CN104987465A - Efficient high-molecular absorbent added with strengthened modified clamshell powder and preparation method thereof - Google Patents

Abstract

The invention discloses an efficient high-molecular absorbent added with strengthened modified clamshell powder. The efficient high-molecular absorbent is characterized by being prepared by, by weight, 4.0-5.0 parts of clamshells, 0.4-0.5 part of vinyl triethoxysilane, an appropriate amount of 1% concentration of diluted hydrochloric acid, an appropriate amount of distilled water, 4-5 parts of polyvinylpyrrolidone, 26-29 parts of butyl acrylate, 17-19 parts of dodecyl methacrylate, 0.16-0.2 part of N,N,-methylene bisacrylamide, 1-1.2 parts of azodiisobutyronitrile, 21-23 parts of ethyl acetate, 0.9-1.2 parts of p-methylstyrene, 1.8-2.5 parts of divinyl benzene, 1-2 parts of nano-aluminum trihydrate, 0.05-0.07 part of silane coupling agent kh450, 1-1.2 parts of di-cotyl phosphoric acid and 0.5-0.6 part of silicone oil. The efficient high-molecular absorbent is of a double-layer porous structure and has high oil absorption rate and higher volume expansion ratio, leakage occurs no longer after absorption, and the harm of toxic steam is reduced.

Description

A kind ofly add efficient polymeric absorbent of enhancing modified river shell powder and preparation method thereof

Technical field

The present invention relates to Material Field, particularly a kind ofly add efficient polymeric absorbent of enhancing modified river shell powder 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 and potential safety hazard 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, after oil suction, easily burning causes heavy losses etc.Therefore, develop dynamical oil suction product and there is important practical usage.

Summary of the invention

The object of this invention is to provide and a kind ofly add efficient polymeric absorbent of enhancing modified river shell powder and preparation method thereof.River shell powder has wide material sources, the advantage such as cheap, add in the synthesis of acrylic resin, the three-dimensional net structure of resin can be improved, and the intensity of resin after compound, product of the present invention not only can solve the low problem of traditional oil-absorbing resin oil suction multiplying power, and can oil-retaining be improved, safe fire-retardant fireproof simultaneously.

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

A kind of efficient polymeric absorbent of adding enhancing modified river shell powder, be made up of the raw material of following weight part: freshwater mussel shell 4.0-5.0, vinyltriethoxysilane 0.4-0.5, concentration is that 1% dilute hydrochloric acid is appropriate, distilled water is appropriate, polyvinylpyrrolidone 4-5, butyl acrylate 26-29, lauryl methacrylate 17-19, N, N'-methylene-bisacrylamide 0.16-0.2, Diisopropyl azodicarboxylate 1-1.2, ethyl acetate 21-23, p-methylstyrene 0.9-1.2, Vinylstyrene 1.8-2.5, nano-aluminum hydroxide 1-2, silane coupling agent kh450 0.05-0.07, di (isooctyl) phosphate 1-1.2, silicone oil 0.5-0.6,

A kind of efficient polymeric absorbent of adding enhancing modified river shell powder of the present invention, be made up of following concrete steps:

(1) freshwater mussel shell being put into concentration is that 1% dilute hydrochloric acid soaks 100-120 minute and goes out surface smut, extremely neutral with distilled water cleaning after removal, put into retort furnace again with the temperature calcination 120-150 minute of 300-400 DEG C, put into pulverizer after taking out cold going and be polished into 200 order powder, then by the distilled water of powder and 5 times amount, vinyltriethoxysilane puts into ball mill, be warming up to 80 DEG C, ball milling 2 hours, cooling leaves standstill, taking precipitate, baking oven is put into after repeatedly cleaning with distilled water, to dry and to obtain surface hydrophobicity modification river shell powder under the condition of 80 DEG C,

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to while stirring dissolve completely, the river shell powder of the surface hydrophobicity modification that step (1) obtains is added after being cooled to room temperature, ethyl acetate is added slowly successively under nitrogen protection after stirring, N, N'-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, 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 appropriate surface modification freshwater mussel shell powder particles, being compared by reaction is evenly distributed in internal layer acrylic resin, because modified river shell powder has certain hydrophobic oleophilic oil effect, the common oil suction of tridimensional network of inner layer resin can be worked in coordination with, 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 present invention is double-layer porous structure, has efficient swelling rate, larger cubical expansivity, and cubical expansivity can reach about 30 times, and can not produce and reveal after absorbing, and significantly reduces noxious vapors harm simultaneously.The present invention can be used for processing water surface Oil spills, dangerous organic liquid leaks, protection met an urgent need by the process of Low emissivity oily(waste)water, aerogenerator lubricating oil leakage, laboratory and factory's medicine, traffic transport industry and motorway Environmental capacity, synthetic resins additive etc.

Specific embodiments

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

A kind of efficient polymeric absorbent of adding enhancing modified river shell powder, be made up of the raw material of following weight part (kilogram): freshwater mussel shell 4.0, vinyltriethoxysilane 0.4, concentration are that 1% dilute hydrochloric acid is appropriate, distilled water appropriate, polyvinylpyrrolidone 4, butyl acrylate 26, lauryl methacrylate 17, N, N'-methylene-bisacrylamide 0.16, Diisopropyl azodicarboxylate 1, ethyl acetate 21, p-methylstyrene 0.9, Vinylstyrene 1.8, nano-aluminum hydroxide 1, silane coupling agent kh450 0.05, di (isooctyl) phosphate 1, silicone oil 0.5;

A kind of efficient polymeric absorbent of adding enhancing modified river shell powder of the present invention, be made up of following concrete steps:

(1) freshwater mussel shell being put into concentration is that 1% dilute hydrochloric acid soaks and within 100 minutes, goes out surface smut, extremely neutral with distilled water cleaning after removal, put into retort furnace again with the temperature calcination 120 minutes of 300-400 DEG C, put into pulverizer after taking out cold going and be polished into 200 order powder, then the distilled water of powder and 5 times amount, vinyltriethoxysilane are put into ball mill, be warming up to 80 DEG C, ball milling 2 hours, cooling leaves standstill, taking precipitate, baking oven is put into, to dry and to obtain surface hydrophobicity modification river shell powder under the condition of 80 DEG C after repeatedly cleaning with distilled water;

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to while stirring dissolve completely, the river shell powder of the surface hydrophobicity modification that step (1) obtains is added after being cooled to room temperature, ethyl acetate is added slowly successively under nitrogen protection after stirring, N, N'-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, 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) 87.4%, specific absorption (trichloroethane) 92.3%; Protect oily rate (0# diesel oil) 81.7%, protect oily rate (trichloroethane) 80.5%, be far longer than inspecting standard.

Claims (2)

1. one kind is added the efficient polymeric absorbent of enhancing modified river shell powder, it is characterized in that, be made up of the raw material of following weight part: freshwater mussel shell 4.0-5.0, vinyltriethoxysilane 0.4-0.5, concentration is that 1% dilute hydrochloric acid is appropriate, distilled water is appropriate, polyvinylpyrrolidone 4-5, butyl acrylate 26-29, lauryl methacrylate 17-19, N, N'-methylene-bisacrylamide 0.16-0.2, Diisopropyl azodicarboxylate 1-1.2, ethyl acetate 21-23, p-methylstyrene 0.9-1.2, Vinylstyrene 1.8-2.5, nano-aluminum hydroxide 1-2, silane coupling agent kh450 0.05-0.07, di (isooctyl) phosphate 1-1.2, silicone oil 0.5-0.6.

2. a kind of efficient polymeric absorbent of adding enhancing modified river shell powder according to claim 1, is characterized in that, be made up of following concrete steps:

(1) freshwater mussel shell being put into concentration is that 1% dilute hydrochloric acid soaks 100-120 minute and goes out surface smut, extremely neutral with distilled water cleaning after removal, put into retort furnace again with the temperature calcination 120-150 minute of 300-400 DEG C, put into pulverizer after taking out cold going and be polished into 200 order powder, then by the distilled water of powder and 5 times amount, vinyltriethoxysilane puts into ball mill, be warming up to 80 DEG C, ball milling 2 hours, cooling leaves standstill, taking precipitate, baking oven is put into after repeatedly cleaning with distilled water, to dry and to obtain surface hydrophobicity modification river shell powder under the condition of 80 DEG C,

(2) polyvinylpyrrolidone is added in the distilled water of 30 times amount, be heated to while stirring dissolve completely, the river shell powder of the surface hydrophobicity modification that step (1) obtains is added after being cooled to room temperature, ethyl acetate is added slowly successively under nitrogen protection after stirring, N, N'-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, 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.