CN114106256A - Resin with core/shell structure and polymerization method thereof - Google Patents
Resin with core/shell structure and polymerization method thereof Download PDFInfo
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- CN114106256A CN114106256A CN202210103723.9A CN202210103723A CN114106256A CN 114106256 A CN114106256 A CN 114106256A CN 202210103723 A CN202210103723 A CN 202210103723A CN 114106256 A CN114106256 A CN 114106256A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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Abstract
The invention provides a core/shell structure resin and a polymerization method thereof, belonging to the technical field of preparation of high polymer materials. The core/shell structure resin provided by the invention is butadiene-butyl acrylate-styrene-acrylonitrile, and the polymerization method of the core/shell structure resin is to synthesize the core/shell structure butadiene-butyl acrylate-styrene-acrylonitrile copolymer by taking butadiene as a first layer core and butyl acrylate as a second layer core through free radical emulsion polymerization and then grafting styrene-acrylonitrile copolymer. The copolymer has higher weather resistance than ABS and simultaneously has higher impact property than ASA.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a core/shell structure resin and a polymerization method thereof.
Background
ABS resin has a two-phase structure, polybutadiene rubber is a dispersed phase, and SAN (styrene-acrylonitrile copolymer, also called AS) is a continuous phase AS a matrix resin. The impact properties of the ABS resin are high due to the presence of polybutadiene rubber, but the weatherability of the ABS resin is poor due to the presence of residual double bonds.
ASA resin also has a two-phase structure, with polybutylacrylate rubber AS the dispersed phase and SAN (styrene-acrylonitrile copolymer, also known AS AS) AS the matrix resin AS the continuous phase. Due to the presence of polybutyl acrylate rubber, ASA resins have excellent weatherability but very low impact properties.
Therefore, a new resin with better comprehensive performance is needed to overcome the problems of the existing resin.
Disclosure of Invention
The invention aims to provide a core/shell structure resin with more excellent comprehensive performance and a polymerization method thereof
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a core/shell structure resin, which is butadiene-butyl acrylate-styrene-acrylonitrile, and the core latex of the core/shell structure resin is prepared from the following raw materials in parts by mass:
6-20 parts of butadiene, 20-34 parts of butyl acrylate, 0.2-1.5 parts of chain extender, 0.8-2.5 parts of emulsifier, 0.2-0.8 part of initiator, 0.1-0.3 part of potassium carbonate and 0.1-0.6 part of dodecyl mercaptan;
the shell latex of the core/shell structure resin is prepared from the following raw materials in parts by mass:
52.6 parts of 38% nuclear latex, 25-35 parts of deionized water, 15 parts of styrene, 5 parts of acrylonitrile, 0.8-1.5 parts of sodium dodecyl sulfate, 0.3-0.6 part of initiator and 0.2-0.8 part of dodecyl mercaptan.
Preferably, the butadiene is a butadiene polymerized monomer and the butyl acrylate is a polybutyl acrylate latex polymerized monomer.
Preferably, the chain extender is one or a mixture of more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, 1, 3-propanediol diacrylate and the like.
Preferably, the emulsifier is one or a mixture of more of rosin soap, stearic acid soap, oleic acid soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the initiator is one or a mixture of potassium sulfate and ammonium persulfate.
Secondly, the present invention provides a polymerization method of a core/shell structure resin, characterized in that the core/shell structure resin is butadiene-butyl acrylate-styrene-acrylonitrile, the polymerization method comprising the steps of:
1) polymerization of polybutadiene latex in the first layer:
(1) adding 25% of disproportionated rosin soap, 10% of oleic acid soap, sodium dodecyl sulfate, potassium persulfate, potassium carbonate and deionized water into a reaction kettle, and uniformly stirring and mixing;
(2) adding butadiene, 1, 6-hexanediol diacrylate and dodecyl mercaptan into a reaction kettle, heating to 65 ℃ for 1 hour, and reacting for 15 hours under the reaction pressure of 0.9MPa to obtain polybutadiene latex;
2) second layer of Poly (butyl acrylate) latex Synthesis
(1) Adding the polybutadiene latex, sodium dodecyl sulfate and deionized water into a polymerization kettle, and stirring for 30min under the protection of nitrogen;
(2) preparing an initiator solution: dissolving potassium persulfate in deionized water to obtain an initiator solution;
(3) preparing a butyl propionate monomer: dissolving dodecyl mercaptan in butyl acrylate to obtain butyl propionate monomer;
(3) heating the polymerization kettle to 65 ℃, synchronously adding the initiator solution and the butyl acrylate monomer for 1.5 hours, and reacting for 2 hours to obtain polybutyl acrylate latex;
3) third layer graft acrylic acid-acrylonitrile copolymer
(1) Adding sodium dodecyl sulfate and deionized water, and stirring for 30 min;
(2) preparing a grafting initiator solution: dissolving potassium persulfate in deionized water to obtain a grafting initiator solution;
(3) preparing mixed monomers: uniformly mixing dodecyl mercaptan, styrene and acrylonitrile to obtain a mixed monomer;
(4) after the temperature of the polymerization kettle is raised to 65 ℃, synchronously dropwise adding the grafting initiator solution and the mixed monomer for 2 hours, and reacting for 2 hours to obtain a polymerization emulsion;
4) coagulation and drying
(1) Diluting the polymerization emulsion to TSC =20%, controlling the temperature at 50 ℃, gradually adding 20% calcium chloride solution, stirring while adding until the copolymer is completely coagulated to obtain a coagulated polymer;
(2) washing the coagulated polymer with deionized water to PH = 7-8;
(3) and (5) placing the core/shell structure resin in an oven, and drying to obtain the core/shell structure resin.
The invention has the beneficial effects that: the resin provided by the invention is used as a substitute of ASA resin and ABS resin, widens the application range of the ASA resin, improves the weather resistance grade of ABS, and has wider application field.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
Example 1
Synthetic polybutadiene latex
(1) The polymerization reaction is carried out in a 10L pressure-resistant polymerization kettle, and the reaction process is carried out under the protection of nitrogen;
(2) adding into a reaction kettle: 25% disproportionated rosin soap: 211g, 10% oleic soap: 66g, sodium lauryl sulfate: 6.6g, potassium persulfate: 11g, potassium carbonate: 14g, deionized water: 4200 g;
(3) after stirring and mixing uniformly, adding butadiene: 2770g, 69g of 1, 6-hexanediol diacrylate and 11g of dodecyl mercaptan;
(4) the temperature was raised to 65 ℃ for 1 hour. Adiabatic reaction at 65 deg.c, reaction temperature not higher than 85 deg.c and reaction pressure not higher than 0.9 MPa. The reaction was terminated after about 15 hours until the conversion reached 98%. And TSC = 38%.
Example 2
(1) 236.8g of the PBL latex synthesized in example 1 were put into a 2000ml polymerization vessel, and 2.34g of sodium lauryl sulfate and 228g of deionized water were added, and the mixture was stirred for 30 minutes under a nitrogen atmosphere.
(2) Preparing an initiator solution: 1.05g of potassium persulfate was dissolved in 66g of deionized water. Preparing a butyl acrylate monomer: 0.84g of dodecanethiol was dissolved in 210g of butyl acrylate.
(3) The temperature of a 2000ml polymerization kettle is raised to 65 ℃, and the following components are synchronously added dropwise: the initiator solution and butyl acrylate monomer are synchronously dripped for 1.5 hours, and react for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Designated BASA-1.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and BASA-1 are mixed evenly according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 2.
Example 3
The first step is as follows: second layer core latex synthesis.
(1) 315.8g of the PBL latex synthesized in example 1 were put into a 2000ml polymerization vessel, and stirred for 30 minutes under nitrogen atmosphere with 1.62g of sodium lauryl sulfate and 176g of deionized water.
(2) Preparing an initiator solution: 0.9g of potassium persulfate was dissolved in 66g of deionized water. Preparing a butyl acrylate monomer: 0.72g of dodecanethiol was dissolved in 180g of butyl acrylate.
(3) The temperature of a 2000ml polymerization kettle is raised to 65 ℃, and the following components are synchronously added dropwise: the initiator solution and butyl acrylate monomer are synchronously dripped for 1 to 1.5 hours, and react for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Designated BASA-2.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and BASA-5 are mixed evenly according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 2.
Example 4
The first step is as follows: second layer core latex synthesis.
(1) 394.7g of the PBL latex synthesized in example 1 were put in a 2000ml polymerization vessel, and 0.9g of sodium lauryl sulfate and 130g of deionized water were added, and the mixture was stirred for 30 minutes under a nitrogen atmosphere.
(2) Preparing an initiator solution: 0.75g of potassium persulfate was dissolved in 62g of deionized water. Preparing a butyl acrylate monomer: 0.6g of dodecanethiol was dissolved in 150g of butyl acrylate.
(3) The temperature of a 2000ml polymerization kettle is raised to 65 ℃, and the following components are synchronously added dropwise: the initiator solution and butyl acrylate monomer are synchronously dripped for 1 to 1.5 hours, and react for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Designated BASA-3.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and BASA-3 are mixed evenly according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) The UV lamp irradiates for 1000 h. Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 2.
Example 5
The first step is as follows: second layer core latex synthesis.
(1) In a 2000ml polymerization kettle, 434.2g of the PBL latex synthesized in example 1 was stirred for 30 minutes under nitrogen protection with 0.54g of sodium dodecyl sulfate and 100g of deionized water.
(2) Preparing an initiator solution: 0.675g of potassium persulfate was dissolved in 68g of deionized water. Preparing a butyl acrylate monomer: 0.54g of dodecanethiol was dissolved in 135g of butyl acrylate.
(3) The temperature of a 2000ml polymerization kettle is raised to 65 ℃, and the following components are synchronously added dropwise: the initiator solution and butyl acrylate monomer are synchronously dripped for 1 to 1.5 hours, and react for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Designated BASA-4.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and BASA-4 are mixed evenly according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 2.
Example 6
The first step is as follows: second layer core latex synthesis.
(1) 473.7g of the PBL latex synthesized in example 1 were put in a 2000ml polymerization vessel, and 0.18g of sodium lauryl sulfate and 80g of deionized water were added thereto, and the mixture was stirred for 30 minutes under a nitrogen atmosphere.
(2) Preparing an initiator solution: 0.6g of potassium persulfate was dissolved in 65g of deionized water. Preparing a butyl acrylate monomer: 0.48g of dodecanethiol was dissolved in 120g of butyl acrylate.
(3) The temperature of a 2000ml polymerization kettle is raised to 65 ℃, and the following components are synchronously added dropwise: the initiator solution and butyl acrylate monomer are synchronously dripped for 1 to 1.5 hours, and react for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Designated BASA-5.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and BASA-5 are mixed evenly according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 2.
Example 7
Synthesis of ABS
The first step is as follows: and (4) grafting a shell layer.
(1) 789.5g of the PBL latex synthesized in example 1 were placed in a 2000ml polymerizer.
(2) 1.8g of lauryl sodium sulfate and 302.5g of deionized water are added, and the mixture is stirred for 30 minutes.
(3) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(4) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The second step is that: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Denoted ABS.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and ABS are evenly mixed according to the proportion of 70:30(wt%), and then are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 1.
Example 8
ASA Synthesis
The first step is as follows: and (4) synthesizing a core latex.
(1) In a 2000ml polymerization kettle, 4.5g of sodium dodecyl sulfate, 0.5g of potassium hydroxide and 300g of deionized water were added and stirred for 30 minutes under the protection of nitrogen.
(2) Preparing an initiator solution: 1.8g of potassium persulfate was dissolved in 125g of deionized water. Preparing a butyl acrylate monomer: 1.2g of dodecanethiol was dissolved in 300g of butyl acrylate.
(3) Heating a 2000ml polymerization kettle to 65 ℃, carrying out polymerization reaction on the initiator solution and the butyl acrylate monomer according to a certain polymerization method, and stopping the reaction when the latex particle size is required to be more than 300nm and the conversion rate can reach more than 98%. And the reaction process is protected by nitrogen.
The second step is that: and (4) grafting a shell layer.
(1) And adding 4.5g of lauryl sodium sulfate and 360g of deionized water, and stirring for 30 minutes.
(2) Preparing an initiator solution: 1.2g of potassium persulfate was dissolved in 80g of deionized water. Preparing a mixed monomer: 1.5g of dodecanethiol, 225g of styrene and 75g of acrylonitrile are uniformly mixed.
(3) A2000 ml polymerization vessel was charged at 65 ℃. Synchronous dropwise adding: the initiator solution and the mixed monomer are synchronously dripped for 2 hours, the reaction is carried out for 2 hours under the protection of nitrogen, and the conversion rate can reach more than 98 percent.
The third step: and (5) condensing and drying.
(1) The above emulsion was diluted to TSC =20% and the temperature was controlled at 50 ℃, and approximately 60g of 20% calcium chloride solution was gradually added with stirring until the polymer was completely coagulated.
(2) The coagulated polymer was washed three times with deionized water until the wash PH = 7-8.
(3) Drying in an oven at 80 ℃. Denoted ASA.
The fourth step: and (5) testing the performance.
(1) SAN-80HF resin and ASA are evenly mixed according to the proportion of 70:30(wt%), and are added into a main feeder of a double-screw extruder for extrusion granulation. The temperatures from the feed section to the head are respectively: 210 ℃, 230 ℃, 220 ℃, 210 ℃ and 230 ℃ of the head temperature. And water cooling and granulating after extrusion. After drying, test specimens were prepared by an injection molding machine.
(2) Weather resistance test conditions: voltage 220V, power 300W, ultraviolet wavelength 280-400nm, and ultraviolet intensity 25 +/-0.4W/m 2.
(3) The results of the performance tests are shown in Table 1.
TABLE 1 Performance test results for ABS and ASA
TABLE 2 BASA-1~Results of BASA-5 Performance test
From the above results, it can be seen that the BASA prepared by the present invention has better weatherability than the existing ABS and better impact properties than ASA.
The technical features of the present invention which are not described in the above embodiments may be implemented by or using the prior art, and are not described herein again, of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, modifications, additions or substitutions which may be made by those skilled in the art within the spirit and scope of the present invention should also fall within the protection scope of the present invention.
Claims (6)
1. The core/shell structure resin is characterized in that the core/shell structure resin is butadiene-butyl acrylate-styrene-acrylonitrile, and the core latex of the core/shell structure resin is prepared from the following raw materials in parts by mass:
6-20 parts of butadiene, 20-34 parts of butyl acrylate, 0.2-1.5 parts of chain extender, 0.8-2.5 parts of emulsifier, 0.2-0.8 part of initiator, 0.1-0.3 part of potassium carbonate and 0.1-0.6 part of dodecyl mercaptan;
the shell latex of the core/shell structure resin is prepared from the following raw materials in parts by mass:
52.6 parts of 38% nuclear latex, 25-35 parts of deionized water, 15 parts of styrene, 5 parts of acrylonitrile, 0.8-1.5 parts of sodium dodecyl sulfate, 0.3-0.6 part of initiator and 0.2-0.8 part of dodecyl mercaptan.
2. The core/shell structured resin of claim 1, wherein the butadiene is a butadiene polymerized monomer and the butyl acrylate is a polybutyl acrylate latex polymerized monomer.
3. The core/shell structured resin according to claim 1, wherein the chain extender is one or a mixture of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, 1, 3-propanediol diacrylate, etc.
4. The core/shell structured resin according to claim 1, wherein the emulsifier is one or more selected from rosin soap, stearic acid soap, oleic acid soap, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate.
5. The core/shell structural resin according to claim 1, wherein the initiator is one or a mixture of potassium sulfate and ammonium persulfate.
6. A polymerization process of a core/shell structured resin, wherein the core/shell structured resin is butadiene-butyl acrylate-styrene-acrylonitrile, comprising the steps of:
1) polymerization of polybutadiene latex in the first layer:
(1) adding 25% of disproportionated rosin soap, 10% of oleic acid soap, sodium dodecyl sulfate, potassium persulfate, potassium carbonate and deionized water into a reaction kettle, and uniformly stirring and mixing;
(2) adding butadiene, 1, 6-hexanediol diacrylate and dodecyl mercaptan into a reaction kettle, heating to 65 ℃ for 1 hour, and reacting for 15 hours under the reaction pressure of 0.9MPa to obtain polybutadiene latex;
2) second layer of Poly (butyl acrylate) latex Synthesis
(1) Adding the polybutadiene latex, sodium dodecyl sulfate and deionized water into a polymerization kettle, and stirring for 30min under the protection of nitrogen;
(2) preparing an initiator solution: dissolving potassium persulfate in deionized water to obtain an initiator solution;
(3) preparing a butyl propionate monomer: dissolving dodecyl mercaptan in butyl acrylate to obtain butyl propionate monomer;
(3) heating the polymerization kettle to 65 ℃, synchronously adding the initiator solution and the butyl acrylate monomer for 1.5 hours, and reacting for 2 hours to obtain polybutyl acrylate latex;
3) third layer graft acrylic acid-acrylonitrile copolymer
(1) Adding sodium dodecyl sulfate and deionized water, and stirring for 30 min;
(2) preparing a grafting initiator solution: dissolving potassium persulfate in deionized water to obtain a grafting initiator solution;
(3) preparing mixed monomers: uniformly mixing dodecyl mercaptan, styrene and acrylonitrile to obtain a mixed monomer;
(4) after the temperature of the polymerization kettle is raised to 65 ℃, synchronously dropwise adding the grafting initiator solution and the mixed monomer for 2 hours, and reacting for 2 hours to obtain a polymerization emulsion;
4) coagulation and drying
(1) Diluting the polymerization emulsion to TSC =20%, controlling the temperature at 50 ℃, gradually adding 20% calcium chloride solution, stirring while adding until the copolymer is completely coagulated to obtain a coagulated polymer;
(2) washing the coagulated polymer with deionized water to PH = 7-8;
(3) and (5) placing the core/shell structure resin in an oven, and drying to obtain the core/shell structure resin.
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