阅读说明：本技术 一种高分子聚合物固体水可降解交联剂反应方法及装置 (Reaction method and device for high-molecular polymer solid water degradable cross-linking agent ) 是由 雅罗斯拉夫 杨晓磊 柳宏伟 于 2021-08-02 设计创作，主要内容包括：本发明涉及一种高分子聚合物固体水可降解交联剂反应方法及装置,其方法为在反应装置中将聚酯、氨基酸单体溶于二甲亚砜和二氯甲烷的混合溶液中,加入丙烯酸循环分散后、加入柠康酸酐、引发剂循环聚合反应、真空回收二氯甲烷,加水搅拌沉淀、出料过滤、真空干燥,反应装置包括反应釜,反应釜内设有旋转的搅拌器,反应釜顶部的反应器包括上套、中套和底套,上套与中套内设有第一流腔,第一流腔内设有叶轮、中柱,中套与底套之间设有第二流腔,采用可降解聚酯氨基酸单体在引发剂作用下与丙烯酸、柠康酸酐接枝反应制备改性多肽接枝聚合物交联剂,循环反应提高效率,可作为交联剂用于高分子聚合物固体水的制备提高吸水性、保水性和可降解性。(The invention relates to a reaction method and a device for preparing a high molecular polymer solid water degradable cross-linking agent, wherein the method comprises the steps of dissolving polyester and amino acid monomers in a mixed solution of dimethyl sulfoxide and dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and an initiator for cyclic polymerization, recovering the dichloromethane in vacuum, adding water for stirring and precipitating, discharging, filtering and drying in vacuum, the reaction device comprises a reaction kettle, a rotary stirrer is arranged in the reaction kettle, the reactor at the top of the reaction kettle comprises an upper sleeve, a middle sleeve and a bottom sleeve, a first flow cavity is arranged in the upper sleeve and the middle sleeve, an impeller and a middle column are arranged in the first flow cavity, a second flow cavity is arranged between the middle sleeve and the bottom sleeve, the degradable polyester amino acid monomers are grafted with the acrylic acid and the citraconic anhydride under the action of the initiator to prepare the modified polypeptide grafted polymer cross-linking agent, and the cyclic reaction is improved in efficiency, can be used as a cross-linking agent for preparing high molecular polymer solid water to improve the water absorption, the water retention and the degradability.)

1. A reaction method of a high molecular polymer solid water degradable cross-linking agent is characterized by comprising the following steps: dissolving polyester and amino acid monomers in a mixed solution of dimethyl sulfoxide and dichloromethane in a reaction device, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and an initiator for cyclic polymerization reaction, recovering dichloromethane in vacuum, adding water for stirring and precipitating, discharging and filtering, taking a precipitate, and drying in vacuum to obtain the modified polypeptide grafted polymer crosslinking agent.

2. The method as claimed in claim 1, wherein the polyester is one or more of polylactic acid, polycaprolactone and polyvinyl alcohol.

3. The method as claimed in claim 1, wherein the amino acid monomer is one or more of glycine, aspartic acid, L-lysine, leucine, serine and alanine.

4. The method as claimed in claim 1, wherein the initiator is azobisisobutyronitrile or benzoyl, and the amount of the initiator is 0.5-5% of the total mass of the reaction system of polyester, amino acid monomer, acrylic acid and citraconic anhydride.

5. The method of claim 1, wherein the ratio of the polyester to the amino acid monomer to the dimethyl sulfoxide to the methylene chloride to the acrylic acid to the citraconic anhydride is: (5-15) kg: (85-150) g: 100L: 50L: (75-200) g: (120-200) g.

6. The method as claimed in claim 1, wherein the stirring rate during the cyclic dispersion is 120-140r/min, the stirring rate during the cyclic polymerization reaction is 80-110r/min, the temperature is 35-50 ℃, and the stirring rate during the stirring precipitation is 50-70 r/min.

7. The reaction device of the reaction method of the high molecular polymer solid water degradable crosslinking agent, according to any one of claims 1 to 6, comprising a reaction kettle (1), wherein a rotary stirrer (2) is arranged in the reaction kettle (1), and is characterized in that a reactor (6) is arranged at the top of the reaction kettle (1), the reactor (6) comprises an upper sleeve (61), a middle sleeve (62) and a bottom sleeve (63) which are sequentially connected, an upper inlet (7) is arranged in the upper sleeve (61), a first flow cavity (8) is arranged in the upper sleeve (61), a middle column (10) is arranged in the upper sleeve (61), the bottom of the impeller (9) extends to the top of the bottom sleeve (63), a plurality of helical blades (11) are arranged on the impeller (9), the cross section of the middle column (10) is of a T-shaped structure, and is provided with a middle hole (12), A plurality of perforations (13) communicating with the central hole (12);

be equipped with side import (14) with first stream chamber (8) intercommunication on well cover (62), be equipped with between well cover (62) and end cover (63) and be located center pillar (10) outside, with second stream chamber (15) of perforation (13) intercommunication, be equipped with on end cover (63) and export (16) with reation kettle (1) and mesopore (12) intercommunication, all be connected with inlet pipe (25) on reation kettle (1) top, last import (7), side import (14), all be connected with circulating pipe (26) between reation kettle (1) bottom and last import (7), side import (14), be equipped with circulating pump (27) on circulating pipe (26).

8. The reaction device of the reaction method of the high molecular polymer solid water degradable crosslinking agent according to claim 7, wherein the servo motor (3) is arranged at the top of the reaction kettle (1), the stirrer (2) comprises a stirring shaft (21) coaxially connected with the servo motor (3), a plurality of side scrapers (22) connected with the stirring shaft (21) and at least one bottom scraper (23), the side scrapers (22) are spiral-belt-shaped and are sequentially arranged in a deflecting spiral manner, a plurality of connecting rods (4) are arranged between the side scrapers (22) and the stirring shaft (21), stirring blades (5) obliquely arranged in opposite directions are arranged on the connecting rods (4), and the bottom scraper (23) is in a C-shaped structure.

9. The reaction device for the reaction method of the high molecular polymer solid water degradable crosslinking agent according to claim 7, wherein the center of the impeller (9) is in an arc structure, at least one notch (17) is formed at the bottom of the impeller (9) and the bottom of the center pillar (10), the first boss (18) matched with the notch (17) is formed at the top of the center pillar (10) and the top of the bottom sleeve (63), the second boss (19) is formed on the center pillar (10), the support plate (20) matched with the bottom of the first boss (18) and the outside of the center pillar (10) is formed in the center sleeve (62), and a plurality of through holes (24) communicated with the first flow cavity (8) and the second flow cavity (15) are formed in the support plate (20).

10. The reaction device for the reaction method of the high molecular polymer solid water degradable crosslinking agent according to claim 7, wherein a discharge pipe (28) connected with a circulating pipe (26) is arranged at the bottom of the reaction kettle (1), and a three-way valve (29) is arranged between the discharge pipe (28) and a feed pipe (25) connected with the upper inlet (7) and the side inlet (14) and the circulating pipe (26).

Technical Field

The invention relates to a reaction method and a device of a high molecular polymer solid water degradable cross-linking agent, belonging to the technical field of solid water production.

Background

At present, the polyacrylamide/acrylate water-absorbing resin is a main product of water-retaining water-absorbing resin, has high cost, cannot be degraded and easily causes environmental pollution, the high-molecular polymer solid water is a high-molecular water-absorbing material, has strong water-absorbing property and water-retaining property, can absorb water with the weight of hundreds of times, is not evaporated when being exposed in the air and cannot permeate when being dispersed into soil, can be reduced into free water to be released in the soil with microorganisms around the root system of a plant, and can be widely applied to the fields of agriculture, forestry, water conservancy, sand industry and the like to play multiple functions of drought resistance, seedling protection, yield increase, soil improvement, wind prevention, sand fixation, water and soil conservation and the like. The physical and chemical properties of the polymer can be improved by connecting linear or branched polymer chains of the cross-linked modified water-absorbing high-molecular polymer monomer into a net-shaped or body-shaped high polymer through covalent bonds, the polymer prepared by using common cross-linking agents such as N, N-dimethylformamide, N-methylene-bisacrylamide and the like is generally not degradable, the application of solid water in the field of agriculture and forestry is limited, meanwhile, a single reaction kettle with a stirrer has weak combination promotion capability, is easy to generate wall deposition, influences the reaction efficiency and uniformity of the cross-linking agent, and is difficult to meet the requirement of the batch production of the high-molecular polymer solid water.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a reaction method and a device of a high molecular polymer solid water degradable cross-linking agent.

The invention is realized by the following technical scheme:

a reaction method of a high molecular polymer solid water degradable cross-linking agent is as follows: dissolving polyester and amino acid monomers in a mixed solution of dimethyl sulfoxide and dichloromethane in a reaction device, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and an initiator for cyclic polymerization reaction, recovering dichloromethane in vacuum, adding water for stirring and precipitating, discharging and filtering, taking a precipitate, and drying in vacuum to obtain the modified polypeptide grafted polymer crosslinking agent.

The reaction method of the high molecular polymer solid water degradable crosslinking agent comprises the following steps of (1) preparing a polyester, wherein the polyester is one or more of polylactic acid, polycaprolactone and polyvinyl alcohol, the amino acid monomer is one or more of glycine, aspartic acid, L-lysine, leucine, serine and alanine, the initiator is azobisisobutyronitrile or benzoyl, the dosage of the initiator accounts for 0.5-5% of the total mass of the reaction system of the polyester, the amino acid monomer, acrylic acid and citraconic anhydride, and the proportion of the polyester, the amino acid monomer, dimethyl sulfoxide, dichloromethane, acrylic acid and citraconic anhydride is as follows: (5-15) kg: (85-150) g: 100L: 50L: (75-200) g: (120-200) g.

The reaction method of the high molecular polymer solid water degradable cross-linking agent comprises the steps of stirring at a speed of 120-140r/min during cyclic dispersion, stirring at a speed of 80-110r/min during cyclic polymerization, and stirring at a temperature of 35-50 ℃ during stirring precipitation at a speed of 50-70 r/min.

The reaction device comprises a reaction kettle, wherein a rotary stirrer is arranged in the reaction kettle, a servo motor is arranged at the top of the reaction kettle, the stirrer comprises a stirring shaft coaxially connected with the servo motor, a plurality of side scrapers and at least one bottom scraper, the side scrapers are connected with the stirring shaft, the side scrapers are spiral-belt-shaped and sequentially deflect and spirally arranged, a plurality of connecting rods are arranged between the side scrapers and the stirring shaft, stirring blades which are obliquely arranged in opposite directions are arranged on the connecting rods, and the bottom scraper is of a C-shaped structure;

the reactor is arranged at the top of the reaction kettle and comprises an upper sleeve, a middle sleeve and a bottom sleeve which are sequentially connected, a first flow cavity is arranged in the upper sleeve, an impeller positioned at the bottom of the upper sleeve and a middle column positioned at the bottom of the impeller and extending to the inner top of the bottom sleeve are arranged in the upper sleeve, a plurality of helical blades are arranged on the impeller, the cross section of the middle column is of a T-shaped structure and is provided with a middle hole and a plurality of perforation holes communicated with the middle hole;

the middle sleeve is provided with a side inlet communicated with the first flow cavity, a second flow cavity which is positioned outside the middle column and communicated with the perforation hole is arranged between the middle sleeve and the bottom sleeve, the bottom sleeve is provided with a bottom outlet communicated with the reaction kettle and the middle hole, the center of the impeller is of an arc structure, the bottom of the impeller and the bottom of the middle column are both provided with at least one notch, the top of the middle column and the top of the bottom sleeve are provided with first bosses matched with the notches, the middle column is provided with second bosses, the middle sleeve is internally provided with a supporting plate matched with the bottom of the first bosses and the outside of the middle column, and the supporting plate is provided with a plurality of through holes communicated with the first flow cavity and the second flow cavity;

the reactor comprises a reaction kettle, and is characterized in that the top of the reaction kettle, an upper inlet and a side inlet are connected with feed pipes, circulating pipes are connected between the bottom of the reaction kettle and the upper inlet and between the bottom of the reaction kettle and the side inlet, circulating pumps are arranged on the circulating pipes, a discharge pipe connected with the circulating pipes is arranged at the bottom of the reaction kettle, and three-way valves are arranged between the discharge pipe, the feed pipes connected with the upper inlet and the side inlet and the circulating pipes.

The invention has the beneficial effects that:

(1) degradable polyester polylactic acid, polycaprolactone and polyvinyl alcohol high molecular polymer are adopted, amino acid monomers are dissolved in mixed solution of dimethyl sulfoxide and dichloromethane and are subjected to graft reaction with acrylic acid and citraconic anhydride under the action of an initiator to prepare a modified polypeptide graft polymer cross-linking agent, the amino acid contains hydrophilic side amino groups, the polypeptide formed by peptide bond coupling, dehydration and condensation is degradable, the hydrophilicity and the swelling rate of the degradable polyester are effectively improved, the modified polypeptide graft polymer cross-linking agent and acrylic acid/citraconic anhydride are subjected to graft modification under the activation effect of azo-bis-isobutyronitrile or benzoyl as an initiator, the yield is improved, branched chains are increased by grafting, and vinyl and carboxyl unsaturated olefin monomers are introduced, so that the modified polypeptide graft polymer cross-linking agent can be used for preparing high molecular polymer solid water to improve the water absorption, the water retention and the degradability.

(2) The stirrer of the reaction device adopts a helical ribbon-shaped side scraper to continuously scrape the inner wall surface of the kettle body and generate axial flow, a bottom scraper in a C-shaped structure continuously scrapes the bottom of the kettle body to prevent the wall surface from depositing and adhering and generate annular shear flow, and stirring blades increase turbulence and improve collision mass transfer efficiency during stirring;

the material entering the upper sleeve from the upper inlet is centrifugally accelerated to shoot into the first flow cavity outside the impeller through the gap between the spiral blade of the impeller and the upper sleeve, the material collides with the inner wall of the upper sleeve to accelerate the mass transfer reaction efficiency and pressure, the material entering the first flow cavity from the side inlet is further mixed, uniformly dispersed to enter the second flow cavity along a plurality of through holes of the supporting disc, flows and collides to a middle hole through a plurality of perforations of the middle column at a Y-shaped high speed, the mass transfer reaction efficiency is accelerated, and the grafting reaction rate, the grafting rate and the yield are increased.

Drawings

FIG. 1 is a schematic diagram of a reaction apparatus according to the present invention.

FIG. 2 is a view showing the construction of the agitator of the present invention.

FIG. 3 is a cross-sectional view of a reactor according to the present invention.

FIG. 4 is a top perspective view of the reactor assembly of the present invention.

FIG. 5 is a bottom perspective view of the reactor assembly of the present invention.

The labels in the figure are: the device comprises a reaction kettle 1, a stirrer 2, a servo motor 3, a stirring shaft 21, a side scraper 22, a bottom scraper 23, a connecting rod 4, a stirring blade 5, a reactor 6, an upper sleeve 61, a middle sleeve 62, a bottom sleeve 63, an upper inlet 7, a first flow cavity 8, an impeller 9, a middle column 10, a spiral blade 11, a middle hole 12, a perforation hole 13, a side inlet 14, a second flow cavity 15, a bottom outlet 16, a notch 17, a first boss 18, a second boss 19, a supporting plate 20, a through hole 24, a feeding pipe 25, a circulating pipe 26, a circulating pump 27, a discharging pipe 28 and a three-way valve 29.

Detailed Description

The following description of the embodiments of the present invention will be made with reference to the accompanying drawings.

A reaction device of a reaction method of a high molecular polymer solid water degradable cross-linking agent comprises a reaction kettle 1, wherein a rotary stirrer 2 is arranged in the reaction kettle 1, a servo motor 3 is arranged at the top of the reaction kettle 1, the stirrer 2 comprises a stirring shaft 21 coaxially connected with the servo motor 3, a plurality of side scrapers 22 connected with the stirring shaft 21 and at least one bottom scraper 23, the side scrapers 22 are in a spiral belt shape and are sequentially arranged in a deflection spiral manner, a plurality of connecting rods 4 are arranged between the side scrapers 22 and the stirring shaft 21, stirring blades 5 which are arranged in an opposite inclined manner are arranged on the connecting rods 4, and the bottom scrapers 23 are in a C-shaped structure;

the reactor 6 is arranged at the top of the reaction kettle 1, the reactor 6 comprises an upper sleeve 61, a middle sleeve 62 and a bottom sleeve 63 which are sequentially connected, an upper inlet 7 is arranged in the upper sleeve 61, a first flow cavity 8 is arranged in the upper sleeve 61 and the middle sleeve 62, an impeller 9 positioned at the bottom in the upper sleeve 61 and a center column 10 positioned at the bottom of the impeller 9 and extending to the top in the bottom sleeve 63 are arranged in the first flow cavity 8, a plurality of helical blades 11 are arranged on the impeller 9, the cross section of the center column 10 is of a T-shaped structure and is provided with a center hole 12 and a plurality of perforation holes 13 communicated with the center hole 12;

the middle sleeve 62 is provided with a side inlet 14 communicated with the first flow cavity 8, a second flow cavity 15 which is positioned outside the middle column 10 and communicated with the perforation 13 is arranged between the middle sleeve 62 and the bottom sleeve 63, the bottom sleeve 63 is provided with a bottom outlet 16 communicated with the reaction kettle 1 and the middle hole 12, the center of the impeller 9 is of an arc structure, the bottom of the impeller 9 and the bottom of the middle column 10 are both provided with at least one notch 17, the top of the middle column 10 and the top of the bottom sleeve 63 are provided with first bosses 18 matched with the notches 17, the middle column 10 is provided with second bosses 19, the middle sleeve 62 is internally provided with a support plate 20 matched with the bottom of the first bosses 18 and the outside of the middle column 10, and the support plate 20 is provided with a plurality of through holes 24 communicated with the first flow cavity 8 and the second flow cavity 15;

all be connected with inlet pipe 25 on reation kettle 1 top, last inlet 7, the side import 14, all be connected with circulating pipe 26 between reation kettle 1 bottom and last inlet 7, the side import 14, be equipped with circulating pump 27 on the circulating pipe 26, discharging pipe 28 that reation kettle 1 bottom and circulating pipe 26 link to each other all is equipped with three-way valve 29 between discharging pipe 28, the inlet pipe 25 that links to each other with last inlet 7, side import 14 and circulating pipe 26.

Example 1:

a reaction method of a high molecular polymer solid water degradable cross-linking agent comprises the following specific steps:

s1: adding 12kg of polyester, 130g of amino acid monomer, 100L of dimethyl sulfoxide and 50L of dichloromethane into a reaction kettle 1 from a feeding pipe 25 at the top of the reaction kettle 1, stirring and mixing, and stirring for 15min at a stirring speed of 120 r/min; the polyester is polylactic acid, and the amino acid monomer is glycine and aspartic acid in a mass ratio of 1:1 combining;

s2: 138g of acrylic acid is added into the reactor 6 through the feeding pipe 25 of the upper inlet 7, the three-way valve 29 is controlled, the circulating pump 27 is started, the mixed solution of the polyester, the amino acid monomer, the dimethyl sulfoxide and the dichloromethane in the reaction kettle 1 enters the reactor 6 through the side inlet 14 through the circulating pipe 26 and flows into the reaction kettle 1 from the bottom outlet 16, and the stirring circulation dispersion is carried out for 15min at the stirring speed of 130 r/min;

s3: a control three-way valve 29 and feeding pipes 25 of an upper inlet 7 and a side inlet 14 respectively add 180g of citraconic anhydride and an initiator with the amount of 1 percent of the total mass of the polyester, amino acid monomer, acrylic acid and citraconic anhydride reaction system into the reactor 6, wherein the initiator is azobisisobutyronitrile, and the initiator flows into the reaction kettle 1 from a bottom outlet 16;

the feed pipe 25 is closed by controlling the three-way valve 29, the circulating pump 27 is started, the materials in the reaction kettle 1 enter the reactor 6 through the circulating pipe 26 and the upper inlet 7 and the side inlet 14, and flow in parallel and enter the reaction kettle 1 from the bottom outlet 16, the stirring speed is 105r/min, and the temperature is 42 ℃ for cyclic polymerization for 2.5 hours;

s4: and (3) closing the circulating pump 27, adding water into the reaction kettle 1, stirring and precipitating for 30min at the stirring speed of 60r/min, discharging, filtering, taking precipitate, and drying in vacuum to obtain the modified polypeptide graft polymer cross-linking agent with the yield of 75.3%.

Example 2:

a reaction method of a high molecular polymer solid water degradable cross-linking agent comprises the following specific steps:

s1: adding 14kg of polyester, 90g of amino acid monomer, 100L of dimethyl sulfoxide and 50L of dichloromethane into a reaction kettle 1 from a feeding pipe 25 at the top of the reaction kettle 1, stirring and mixing, and stirring for 12min at a stirring speed of 130 r/min; the polyester is polycaprolactone, and the amino acid monomer is L-lysine and leucine in a mass ratio of 1:1 combining;

s2: adding 165g of acrylic acid into the reactor 6 through a feeding pipe 25 of an upper inlet 7, controlling a three-way valve 29, starting a circulating pump 27, feeding a mixed solution of polyester, amino acid monomer, dimethyl sulfoxide and dichloromethane in the reaction kettle 1 into the reactor 6 through a circulating pipe 26 through a side inlet 14, enabling the mixed solution to flow in parallel into the reaction kettle 1 from a bottom outlet 16, and stirring and circularly dispersing for 12min at a stirring speed of 130 r/min;

s3: respectively adding 170g of citraconic anhydride and an initiator which accounts for 1.3 percent of the total mass of the polyester, the amino acid monomer, the acrylic acid and the citraconic anhydride into the reactor 6 through a control three-way valve 29 and a feeding pipe 25 of an upper inlet 7 and a side inlet 14, wherein the initiator is azobisisobutyronitrile, and the initiator flows into the reaction kettle 1 from a bottom outlet 16;

the feed pipe 25 is closed by controlling the three-way valve 29, the circulating pump 27 is started, the materials in the reaction kettle 1 enter the reactor 6 through the circulating pipe 26 and the upper inlet 7 and the side inlet 14, and flow in parallel and enter the reaction kettle 1 from the bottom outlet 16, and the cyclic polymerization reaction is carried out for 3 hours at the stirring speed of 95r/min and the temperature of 45 ℃;

s4: and (3) closing the circulating pump 27, adding water into the reaction kettle 1, stirring and precipitating for 30min at the stirring speed of 55r/min, discharging, filtering, taking the precipitate, and drying in vacuum to obtain the modified polypeptide graft polymer cross-linking agent with the yield of 69.4%.

Example 3:

a reaction method of a high molecular polymer solid water degradable cross-linking agent comprises the following specific steps:

s1: adding 8kg of polyester, 100g of amino acid monomer, 100L of dimethyl sulfoxide and 50L of dichloromethane into a reaction kettle 1 from a feeding pipe 25 at the top of the reaction kettle 1, stirring and mixing, and stirring for 14min at the stirring speed of 135 r/min; the polyester is composed of polylactic acid and polyvinyl alcohol according to a mass ratio of 1:1, and the amino acid monomer is composed of serine and alanine according to a mass ratio of 1:1, preparing a composition;

s2: adding 90g of acrylic acid into the reactor 6 through the feeding pipe 25 of the upper inlet 7, controlling the three-way valve 29, starting the circulating pump 27, feeding the mixed solution of polyester, amino acid monomer, dimethyl sulfoxide and dichloromethane in the reaction kettle 1 into the reactor 6 through the circulating pipe 26 through the side inlet 14, and feeding the mixed solution into the reaction kettle 1 from the bottom outlet 16 in a parallel flow manner, and stirring and circularly dispersing for 15min at the stirring speed of 120 r/min;

s3: a control three-way valve 29 and feeding pipes 25 of an upper inlet 7 and a side inlet 14 respectively feed 190g of citraconic anhydride and an initiator which accounts for 3 percent of the total mass of the polyester, amino acid monomer, acrylic acid and citraconic anhydride reaction system into the reactor 6, wherein the initiator is benzoyl, and the benzoyl flows into the reaction kettle 1 from a bottom outlet 16;

the feed pipe 25 is closed by controlling the three-way valve 29, the circulating pump 27 is started, the materials in the reaction kettle 1 enter the reactor 6 through the circulating pipe 26 and the upper inlet 7 and the side inlet 14, and flow in parallel and enter the reaction kettle 1 from the bottom outlet 16, the stirring speed is 105r/min, and the temperature is 50 ℃ for cyclic polymerization reaction for 3 hours;

s4: and (3) closing the circulating pump 27, adding water into the reaction kettle 1, stirring and precipitating for 30min at the stirring speed of 65r/min, discharging, filtering, taking precipitate, and drying in vacuum to obtain the modified polypeptide graft polymer cross-linking agent with the yield of 66.1%.

The stirring shaft 21 is driven by the servo motor 3 to rotate in the reaction kettle 1, a plurality of spiral-belt-shaped side scrapers 22 which are sequentially deflected by a spiral are driven to continuously scrape the inner wall surface of a kettle body and generate axial flow, a bottom scraper 23 which is of a C-shaped structure continuously scrapes the bottom of the kettle body to prevent wall surface deposition and adhesion and generate annular shear flow, and a plurality of connecting rods 4 support the side scrapers 22 and increase turbulence through stirring blades 5 which are obliquely arranged oppositely, so that collision mass transfer and heat transfer efficiency during stirring are improved;

the bottom of the impeller 9 is clamped with a first boss 18 at the top of the central column through at least one notch 17 to ensure the positioning of the impeller 9, the impeller 9 is arranged at the bottom in the upper sleeve 61 to fix the impeller 9, the central column 10 is matched with the bottom of a second boss 19 and the outside of the central column 10 through a support plate 20 to be limited and supported, the bottom is matched with the first boss 18 of the bottom sleeve 63 through the first notch 17 to be positioned and hermetically assembled to prevent the deflection displacement of the impeller 9 and the central column 10, and the upper sleeve 61, the central sleeve 62 and the bottom sleeve 63 are connected through flanges to realize the assembly of the reactor 6;

the materials entering the upper sleeve 61 from the upper inlet 7 and centrifugally accelerated to shoot into the first flow cavity 8 outside the impeller 9 through the gap between the helical blades 11 of the impeller 9 and the upper sleeve 61, the material flow collides with the inner wall of the upper sleeve 61 to accelerate the mass transfer reaction efficiency and pressure, the center of the impeller 9 is in an arc structure to play a role of buffering and drainage, the materials entering the first flow cavity 8 from the upper inlet 7 and the materials entering the first flow cavity 8 from the side inlet 14 are further mixed, uniformly dispersed to enter the second flow cavity 15 along a plurality of through holes 24 of the supporting disc, flow and collide to the middle hole 12 through a plurality of perforations 13 of the middle column 10 at a Y-shaped high speed to accelerate the mass transfer reaction efficiency, and are ejected to the reaction kettle 1 along the bottom outlet 16 of the lower sleeve in a cavitation mode, so that the grafting reaction rate, the grafting rate and the yield are increased;

the cross-linking agent N, N-dimethylformamide is used as a comparative example, and the cross-linking agent of the modified polypeptide graft polymer prepared in the examples 1 to 3 and the acrylamide monomer are respectively subjected to cross-linking reaction to prepare a gel material for detection:

and (3) water absorption detection: weighing 0.5g of gel material, putting the gel material into a beaker, adding water to fully swell, filtering to remove excessive water, weighing the mass of the water-absorbing gel, and calculating the water absorption times, wherein the water absorption times of the comparative example and the examples 1-3 are 105, 468, 405 and 383 times respectively;

and (3) water retention rate detection: weighing 0.15g of gel material, placing the gel material in distilled water, standing, swelling and weighing m1, processing the gel material by a centrifugal machine 4000R/min for 5min, weighing m2, and calculating according to the water retention rate R being m2/m1 x 100 percent, wherein the water retention rates of the comparative example and the examples 1-3 are 32.8 percent, 79.4 percent, 82.1 percent and 69.9 percent respectively;

weighing 75mg of helicase, dissolving the helicase in 50nl of buffer solution of acetic acid and sodium acetate, and stirring the solution at 40 ℃ to measure the degradation rate, wherein the comparative example cannot be completely degraded, and the complete degradation time of examples 1, 2 and 3 is 45h, 52h and 39h respectively;

degradable polyester polylactic acid, polycaprolactone and polyvinyl alcohol high molecular polymer are adopted, amino acid monomers are dissolved in mixed solution of dimethyl sulfoxide and dichloromethane and are subjected to graft reaction with acrylic acid and citraconic anhydride under the action of an initiator to prepare a modified polypeptide graft polymer cross-linking agent, amino acids including but not limited to glycine, aspartic acid, L-lysine, leucine, serine and alanine contain hydrophilic side amino groups, the polypeptide formed by peptide bond coupling, dehydration and condensation is degradable, the hydrophilicity and the swelling rate of the degradable polyester are effectively improved, the modified polypeptide graft polymer cross-linking agent and acrylic acid/citraconic anhydride are subjected to graft modification under the activation action of azo diisobutyronitrile or benzoyl as the initiator, the yield is improved, branched chains are increased by grafting, vinyl and carboxyl unsaturated olefin monomers are introduced, and the modified polypeptide graft polymer cross-linking agent can be used for preparing high molecular polymer solid water to improve water absorption, and, Water retention and degradability.

In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; either mechanically or indirectly through intervening media, or both. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.