CN102199243B - Polyacrylate elastomer with core-shell structure and its preparation method - Google Patents
Polyacrylate elastomer with core-shell structure and its preparation method Download PDFInfo
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- CN102199243B CN102199243B CN 201110085909 CN201110085909A CN102199243B CN 102199243 B CN102199243 B CN 102199243B CN 201110085909 CN201110085909 CN 201110085909 CN 201110085909 A CN201110085909 A CN 201110085909A CN 102199243 B CN102199243 B CN 102199243B
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Abstract
The invention discloses polyacrylate elastomer with a core-shell structure and its preparation method. The polyacrylate elastomer with the core-shell structure is obtained by using acrylic acid ester, metacrylic acid ester and a reactive type ultraviolet ray absorber according to a certain ratio through a method of the polymerization of seed emulsion in a semicontinuous feeding mode, wherein the color of the appearance is white, light yellow or yellow, and the weight average molecular weight is 2 to 10xe<5>g/mol. Polymer latex particles appear as a microsphere state before the demulsification of the elastomer, a three-layer structure of the latex particles microsphere can be observed after dyeing by phosphor-tungstic acid, the three layers comprise a core layer, a transition layer and a shell layer sequentially from the inside to the outside. According to the invention, polyacrylate elastomer with the core-shell structure reacts the polymer material by a melt blending process so that the ultraviolet light stability of the high-molecular material can be enhanced and the polymer material can be effectively is toughened, and the emulsion polymerisation method has the advantages of environmental protection without pollution, mature technology and easy realization of industrialization.
Description
Technical field
The invention belongs to polyacrylate(s) elastomerics and preparing technical field thereof, be specifically related to a kind of Core-Shell Polyacrylic-ester Copolymer elastomerics that is used as ultraviolet absorbers and preparation method thereof.
Background technology
As everyone knows, degradation with aging occurs in macromolecular material easily under the effect of the environmental factorss such as extraneous UV-light, oxygen, heat, the deteriorated of outward appearance and physical and mechanical properties appears, be usually expressed as variable color, crazing occurs, impact property, the elongation degradation of the decline, particularly material of be full of cracks and mechanical property be violent.In order to improve the ultraviolet resistance stability of macromolecular material, prolong the work-ing life of macromolecular material, people adopt the method for adding various auxiliary agents to realize more.
The normal auxiliary agent that adds has benzophenone at present, the photostabilizer such as benzotriazole category or hindered amines or carbon black, titanium dioxide, zinc oxide, the photomask agent such as cerium dioxide, such as patent US 5294661, DE 4442167, DE4442123, JP 0,627,965 1 etc. are described, but because these organic photostabilizers or inorganic photomask agent all belong to the small molecules auxiliary agent, poor with the consistency of macromolecular material matrix, lack good interface combination, not only can reduce the mechanical property of material after the interpolation, and also volatile, easily migration is greatly affected the fast light persistence of material.For this situation, the scientific and technical personnel both domestic and external new photostabilizer that begins one's study, existing research direction to photostabilizer mainly concentrates on: how to make quantifications of photostabilizer polymer, polymer bonds combination, the interior multifunction of molecule etc.
Wherein the photostabilizer polymer is quantized effectively to reduce volatilization, migration and the solvent extractable of stablizer, thereby can improve its effectiveness persistence and safety in utilization.The photostabilizer polymer quantizes to be the autohemagglutination by response type UV light stabilizing agent itself or to realize with the mode of the copolymerization of other monomers.At present, the achievement in research of relevant response type UV light stabilizing agent is a lot, such as US 3162676; Shang-Tzen chang, Pai-Lung Chou, Polymer Degradation and Stability, 2000,69:355～360; Cs.Kosa, S.Chmela, B.Pawelke, G.Theumer, W.D.Habicher, Polymer Degradation and Stability, 2003,81:453～461; Pieter Gijsman, Polymer, 2002,43:1573～1579.Although and the photostabilizer that the resulting polymer of these achievements in research quantizes can improve volatilization, the migration of photostabilizer to a certain extent effectively, make polymkeric substance have inherent " permanent " light stabilising effect, but because itself not possessing the good toughness of elastomerics, can not make contributions to the toughness of macromolecular material after the adding, so the toughness that macromolecular material is possessed is relatively poor, limited the range of application of macromolecular material after wearing out.
Summary of the invention
The objective of the invention is the problem for the prior art existence, a kind of Core-Shell Polyacrylic-ester Copolymer elastomerics that can be used as ultraviolet absorbers that provides.
Another object of the present invention provides a kind ofly prepares the above-mentioned elastomeric method of Core-Shell Polyacrylic-ester Copolymer that can be used as ultraviolet absorbers.
The invention provides a kind of Core-Shell Polyacrylic-ester Copolymer elastomerics that can be used as ultraviolet absorbers, it is characterized in that this elastomerics is to obtain by the seeded emulsion polymerization method of following prescription by the semi-continuous charging mode, its appearance luster is white, light yellow or yellow, and weight-average molecular weight is 2～10xe
5G/mol, formed polymer emulsion particle is microspheroidal before the breakdown of emulsion, particle diameter is 50-100nm, and after phospho-wolframic acid dyeing, can be observed the latex particle microballoon and be three-decker, be followed successively by from the inside to the outside stratum nucleare, transition layer and shell, the recipe ingredient that wherein forms this elastomerics stratum nucleare is counted by mass parts:
Acrylate 40-70 part
Methacrylic ester 0-10 part
2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 0-10 part;
The recipe ingredient that forms this elastomerics shell is counted by mass parts:
Methacrylic ester 10-40 part
Acrylate 0-10 part
2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 10-20 part.
The method of the polyacrylate elastomer of the nucleocapsid structure that preparation provided by the invention is above-mentioned is characterized in that the processing step of the method and condition are as follows:
(1) with acrylate 40-70 part, methacrylic ester 0-10 part, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 0-10 part, the 50-70% of compound emulsifying agent total mass and the 50-70% of deionized water total mass, fully mixes and make the nuclear layer monomer pre-emulsion;
(2) with methacrylic ester 10-40 part, acrylate 0-10 part, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 10-20 part, the 30-50% of compound emulsifying agent total mass and the 30-50% of deionized water total mass, fully mix and make the shell monomers pre-emulsion;
(3) with the 30-50% of the resulting nuclear layer monomer pre-emulsion of step (1) total mass, the 50-70% of pH adjusting agent total mass and the 15-30% of initiator total mass, mix and be warming up to 70～75 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 30～40 minutes;
(4) the sub-microemulsion of nuclear species that first step (3) is made is warming up to 75～80 ℃, then respectively the 50-70% of nuclear layer monomer pre-emulsion total mass and the 20-30% while average rate of initiator total mass are dripped wherein, drip 75～80 ℃ of insulations of rear continuation 30～40 minutes, make the nuclear polymer emulsion;
(5) first the prepared nuclear polymer emulsion of step (4) is warming up to 80～85 ℃, add remaining pH adjusting agent, then respectively the resulting shell monomers pre-emulsion of step (2) and remaining initiator solution while average rate are dripped wherein, under 80～85 ℃, be incubated 30～40 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion;
(6) at room temperature, 60～80 parts of the aqueous electrolyte liquids of mass percent concentration 5～10% are joined in the prepared nucleocapsid structure acrylate polymer emulsion of step (5) carry out breakdown of emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product
The total mass of wherein said compound emulsifying agent is 2～5% of monomer total mass, and by anionic emulsifier and nonionic emulsifier in mass ratio 1.5～2.5: 1 is formulated; Described initiator total mass is 0.3～1.0% of monomer total mass, is configured to mass percent concentration during use and is drip behind 1.5～5% the initiator solution; Described pH adjusting agent total mass is 0.2～0.4% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1～2: 1.
Acrylate described in the above method is at least a in butyl acrylate, ethyl propenoate and the vinylformic acid ethylhexyl; Methacrylic ester is at least a in methyl methacrylate, β-dimethyl-aminoethylmethacrylate and the Propenoic acid, 2-methyl, isobutyl ester.
Anionic emulsifier described in the above method is any in sodium laurylsulfonate, sodium lauryl sulphate or the Sodium dodecylbenzene sulfonate; Described nonionic emulsifier is polyoxyethylene nonylphenol ether or polyoxyethylene octylphenol ether.
Initiator described in the above method is any in Potassium Persulphate, ammonium persulphate or the Sodium Persulfate.
PH adjusting agent described in the above method is any in yellow soda ash, sodium bicarbonate, sodium-acetate or the Sodium phosphate dibasic.
Aqueous electrolyte liquid described in the above method is formulated with in sodium-chlor, calcium chloride, Tai-Ace S 150, sulfuric acid or the hydrochloric acid any.
Whether formed nucleocapsid structure in order to investigate prepared polyacrylate elastomer, the present invention has carried out the acrylate polymer emulsion of gained to observe shooting with transmission electron microscope, and the gained photo as shown in Figure 1.As can be seen from Figure, the polymer emulsion particle becomes microspheric, particle diameter is greatly between 50-100nm, and after phospho-wolframic acid dyeing, can observe clearly, the emulsion particle microballoon is three-decker, be respectively from inside to outside stratum nucleare, transition layer, shell, and the interface is clearly demarcated between level, illustrates to form nucleocapsid structure.Secondly, whether the response type ultraviolet absorbers has produced copolymerization with acrylic ester monomer in the prepared polyacrylate elastomer in order to investigate, and the present invention has also carried out the test of infrared absorption spectrum to it, and the result as shown in Figure 2.1578cm among the figure
-1, 703cm
-1Charateristic avsorption band for phenyl ring; 1624cm
-1Charateristic avsorption band for the ketone carbonyl; 1743cm
-1Charateristic avsorption band for ester carbonyl group; 2958cm
-1For the feature of methyl is inhaled the peak; Other absorption peak also can find respective home.The result shows, the response type ultraviolet absorbers really and acrylic ester monomer copolymerization has occured.In addition, also to its test of having carried out ultraviolet absorption effect, test result is seen Fig. 3 in the present invention.It very strong ultraviolet absorption peak occurs at 288nm and 323nm place as can be seen from Figure 3, this response type ultraviolet absorbers Core-Shell Polyacrylic-ester Copolymer class elastomerics that is grafted with that shows preparation has strong sorption to the UV-light in 250～400nm wavelength region, can be used as a kind of ultraviolet absorbers.
The present invention has following remarkable advantage compared with prior art:
1. because the present invention passes through molecular designing, response type UV light absorber 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone is grafted on the Core-Shell Polyacrylic-ester Copolymer elastomerics, thereby both provided a kind of new Core-Shell Polyacrylic-ester Copolymer class elastomerics that can be used as ultraviolet absorbers for this area, and wherein has 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone of ultraviolet absorption effect because being aggregated on the macromole, the polymer of having realized the small molecules UV light absorber quantizes, reduced the migration of UV light absorber, volatilize, kept the persistence of photo-stability efficiency.
2. because the Core-Shell Polyacrylic-ester Copolymer that is used as ultraviolet absorbers provided by the invention is a kind of elastomerics, thereby when with it during as the ultraviolet absorbers of certain macromolecular material, it both can give the ultraviolet light performance of macromolecular material " permanent ", can carry out the effectively toughness reinforcing mechanical property of improving macromolecular material to it again, especially the elongation at break of material and shock strength can avoid the stable modification agent of small molecules light and photooxidation resistance on the impact of the macromolecule matrix mechanical property of materials.
3. because the Core-Shell Polyacrylic-ester Copolymer that is used as ultraviolet absorbers provided by the invention is the material that small molecules UV light absorber polymer quantizes, thereby according to the consistency principle, its not only have and the matrix of macromolecular material between interface compatibility, and also can by changing the elastomeric nucleus shell structure of Core-Shell Polyacrylic-ester Copolymer class, improve its dispersiveness in different polymeric matrixs.
4. because being the employing emulsion polymerization, the present invention prepares the Core-Shell Polyacrylic-ester Copolymer elastomerics, thus environment friendly and pollution-free, and technology maturation realizes industrialization easily.
Description of drawings
Fig. 1 is the transmission electron microscope photo that is grafted with the nucleocapsid structure acrylate polymer emulsion of response type ultraviolet absorbers.
Fig. 2 is the elastomeric infrared absorpting light spectra of Core-Shell Polyacrylic-ester Copolymer class that is grafted with the response type UV light absorber.
Fig. 3 is the elastomeric uv absorption spectra of Core-Shell Polyacrylic-ester Copolymer class that is grafted with the response type ultraviolet absorbers.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples just are used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the foregoing invention content still belong to protection scope of the present invention.
In addition, what deserves to be explained is that the added umber of each material of following examples is mass parts.
Embodiment 1
With 50% of 50% and deionized water total mass of 10 parts of benzophenone of 40 parts of butyl acrylates, 10 parts of methyl methacrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 50% of 50% and deionized water total mass of 10 parts of benzophenone of 10 parts of methyl methacrylates, 10 parts of butyl acrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 30%, 50% and initiator total mass of pH adjusting agent total mass 15%, mix and be warming up to 70 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 30 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 75 ℃, then respectively with 70% and initiator total mass of nuclear layer monomer pre-emulsion total mass 30% simultaneously average rate drip wherein, drip rear continuation 75 ℃ of insulations 30 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 80 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 80 ℃, be incubated 30 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 80 parts of the calcium chloride waters of mass percent concentration 5% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 2% of monomer total mass, by sodium laurylsulfonate and polyoxyethylene nonylphenol ether in mass ratio 1.5: 1 formulated; Described initiator potassium persulfate total mass is 1.0% of monomer total mass, is configured to mass percent concentration during use and is drip behind 1.5% the initiator solution; Described pH adjusting agent yellow soda ash total mass is 0.4% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1.2: 1.
Embodiment 2
With 50% of 50% and deionized water total mass of 40 parts of butyl acrylates, 30 parts of ethyl propenoates, compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 50% of 50% and deionized water total mass of 20 parts of benzophenone of methacrylic ester EMA10 part, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 50%, 50% and initiator total mass of pH adjusting agent total mass 30%, mix and be warming up to 70 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 30 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 75 ℃, then respectively with 50% and initiator total mass of nuclear layer monomer pre-emulsion total mass 20% simultaneously average rate drip wherein, drip rear continuation 75 ℃ of insulations 40 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 80 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 80 ℃, be incubated 40 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 80 parts of the sodium chloride aqueous solutions of mass percent concentration 5% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 2% of monomer total mass, by sodium laurylsulfonate and polyoxyethylene octylphenol ether in mass ratio 2: 1 formulated; Described initiator ammonium persulfate total mass is 0.6% of monomer total mass, is configured to mass percent concentration during use and is drip behind 2.5% the initiator solution; Described pH adjusting agent sodium bicarbonate total mass is 0.3% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1.5: 1.
Embodiment 3
With 60% of 60% and deionized water total mass of 5 parts of benzophenone of 20 parts of ethyl propenoates, 25 parts of vinylformic acid ethylhexyls, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 40% of 40% and deionized water total mass of 10 parts of benzophenone of 20 parts of β-dimethyl-aminoethylmethacrylates, 20 parts of Propenoic acid, 2-methyl, isobutyl esters, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 30%, 60% and initiator total mass of pH adjusting agent total mass 20%, mix and be warming up to 75 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 40 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 80 ℃, then respectively with 70% and initiator total mass of nuclear layer monomer pre-emulsion total mass 30% simultaneously average rate drip wherein, drip rear continuation 80 ℃ of insulations 40 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 83 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 83 ℃, be incubated 40 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 60 parts of the aluminum sulfate aqueous solutions of mass percent concentration 10% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 4% of monomer total mass, by sodium lauryl sulphate and polyoxyethylene nonylphenol ether in mass ratio 2: 1 formulated; Described initiator potassium persulfate total mass is 0.3% of monomer total mass, is configured to mass percent concentration during use and is drip behind 3% the initiator solution; Described pH adjusting agent SODIUM PHOSPHATE, MONOBASIC total mass is 0.2% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1.7: 1.
Embodiment 4
With 70% of 70% and deionized water total mass of 50 parts of butyl acrylates, 5 parts of methyl methacrylates, compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 30% of 30% and deionized water total mass of 15 parts of benzophenone of 20 parts of methyl methacrylates, 10 parts of butyl acrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 40%, 60% and initiator total mass of pH adjusting agent total mass 30%, mix and be warming up to 75 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 35 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 80 ℃, then respectively with 60% and initiator total mass of nuclear layer monomer pre-emulsion total mass 20% simultaneously average rate drip wherein, drip rear continuation 80 ℃ of insulations 35 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 85 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 85 ℃, be incubated 30 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 70 parts of the calcium chloride waters of mass percent concentration 7% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 3% of monomer total mass, by sodium laurylsulfonate and polyoxyethylene nonylphenol ether in mass ratio 2: 1 formulated; Described initiator potassium persulfate total mass is 0.5% of monomer total mass, is configured to mass percent concentration during use and is drip behind 5% the initiator solution; Described pH adjusting agent sodium-acetate total mass is 0.2% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1: 1.
Embodiment 5
With 70% of 70% and deionized water total mass of 8 parts of benzophenone of 25 parts of butyl acrylates, 30 parts of ethyl propenoates, 8 parts of methyl methacrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 30% of 30% and deionized water total mass of 12 parts of benzophenone of 12 parts of methyl methacrylates, 5 parts of butyl acrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 50%, 70% and initiator total mass of pH adjusting agent total mass 30%, mix and be warming up to 72 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 35 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 78 ℃, then respectively with 50% and initiator total mass of nuclear layer monomer pre-emulsion total mass 30% simultaneously average rate drip wherein, drip rear continuation 78 ℃ of insulations 35 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 85 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 85 ℃, be incubated 35 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 80 parts of the calcium chloride waters of mass percent concentration 8% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 3% of monomer total mass, by Sodium dodecylbenzene sulfonate and polyoxyethylene nonylphenol ether in mass ratio 2.5: 1 formulated; Described initiator Sodium Persulfate total mass is 0.3% of monomer total mass, is configured to mass percent concentration during use and is drip behind 1.5% the initiator solution; Described pH adjusting agent sodium bicarbonate total mass is 0.3% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1.4: 1.
Embodiment 6
With 50% of 50% and deionized water total mass of 5 parts of benzophenone of 40 parts of butyl acrylates, 5 parts of methyl methacrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the nuclear layer monomer pre-emulsion; With 50% of 50% and deionized water total mass of 15 parts of benzophenone of 15 parts of methyl methacrylates, 15 parts of Propenoic acid, 2-methyl, isobutyl esters, 5 parts of butyl acrylates, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-), compound emulsifying agent total mass, fully mix and make the shell monomers pre-emulsion; With gained nuclear layer monomer pre-emulsion total mass 30%, 50% and initiator total mass of pH adjusting agent total mass 15%, mix and be warming up to 75 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 40 minutes; First the sub-microemulsion of the nuclear species that makes is warming up to 80 ℃, then respectively with 50% and initiator total mass of nuclear layer monomer pre-emulsion total mass 30% simultaneously average rate drip wherein, drip rear continuation 80 ℃ of insulations 40 minutes, make the nuclear polymer emulsion; First the nuclear polymer emulsion that makes is warming up to 80 ℃, add remaining pH adjusting agent, then respectively shell monomers pre-emulsion and remaining initiator solution while average rate are dripped wherein, under 80 ℃, be incubated 40 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion; At room temperature, 80 parts of the calcium chloride waters of mass percent concentration 10% are joined carry out breakdown of emulsion in the nucleocapsid structure acrylate polymer emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product.
The total mass of wherein said compound emulsifying agent is 5% of monomer total mass, by sodium laurylsulfonate and polyoxyethylene octylphenol ether in mass ratio 2.5: 1 formulated; Described initiator potassium persulfate total mass is 0.8% of monomer total mass, is configured to mass percent concentration during use and is drip behind 2.5% the initiator solution; Described pH adjusting agent yellow soda ash total mass is 0.3% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 2: 1.
In order to investigate Core-Shell Polyacrylic-ester Copolymer class elastomerics of the present invention to the light stable modification effect of macromolecular material, the present invention selects the relatively poor macromolecular material of a kind of anti-ultraviolet aging---and polyoxymethylene (POM) is as the modification object.The weight-average molecular weight that namely first the present invention is prepared is 5.3124xe
5The Core-Shell Polyacrylic-ester Copolymer class elastomerics of g/mol adds polyoxymethylene to by 13% massfraction and mixes, and then puts into and extrudes blend on the twin screw extruder, and granulation is injection molded into standard test specimen at injection moulding machine at last.And with this standard test specimen (application examples), pure polyoxymethylene and directly add 1% the organic light absorber UV-0 of benzophenone and 12% polyacrylate(s) elastomerics at pure polyoxymethylene (irradiance is 3.0W/m through UV-light
2) irradiation is after 1000 hours, according to its tensile property of GB1040-92 standard test, draw speed 50mm/min, according to its impact property of GB1843-96 standard test, its test result is as shown in the table:
Table
The result shows that the ultraviolet light performance of the polyoxymethylene after nucleocapsid is elastomer-modified and mechanical property conservation rate all are better than unmodified and with the POM of the organic light absorber UV-0 of benzophenone and the simultaneously modification of polyacrylate(s) elastomerics.
Claims (10)
1. the polyacrylate elastomer of a nucleocapsid structure is characterized in that this elastomerics is to obtain by the seeded emulsion polymerization method of following prescription by the semi-continuous charging mode, and its appearance luster is white, light yellow or yellow, and weight-average molecular weight is 2～10xe
5G/mol, formed polymer emulsion particle is microspheroidal before the elastomerics breakdown of emulsion, particle diameter is 50-100nm, and after phospho-wolframic acid dyeing, can be observed the latex particle microballoon and be three-decker, be followed successively by from the inside to the outside stratum nucleare, transition layer and shell, the recipe ingredient that wherein forms this elastomerics stratum nucleare is counted by mass parts:
Acrylate 40-70 part
Methacrylic ester 0-10 part
2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 0-10 part;
The recipe ingredient that forms this elastomerics shell is counted by mass parts:
Methacrylic ester 10-40 part
Acrylate 0-10 part
2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 10-20 part.
2. method for preparing the polyacrylate elastomer of nucleocapsid structure claimed in claim 1 is characterized in that the processing step of the method and condition are as follows:
(1) with acrylate 40-70 part, methacrylic ester 0-10 part, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 0-10 part, the 50-70% of compound emulsifying agent total mass and the 50-70% of deionized water total mass, fully mixes and make the nuclear layer monomer pre-emulsion;
(2) with methacrylic ester 10-40 part, acrylate 0-10 part, 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone 10-20 part, the 30-50% of compound emulsifying agent total mass and the 30-50% of deionized water total mass, fully mix and make the shell monomers pre-emulsion;
(3) with the 30-50% of the resulting nuclear layer monomer pre-emulsion of step (1) total mass, the 50-70% of pH adjusting agent total mass and the 15-30% of initiator total mass, mix and be warming up to 70～75 ℃, treat that blue phase appears in emulsion, continue to stir insulation and made the sub-microemulsion of nuclear species in 30～40 minutes;
(4) the sub-microemulsion of nuclear species that first step (3) is made is warming up to 75～80 ℃, then respectively the 50-70% of nuclear layer monomer pre-emulsion total mass and the 20-30% while average rate of initiator total mass are dripped wherein, drip 75～80 ℃ of insulations of rear continuation 30～40 minutes, make the nuclear polymer emulsion;
(5) first the prepared nuclear polymer emulsion of step (4) is warming up to 80～85 ℃, add remaining pH adjusting agent, then respectively the resulting shell monomers pre-emulsion of step (2) and remaining initiator solution while average rate are dripped wherein, under 80～85 ℃, be incubated 30～40 minutes after dripping, then be down to room temperature, make the nucleocapsid structure acrylate polymer emulsion;
(6) at room temperature, 60～80 parts of the aqueous electrolyte liquids of mass percent concentration 5～10% are joined in the prepared nucleocapsid structure acrylate polymer emulsion of step (5) carry out breakdown of emulsion, wash throw out with water to remove residual monomer and emulsifying agent, final drying gets final product
The total mass of wherein said compound emulsifying agent is 2～5% of monomer total mass, and by anionic emulsifier and nonionic emulsifier in mass ratio 1.5～2.5: 1 is formulated; Described initiator total mass is 0.3～1.0% of monomer total mass, is configured to mass percent concentration during use and is drip behind 1.5～5% the initiator solution; Described pH adjusting agent total mass is 0.2～0.4% of monomer total mass; The total mass of described deionized water and the total mass ratio of monomer are 1～2: 1.
3. the preparation method of the polyacrylate elastomer of nucleocapsid structure according to claim 2 is characterized in that the acrylate described in the method is at least a in butyl acrylate, ethyl propenoate and the vinylformic acid ethylhexyl; Methacrylic ester is at least a in methyl methacrylate, β-dimethyl-aminoethylmethacrylate and the Propenoic acid, 2-methyl, isobutyl ester.
4. according to claim 2 or the preparation method of the polyacrylate elastomer of 3 described nucleocapsid structures, it is characterized in that the anionic emulsifier described in the method is any in sodium laurylsulfonate, sodium lauryl sulphate or the Sodium dodecylbenzene sulfonate; Described nonionic emulsifier is polyoxyethylene nonylphenol ether or polyoxyethylene octylphenol ether.
5. according to claim 2 or the preparation method of the polyacrylate elastomer of 3 described nucleocapsid structures, it is characterized in that the initiator described in the method is any in Potassium Persulphate, ammonium persulphate or the Sodium Persulfate.
6. the preparation method of the polyacrylate elastomer of nucleocapsid structure according to claim 4 is characterized in that the initiator described in the method is any in Potassium Persulphate, ammonium persulphate or the Sodium Persulfate.
7. according to claim 2 or the preparation method of the polyacrylate elastomer of 3 described nucleocapsid structures, it is characterized in that the pH adjusting agent described in the method is any in yellow soda ash, sodium bicarbonate, sodium-acetate or the Sodium phosphate dibasic.
8. the preparation method of the polyacrylate elastomer of nucleocapsid structure according to claim 6 is characterized in that the pH adjusting agent described in the method is any in yellow soda ash, sodium bicarbonate, sodium-acetate or the Sodium phosphate dibasic.
9. according to claim 2 or the preparation method of the polyacrylate elastomer of 3 described nucleocapsid structures, it is characterized in that the aqueous electrolyte liquid described in the method is formulated with in sodium-chlor, calcium chloride, Tai-Ace S 150, sulfuric acid or the hydrochloric acid any.
10. the preparation method of the polyacrylate elastomer of nucleocapsid structure according to claim 8 is characterized in that the aqueous electrolyte liquid described in the method is formulated with in sodium-chlor, calcium chloride, Tai-Ace S 150, sulfuric acid or the hydrochloric acid any.
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| CN102675523B (en) * | 2012-04-23 | 2014-11-05 | 奇瑞汽车股份有限公司 | Polylactic acid flexibilizer and preparation method thereof and modified polylactic acid and preparation method thereof |
| CN102936386B (en) * | 2012-11-09 | 2015-12-16 | 广州市高士实业有限公司 | Viton rubber master batch and preparation method thereof |
| CN103289011A (en) * | 2013-06-17 | 2013-09-11 | 四川大学 | Polyacrylate elastomer containing low-alkalinity hindered amine and preparation method thereof |
| CN103641943B (en) * | 2013-11-12 | 2016-04-13 | 常州大学 | The method of semi-continuous emulsion polymerizing synthesizing multilayer shell structure polymer particle |
| CN104371053B (en) * | 2014-09-11 | 2017-05-03 | 四川大学 | Hindered amine light stabilizer with characteristics of high molecular weight and narrow molecular weight distribution, and preparation method thereof |
| CN104446102B (en) * | 2014-11-25 | 2016-06-01 | 江苏苏博特新材料股份有限公司 | A kind of admixture and its preparation method promoting the anti-folding of cement-based material and tensile strength |
| CN104609759B (en) * | 2014-11-25 | 2017-04-12 | 江苏苏博特新材料股份有限公司 | Additive capable of improving bending strength and tensile strength of cement base material and its preparation method |
| CN105801872B (en) * | 2016-05-24 | 2018-09-25 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the toughener with nucleocapsid |
| CN106977669B (en) * | 2017-05-08 | 2019-05-31 | 南通艾德旺化工有限公司 | Nuclear-shell structure type ACR resin and preparation method thereof |
| CN109233504A (en) * | 2017-05-11 | 2019-01-18 | 立邦涂料（中国）有限公司 | A kind of surface super hydrophilic type exterior wall anti-pollution paint and preparation method thereof |
| CN113249097A (en) * | 2021-05-20 | 2021-08-13 | 浙江传化功能新材料有限公司 | Polyacrylate phase-change microcapsule and preparation method thereof |
| CN114507320B (en) * | 2022-03-17 | 2022-08-23 | 嘉兴金门量子材料科技有限公司 | Acrylate prepolymer and preparation method and application thereof |
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