CN105254576A - Method for preparing glutamic piperazinedione - Google Patents

Method for preparing glutamic piperazinedione Download PDF

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CN105254576A
CN105254576A CN201510800781.7A CN201510800781A CN105254576A CN 105254576 A CN105254576 A CN 105254576A CN 201510800781 A CN201510800781 A CN 201510800781A CN 105254576 A CN105254576 A CN 105254576A
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formula
polyesteramide
monomer
polycondensation
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王松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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

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Abstract

The invention provides a method for preparing glutamic piperazinedione, which comprises the step of directly heating a glutamic acid to carry out dimerization reaction, so that glutamic piperazinedione is obtained. The glutamic piperazinedione prepared according to the method provided by the invention can be used for preparing polyesteramide, and the polyesteramide prepared by using the glutamic piperazinedione has good biodegradability, thereby avoiding the problem of environmental pollution. In addition, the glutamic piperazinedione in the invention is prepared by taking a glutamic acid as a raw material, and the glutamic acid is a renewable material, so that the preparation of glutamic piperazinedione by taking the glutamic acid as a raw material can save energy, and the cost of preparing polyesteramide by using glutamic piperazinedione is low. Experimental results show that polyesteramide prepared by using glutamic piperazinedione prepared by using the method provided by the invention is degraded in a phosphate-buffered solution with a pH value of 7.4, and then the molecular weight of the polyesteramide in 10 weeks is reduced by 53-80%, therefore, the polyesteramide has good biodegradability.

Description

A kind of preparation method of L-glutamic acid diketopiperazine
The divisional application that the application is application number 201410066476.5, on 02 26th, 2014 applying date, title " a kind of polyesteramide and preparation method thereof " are applied for.
Technical field
The present invention relates to high molecular polymer preparing technical field, particularly relate to a kind of preparation method of L-glutamic acid diketopiperazine.
Background technology
Polyesteramide is the polymkeric substance containing ester chain and amido linkage on molecular backbone chain.Polyesteramide is divided into linear polyesters acid amides and cross-linking type polyesteramide, and linear polyesters acid amides is mainly used as dress material and the ornament of Silk; Cross-linking type polyesteramide can be used as plastics or the reinforced plastics component for fields such as machinery and electrical equipment.
The preparation method of polyesteramide is generally and dibasic alcohol and diprotic acid is carried out esterification, obtains intermediate product, described intermediate product and diamine is carried out polycondensation, obtains polyesteramide.As the application number Chinese patent that is 201010276371.4 discloses a kind of preparation method of polyester amide hot melt adhesive, detailed process is: terephthalic acid and propylene glycol and glycol ether are carried out esterification under tetrabutyl titanate catalyst effect; M-phthalic acid, aliphatic dicarboxylic acid, decamethylene diamine and hexanolactam are joined in the product of above-mentioned esterification, carry out polycondensation; In above-mentioned polycondensation reaction system, add polycondensation stablizer 2,6-tert-butyl-4-methyl-Phenol, carry out decompression copolycondensation, obtain polyester amide hot melt adhesive.Although the polyesteramide that prior art prepares has good thermostability, thermotolerance and winter hardiness, the polyesteramide that this method prepares cannot carry out biological degradation, causes more serious problem of environmental pollution.Therefore, preparing biodegradable polyesteramide is the emphasis studying polyesteramide at present.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of L-glutamic acid diketopiperazine, L-glutamic acid diketopiperazine prepared by method provided by the invention can be used for preparing polyesteramide, and the polyesteramide adopting L-glutamic acid diketopiperazine to prepare has good biodegradable.
The invention provides a kind of preparation method of L-glutamic acid diketopiperazine, comprising:
L-glutamic acid direct heating is carried out dimerization reaction, obtains L-glutamic acid diketopiperazine.
Preferably, described dimerization reaction is without the need to catalyzer.
Preferably, described dimerization reaction is without the need to solvent.
Preferably, the temperature of described dimerization reaction is 100 DEG C ~ 240 DEG C.
Preferably, the time of described dimerization reaction is 0.1 hour ~ 24 hours.
The invention provides a kind of preparation method of L-glutamic acid diketopiperazine, comprising: L-glutamic acid direct heating is carried out dimerization reaction, obtain L-glutamic acid diketopiperazine.The L-glutamic acid diketopiperazine that method provided by the invention prepares can be used for preparing polyesteramide, and the polyesteramide adopting L-glutamic acid diketopiperazine to prepare has good biodegradable, avoids the problem of environmental pollution.In addition, Glutamic Acid diketopiperazine of the present invention is that raw material prepares with L-glutamic acid, and L-glutamic acid is recyclable materials, adopt L-glutamic acid be raw material prepare L-glutamic acid diketopiperazine can save energy, L-glutamic acid diketopiperazine can be made to prepare the cost of polyesteramide lower.Experimental result shows, polyesteramide prepared by the L-glutamic acid diketopiperazine adopting method provided by the invention to prepare is degrade in the phosphate buffer solution of 7.4 in pH value, the molecular weight and molecular weight 53% ~ 80% of polyesteramide, has good biodegradable in 10 weeks.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra of the polyesteramide prepolymer that the embodiment of the present invention 1 obtains;
Fig. 2 is the degraded test result of the polyesteramide that the embodiment of the present invention 1 obtains;
Fig. 3 is the nmr spectrum of the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares;
Fig. 4 is the mass spectrum of the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares.
Embodiment
The invention provides a kind of polyesteramide, comprise the repeating unit with structure shown in formula (I):
In formula (I), R is alkylene, ether or polyether-based.
In the present invention, the R in described formula (I) is preferably alkylene, ether or the polyether-based that carbonatoms is 2 ~ 24; Be more preferably alkylene, ether or polyether-based that carbonatoms is 2 ~ 18; Most preferably be alkylene, ether or polyether-based that carbonatoms is 2 ~ 12.In the present invention, described alkylene is that hydrocarbon compound loses remaining group after two hydrogen atoms, and described hydrocarbon compound comprises aliphatic hydrocarbon and aromatic hydrocarbon.
The polyesteramide comprising structural repeat unit shown in formula (I) provided by the invention is obtained by the alcohol compound polycondensation of L-glutamic acid and hydroxyl value >=2.In the present invention, time in the alcohol compound of described hydroxyl value >=2 containing ehter bond, the R in above-mentioned formula (I) is ether, and time in the alcohol compound of described hydroxyl value >=2 containing polyethers key, the R in above-mentioned formula (I) is polyether-based.In the present invention, the linear polyesters acid amides with the first structural formula is obtained when L-glutamic acid and a kind of dibasic alcohol polycondensation.In the present invention, there is described in the repeating unit only containing structure shown in formula (i) in the linear polyesters acid amides of the first structural formula:
In formula (i), R 1for a kind of alkylene, ether or polyether-based.In the present invention, described first structural formula is such as formula shown in (A):
In formula (A), R 1for a kind of alkylene, ether or polyether-based; n 1for the polymerization degree, 1≤n 1≤ 1000, preferably, 100≤n 1≤ 800, preferred, 200≤n 1≤ 600.
In the present invention, the linear polyesters acid amides with the second structural formula is obtained when L-glutamic acid and multiple dibasic alcohol polycondensation.In the present invention, described in have containing multiple repeating unit in the linear polyesters acid amides of the second structural formula, these repeating units can represent by formula (ii), formula (iii) and formula (iv):
R in formula (ii), formula (iii) and formula (iv) 2, R 3and R nmultiple alkylene, multiple ether or multiple polyether-based can be represented; Also multiple alkylene and ether, multiple alkylene and polyether-based or multiple ether and polyether-based can be represented; Multiple alkylene, ether and polyether-based can also be represented.In the present invention, described second structural formula is formed by connecting without sequence rules, shown in (B) by the multiple repeating unit with structure shown in formula (ii), formula (iii) and formula (iv):
In formula (B), R 2, R 3and R nmultiple alkylene, multiple ether or multiple polyether-based can be represented; Also multiple alkylene and ether, multiple alkylene and polyether-based or multiple ether and polyether-based can be represented; Multiple alkylene, ether and polyether-based can also be represented; n 2, n 3and n nfor the polymerization degree, 1≤n 2≤ 1000,1≤n 3≤ 1000,1≤n n≤ 1000; Preferably, 100≤n 2≤ 800,100≤n 3≤ 800,100≤n n≤ 800; Preferred, 200≤n 2≤ 600,200≤n 3≤ 600,200≤n n≤ 600.
In the present invention, described dibasic alcohol is preferably ethylene glycol, 1, ammediol, 1, 4-butyleneglycol, 1, 5-pentanediol, 1, 6-hexylene glycol, 1, 8-ethohexadiol, Isosorbide, terephthalyl alcohol, isophthalic alcohol, phthalyl alcohol, 1, 2-propylene glycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, neopentyl glycol, 1, 2-pentanediol, 1, 3-ring pentanediol, 1, 2-hexylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, glycol ether, dipropylene glycol, tripropylene glycol, tetraethylene-glycol, 1, 7-heptanediol, 1, 2-ethohexadiol, 1, 2-ring ethohexadiol, 1, 9-nonanediol, 1, 2-decanediol, 1, 10-decanediol, five glycol, hexaethylene glycol, seven glycol, eight glycol, nine glycol, ten glycol, ten glycol ethers, rostenediol, estradiol, polyoxyethylene glycol or polytetramethylene glycol, be more preferably ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, Isosorbide, terephthalyl alcohol, isophthalic alcohol, phthalyl alcohol, 1,2-propylene glycol, 1,3 butylene glycol, 2,3-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-ring pentanediol, glycol ether or polyoxyethylene glycol, most preferably be ethylene glycol, 1,3-PD, 1,3-ring pentanediol, isophthalic alcohol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,5-PD, glycol ether, polyoxyethylene glycol or BDO.
In the present invention, obtain cross-linking type polyesteramide when L-glutamic acid and polyhydric alcohol, the cross-linking monomer of described cross-linking type polyesteramide comprises the monomer with structure shown in formula (v):
In formula (v), E is that polyvalent alcohol loses remaining group after a hydroxyl.In the present invention, obtain the first cross-linking type polyesteramide when L-glutamic acid and a kind of polyhydric alcohol, the cross-linking monomer of described first cross-linking type polyesteramide only includes the monomer with structure shown in formula (vi):
In formula (vi), E 1for a kind of polyvalent alcohol loses remaining group after a hydroxyl.In the present invention, described first cross-linking type polyesteramide is for having the cross-linked polymer of structures alone polycondensation shown in formula (vi), and described polycondensation be not at the same dehydrating condensation with hydroxyl on the shown structures alone of formula (vi) and carboxyl.
In the present invention, obtain the second cross-linking type polyesteramide when L-glutamic acid and a kind of polyvalent alcohol and a kind of dibasic alcohol polycondensation, the cross-linking monomer of described second cross-linking type polyesteramide only includes the monomer with structure shown in formula (vi) and formula (vii):
In formula (vii), R 3for a kind of alkylene, ether or polyether-based.In the present invention, described second cross-linking type polyesteramide is for having the cross-linked polymer of structures alone polycondensation shown in formula (vi) and formula (vii), and described polycondensation be not at the same dehydrating condensation with hydroxyl on formula (vi) or the shown structures alone of formula (vii) and carboxyl.
In the present invention, obtain the 3rd cross-linking type polyesteramide when L-glutamic acid and a kind of polyvalent alcohol and multiple dibasic alcohol polycondensation, the cross-linking monomer of described 3rd cross-linking type polyesteramide comprises the monomer and the multiple monomer represented by formula (viii), formula (ix) and formula (x) with structure shown in formula (vi):
R in formula (viii), formula (ix) and formula (x) 4, R 5and R mmultiple alkylene, multiple ether or multiple polyether-based can be represented; Also multiple alkylene and ether, multiple alkylene and polyether-based or multiple ether and polyether-based can be represented; Multiple alkylene, ether and polyether-based can also be represented.In the present invention, described 3rd cross-linking type polyesteramide is for having structures alone shown in formula (vi) and the multiple cross-linked polymer with the monomer polycondensation of structure shown in formula (viii), formula (ix) and formula (x), and described polycondensation be the monomer that do not have a shown structure of formula (vi) same or the multiple dehydrating condensation with hydroxyl on the shown structures alone of formula (viii), formula (ix) and formula (x) and carboxyl.
In the present invention, the 4th cross-linking type polyesteramide is obtained when L-glutamic acid and multiple polyhydric alcohol, the cross-linking monomer of described 4th cross-linking type polyesteramide comprises various of monomer, and these monomers can represent by formula (xi), formula (xii) and formula (xiii):
E in formula (xi), formula (xii) and formula (xiii) 2, E 3and E nrepresent that multiple polyvalent alcohol loses remaining group after a hydroxyl respectively.In the present invention, described 4th cross-linking type polyesteramide is the multiple cross-linked polymer with the monomer polycondensation of structure shown in formula (xi), formula (xii) and formula (xiii), and described polycondensation be not at the same multiple dehydrating condensation with hydroxyl on the shown structures alone of formula (xi), formula (xii) or formula (xiii) and carboxyl.
In the present invention, the 5th cross-linking type polyesteramide is obtained when L-glutamic acid and multiple polyvalent alcohol and a kind of dibasic alcohol polycondensation, the cross-linking monomer of described 5th cross-linking type polyesteramide comprises and multiplely has formula (xi), structures alone shown in formula (xii) and formula (xiii) and there is the monomer of structure shown in formula (vii), described 5th cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and the cross-linked polymer of monomer polycondensation with structure shown in formula (vii), described polycondensation is not in the same multiple formula (xi) that has, the dehydrating condensation of structures alone or the hydroxyl had on structures alone shown in formula (vii) and carboxyl shown in formula (xii) and formula (xiii).
In the present invention, the 6th cross-linking type polyesteramide is obtained when L-glutamic acid and multiple polyvalent alcohol and multiple dibasic alcohol polycondensation, the cross-linking monomer of described 6th cross-linking type polyesteramide comprises and multiplely has formula (xi), structures alone shown in formula (xii) and formula (xiii) and multiple there is formula (viii), the monomer of structure shown in formula (ix) and formula (x), described 6th cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and multiple there is formula (viii), the cross-linked polymer of the monomer polycondensation of structure shown in formula (ix) and formula (x), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii) or there is formula (viii), hydroxyl on structures alone shown in formula (ix) and formula (x) and the dehydrating condensation of carboxyl.
In the present invention, described polyvalent alcohol is preferably trivalent alcohol, tetravalent alcohol or pentavalent alcohol, is more preferably glycerol, BT, 1,2,6-hexanetriol, tetramethylolmethane or Xylitol.
Polyesteramide provided by the invention preferably also comprises the repeating unit with structure shown in formula (II):
In formula (II), D is alkylene, and T is alkylene, ether or polyether-based;
Above-mentioned formula (I) and formula (II) are according to the anatomical connectivity shown in formula (III):
In formula (III), R and T is independently selected from alkylene, ether or polyether-based, and D is alkylene.
In the present invention, the D in described formula (II) is preferably the alkylene that carbonatoms is 2 ~ 24; Be more preferably the alkylene that carbonatoms is 2 ~ 18; Most preferably be the alkylene that carbonatoms is 2 ~ 12.In the present invention, the T in described formula (II) is preferably alkylene, ether or the polyether-based that carbonatoms is 2 ~ 24; Be more preferably alkylene, ether or polyether-based that carbonatoms is 2 ~ 18; Most preferably be alkylene, ether or polyether-based that carbonatoms is 2 ~ 12.In the present invention, described alkylene is that hydrocarbon compound loses remaining group after two hydrogen atoms, and described hydrocarbon compound comprises aliphatic hydrocarbon and aromatic hydrocarbon.
Polyesteramide provided by the invention preferably includes the repeating unit with structure shown in formula (I) and formula (II), and this polyesteramide is obtained by the alcohol compound of L-glutamic acid, hydroxyl value >=2 and the carboxylic acid polycondensation of carboxyl number >=2.In the present invention, time in the alcohol compound of described hydroxyl value >=2 containing ehter bond, the T in above-mentioned formula (II) is ether, and time in the alcohol compound of described hydroxyl value >=2 containing polyethers key, the T in above-mentioned formula (II) is polyether-based.In the present invention, obtain having the linear polyesters acid amides of the 3rd structural formula when L-glutamic acid and a kind of dibasic alcohol and a kind of di-carboxylic acid carry out polycondensation.In the present invention, there is described in the linear polyesters acid amides of the 3rd structural formula the repeating unit only including and have structure shown in formula (i) and formula (xiv):
In formula (xiv), R 1for a kind of alkylene, ether or polyether-based, D 1for a kind of alkylene.In the present invention, described 3rd structural formula is formed by connecting without sequence rules, shown in (C) by the repeating unit with structure shown in formula (i) and formula (xiv):
In formula (C), R 1for a kind of alkylene, ether or polyether-based; D 1for a kind of alkylene; n 1and m 1for the polymerization degree, 1≤n 1≤ 1000,1≤m 1≤ 1000; Preferably, 100≤n 1≤ 800,100≤m 1≤ 800; Preferred, 200≤n 1≤ 600,200≤m 1≤ 600.
In the present invention, obtain having the linear polyesters acid amides of the 4th structural formula when L-glutamic acid and a kind of dibasic alcohol and multiple di-carboxylic acid carry out polycondensation.In the present invention, the linear polyesters acid amides described in the 4th structural formula comprises the repeating unit and the multiple repeating unit represented by formula (xv), formula (xvi) and formula (xvii) with structure shown in formula (i):
D in formula (xv), formula (xvi) and formula (xvii) 2, D 3and D nrepresent multiple alkylene, R 1for a kind of alkylene, ether or polyether-based.In the present invention, described 4th structural formula is formed by connecting without sequence rules by the repeating unit and the multiple repeating unit with structure shown in formula (xv), formula (xvi) and formula (xvii) with structure shown in formula (i).
In the present invention, obtain having the linear polyesters acid amides of the 5th structural formula when L-glutamic acid and multiple dibasic alcohol and a kind of di-carboxylic acid carry out polycondensation.In the present invention, the linear polyesters acid amides described in the 5th structural formula comprises and multiplely has the repeating unit of structure shown in formula (ii), formula (iii) and formula (iv) and the multiple repeating unit with the shown structure of formula (xviii), formula (xix) and formula (xx):
D in formula (xviii), formula (xix) and formula (xx) 1for a kind of alkylene, R 2, R 3and R nmultiple alkylene, multiple ether or multiple polyether-based can be represented; Also multiple alkylene and ether, multiple alkylene and polyether-based or multiple ether and polyether-based can be represented; Multiple alkylene, ether and polyether-based can also be represented.In the present invention, the described 5th structural formula repeating unit that has a structure shown in formula (ii), formula (iii) and formula (iv) by multiple and the multiple repeating unit with the shown structure of formula (xviii), formula (xix) and formula (xx) are formed by connecting without sequence rules.
In the present invention, obtain having the linear polyesters acid amides of the 6th structural formula when L-glutamic acid and multiple dibasic alcohol and multiple di-carboxylic acid carry out polycondensation.In the present invention, the linear polyesters acid amides described in the 6th structural formula comprises and multiplely has the repeating unit of structure shown in formula (ii), formula (iii) and formula (iv) and be the repeating unit that monomer polycondensation obtains by any one dibasic alcohol in above-mentioned multiple dibasic alcohol and multiple di-carboxylic acid and di-carboxylic acid.In the present invention, the described 6th structural formula repeating unit that there is structure shown in formula (ii), formula (iii) and formula (iv) by multiple and multiple be that the repeating unit that monomer polycondensation obtains is formed by connecting without sequence rules by any one dibasic alcohol and di-carboxylic acid.
In the present invention, when L-glutamic acid, a kind of polyvalent alcohol and a kind of di-carboxylic acid polycondensation time obtain the 7th cross-linking type polyesteramide, the cross-linking monomer of described 7th cross-linking type polyesteramide only includes has structures alone and a kind of dibasic carboxylic acid monomers shown in formula (vi), described 7th cross-linking type polyesteramide is for having the cross-linked polymer of structures alone shown in formula (vi) and a kind of dibasic carboxylic acid monomers's polycondensation, and described polycondensation be not at the same dehydrating condensation with hydroxyl on the shown structures alone of formula (vi) or a kind of dibasic carboxylic acid monomers and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 8th cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 8th cross-linking type polyesteramide only includes has structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii) and a kind of dibasic carboxylic acid monomers, described 8th cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the monomer of structure and a kind of cross-linked polymer of dibasic carboxylic acid monomers's polycondensation shown in formula (vii), described polycondensation is not for having structures alone shown in formula (vi) same, there is the dehydrating condensation of hydroxyl on structures alone shown in formula (vii) or a kind of dibasic carboxylic acid monomers and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 9th cross-linking type polyesteramide is obtained when multiple dibasic alcohol and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 9th cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and a kind of dibasic carboxylic acid monomers, described 9th cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure and a kind of cross-linked polymer of dibasic carboxylic acid monomers's polycondensation shown in formula (ix) and formula (x), described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), hydroxyl on structures alone shown in formula (ix) and formula (x) or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, when L-glutamic acid, a kind of polyvalent alcohol and multiple di-carboxylic acid polycondensation time obtain the tenth cross-linking type polyesteramide, the cross-linking monomer of described tenth cross-linking type polyesteramide comprises and has structures alone shown in formula (vi) and multiple dibasic carboxylic acid monomers, described tenth cross-linking type polyesteramide is for having the cross-linked polymer of structures alone shown in formula (vi) and multiple dibasic carboxylic acid monomers's polycondensation, and described polycondensation be not at the same dehydrating condensation with hydroxyl on the shown structures alone of formula (vi) or multiple dibasic carboxylic acid monomers and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 11 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 11 cross-linking type polyesteramide comprises the monomer with structure shown in formula (vi), there is the structures alone shown in formula (vii) and multiple dibasic carboxylic acid monomers, described 11 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the cross-linked polymer of structures alone and multiple dibasic carboxylic acid monomers's polycondensation shown in formula (vii), described polycondensation is not at the same monomer with structure shown in formula (vi), there is the dehydrating condensation of hydroxyl on the structures alone shown in formula (vii) or multiple dibasic carboxylic acid monomers and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 12 cross-linking type polyesteramide is obtained when multiple dibasic alcohol and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 12 cross-linking type polyesteramide comprises the monomer with structure shown in formula (vi), multiple have formula (viii), formula (ix) and the structures alone shown in formula (x) and multiple dibasic carboxylic acid monomers, described 12 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the cross-linked polymer of formula (ix) and the structures alone shown in formula (x) and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not at the same monomer with structure shown in formula (vi), multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, the 13 cross-linking type polyesteramide is obtained when multiple polyvalent alcohol and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 13 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and a kind of dibasic carboxylic acid monomers, described 13 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure and a kind of cross-linked polymer of dibasic carboxylic acid monomers's polycondensation shown in formula (xii) and formula (xiii), described polycondensation is not in the same multiple formula (xi) that has, hydroxyl on the monomer of structure shown in formula (xii) and formula (xiii) or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, multiple polyvalent alcohol, the 14 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 14 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii) and a kind of dibasic carboxylic acid monomers, described 14 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure and a kind of cross-linked polymer of dibasic carboxylic acid monomers's polycondensation shown in formula (vii), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the dehydrating condensation of hydroxyl on the monomer of structure shown in formula (vii) or a kind of dibasic carboxylic acid monomers and carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, obtain the 15 cross-linking type polyesteramide when multiple dibasic alcohol and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 15 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and a kind of dibasic carboxylic acid monomers, described 15 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure and a kind of cross-linked polymer of dibasic carboxylic acid monomers's polycondensation shown in formula (ix) and formula (x), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, the 16 cross-linking type polyesteramide is obtained when multiple polyvalent alcohol and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 16 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and multiple dibasic carboxylic acid monomers, described 16 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure and the cross-linked polymer of multiple dibasic carboxylic acid monomers's polycondensation shown in formula (xii) and formula (xiii), described polycondensation is not in the same multiple formula (xi) that has, hydroxyl on the monomer of structure shown in formula (xii) and formula (xiii) or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, multiple polyvalent alcohol, the 17 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 17 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii) and multiple dibasic carboxylic acid monomers, described 17 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure and the cross-linked polymer of multiple dibasic carboxylic acid monomers's polycondensation shown in formula (vii), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the dehydrating condensation of hydroxyl on the monomer of structure shown in formula (vii) or multiple dibasic carboxylic acid monomers and carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, obtain the 18 cross-linking type polyesteramide when multiple dibasic alcohol and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 18 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and multiple dibasic carboxylic acid monomers, described 18 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure and the cross-linked polymer of multiple dibasic carboxylic acid monomers's polycondensation shown in formula (ix) and formula (x), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, described di-carboxylic acid is preferably terephthalic acid, phthalic acid, m-phthalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or sebacic acid, is more preferably terephthalic acid, phthalic acid or m-phthalic acid.
In the present invention, when L-glutamic acid, a kind of polyvalent alcohol and a kind of polycarboxylic acid polycondensation time obtain the 19 cross-linking type polyesteramide, the cross-linking monomer of described 19 cross-linking type polyesteramide only includes has structures alone and a kind of polycarboxylic acid monomer shown in formula (vi), described 19 cross-linking type polyesteramide is for having the cross-linked polymer of structures alone shown in formula (vi) and a kind of polycarboxylic acid monomer's polycondensation, and described polycondensation be not at the same dehydrating condensation with hydroxyl on the shown structures alone of formula (vi) or a kind of polycarboxylic acid monomer and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 20 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and a kind of polycarboxylic acid polycondensation, the cross-linking monomer of described 20 cross-linking type polyesteramide only includes has structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii) and a kind of polycarboxylic acid monomer, described 20 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the monomer of structure and a kind of cross-linked polymer of polycarboxylic acid monomer's polycondensation shown in formula (vii), described polycondensation is not for having structures alone shown in formula (vi) same, there is the dehydrating condensation of hydroxyl on the monomer of structure shown in formula (vii) or a kind of polycarboxylic acid monomer and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 21 cross-linking type polyesteramide is obtained when multiple dibasic alcohol and a kind of polycarboxylic acid polycondensation, the cross-linking monomer of described 21 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and a kind of polycarboxylic acid monomer, described 21 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure and a kind of cross-linked polymer of polycarboxylic acid monomer's polycondensation shown in formula (ix) and formula (x), described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or a kind of polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, a kind of dibasic alcohol, the 22 cross-linking type polyesteramide is obtained when a kind of polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 22 cross-linking type polyesteramide only includes has structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), a kind of polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 22 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), the cross-linked polymer of a kind of polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, there is the monomer of structure shown in formula (vii), hydroxyl on a kind of polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, a kind of polyvalent alcohol, multiple dibasic alcohol, obtain the 23 cross-linking type polyesteramide when a kind of polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 23 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a kind of polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 23 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a cross-linked polymer for polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on a kind of polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, a kind of dibasic alcohol, the 24 cross-linking type polyesteramide is obtained when a kind of polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 24 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), there is structures alone shown in formula (vii), a kind of polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 24 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is structures alone shown in formula (vii), the cross-linked polymer of a kind of polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, there is structures alone shown in formula (vii), hydroxyl on a kind of polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, a kind of polyvalent alcohol, multiple dibasic alcohol, obtain the 25 cross-linking type polyesteramide when a kind of polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 25 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a kind of polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 25 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a cross-linked polymer for polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on a kind of polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, when L-glutamic acid, a kind of polyvalent alcohol and multiple polycarboxylic acid polycondensation time obtain the 26 cross-linking type polyesteramide, the cross-linking monomer of described 26 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi) and multiple polycarboxylic acid monomer, described 26 cross-linking type polyesteramide is for having the cross-linked polymer of structures alone shown in formula (vi) and multiple polycarboxylic acid monomer's polycondensation, and described polycondensation be not at the same dehydrating condensation with hydroxyl on the shown structures alone of formula (vi) or multiple polycarboxylic acid monomer and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 27 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and multiple polycarboxylic acid polycondensation, the cross-linking monomer of described 27 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), there is structures alone and multiple polycarboxylic acid monomer shown in formula (vii), described 27 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the cross-linked polymer of structures alone and multiple polycarboxylic acid monomer's polycondensation shown in formula (vii), described polycondensation is not for having structures alone shown in formula (vi) same, there is the dehydrating condensation of hydroxyl on structures alone shown in formula (vii) or multiple polycarboxylic acid monomer and carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, the 28 cross-linking type polyesteramide is obtained when multiple dibasic alcohol and multiple polycarboxylic acid polycondensation, the cross-linking monomer of described 28 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and multiple polycarboxylic acid monomer, described 28 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure and the cross-linked polymer of multiple polycarboxylic acid monomer's polycondensation shown in formula (ix) and formula (x), described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or multiple polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, a kind of dibasic alcohol, the 29 cross-linking type polyesteramide is obtained when multiple polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 29 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 29 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), the cross-linked polymer of multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, there is the monomer of structure shown in formula (vii), hydroxyl on multiple polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, a kind of polyvalent alcohol, a kind of dibasic alcohol, the 30 cross-linking type polyesteramide is obtained when multiple polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 30 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 30 cross-linking type polyesteramide is for having structures alone shown in formula (vi), there is the monomer of structure shown in formula (vii), the cross-linked polymer of multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, there is the monomer of structure shown in formula (vii), hydroxyl on multiple polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, a kind of polyvalent alcohol, multiple dibasic alcohol, obtain the 31 cross-linking type polyesteramide when multiple polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 31 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 31 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), the cross-linked polymer of multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on multiple polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, a kind of polyvalent alcohol, multiple dibasic alcohol, obtain the 32 cross-linking type polyesteramide when multiple polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 32 cross-linking type polyesteramide comprises and has structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 32 cross-linking type polyesteramide is for having structures alone shown in formula (vi), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), the cross-linked polymer of multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not for having structures alone shown in formula (vi) same, multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on multiple polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, the 33 cross-linking type polyesteramide is obtained when multiple polyvalent alcohol and a kind of polycarboxylic acid polycondensation, the cross-linking monomer of described 33 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and a kind of polycarboxylic acid monomer, described 33 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure and a kind of cross-linked polymer of polycarboxylic acid monomer's polycondensation shown in formula (xii) and formula (xiii), described polycondensation is not in the same multiple formula (xi) that has, hydroxyl on the monomer of structure shown in formula (xii) and formula (xiii) or a kind of polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, multiple polyvalent alcohol, the 34 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and a kind of polycarboxylic acid polycondensation, the cross-linking monomer of described 34 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii) and a kind of polycarboxylic acid monomer, described 34 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure and a kind of cross-linked polymer of polycarboxylic acid monomer's polycondensation shown in formula (vii), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the dehydrating condensation of hydroxyl on the monomer of structure shown in formula (vii) or a kind of polycarboxylic acid monomer and carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, obtain the 35 cross-linking type polyesteramide when multiple dibasic alcohol and a kind of polycarboxylic acid polycondensation, the cross-linking monomer of described 35 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and a kind of polycarboxylic acid monomer, described 35 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure and a kind of cross-linked polymer of polycarboxylic acid monomer's polycondensation shown in formula (ix) and formula (x), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or a kind of polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, a kind of dibasic alcohol, obtain the 36 cross-linking type polyesteramide when a kind of polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 36 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), a kind of polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 36 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), a cross-linked polymer for polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), hydroxyl on a kind of polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, a kind of dibasic alcohol, obtain the 37 cross-linking type polyesteramide when a kind of polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 37 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), a kind of polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 37 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), a cross-linked polymer for polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), hydroxyl on a kind of polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, multiple dibasic alcohol, obtain the 38 cross-linking type polyesteramide when a kind of polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 38 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a kind of polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 38 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a cross-linked polymer for polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on a kind of polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, multiple dibasic alcohol, obtain the 39 cross-linking type polyesteramide when a kind of polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 39 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a kind of polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 39 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), a cross-linked polymer for polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on a kind of polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, the 40 cross-linking type polyesteramide is obtained when multiple polyvalent alcohol and multiple polycarboxylic acid polycondensation, the cross-linking monomer of described 40 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii) and multiple polycarboxylic acid monomer, described 40 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure and the cross-linked polymer of multiple polycarboxylic acid monomer's polycondensation shown in formula (xii) and formula (xiii), described polycondensation is not in the same multiple formula (xi) that has, hydroxyl on the monomer of structure shown in formula (xii) and formula (xiii) or multiple polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, work as L-glutamic acid, multiple polyvalent alcohol, the 41 cross-linking type polyesteramide is obtained when a kind of dibasic alcohol and multiple polycarboxylic acid polycondensation, the cross-linking monomer of described 41 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii) and multiple polycarboxylic acid monomer, described 41 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure and the cross-linked polymer of multiple polycarboxylic acid monomer's polycondensation shown in formula (vii), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the dehydrating condensation of hydroxyl on the monomer of structure shown in formula (vii) or multiple polycarboxylic acid monomer and carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, obtain the 42 cross-linking type polyesteramide when multiple dibasic alcohol and multiple polycarboxylic acid polycondensation, the cross-linking monomer of described 42 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x) and multiple polycarboxylic acid monomer, described 42 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure and the cross-linked polymer of multiple polycarboxylic acid monomer's polycondensation shown in formula (ix) and formula (x), described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), hydroxyl on the monomer of structure shown in formula (ix) and formula (x) or multiple polycarboxylic acid monomer and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, a kind of dibasic alcohol, obtain the 43 cross-linking type polyesteramide when multiple polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 43 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 43 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), the cross-linked polymer of multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), hydroxyl on multiple polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, a kind of dibasic alcohol, obtain the 44 cross-linking type polyesteramide when multiple polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 44 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 44 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), the cross-linked polymer of multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), there is the monomer of structure shown in formula (vii), hydroxyl on multiple polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, multiple dibasic alcohol, obtain the 45 cross-linking type polyesteramide when multiple polycarboxylic acid and a kind of di-carboxylic acid polycondensation, the cross-linking monomer of described 45 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers, described 45 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), the cross-linked polymer of multiple polycarboxylic acid monomer and a kind of dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on multiple polycarboxylic acid monomer or a kind of dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
In the present invention, L-glutamic acid is worked as, multiple polyvalent alcohol, multiple dibasic alcohol, obtain the 46 cross-linking type polyesteramide when multiple polycarboxylic acid and multiple di-carboxylic acid polycondensation, the cross-linking monomer of described 46 cross-linking type polyesteramide comprises and multiplely has formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers, described 46 cross-linking type polyesteramide is multiplely have formula (xi), the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), the cross-linked polymer of multiple polycarboxylic acid monomer and multiple dibasic carboxylic acid monomers's polycondensation, described polycondensation is not in the same multiple formula (xi) that has, the monomer of structure shown in formula (xii) and formula (xiii), multiple have formula (viii), the monomer of structure shown in formula (ix) and formula (x), hydroxyl on multiple polycarboxylic acid monomer or multiple dibasic carboxylic acid monomers and the dehydrating condensation of carboxyl.
The kind of the present invention to described polycarboxylic acid does not have special restriction, adopts polycarboxylic acid well known to those skilled in the art; In the present invention, described polycarboxylic acid is preferably citric acid.
Repeating unit containing structure shown in formula (I) in polyesteramide provided by the invention, this polyesteramide has good biodegradable, avoids the problem of environmental pollution.
The invention provides a kind of preparation method of polyesteramide, comprising:
Under the effect of catalyzer, the alcohol compound of L-glutamic acid and hydroxyl value >=2 is carried out polycondensation, obtains polyesteramide.
The present invention adopts the alcohol compound of L-glutamic acid and hydroxyl value >=2 to be that polyesteramide prepared by raw material, because L-glutamic acid is biomass derived material, biodegradable, the polyesteramide that the present invention is prepared also has good biodegradable, avoids the problem of environmental pollution.In addition, L-glutamic acid is recyclable materials, the present invention adopt L-glutamic acid be raw material prepare polyesteramide can save energy, therefore preparation method's cost of polyesteramide provided by the invention is lower.
The alcohol compound of L-glutamic acid and hydroxyl value >=2, under the effect of catalyzer, is carried out polycondensation, obtains polyesteramide by the present invention.In the present invention, described catalyzer preferably includes one or more in tetrabutyl titanate, stannous octoate, antimonous oxide, metatitanic acid four isopropyl ester, zinc acetate and trifluoromethane sulfonic acid scandium, more preferably comprises the one in tetrabutyl titanate, stannous octoate, antimonous oxide, metatitanic acid four isopropyl ester, zinc acetate and trifluoromethane sulfonic acid scandium.The source of the present invention to described catalyzer does not have special restriction, adopts the catalyzer of mentioned kind well known to those skilled in the art, obtains as bought by market.The source of the present invention to described L-glutamic acid does not have special restriction, can be bought obtain by market, concrete, the L-glutamic acid that the present invention can adopt Aladdin Reagent Company to provide.In the present invention, the mass ratio of described catalyzer and L-glutamic acid is preferably 1:(40 ~ 10000), be more preferably 1:(100 ~ 5000), most preferably be 1:(300 ~ 1000).
In the present invention, the alcohol compound of described hydroxyl value >=2 comprises one or more in dibasic alcohol and polyvalent alcohol; The kind of the present invention to described dibasic alcohol and polyvalent alcohol does not have special restriction, adopts dibasic alcohol well known to those skilled in the art and polyvalent alcohol.In the present invention, as several during the alcohol compound of described hydroxyl value >=2 is dibasic alcohol and polyvalent alcohol, the usage ratio between several dibasic alcohol or polyvalent alcohol can be arbitrary proportion.
In the present invention, described dibasic alcohol preferably includes ethylene glycol, 1, ammediol, 1, 4-butyleneglycol, 1, 5-pentanediol, 1, 6-hexylene glycol, 1, 8-ethohexadiol, Isosorbide, terephthalyl alcohol, isophthalic alcohol, phthalyl alcohol, 1, 2-propylene glycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, neopentyl glycol, 1, 2-pentanediol, 1, 3-ring pentanediol, 1, 2-hexylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, glycol ether, dipropylene glycol, tripropylene glycol, tetraethylene-glycol, 1, 7-heptanediol, 1, 2-ethohexadiol, 1, 2-ring ethohexadiol, 1, 9-nonanediol, 1, 2-decanediol, 1, 10-decanediol, five glycol, hexaethylene glycol, seven glycol, eight glycol, nine glycol, ten glycol, ten glycol ethers, rostenediol, estradiol, one or more in polyoxyethylene glycol and polytetramethylene glycol, more preferably ethylene glycol, 1 is comprised, ammediol, 1,4-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, Isosorbide, terephthalyl alcohol, isophthalic alcohol, phthalyl alcohol, 1,2-propylene glycol, 1,3 butylene glycol, 2,3-butanediol, neopentyl glycol, 1, one or more in 2-pentanediol, 1,3-ring pentanediol, glycol ether and polyoxyethylene glycol, most preferably comprise one or more in ethylene glycol, 1,3-PD, 1,3-ring pentanediol, isophthalic alcohol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,5-PD, glycol ether, polyoxyethylene glycol and BDO.
In the present invention, described polyvalent alcohol preferably includes one or more in trivalent alcohol, tetravalent alcohol and pentavalent alcohol, more preferably comprises one or more in trivalent alcohol and tetravalent alcohol.In the present invention, described trivalent alcohol preferably includes one or more in glycerol, BT and 1,2,6-hexanetriol, is more preferably glycerol; Described tetravalent alcohol is preferably tetramethylolmethane; Described pentavalent alcohol is preferably Xylitol.In the present invention, the mol ratio of the alcohol compound of described L-glutamic acid and hydroxyl value >=2 is preferably (0.5 ~ 5): 1, is more preferably (1 ~ 3): 1, most preferably is (1.5 ~ 2.5): 1.
In the present invention, the temperature of reaction of described polycondensation is preferably 120 DEG C ~ 260 DEG C, is more preferably 150 DEG C ~ 240 DEG C, most preferably is 170 DEG C ~ 220 DEG C.The present invention does not have special restriction in the reaction times to described polycondensation, and the reaction times of described polycondensation makes the reaction raw materials complete reaction of described polycondensation.In the present invention, the reaction times of described polycondensation is preferably 3.5 hours ~ 15 hours, is more preferably 4.5 hours ~ 12.5 hours, most preferably is 5.5 hours ~ 12 hours.
In the present invention, when the alcohol compound of L-glutamic acid and hydroxyl value >=2 carries out polycondensation, the speed that the speed ratio L-glutamic acid of L-glutamic acid polymerization generation L-glutamic acid diketopiperazine and the alcohol compound of hydroxyl value >=2 carry out polycondensation is faster, the alcohol compound of L-glutamic acid and hydroxyl value >=2 carries out in the process of polycondensation, L-glutamic acid preferentially carries out polyreaction, obtain L-glutamic acid diketopiperazine, the L-glutamic acid diketopiperazine obtained carries out polyreaction with the alcohol compound of hydroxyl value >=2 again, obtains polyesteramide.Therefore, the present invention preferably prepares polyesteramide by the following method:
L-glutamic acid is carried out dimerization reaction, obtains L-glutamic acid diketopiperazine;
Under the effect of catalyzer, the alcohol compound of described L-glutamic acid diketopiperazine and hydroxyl value >=2 is carried out polyreaction, obtains polyesteramide.
In the present invention, the preparation method of described L-glutamic acid diketopiperazine is: L-glutamic acid direct heating is carried out dimerization reaction, obtains L-glutamic acid diketopiperazine.In the present invention, described L-glutamic acid diketopiperazine has the structure shown in formula a:
In the present invention, the temperature of reaction of described dimerization reaction is preferably 100 DEG C ~ 240 DEG C, is more preferably 120 DEG C ~ 210 DEG C, is more preferably 150 DEG C ~ 200 DEG C, most preferably is 170 DEG C ~ 190 DEG C.In an embodiment of the present invention, described dimerization reaction can carry out in the absence of a solvent.L-glutamic acid preferably heats and carries out dimerization reaction by the present invention in a solvent, obtains L-glutamic acid diketopiperazine.In the present invention, the temperature of described heating is consistent with the temperature of reaction of above-mentioned dimerization reaction, does not repeat them here.In the present invention, described solvent does not react with the reaction raw materials of above-mentioned dimerization reaction, and described solvent is preferably one or more in phenylate, benzyl oxide and phenyl ethyl ether.
In an embodiment of the present invention, described dimerization reaction can carry out under the condition of catalyst-free.In order to improve the efficiency of above-mentioned dimerization reaction, L-glutamic acid, preferably under the effect of catalyzer, is carried out dimerization reaction by the present invention, obtains L-glutamic acid diketopiperazine.In the present invention, the catalyzer of described dimerization reaction preferably includes one or more in tetrabutyl titanate, stannous octoate, antimonous oxide, metatitanic acid four isopropyl ester, zinc acetate and trifluoromethane sulfonic acid scandium, more preferably comprises the one in tetrabutyl titanate, stannous octoate, antimonous oxide, metatitanic acid four isopropyl ester, zinc acetate and trifluoromethane sulfonic acid scandium.The consumption of the present invention to described dimerization reaction catalyzer does not have special restriction, adopts the catalyst levels that L-glutamic acid well known to those skilled in the art is polymerized.In the present invention, the mass ratio of described dimerization reaction catalyzer and L-glutamic acid is preferably 1:(40 ~ 10000), be more preferably 1:(100 ~ 5000), most preferably be 1:(300 ~ 1000).
The present invention does not have special restriction in the reaction times to described dimerization reaction, and the reaction times of described dimerization reaction makes above-mentioned L-glutamic acid be polymerized completely.In the present invention, the reaction times of described dimerization reaction is preferably 0.1 hour ~ 24 hours, is more preferably 1 hour ~ 10 hours, is more preferably 2 hours ~ 8 hours, most preferably is 3 hours ~ 6 hours.
After obtaining L-glutamic acid diketopiperazine, the alcohol compound of described L-glutamic acid diketopiperazine and hydroxyl value >=2, preferably under the effect of catalyzer, is carried out polyreaction, obtains polyesteramide by the present invention.In the present invention, kind, the consumption of the kind of the catalyzer of described polyreaction and the alcohol compound of hydroxyl value >=2, consumption and source and the catalyzer of polycondensation described in technique scheme and the alcohol compound of hydroxyl value >=2 and originate consistent, do not repeat them here.In the present invention, the mol ratio of the alcohol compound of the L-glutamic acid of above-mentioned first polyreaction and hydroxyl value >=2 of the second polyreaction is preferably (0.5 ~ 5): 1, be more preferably (1 ~ 3): 1, most preferably be (1.5 ~ 2.5): 1.In the present invention, temperature of reaction and the reaction times of the temperature of reaction of described polyreaction and reaction times and the polycondensation described in technique scheme are consistent, do not repeat them here.
The present invention prepares in the process of polyesteramide carrying out above-mentioned polycondensation, unnecessary micromolecular compound is there is in reaction system, as the alcohol compound of water or hydroxyl value >=2, in order to improve the polymerization degree of the polyesteramide obtained, the present invention preferably removes described micromolecular compound by the following method, prepares polyesteramide:
Under the effect of catalyzer, the alcohol compound of L-glutamic acid and hydroxyl value >=2 is warming up to the first temperature, carries out the polycondensation of first stage, obtain reaction product; The reaction product obtained carried out obtaining polyesteramide prepolymer after water treatment, described first temperature is 160 DEG C ~ 210 DEG C;
Described polyesteramide prepolymer is warming up to the second temperature, carries out the polycondensation of subordinate phase, described second temperature is 200 DEG C ~ 260 DEG C;
Under the condition of described second temperature, reduce system pressure to 1 × 10 of described subordinate phase polycondensation -4mPa ~ 5 × 10 -4mPa, carries out the polycondensation of phase III, obtains polyesteramide.
The alcohol compound of L-glutamic acid and hydroxyl value >=2, preferably under the effect of catalyzer, is warming up to the first temperature, carries out the polycondensation of first stage, obtain reaction product by the present invention, and described first temperature is 160 DEG C ~ 210 DEG C; More preferably under the effect of catalyzer, stir condition under, the alcohol compound of L-glutamic acid and hydroxyl value >=2 is warming up to the first temperature, carries out the polycondensation of first stage, obtain reaction product.The method of the present invention to described stirring does not have special restriction, adopts stirring technique scheme well known to those skilled in the art.In the present invention, described first temperature is more preferably 170 DEG C ~ 200 DEG C, most preferably is 180 DEG C ~ 190 DEG C.In the present invention, the time of the polycondensation of described first stage is preferably 1 hour ~ 6 hours, is more preferably 1.5 hours ~ 5 hours, most preferably is 2 hours ~ 4 hours.
In the present invention, the kind of the alcohol compound of the catalyzer of the kind of described catalyzer, L-glutamic acid and the alcohol compound of hydroxyl value >=2, source and consumption and the polycondensation described in technique scheme, L-glutamic acid and hydroxyl value >=2, source and consumption are consistent, do not repeat them here.
After the polycondensation of described first stage completes, the reaction product obtained preferably carries out, except water treatment, obtaining polyesteramide prepolymer by the present invention.The present invention does not have special restriction to the described method except water treatment, adopt the technical scheme except water treatment well known to those skilled in the art, concrete, in an embodiment of the present invention, Dean-Stark trap (Dean-Starkapparatus) can be adopted to carry out except water treatment.
After obtaining polyesteramide prepolymer, described polyesteramide prepolymer is preferably warming up to the second temperature by the present invention, carries out the polycondensation of subordinate phase, and described second temperature is 200 DEG C ~ 260 DEG C; More preferably described polyesteramide prepolymer is warming up to the second temperature, under the condition stirred, carries out the polycondensation of subordinate phase.The present invention does not have special restriction to described stirring means, adopts stirring technique scheme well known to those skilled in the art.In the present invention, described second temperature is more preferably 205 DEG C ~ 240 DEG C, most preferably is 210 DEG C ~ 220 DEG C.Described polyesteramide prepolymer is warming up to the second temperature and can accelerates the speed of the polycondensation of described subordinate phase and the alcohol compound distillation of the moisture in described polyesteramide prepolymer or residual hydroxyl value >=2 be removed by the present invention.In the present invention, the time of the polycondensation of described subordinate phase is preferably 1.5 hours ~ 5 hours, is more preferably 2 hours ~ 4 hours.
After the polycondensation of described subordinate phase completes, the present invention, preferably under the condition of described second temperature, reduces system pressure to 1 × 10 of described subordinate phase polycondensation -4mPa ~ 5 × 10 -4mPa, carries out the polycondensation of phase III, obtains polyesteramide.The system pressure that the present invention reduces described subordinate phase polycondensation can remove the alcohol compound of moisture in above-mentioned polyesteramide prepolymer or residual hydroxyl value >=2 further, improves the polymerization degree of the polyesteramide that the present invention obtains.In the present invention, the system pressure of described subordinate phase polycondensation is preferably down to 1 × 10 -4mPa ~ 5 × 10 -4mPa, is more preferably down to 1 × 10 -4mPa ~ 3 × 10 -4mPa, is most preferably down to 1 × 10 -4mPa.In the present invention, the time of the polycondensation of described phase III is preferably 0.5 hour ~ 2 hours, is more preferably 1 hour ~ 1.5 hours.
In the present invention, the reaction raw materials of above-mentioned polycondensation preferably also comprises the carboxylic acid of carboxyl number >=2, the carboxylic acid of the alcohol compound of L-glutamic acid, hydroxyl value >=2 and carboxyl number >=2, preferably under the effect of catalyzer, is carried out polycondensation, obtains polyesteramide by the present invention.In the present invention, kind, the consumption of the alcohol compound of the catalyzer of the kind of described catalyzer, L-glutamic acid and the alcohol compound of hydroxyl value >=2, consumption and source and polycondensation described in technique scheme, L-glutamic acid and hydroxyl value >=2 and originate consistent, do not repeat them here; In the present invention, temperature of reaction and the reaction times of the temperature of reaction of described polycondensation and reaction times and the polycondensation described in technique scheme are consistent, do not repeat them here.The carboxylic acid of described carboxyl number >=2 under the effect of catalyzer, can be carried out above-mentioned polycondensation with L-glutamic acid, obtains polyesteramide by the present invention together with the alcohol compound of hydroxyl value >=2; Also L-glutamic acid can be carried out above-mentioned dimerization reaction, obtain L-glutamic acid diketopiperazine, under the effect of catalyzer, the L-glutamic acid diketopiperazine obtained and the carboxylic acid of carboxyl number >=2 and the alcohol compound of hydroxyl value >=2 are carried out above-mentioned polyreaction, obtains polyesteramide.
In the present invention, the carboxylic acid of described carboxyl number >=2 comprises one or more in di-carboxylic acid and polycarboxylic acid, preferably includes one or more in di-carboxylic acid.In the present invention, described di-carboxylic acid preferably includes one or more in terephthalic acid, phthalic acid, m-phthalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid, more preferably comprises one or more in terephthalic acid, phthalic acid and m-phthalic acid.In the present invention, described polycarboxylic acid is preferably citric acid.The source of the present invention to the carboxylic acid of described carboxyl number >=2 does not have special restriction, adopts the carboxylic acid of mentioned kind well known to those skilled in the art, obtains as bought by market.In the present invention, the mol ratio of the carboxylic acid of described L-glutamic acid and carboxyl number >=2 is preferably a:b, 0 < a < 100,0 < b < 100, a+b=100; Preferred, 40≤a≤80,20≤b≤60; Most preferred, 50≤a≤70,30≤b≤50.In the present invention, when to comprise in di-carboxylic acid and polycarboxylic acid several for the carboxylic acid of described carboxyl number >=2, the usage ratio between several di-carboxylic acid or polycarboxylic acid can be arbitrary proportion.
L-glutamic acid diketopiperazine 5mg the present invention prepared carries out proton nmr spectra detection after adding the deuterated water concussion dissolving completely of 0.5mL; L-glutamic acid diketopiperazine the present invention prepared carries out mass spectrometric detection; Detected result is, according to detecting the nmr spectrum and mass spectrum that obtain, the L-glutamic acid diketopiperazine that the present invention prepares has the structure shown in formula a.
Polyesteramide the present invention prepared carries out magnetic resonance detection in deuterated water, obtain proton nmr spectra, proton nmr spectra according to obtaining is analyzed, containing the repeating unit with structure shown in formula (I) in polyesteramide provided by the invention.Polyesteramide the present invention obtained carries out degraded test, test result is, polyesteramide provided by the invention is degrade in the phosphate buffer solution of 7.4 in pH value, in the time of 10 weeks, the molecular weight and molecular weight of polyesteramide 53% ~ 80%, polyesteramide provided by the invention has good biodegradable.
The invention provides a kind of polyesteramide, comprise the repeating unit with structure shown in formula (I).Repeating unit containing structure shown in formula (I) in polyesteramide provided by the invention, this polyesteramide has good biodegradable, avoids the problem of environmental pollution.In addition, the present invention with the alcohol compound of L-glutamic acid and hydroxyl value >=2 for polyesteramide prepared by raw material, L-glutamic acid is recyclable materials, the present invention adopt L-glutamic acid be raw material prepare polyesteramide can save energy, therefore preparation method's cost of polyesteramide provided by the invention is lower.
In order to make those skilled in the art better understand technical scheme of the present invention, below in conjunction with specific embodiment, the present invention is described in more detail, but it should be appreciated by those skilled in the art that protection scope of the present invention is not limited to these specific embodiments.
Reaction raw materials used in following examples of the present invention is commercial goods.
Embodiment 1
10 grams of L-glutamic acid, 2.1 grams of ethylene glycol and 0.1 gram of tetrabutyl titanate is added in the round-bottomed flask of 50 milliliters, above-mentioned substance is heated to the polycondensation that 160 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 200 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 200 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 1 obtained carries out magnetic resonance detection in deuterated water, detected result as shown in Figure 1, Fig. 1 is the proton nmr spectra of the polyesteramide prepolymer that the embodiment of the present invention 1 obtains, by analyzing Fig. 1, the polyesteramide that the embodiment of the present invention 1 obtains has the structure shown in formula (1):
In formula (1), n is 200.
The polyesteramide embodiment of the present invention 1 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result as shown in Figure 2, Fig. 2 is the degraded test result of the polyesteramide that the embodiment of the present invention 1 obtains, as shown in Figure 2, molecular weight and molecular weight 76% in the polyesteramide time of 10 weeks that embodiment 1 obtains, first 3 weeks molecular weight and molecular weight speed, decline weekly about 20%, within latter 7 weeks, molecular weight and molecular weight speed is comparatively slow, about declines 10% weekly, now the molecular weight of polyesteramide.The polyesteramide that the embodiment of the present invention 1 obtains has good biodegradable.
Embodiment 2
Add in the round-bottomed flask of 100 milliliters 20 grams of L-glutamic acid, 5.2 gram 1,3-ring pentanediol and 20 milligrams of metatitanic acid four isopropyl esters, above-mentioned substance is heated to the polycondensation that 170 DEG C are carried out the first stage of 5 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 210 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 210 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 2 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 2 obtains has the structure shown in formula (2):
In formula (2), n is 400.
The polyesteramide embodiment of the present invention 2 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 70% in the polyesteramide time of 10 weeks that embodiment 2 obtains, the polyesteramide that the embodiment of the present invention 2 obtains has good biodegradable.
Embodiment 3
5 grams of L-glutamic acid, 2 grams of isophthalic alcohols and 125 milligrams of zinc acetates are added in the round-bottomed flask of 50 milliliters, above-mentioned substance is heated to the polycondensation that 180 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 220 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 5 hours;
At 220 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 3 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 3 obtains has the structure shown in formula (3):
In formula (3), n is 100.
The polyesteramide embodiment of the present invention 3 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 67% in the polyesteramide time of 10 weeks that embodiment 3 obtains, the polyesteramide that the embodiment of the present invention 3 obtains has good biodegradable.
Embodiment 4
15 grams of L-glutamic acid, 8 grams of glycol ethers and 3 milligrams of trifluoromethane sulfonic acid scandiums are added in the round-bottomed flask of 100 milliliters, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 4 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1.5 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 4 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 4 obtains has the structure shown in formula (4):
In formula (4), n is 80.
The polyesteramide embodiment of the present invention 4 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 64% in the polyesteramide time of 10 weeks that embodiment 4 obtains, the polyesteramide that the embodiment of the present invention 4 obtains has good biodegradable.
Embodiment 5
30 grams of L-glutamic acid, 230 grams of polyoxyethylene glycol and 3 milligrams of trifluoromethane sulfonic acid scandiums are added in the round-bottomed flask of 250 milliliters, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 4 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1.5 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 5 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 5 obtains has the structure shown in formula (5):
In formula (5), n is 60.
The polyesteramide embodiment of the present invention 5 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 64% in the polyesteramide time of 10 weeks that embodiment 5 obtains, the polyesteramide that the embodiment of the present invention 5 obtains has good biodegradable.
Embodiment 6
5 grams of L-glutamic acid, 5 grams of m-phthalic acids, 2.2 grams of ethylene glycol, 0.06 gram of tetrabutyl titanate and 0.04 gram of metatitanic acid four isopropyl ester are added in the round-bottomed flask of 100 milliliters, above-mentioned substance is heated to the polycondensation that 175 DEG C are carried out the first stage of 4 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 260 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 260 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 6 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 6 obtains has the structure shown in formula (6):
In formula (6), n is 100, m is 60.
The polyesteramide embodiment of the present invention 6 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 55% in the polyesteramide time of 10 weeks that embodiment 6 obtains, the polyesteramide that the embodiment of the present invention 6 obtains has good biodegradable.
Embodiment 7
Add in the round-bottomed flask of 100 milliliters 3.2 grams of L-glutamic acid, 6 grams of terephthalic acids, 4.5 gram 1,5-pentanediol and 0.1 gram of tetrabutyl titanate, above-mentioned substance is heated to the polycondensation that 200 DEG C are carried out the first stage of 1 hour under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 7 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 7 obtains has the structure shown in formula (7):
In formula (7), n is 80, m is 100.
The polyesteramide embodiment of the present invention 7 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 53% in the polyesteramide time of 10 weeks that embodiment 7 obtains, the polyesteramide that the embodiment of the present invention 7 obtains has good biodegradable.
Embodiment 8
Add in the round-bottomed flask of 100 milliliters 7 grams of L-glutamic acid, 3 grams of phthalic acids, 3.6 gram 1,4-butyleneglycol and 0.1 gram of tetrabutyl titanate, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 8 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 8 obtains has the structure shown in formula (8):
In formula (8), n is 100, m is 200.
The polyesteramide embodiment of the present invention 8 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 62% in the polyesteramide time of 10 weeks that embodiment 8 obtains, the polyesteramide that the embodiment of the present invention 8 obtains has good biodegradable.
Embodiment 9
Add in the round-bottomed flask of 100 milliliters 15 grams of L-glutamic acid, 1.8 grams of ethylene glycol, 1.8 gram 1, ammediol and 0.15 gram of tetrabutyl titanate, above-mentioned substance is heated to the polycondensation that 160 DEG C are carried out the first stage of 8 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 2 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 9 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 9 obtains has the structure shown in formula (9):
In formula (9), n is 160, m is 140.
The polyesteramide embodiment of the present invention 9 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 72% in the polyesteramide time of 10 weeks that embodiment 9 obtains, the polyesteramide that the embodiment of the present invention 9 obtains has good biodegradable.
Embodiment 10
Add in the round-bottomed flask of 250 milliliters 35 grams of L-glutamic acid, 2.5 grams of ethylene glycol, 5 gram 1,4-butyleneglycol, 3.2 gram 1,6-hexylene glycol and 0.35 gram of tetrabutyl titanate, above-mentioned substance is heated to the polycondensation that 200 DEG C are carried out the first stage of 1 hour under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 1.5 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 10 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 10 obtains has the structure shown in formula (10):
In formula (10), x is 100, y be 200, z is 100.
The polyesteramide embodiment of the present invention 10 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 80% in the polyesteramide time of 10 weeks that embodiment 10 obtains, the polyesteramide that the embodiment of the present invention 10 obtains has good biodegradable.
Embodiment 11
10 grams of L-glutamic acid, 1.8 grams of ethylene glycol, 0.5 gram of glycerol and 0.1 gram of tetrabutyl titanate are added in the round-bottomed flask of 100 milliliters, above-mentioned substance is heated to the polycondensation that 180 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 220 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 1.5 hours;
At 220 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide that the embodiment of the present invention 11 obtains is cross-linking type polyesteramide, its crosslinked monomer comprises the monomer with the structure shown in formula (110) and formula (111), and the cross-linking type polyesteramide that the embodiment of the present invention 11 obtains is not at the same cross-linked polymer with hydroxyl on formula (110) or the shown structures alone of formula (111) and carboxyl polycondensation:
The polyesteramide embodiment of the present invention 11 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 77% in the polyesteramide time of 10 weeks that embodiment 11 obtains, the polyesteramide that the embodiment of the present invention 11 obtains has good biodegradable.
Embodiment 12
Add in the round-bottomed flask of 100 milliliters 42 grams of L-glutamic acid, 1.8 grams of ethylene glycol, 1.2 gram 1,4-butyleneglycol, 2 grams of tetramethylolmethanes and 0.2 gram of stannous octoate, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide that the embodiment of the present invention 12 obtains is cross-linking type polyesteramide, its crosslinked monomer comprises the monomer with structure shown in formula (120), formula (121) and formula (122), and the cross-linking type polyesteramide that the embodiment of the present invention 12 obtains is not at the same cross-linked polymer with hydroxyl on the shown structures alone of formula (120), formula (121) or formula (122) and carboxyl polycondensation:
The polyesteramide embodiment of the present invention 12 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 78% in the polyesteramide time of 10 weeks that embodiment 12 obtains, the polyesteramide that the embodiment of the present invention 12 obtains has good biodegradable.
Embodiment 13
In the round-bottomed flask of 50 milliliters, add the dimerization reaction that 10 grams of L-glutamic acid carry out 5 hours at 160 DEG C, obtain L-glutamic acid diketopiperazine;
2.1 grams of ethylene glycol and 0.1 gram of stannous octoate is added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 160 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 200 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 200 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
According to the method described in technique scheme, magnetic resonance detection and mass spectrometric detection are carried out to the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares, detected result as shown in Figure 3 and Figure 4, Fig. 3 is the nmr spectrum of the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares, Fig. 4 is the mass spectrum of the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares, from Fig. 3 and Fig. 4, the L-glutamic acid diketopiperazine that the embodiment of the present invention 13 prepares has the structure shown in formula a.
The polyesteramide prepolymer embodiment of the present invention 13 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 13 obtains has the structure shown in formula (13):
In formula (13), n is 300.
The polyesteramide embodiment of the present invention 13 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 76% in the polyesteramide time of 10 weeks that embodiment 13 obtains, the polyesteramide that the embodiment of the present invention 13 obtains has good biodegradable.
Embodiment 14
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 20 grams of L-glutamic acid carry out 6 hours at 170 DEG C, obtain L-glutamic acid diketopiperazine;
5.2 gram 1 is added in the L-glutamic acid diketopiperazine obtained, 3-ring pentanediol and 20 milligrams of stannous octoates, above-mentioned substance is heated to the polycondensation that 170 DEG C are carried out the first stage of 4 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 210 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 210 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 14 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 14 obtains has the structure shown in formula (14):
In formula (14), n is 500.
The polyesteramide embodiment of the present invention 14 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 70% in the polyesteramide time of 10 weeks that embodiment 14 obtains, the polyesteramide that the embodiment of the present invention 14 obtains has good biodegradable.
Embodiment 15
In the round-bottomed flask of 50 milliliters, add the dimerization reaction that 5 grams of L-glutamic acid carry out 4 hours at 180 DEG C, obtain L-glutamic acid diketopiperazine;
2.0 grams of isophthalic alcohols and 125 milligrams of stannous octoates are added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 180 DEG C are carried out the first stage of 1.5 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 220 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 5 hours;
At 220 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 15 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 15 obtains has the structure shown in formula (15):
In formula (15), n is 240.
The polyesteramide embodiment of the present invention 15 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 67% in the polyesteramide time of 10 weeks that embodiment 15 obtains, the polyesteramide that the embodiment of the present invention 15 obtains has good biodegradable.
Embodiment 16
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 15 grams of L-glutamic acid carry out 3 hours at 190 DEG C, obtain L-glutamic acid diketopiperazine;
8 grams of glycol ethers and 3 milligrams of stannous octoates are added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 4 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1.5 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 16 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 16 obtains has the structure shown in formula (16):
In formula (16), n is 100.
The polyesteramide embodiment of the present invention 16 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 64% in the polyesteramide time of 10 weeks that embodiment 16 obtains, the polyesteramide that the embodiment of the present invention 16 obtains has good biodegradable.
Embodiment 17
In the round-bottomed flask of 250 milliliters, add the dimerization reaction that 30 grams of L-glutamic acid carry out 3 hours at 190 DEG C, obtain L-glutamic acid diketopiperazine;
230 grams of polyoxyethylene glycol and 3 milligrams of stannous octoates are added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 4 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1.5 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 17 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 17 obtains has the structure shown in formula (17):
In formula (17), n is 60.
The polyesteramide embodiment of the present invention 17 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 64% in the polyesteramide time of 10 weeks that embodiment 17 obtains, the polyesteramide that the embodiment of the present invention 17 obtains has good biodegradable.
Embodiment 18
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 5 grams of L-glutamic acid carry out 6 hours at 150 DEG C, obtain L-glutamic acid diketopiperazine;
5 grams of m-phthalic acids, 2.2 grams of ethylene glycol and 0.1 gram of antimonous oxide is added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 175 DEG C are carried out the first stage of 3 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 260 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 260 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 18 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 18 obtains has the structure shown in formula (18):
In formula (18), n is 100, m is 60.
The polyesteramide embodiment of the present invention 18 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 55% in the polyesteramide time of 10 weeks that embodiment 18 obtains, the polyesteramide that the embodiment of the present invention 18 obtains has good biodegradable.
Embodiment 19
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 4 grams of L-glutamic acid carry out 8 hours at 120 DEG C, obtain L-glutamic acid diketopiperazine;
Add in the L-glutamic acid diketopiperazine obtained 6 grams of terephthalic acids, 4.5 gram 1,5-pentanediol and 0.1 gram of antimonous oxide, above-mentioned substance is heated to the polycondensation that 200 DEG C are carried out the first stage of 1 hour under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 3 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 19 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 19 obtains has the structure shown in formula (19):
In formula (19), n is 80, m is 100.
The polyesteramide embodiment of the present invention 19 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 53% in the polyesteramide time of 10 weeks that embodiment 19 obtains, the polyesteramide that the embodiment of the present invention 19 obtains has good biodegradable.
Embodiment 20
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 7 grams of L-glutamic acid carry out 2 hours at 200 DEG C, obtain L-glutamic acid diketopiperazine;
Add in the L-glutamic acid diketopiperazine obtained 3 grams of phthalic acids, 3.6 gram 1,4-butyleneglycol and 0.1 gram of antimonous oxide, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 1 hour under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 0.5 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 20 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 20 obtains has the structure shown in formula (20):
In formula (20), n is 100, m is 200.
The polyesteramide embodiment of the present invention 20 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 62% in the polyesteramide time of 10 weeks that embodiment 20 obtains, the polyesteramide that the embodiment of the present invention 20 obtains has good biodegradable.
Embodiment 21
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 15 grams of L-glutamic acid carry out 1 hour at 210 DEG C, obtain L-glutamic acid diketopiperazine;
Add in the L-glutamic acid diketopiperazine obtained 1.8 grams of ethylene glycol, 1.8 gram 1, ammediol and 0.15 gram of antimonous oxide, above-mentioned substance is heated to the polycondensation that 160 DEG C are carried out the first stage of 6 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 2 hours, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 21 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 21 obtains has the structure shown in formula (21):
In formula (21), n is 260, m is 240.
The polyesteramide embodiment of the present invention 21 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 72% in the polyesteramide time of 10 weeks that embodiment 21 obtains, the polyesteramide that the embodiment of the present invention 21 obtains has good biodegradable.
Embodiment 22
In the round-bottomed flask of 250 milliliters, add the dimerization reaction that 35 grams of L-glutamic acid carry out 6 hours at 190 DEG C, obtain L-glutamic acid diketopiperazine;
Add in the L-glutamic acid diketopiperazine obtained 2.5 grams of ethylene glycol, 5 gram 1,4-butyleneglycol, 3.2 gram 1,6-hexylene glycol and 0.35 gram of antimonous oxide, above-mentioned substance is heated to the polycondensation that 200 DEG C are carried out the first stage of 1 hour under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 240 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 1.5 hours;
At 240 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide prepolymer embodiment of the present invention 22 obtained carries out magnetic resonance detection in deuterated water, and detected result is, the polyesteramide that the embodiment of the present invention 22 obtains has the structure shown in formula (22):
In formula (22), x is 80, y be 200, z is 80.
The polyesteramide embodiment of the present invention 22 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 80% in the polyesteramide time of 10 weeks that embodiment 22 obtains, the polyesteramide that the embodiment of the present invention 22 obtains has good biodegradable.
Embodiment 23
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 10 grams of L-glutamic acid carry out 6 hours at 170 DEG C, obtain L-glutamic acid diketopiperazine;
1.8 grams of ethylene glycol, 0.5 gram of glycerol and 0.1 gram of antimonous oxide is added in the L-glutamic acid diketopiperazine obtained, above-mentioned substance is heated to the polycondensation that 180 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 220 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 1.5 hours;
At 220 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide that the embodiment of the present invention 23 obtains is cross-linking type polyesteramide, its crosslinked monomer comprises the monomer with the structure shown in formula (230) and formula (231), and the cross-linking type polyesteramide that the embodiment of the present invention 23 obtains is not at the same cross-linked polymer with hydroxyl on formula (230) or the shown structures alone of formula (231) and carboxyl polycondensation:
The polyesteramide embodiment of the present invention 23 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 77% in the polyesteramide time of 10 weeks that embodiment 23 obtains, the polyesteramide that the embodiment of the present invention 23 obtains has good biodegradable.
Embodiment 24
In the round-bottomed flask of 100 milliliters, add the dimerization reaction that 20 grams of L-glutamic acid carry out 10 hours at 170 DEG C, obtain L-glutamic acid diketopiperazine;
Add in the L-glutamic acid diketopiperazine obtained 1.8 grams of ethylene glycol, 1.2 gram 1,4-butyleneglycol, 5 grams of tetramethylolmethanes and 0.2 gram of antimonous oxide, above-mentioned substance is heated to the polycondensation that 190 DEG C are carried out the first stage of 2 hours under the condition stirred, by the reaction product Dean-Stark trap removing moisture wherein obtained, obtain polyesteramide prepolymer;
The polyesteramide prepolymer obtained is heated to 230 DEG C, under the condition stirred, carries out the polycondensation of the subordinate phase of 2 hours;
At 230 DEG C, reduce system pressure to 1 × 10 of above-mentioned subordinate phase polycondensation -4mPa, carries out the polycondensation of the phase III of 1 hour, obtains polyesteramide.
The polyesteramide that the embodiment of the present invention 24 obtains is cross-linking type polyesteramide, its crosslinked monomer comprises the monomer with structure shown in formula (240), formula (241) and formula (242), and the cross-linking type polyesteramide that the embodiment of the present invention 24 obtains is not at the same cross-linked polymer with hydroxyl on the shown structures alone of formula (240), formula (241) or formula (242) and carboxyl polycondensation:
The polyesteramide embodiment of the present invention 24 obtained is carry out degraded test in 7.4 phosphate buffer solutions in pH value, test result is, molecular weight and molecular weight 78% in the polyesteramide time of 10 weeks that embodiment 24 obtains, the polyesteramide that the embodiment of the present invention 24 obtains has good biodegradable.
Embodiment 25
In the round-bottomed flask of 50 milliliters, add the dimerization reaction that 10 grams of L-glutamic acid carry out 24 hours at 100 DEG C, obtain L-glutamic acid diketopiperazine.
According to the method described in technique scheme, magnetic resonance detection and mass spectrometric detection are carried out to the L-glutamic acid diketopiperazine that the embodiment of the present invention 25 prepares, detected result is, the L-glutamic acid diketopiperazine that the embodiment of the present invention 25 prepares has the structure shown in formula a.
Embodiment 26
In the round-bottomed flask of 50 milliliters, add the dimerization reaction that 10 grams of L-glutamic acid carry out 0.1 hour at 240 DEG C, obtain L-glutamic acid diketopiperazine.
According to the method described in technique scheme, magnetic resonance detection and mass spectrometric detection are carried out to the L-glutamic acid diketopiperazine that the embodiment of the present invention 26 prepares, detected result is, the L-glutamic acid diketopiperazine that the embodiment of the present invention 26 prepares has the structure shown in formula a.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.Be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (5)

1. a preparation method for L-glutamic acid diketopiperazine, comprising:
L-glutamic acid direct heating is carried out dimerization reaction, obtains L-glutamic acid diketopiperazine.
2. method according to claim 1, is characterized in that, described dimerization reaction is without the need to catalyzer.
3. method according to claim 1, is characterized in that, described dimerization reaction is without the need to solvent.
4. method according to claim 1, is characterized in that, the temperature of described dimerization reaction is 100 DEG C ~ 240 DEG C.
5. method according to claim 1, is characterized in that, the time of described dimerization reaction is 0.1 hour ~ 24 hours.
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