CN115073729B - 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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CN115073729B
CN115073729B CN202210805627.9A CN202210805627A CN115073729B CN 115073729 B CN115073729 B CN 115073729B CN 202210805627 A CN202210805627 A CN 202210805627A CN 115073729 B CN115073729 B CN 115073729B
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polylysine
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CN115073729A (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
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/287—Polyamides
    • 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
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a polylysine macromolecule P alpha LA and a preparation method and application thereof, belonging to the technical field of functional polymer materials. Polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The structural formula of the modified amino acid is shown as I:where m=40-230, x=10-50, a=5-30. When the polylysine macromolecules P alpha LA are used as the concrete water reducing agent, the polylysine macromolecules P alpha LA not only have excellent water reducing dispersion performance, but also have remarkable mud resistance sensitivity. In addition, the polylysine macromolecule production process is mild and easy to operate, and can be used as a cement concrete water reducer by optimizing and controlling the quantity of lysine polymerization units and the type and the proportion of grafted carboxylic acid or anhydride, and meanwhile, the polylysine macromolecule can be applied to the fields of gypsum, ceramics, water resistance and the like, so that the polylysine macromolecule water reducer has a 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 a polylysine macromolecule, a preparation method and application thereof.
Background
The addition of water reducers has proven to be one of the most effective means for improving the fluidity of fresh concrete, and in many water reducer systems, the third-generation high-performance polycarboxylate water reducer PCEs can remarkably improve the fluidity and workability of fresh concrete and the mechanical properties of the hardened concrete under the condition of low mixing amount, and the excellent water reducing performance is mainly due to the synergistic effect of the electrostatic effect of carboxyl and the steric effect of PEG branched chains. Although the polycarboxylate water reducer has remarkable water reducing performance, the polycarboxylate water reducer 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 polycarboxylate water reducer in practical engineering is restricted to a certain extent.
Since the last century, PCEs, which are polycarboxylic acids, were used as water reducers, a great deal of effective research work has been carried out by researchers at home and abroad regarding the structure-activity relationship between PCEs and the fluidity of cement-based materials. The influence rule and the action mechanism of the dispersion performance of the polycarboxylate superplasticizer are summarized and explored from the macroscopic and microscopic level, and good application and theoretical guidance are provided for the research and application of the high performance of the polycarboxylate superplasticizer. Along with the rapid development of the infrastructure, the polycarboxylate water reducer is widely applied from high end to middle and low end downward detection, the updating and functionalization of the polycarboxylate water reducer are also continuously advanced, and the polycarboxylate water reducer with high slump retention, high adaptation, mud resistance sensitivity, shrinkage reduction and the like developed from the aspect of molecular structure design is typical.
Previous researches of the inventor show that (CN 201910140420.2, CN202111094415.6, colloids and Surfaces A: physicochemical and Engineering Aspects,2022,634,127953.) the polyamino acid macromolecules not only have the advantages of good biocompatibility, no toxicity, degradability and the like, but also have similar structures with the PCEs of the high-performance polycarboxylate superplasticizer, such as rich carboxyl, amino, amide groups and the like. In addition, the molecular structure of the modified polyurethane has a large number of groups with potential reactivity, which is very beneficial to chemical modification and structural modification. Therefore, the polyamino acid macromolecules have ideal application prospect when being used as concrete additives. Therefore, the invention starts from the design of the polyamino acid macromolecule structure, designs and prepares a novel polylysine macromolecule P alpha LA, which is used for researching and applying the water-reducing dispersion and mud-resistant sensitivity of a cement concrete system, and simultaneously gives consideration to the water-reducing dispersion application in the fields of construction, building materials, gypsum, ceramics, water resistance and the like.
Disclosure of Invention
Aiming at the defects existing 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 invention adopts the following technical scheme:
a polylysine macromolecule P alpha LA is PEG-b-P alpha L which is an intermediate of polyethylene glycol-b-poly alpha lysine x The structural formula of the polymer is shown as (I):
where m=40-230, x=10-50, a=5-30.
Further, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x Has the structure of formula II:
further, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The synthesis method of (2) is as follows: weighing amine-terminated polyethylene glycol derivative mPEG-NH 2 And N 6 Dissolving benzyloxycarbonyl-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, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-pαL of formula II x In the above, the polyethylene glycolThe molecular weight Mw of the alcohol PEG chain segment is 500-20000.
Further, polyethylene glycol-b-poly alpha lysine intermediate PEG-b-pαL of formula II x In the above, the poly alpha lysine pαL x The molecular weight Mw of the segments is 1530-30600.
Further, the polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x Wherein the molecular weight Mw of the polyethylene glycol PEG chain segment is 2000-10000; poly alpha lysine palpha L x The molecular weight Mw of the segments 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, methyl succinic acid, methyl succinic anhydride, itaconic acid, itaconic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, suberic anhydride, sebacic anhydride, ethylenediamine tetraacetic acid, ethylenediamine tetraacetic anhydride, diethylenetriamine pentaacetic acid and diethylenetriamine pentaacetic anhydride.
Further, the carboxylic acid functional monomer is one or more of malonic acid, nitrilotriacetic acid, succinic anhydride, methyl succinic acid, methyl succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, ethylenediamine tetraacetic acid anhydride, diethylenetriamine pentaacetic acid and diethylenetriamine pentaacetic acid anhydride.
Further, R1 in the formula I is a skeleton part after the reaction of the carboxylic acid functional monomer and the amino group.
Further, the polyethylene glycol-b-poly alpha lysine intermediate PEG-b-P alpha L x The molar ratio of the catalyst to the carboxylic acid functional monomer is 1:5.0-30.0.
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: PEG-b-pαL as intermediate of polyethylene glycol-b-poly- αlysine x And adding the polymer and carboxylic acid functional monomer into deionized water, regulating the pH of the solution to 8-9 by using sodium hydroxide solution, and reacting for 5-12 h at room temperature to obtain the polylysine macromolecule P alpha LA.
The application of polylysine macromolecules P alpha LA is applied to the fields of building materials, gypsum, ceramics, water resistance 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 has excellent water reducing dispersion performance, but also has remarkable mud resistance sensitivity.
(2) The novel polylysine macromolecule P alpha LA has simple production process, can be used as a cement concrete water reducer by optimizing and controlling the quantity of lysine polymerization units and the type and the proportion of grafted carboxylic acid or anhydride, and can be used in other related application fields, so that the novel polylysine macromolecule P alpha LA has wide application prospect.
Drawings
FIG. 1 is a synthetic route diagram of a polylysine macromolecule P.alpha.LA of the present invention;
FIG. 2 shows the net pulp fluidity performance of the novel polylysine macromolecules P alpha LA with different montmorillonite doping amounts (0-5.0 percent);
FIG. 3 shows the flow properties of the novel polylysine macromolecules P.alpha.LA in the form of a clear slurry with a fixed montmorillonite loading (2.0%).
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The preparation method of the polylysine macromolecule P alpha LA comprises the following operation steps: 5.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x The molecular weight Mw is about 5060, wherein the PEG chain segment Mw is about 2000, the P alpha L chain segment (Mw is about 3060, x is about 10) and 1.06g malonic acid (Mw is about 106) are placed in 30g deionized water, the pH value of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature to obtain the polylysine macromolecules (P alpha LA).
Example 2
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 8.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x Molecular weight Mw is approximately equal to 8120, wherein the PEG chain segment Mw is approximately equal to 2000, and the P alpha L chain segment(Mw is approximately equal to 6120, 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 3
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 5.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x The molecular weight Mw is about 5060, wherein the PEG chain segment Mw is about 2000, the P alpha L chain segment (Mw is about 3060, x is about 10) and 1.0g succinic anhydride (Mw is about 100) are placed in 30g deionized water, the pH value of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature to obtain the polylysine macromolecules P alpha LA.
Example 4
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 8.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 5
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 5.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x The molecular weight Mw is about 5060, wherein the PEG chain segment Mw is about 2000, the P alpha L chain segment (Mw is about 3060, x is about 10) and 0.96g of nitrilotriacetic acid (Mw is about 119) are placed in 30g of deionized water, the pH value of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature to obtain the polylysine macromolecules P alpha LA.
Example 6
The preparation method of the polylysine macromolecule P alpha LA comprises the following operation steps: 8.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 7
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 6.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x 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 1.06g malonic acid (Mw is approximately equal to 119) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 8
The preparation method of the polylysine macromolecule P alpha LA comprises the following operation steps: 6.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x 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 1.0g 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 9
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 6.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x 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 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 10
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 11.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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 malonic acid (Mw is approximately equal to 106) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 11
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 11.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x Molecular weight (Mw) And (3) about 11120, wherein the Mw of the PEG chain segment is about 5000, the P alpha L chain segment (Mw is about 6120, x is about 20) and 2.0g of succinic anhydride (Mw is about 100) are placed in 30g of deionized water, the pH of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 12
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 11.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 13
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 9.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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, x is approximately equal to 20) and 1.06g malonic acid (Mw is approximately equal to 119) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 14
The preparation method of the novel polylysine macromolecule P alpha LA comprises the following steps: 16.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 15
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 6.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x The molecular weight (Mw) is about 6120, wherein the PEG chain segment Mw is about 3000, the P alpha L chain segment (Mw is about 3060, x is about 10) and 1.91g of nitrilotriacetic acid (Mw is about 191) are placed in 30g of deionized water, the pH value of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution is reacted for 6 hours at room temperature, thus obtaining the catalystPolylysine macromolecules P alpha LA.
Example 16
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 8.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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, x is approximately equal to 10) and 1.32g of methyl succinic acid (Mw is approximately equal to 132) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 17
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 9.6g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x The molecular weight (Mw) is approximately 9600, wherein the PEG chain segment Mw is approximately 5000, the P alpha L chain segment (Mw is approximately 4600 and x is approximately 15) and 1.14g of glutaric anhydride (Mw is approximately 114) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 18
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 11.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x The molecular weight (Mw) is approximately equal to 11120, 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 1.28g of adipic anhydride (Mw is approximately equal to 128) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, so that the polylysine macromolecules P alpha LA are obtained.
Example 19
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 9.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x 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, 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 20
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: will be6.06g polyethylene glycol-b-poly alpha lysine intermediate PEG-b-palpha L x 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 1.46g of ethylenediamine tetraacetic acid (Mw is approximately equal to 292) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 21
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 6.06g of PEG-b-pαL as an intermediate of polyethylene glycol-b-poly- αlysine x 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 diethyl triamine 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 sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecule P alpha LA.
Example 22
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 14.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x The molecular weight (Mw) is approximately equal to 14120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 9120, x is approximately equal to 30) and 1.46g of ethylenediamine tetraacetic acid (Mw is approximately equal to 292) are placed in 30g of deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 23
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 14.12g of PEG-b-pαL, a polyethylene glycol-b-poly- αlysine intermediate x The molecular weight (Mw) is approximately equal to 14120, wherein the PEG chain segment Mw is approximately equal to 5000, the P alpha L chain segment (Mw is approximately equal to 9120, x is approximately equal to 30) and 1.06g malonic acid (Mw is approximately equal to 106) are placed in 30g deionized water, the pH value of the solution is adjusted to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Example 24
The preparation method of the polylysine macromolecule P alpha LA comprises the following steps: 11.06g of PEG-b-pαL as intermediate of polyethylene glycol-b-poly- αlysine x Molecular weight (Mw) ≡11060, where the PEG segments Mw≡8000, PαL segments (Mw≡3060, x≡10) and 0.96g diethylenetriaminePentaacetic acid (Mw is equal to 393) is added into 30g deionized water, the pH value of the solution is regulated to 8-9 by sodium hydroxide solution, and the solution reacts for 6 hours at room temperature, thus obtaining the polylysine macromolecules P alpha LA.
Performance testing
The invention selects the polycarboxylic acid water reducer (PCE) 0 ) For comparison, the fluidity of the cement paste doped with the novel polylysine macromolecule P alpha LA prepared by the typical example of the present invention was measured with reference to the national standard GB/T8076-2008 concrete admixture, and the concrete results are shown in Table 1.
TABLE 1 fluidity and setting time of Cement paste doped with polylysine macromolecules P alpha LA
As can be seen from Table 1, the polylysine macromolecules P.alpha.LA prepared by the present invention have excellent water-reducing dispersibility, and as can be seen from the typical examples 9, 12, 13, 14, 19, 23, the polylysine macromolecules P.alpha.LA also have excellent cement paste flow properties over time. Meanwhile, the setting time of the cement system doped with the polylysine macromolecules P alpha LA is measured, and the result shows that the setting time is similar to that of the traditional polycarboxylate water reducer, and the setting time has a certain setting retarding effect, and the difference is that the setting retarding effect of the novel polylysine macromolecules P alpha LA obtained by the invention is increased along with the increase of the proportion of grafted carboxylic acid functional monomers.
In addition, because the content and the type region of the mud in the concrete are obviously different, the invention further selects montmorillonite as typical representative clay, and the determination of the paste flow property of the cement/montmorillonite system doped with the polylysine macromolecules P alpha LA prepared by the typical embodiment of the invention is carried out, wherein the concrete experiment comprises the following steps: firstly, the mixing amount (2.0% and cement mass ratio) of polylysine macromolecules P alpha LA is kept unchanged, and the content (1.0%, 2.0%, 3.0%, 4.0% and 5.0% and cement mass ratio) of montmorillonite in cement is changed, so that the test result of the flowing property of cement paste is shown in figure 2; next, the cement paste fluidity with time was tested by keeping the montmorillonite blend amount (2.0%, cement mass ratio) and the polylysine macromolecule pαla blend amount (0.2%, cement mass ratio) unchanged, and the results are shown in fig. 3. The result shows that the polylysine macromolecule P alpha LA of the present invention shows excellent mud resistance sensitivity.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.

Claims (5)

1. A polylysine macromolecule P alpha LA is characterized by using polyethylene glycol-bPoly alpha lysine intermediate PEG-b-PαL x The structural formula of the polymer is shown as (I):
；
wherein m=40-230, x=10-50, a=5-30;
the polyethylene glycol-bPoly alpha lysine intermediate PEG-b-PαL x Wherein the molecular weight Mw of the polyethylene glycol PEG chain segment is 2000-10000; poly alpha lysine palpha L x The molecular weight Mw of the chain segment is 3060-9120;
the carboxylic acid functional monomer refers to carboxylic acid containing two or more carboxyl groups and corresponding anhydride compounds thereof;
r in the formula I 1 Is a skeleton part after the reaction of carboxylic acid functional monomer and amino.
2. The polylysine macromolecule P alpha LA according to claim 1, wherein the carboxylic acid functional monomer is one or more of malonic acid, nitrilotriacetic acid, succinic anhydride, methyl succinic acid, methyl succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, ethylenediamine tetraacetic acid anhydride, diethylenetriamine pentaacetic acid anhydride.
3. The polylysine macromolecule P.alpha.LA according to claim 1 wherein said polyethylene glycol-bPoly alpha lysine intermediate PEG-b-PαL x The molar ratio of the catalyst to the carboxylic acid functional monomer is 1:5.0-30.0.
4. A method for preparing a polylysine macromolecule P alpha LA according to any of claims 1-3, comprising the steps of: polyethylene glycol-bPoly alpha lysine intermediate PEG-b-PαL x And adding the polymer and carboxylic acid functional monomer into deionized water, regulating the pH of the solution to 8-9 by using sodium hydroxide solution, and reacting for 5-12 h at room temperature to obtain the polylysine macromolecule P alpha LA.
5. Use of a polylysine macromolecule P alpha LA according to any of claims 1-3 for building materials, gypsum, ceramics and waterproofing.
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