CN113968942A - High oil absorption resin and preparation method thereof - Google Patents
High oil absorption resin and preparation method thereof Download PDFInfo
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- CN113968942A CN113968942A CN202111390512.XA CN202111390512A CN113968942A CN 113968942 A CN113968942 A CN 113968942A CN 202111390512 A CN202111390512 A CN 202111390512A CN 113968942 A CN113968942 A CN 113968942A
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 149
- 239000011347 resin Substances 0.000 title claims abstract description 90
- 229920005989 resin Polymers 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 94
- 239000007864 aqueous solution Substances 0.000 claims abstract description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003999 initiator Substances 0.000 claims abstract description 56
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 150000002978 peroxides Chemical class 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 60
- 239000000839 emulsion Substances 0.000 claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 31
- 229920001577 copolymer Polymers 0.000 claims description 31
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 claims description 30
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 27
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 15
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 200
- 238000005303 weighing Methods 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000004033 plastic Substances 0.000 description 12
- 229920000136 polysorbate Polymers 0.000 description 12
- 238000005086 pumping Methods 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- LQEJKDNALLXRCT-UHFFFAOYSA-N chloroform;toluene Chemical compound ClC(Cl)Cl.CC1=CC=CC=C1 LQEJKDNALLXRCT-UHFFFAOYSA-N 0.000 description 10
- 239000003350 kerosene Substances 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 238000010009 beating Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- 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
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a high oil absorption resin and a preparation method thereof, which are applied to the technical field of high polymer polymerization, and the method comprises the following steps: adding a first comonomer into deionized water, uniformly mixing to obtain a pre-polymerization aqueous solution, then adding a composite initiator into the pre-polymerization aqueous solution, and introducing nitrogen to carry out a polymerization reaction to obtain an interpenetrating polymer; adding the interpenetrating polymer into deionized water to prepare an interpenetrating polymer aqueous solution; and uniformly mixing the interpenetrating polymer aqueous solution, the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator to obtain a mixture, introducing nitrogen into the mixture, and adding a reduction initiator to perform a polymerization reaction to obtain the high oil absorption resin with the interpenetrating network structure. The high oil absorption resin prepared by the invention has excellent oil absorption effect and gel strength.
Description
Technical Field
The invention relates to the technical field of high polymer polymerization, and particularly relates to a high oil absorption resin and a preparation method thereof.
Background
At present, the pollution caused by oily waste is increasingly harmful to the environment, and the survival of human beings, animals and plants is directly threatened. Therefore, the oil absorption material is required to be used for carrying out oil absorption treatment on the oil-containing waste, the high oil absorption resin is a body type polymer resin with a low three-dimensional network cross-linked structure, and has the advantages of large oil absorption amount, multiple oil absorption types, good oil-water selectivity, strong oil retention capacity, easiness in storage and transportation and the like, so that the high oil absorption resin is widely applied to the industries of environmental protection, rubber, pesticide, papermaking and the like and is used as various oil-based treating agents, base materials, oil mist filtering materials, rubber modifiers, paper additives and the like.
According to the difference of monomer types, the high oil absorption resin is mainly divided into two types: one is an alkyl acrylate resin and the other is an olefin resin. Wherein, the acrylic alkyl ester has ester polar group in the molecular structure, so the oil absorption capability to nonpolar oil is not too high and the oil absorption rigid degree is not too good, and the acrylic alkyl ester is in a slurry shape and is not beneficial to practical use. The olefin resin is nonpolar resin, has strong affinity with oil products, but has poor polymerization capability, is difficult to prepare oil absorption resin with high gel amount, has no rigid structure in a molecular structure, has large molecular chain flexibility and low resin rigidity, and is in a slurry shape after oil absorption, thus being not beneficial to practical use.
Therefore, a high oil absorption resin which has good affinity with oil and good rigidity after oil absorption is urgently needed.
Disclosure of Invention
The embodiment of the invention provides a high oil absorption resin and a preparation method thereof, and can provide the high oil absorption resin which has the advantages of high oil absorption speed, high oil absorption amount, high oil retention amount and good rigidity after oil absorption.
In a first aspect, the present invention provides a method for preparing a high oil absorption resin, comprising the steps of:
(1) adding a first comonomer into deionized water, uniformly mixing to obtain a pre-polymerization aqueous solution, then adding a composite initiator into the pre-polymerization aqueous solution, and introducing nitrogen to carry out a polymerization reaction to obtain an interpenetrating polymer; adding the interpenetrating polymer into deionized water to prepare an interpenetrating polymer aqueous solution;
(2) and uniformly mixing the interpenetrating polymer aqueous solution, the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator to obtain a mixture, introducing nitrogen into the mixture, and adding a reduction initiator to perform a polymerization reaction to obtain the high oil absorption resin with the interpenetrating network structure.
Preferably, in the step (1), the mass parts of the raw material components for preparing the interpenetrating polymer are as follows:
100 parts of the first comonomer, 200-300 parts of deionized water and 0.02-0.03 part of composite initiator.
Preferably, in the step (2), the mass parts of the raw material components for preparing the high oil absorption resin are as follows:
100 parts of interpenetrating polymer aqueous solution, 90-110 parts of second comonomer, 70-90 parts of white oil, 4-8 parts of emulsifier, 0.2-1 part of cross-linking agent, 0.01 part of peroxide initiator and 0.006-0.01 part of reduction initiator.
Preferably, in step (1), the first comonomer comprises acrylic acid, butyl methacrylate, 2-ethylhexyl acrylate, styrene.
Preferably, in step (2), the second comonomer comprises butyl methacrylate, 2-ethylhexyl acrylate.
Preferably, in the step (1), the mass parts of the components in the first comonomer are as follows:
10 parts of acrylic acid, 2-3 parts of butyl methacrylate, 1-2 parts of acrylic acid-2-ethylhexyl ester and 0.5-1 part of styrene;
in the step (2), the second comonomer comprises the following components in parts by weight:
2 parts of butyl methacrylate and 1 part of 2-ethylhexyl acrylate.
Preferably, after the obtaining of the pre-polymerization aqueous solution, the method further comprises adjusting the temperature of the pre-polymerization aqueous solution to 5-10 ℃.
Preferably, the mass fraction of the interpenetrating polymer in the interpenetrating polymer aqueous solution is 0.1-0.5%.
Preferably, the step (2) further comprises the sub-steps of:
nitrogen is added into the mixture, the temperature rising rate of the mixture is controlled while the reduction initiator is added, and when the temperature of the mixture is 38-40 ℃, the mixture is kept warm for 3-4 hours, so that copolymer emulsion with an interpenetrating network structure is obtained; wherein the heating rate is 0.0033-0.005 ℃/s;
and (3) freezing the copolymer emulsion at-20 to-35 ℃ for 4.5 to 6 hours, and then demulsifying to obtain the high oil absorption resin.
Preferably, the composite initiator comprises diisobutyl peroxydicarbonate, hydrogen peroxide and sodium bisulfite; the composite initiator comprises, by mass, 1 part of diisobutyl peroxydicarbonate, 0.1-0.2 part of hydrogen peroxide and 0.5-0.7 part of sodium bisulfite.
Preferably, the peroxide initiator comprises diisobutyl peroxydicarbonate and hydrogen peroxide; wherein the peroxide initiator comprises 1 part by mass of diisobutyl peroxydicarbonate and 0.1-0.2 part by mass of hydrogen peroxide;
the reduction initiator is a 1% strength aqueous solution of sodium bisulfite.
Preferably, the emulsifier is a mixture of span 80 and tween 80; wherein the mass ratio of span 80 to Tween 80 is (3-5) to 1;
the cross-linking agent is N, N-methylene bisacrylamide.
In a second aspect, the invention provides a high oil-absorption resin prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
in the invention, the interpenetrating polymer is prepared firstly, then the interpenetrating polymer is prepared into interpenetrating polymer aqueous solution, the interpenetrating polymer aqueous solution is mixed with the second comonomer, white oil, emulsifier, cross-linking agent and peroxide initiator are added, then nitrogen is introduced and reduction initiator is added to initiate polymerization reaction, and the high oil-absorbing resin with interpenetrating network structure is obtained. The preparation method provided by the invention firstly prepares the interpenetrating polymer, the interpenetrating polymer is a high polymer with a network structure, the interpenetrating polymer with the network structure and the second comonomer are mixed and have polymerization reaction under the action of the auxiliary agent, the second comonomer is crosslinked and polymerized in the gaps of the network structure of the interpenetrating polymer to form a new network structure, and the two network structures are interpenetrated to form the high oil absorption resin with the interpenetrating network structure.
The monomers of the high oil absorption resin with the interpenetrating network structure are subjected to cross permeation and mechanical entanglement through the interpenetrating network structure, and forced mutual capacitance and cooperation are realized among the monomers, so that the polarity of the high oil absorption resin is reduced, the oil affinity of the high oil absorption resin is increased, and the gel strength of the high oil absorption resin is increased. Therefore, the interpenetrating network structure ensures that the high oil absorption resin provided by the invention has the performances of high oil absorption speed, high oil absorption amount, high oil retention amount and good rigidity after oil absorption.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a preparation method of high oil absorption resin, which comprises the following steps:
(1) adding a first comonomer into deionized water, uniformly mixing to obtain a pre-polymerization aqueous solution, then adding a composite initiator into the pre-polymerization aqueous solution, and introducing nitrogen to carry out a polymerization reaction to obtain an interpenetrating polymer; adding the interpenetrating polymer into deionized water to prepare an interpenetrating polymer aqueous solution;
(2) and uniformly mixing the interpenetrating polymer aqueous solution, the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator to obtain a mixture, introducing nitrogen into the mixture, and adding a reduction initiator to perform a polymerization reaction to obtain the high oil absorption resin with the interpenetrating network structure.
In the invention, the interpenetrating polymer is prepared firstly, then the interpenetrating polymer is prepared into interpenetrating polymer aqueous solution, the interpenetrating polymer aqueous solution is mixed with the second comonomer, white oil, emulsifier, cross-linking agent and peroxide initiator are added, then nitrogen is introduced and reduction initiator is added to initiate polymerization reaction, and the high oil-absorbing resin with interpenetrating network structure is obtained. The preparation method provided by the invention firstly prepares the interpenetrating polymer, the interpenetrating polymer is a high polymer with a network structure, the interpenetrating polymer with the network structure and the second comonomer are mixed and have polymerization reaction under the action of the auxiliary agent, the second comonomer is crosslinked and polymerized in the gaps of the network structure of the interpenetrating polymer to form a new network structure, and the two network structures are interpenetrated to form the high oil absorption resin with the interpenetrating network structure.
The monomers of the high oil absorption resin with the interpenetrating network structure are subjected to cross permeation and mechanical entanglement through the interpenetrating network structure, and forced mutual capacitance and cooperation are realized among the monomers, so that the polarity of the high oil absorption resin is reduced, the oil affinity of the high oil absorption resin is increased, and the gel strength of the high oil absorption resin is increased. Therefore, the interpenetrating network structure ensures that the high oil absorption resin provided by the invention has the performances of high oil absorption speed, high oil absorption amount, high oil retention amount and good rigidity after oil absorption.
In the invention, the molecular weight of the interpenetrating polymer is 800-1200 ten thousand, the molecular weight of the high oil absorption resin can be increased from 400 ten thousand to 1000-2000 ten thousand after the interpenetrating polymer is introduced, and the rigidity of the high oil absorption resin is improved due to the increase of the molecular weight.
In the present invention, the specific method for preparing the interpenetrating polymer aqueous solution in step (1) is to crush the reactant obtained from the polymerization reaction, dry the reactant for 2 to 4 hours (for example, 2 hours, 3 hours or 4 hours) at 150 to 170 ℃ (for example, 150 ℃, 160 ℃ or 170 ℃) to obtain the interpenetrating polymer, crush the interpenetrating polymer and add the crushed interpenetrating polymer into deionized water to obtain the interpenetrating polymer aqueous solution.
The polymerization reaction in step (1) is an exothermic reaction, and the reaction is completed when the temperature of the reaction system is not increased any more.
In the present invention, in the step (2), the interpenetrating polymer aqueous solution, the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator need to be uniformly mixed, and the mixed system is stirred until the viscosity is 900 to 1100cps (for example, 900cps, 1000cps or 1100cps), which is regarded as uniform mixing.
In the present invention, since oxygen acts as a polymerization inhibitor in the polymerization reaction, and causes a chain termination phenomenon in the polymerization reaction in the step (1) and the step (2), it is necessary to introduce nitrogen to discharge oxygen.
In the present invention, white oil is used to increase the plasticity of the high oil absorbent resin.
According to some preferred embodiments, in step (1), the mass parts of the raw material components for preparing the interpenetrating polymer are as follows:
100 parts of the first comonomer, 200-300 parts (for example, 200 parts, 220 parts, 240 parts, 260 parts, 280 parts or 300 parts) of the deionized water, and 0.02-0.03 part (for example, 0.02 part, 0.025 part or 0.03 part) of the composite initiator.
According to some preferred embodiments, in the step (2), the mass parts of the raw material components for preparing the high oil absorption resin are as follows:
100 parts of the interpenetrating polymer aqueous solution, 90-110 parts (for example, 90 parts, 95 parts, 100 parts, 105 parts or 110 parts) of the second comonomer, 70-90 parts (70 parts, 80 parts or 90 parts) of the white oil, 4-8 parts (for example, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts) of the emulsifier, 0.2-1 part (for example, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts or 1 part) of the cross-linking agent, 0.01 part of the peroxide initiator, and 0.006-0.01 part (for example, 0.006 part, 0.008 part or 0.01 part) of the reduction initiator.
In the invention, the mass parts of the interpenetrating polymer aqueous solution and the second comonomer are 100 parts and 90-110 parts, and the mass parts of the interpenetrating polymer aqueous solution and the second comonomer are controlled in the above range, so that the copolymerization reaction is stable and controllable, and the monomer residue is reduced. If the mass fraction of the second comonomer is more than 110 parts, implosion can occur, large agglomeration is generated, and the obtained product has poor quality; if the mass part of the second comonomer is less than 90 parts, a large amount of monomer residues are caused, and the use efficiency of raw materials is reduced.
According to some preferred embodiments, in step (1), the first comonomer comprises acrylic acid, butyl methacrylate, 2-ethylhexyl acrylate, styrene.
In the invention, the styrene in the first comonomer has a benzene ring structure, and the benzene ring structure increases the rigidity of the prepared high oil absorption resin, so that the high oil absorption resin keeps excellent gel strength after absorbing oil. In addition, according to the principle of similar compatibility, styrene can also increase the lipophilicity of the prepared high oil absorption resin.
According to some preferred embodiments, in step (2), the second comonomer comprises butyl methacrylate, 2-ethylhexyl acrylate.
It should be noted that, according to the principle of similar compatibility, the ester organic substance can increase the oil absorption effect of the high oil absorption resin. Experiments prove that the oil absorption effect of the prepared high oil absorption resin is improved to the maximum extent by selecting butyl methacrylate and 2-ethylhexyl acrylate as the ester organic matter.
According to some preferred embodiments, in step (1), the mass parts of the components in the first comonomer are as follows:
10 parts of acrylic acid, 2-3 parts (for example, 2 parts, 2.5 parts or 3 parts) of butyl methacrylate, 1-2 parts (for example, 1 part, 1.5 parts or 2 parts) of 2-ethylhexyl acrylate, and 0.5-1 part (for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part) of styrene;
in the step (2), the second comonomer comprises the following components in parts by weight:
2 parts of butyl methacrylate and 1 part of 2-ethylhexyl acrylate.
In the invention, the mass part of the styrene in the first comonomer is 0.5-1, and the mass part of the styrene is controlled in the range, so that the rigidity and the oil absorption effect of the prepared high oil absorption resin are obviously improved. If the mass part of the styrene exceeds 1 part, the prepared high oil absorption resin has strong brittleness and is easy to crack; if the mass part of the styrene is less than 0.5 part, the rigidity and the oil absorption effect of the prepared high oil absorption resin are not obviously improved.
According to some preferred embodiments, after the obtaining of the aqueous prepolymer solution, the method further comprises adjusting the temperature of the aqueous prepolymer solution to 5 to 10 ℃ (for example, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃ or 10 ℃).
In the invention, the temperature of the prepolymerization aqueous solution is reduced to 5-10 ℃, so that the molecular weight of the interpenetrating polymer can be increased, and the rigidity and the oil absorption effect of the prepared high oil absorption resin are obviously improved.
According to some preferred embodiments, the mass fraction of the interpenetrating polymer in the aqueous solution of interpenetrating polymer is 0.1 to 0.5% (e.g., may be 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%).
In the invention, the mass fraction of the interpenetrating polymer aqueous solution is controlled to be 0.1-0.5%, so that the prepared interpenetrating polymer aqueous solution has moderate viscosity and can be well and uniformly mixed with the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator in the step (2). If the mass fraction of the interpenetrating polymer aqueous solution exceeds 0.5%, the viscosity of the interpenetrating polymer aqueous solution is too high to be miscible with other substances in the step (2); if the mass part of the interpenetrating polymer aqueous solution is less than 0.1 percent, the prepared high oil absorption resin has poor rigidity and oil absorption effect.
According to some preferred embodiments, said step (2) further comprises the sub-steps of:
passing nitrogen through the mixture, and controlling the temperature rising rate of the mixture while adding the reduction initiator until the temperature of the mixture is 38-40 ℃ (for example, 38 ℃, 39 ℃ or 40 ℃), and preserving the heat for 3-4 h (for example, 3h, 3.5h or 4h) to obtain a copolymer emulsion with an interpenetrating network structure; wherein the heating rate is 0.0033-0.005 ℃/s (for example, 0.0033 ℃/s, 0.004 ℃/s or 0.005 ℃/s);
and (2) the copolymer emulsion is placed at-20 to-35 ℃ (for example, -20 ℃, -25 ℃, -30 ℃ or-35 ℃) and is frozen for 4.5 to 6 hours (for example, 4.5 hours, 5 hours, 5.5 hours or 6 hours), and then demulsification is carried out, so as to obtain the high oil absorption resin.
In the invention, the heating rate of the mixture is controlled by controlling the rate of adding the reduction initiator into the mixture, specifically, firstly, the peroxide initiator is added into the mixture, the peroxide initiator is uniformly distributed in the mixture by stirring, then, the reduction initiator is slowly added, a small amount of the reduction initiator added into the mixture and the peroxide initiator distributed in the mixture form a redox system, and the polymerization reaction is initiated. Because the amount of the added reduction initiator is less, the initiated polymerization reaction scale is also smaller, and the released heat is low, the temperature control effect is realized by slowly adding the reduction initiator, and the stable and controllable polymerization reaction ensures that the prepared high oil absorption resin has long molecular chain and high gel strength.
It should be noted that the temperature of the mixture system is controlled to rise slowly to avoid implosion, so that the reaction is stable and controllable. Controlling the temperature at 38-40 ℃ for 4.5-6 h to ensure that the mixture fully reacts.
The copolymer emulsion obtained was an oil-in-water emulsion.
In the invention, an oil phase is obtained after demulsification, and the oil phase is subjected to suction filtration, washing and drying to obtain the high oil absorption resin, wherein the high oil absorption resin can be crushed and sieved to uniform the particle size according to requirements.
According to some preferred embodiments, the composite initiator comprises diisobutyl peroxydicarbonate, hydrogen peroxide, sodium bisulfite; the composite initiator comprises, by mass, 1 part of diisobutyl peroxydicarbonate, 0.1-0.2 part (for example, 0.1 part, 0.15 part or 0.2 part) of hydrogen peroxide, and 0.5-0.7 part (for example, 0.5 part, 0.6 part or 0.7 part) of sodium bisulfite.
In the present invention, the composite initiator provides a redox system to initiate polymerization.
According to some preferred embodiments, the peroxide initiator comprises diisobutyl peroxydicarbonate, hydrogen peroxide; wherein the peroxide initiator comprises 1 part by mass of diisobutyl peroxydicarbonate and 0.1-0.2 part by mass of hydrogen peroxide;
the reduction initiator is a 1% strength aqueous solution of sodium bisulfite.
In the step (2), the peroxide initiator and the reduction initiator are added step by step to ensure that the reaction is stable and controllable, and the occurrence of implosion is avoided.
According to some preferred embodiments, the emulsifier is a mixture of span 80 and tween 80; wherein the mass ratio of span 80 to Tween 80 is (3-5) to 1;
the cross-linking agent is N, N-methylene bisacrylamide.
In the invention, the mass ratio of span 80 to Tween 80 is (3-5): 1, so that the HLB value is 6-7, and the oil phase and the water phase are fully emulsified.
The invention also provides a high oil absorption resin prepared by the preparation method provided by the invention.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a high oil absorption resin and a preparation method thereof are described in detail by several examples.
Example 1:
(1) weighing 200 parts of acrylic acid, 40 parts of butyl methacrylate, 20 parts of acrylic acid-2-ethylhexyl ester, 10 parts of styrene, 810 parts of deionized water, 0.03 part of diisobutyl peroxydicarbonate, 0.005 part of hydrogen peroxide and 0.02 part of sodium bisulfite, uniformly mixing, cooling to 10 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to a mass ratio of 3: 1000;
(2) weighing 360 parts by weight of interpenetrating polymer aqueous solution, 240 parts by weight of butyl methacrylate, 120 parts by weight of 2-ethylhexyl acrylate, 252 parts by weight of white oil, 8010.8 parts by weight of span, 803.6 parts by weight of tween, 0.72 part by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.006 part by weight of hydrogen peroxide, uniformly mixing, then viscosity increasing to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.005 ℃/s by controlling the speed (2.16 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the completion to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Example 2:
(1) weighing 220 parts by weight of acrylic acid, 55 parts by weight of butyl methacrylate, 33 parts by weight of acrylic acid-2-ethylhexyl ester, 17 parts by weight of styrene, 715 parts by weight of deionized water, 0.047 part by weight of diisobutyl peroxydicarbonate, 0.007 part by weight of hydrogen peroxide and 0.0305 part by weight of sodium bisulfite, uniformly mixing, cooling to 8 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to the mass ratio of 2: 1000;
(2) weighing 345 parts by weight of interpenetrating polymer aqueous solution, 230 parts by weight of butyl methacrylate, 115 parts by weight of 2-ethylhexyl acrylate, 276 parts by weight of white oil, 8010.35 parts by weight of span, 803.45 parts by weight of tween, 1.38 parts by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.0045 part by weight of hydrogen peroxide, uniformly mixing, then viscosity increasing to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.0033 ℃/s by controlling the speed (3.45 parts by weight) of pumping 1% sodium bisulfite aqueous solution, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the completion to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Example 3:
(1) weighing 230 parts of acrylic acid, 46 parts of butyl methacrylate, 46 parts of acrylic acid-2-ethylhexyl ester, 23 parts of styrene, 897 parts of deionized water, 0.04 part of diisobutyl peroxydicarbonate, 0.004 part of hydrogen peroxide and 0.025 part of sodium bisulfite, uniformly mixing, cooling to 6 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to a mass ratio of 3.5: 1000;
(2) weighing 330 parts by weight of interpenetrating polymer aqueous solution, 220 parts by weight of butyl methacrylate, 110 parts by weight of 2-ethylhexyl acrylate, 264 parts by weight of white oil, 8016.5 parts by weight of span, 803.3 parts by weight of tween, 2.31 parts by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.003 part by weight of hydrogen peroxide, uniformly mixing, then beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.004 ℃/s by controlling the speed (2.64 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the completion to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Example 4:
(1) weighing 250 parts of acrylic acid, 50 parts of butyl methacrylate, 25 parts of acrylic acid-2-ethylhexyl ester, 15 parts of styrene, 850 parts of deionized water, 0.06 part of diisobutyl peroxydicarbonate, 0.01 part of hydrogen peroxide and 0.032 part of sodium bisulfite, uniformly mixing, cooling to 5 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to a mass ratio of 4: 1000;
(2) weighing 390 parts by weight of interpenetrating polymer aqueous solution, 260 parts by weight of butyl methacrylate, 130 parts by weight of acrylic acid-2-ethylhexyl ester, 351 parts by weight of white oil, 8023.4 parts by weight of span, 807.8 parts by weight of tween, 3.9 parts by weight of N, N-methylene bisacrylamide, 0.0325 parts by weight of diisobutyl peroxydicarbonate and 0.0065 parts by weight of hydrogen peroxide, uniformly mixing, then beating to viscosity of 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.0033 ℃/s by controlling the speed (3.9 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃, controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the temperature is finished to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Example 5:
(1) weighing 180 parts of acrylic acid, 45 parts of butyl methacrylate, 27 parts of acrylic acid-2-ethylhexyl ester, 9 parts of styrene, 783 parts of deionized water, 0.029 part of diisobutyl peroxydicarbonate, 0.00435 parts of hydrogen peroxide and 0.01885 parts of sodium bisulfite, uniformly mixing, cooling to 10 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to a mass ratio of 4.5: 1000;
(2) weighing 370 parts by weight of interpenetrating polymer aqueous solution, 250 parts by weight of butyl methacrylate, 125 parts by weight of 2-ethylhexyl acrylate, 300 parts by weight of white oil, 8018 parts by weight of span, 804.5 parts by weight of tween, 1.5 parts by weight of N, N-methylene bisacrylamide, 0.03125 parts by weight of diisobutyl peroxydicarbonate and 0.00625 parts by weight of hydrogen peroxide, uniformly mixing, then beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to 0.005 ℃/s by controlling the speed (3 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the completion to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Example 6:
(1) weighing 190 parts by weight of acrylic acid, 38 parts by weight of butyl methacrylate, 19 parts by weight of acrylic acid-2-ethylhexyl ester, 19 parts by weight of styrene, 798 parts by weight of deionized water, 0.047 part by weight of diisobutyl peroxydicarbonate, 0.0047 part by weight of hydrogen peroxide and 0.0281 parts by weight of sodium bisulfite, uniformly mixing, cooling to 10 ℃, adding into a reaction kettle, blowing high-purity nitrogen to remove oxygen to initiate polymerization reaction, taking out the polymer from the reaction kettle after the temperature does not rise any more, crushing, drying for 3 hours at 160 ℃, crushing to obtain an interpenetrating polymer, and preparing the interpenetrating polymer and the deionized water into an interpenetrating polymer aqueous solution according to the mass ratio of 5: 1000;
(2) weighing 315 parts by weight of interpenetrating polymer aqueous solution, 210 parts by weight of butyl methacrylate, 105 parts by weight of 2-ethylhexyl acrylate, 252 parts by weight of white oil, 8018.9 parts by weight of span, 806.3 parts by weight of tween, 1.26 parts by weight of N, N-methylene bisacrylamide, 0.02625 parts by weight of diisobutyl peroxydicarbonate and 0.00525 parts by weight of hydrogen peroxide, uniformly mixing, beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.004 ℃/s by controlling the speed (2.52 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the completion to obtain the interpenetrating network copolymer emulsion;
(3) and (3) freezing the interpenetrating network copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin with the interpenetrating network structure.
Comparative example 1:
(1) weighing 360 parts by weight of deionized water, 240 parts by weight of butyl methacrylate, 120 parts by weight of 2-ethylhexyl acrylate, 252 parts by weight of white oil, 8010.8 parts by weight of span, 803.6 parts by weight of tween, 0.72 part by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.006 part by weight of hydrogen peroxide, uniformly mixing, stirring to reach 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.005 ℃/s by controlling the speed (2.16 parts by weight) of pumping sodium bisulfite aqueous solution with the concentration of 1%, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the reaction is finished to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
Comparative example 2:
(1) weighing 345 parts by weight of deionized water, 230 parts by weight of butyl methacrylate, 115 parts by weight of acrylic acid-2-ethylhexyl ester, 276 parts by weight of white oil, 8010.35 parts by weight of span, 803.45 parts by weight of tween, 1.38 parts by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.0045 part by weight of hydrogen peroxide, uniformly mixing, then beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.0033 ℃/s by controlling the speed (3.45 parts by weight) of pumping in 1% sodium bisulfite aqueous solution, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the reaction is finished to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
Comparative example 3:
(1) weighing 330 parts by weight of deionized water, 220 parts by weight of butyl methacrylate, 110 parts by weight of 2-ethylhexyl acrylate, 264 parts by weight of white oil, 8016.5 parts by weight of span, 803.3 parts by weight of tween, 2.31 parts by weight of N, N-methylene bisacrylamide, 0.03 part by weight of diisobutyl peroxydicarbonate and 0.003 part by weight of hydrogen peroxide, uniformly mixing, then beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.004 ℃/s by controlling the speed (2.64 parts by weight) of pumping in 1% sodium bisulfite aqueous solution, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the reaction is finished to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
Comparative example 4:
(1) weighing 390 parts by weight of deionized water, 260 parts by weight of butyl methacrylate, 130 parts by weight of acrylic acid-2-ethylhexyl ester, 351 parts by weight of white oil, 8023.4 parts by weight of span, 807.8 parts by weight of tween, 3.9 parts by weight of N, N-methylene bisacrylamide, 0.0325 parts by weight of diisobutyl peroxydicarbonate and 0.0065 parts by weight of hydrogen peroxide, uniformly mixing, then beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to 0.0033 ℃/s by controlling the speed (3.9 parts by weight) of pumping in 1% sodium bisulfite aqueous solution, heating to 40 ℃ and controlling the temperature at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the temperature is controlled to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
Comparative example 5:
(1) weighing 370 parts by weight of deionized water, 250 parts by weight of butyl methacrylate, 125 parts by weight of acrylic acid-2-ethylhexyl ester, 300 parts by weight of white oil, 8018 parts by weight of span, 804.5 parts by weight of tween, 1.5 parts by weight of N, N-methylene bisacrylamide, 0.03125 parts by weight of diisobutyl peroxydicarbonate and 0.00625 parts by weight of hydrogen peroxide, uniformly mixing, beating to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to 0.005 ℃/s by controlling the speed (3 parts by weight) of pumping 1% sodium bisulfite aqueous solution, controlling the temperature to 3 hours at 40 ℃ when the temperature is raised to 40 ℃, and cooling the emulsion to room temperature after the temperature is over to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
Comparative example 6:
(1) weighing 315 parts by weight of deionized water, 210 parts by weight of butyl methacrylate, 105 parts by weight of acrylic acid-2-ethylhexyl ester, 252 parts by weight of white oil, 8018.9 parts by weight of span, 806.3 parts by weight of tween, 1.26 parts by weight of N, N-methylene bisacrylamide, 0.02625 parts by weight of diisobutyl peroxydicarbonate and 0.00525 parts by weight of hydrogen peroxide, uniformly mixing, beating the viscosity to 1000cps, introducing nitrogen to remove oxygen for 30 minutes, controlling the heating rate to be 0.004 ℃/s by controlling the speed of pumping sodium bisulfite aqueous solution with the concentration of 1% (2.52 parts by weight) until the temperature is raised to 40 ℃ and controlled at 40 ℃ for 3 hours, and cooling the emulsion to room temperature after the temperature is over to obtain copolymer emulsion;
(2) and (3) freezing the copolymer emulsion for 5 hours at the temperature of-25 ℃ to demulsify, and then carrying out suction filtration, ethanol washing, drying (160 ℃, 3 hours), crushing and screening to obtain the high oil absorption resin.
The high oil absorption resins obtained in examples 1 to 6 and comparative examples 1 to 6 were subjected to performance tests, the test results are shown in tables 1 to 12, and the test methods are as follows:
(1) saturated oil absorption: accurately weighing 1g of high oil absorption resin, and recording the weight of the high oil absorption resin to be 0.01gIs M0Putting the oil-absorbing gel into a polyester non-woven cloth bag, immersing the oil-absorbing gel into the oil to be detected for 24 hours at normal temperature, and weighing the mass M of the oil-absorbing gel (containing the cloth bag)1And the same measurement is carried out on the empty bags at the same time and is recorded as M2；
Saturated oil absorption ═ M1-M2-M0)/M0；
(2) Oil retention: accurately weighing 1g of saturated oil absorption gel of high oil absorption resin, and recording the gel as M when the gel is accurate to 0.01g1Centrifuging in a centrifuge with the rotation speed of 1000r/min for 5min, taking out and weighing, and recording the mass as M0；
Oil retention rate (M)0/M1)×100％；
(3) Oil absorption rate: accurately weighing 2g of high oil absorption resin, accurately weighing the high oil absorption resin to 0.01g, weighing 50g of oil to be detected in a 100ml glass beaker, adjusting the test temperature to 25 ℃, placing the beaker containing the oil to be detected on a magnetic stirrer at the rotating speed of 600r/min, adding the high oil absorption resin into the beaker at one time, starting timing, recording the time when a magneton is still, wherein the time is the oil absorption speed of the high oil absorption resin.
(4) Absorption rate under pressure:
(4.1) instruments and reagents: a plastic barrel with the inner diameter of 25mm, the outer diameter of 31mm and the height of 32mm, wherein a nylon net with the mesh diameter of 63 mu m is adhered to the bottom surface;
the plastic piston (2068Pa) with the sticky weight is cylindrical, has the outer diameter of 25mm, can be tightly connected with the plastic cylinder, and can freely move up and down;
an electronic balance with a sensing quantity of 0.001 g;
a shallow chassis with the inner diameter of 85mm and the height of 20mm, and is adhered with a spacing bar with the diameter of 2 mm;
physiological saline, concentration 0.9%.
(4.2) test method
The determination should be carried out in the environment of (23 + -2) ° C, 25g of standard normal saline with the temperature of (23 + -2) ° C is added into a shallow base plate, the plate is placed on a platform, 0.160g of high oil absorption resin is weighed, and the M is recorded as 0.001g of the high oil absorption resin1Loading into plastic drum, loading the plastic piston with weight in itIn a plastic cylinder of oil resin, the mass of the plastic piston and the plastic cylinder is measured and recorded as M2Placing the plastic barrel filled with the high oil absorption resin at the center of the shallow chassis, taking the plastic barrel out of the shallow chassis after 60min, weighing the mass of the plastic barrel comprising the plastic piston and the high oil absorption resin and recording as M3；
Absorption rate under pressure (g/g) ═ M3-M2)/M1
And (4) carrying out measurement twice at the same time, and taking the arithmetic mean value of the measurement results as a measurement result, wherein the result is accurate to one digit after the decimal point.
The results of the performance test of example 1 are shown in Table 1
TABLE 1
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 35.3 | 37.2 | 29.5 | 31.5 |
| Oil retention rate | 99％ | 99％ | 99％ | 99％ |
| Rate of oil absorption | 3min | 2min | 5min | 4min |
| Absorption rate under pressure | 15.6 | 16.3 | 16.5 | 15.9 |
The results of the performance testing of example 2 are shown in table 2:
TABLE 2
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 30.3 | 29.6 | 31.3 | 32.6 |
| Oil retention rate | 99％ | 98％ | 99％ | 99％ |
| Rate of oil absorption | 5min | 7min | 4min | 3min |
| Absorption rate under pressure | 16.3 | 15.8 | 16.2 | 16.5 |
The results of the performance testing of example 3 are shown in table 3:
TABLE 3
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 27.2 | 32.7 | 30.5 | 33.1 |
| Oil retention rate | 99％ | 99％ | 99％ | 99％ |
| Rate of oil absorption | 6min | 4min | 5min | 4min |
| Absorption rate under pressure | 17.1 | 16.5 | 16.6 | 16.3 |
The results of the performance testing of example 4 are shown in table 4:
TABLE 4
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 28.1 | 29.9 | 35.6 | 34.9 |
| Oil retention rate | 99％ | 99％ | 99％ | 99％ |
| Rate of oil absorption | 8min | 6min | 3min | 3min |
| Absorption rate under pressure | 15.9 | 16.3 | 16.3 | 15.9 |
The results of the performance testing of example 5 are shown in table 5:
TABLE 5
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 26.3 | 32.4 | 33.5 | 27.8 |
| Oil retention rate | 99％ | 99％ | 99％ | 98％ |
| Rate of oil absorption | 7min | 3min | 3min | 7min |
| Absorption rate under pressure | 15.7 | 16.5 | 16.3 | 15.9 |
The results of the performance testing of example 6 are shown in table 6:
TABLE 6
The results of the performance test of comparative example 1 are shown in table 7:
TABLE 7
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 6.2 | 4.9 | 4.7 | 4.5 |
| Oil retention rate | 83％ | 89％ | 91％ | 87％ |
| Rate of oil absorption | 27min | 37min | 35min | 36min |
| Absorption rate under pressure | 5.6 | 6.3 | 4.5 | 4.3 |
The results of the performance test of comparative example 2 are shown in table 8:
TABLE 8
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 4.3 | 3.9 | 5.7 | 6.6 |
| Oil retention rate | 87％ | 85％ | 93％ | 95％ |
| Rate of oil absorption | 32min | 34min | 25min | 26min |
| Absorption rate under pressure | 6.7 | 6.3 | 7.2 | 5.6 |
The results of the performance test of comparative example 3 are shown in table 9:
TABLE 9
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 7.0 | 3.7 | 4.2 | 5.3 |
| Oil retention rate | 90％ | 81％ | 85％ | 89％ |
| Rate of oil absorption | 27min | 36min | 38min | 34min |
| Absorption rate under pressure | 8.2 | 5.6 | 5.3 | 6.1 |
The results of the performance test of comparative example 4 are shown in table 10:
watch 10
The results of the performance test of comparative example 5 are shown in table 11:
TABLE 11
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 6.2 | 5.3 | 6.7 | 5.4 |
| Oil retention rate | 93％ | 80％ | 92％ | 87％ |
| Rate of oil absorption | 32min | 41min | 31min | 36min |
| Absorption rate under pressure | 6.3 | 6.5 | 4.3 | 3.8 |
The results of the performance test of comparative example 6 are shown in table 12:
TABLE 12
| Oils, their preparation and their use | Kerosene oil | Chloroform | Toluene | Xylene |
| Saturated oil absorption | 5.7 | 7.7 | 4.3 | 3.8 |
| Oil retention rate | 83％ | 95％ | 85％ | 87％ |
| Rate of oil absorption | 27min | 29min | 32min | 28min |
| Absorption rate under pressure | 7.2 | 9.5 | 5.4 | 6.2 |
Through the performance test comparison results of the embodiments 1 to 6 and the comparative examples 1 to 6, it can be seen that the high oil absorption resin with the network interpenetrating structure has higher saturated oil absorption rate and faster oil absorption speed, and the oil retention rate is higher, and meanwhile, the high oil absorption resin has excellent pressure absorption rate, and the pressure absorption rate and the gel strength are in positive correlation, so that the high oil absorption resin with the network interpenetrating structure has excellent gel strength, and the high oil absorption resin has excellent rigidity after oil absorption.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a high oil absorption resin is characterized by comprising the following steps:
(1) adding a first comonomer into deionized water, uniformly mixing to obtain a pre-polymerization aqueous solution, then adding a composite initiator into the pre-polymerization aqueous solution, and introducing nitrogen to carry out a polymerization reaction to obtain an interpenetrating polymer; adding the interpenetrating polymer into deionized water to prepare an interpenetrating polymer aqueous solution;
(2) and uniformly mixing the interpenetrating polymer aqueous solution, the second comonomer, the white oil, the emulsifier, the cross-linking agent and the peroxide initiator to obtain a mixture, introducing nitrogen into the mixture, and adding a reduction initiator to perform a polymerization reaction to obtain the high oil absorption resin with the interpenetrating network structure.
2. The method of claim 1, wherein:
in the step (1), the interpenetrating polymer is prepared from the following raw material components in parts by mass:
100 parts of the first comonomer, 200-300 parts of deionized water and 0.02-0.03 part of composite initiator; and/or
In the step (2), the high oil absorption resin is prepared from the following raw material components in parts by mass:
100 parts of interpenetrating polymer aqueous solution, 90-110 parts of second comonomer, 70-90 parts of white oil, 4-8 parts of emulsifier, 0.2-1 part of cross-linking agent, 0.01 part of peroxide initiator and 0.006-0.01 part of reduction initiator.
3. The method of claim 1, wherein:
in step (1), the first comonomer comprises acrylic acid, butyl methacrylate, 2-ethylhexyl acrylate, styrene; and/or
In step (2), the second comonomer comprises butyl methacrylate, 2-ethylhexyl acrylate.
4. The production method according to claim 3, characterized in that:
in the step (1), the first comonomer comprises the following components in parts by weight:
10 parts of acrylic acid, 2-3 parts of butyl methacrylate, 1-2 parts of acrylic acid-2-ethylhexyl ester and 0.5-1 part of styrene;
in the step (2), the second comonomer comprises the following components in parts by weight:
2 parts of butyl methacrylate and 1 part of 2-ethylhexyl acrylate.
5. The production method according to claim 1, wherein in step (1):
after the pre-polymerization aqueous solution is obtained, adjusting the temperature of the pre-polymerization aqueous solution to 5-10 ℃; and/or
The mass fraction of the interpenetrating polymer in the interpenetrating polymer aqueous solution is 0.1-0.5%.
6. The method of claim 1, wherein:
the step (2) further comprises the following sub-steps:
nitrogen is added into the mixture, the temperature rising rate of the mixture is controlled while the reduction initiator is added, and when the temperature of the mixture is 38-40 ℃, the mixture is kept warm for 3-4 hours, so that copolymer emulsion with an interpenetrating network structure is obtained; wherein the heating rate is 0.0033-0.005 ℃/s;
and (3) freezing the copolymer emulsion at-20 to-35 ℃ for 4.5 to 6 hours, and then demulsifying to obtain the high oil absorption resin.
7. The method of claim 1, wherein:
the composite initiator comprises diisobutyl peroxydicarbonate, hydrogen peroxide and sodium bisulfite; the composite initiator comprises, by mass, 1 part of diisobutyl peroxydicarbonate, 0.1-0.2 part of hydrogen peroxide and 0.5-0.7 part of sodium bisulfite.
8. The method of claim 1, wherein:
the peroxide initiator comprises diisobutyl peroxydicarbonate and hydrogen peroxide; wherein the peroxide initiator comprises 1 part by mass of diisobutyl peroxydicarbonate and 0.1-0.2 part by mass of hydrogen peroxide;
the reduction initiator is a 1% strength aqueous solution of sodium bisulfite.
9. The method of claim 1, wherein:
the emulsifier is a mixture of span 80 and tween 80; wherein the mass ratio of span 80 to Tween 80 is (3-5) to 1;
the cross-linking agent is N, N-methylene bisacrylamide.
10. A high oil-absorbing resin, which is prepared by the preparation method of any one of claims 1 to 9.
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| CN202111390512.XA CN113968942B (en) | 2021-11-23 | High oil absorption resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN101314624A (en) * | 2008-05-21 | 2008-12-03 | 安徽省电力公司合肥供电公司 | High oil suction resin and uses thereof |
| CN111957303A (en) * | 2020-08-04 | 2020-11-20 | 江门谦信化工发展有限公司 | High-adsorptivity resin and preparation method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN101314624A (en) * | 2008-05-21 | 2008-12-03 | 安徽省电力公司合肥供电公司 | High oil suction resin and uses thereof |
| CN111957303A (en) * | 2020-08-04 | 2020-11-20 | 江门谦信化工发展有限公司 | High-adsorptivity resin and preparation method thereof |
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