CN110508033A - A kind of polymeric absorbent and preparation method thereof - Google Patents
A kind of polymeric absorbent and preparation method thereof Download PDFInfo
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- CN110508033A CN110508033A CN201910722997.4A CN201910722997A CN110508033A CN 110508033 A CN110508033 A CN 110508033A CN 201910722997 A CN201910722997 A CN 201910722997A CN 110508033 A CN110508033 A CN 110508033A
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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
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- 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
- 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
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- 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
Abstract
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.
Description
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.
Embodiment 1
By 1g phenylstilbene bromide, 0.02g divinylbenzene, 2g butadiene, 5g dodecyl acrylate and 0.005g BPO
Sealing reaction kettle is added in (dibenzoyl peroxide), adds 30g deionized water and 0.5g polyvinyl alcohol；Then toward sealing reaction
It is passed through pure nitrogen gas in kettle, 80 DEG C are warming up under stirring, reacts 6h；Room temperature is cooled to after reaction, by what is generated in sealing reaction kettle
The filtering of spherical high polymer product and drying, obtain polymeric absorbent.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 1, in formula: where L is integer greater than 0, K be greater than etc.
In 0 integer, M is the integer more than or equal to 0, and N is the integer greater than 0；L, the summation of K, M, N are greater than 100 less than 1000；Specifically
Ground, the numberical range of L are 5-200, and the numberical range of K is 100-600, and the numberical range of M is 50-500, and the numberical range of N is
1-50；Further, the numberical range of L is 10-100, the number of the numberical range 100-300, N of the numberical range 200-500, M of K
It is worth range 1-20；Further, the numberical range of L is 10-50, and the numberical range of K is 200-500, and the numberical range of M is
The numberical range of 100-200, N are 1-10.It should be noted that the measurement of above-mentioned L, K, M, N numerical value, with reference to " high molecular material
With Engineering Speciality experiment textbook " (Shen Xinyuan polymer materials and engineering experiment textbook [M] China Textiles Press,
2010.) second " Experiment of Polymer Chemistry " " measurement of the experiment 30--- degree of polymerization " carries out the survey of degree of polymerization average value in
It is fixed.
Solid granular is presented in the polymeric absorbent, and the mean values that the mean values of L are 10, K are 500, M's
The mean values that mean values are 100, N are 10, performance parameter (referring to HG/T 5310-2018 and GB/T 2406-2008)
As described in Table 1；
The technical indicator of 1 polymeric absorbent of table
Embodiment 2
It is substantially the same with embodiment 1, the difference is that replacing the phenylstilbene bromide of embodiment 1 using 2g vinyl chloride.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 2；Solid granular, L is presented in the polymeric absorbent
Mean values be 50, K mean values be 200, M mean values be 200, N mean values be 1, performance parameter (ginseng
According to HG/T 5310-2018 and GB/T 2406-2008) as described in Table 2；
The technical indicator of 2 polymeric absorbent of table
Embodiment 3
It is substantially the same with embodiment 2, the difference is that the butadiene of removal embodiment 1.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 3；Solid granular, L is presented in the polymeric absorbent
Mean values be 100, K mean values be 200, M mean values be 300, N mean values be 20, performance parameter
(referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 3；
The technical indicator of 3 polymeric absorbent of table
Embodiment 4
It is substantially the same with embodiment 1, the difference is that replacing the butadiene of embodiment 1 using 2g styrene.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 4；Solid granular, L is presented in the polymeric absorbent
Mean values be 80, K mean values be 400, M mean values be 250, N mean values be 15, performance parameter
(referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 4；
The technical indicator of 4 polymeric absorbent of table
Embodiment 5
It is substantially the same with embodiment 1, the difference is that the butadiene of removal embodiment 1.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 5；Solid granular, L is presented in the polymeric absorbent
Mean values be 5, K mean values be 600, M mean values be 50, N mean values be 50, performance parameter (ginseng
According to HG/T 5310-2018 and GB/T 2406-2008) as described in Table 5；
The technical indicator of 5 polymeric absorbent of table
Embodiment 6
It is substantially the same with embodiment 4, the difference is that replacing the dodecyl propylene of embodiment 4 using 4g butadiene
Acid esters.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 6；Solid granular, L is presented in the polymeric absorbent
Mean values be 200, K mean values be 100, M mean values be 500, N mean values be 10, performance parameter
(referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 6；
The technical indicator of 6 polymeric absorbent of table
Embodiment 7
It is substantially the same with embodiment 1, the difference is that replacing the diethyl of embodiment 1 using Isosorbide-5-Nitrae-di isopropenylbenzene
Alkene benzene.
The structural formula of above-mentioned polymeric absorbent is as shown in Figure 7；Solid granular is presented in the polymeric absorbent, L
Mean values be 30, K mean values be 300, M mean values be 150, N mean values be 10, performance parameter
(referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 7；
The technical indicator of 7 polymeric absorbent of table
Embodiment 8
It is substantially the same with embodiment 3, the difference is that replacing embodiment 1 using ethylene glycol dimethacrylate
Divinylbenzene.
Above-mentioned reaction process is as shown in Figure 8；Solid granular is presented in the polymeric absorbent, and the mean values of L are
The mean values that the mean values that 180, K mean values are 400, M are 400, N are 30, and performance parameter is (referring to HG/T
5310-2018 and GB/T 2406-2008) as described in Table 8；
The technical indicator of 8 polymeric absorbent of table
Embodiment 9
It is substantially the same with embodiment 1, the difference is that replacing the dodecyl of embodiment 1 using vinyl laurate
Acrylate.
Above-mentioned reaction process is as shown in Figure 9；Solid granular is presented in the polymeric absorbent, and the mean values of L are
The mean values that the mean values that 40, K mean values are 350, M are 200, N are 30, and performance parameter is (referring to HG/T
5310-2018 and GB/T 2406-2008) as described in Table 9；
The technical indicator of 9 polymeric absorbent of table
Embodiment 10
It is substantially the same with embodiment 1, the difference is that replacing the dodecyl of embodiment 1 using acrylic acid n-pentyl ester
Acrylate.
Above-mentioned reaction process is as shown in Figure 10；Solid granular is presented in the polymeric absorbent, and the mean values of L are
The mean values that the mean values that 150, K mean values are 600, M are 250, N are 20, and performance parameter is (referring to HG/T
5310-2018 and GB/T 2406-2008) as described in Table 10；
The technical indicator of 10 polymeric absorbent of table
Embodiment 11
It is substantially the same with embodiment 1, the difference is that replacing the divinylbenzene of embodiment 1 using 2-methyl styrene.
Above-mentioned reaction process is as shown in figure 11；Solid granular is presented in the polymeric absorbent, and the mean values of L are
The mean values that the mean values that 100, K mean values are 200, M are 200, N are 10, and performance parameter is (referring to HG/T
5310-2018 and GB/T 2406-2008) as described in Table 11；
The technical indicator of 11 polymeric absorbent of table
Comparative example 1
Substantially the same with embodiment 7, the structural formula of above-mentioned polymeric absorbent is as shown in fig. 7, the polymeric absorbent
Solid granular is presented in agent, the difference is that the mean values that the mean values that the mean values of its L are 250, K are 650, M are
150, N mean values are 10, and performance parameter (referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 12；
The technical indicator of 12 polymeric absorbent of table
Comparative example 2
Substantially the same with embodiment 7, the structural formula of above-mentioned polymeric absorbent is as shown in fig. 7, the polymeric absorbent
Solid granular is presented in agent, the difference is that the mean values that the mean values that the mean values of its L are 30, K are 300, M are
550, N mean values are 55, and performance parameter (referring to HG/T 5310-2018 and GB/T 2406-2008) is as described in Table 13；
The technical indicator of 13 polymeric absorbent of table
Comparative example 3
Chinese invention patent, application number: 201810882562.1, open notification number: CN108948312A discloses a kind of benzene
Ethylene-acrylate oil suction is swollen elastomer, referring to the embodiment 4 of its specification；
It is as follows that the present embodiment cinnamic acrylic ester oil suction is swollen method for producing elastomers:
By 28 parts of dodecyl acrylate, 13 parts of ethyl methacrylate, 15 parts of styrene, 6.5 parts of hydroxy-ethyl acrylate, mix
After closing stirring, 31 parts of ethyl acetate are added, 1 part of initiator, dissolution is sufficiently stirred and obtains mixture；
Said mixture is divided into etc. two parts of quality, portion is placed in three diameter bottles, and portion is placed in constant pressure funnel,
Nitrogen is passed through into three-neck flask to eliminate oxygen in bottle, mixing speed control is 300rmp/min, and three diameter bottles are heated to 75
DEG C insulation reaction after reaction 5 hours, controls liquid in constant pressure funnel and is keeping instilling in three diameter bottles in 75 DEG C of constant temperature 2h,
It is warming up to 80 DEG C of reaction 2h.Cooled to room temperature is evaporated under reduced pressure, oil suction swellable resins is obtained after so that solvent is volatilized completely.
The performance parameter of above-mentioned cinnamic acrylic ester oil suction swelling elastomer is (referring to HG/T 5310-2018 and GB/T
2406-2008) as described in Table 14；
14 technical indicator of table
Comparative example 4
Chinese invention patent, application number: 201510389589.3, open notification number: CN104987591A discloses a kind of tool
There are the expanded polypropylene and polymeric absorbent composite material and preparation method of flame retardant effect, referring to the specific reality of its specification
Apply scheme；
Expanded polypropylene and polymeric absorbent composite material with flame retardant effect, by the original of following parts by weight (kilogram)
Material is made: high melt strength, propylene 95, low density polyethylene (LDPE) 2, diisopropyl azodiformate 2, polydimethylsiloxanes
Alkane 0.6, antimony oxide 3, red phosphorus 1, appropriate deionized water, methylcellulose 4, butyl acrylate 13, methacrylic acid 12
Ester 7.5, N, N '-methylene-bisacrylamide 0.08, azodiisobutyronitrile 0.5, ethyl acetate 11, di (isooctyl) phosphate 2；
The above-mentioned expanded polypropylene with flame retardant effect and polymeric absorbent composite material, by step system in detail below
At:
(1) methylcellulose is added in the deionized water of 30 times of amounts, is heated to being completely dissolved while stirring, is cooled to room
Ethyl acetate, N, N '-methylene-bisacrylamide, azodiisobutyronitrile, third is successively slowly added after temperature under nitrogen protection
Olefin(e) acid butyl ester, lauryl methacrylate, di (isooctyl) phosphate, control mixing speed are 1000 revs/min, are then to slowly warm up to
40 DEG C, be stirred to react after ten minutes, be continuously heating to 70 DEG C, be stirred to react after twenty minutes, be continuously heating to 80 DEG C, with 400 turns/
The speed divided is stirred to react 1 hour, obtains microspheres with solid, reaction system is down to room temperature, and obtained microspheres with solid is filtered, and is used
80 DEG C of deionized waters are washed 3 times, dry 24 hours at 50 DEG C finally up to polymer resin microspheres；
(2) antimony oxide, red phosphorus, dimethyl silicone polymer are put into ball mill, are warming up to 60-70 DEG C, ball milling 30
It is taken out after minute, is then put into high-speed mixer and is uniformly mixed jointly with low density polyethylene (LDPE), diisopropyl azodiformate,
Then modified particles are obtained by extruder extruding pelletization, control extruder extrusion temperature is 100-120 DEG C, and screw speed is
300 revs/min；
(3) polymer resin microspheres for obtaining high melt strength, propylene, foaming modification particle and step (1) mix
It is put into the hopper of Bitruder afterwards, extruding machine starts screw rod knob after being warming up to 180-200 DEG C, plasticizing is kneaded 120
Minute, carry out first time foaming；After cylinder, which interrupts mixture, has melted plasticizing uniformly, dioxy is injected under the conditions of 10MPa
Change carbon gas (being the 10% of melting materialss quality by the additional amount that flow control valve controls carbon dioxide), is kept for 40 minutes
Afterwards, then it is down to normal pressure, then foamed；The melt extrusion that will be plasticized, the temperature that control squeezes out head is 200-210 DEG C, i.e.,
Side wall can be obtained and be covered with microporous foam pipe, foaming poly- third can be prepared with dedicated pelleter pelletizing after air natural cooling
Alkene and the compound particle of macromolecule resin.
The performance parameter of the above-mentioned expanded polypropylene with flame retardant effect and polymeric absorbent composite material is (referring to HG/T
5310-2018 and GB/T 2406-2008) as described in Table 15；
15 technical indicator of table
Comparative example 5
Chinese invention patent, application number: 201510389510.7, open notification number: CN104987641A discloses a kind of tool
There is the polymeric absorbent and preparation method thereof of dual flame retardant efficiency, referring to the specific embodiment of its specification；
Polymeric absorbent with dual flame retardant efficiency is made: propylene of the raw material of following parts by weight (kilogram)
Sour methyl esters 26, octadecyl methacrylate 18, ethylene glycol dimethacrylate 0.16, methylcellulose 4, sodium pyrophosphate 0.4,
Ethyl acetate 21, benzoyl peroxide 1, ceramic fiber cotton 3, silicone resin emulsion 2, melamine cyanurate 2, to methylbenzene
Ethylene 0.9, divinylbenzene 1.8, nano-aluminum hydroxide 1, silane coupling agent kh4500.05, di (isooctyl) phosphate 1, silicone oil
0.5, appropriate amount of water is distilled；
The above-mentioned polymeric absorbent with dual flame retardant efficiency, is made by the following specific steps:
(1) by melamine cyanurate and silicone resin emulsion mixing and ball milling 60 minutes, ceramic fiber cotton is put into powder
It is added in ball mill after being ground into 200 mesh powder in broken machine, is heated to 40-50 DEG C of continuation ball milling and is taken out after 30 minutes, be put into baking
In case, with the modified mixed powder in 70-80 DEG C of surface obtained by drying；
(2) methylcellulose is added in the distilled water of 30 times of amounts, is heated to 80-90 DEG C, after stirring to quick dissolution, delays
Slowly it is cooled to room temperature, sodium pyrophosphate is added, stirs the mixed powder modified to the surface that addition step (1) obtains after completely dissolution
Ethyl acetate, ethylene glycol dimethacrylate, benzoyl peroxide is successively slowly added in material under nitrogen protection after mixing evenly
Formyl, methyl acrylate, octadecyl methacrylate, control mixing speed are 1000 revs/min, are then to slowly warm up to 40 DEG C,
It is stirred to react after ten minutes, is continuously heating to 70 DEG C, be stirred to react after twenty minutes, be continuously heating to 80 DEG C, with 400 revs/min
Speed is stirred to react 1 hour, obtains polymer resin microspheres；
(3) nano-aluminum hydroxide is put into ball milling in ball mill with silane coupling agent kh450 to take out after sixty minutes, phosphorus is added
Sour di-isooctyl continues to be uniformly mixed, and p-methylstyrene, divinylbenzene and remaining residual components are then added, stir
It being added in the reaction system of step (2) after mixing uniformly, 80 DEG C of temperature control, with 1000 revs/min of speed, the reaction was continued 1.5 hours,
I.e. in the surface structure for preparing one layer of high-crosslinking-degree on polymer resin microspheres surface；
(4) reaction system is down to room temperature, by obtained solid polymer microballoon filter, with 80 DEG C distillation water washing 3 times,
24 hours are dried at 50 DEG C finally up to final products.
The performance parameter of the above-mentioned polymeric absorbent with dual flame retardant efficiency is (referring to HG/T 5310-2018 and GB/T
2406-2008) as described in Table 16；
16 technical indicator of table
In conclusion it can be seen that the performance parameter of the polymeric absorbent of consolidated statement 1-16, embodiment 1-11 preparation is aobvious
It writes and is better than comparative example 1-5, the performance parameters such as absorbency, retention rate and the limit oxygen index of common organic reagent show excellent
It is different, and the value range of L, K, M, N also have conspicuousness influence to its performance in polymeric absorbent.
Embodiment 12
The concrete application of polymeric absorbent in embodiment 1-11
Hydrosol product: the hydrosol is made by conventional emulsion polymerisation process in polymeric absorbent；The hydrosol can also lead to
It crosses jet drying and powder or granular materials is made；In addition, hydrosol itself can be used to be made into oil suction flame retardant coating or film.
Bulk material product: bulk material is made by bulk polymerization in polymeric absorbent；Bulk material can be with
It is cut into the shape of various needs；Bulk material can also be machined into powder or granular materials.
Spherical particle product: spherical particle is made by suspension polymerization in polymeric absorbent；The diameter of spherical particle
It can be adjusted by the different amounts of different mixing speed and dispersing agent to 0.1mm-3mm.
Oil suction bag product: the polymeric absorbent of spherical particle is wrapped in liquid permeable cloth or film and is made
Oil suction bag.Oil suction bag can be used for the first aid process of dangerous liquid leakage.
Filtering material product: the polymeric absorbent of spherical particle is inserted into Filter column；This Filter column can be used to purify
Water also is used as in oil water separator.
Schematically the present invention and embodiments thereof are described above, description is not limiting, institute in attached drawing
What is shown is also one of embodiments of the present invention, and actual structure is not limited to this.So if the common skill of this field
Art personnel are enlightened by it, without departing from the spirit of the invention, are not inventively designed and the technical solution
Similar frame mode and embodiment, are within the scope of protection of the invention.
Claims (9)
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%.
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