CN105037638A - Inorganic filling material modified high-molecular absorbent, and preparation method thereof - Google Patents

Abstract

The invention discloses an inorganic filling material modified high-molecular absorbent. The inorganic filling material modified high-molecular absorbent is prepared from, by weight, 3 to 4 parts of bentonite, 2 to 3 parts of calcium carbonate, 1 to 2 parts of hexadecyl trimethyl ammonium bromide, 0.3 to 0.5 parts of liquid paraffin, 0.2 to 0.3 part of titanate coupling agent TC-F, 23 to 25 parts of butyl methacrylate, 22 to 24 parts of tetradecyl acrylate, 4 to 5 parts of tetradecyl acrylate, 21 to 23 parts of ethyl acetate, 1 to 1.2 parts of azodiisobutyronitrile, 0.15 to 0.2 part of ethylene glycol dimethacrylate, 0.9 to 1.2 parts of p-methylstyrene, 1.8 to 2.5 parts of divinyl benzene, 1 to 2 parts of nano aluminium hydroxide, 0.05 to 0.07 part of silane coupling agent kh450, 1 to 1.2 parts of di(isooctyl) phosphate, 0.5 to 0.6 part of silicone oil, and an appropriate amount of distilled water. The inorganic filling material modified high-molecular absorbent is wide in application range, rapid in absorption speed, and convenient and efficient for application.

Description

Polymeric absorbent of a kind of mineral filler modification and preparation method thereof

Technical field

The present invention relates to Material Field, polymeric absorbent of particularly a kind of mineral filler modification and preparation method thereof.

Background technology

With the continuous progress of society and the fast development of industry; in the processes such as industrial production, petroleum transportation, mankind's activity, natural disaster, often can discharge and produce waste pollution material; these leakage accidents and discharge process often cause the loss of the energy and the threat of environment; even affect the health of the mankind; therefore, find out the method removing oil product and organic pollution materials to be efficiently very important.

Traditional oil absorption material is that inorganic materials and organic materials pass through physical method mostly, form through modification, mixing, compacting, can be divided into according to its Oil-absorptive mechanism and contain type oil absorption material, gel-type oil absorption material and contain the compound oil absorption material of gel, this kind of oil absorption material be utilize its surface, the capillary force in gap and cavity carries out oil suction and/or utilizes the physical condensation power between intermolecular or material, the clearance space produced in the process that net structure is formed and wrap up oil suction, and the oil-absorbing resin of existing existence, be polymerized by two kinds and two or more acrylic ester or olefines reaction monomers, there is certain oil suction multiplying power, but oil suction multiplying power is not very high, this is because resin is chemically crosslinked, covalent linkage has larger bond energy, have stronger bound to molecular chain, segment between cross-linking set is compared with short and cross-linking density is large, after oil suction, resin network segment is stretched at utmost very soon, so high oil absorbing resin has lower oil suction multiplying power, and speed of oil absorption is slow, oil number is few, Oil keeping is poor, numerous inconvenience is there is in actually operating, as the oil absorption material oil content in transport and storage process absorbed after oil content can be discharged in environment again, cause secondary pollution.Therefore, develop dynamical oil suction product and there is important practical usage.

Summary of the invention

The object of this invention is to provide polymeric absorbent of a kind of mineral filler modification and preparation method thereof.Wilkinite, calcium carbonate have wide material sources, the advantage such as cheap, the natural materials of modification is added in the synthesis of resin, the three-dimensional net structure of resin can be improved, improve the self-strength of compound resin, not only can solve the problem that traditional oil-absorbing resin oil suction multiplying power is low, and the oil-retaining of compound resin can be improved, resin can repeatedly use simultaneously.

In order to realize object of the present invention, the present invention is by following scheme implementation:

A kind of polymeric absorbent of mineral filler modification, be made up of the raw material of following weight part: wilkinite 3-4, calcium carbonate 2-3, cetyl trimethylammonium bromide 1-2, whiteruss 0.3-0.5, titanate coupling agent TC-F0.2-0.3, butyl methacrylate 23-25, tetradecyl acrylate 22-24, polyvinylpyrrolidone 4-5, ethyl acetate 21-23, Diisopropyl azodicarboxylate 1-1.2, Ethylene glycol dimethacrylate 0.15-0.2, p-methylstyrene 0.9-1.2, Vinylstyrene 1.8-2.5, nano-aluminum hydroxide 1-2, silane coupling agent kh4500.05-0.07, di (isooctyl) phosphate 1-1.2, silicone oil 0.5-0.6, distilled water is appropriate,

The polymeric absorbent of a kind of mineral filler modification of the present invention, be made up of following concrete steps:

(1) 10 minutes are heated with the power microwave of 700W after being mixed with calcium carbonate by wilkinite, take out the distilled water adding total amount 3 times amount in after image mixed powder, stir into suspension, then cetyl trimethylammonium bromide is added, heating is stopped after stirred for several hour at 70-80 DEG C, treat solution left standstill layering, taking precipitate, with distilled water suction filtration several, whiteruss is mixed with titanate coupling agent TC-F, be sprayed at the precipitating species after suction filtration equably, be put in 80 DEG C of oven dry in baking oven after stirring, grind to form 200 order powder;

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the powder that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, Diisopropyl azodicarboxylate, Ethylene glycol dimethacrylate, butyl methacrylate, tetradecyl acrylate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain polymer resin microspheres,

(3) nano-aluminum hydroxide and silane coupling agent kh450 are put into ball mill ball milling to take out after 60 minutes, add di (isooctyl) phosphate to continue to be uniformly mixed, then p-methylstyrene, Vinylstyrene and all the other remaining components is added, join in the reaction system of step (2) after stirring, temperature control 80 DEG C, reaction 1.5-2 hour is continued, namely at the surface structure preparing one deck high-crosslinking-degree on polymer resin microspheres surface with the speed of 1000 revs/min;

(4) reaction system is down to room temperature, is filtered the solid polymer microballoon that obtains, with 80 DEG C of distilled water washs 3 times, finally at 50 DEG C, namely drying obtains the finished product in 24 hours.

The invention has the beneficial effects as follows: the present invention adds wilkinite and the calcium carbonate of appropriate modification, can be evenly dispersed in internal layer acrylic resin by polyreaction, because modified mixed powder has certain hydrophobic oleophilic oil effect, the tridimensional network of inner layer resin and the common oil suction of the laminated structure of mixed powder, play synergy, and then increase the oil suction multiplying power of inner layer resin, and the thermostability of internal layer compound resin obtains raising to a certain extent.

The present invention is while the polymerization of internal layer compound resin, the p-methylstyrene cross-linked polymer of surface aggregation thin layer outside, less on the oil suction multiplying power impact of internal layer compound resin, include the nano-aluminum hydroxide after hydrophobically modified and di (isooctyl) phosphate simultaneously, improve flame retardant properties, simultaneously because outer layer copolymer cross-linking density is higher than internal layer polymer, coordinate the effect of pore-creating agent silicone oil, impart the surface-area that oil-absorbing resin microballoon is larger, for absorption provides larger power, improve swelling rate, simultaneously due to high cross-linked surface, resin polarity can be improved, rigidity, avoid cohering between oil-absorbing resin particle.

The features such as the present invention has applied range, and absorption rate is fast, convenient to use.Special in hazardous and noxious substances, can safe handling, the secondary pollution of effective preventing pollution liquid.Have larger cubical expansivity, cubical expansivity can reach about 30 times, and the oil absorbing surface that this structure increases resin amasss, and speed of oil absorption is fast, and the regenerability of resin is relatively good, can repeatedly reuse.

Absorbing material of the present invention can absorb nearly all liquid organic chemicals, comprises the fuel such as gasoline, diesel oil, Aviation Fuel, crude oil, the aromatic solvent such as benzene, dimethylbenzene, and the chlorinated solvent such as tetrachloroethylene, methyl ethyl ketone and polar compound.Be widely used in oil leakage, water pollution control, oily water separation and the field such as hazardous chemical protection and emergency processing.

Specific embodiments

Below by specific examples, the present invention is described in detail.

A kind of polymeric absorbent of mineral filler modification, be made up of the raw material of following weight part (kilogram): wilkinite 3, calcium carbonate 2, cetyl trimethylammonium bromide 1, whiteruss 0.3, titanate coupling agent TC-F0.2, butyl methacrylate 23, tetradecyl acrylate 22, polyvinylpyrrolidone 4, ethyl acetate 21, Diisopropyl azodicarboxylate 1, Ethylene glycol dimethacrylate 0.15, p-methylstyrene 0.9, Vinylstyrene 1.8, nano-aluminum hydroxide 1, silane coupling agent kh4500.05, di (isooctyl) phosphate 1, silicone oil 0.5, distilled water is appropriate,

The polymeric absorbent of a kind of mineral filler modification of the present invention, be made up of following concrete steps:

(1) 10 minutes are heated with the power microwave of 700W after being mixed with calcium carbonate by wilkinite, take out the distilled water adding total amount 3 times amount in after image mixed powder, stir into suspension, then cetyl trimethylammonium bromide is added, heating is stopped after stirred for several hour at 70-80 DEG C, treat solution left standstill layering, taking precipitate, with distilled water suction filtration several, whiteruss is mixed with titanate coupling agent TC-F, be sprayed at the precipitating species after suction filtration equably, be put in 80 DEG C of oven dry in baking oven after stirring, grind to form 200 order powder;

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the powder that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, Diisopropyl azodicarboxylate, Ethylene glycol dimethacrylate, butyl methacrylate, tetradecyl acrylate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain polymer resin microspheres,

(3) nano-aluminum hydroxide and silane coupling agent kh450 are put into ball mill ball milling to take out after 60 minutes, add di (isooctyl) phosphate to continue to be uniformly mixed, then p-methylstyrene, Vinylstyrene and all the other remaining components is added, join in the reaction system of step (2) after stirring, temperature control 80 DEG C, reaction 1.5 hours is continued, namely at the surface structure preparing one deck high-crosslinking-degree on polymer resin microspheres surface with the speed of 1000 revs/min;

(4) reaction system is down to room temperature, is filtered the solid polymer microballoon that obtains, with 80 DEG C of distilled water washs 3 times, finally at 50 DEG C, namely drying obtains the finished product in 24 hours.

Product of the present invention is the opaque spherical particle of oyster white, detects it, and result is specific absorption (0# diesel oil) 89.5%, specific absorption (trichloroethane) 92.0%; Protect oily rate (0# diesel oil) 82.9%, protect oily rate (trichloroethane) 80.7%, be far longer than inspecting standard.

Claims (2)

1. the polymeric absorbent of a mineral filler modification, it is characterized in that, be made up of the raw material of following weight part: wilkinite 3-4, calcium carbonate 2-3, cetyl trimethylammonium bromide 1-2, whiteruss 0.3-0.5, titanate coupling agent TC-F0.2-0.3, butyl methacrylate 23-25, tetradecyl acrylate 22-24, polyvinylpyrrolidone 4-5, ethyl acetate 21-23, Diisopropyl azodicarboxylate 1-1.2, Ethylene glycol dimethacrylate 0.15-0.2, p-methylstyrene 0.9-1.2, Vinylstyrene 1.8-2.5, nano-aluminum hydroxide 1-2, silane coupling agent kh4500.05-0.07, di (isooctyl) phosphate 1-1.2, silicone oil 0.5-0.6, distilled water is appropriate.

2. the polymeric absorbent of a kind of mineral filler modification according to claim 1, is characterized in that, is made up of following concrete steps:

(1) 10 minutes are heated with the power microwave of 700W after being mixed with calcium carbonate by wilkinite, take out the distilled water adding total amount 3 times amount in after image mixed powder, stir into suspension, then cetyl trimethylammonium bromide is added, heating is stopped after stirred for several hour at 70-80 DEG C, treat solution left standstill layering, taking precipitate, with distilled water suction filtration several, whiteruss is mixed with titanate coupling agent TC-F, be sprayed at the precipitating species after suction filtration equably, be put in 80 DEG C of oven dry in baking oven after stirring, grind to form 200 order powder;

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the powder that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, Diisopropyl azodicarboxylate, Ethylene glycol dimethacrylate, butyl methacrylate, tetradecyl acrylate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain polymer resin microspheres,

(3) nano-aluminum hydroxide and silane coupling agent kh450 are put into ball mill ball milling to take out after 60 minutes, add di (isooctyl) phosphate to continue to be uniformly mixed, then p-methylstyrene, Vinylstyrene and all the other remaining components is added, join in the reaction system of step (2) after stirring, temperature control 80 DEG C, reaction 1.5-2 hour is continued, namely at the surface structure preparing one deck high-crosslinking-degree on polymer resin microspheres surface with the speed of 1000 revs/min;

(4) reaction system is down to room temperature, is filtered the solid polymer microballoon that obtains, with 80 DEG C of distilled water washs 3 times, finally at 50 DEG C, namely drying obtains the finished product in 24 hours.