CN102382239B - Hollow polymer emulsion and preparation method thereof - Google Patents
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Abstract
The invention discloses a hollow polymer emulsion and a preparation method thereof. The preparation method adopts the processes of emulsion polymerization, core-shell emulsion polymerization and the like to prepare the hollow polymer emulsion. An emulsion particle is of a structure with a hard shell and a soft shell, and the void fraction of a film formed by the emulsion reaches more than 50 percent. A variety of unsaturated monomers, emulsifier and initiator are adopted to prepare the hollow polymer emulsion, in particular, isobornyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate are chosen as shell monomers, the contents of isobornyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate respectively account for 2 to 5 percent and 3 to 6 percent by weight of the total amount of the emulsion, and the mechanical properties, the weather fastness and the dirt resistance of the emulsion film are effectively enhanced. The product has an excellent dry hiding effect, can decrease the density of the film and improve handle, and can be applied in the fields of water-borne coating, paper coating, industrial coating, ink and the like.
Description
Technical field
The present invention relates to polymer emulsion and preparation method, the fields such as coating, paper coating, printing ink that particularly are applied to have a kind of hollow polymer emulsion of good opacifying power and elongation at break and preparation method thereof.
Technical background
In recent years, there were successively some documents and patent to announce the preparation of relevant hollow polymer emulsion.Hollow polymer emulsion inside is cavity, be full of air in it, due to the high scattering to light of the difference of the refractive index at air/polymer interface place and air filled cavity, the hollow polymer microsphere has very strong covering effect, therefore can be used for opacity polymer in water-borne coatings.Can also improve in addition outdoor tint retention of the contamination resistance of coating and scrub resistance, raising coating etc.
Existing emulsion polymerization technique synthesizes the emulsion polymer of hydrophilic core, hydrophobicity shell.But when the ratio that accounts for the emulsion particle volume when nuclear monomer is greater than 20%, adopt traditional technology to be difficult to core is coated fully, the destruction that can cause the alkali swelling to cause nucleocapsid structure, be not easy to obtain the hollow polymer emulsion that hollow volume is larger.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, expand the Application Areas of hollow polymerized emulsion, and a kind of hollow polymerized emulsion and preparation method thereof is provided.
The hollow polymer emulsion the present invention relates to, as a kind of hud typed emulsion polymer, comprising: a stratum nucleare polymkeric substance and two-layer shell polymkeric substance, and the stratum nucleare polymkeric substance is water-absorbing resin, shell is divided into crust polymer and soft shell polymkeric substance.
Its technical scheme comprises: contain unsaturated monomer, emulsifying agent, initiator and water in formula, have the structure of a duricrust and a soft shell, it is characterized in that: in the first layer duricrust isobornyl methacrylate account for total amount 2 ~ 5%; In second layer soft shell, vinylformic acid hexafluoro butyl ester accounts for total amount 3 ~ 6%; The monomer consumption of nuclear structure accounts for 10% of total amount.
The per-cent that described monocoque accounts for gross weight is 15 ~ 25%, and second-order transition temperature is 40 ~ 60 ℃; Described soft shell structure accounts for 15 ~ 25% of total weight percent, and second-order transition temperature is-20 ~-10 ℃.
The preparation method of above-mentioned hollow polymer emulsion, comprise the steps:
(1) by 80 ~ 90 weight parts waters, 2.5 ~ 3 weight part emulsifying agents and 1.2 ~ 1.5 weight part Sodium dodecylbenzene sulfonatees, 95 ~ 104 weight part unsaturated monomer mixing and emulsifyings, make pre-emulsion A;
(2) 165 ~ 175 weight parts waters, 4.5 ~ 5.8 weight part emulsifying agents, 1.8 ~ 2.2 weight part Witco 1298 Soft Acids are added to the unsaturated monomer of 39 ~ 53 weight parts after mixing; comprising 12-13 weight part isobornyl methacrylate, emulsification makes pre-emulsion B;
After (3) 98 ~ 100 weight parts waters, 2.6 ~ 3 weight part oxidation inhibitor, 1 ~ 1.2 weight part emulsifying agent and 28 ~ 32 weight part Witco 1298 Soft Acids mix; the unsaturated monomer that adds 91.6 ~ 102.4 weight parts; comprising vinylformic acid hexafluoro butyl ester 8.8 ~ 9.2 weight parts, emulsification makes pre-emulsion C;
(4) 98 ~ 100 weight parts waters, 80 ~ 90 weight part emulsifying agents and 3.6 ~ 4 weight part Sodium dodecylbenzene sulfonate Hybrid Heating are warming up to 80-85 ℃; add pre-emulsion A, pre-emulsion B and 57 ~ 63 weight part initiator solutions; make the first layer duricrust, and form the core-shell emulsion that water-absorbing resin is core;
(5) add the PH conditioning agent in above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, keep emulsion temperature to stir under 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core;
(6) be cooled to 78 ~ 80 ℃, in above-mentioned core-shell emulsion, add pre-emulsion C and 18 ~ 22 weight part initiator solutions, be cooled to 60 ~ 65 ℃ after being incubated 25 ~ 35 minutes, add 0.3 ~ 0.4 weight part hydrogen peroxide and 0.2 ~ 0.3 weight part FF
6the aqueous solution, be incubated 25 ~ 35 minutes and remove residual monomer, then is cooled to below 40 ℃, adds 0.18 ~ 0.22 weight part oxidation inhibitor and 1.8-2.2 weight part sterilant to stir, and makes the hollow polymerized emulsion.
Emulsifying agent in described step (1) is the OP-9 emulsifying agent, unsaturated monomer also comprises ethyl propenoate, high purity acrylic acid, vinylformic acid, the DAP monomer, the combination that the emulsifying agent of described step (2) is CO-436 emulsifying agent and A-103 emulsifying agent, described unsaturated monomer also comprises methacrylic acid, the combination of vinylbenzene and butyl acrylate, the antioxidant of described step (3) is AT-10 oxidation inhibitor, emulsifying agent is the AMPS-2404 emulsifying agent, unsaturated monomer also comprises vinyl cyanide, methacrylic acid, described step (4) emulsifying agent is the OP-21 emulsifying agent, initiator solution is the 3.2%NPS aqueous solution, described step (5) PH conditioning agent is the AMP-95 aqueous solution, initiator solution in described step (6) is the 3.2%NPS aqueous solution, oxidation inhibitor is AT-2401 oxidation inhibitor, sterilant is the RS sterilant.
Above-mentioned preparation method is further preferred, comprises lower step:
(1) add deionized water 80 ~ 90 weight parts, OP-9 emulsifying agent 2.5 ~ 3 weight parts and Sodium dodecylbenzene sulfonate 1.2 ~ 1.5 weight parts in pre-emulsification tank A; in whipping process; add ethyl propenoate 28 ~ 32 weight parts, vinylformic acid 58-62 weight part and DAP monomer 9 ~ 10 weight parts; high-speed stirring 25-35 minute, make pre-emulsion A;
(2) add deionized water 165 ~ 175 weight parts, CO-436 emulsifying agent 3.5 ~ 4.5 weight parts, A-103 emulsifying agent 1 ~ 1.3 weight part, Witco 1298 Soft Acid 1.8 ~ 2.2 weight parts in pre-emulsification tank B; in whipping process; add isobornyl methacrylate 12 ~ 13 weight parts, methacrylic acid 5 ~ 6 weight parts, vinylbenzene 12 ~ 13 weight parts and butyl acrylate 10 ~ 11 weight parts; high-speed stirring 25 ~ 35 minutes, make pre-emulsion B;
(3) add deionized water 98 ~ 100 weight parts, AT-10 oxidation inhibitor 2.6 ~ 3 weight parts, AMPS-2404 emulsifying agent 1 ~ 1.2 weight part and Witco 1298 Soft Acid 28 ~ 32 weight parts in pre-emulsification tank C; in whipping process; add vinyl cyanide 80 ~ 90 weight parts, methacrylic acid 2.8 ~ 3.2 weight parts and vinylformic acid hexafluoro butyl ester 8.8 ~ 9.2 weight parts; high-speed stirring 25 ~ 35 minutes, make pre-emulsion C;
(4) add deionized water 98 ~ 100 weight parts, OP-21 emulsifying agent 80 ~ 90 weight parts and Sodium dodecylbenzene sulfonate 3.6 ~ 4 weight parts in reactor; start to drip pre-emulsion A and 3.2%NPS initiator solution 19 ~ 21 weight parts after being heated to 80-85 ℃; make the hydroscopicity seed emulsion; be incubated after 25 ~ 35 minutes and start to drip pre-emulsion B and 3.2%NaPS initiator solution 38 ~ 42 weight parts; make the first layer duricrust, and form the core-shell emulsion that water-absorbing resin is core;
(5) slowly drip the PH conditioning agent AMP-95 aqueous solution 1.5 ~ 2.8 weight parts in above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, then stir 25 ~ 35 minutes, keep emulsion temperature at 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core;
(6) temperature of reactor is down to 78 ~ 80 ℃, then starts to drip pre-emulsion C and 3.2%NaPS initiator solution 18 ~ 22 weight parts, be cooled to 60 ~ 65 ℃ be incubated 25 ~ 35 minutes after dropwising after, add hydrogen peroxide 0.3 ~ 0.4 weight part and FF
60.2 ~ 0.3 weight parts water solution, be incubated 25 ~ 35 minutes and remove residual monomer, then is cooled to below 40 ℃, adds AT-2401 oxidation inhibitor 0.18 ~ 0.22 weight part and RS sterilant 1.8-2.2 weight part to stir, and makes the elastic hollow polymerized emulsion.
The hollow polymer emulsion obtained according to the method described above, because nuclear structure has very high water-absorbent, inflatable 200 times of volume after the core water suction, make voidage can reach more than 50%, the hollow polymer emulsion prepared higher than traditional technique, and outside elastic container structure and the employing fluorine modification technology of adopting, especially select isobornyl methacrylate and vinylformic acid hexafluoro butyl ester as shell monomers, the account for weight percent of its content in the emulsion total amount is respectively 2 ~ 5%, 3 ~ 6%, effectively raise the mechanical property of emulsion film, weathering resistance and antifouling property, make emulsion film there is very high opacifying power, elongation at break and anti-pollution characteristic.Can the widespread use paper coating and the preparation of emulsion paint, whiteness, color, print gloss, ink absorption and wet picking strength that the consumption that can reduce pigment and resin improves paper have obvious improvement.
embodiment:
Below by several exemplary embodiments, be described further.
Embodiment 1
1, add deionized water 80kg, OP-9 emulsifying agent 2.7kg, Sodium dodecylbenzene sulfonate (SDBS) 1.4kg in pre-emulsification tank A, stirring makes it even, keeping under agitation condition, add ethyl propenoate 30kg, vinylformic acid 60kg, DAP monomer 10kg in the pre-emulsification tank, high-speed stirring 30 minutes, make pre-emulsion A standby.
2, add deionized water 170kg, CO-436 emulsifying agent 4kg, A-103 emulsifying agent 1.2kg, Witco 1298 Soft Acid (DSB) 2.0kg in pre-emulsification tank B, stirring makes it even, keeping under agitation condition, add isobornyl methacrylate 12.5kg, methacrylic acid 5kg, vinylbenzene 12.5kg, butyl acrylate 10.5kg in the pre-emulsification tank, high-speed stirring 30 minutes, make pre-emulsion B standby.
3, to adding deionized water 100kg, AT-10 oxidation inhibitor 2.8kg, 30% AMPS-2404 emulsifying agent 1.2kg, DSB 28kg in pre-emulsification tank C, stirring makes it even, keeping under agitation condition, add vinyl cyanide 85kg, methacrylic acid 3kg, vinylformic acid hexafluoro butyl ester 9kg in the pre-emulsification tank, high-speed stirring 30 minutes, make pre-emulsion C standby.
4, in being housed, the stainless steel cauldron of condenser adds deionized water 100kg, OP-21 emulsifying agent 85kg, SDBS 3.8kg, then be heated to 80 ~ 85 ℃, then start to drip pre-emulsion A and NPS initiator solution 20kg, time for adding is controlled at 2 hours, makes the hydroscopicity seed emulsion.Be incubated 30 minutes, then start to drip the NaPS initiator solution 40kg of B pre-emulsion and 3.2%, time for adding is controlled at 2.5 hours, makes the first layer duricrust, the core-shell emulsion that the formation water-absorbing resin is core.
5, slowly drip the AMP-95 aqueous solution 1.5 ~ 2.8kg at above-mentioned core-shell emulsion, regulate emulsion Ph value to 7.5 ~ 8.5, then stir 30 minutes, keep emulsion temperature at 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core.
6, the temperature of reactor is down to 78 ~ 80 ℃, then starts to drip the NaPS initiator solution 20kg of C pre-emulsion and 3.2%.Time for adding is controlled at 2.5 hours, and after dropwising, insulation is 30 minutes, then is cooled to 60 ~ 65 ℃, adds the H202(hydrogen peroxide) 0.35kg and FF
6aqueous solution 0.25kg, be incubated 30 minutes and remove residual monomer, then is cooled to below 40 ℃, adds AT-2401 oxidation inhibitor 0.2kg, sterilant (RS) 2kg to stir, and makes elastic hollow acroleic acid polymerization emulsion.
Embodiment 2
1, add deionized water 90kg, OP-9 emulsifying agent 3.0kg, SDBS 1.5kg in pre-emulsification tank A, stirring makes it even, keeping under agitation condition, add ethyl propenoate 32kg, vinylformic acid 62kg, DAP monomer 10kg in the pre-emulsification tank, high-speed stirring 32 minutes, make pre-emulsion A standby.
2, add deionized water 175kg, CO-436 emulsifying agent 4.5kg, A-103 emulsifying agent 1.2kg, DSB 2.2kg in pre-emulsification tank B, stirring makes it even, keeping under agitation condition, add isobornyl methacrylate 13kg, methacrylic acid 6kg, vinylbenzene 13kg, butyl acrylate 11kg in the pre-emulsification tank, high-speed stirring 35 minutes, make pre-emulsion B standby.
3, add deionized water 100kg, AT-10 oxidation inhibitor 3kg, AMPS-2404 emulsifying agent 1.2kg, DSB32kg in pre-emulsification tank C, stirring makes it even, keeping under agitation condition, add vinyl cyanide 90kg, methacrylic acid 3.2kg, vinylformic acid hexafluoro butyl ester 9.2kg in the pre-emulsification tank, high-speed stirring 35 minutes, make pre-emulsion C standby.
4, in being housed, the stainless steel cauldron of condenser adds deionized water 100kg, OP-21 emulsifying agent 90kg, SDBS 4kg, then be heated to 80 ~ 85 ℃, then start to drip pre-emulsion A and NPS initiator solution 21kg, time for adding is controlled at 2 hours, makes the hydroscopicity seed emulsion.Be incubated 30 minutes, then start to drip the NaPS initiator solution 42kg of B pre-emulsion and 3.2%, time for adding is controlled at 2.5 hours, makes the first layer duricrust, the core-shell emulsion that the formation water-absorbing resin is core.
5, slowly drip the AMP-95 aqueous solution 1.5 ~ 2.8kg at above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, then stir 35 minutes, keep emulsion temperature at 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core.
6, the temperature of reactor is down to 78 ~ 80 ℃, then starts to drip the NaPS initiator solution 22kg of C pre-emulsion and 3.2%.Time for adding is controlled at 2.5 hours, and after dropwising, insulation is 30 minutes, then is cooled to 60 ~ 65 ℃, adds hydrogen peroxide 0.4kg and FF
6aqueous solution 0.3kg, be incubated 30 minutes and remove residual monomer, then is cooled to below 40 ℃, adds AT-2401 oxidation inhibitor 0.22kg, RS sterilant 2.2kg to stir, and makes elastic hollow acroleic acid polymerization emulsion.
Embodiment 3
1, add deionized water 80kg, OP-9 emulsifying agent 2.5kg, SDBS 1.2kg in pre-emulsification tank A, stirring makes it even, keeping under agitation condition, add ethyl propenoate 28kg, vinylformic acid 58kg, DAP monomer 9kg in the pre-emulsification tank, high-speed stirring 25 minutes, make pre-emulsion A standby.
2, add deionized water 165kg, CO-436 emulsifying agent 3.5kg, A-103 emulsifying agent 1kg, DSB 1.8kg in pre-emulsification tank B, stirring makes it even, keeping under agitation condition, add isobornyl methacrylate 12kg, methacrylic acid 5kg, vinylbenzene 12kg, butyl acrylate 10kg in the pre-emulsification tank, high-speed stirring 25 minutes, make pre-emulsion B standby.
3, add deionized water 98kg, AT-10 oxidation inhibitor 2.6kg, AMPS-2404 emulsifying agent 1kg, DSB 28kg in pre-emulsification tank C, stirring makes it even, keeping under agitation condition, add vinyl cyanide 80kg, methacrylic acid 2.8kg, vinylformic acid hexafluoro butyl ester 8.8kg in the pre-emulsification tank, high-speed stirring 25 minutes, make pre-emulsion C standby.
4, in being housed, the condenser stainless steel cauldron adds deionized water 98kg, OP-21 emulsifying agent 80kg, SDBS 3.6kg, then be heated to 80 ~ 85 ℃, then start to drip pre-emulsion A and NPS initiator solution 19kg, time for adding is controlled at 2 hours, makes the hydroscopicity seed emulsion.Be incubated 30 minutes, then start to drip the NaPS initiator solution 38kg of pre-emulsion B and 3.2%, time for adding is controlled at 2.5 hours, makes the first layer duricrust, the core-shell emulsion that the formation water-absorbing resin is core.
5, slowly drip the AMP-95 aqueous solution 1.5 ~ 2.8kg at above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, then stir 30 minutes, keep emulsion temperature at 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core.
6, the temperature of reactor is down to 78 ℃, then starts to drip the NaPS initiator solution 18kg of C pre-emulsion and 3.2%.Time for adding is controlled at 2.5 hours, and after dropwising, insulation is 30 minutes, then is cooled to 60 ℃, adds hydrogen peroxide 0.3kg and FF
6residual monomer is removed in aqueous solution 0.2kg insulation in 30 minutes, then is cooled to 35 ℃, adds AT-2401 oxidation inhibitor 0.18kg, sterilant (RS) 1.8kg to stir, and makes elastic hollow acroleic acid polymerization emulsion.
Embodiment 1-3 is the preferred embodiments of the present invention, and in resulting product, in the first layer duricrust, to account for the per-cent of gross weight be 15 ~ 25% to monocoque, and second-order transition temperature is 40 ~ 60 ℃, and isobornyl methacrylate accounts for 2 ~ 5% of total amount; The described soft shell structure of the second layer accounts for 15 ~ 25% of total weight percent, and second-order transition temperature is-20 ~-10 ℃, and in soft shell, vinylformic acid hexafluoro butyl ester accounts for total amount 3 ~ 6%; The monomer consumption of nuclear structure accounts for 10% of total amount.
Unsaturated monomer in embodiment and emulsifying agent can again be chosen and reconfigure, and all can access this above-mentioned hollow polymerized emulsion, at this, just do not enumerate.
Initiator, oxidation inhibitor, sterilant, Ph conditioning agent etc. are the raw material commonly used of this area, and which kind of and consumption it specifically select suitably to adjust according to actual needs.
Claims (4)
1. the preparation method of a hollow polymer emulsion, contain unsaturated monomer, emulsifying agent, initiator and water in formula, has the structure of a duricrust and a soft shell, it is characterized in that: in the first layer duricrust isobornyl methacrylate account for total amount 2 ~ 5%; In second layer soft shell, vinylformic acid hexafluoro butyl ester accounts for total amount 3 ~ 6%; The monomer consumption of nuclear structure accounts for 10% of total amount; Specifically comprise the steps:
(1) by 80 ~ 90 weight parts waters, 2.5 ~ 3 weight part emulsifying agents and 1.2 ~ 1.5 weight part Sodium dodecylbenzene sulfonatees, 95 ~ 104 weight part unsaturated monomer mixing and emulsifyings, make pre-emulsion A;
(2) 165 ~ 175 weight parts waters, 4.5 ~ 5.8 weight part emulsifying agents, 1.8 ~ 2.2 weight part Witco 1298 Soft Acids are added to the unsaturated monomer of 39 ~ 53 weight parts after mixing; comprising 12-13 weight part isobornyl methacrylate, emulsification makes pre-emulsion B;
After (3) 98 ~ 100 weight parts waters, 2.6 ~ 3 weight part oxidation inhibitor, 1 ~ 1.2 weight part emulsifying agent and 28 ~ 32 weight part Witco 1298 Soft Acids mix; the unsaturated monomer that adds 91.6 ~ 102.4 weight parts; comprising vinylformic acid hexafluoro butyl ester 8.8 ~ 9.2 weight parts, emulsification makes pre-emulsion C;
(4) 98 ~ 100 weight parts waters, 80 ~ 90 weight part emulsifying agents and 3.6 ~ 4 weight part Sodium dodecylbenzene sulfonate Hybrid Heating are warming up to 80-85 ℃; add pre-emulsion A, pre-emulsion B and 57 ~ 63 weight part initiator solutions; make the first layer duricrust, and form the core-shell emulsion that water-absorbing resin is core;
(5) add the PH conditioning agent in above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, keep emulsion temperature to stir under 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core;
(6) be cooled to 78 ~ 80 ℃, in above-mentioned core-shell emulsion, add pre-emulsion C and 18 ~ 22 weight part initiator solutions, be cooled to 60 ~ 65 ℃ after being incubated 25 ~ 35 minutes, add 0.3 ~ 0.4 weight part hydrogen peroxide and 0.2 ~ 0.3 weight part FF
6the aqueous solution, be incubated 25 ~ 35 minutes and remove residual monomer, then is cooled to below 40 ℃, adds 0.18 ~ 0.22 weight part oxidation inhibitor and 1.8-2.2 weight part sterilant to stir, and makes hollow polymer emulsion;
Unsaturated monomer in described step (1) also comprises ethyl propenoate, vinylformic acid, DAP monomer;
Unsaturated monomer in described step (2) comprises the combination of methacrylic acid, vinylbenzene and butyl acrylate;
Unsaturated monomer in described step (3) also comprises vinyl cyanide, methacrylic acid.
2. the preparation method of hollow polymer emulsion according to claim 1, it is characterized in that: the per-cent that described monocoque accounts for gross weight is 15 ~ 25%, and second-order transition temperature is 40 ~ 60 ℃; Described soft shell structure accounts for 15 ~ 25% of total weight percent, and second-order transition temperature is-20 ~-10 ℃.
3. the preparation method of hollow polymer emulsion according to claim 1, is characterized in that,
Emulsifying agent in described step (1) is the OP-9 emulsifying agent;
The combination that the emulsifying agent of described step (2) is CO-436 and emulsifying agent A-103 emulsifying agent;
The oxygenant of described step (3) is AT-10 oxidation inhibitor, and emulsifying agent is the AMPS-2404 emulsifying agent;
Described step (4) emulsifying agent is the OP-21 emulsifying agent, and initiator solution is the 3.2%NPS aqueous solution;
Described step (5) PH conditioning agent is the AMP-95 aqueous solution;
Initiator solution in described step (6) is the 3.2%NPS aqueous solution, and oxidation inhibitor is that AT-2401 oxidation inhibitor, sterilant are the RS sterilant.
4. the preparation method of hollow polymer emulsion according to claim 3, is characterized in that, comprises the steps:
(1) add deionized water 80 ~ 90 weight parts, OP-9 emulsifying agent 2.5 ~ 3 weight parts and Sodium dodecylbenzene sulfonate 1.2 ~ 1.5 weight parts in pre-emulsification tank A; in whipping process; add ethyl propenoate 28 ~ 32 weight parts, vinylformic acid 58-62 weight part and DAP monomer 9 ~ 10 weight parts; high-speed stirring 25-35 minute, make pre-emulsion A;
(2) add deionized water 165 ~ 175 weight parts, CO-436 emulsifying agent 3.5 ~ 4.5 weight parts, A-103 emulsifying agent 1 ~ 1.3 weight part, Witco 1298 Soft Acid 1.8 ~ 2.2 weight parts in pre-emulsification tank B; in whipping process; add isobornyl methacrylate 12 ~ 13 weight parts, methacrylic acid 5 ~ 6 weight parts, vinylbenzene 12 ~ 13 weight parts and butyl acrylate 10 ~ 11 weight parts; high-speed stirring 25 ~ 35 minutes, make pre-emulsion B;
(3) add deionized water 98 ~ 100 weight parts, AT-10 oxidation inhibitor 2.6 ~ 3 weight parts, AMPS-2404 emulsifying agent 1 ~ 1.2 weight part and Witco 1298 Soft Acid 28 ~ 32 weight parts in pre-emulsification tank C; in whipping process; add vinyl cyanide 80 ~ 90 weight parts, methacrylic acid 2.8 ~ 3.2 weight parts and vinylformic acid hexafluoro butyl ester 8.8 ~ 9.2 weight parts; high-speed stirring 25 ~ 35 minutes, make pre-emulsion C;
(4) add deionized water 98 ~ 100 weight parts, OP-21 emulsifying agent 80 ~ 90 weight parts and Sodium dodecylbenzene sulfonate 3.6 ~ 4 weight parts in reactor; start to drip pre-emulsion A and 3.2%NPS initiator solution 19 ~ 21 weight parts after being heated to 80-85 ℃; make the hydroscopicity seed emulsion; be incubated after 25 ~ 35 minutes and start to drip pre-emulsion B and 3.2%NaPS initiator solution 38 ~ 42 weight parts; make the first layer duricrust, and form the core-shell emulsion that water-absorbing resin is core;
(5) slowly drip the PH conditioning agent AMP-95 aqueous solution 1.5 ~ 2.8 weight parts in above-mentioned core-shell emulsion, regulate emulsion pH value to 7.5 ~ 8.5, then stir 25 ~ 35 minutes, keep emulsion temperature at 85 ~ 90 ℃, make the abundant water-swelling of water-absorbing resin core;
(6) temperature of reactor is down to 78 ~ 80 ℃, then starts to drip pre-emulsion C and 3.2%NaPS initiator solution 18 ~ 22 weight parts, be cooled to 60 ~ 65 ℃ be incubated 25 ~ 35 minutes after dropwising after, add hydrogen peroxide 0.3 ~ 0.4 weight part and FF
60.2 ~ 0.3 weight parts water solution, be incubated 25 ~ 35 minutes and remove residual monomer, then is cooled to below 40 ℃, adds AT-2401 oxidation inhibitor 0.18 ~ 0.22 weight part and RS sterilant 1.8-2.2 weight part to stir, and makes hollow polymer emulsion.
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| CN107056977A (en) * | 2017-05-22 | 2017-08-18 | 宁德师范学院 | The preparation method of aqueous cowboy's rubber cement covering hollow microsphere emulsion |
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| GB1583671A (en) * | 1976-06-17 | 1981-01-28 | Rohm & Haas | Polymers for the treatment of textiles leather and nonwovepolymers for the treatment of textiles leather and nonwoven fabrics n fabrics |
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| CA2092987A1 (en) * | 1992-04-10 | 1993-10-11 | Robert Mitchell Blankenship | Synthesis of latex capsules |
| CN101679709A (en) * | 2006-12-19 | 2010-03-24 | 汉高公司 | Cyanoacrylate compositions containing dispersions of core shell rubbers in (meth)acrylates |
| CN101092469A (en) * | 2007-05-28 | 2007-12-26 | 周伯涛 | Emulsion of sunlight irradiation crosslinking hud polymer, preparation method and application |
| CN101250245A (en) * | 2008-04-03 | 2008-08-27 | 武汉昂泰科技有限公司 | Polymer phase-change microsphere and preparation method thereof |
| CN101481437A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Preparation of high closeness polyacrylacid ester dispersion |
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