CN110508033B - High-molecular absorbent and preparation method thereof - Google Patents

High-molecular absorbent and preparation method thereof Download PDF

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CN110508033B
CN110508033B CN201910722997.4A CN201910722997A CN110508033B CN 110508033 B CN110508033 B CN 110508033B CN 201910722997 A CN201910722997 A CN 201910722997A CN 110508033 B CN110508033 B CN 110508033B
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olefin
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沈向洋
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Hefei Chenwei New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • C—CHEMISTRY; METALLURGY
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    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
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    • C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
    • C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine

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Abstract

The invention discloses a high-molecular absorbent and a preparation method thereof, belonging to the technical field of functional high-molecular materials. The macromolecular absorbent is mainly prepared by polymerizing the following monomers, (1) at least comprising two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer, and (2) further comprising one or two monomers of an olefin monomer and an olefin-containing ester monomer. The macromolecular absorbent prepared by the invention has the advantages of high absorption rate, multiple absorption types, good flame retardant property, simple synthetic route and cheap raw materials; in addition, the polymer absorbent can be made into different types according to the requirements of the application environment of the product, and can be applied to the situations of treating petroleum leakage on the water surface, dangerous organic liquid leakage, low-radiation oily wastewater treatment, wind driven generator oil leakage, laboratory and factory drug emergency protection, transportation industry, highway pollution control and the like.

Description

High-molecular absorbent and preparation method thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a polymer absorbent and a preparation method thereof.
Background
With the development of world industry, pollutants generated in the production and living processes of mankind, such as oil tanker accident pollution, oily wastewater discharge, chemical leakage, and the like, have serious influence on rivers and oceans and even seriously threaten the ecological environment. People pay more attention to environmental pollution, and aiming at solving the pollution problem, an effective oil absorption and industrial wastewater purification material of high oil absorption resin is developed. The material is different from a physical adsorption mechanism of a traditional oil absorption material, a three-dimensional cross-linked network structure with certain gaps is formed in the material, and meanwhile, lipophilic ester groups exist in resin molecules, so that oil molecules can enter a resin network to swell the resin, and are enclosed in the polymer network structure to play a role in absorbing and retaining oil. Therefore, the polymer oil absorption material (also called as polymer absorbent) has the advantages of oil absorption without water absorption, high oil absorption rate, high oil absorption speed, no leakage under pressure after oil absorption and no secondary pollution, can replace the traditional oil absorption material, has lower density than water, can still float on the water surface after oil absorption, and is convenient to recover and salvage. However, the existing polymeric absorbent has poor absorption effect on liquid organic chemicals, has few types of liquid organic chemicals, is easy to be dissolved by the liquid organic chemicals to be absorbed, has overlong absorption time, and has the danger of combustibility after absorbing flammable, explosive and evaporative liquid organic chemicals. Although the conventional high absorption efficiency polymer absorbent has certain oil absorption performance, the oil absorption performance and efficiency of the conventional high absorption efficiency polymer absorbent are greatly reduced after the flame retardant is added, and the flame retardant which does not influence the oil absorption efficiency cannot be obtained by structural and theoretical conjecture.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems in the prior art, the invention provides the polymer absorbent and the preparation method thereof, compared with the traditional polymer absorbent, the polymer absorbent has the advantages of high absorption rate, multiple absorption types, good flame retardant property, simple synthetic route, cheap raw materials and capability of being applied to various harsh environments.
2. Technical scheme
In order to solve the problems, the technical scheme provided by the invention is as follows:
a high molecular absorbent is mainly prepared by polymerizing the following monomers,
(1) at least comprises two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer,
(2) also comprises one or two of olefin monomer and ester monomer containing alkylene;
which is mainly formed by polymerizing the following monomers,
(1) at least comprises two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer,
(2) also comprises one or two of olefin monomer and ester monomer containing alkylene;
wherein the halogen-containing alkylene monomer is represented by formula (I) or formula (II):
Figure BDA0002157893920000021
wherein X represents Cl or Br, and Y represents H, Cl or Br; it is to be noted that the meaning of "— X" in the formula (II) includes not only monohalogen substitution (without limiting the substitution position of halogen) but also polyhalogen substitution (without limiting the substitution position of halogen), such as monochloro substitution, dichloro substitution, trichloro substitution, monobromo substitution, dibromo substitution, tribromo substitution, and the like;
wherein the crosslinking monomer containing alkylene is represented by divinylbenzene, formula (III) or formula (IV),
Figure BDA0002157893920000022
in the formula, R1Represents a hydrogen atom or an alkyl group, R2Represents an alkyl group or an alkenyl group;
wherein the olefin monomer is shown as a formula (V) and/or a formula (VI),
Figure BDA0002157893920000023
Figure BDA0002157893920000031
in the formula, R3Represents an alkyl or alkenyl group, R4Represents an alkyl group;
wherein the ester monomer containing alkylene is shown as a formula (VII) or a formula (VIII),
Figure BDA0002157893920000032
in the formula, R5Represents a hydrogen atom or an alkyl group, R6Represents an alkyl group having 3 or more carbons;
substances which belong to the same homologues as the above-mentioned monomers and which may have the same action are also intended to fall within the scope of the choice of raw materials according to the invention.
Preferably, R in the crosslinking monomer containing an alkenyl group1Is a hydrogen atom or a methyl group.
Preferably, R in the crosslinking monomer containing an alkenyl group2Is methyl, ethyl, propyl, ethenyl or propenyl.
Preferably, R in the olefin monomer3Is methyl, ethyl, propyl, ethenyl or propenyl.
Preferably, R in the olefin monomer4Is methyl, ethyl, propyl, isopropyl, butyl, pentyl, cyclopentyl or hexyl.
Preferably, R in the alkene-containing ester monomer5Is a hydrogen atom or a methyl group.
Preferably, R in the alkene-containing ester monomer6is-CnH2n+1Wherein n is>3 and n is an integer greater than zero, n being 4, 5, 6, 7, 8, 11, 20, 25 or 32.
A preparation method of a macromolecule absorbent comprises the following steps,
(1) preparing two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer;
(2) preparing one or two of an olefin monomer and an ester monomer containing an alkylene;
(3) and (3) mixing the monomer in the step (1), the monomer in the step (2), an initiator and a surfactant, reacting at a high temperature under the protection of inert gas, and cooling to obtain the polymer absorbent.
Preferably, the initiator is dibenzoyl peroxide and the surfactant is polyvinyl alcohol.
Preferably, the weight percentage of the alkenyl monomer containing halogen is 10% -50%, and the weight percentage of the crosslinking monomer containing alkenyl is 0.01% -5%.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the macromolecular absorbent prepared by the invention has the advantages of high absorption rate, multiple absorption types, good flame retardant property, simple synthetic route and cheap raw materials; in addition, the polymer absorbent can be made into different types according to the requirements of the application environment of the product, and can be applied to the situations of treating petroleum leakage on the water surface, dangerous organic liquid leakage, low-radiation oily wastewater treatment, wind driven generator oil leakage, laboratory and factory drug emergency protection, transportation industry, highway pollution control and the like.
Drawings
FIG. 1 is a structural formula of a chemical polymer absorbent in example 1 of the present invention;
FIG. 2 is a structural formula of a chemical polymer absorbent in example 2 of the present invention;
FIG. 3 is a structural formula of a chemical polymer absorbent in example 3 of the present invention;
FIG. 4 is a structural formula of a chemical polymer absorbent in example 4 of the present invention;
FIG. 5 is a structural formula of a chemical polymer absorbent in example 5 of the present invention;
FIG. 6 is a structural formula of a chemical polymer absorbent of example 6 of the present invention;
FIG. 7 is a structural formula of a chemical polymer absorbent of example 7 of the present invention;
FIG. 8 is a structural formula of a chemical polymer absorbent of example 8 of the present invention;
FIG. 9 is a structural formula of a chemical polymer absorbent in example 9 of the present invention;
FIG. 10 is a structural formula of a chemical polymer absorbent in example 10 of the present invention;
FIG. 11 shows the structure of the chemical polymer absorbent of example 11 of the present invention.
Detailed Description
The invention is further described with reference to specific embodiments and the accompanying drawings.
Example 1
Adding 1g of tribromostyrene, 0.02g of divinylbenzene, 2g of butadiene, 5g of dodecyl acrylate and 0.005g of BPO (dibenzoyl peroxide) into a sealed reaction kettle, and then adding 30g of deionized water and 0.5g of polyvinyl alcohol; then introducing pure nitrogen into the sealed reaction kettle, heating to 80 ℃ under stirring, and reacting for 6 hours; and cooling to room temperature after reaction, and filtering and drying the spherical polymer product generated in the sealed reaction kettle to obtain the polymer absorbent.
The structural formula of the polymeric absorbent is shown in figure 1, wherein: wherein L is an integer greater than 0, K is an integer greater than or equal to 0, M is an integer greater than or equal to 0, and N is an integer greater than 0; l, K, M, N is greater than 100 and less than 1000; specifically, the value range of L is 5-200, the value range of K is 100-600, the value range of M is 50-500, and the value range of N is 1-50; further, the value range of L is 10-100, the value range of K is 200-500, the value range of M is 100-300, and the value range of N is 1-20; furthermore, L is in the range of 10-50, K is in the range of 200-500, M is in the range of 100-200, and N is in the range of 1-10. It should be noted that the L, K, M, N value is measured by referring to experiment 30-degree of polymerization of the second experiment in experiment 30 of polymer physics in experiment engineering for polymer materials and engineering profession (Shenxin. polymer materials and engineering profession experiment course [ M ]. Chinese textile Press, 2010.).
The polymer absorbent is in a solid particle shape, the average value of L is 10, the average value of K is 500, the average value of M is 100, the average value of N is 10, and the performance parameters (refer to HG/T5310-;
TABLE 1 technical indices of polymeric absorbents
Figure BDA0002157893920000051
Example 2
Essentially the same as example 1, except that 2g of vinyl chloride was used in place of tribromostyrene of example 1.
The structural formula of the macromolecular absorbent is shown in figure 2; the polymer absorbent is in a solid particle shape, the average value of L is 50, the average value of K is 200, the average value of M is 200, the average value of N is 1, and the performance parameters (refer to HG/T5310-;
TABLE 2 technical indices of polymeric absorbents
Figure BDA0002157893920000061
Example 3
Essentially the same as example 2, except that the butadiene of example 1 was removed.
The structural formula of the macromolecular absorbent is shown in figure 3; the polymer absorbent is in solid particle shape, the average value of L is 100, the average value of K is 200, the average value of M is 300, the average value of N is 20, and the performance parameters (refer to HG/T5310-;
TABLE 3 technical indices of polymeric absorbents
Figure BDA0002157893920000062
Figure BDA0002157893920000071
Example 4
Essentially the same as in example 1, except that 2g of styrene was used in place of the butadiene in example 1.
The structural formula of the macromolecular absorbent is shown in figure 4; the polymer absorbent is in solid particle shape, the average value of L is 80, the average value of K is 400, the average value of M is 250, the average value of N is 15, and the performance parameters (refer to HG/T5310-;
TABLE 4 technical indices of polymeric absorbents
Figure BDA0002157893920000072
Figure BDA0002157893920000081
Example 5
Essentially the same as example 1, except that the butadiene of example 1 was removed.
The structural formula of the macromolecular absorbent is shown in figure 5; the polymer absorbent is in solid particle shape, the average value of L is 5, the average value of K is 600, the average value of M is 50, the average value of N is 50, and the performance parameters (refer to HG/T5310-;
TABLE 5 technical indices of polymeric absorbents
Figure BDA0002157893920000082
Figure BDA0002157893920000091
Example 6
Essentially the same as example 4, except that 4g of butadiene was used instead of the dodecyl acrylate of example 4.
The structural formula of the macromolecular absorbent is shown in figure 6; the polymer absorbent is in solid particle shape, the average value of L is 200, the average value of K is 100, the average value of M is 500, the average value of N is 10, and the performance parameters (refer to HG/T5310-;
TABLE 6 technical indices of polymeric absorbents
Figure BDA0002157893920000092
Figure BDA0002157893920000101
Example 7
Essentially the same as example 1, except that 1, 4-diisopropenylbenzene was used in place of divinylbenzene in example 1.
The structural formula of the macromolecular absorbent is shown in figure 7; the polymeric absorbent is in solid particle shape, the average value of L is 30, the average value of K is 300, the average value of M is 150, the average value of N is 10, and the performance parameters (refer to HG/T5310-;
TABLE 7 technical indices of polymeric absorbents
Figure BDA0002157893920000102
Figure BDA0002157893920000111
Example 8
Essentially the same as example 3, except that ethylene glycol dimethacrylate was used in place of divinylbenzene in example 1.
The reaction process is shown in figure 8; the polymer absorbent is in solid particle shape, the average value of L is 180, the average value of K is 400, the average value of M is 400, the average value of N is 30, and the performance parameters (refer to HG/T5310-;
TABLE 8 technical indices of polymeric absorbents
Figure BDA0002157893920000112
Figure BDA0002157893920000121
Example 9
Essentially the same as example 1, except that vinyl laurate was used in place of the dodecyl acrylate of example 1.
The reaction process is shown in figure 9; the polymer absorbent is in solid particle shape, the average value of L is 40, the average value of K is 350, the average value of M is 200, the average value of N is 30, and the performance parameters (refer to HG/T5310-;
TABLE 9 technical indices of polymeric absorbents
Figure BDA0002157893920000122
Figure BDA0002157893920000131
Example 10
Essentially the same as example 1, except that n-pentyl acrylate was used instead of the dodecyl acrylate of example 1.
The reaction process is shown in figure 10; the polymer absorbent is in solid particle shape, the average value of L is 150, the average value of K is 600, the average value of M is 250, the average value of N is 20, and the performance parameters (refer to HG/T5310-;
TABLE 10 technical indices of polymeric absorbents
Figure BDA0002157893920000132
Figure BDA0002157893920000141
Example 11
Essentially the same as example 1, except that 2-methylstyrene was used in place of divinylbenzene in example 1.
The reaction process is shown in FIG. 11; the polymeric absorbent is in the form of solid particles, the average value of L is 100, the average value of K is 200, the average value of M is 200, the average value of N is 10, and the performance parameters (refer to HG/T5310-;
TABLE 11 technical indices of polymeric absorbents
Figure BDA0002157893920000142
Comparative example 1
Substantially the same as example 7, the structural formula of the polymeric absorbent is shown in FIG. 7, and the polymeric absorbent is in the form of solid particles, except that the average value of L is 250, the average value of K is 650, the average value of M is 150, the average value of N is 10, and the performance parameters (refer to HG/T5310-;
TABLE 12 technical indices of polymeric absorbents
Figure BDA0002157893920000151
Comparative example 2
Substantially the same as example 7, the structural formula of the polymeric absorbent is shown in FIG. 7, and the polymeric absorbent is in the form of solid particles, except that the average value of L is 30, the average value of K is 300, the average value of M is 550, the average value of N is 55, and the performance parameters (refer to HG/T5310-;
TABLE 13 technical indices of polymeric absorbents
Figure BDA0002157893920000161
Comparative example 3
Chinese invention patent, application number: 201810882562.1, publication number: CN108948312A, discloses a styrene-acrylate oil-absorbing swelling elastomer, refer to example 4 of its specification;
the preparation method of the styrene-acrylate oil-absorbing swelling elastomer of the embodiment is as follows:
mixing and stirring 28 parts of lauryl acrylate, 13 parts of ethyl methacrylate, 15 parts of styrene and 6.5 parts of hydroxyethyl acrylate, adding 31 parts of ethyl acetate and 1 part of initiator, and fully stirring and dissolving to obtain a mixture;
dividing the mixture into two parts with equal mass, placing one part in a three-diameter bottle, placing the other part in a constant-pressure dropping funnel, introducing nitrogen into the three-neck flask to remove oxygen in the bottle, controlling the stirring speed to be 300rmp/min, heating the three-diameter bottle to 75 ℃, carrying out heat preservation reaction, after 5 hours of reaction, controlling the liquid in the constant-pressure dropping funnel to drop into the three-diameter bottle within 2 hours of keeping the constant temperature of 75 ℃, and heating to 80 ℃ for reaction for 2 hours. Naturally cooling to room temperature, decompressing and evaporating to completely volatilize the solvent to obtain the oil-absorbing swelling resin.
The performance parameters of the styrene-acrylate oil-absorbing swelling elastomer (refer to HG/T5310-2018 and GB/T2406-2008) are shown in Table 14;
TABLE 14 technical indices
Figure BDA0002157893920000171
Comparative example 4
Chinese invention patent, application number: 201510389589.3, publication number: CN104987591A, disclosing a composite material of foamed polypropylene and polymer absorbent with flame retardant effect and a preparation method thereof, referring to the specific embodiment of the specification;
the composite material of foamed polypropylene and a high molecular absorbent with flame retardant effect is prepared from the following raw materials in parts by weight (kilogram): high melt strength polypropylene 95, low density polyethylene 2, diisopropyl azodicarboxylate 2, polydimethylsiloxane 0.6, antimony trioxide 3, red phosphorus 1, a proper amount of deionized water, methyl cellulose 4, butyl acrylate 13, lauryl methacrylate 7.5, N' -methylene bisacrylamide 0.08, azobisisobutyronitrile 0.5, ethyl acetate 11, and diisooctyl phosphate 2;
the composite material of the foamed polypropylene and the polymer absorbent with the flame-retardant effect is prepared by the following specific steps:
(1) adding methylcellulose into deionized water of 30 times, heating while stirring until the methylcellulose is completely dissolved, cooling to room temperature, sequentially and slowly adding ethyl acetate, N' -methylenebisacrylamide, azobisisobutyronitrile, butyl acrylate, lauryl methacrylate and diisooctyl phosphate under the protection of nitrogen, controlling the stirring speed to be 1000 r/min, slowly heating to 40 ℃, stirring for reaction for 10 minutes, continuously heating to 70 ℃, stirring for reaction for 20 minutes, continuously heating to 80 ℃, stirring for reaction for 1 hour at the speed of 400 r/min to obtain solid microspheres, cooling the reaction system to room temperature, filtering the obtained solid microspheres, washing for 3 times by using deionized water at 80 ℃, and finally drying for 24 hours at 50 ℃ to obtain the high molecular resin microspheres;
(2) putting antimony trioxide, red phosphorus and polydimethylsiloxane into a ball mill, heating to 60-70 ℃, ball-milling for 30 minutes, taking out, then putting the antimony trioxide, the red phosphorus and the polydimethylsiloxane together with low-density polyethylene and diisopropyl azodicarboxylate into a high-speed mixer for uniform mixing, and then extruding and granulating through an extruder to obtain modified particles, wherein the extrusion temperature of the extruder is controlled to be 120 ℃ and the rotation speed of a screw is 300 revolutions per minute;
(3) mixing the high melt strength polypropylene, the foaming modified particles and the polymer resin microspheres obtained in the step (1), putting the mixture into a hopper of a double-screw extruder, heating the extruder to 180 ℃ and 200 ℃, starting a screw knob, plasticizing and mixing for 120 minutes, and performing primary foaming; after the mixture is melted and uniformly plasticized after the cylinder is interrupted, injecting carbon dioxide gas under the condition of 10MPa (the adding amount of the carbon dioxide is controlled to be 10 percent of the mass of the melted material through a flow control valve), keeping for 40 minutes, reducing to normal pressure, and foaming; and extruding the plasticized melt, controlling the temperature of an extruder head to be 200-210 ℃, obtaining a foaming tube with micropores distributed on the side wall, naturally cooling by air, and then granulating by using a special granulator to prepare the particle compounded by the foamed polypropylene and the high polymer resin.
The performance parameters of the composite material of foamed polypropylene and polymer absorbent with flame retardant effect (refer to HG/T5310-2018 and GB/T2406-2008) are shown in Table 15;
TABLE 15 technical indices
Figure BDA0002157893920000181
Figure BDA0002157893920000191
Comparative example 5
Chinese invention patent, application number: 201510389510.7, publication number: CN104987641A, discloses a macromolecular absorbent with double flame-retardant efficacy and a preparation method thereof, and refers to the specific embodiment of the specification;
the macromolecular absorbent with double flame-retardant effects is prepared from the following raw materials in parts by weight (kilogram): 26 parts of methyl acrylate, 18 parts of octadecyl methacrylate, 0.16 part of ethylene glycol dimethacrylate, 4 parts of methyl cellulose, 0.4 part of sodium pyrophosphate, 21 parts of ethyl acetate, 1 part of benzoyl peroxide, 3 parts of ceramic fiber cotton, 2 parts of silicone resin emulsion, 2 parts of melamine cyanurate, 0.9 part of p-methylstyrene, 1.8 parts of divinylbenzene, 1 part of nano aluminum hydroxide, kh4500.05 parts of a silane coupling agent, 1 part of diisooctyl phosphate, 0.5 part of silicone oil and a proper amount of distilled water;
the macromolecular absorbent with double flame-retardant effects is prepared by the following specific steps:
(1) mixing melamine cyanurate and organic silicon resin emulsion, ball-milling for 60 minutes, putting the ceramic fiber cotton into a pulverizer, pulverizing into 200-mesh powder, adding the powder into the ball mill, heating to 40-50 ℃, continuing ball-milling for 30 minutes, taking out, putting into an oven, and drying at 70-80 ℃ to obtain surface-modified mixed powder;
(2) adding methylcellulose into distilled water of 30 times, heating to 80-90 ℃, stirring to quickly dissolve, slowly cooling to room temperature, adding sodium pyrophosphate, stirring to fully dissolve, adding the surface-modified mixed powder obtained in the step (1), stirring uniformly, then sequentially and slowly adding ethyl acetate, ethylene glycol dimethacrylate, benzoyl peroxide, methyl acrylate and octadecyl methacrylate under the protection of nitrogen, controlling the stirring speed to be 1000 rpm, then slowly heating to 40 ℃, stirring for reacting for 10 minutes, then continuously heating to 70 ℃, stirring for reacting for 20 minutes, continuously heating to 80 ℃, and stirring for reacting for 1 hour at the speed of 400 rpm to obtain the polymer resin microspheres;
(3) putting nano aluminum hydroxide and a silane coupling agent kh450 into a ball mill, performing ball milling for 60 minutes, taking out, adding diisooctyl phosphate, continuously stirring and mixing uniformly, then adding p-methylstyrene, divinylbenzene and the rest of components, stirring uniformly, adding into the reaction system in the step (2), controlling the temperature at 80 ℃, and continuously reacting for 1.5 hours at the speed of 1000 revolutions per minute, namely preparing a layer of surface layer structure with high crosslinking degree on the surface of the polymer resin microspheres;
(4) cooling the reaction system to room temperature, filtering the obtained solid polymer microspheres, washing with distilled water at 80 ℃ for 3 times, and finally drying at 50 ℃ for 24 hours to obtain the final product.
The performance parameters of the polymer absorbent with dual flame retardant effects (refer to HG/T5310-2018 and GB/T2406-2008) are shown in Table 16;
TABLE 16 technical indices
Figure BDA0002157893920000201
Figure BDA0002157893920000211
In summary, it can be seen that, by combining tables 1 to 16, the performance parameters of the polymeric absorbents prepared in examples 1 to 11 are significantly better than those of comparative examples 1 to 5, the performance parameters such as absorption rate, retention rate and limiting oxygen index of common organic reagents are all excellent, and the value range of L, K, M, N in the polymeric absorbents also has significant influence on the performance.
Example 12
Specific application of polymeric absorbents in examples 1-11
Hydrosol product: the polymer absorbent is prepared into hydrosol by a conventional emulsion polymerization method; the hydrosol can also be dried by air injection to be made into powder or granular material; in addition, the hydrosol itself can be used to make oil absorbing flame retardant coatings or films.
Bulk material production: the polymer absorbent is made into a block material by a bulk polymerization method; the block material can also be cut into various desired shapes; bulk materials may also be machined into powder or granular materials.
Spherical particle product: the polymer absorbent is made into spherical particles by a suspension polymerization method; the diameter of the spherical particles can be adjusted to 0.1mm-3mm by different stirring speeds and different amounts of dispersant.
An oil absorption bag product: the oil absorption bag is made by wrapping the macromolecule absorbent of the spherical particles in a liquid permeable cloth or film. The oil absorption bag can be used for emergency treatment of dangerous liquid leakage.
A filter material product: filling a high molecular absorbent of spherical particles into a filter column; the filter column can be used for purifying water, and can also be used in an oil-water separator.
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.

Claims (9)

1. A polymeric absorbent characterized by:
which is mainly formed by polymerizing the following monomers,
(1) at least comprises two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer,
(2) also comprises one or two of olefin monomer and ester monomer containing alkylene;
wherein the halogen-containing alkylene monomer is represented by formula (I) or formula (II):
Figure FDA0002957208940000011
wherein X represents Cl or Br, and Y represents H, Cl or Br;
wherein the crosslinking monomer containing alkylene is represented by divinylbenzene, formula (III) or formula (IV),
Figure FDA0002957208940000012
in the formula, R1Represents a hydrogen atom or an alkyl group, R2Represents an alkyl group or an alkenyl group;
wherein the olefin monomer is shown as a formula (V) and/or a formula (VI),
Figure FDA0002957208940000013
Figure FDA0002957208940000021
in the formula, R3Represents an alkyl or alkenyl group, R4Represents an alkyl group;
wherein the ester monomer containing alkylene is shown as a formula (VII) or a formula (VIII),
Figure FDA0002957208940000022
in the formula, R5Represents a hydrogen atom or an alkyl group,R6represents an alkyl group having 3 or more carbons.
2. A polymeric absorbent according to claim 1, wherein: r in the crosslinking monomer containing alkylene1Is a hydrogen atom or a methyl group.
3. A polymeric absorbent according to claim 1, wherein: r in the crosslinking monomer containing alkylene2Is methyl, ethyl, propyl, ethenyl or propenyl.
4. A polymeric absorbent according to claim 1, wherein: r in the olefin monomer3Is methyl, ethyl, propyl, ethenyl or propenyl.
5. A polymeric absorbent according to claim 1, wherein: r in the olefin monomer4Is methyl, ethyl, propyl, isopropyl, butyl, pentyl, cyclopentyl or hexyl.
6. A polymeric absorbent according to claim 1, wherein: r in the alkene group-containing ester monomer5Is a hydrogen atom or a methyl group.
7. A polymeric absorbent according to claim 1, wherein: r in the alkene group-containing ester monomer6is-CnH2n+1Wherein n is greater than 3, n is an integer greater than zero, and n is 4, 5, 6, 7, 8, 11, 20, 25, or 32.
8. A preparation method of a polymer absorbent is characterized by comprising the following steps:
comprises the following steps of (a) carrying out,
(1) preparing two monomers of a halogen-containing olefin-based monomer and an olefin-containing crosslinking monomer;
(2) preparing one or two of an olefin monomer and an ester monomer containing an alkylene;
(3) and (3) mixing the monomer in the step (1), the monomer in the step (2), an initiator and a surfactant, heating for reaction under the protection of inert gas, and cooling to obtain the polymer absorbent.
9. The method for preparing a polymeric absorbent according to claim 8, wherein: the initiator is dibenzoyl peroxide, and the surfactant is polyvinyl alcohol; the weight percentage of the alkenyl monomer containing halogen is 10-50%, and the weight percentage of the crosslinking monomer containing alkenyl is 0.01-5%.
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