A kind of polymeric absorbent and preparation method thereof
阅读说明：本技术 一种高分子吸收剂及其制备方法 (A kind of polymeric absorbent and preparation method thereof ) 是由 沈向洋 于 2019-08-06 设计创作，主要内容包括：本发明公开了一种高分子吸收剂及其制备方法,属于功能高分子材料技术领域。所述高分子吸收剂,其主要由以下单体聚合而成,(1)至少包括含卤素的烯烃基单体和含烯烃基的交联单体两种单体,(2)还包括烯烃单体与含烯烃基的酯类单体两种单体的一种或两种。本发明中制备的高分子吸收剂,具有吸收速率快、吸收种类多及良好的阻燃性能,并且合成路线简单、原料便宜；此外,高分子吸收剂根据产品应用环境的需求可以制成不同的样式,并可应用于处理水面石油泄漏、危险有机液体泄漏、低辐射含油废水的处理、风力发电机机油泄漏、实验室及工厂药品应急防护、交通运输行业及高速公路污染控制等情形。(The invention discloses a kind of polymeric absorbents and preparation method thereof, belong to Functional polymer materials technology field.The polymeric absorbent, it is mainly formed by following monomer polymerization, (1) two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base are included at least, (2) further include the one or two of two kinds of monomers of esters monomer of olefinic monomer and olefin-containing base.The polymeric absorbent prepared in the present invention, has that absorption rate is fast, the more and good flame retardant property that absorbs type, and synthetic route is simple, raw material is cheap；Furthermore, different patterns can be made according to the demand of products application environment in polymeric absorbent, and can be applied to processing water surface Oil spills, dangerous organic liquid leakage, the processing of Low emissivity oily waste water, wind-driven generator lubricating oil leakage, laboratory and factory's drug emergency protect, the situations such as traffic transport industry and highway contamination control.)
1. a kind of polymeric absorbent, it is characterised in that:
It is mainly formed by following monomer polymerization,
(1) two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base are included at least,
(2) further include olefinic monomer and olefin-containing base two kinds of monomers of esters monomer one or two；
Wherein shown in halogen-containing alkylene monomer such as formula (I) or formula (II):
In formula, X indicates that Cl or Br, Y indicate H or Cl or Br；
Wherein shown in the cross-linking monomer of olefin-containing base such as divinylbenzene, formula (III) or formula (IV),
In formula, R1Indicate hydrogen atom or alkyl, R2Indicate alkyl or alkylene；
Wherein olefinic monomer be as shown in formula (V) and/or formula (VI),
In formula, R3Indicate alkyl or alkylene, R4Indicate alkyl；
Wherein the esters monomer of olefin-containing base such as formula (VII) or formula (VIII) are shown,
In formula, R5Indicate hydrogen atom or alkyl, R6Indicate the alkyl with 3 carbon or more.
2. a kind of polymeric absorbent according to claim 1, it is characterised in that: in the cross-linking monomer of the olefin-containing base R1For hydrogen atom or methyl.
3. a kind of polymeric absorbent according to claim 1, it is characterised in that: in the cross-linking monomer of the olefin-containing base R2For methyl, ethyl, propyl, vinyl or acrylic.
4. a kind of polymeric absorbent according to claim 1, it is characterised in that: R in the olefinic monomer3For methyl, second Base, propyl, vinyl or acrylic.
5. a kind of polymeric absorbent according to claim 1, it is characterised in that: R in the olefinic monomer4For methyl, second Base, propyl, isopropyl, butyl, amyl, cyclopenta or hexyl.
6. a kind of polymeric absorbent according to claim 1, it is characterised in that: in the esters monomer of the olefin-containing base R5For hydrogen atom or methyl.
7. a kind of polymeric absorbent according to claim 1, it is characterised in that: in the esters monomer of the olefin-containing base R6For-CnH2n+1, wherein n > 3, and n is the integer greater than zero, n takes 4,5,6,7,8,11,20,25 or 32.
8. a kind of preparation method of polymeric absorbent, it is characterised in that:
Include the following steps,
(1) prepare two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base；
(2) prepare the one or two of two kinds of monomers of esters monomer of olefinic monomer and olefin-containing base；
(3) monomer, initiator and the surfactant of the monomer of step (1), step (2) are mixed, inert gas shielding Lower pyroreaction cools down up to polymeric absorbent.
9. a kind of preparation method of polymeric absorbent according to claim 8, it is characterised in that: the initiator was Dibenzoyl is aoxidized, the surfactant is polyvinyl alcohol；The weight percent of the halogen-containing alkylene monomer is 10%-50%, the weight percent of the cross-linking monomer of the olefin-containing base are 0.01%-5%.
Technical field
The invention belongs to Functional polymer materials technology fields, specifically, being related to a kind of polymeric absorbent and its system Preparation Method.
Background technique
With the development of world industry, the human production lifes such as oil carrier accidental pollution, oily waste water discharge, chemical leakage The pollutant that process generates, which produces river, ocean, to be seriously affected, or even seriously threatens ecological environment.People are to environment dirt The concern of dye increasingly increases, for above-mentioned pollution problem is solved, have developed this effective oil product of high oil-absorbing resin absorb and Industrial waste water purifying material.It is different from the physical absorption mechanism of traditional oil absorption material, such material is to form to have inside it The three-dimensional cross-linked reticular structure of one fixed gap, while with the presence of lipophilic ester group in molecular resin, so that oil molecule can To enter resin network internal, it is swollen resin, oil molecule is enclosed in polymer network structure, plays oil suction Protect the effect of oil.Therefore, polymer oil absorption material (also referred to as polymeric absorbent) have oil suction but do not absorb water, oil absorbency is high, Speed of oil absorption is fast, be pressurized after oil suction do not reveal, advantage without secondary pollution, can not only substitute traditional oil absorption material, Er Qieqi Density ratio water is small, still is able to float on the water surface after oil suction, salvages convenient for recycling.But existing polymeric absorbent is for liquid The assimilation effect of body organic chemicals is poor, and absorption liquid organic chemicals type is few, is easy to by liquid organic chemistry to be absorbed Product dissolution, and soak time is too long, additionally, there may be after absorbing inflammable and explosive evaporable liquid organic chemicals that there are flammable Danger.Although existing high-selenium corn efficiency polymeric absorbent has certain oil absorbency, after adding fire retardant, oil suction Performance and efficiency can largely decline, and can not from structure and theoretically speculate the fire retardant for not influenced oil absorption efficiency.
Summary of the invention
1, it to solve the problems, such as
For above-mentioned problems of the prior art, the present invention provides a kind of polymeric absorbent and preparation method thereof, Have that absorption rate is fast, absorbs more than type and good flame retardant property compared with traditional polymeric absorbent, and synthesizes road Line is simple, raw material is cheap, can also be applied to various harsh environments.
2, technical solution
To solve the above problems, technical solution provided by the invention are as follows:
A kind of polymeric absorbent is mainly formed by following monomer polymerization,
(1) two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base are included at least,
(2) further include olefinic monomer and olefin-containing base two kinds of monomers of esters monomer one or two；
It is mainly formed by following monomer polymerization,
(1) two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base are included at least,
(2) further include olefinic monomer and olefin-containing base two kinds of monomers of esters monomer one or two；
Wherein shown in halogen-containing alkylene monomer such as formula (I) or formula (II):
In formula, X indicates that Cl or Br, Y indicate H or Cl or Br；It should be noted that the meaning of "-X " in formula (II), no It only include that single halogen replaces (the position of substitution of unlimited brewed brine element), but also replaces (the substitution position of unlimited brewed brine element including more halogen Set), such as a chlorine replaces, dichloro replaces, trichlorine replaces, monobromo replaces, dibromo replaces, tribromo replaces etc.；
Wherein shown in the cross-linking monomer of olefin-containing base such as divinylbenzene, formula (III) or formula (IV),
In formula, R1Indicate hydrogen atom or alkyl, R2Indicate alkyl or alkylene；
Wherein olefinic monomer be as shown in formula (V) and/or formula (VI),
In formula, R3Indicate alkyl or alkylene, R4Indicate alkyl；
Wherein the esters monomer of olefin-containing base such as formula (VII) or formula (VIII) are shown,
In formula, R5Indicate hydrogen atom or alkyl, R6Indicate the alkyl with 3 carbon or more；
Belong to same homologue with above-mentioned monomer, there can be the substance of phase same-action also to should belong to raw material selection of the invention In scope.
Preferably, R in the cross-linking monomer of the olefin-containing base1For hydrogen atom or methyl.
Preferably, R in the cross-linking monomer of the olefin-containing base2For methyl, ethyl, propyl, vinyl or acrylic.
Preferably, R in the olefinic monomer3For methyl, ethyl, propyl, vinyl or acrylic.
Preferably, R in the olefinic monomer4For methyl, ethyl, propyl, isopropyl, butyl, amyl, cyclopenta or oneself Base.
Preferably, R in the esters monomer of the olefin-containing base5For hydrogen atom or methyl.
Preferably, R in the esters monomer of the olefin-containing base6For-CnH2n+1, wherein n > 3, and n is greater than zero integer, n Take 4,5,6,7,8,11,20,25 or 32.
A kind of preparation method of polymeric absorbent, includes the following steps,
(1) prepare two kinds of monomers of cross-linking monomer of halogen-containing alkylene monomer and olefin-containing base；
(2) prepare the one or two of two kinds of monomers of esters monomer of olefinic monomer and olefin-containing base；
(3) monomer, initiator and the surfactant of the monomer of step (1), step (2) are mixed, inert gas Lower pyroreaction is protected, is cooled down up to polymeric absorbent.
Preferably, the initiator is dibenzoyl peroxide, and the surfactant is polyvinyl alcohol.
Preferably, the weight percent of the halogen-containing alkylene monomer is 10%-50%, the friendship of the olefin-containing base The weight percent of receipts or other documents in duplicate body is 0.01%-5%.
3, beneficial effect
Compared with the prior art, the invention has the benefit that
The polymeric absorbent prepared in the present invention, has that absorption rate is fast, the more and good flame retardant property that absorbs type, And synthetic route is simple, raw material is cheap；In addition, difference can be made according to the demand of products application environment in polymeric absorbent Pattern, and can be applied to processing water surface Oil spills, the leakage of dangerous organic liquid, the processing of Low emissivity oily waste water, wind-force Generator lubricating oil leakage, laboratory and the situations such as the protection of factory's drug emergency, traffic transport industry and highway contamination control.
Detailed description of the invention
Fig. 1 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 1；
Fig. 2 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 2；
Fig. 3 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 3；
Fig. 4 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 4；
Fig. 5 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 5；
Fig. 6 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 6；
Fig. 7 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 7；
Fig. 8 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 8；
Fig. 9 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 9；
Figure 10 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 10；
Figure 11 is the structural formula of the chemical polymeric absorbent of the embodiment of the present invention 11.
Specific embodiment
The present invention is further described below with attached drawing combined with specific embodiments below.
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