CN104987464A - Macromolecule absorbent with modified high thermal stability based on nanosilicon dioxide polylactic acid and preparation method thereof - Google Patents

Abstract

The invention discloses a macromolecule absorbent with modified high thermal stability based on nanosilicon dioxide polylactic acid and a preparation method thereof. The macromolecule absorbent is characterized in that the macromolecule absorbent comprises, by weight, the following raw materials of 26-28 parts of cyclohexyl acrylate, 17-20 parts of butyl acrylate, 3-4 parts of polylactic acid, 3-4 parts of nanosilicon dioxide, 0.3-0.4 part of gamma-methacrylamide acyloxy propyl trimethoxy silane, 0.16-0.2 part of acrylic ester, 4-5 parts of carboxymethylcellulose, 22-24 parts of ethyl acetate, 1-1.2 parts of benzoyl peroxide, 0.9-1.2 parts of p-methylstyrene, 1.8-2.5 parts of divinyl benzene, 1-2 parts of nano aluminum hydroxide, 0.05-0.07 part of silane coupling agent kh450, 1-1.2 parts of di (isooctyl) phosphate, 0.5-0.6 part of silicone oil and moderate distilled water. The macromolecule absorbent with modified high thermal stability based on the nanosilicon dioxide polylactic acid is of a double-layer porous structure, a big volume expansion ratio is achieved, the thermal stability is high, and certain fire resistance is achieved.

Description

Polymeric absorbent of a kind of high thermal stability polylactic acid modified based on nano silicon and preparation method thereof

Technical field

The present invention relates to Material Field, particularly a kind of polymeric absorbent and preparation method thereof of the high thermal stability polylactic acid modified based on nano silicon.

Background technology

Day by day frequent along with offshore oil exploitation and transport, offshore oil tank oil accident happens occasionally, and the discharge of oily(waste)water.Oils enters ocean, to physical environment, aquaculture, shallow water seashore, harbour industry etc. all can cause harm difficult to the appraisal at present to the process of these source of pollution be mostly by oil absorption material by oil slick absorb with the purification reaching source of pollution.

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, poor heat stability, 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, easily burn after absorbing oil-based solvent.Therefore, develop dynamical oil suction product and there is important practical usage.

Nano silicon is unformed white powder, and its molecule is three-dimensional chain, reticulated structure or masonry structure etc.Generally speaking, nano silicon is introduced polymkeric substance and prepares nano composite material, be conducive to the modulus of raising polymkeric substance, intensity and thermostability, thus also receive much concern in polymer nanocomposites.Nano-silica surface is rich in hydrophilic silicone hydroxyl, thus with organism poor compatibility, is difficult to be uniformly dispersed wherein.General use silane coupling agent and nano-silica surface hydroxyl generation Silanization reaction, eliminate or reduce surface silanol group, making it become hydrophobicity from wetting ability.The consistency of the nano silicon after surface modification and monomer or polymkeric substance increases, by being polymerized with acrylic ester monomer with the blended rear of poly(lactic acid), the intensity of polymkeric substance, thermostability can be improved, simultaneously due to the polymerization of poly(lactic acid), there is the characteristic of super-hydrophobic super-oleophylic, porous.

Summary of the invention

The object of this invention is to provide polymeric absorbent of a kind of high thermal stability polylactic acid modified based on nano silicon and preparation method thereof.The polymeric material of nano silicon and poly(lactic acid) is added in the synthesis of polyacrylics, the three-dimensional net structure of resin can be improved, improve self-strength, the thermostability of product, product of the present invention not only can solve the low problem of traditional oil-absorbing resin oil suction multiplying power, 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 the high thermal stability polylactic acid modified based on nano silicon, be made up of the raw material of following weight part: cyclohexylacrylic ester 26-28, butyl acrylate 17-20, poly(lactic acid) 3-4, nano silicon 3-4, γ-methacryloxypropyl trimethoxy silane 0.3-0.4, diacrylate 0.16-0.2, carboxymethyl cellulose 4-5, ethyl acetate 22-24, benzoyl peroxide 1-1.2, 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, water distilled water is appropriate,

The polymeric absorbent of a kind of high thermal stability polylactic acid modified based on nano silicon of the present invention, be made up of following concrete steps:

(1) nano silicon and γ-methacryloxypropyl trimethoxy silane are put into ball mill, with 70-80 DEG C after mixing and ball milling 40-60 minute, then extruding granulator is together put into the temperature of 180-190 DEG C with poly(lactic acid), extruding pelletization behind 60-80 rev/min the mixing 5-7 of speed minute, will be ground into 200 order powder after particle drying;

(2) carboxymethyl cellulose is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the product that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, benzoyl peroxide, diacrylate, cyclohexylacrylic ester, butyl 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 in internal layer acrylic resin after the nano silicon of appropriate hydrophobically modified and poly(lactic acid) being reacted, the tridimensional network of inner layer resin can be improved, play the effect of collaborative hydrophobic oil suction, 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 larger cubical expansivity, and cubical expansivity can reach about 30 times, and thermostability is high, has certain flame retardant resistance.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, the features such as have applied range, absorption rate is fast, convenient to use.

Specific embodiments

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

A kind of polymeric absorbent of the high thermal stability polylactic acid modified based on nano silicon, be made up of the raw material of following weight part (kilogram): cyclohexylacrylic ester 26, butyl acrylate 17, poly(lactic acid) 3, nano silicon 3, γ-methacryloxypropyl trimethoxy silane 0.3, diacrylate 0.16, carboxymethyl cellulose 4, ethyl acetate 22, benzoyl peroxide 1, 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, water distilled water is appropriate,

The polymeric absorbent of a kind of high thermal stability polylactic acid modified based on nano silicon of the present invention, be made up of following concrete steps:

(1) nano silicon and γ-methacryloxypropyl trimethoxy silane are put into ball mill, with 70-80 DEG C of mixing and ball milling after 40 minutes, then extruding granulator is together put into the temperature of 180-190 DEG C with poly(lactic acid), the speed of 60 revs/min extruding pelletization after mixing 5 minutes, will be ground into 200 order powder after particle drying;

(2) carboxymethyl cellulose is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the product that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, benzoyl peroxide, diacrylate, cyclohexylacrylic ester, butyl 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) 87.5%, specific absorption (trichloroethane) 84.1%; Protect oily rate (0# diesel oil) 83.0%, protect oily rate (trichloroethane) 79.8%, be far longer than inspecting standard.

Claims (2)

1. the polymeric absorbent based on the polylactic acid modified high thermal stability of nano silicon, it is characterized in that, be made up of the raw material of following weight part: cyclohexylacrylic ester 26-28, butyl acrylate 17-20, poly(lactic acid) 3-4, nano silicon 3-4, γ-methacryloxypropyl trimethoxy silane 0.3-0.4, diacrylate 0.16-0.2, carboxymethyl cellulose 4-5, ethyl acetate 22-24, benzoyl peroxide 1-1.2, 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, water distilled water is appropriate.

2. the polymeric absorbent of a kind of high thermal stability polylactic acid modified based on nano silicon according to claim 1, is characterized in that, be made up of following concrete steps:

(1) nano silicon and γ-methacryloxypropyl trimethoxy silane are put into ball mill, with 70-80 DEG C after mixing and ball milling 40-60 minute, then extruding granulator is together put into the temperature of 180-190 DEG C with poly(lactic acid), extruding pelletization behind 60-80 rev/min the mixing 5-7 of speed minute, will be ground into 200 order powder after particle drying;

(2) carboxymethyl cellulose is added in the distilled water of 30 times amount, be heated to dissolve completely, slow cooling is to room temperature, add the product that step (1) obtains, continue to be stirred to and be uniformly dispersed, then ethyl acetate is added slowly successively under nitrogen protection, benzoyl peroxide, diacrylate, cyclohexylacrylic ester, butyl 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.