 2- hydroxyethyl methacrylates, (2 or 3)-hydroxypropyl acrylate, (2 or 3)-methyl Hydroxypropyl acrylate, 4- hydroxyl butyl propyleneglycol acid esters, 4- hydroxybutyl methacrylates, glycidyl acrylate, methyl-prop Olefin(e) acid ethylene oxidic ester, ACEtmClass hydroxy-acrylate monomer.
31. compounds according to claim 28, it is characterised in that be aqueous pu dispersions.
32. compounds according to claim 28, it is characterised in that be alcohol type, or alcohol/water mixed type solution or dispersion Liquid.
33. copolymers according to claim 30, it is characterised in that be aqueous pu dispersions.
34. copolymers according to claim 30, it is characterised in that be alcohol type, or alcohol/water mixed type solution or dispersion Liquid.
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