CN115073729A - Polylysine macromolecule P alpha LA and preparation method and application thereof - Google Patents

Polylysine macromolecule P alpha LA and preparation method and application thereof Download PDF

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CN115073729A
CN115073729A CN202210805627.9A CN202210805627A CN115073729A CN 115073729 A CN115073729 A CN 115073729A CN 202210805627 A CN202210805627 A CN 202210805627A CN 115073729 A CN115073729 A CN 115073729A
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polylysine
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CN115073729B (en
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李因文
张伟
李兴建
冯恩娟
马建峰
徐守芳
李法强
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Linyi University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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Abstract

The invention discloses polylysine macromolecule polyalpha LA and a preparation method and application thereof, and belongs to the technical field of functional polymer materials. Is prepared from the intermediate PEG-b-P alpha L of polyethylene glycol-b-poly alpha lysine x The functional group is obtained by graft reaction of active amidocyanogen on the branched chain and carboxylic acid functional monomer, and the structural formula is shown as I:
Figure DDA0003737176380000011
wherein m is 40-230, x is 10-50, and a is 5-30. When the polylysine macromolecule P alpha LA is used as a concrete water reducing agent, the polylysine macromolecule P alpha LA not only shows excellent water reducing dispersibility, but also has remarkable mud sensitivity resistance. In addition, the present inventionThe production process of the Ming-polylysine macromolecule is mild and easy to operate, the number of lysine polymerization units and the type and proportion of the grafted carboxylic acid or the anhydride can be optimally regulated and controlled to meet the requirement of being used as a cement concrete water reducing agent, and meanwhile, the Ming-polylysine macromolecule can be applied to the fields of gypsum, ceramics, water resistance and the like, so the Ming-polylysine macromolecule has wide application prospect.

Description

Polylysine macromolecule P alpha LA and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to polylysine macromolecules and a preparation method and application thereof.
Background
The addition of the water reducing agent proves to be one of the most effective means for improving the flowability of the fresh concrete, and in a plurality of water reducing agent systems, the third generation of high-performance polycarboxylate water reducing agent PCEs can obviously improve the flowability and the workability of the fresh concrete and the mechanical property of the hardened concrete under the condition of low doping amount, and the excellent water reducing performance is mainly attributed to the synergistic effect of the electrostatic effect of carboxyl and the steric effect of PEG branched chain. Although the polycarboxylic acid water reducing agent has remarkable water reducing performance, the polycarboxylic acid water reducing agent also has the problems of poor adaptability, poor workability, sensitivity to the content of aggregate mud and the like in practical application. Therefore, the further wide application of the polycarboxylic acid water reducing agent in practical engineering is limited to a certain extent.
Since the polycarboxylic acids PCEs are used as the water reducing agent in the last 80 th century, a great deal of research work with great success is carried out by domestic and foreign researchers on the structure-activity relationship between the PCEs and the flow property of a cement-based material. The influence rule and action mechanism of the dispersing performance of the polycarboxylate superplasticizer are summarized and explored on a macroscopic level and a microscopic level, and good application and theoretical guidance are provided for the research and application of high performance of the polycarboxylate superplasticizer. Along with the rapid development of infrastructure, the polycarboxylate superplasticizers are widely applied from a high-end to a middle-end and a low-end mode continuously, the updating and the functionalization of the polycarboxylate superplasticizers are promoted continuously, and the polycarboxylate superplasticizers developed from the perspective of molecular structure design, such as high slump loss resistant type, high adaptive type, mud sensitivity resistant type, shrinkage reducing type and the like, are typical representatives.
The inventor finds that (CN201910140420.2, CN202111094415.6, Colloids and Surfaces A: physical and Engineering industries, 2022,634,127953.) the polyamino acid macromolecules not only have the advantages of good biocompatibility, no toxicity, degradability and the like, but also have the similar structure with high-performance polycarboxylic acid water reducing agents PCEs, such as containing abundant carboxyl, amino and amide groups and the like. In addition, the molecular structure of the compound also has a large number of groups with potential reactivity, thereby being very beneficial to easy chemical modification and structural modification. Therefore, the polyamino acid macromolecules have ideal application prospect when being used as concrete admixtures. Therefore, the invention designs and prepares a novel polylysine macromolecule P alpha LA from the design of the polyamino acid macromolecule structure, which is used for the research and application of the water reducing dispersion and mud resistance sensitivity of a cement concrete system, and also can be used for the water reducing dispersion in the fields of buildings, building materials, gypsum, ceramics, water resistance and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention designs and prepares a novel polylysine macromolecule P alpha LA from the design of a polymer molecular structure, and discloses a preparation method and application thereof.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a polylysine macromolecule P alpha LA is prepared from polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The functional group is obtained by the graft reaction of active amidocyanogen on the branched chain and carboxylic acid functional monomer, and the structural formula is shown as (I):
Figure BDA0003737176360000021
wherein m is 40-230, x is 10-50, and a is 5-30.
Further, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x Has a structure of formula II:
Figure BDA0003737176360000022
further, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The synthesis method comprises the following steps: weighing amino-terminated polyethylene glycol derivative mPEG-NH 2 And N 6 Dissolving carbobenzoxy-L-lysine cyclic anhydride in N, N-dimethylformamide DMF, reacting at room temperature for 48-96 h, precipitating with petroleum ether after the reaction is finished, filtering, dissolving the collected solid in trifluoroacetic acid TFA/hydrobromic acid HBr, reacting at room temperature for 3-5 h, concentrating, precipitating with petroleum ether, and collecting to obtain polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x 。
Further, the intermediate PEG-b-P alpha L of polyethylene glycol-b-poly alpha lysine of formula II x Wherein the molecular weight Mw of the polyethylene glycol PEG chain segment is 500-20000.
Further, the intermediate PEG-b-P alpha L of polyethylene glycol-b-poly alpha lysine of formula II x In (b), the poly-alpha-lysine P alpha L x The molecular weight Mw of the chain segment ranges from 1530 to 30600.
Further, the intermediate PEG-b-P alpha L of the polyethylene glycol-b-poly alpha lysine x In the preparation method, the molecular weight Mw of a polyethylene glycol (PEG) chain segment is 2000-10000; poly alpha lysine P alpha L x The molecular weight Mw of the chain segment is 3060-9120.
Further, the carboxylic acid functional monomer refers to carboxylic acid containing two or more carboxyl groups and corresponding anhydride compounds thereof.
Further, the carboxylic acid functional monomer is one or more of malonic acid, nitrilotriacetic acid, succinic anhydride, methylsuccinic acid, methylsuccinic anhydride, itaconic acid, itaconic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, suberic anhydride, sebacic anhydride, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic anhydride, diethyltriaminepentaacetic acid, and diethyltriaminepentaacetic anhydride.
Further, the carboxylic acid functional monomer is one or more of malonic acid, nitrilotriacetic acid, succinic anhydride, methylsuccinic acid, methylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic anhydride, diethyltriaminepentaacetic acid, and diethyltriaminepentaacetic anhydride.
Furthermore, R1 in the formula I is a skeleton part after a carboxylic acid functional monomer reacts with amino.
Further, the intermediate PEG-b-P alpha L of the polyethylene glycol-b-poly alpha lysine x The molar ratio of the carboxylic acid functional monomer to the carboxylic acid functional monomer is 1: 5.0-30.0.
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And adding the polylysine and the carboxylic acid functional monomer into deionized water, adjusting the pH of the solution to 8-9 by using a sodium hydroxide solution, and reacting at room temperature for 5-12 hours to obtain the polylysine macromolecule polyalphaLA.
An application of polylysine macromolecule P alpha LA is applied to the fields of building materials, gypsum, ceramics, water proofing and the like.
Advantageous effects
(1) When the novel polylysine macromolecule P alpha LA is used as a concrete water reducing agent, the novel polylysine macromolecule P alpha LA not only shows excellent water reducing dispersibility, but also has remarkable mud sensitivity resistance.
(2) The novel polylysine macromolecule P alpha LA has simple production process, can meet the requirement of being used as a cement concrete water reducing agent by optimally regulating and controlling the number of lysine polymerization units and the type and the proportion of the grafted carboxylic acid or the anhydride, and can also consider other related application fields, thereby having wide application prospect.
Drawings
FIG. 1 is a synthetic route diagram of polylysine-based macromolecule P α LA of the present invention;
FIG. 2 shows the neat paste fluidity performance of the novel polylysine macromolecule P alpha LA under different montmorillonite mixing amounts (0-5.0%);
FIG. 3 shows the time-lapse neat paste fluidity performance of the novel polylysine macromolecule P alpha LA under the fixed montmorillonite mixing amount (2.0%).
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
A preparation method of polylysine macromolecule P alpha LA comprises the following operation steps: 5.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 5060, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.06g of malonic acid (Mw is approximately equal to 106) are put into 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule (P alpha LA) is obtained after reaction for 6h at room temperature.
Example 2
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 8.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 2.12g of malonic acid (Mw is approximately equal to 106) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the reaction is carried out for 6 hours at room temperature.
Example 3
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 5.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 5060, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.0g succinic anhydride (Mw is approximately equal to 100) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Example 4
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 8.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 2.0g of succinic acid (Mw is approximately equal to 100) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the reaction is carried out for 6 hours at room temperature.
Example 5
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 5.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x Molecular weight ofAnd Mw is approximately equal to 5060, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 0.96g of nitrilotriacetic acid (Mw is approximately equal to 119) are placed in 30g of deionized water, the pH of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the reaction is carried out for 6h at room temperature.
Example 6
A preparation method of polylysine macromolecule P alpha LA comprises the following operation steps: 8.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 2000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 1.91g of nitrilotriacetic acid (Mw is approximately equal to 119) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after reaction for 6 hours at room temperature.
Example 7
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 6.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The molecular weight Mw is about 6060, wherein a PEG chain segment Mw is about 3000, a P alpha L chain segment (Mw is about 3060, x is about 10) and 1.06g of malonic acid (Mw is about 119) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after reaction for 6 hours at room temperature.
Example 8
A preparation method of polylysine macromolecule P alpha LA comprises the following operation steps: 6.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is about 6060, wherein the PEG chain segment Mw is about 3000, the polyalpha L chain segment (Mw is about 3060, and x is about 10) and 1.0g succinic anhydride (Mw is about 100) are placed in 30g deionized water, the pH of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule polyalpha LA is obtained after the room temperature reaction for 6 h.
Example 9
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 6.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The molecular weight Mw is about 6060, wherein the PEG chain segment Mw is about 3000, the P alpha L chain segment (Mw is about 3060, x is about 10) and 0.96g nitrilotriacetic acid (Mw is about 191) are put in 30g deionized water, the pH of the solution is adjusted to 8-9 by sodium hydroxide solution, and the reaction is carried out for 6h at room temperature, thus obtaining the polylysineAcid macromolecule P alpha LA.
Example 10
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 11.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight Mw is approximately equal to 11120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 2.12g of malonic acid (Mw is approximately equal to 106) are placed in 30g of deionized water, the pH of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the reaction is carried out for 6 hours at room temperature.
Example 11
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 11.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 11120, wherein the PEG chain segment Mw is approximately equal to 5000, the polyalpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 2.0g of succinic anhydride (Mw is approximately equal to 100) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule polyalpha LA is obtained after the room temperature reaction is carried out for 6 h.
Example 12
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 11.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 11120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 0.96g of nitrilotriacetic acid (Mw is approximately equal to 191) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Example 13
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 9.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 9120, wherein the PEG chain segment Mw is approximately equal to 3000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 1.06g of malonic acid (Mw is approximately equal to 119) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after reaction for 6h at room temperature.
Example 14
A preparation method of novel polylysine macromolecule P alpha LA comprises the following steps: 16.12g of polyethyleneDiol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 11200 and x is approximately equal to 30) and 1.5g succinic anhydride (Mw is approximately equal to 100) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction is carried out for 6 h.
Example 15
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 6.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 6120, wherein the PEG chain segment Mw is approximately equal to 3000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.91g of nitrilotriacetic acid (Mw is approximately equal to 191) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Example 16
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 8.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment () (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.32g of methylsuccinic acid (Mw is approximately equal to 132) are put into 30g of deionized water, the pH of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Example 17
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 9.6g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 9600, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 4600 and x is approximately equal to 15) and 1.14g glutaric anhydride (Mw is approximately equal to 114) are placed in 30g deionized water, the pH of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction is carried out for 6 h.
Example 18
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 11.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x Molecular weight (Mw) 11120, with the PEG segment Mw 8000, the P.alpha.L segment (Mw 3060, x 10) and 1.28g of adipic anhydride (Mw 128) in 30g of deionized water,and (3) adjusting the pH value of the solution to 8-9 by using a sodium hydroxide solution, and reacting at room temperature for 6 hours to obtain the polylysine macromolecule P alpha LA.
Example 19
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 9.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 9120, wherein the PEG chain segment Mw is approximately equal to 3000, the P alpha L chain segment (Mw is approximately equal to 6120 and x is approximately equal to 20) and 0.96g of nitrilotriacetic acid (Mw is approximately equal to 191) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after reaction for 6 hours at room temperature.
Example 20
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 6.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 6060, wherein the PEG chain segment Mw is approximately equal to 3000, the polyalpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.46g of ethylene diamine tetraacetic acid (Mw is approximately equal to 292) are put into 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule polyalpha LA is obtained after reaction for 6 hours at room temperature.
Example 21
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 6.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 6060, wherein the PEG chain segment Mw is approximately equal to 3000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 1.96g of diethyltriamine pentaacetic acid (Mw is approximately equal to 393) are put into 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Example 22
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 14.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 14120, wherein the PEG chain segment Mw is approximately equal to 5000, the polyalpha L chain segment (Mw is approximately equal to 9120 and x is approximately equal to 30) and 1.46g of ethylene diamine tetraacetic acid (Mw is approximately equal to 292) are put into 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule polyalpha LA is obtained after reaction for 6h at room temperature.
Example 23
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 14.12g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 14120, wherein the PEG chain segment Mw is approximately equal to 5000, the polyalphaL chain segment (Mw is approximately equal to 9120 and x is approximately equal to 30) and 1.06g of malonic acid (Mw is approximately equal to 106) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule polyalphaLA is obtained after reaction for 6 hours at room temperature.
Example 24
A preparation method of polylysine macromolecule P alpha LA comprises the following steps: 11.06g of polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And the molecular weight (Mw) is approximately equal to 11060, wherein the PEG chain segment Mw is approximately equal to 8000, the P alpha L chain segment (Mw is approximately equal to 3060 and x is approximately equal to 10) and 0.96g of diethyltriamine pentaacetic acid (Mw is approximately equal to 393) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by using a sodium hydroxide solution, and the polylysine macromolecule P alpha LA is obtained after the room temperature reaction for 6 h.
Performance testing
The invention selects a commercial polycarboxylic acid water reducing agent (PCE) 0 ) For comparison, the fluidity of cement paste doped with the novel polylysine-based macromolecule P alpha LA prepared by the exemplary embodiment of the invention is measured by referring to the national standard GB/T8076-2008 concrete admixture, and the specific results are shown in Table 1.
TABLE 1 mobility and setting time of neat cement slurry doped with polylysine macromolecule P alpha LA
Figure BDA0003737176360000081
As can be seen from table 1, the polylysine-based macromolecule P α LA prepared by the present invention has excellent water-reducing dispersibility, and as can be seen from typical examples 9, 12, 13, 14, 19 and 23, the polylysine-based macromolecule P α LA also has excellent cement paste flow performance over time. Meanwhile, the invention also measures the setting time of a cement system doped with the polylysine macromolecule polyalphala, and the result shows that the setting time is similar to that of the traditional polycarboxylic acid water reducing agent and has certain retardation effect, and the difference is that the retardation effect of the novel polylysine macromolecule polyalphala obtained by the invention is increased along with the increase of the proportion of the grafted carboxylic acid functional monomer.
In addition, because the content and the type and the region difference of the mud in the concrete are obvious, the invention further selects montmorillonite as the typical representative clay, and the net slurry flow property of the cement/montmorillonite system doped with the polylysine macromolecule P alpha LA prepared by the typical embodiment of the invention is measured, and the specific experiment comprises the following steps: firstly, the content of montmorillonite in cement (1.0%, 2.0%, 3.0%, 4.0% and 5.0%, cement mass ratio) is changed while the doping amount (2.0% to cement mass ratio) of polylysine macromolecule P [ alpha ] LA is kept unchanged, and the test result of the fluidity of the cement paste is obtained and is shown in FIG. 2; secondly, the mixing amount of montmorillonite (2.0 percent, cement mass ratio) and the mixing amount of polylysine macromolecule P alpha LA (0.2 percent, cement mass ratio) are kept unchanged, and the cement paste fluidity is tested over time, and the result is shown in figure 3. The result shows that the polylysine macromolecule P alpha LA shows excellent mud resistance sensitivity.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.

Claims (8)

1. A polylysine macromolecule P alpha LA is characterized in that a polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L is utilized x The functional group is obtained by the graft reaction of active amidocyanogen on the branched chain and carboxylic acid functional monomer, and the structural formula is shown as (I):
Figure FDA0003737176350000011
wherein m is 40-230, x is 10-50, and a is 5-30.
2. The polylysine-based macromolecule Ppha LA as claimed in claim 1, wherein the polyethylene glycol-b-Poly alpha lysine intermediate PEG-b-P alpha L x In the preparation method, the molecular weight Mw of a polyethylene glycol (PEG) chain segment is 2000-10000; poly alpha lysine P alpha L x The molecular weight Mw of the chain segment is 3060-9120.
3. The polylysine-based macromolecule Pa LA according to claim 1, wherein the carboxylic acid functional monomer is a carboxylic acid having two or more carboxyl groups and a corresponding acid anhydride compound.
4. The polylysine-based macromolecule Pa LA according to claim 3, wherein the carboxylic acid functional monomer is one or more of malonic acid, nitrilotriacetic acid, succinic anhydride, methylsuccinic acid, methylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, and diethyltriaminepentaacetic anhydride.
5. The polylysine macromolecule Pa LA as claimed in claim 1, wherein R1 is a backbone portion of carboxylic acid functional monomer reacted with amine group.
6. The polylysine-based macromolecule Pa LA according to claim 1, wherein the PEG-b-polyalphalysine intermediate PEG-b-polyalphaL x The molar ratio of the carboxylic acid functional monomer to the carboxylic acid functional monomer is 1: 5.0-30.0.
7. A method for preparing polylysine-based macromolecule Pa LA according to any one of claims 1-6, comprising the steps of: polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x And adding the polylysine and the carboxylic acid functional monomer into deionized water, adjusting the pH of the solution to 8-9 by using a sodium hydroxide solution, and reacting at room temperature for 5-12 hours to obtain the polylysine macromolecule polyalphaLA.
8. The application of the polylysine macromolecule Pa LA as defined in any one of claims 1 to 6, which is characterized in that the polylysine macromolecule Pa LA is applied to the fields of building materials, gypsum, ceramics, water proofing and the like.
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