CN114230735A - Preparation method and application of styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer - Google Patents
Preparation method and application of styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer Download PDFInfo
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Abstract
The invention discloses a preparation method and application of styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer, wherein the method comprises the following steps: firstly, preparing terpolymer seed emulsion by adopting a seed emulsion polymerization method, and then preparing styrene-isoprene-butadiene terpolymer integrated latex by adopting polymerization; and secondly, adopting an emulsion grafting method, firstly carrying out polymerization reaction, filtering, coagulating and vacuum drying to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer. The invention adopts a two-stage seed emulsion polymerization method to prepare the styrene-isoprene-butadiene terpolymer integrated latex, realizes the control of the size and the distribution of the styrene-isoprene-butadiene terpolymer integrated latex by controlling the polymerization process, obtains the styrene-isoprene-butadiene terpolymer integrated rubber emulsion graft copolymer by polymerization grafting as the raw material of the ABS resin, and improves the tensile strength and the impact strength of the ABS resin.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method and application of a styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
Background
ABS resin (acrylonitrile-butadiene-styrene copolymer) is a tough, hard and rigid polymer material with easily available raw materials, low price and wide application, has the characteristics of excellent mechanical property, heat resistance, electrical property, easy forming and processing and the like, and is widely applied to manufacturing industries of machinery, electronics and electricity, automobiles, textiles and the like and chemical engineering. The ABS resin usually adopts a rubber toughening agent, the styrene-isoprene-butadiene ternary integrated rubber is well applied to the field of automobile tires due to the outstanding comprehensive performance, and a plurality of researchers introduce the ternary integrated rubber into the field of rubber toughening ABS resin.
The patent of publication No. CN102924840A adopts a high-temperature emulsion polymerization method to prepare styrene-isoprene-butadiene terpolymer integrated latex, the particle size of the latex is 50 nm-200 nm, the particle size of the agglomerated latex can reach 200 nm-400 nm, but the particle size control of the agglomeration process is difficult, the crosslinking degree is high, and the toughness of the prepared product is poor. The patent of publication No. CN105732908A adopts a one-step method of seed emulsion polymerization to prepare isoprene-butadiene latex, the particle size of the latex is 250 nm-350 nm, then styrene and acrylonitrile monomers are grafted to obtain a rubber graft copolymer, and the impact strength of the prepared ABS resin reaches more than 300J/m. In most cases, the toughening resin is different from the base rubber, the ternary integrated rubber integrates the characteristics of polybutadiene rubber, polyisoprene rubber, butadiene-isoprene rubber and styrene-butadiene rubber, and the serialization of styrene-isoprene-butadiene terpolymer integrated rubber products can be realized by adjusting the proportion, the microcosmic structure and the sequence structure of the three monomers.
The grain size of latex particles used as toughened ABS resin is required to be more than 250nm, and the grain size of rubber can limit the volume deformation in the crack propagation process, so that the grain size of the latex is a key factor of the toughened resin. The large particle size latex particles are useful for improving toughness, while the small particle size latex particles are useful for maintaining rigidity. For the rubber toughened resin, the cavitation of rubber particles is one of the most important toughening mechanisms of the ABS resin, and the rubber copolymer particles with a bimodal distribution structure can generate deep and continuously expanded cavitation phenomena due to the difference of the sizes of inner and outer particles, so that the mechanical property of the toughened resin is determined. Thus, rubber particle size and its distribution are key factors in toughening resins.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer aiming at the defects of the prior art. The method adopts a two-stage seed emulsion polymerization method to prepare the styrene-isoprene-butadiene terpolymer integrated latex, realizes the control of the size and the distribution of the styrene-isoprene-butadiene terpolymer integrated latex by controlling the polymerization process, and further obtains the styrene-isoprene-butadiene terpolymer integrated rubber emulsion graft copolymer by polymerization grafting as the raw material of the ABS resin, thereby obviously improving the tensile strength and the impact strength of the ABS resin.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized by comprising the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding a styrene monomer A, an isoprene monomer A, a butadiene monomer A, soft water, an initiator and an emulsifier into a polymerization kettle, and then polymerizing for 20-40 h at the temperature of 50-80 ℃ by adopting nitrogen replacement protection to obtain a terpolymer seed emulsion;
the adding mass of the soft water is 0.5-1.5 times of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A, the adding mass of the emulsifier is 0.01-0.05 time of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A, and the adding mass of the initiator is 0.001-0.004 time of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A;
the mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A is 45% of that of the styrene monomer, the isoprene monomer and the butadiene monomer added in the preparation process;
102, supplementing soft water, an emulsifier, an initiator, a styrene monomer B, an isoprene monomer B and a butadiene monomer B into the terpolymer seed emulsion obtained in the step 101 for polymerization, dropwise adding the remaining mixture of the styrene monomer C, the isoprene monomer C and the butadiene monomer C within 6-8 h, and polymerizing for 20-40 h at the temperature of 50-80 ℃ under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex; the particle size of the styrene-isoprene-butadiene terpolymer integrated latex is 400-500 nm, the gel content is 60-80%, and the monomer conversion rate is 92-95%;
the supplementary mass of the soft water is 0.1-1 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B, the supplementary mass of the emulsifier is 0.01-0.05 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B, and the supplementary mass of the initiator is 0.002-0.008 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B;
the mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B is 36 percent of that of the styrene monomer, the isoprene monomer and the butadiene monomer added in the preparation process;
the styrene monomer added in the preparation process comprises a styrene monomer A, a styrene monomer B and a styrene monomer C, the isoprene monomer added in the preparation process comprises an isoprene monomer A, an isoprene monomer B and an isoprene monomer C, and the butadiene monomer added in the preparation process comprises a butadiene monomer A, a butadiene monomer B and a butadiene monomer C;
the mass content of the styrene monomer in the total mass of the styrene monomer, the isoprene monomer and the butadiene monomer is 20-30%, the mass content of the isoprene monomer is 30-40%, and the mass content of the butadiene monomer is 30-40%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding the styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, soft water, an initiator, a chelating agent, a reducing agent and an auxiliary reducing agent into a reaction kettle, then dropwise adding a grafting monomer styrene monomer and an acrylonitrile monomer within 4-6 h, and polymerizing for 2-5 h at the temperature of 50-80 ℃ under the protection of nitrogen to obtain a polymerization product system;
the adding mass of the soft water is 10-20% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the initiator is 0.1-0.4% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the chelating agent is 0.1-0.5% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the reducing agent is 0.001-0.1% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, and the adding mass of the auxiliary reducing agent is 0.1-1% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex;
the mass of the dropwise addition of the styrene monomer is 10-30% of that of the styrene-isoprene-butadiene terpolymer integrated latex, and the mass of the dropwise addition of the acrylonitrile monomer is 5-10% of that of the styrene-isoprene-butadiene terpolymer integrated latex;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
The invention firstly prepares styrene-isoprene-butadiene terpolymer integrated latex by a two-stage seed emulsion polymerization method, and the styrene-isoprene-butadiene terpolymer integrated latex is polymerized step by controlling the addition of each monomer and raw materials in each stage and polymerization process parameters, so that the obtained latex has large average particle size (400 nm-500 nm) and a bimodal distribution structure, does not need an agglomeration process, realizes the control of the size and the distribution of the styrene-isoprene-butadiene terpolymer integrated latex, meets the requirement of toughening latex particle size, and has the monomer conversion rate higher than 92 percent; and then adopting an emulsion grafting method to polymerize the styrene-isoprene-butadiene terpolymer integrated latex with styrene and acrylonitrile monomers to prepare the styrene-isoprene-butadiene terpolymer integrated rubber emulsion graft copolymer, and using the copolymer as a raw material to prepare the toughened ABS resin, so that the mechanical properties of the ABS resin, particularly the tensile strength and the impact strength, are remarkably improved.
The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized in that the initiator in the first step and the initiator in the second step is a potassium persulfate or cumene hydroperoxide-ferrous sulfate composite initiator.
The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized in that in the step one, the emulsifier is one or more than two of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and rosin acid alkyl salt.
The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized in that the chelating agent in the second step is sodium pyrophosphate or/and potassium pyrophosphate.
The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized in that the reducing agent in the step two is ferrous sulfate or/and ferrous phosphate.
The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized in that in the second step, the auxiliary reducing agent is one or more of glucose, sodium hydrogen phosphite and sodium sulfite.
In addition, the invention also discloses application of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared by the method in ABS resin synthesis. Generally, the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared by the method is introduced into the synthesis of ABS resin according to a blending and granulating method, so that the function of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is effectively exerted, the tensile strength and the impact strength of the ABS resin are obviously improved, and the method is simple and easy to realize.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a two-stage seed emulsion polymerization method to prepare the styrene-isoprene-butadiene terpolymer integrated latex, realizes the control of the size and the distribution of the styrene-isoprene-butadiene terpolymer integrated latex by controlling the polymerization process, and further obtains the styrene-isoprene-butadiene terpolymer integrated rubber emulsion graft copolymer by polymerization grafting as the raw material of the ABS resin, thereby obviously improving the tensile strength (>50MPa) and the impact strength (>300J/m) of the ABS resin.
2. The styrene-isoprene-butadiene terpolymer integrated latex prepared by the invention has large average particle size (400 nm-500 nm), a bimodal distribution structure and controllable size, the monomer conversion rate is higher than 92%, and the gel content is higher than 60%.
3. The preparation process of the styrene-isoprene-butadiene terpolymer integrated latex does not need an agglomeration process, so that the preparation process is shortened, and the preparation process is simplified.
4. The styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared by the invention is introduced into the synthesis of ABS resin according to a blending and granulating method, so that the function of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is effectively exerted, the tensile strength and the impact strength of the ABS resin are obviously improved, and the method is simple and easy to realize.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a graph showing the particle size distribution of a styrene-isoprene-butadiene terpolymer-integrated latex prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope photograph of a styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope photograph of a styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding 98g of styrene monomer A, 196g of isoprene monomer A, 196g of butadiene monomer A, 680g of soft water, 1.5g of potassium persulfate and 21g of disproportionated potassium rosinate soap into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, introducing nitrogen, and stirring and polymerizing 30 at the constant temperature of 60 ℃ and the stirring speed of 250r/min by adopting nitrogen replacement protection to obtain terpolymer seed emulsion;
102, supplementing 107g of soft water, 19g of disproportionated potassium rosinate soap, 2.0g of potassium persulfate, 78g of styrene monomer B, 155g of isoprene monomer B and 155g of butadiene monomer B into the terpolymer seed emulsion obtained in the step 101, continuing stirring and polymerizing, dropwise adding a mixture of 39g of styrene monomer C, 78g of isoprene monomer C and 78g of butadiene monomer C at a constant speed within 8h of stirring and polymerizing, and polymerizing and aging at the temperature of 60 ℃ for 20h under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex;
through detection, the average particle size of the styrene-isoprene-butadiene terpolymer integrated latex is 450nm, the gel content is 65.08 percent, and the glass transition temperature T isgAt-53.2 ℃ and a monomer conversion of 92.79%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding 763g of styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, 95g of soft water, 1.75g of cumene hydroperoxide, 1g of sodium pyrophosphate, 0.021g of ferrous sulfate and 0.85g of glucose into a 2L four-neck flask with a reflux condenser, a thermometer, a pressure balance dropping funnel and magnetic stirring, introducing nitrogen for protection, stirring for 15min at a constant temperature of 60 ℃ and a stirring speed of 100r/min, then dropwise adding 156g of styrene monomer and 53g of acrylonitrile monomer into a grafting monomer within 4h at a constant speed, stirring and polymerizing for 3h at the constant temperature of 60 ℃ and the stirring speed of 400r/min under the protection of nitrogen, and obtaining a polymerization product system;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
Through detection, the grafting rate of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer obtained in the embodiment is 35.15%, and the grafting efficiency is 52.72%.
FIG. 1 is a particle size distribution diagram of the styrene-isoprene-butadiene terpolymer integrated latex prepared in this example, and it can be seen from FIG. 1 that the average particle size of the styrene-isoprene-butadiene terpolymer integrated latex is large (400 nm-500 nm) and has a bimodal distribution structure, and the structure affects the impact strength of the toughened resin when polymerized with styrene and acrylonitrile monomers.
FIG. 2 is a transmission electron microscope photograph of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared in this example, and it can be seen from FIG. 2 that the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer has a typical "sea-island" structure and a relatively uniform spatial distribution.
FIG. 3 is a scanning electron microscope image of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared in this example, and it can be seen from FIG. 3 that the stress whitening region of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer has deep cavitation and enlarged whitening, which is helpful for improving the toughness of ABS resin.
In the first step and the second step of this embodiment, the initiator may also be cumene hydroperoxide-ferrous sulfate composite initiator; the emulsifier in step one of this embodiment may be one or more of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and abietic acid alkyl salt other than disproportionated abietic acid potassium soap; the chelating agent in step two of this embodiment may also be potassium pyrophosphate or a combination of sodium pyrophosphate and potassium pyrophosphate, the reducing agent may also be ferrous phosphate or a combination of ferrous sulfate and ferrous phosphate, and the reducing agent may also be one or more than two of glucose other than glucose, sodium hydrogen phosphite and sodium sulfite.
Example 2
The embodiment comprises the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding 147g of styrene monomer A, 147g of isoprene monomer A, 196g of butadiene monomer A, 250g of soft water, 0.5g of potassium persulfate and 5g of disproportionated potassium rosinate soap into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, introducing nitrogen, and stirring and polymerizing for 40 hours at the constant temperature of 80 ℃ and the stirring speed of 250r/min by adopting nitrogen replacement protection to obtain terpolymer seed emulsion;
step 102, supplementing 385g of soft water, 12g of disproportionated potassium rosinate soap, 1.0g of potassium persulfate, 116g of styrene monomer B, 116g of isoprene monomer B and 155g of butadiene monomer B into the terpolymer seed emulsion obtained in the step 101, continuously stirring and polymerizing, dropwise adding a mixture of 59g of styrene monomer C, 59g of isoprene monomer C and 78g of butadiene monomer C at a constant speed within 6h of stirring and polymerizing, and polymerizing and aging at the temperature of 50 ℃ for 30h under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex;
the detection shows that the average particle diameter of the styrene-isoprene-butadiene terpolymer integrated latex is 400nm, and the gel content isIn an amount of 79.75%, glass transition temperature TgAt-48.6 ℃ and a monomer conversion of 93.57%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding 763g of styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, 78g of soft water, 0.75g of cumene hydroperoxide, 3g of sodium pyrophosphate, 0.01g of ferrous sulfate and 2.55g of glucose into a 2L four-neck flask with a reflux condenser, a thermometer, a pressure balance dropping funnel and magnetic stirring, introducing nitrogen for protection, stirring for 15min at a constant temperature of 80 ℃ and a stirring speed of 100r/min, then dropwise adding 228g of styrene monomer and 76g of acrylonitrile monomer into the flask at a constant speed within 6h, stirring and polymerizing for 2h at a constant temperature of 80 ℃ and a stirring speed of 400r/min under the protection of nitrogen, and obtaining a polymerization product system;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
Through detection, the grafting rate of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer obtained in the embodiment is 33.27%, and the grafting efficiency is 49.90%.
The initiator in the first step and the second step can also be a cumene hydroperoxide-ferrous sulfate composite initiator; the emulsifier in step one of this embodiment may be one or more of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and abietic acid alkyl salt other than disproportionated abietic acid potassium soap; the chelating agent in step two of this embodiment may also be potassium pyrophosphate or a combination of sodium pyrophosphate and potassium pyrophosphate, the reducing agent may also be ferrous phosphate or a combination of ferrous sulfate and ferrous phosphate, and the reducing agent may also be one or more than two of glucose other than glucose, sodium hydrogen phosphite and sodium sulfite.
Example 3
The embodiment comprises the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding 145g of styrene monomer A, 193g of isoprene monomer A, 145g of butadiene monomer A, 550g of soft water, 1.5g of potassium persulfate and 25g of disproportionated potassium rosinate soap into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, introducing nitrogen, and stirring and polymerizing for 20 hours at the constant temperature of 80 ℃ and the stirring speed of 250r/min by adopting nitrogen replacement protection to obtain terpolymer seed emulsion;
102, supplementing 42g of soft water, 5g of disproportionated potassium rosinate soap, 2.0g of potassium persulfate, 116g of styrene monomer B, 154g of isoprene monomer B and 116g of butadiene monomer B in the terpolymer seed emulsion obtained in the step 101, continuing stirring and polymerizing, dropwise adding a mixture of 61g of styrene monomer C, 82g of isoprene monomer C and 61g of butadiene monomer C at a constant speed within 7h of stirring and polymerizing, and polymerizing and aging at the temperature of 70 ℃ for 40h under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex;
through detection, the average particle diameter of the styrene-isoprene-butadiene terpolymer integrated latex is 460nm, the gel content is 68.02%, and the glass transition temperature T isgAt-49.9 ℃ and a monomer conversion of 94.96%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding 763g of styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, 108g of soft water, 2.25g of cumene hydroperoxide, 2g of potassium pyrophosphate, 0.032g of ferrous sulfate and 1.27g of glucose into a 2L four-neck flask with a reflux condenser, a thermometer, a pressure balance dropping funnel and magnetic stirring, introducing nitrogen for protection, stirring for 15min at a constant temperature of 50 ℃ and a stirring speed of 100r/min, then dropwise adding 76g of styrene monomer and 39g of acrylonitrile monomer at a constant speed within 4h, stirring and polymerizing for 5h at a constant temperature of 50 ℃ and a stirring speed of 400r/min under the protection of nitrogen, and obtaining a polymerization product system;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
Through detection, the grafting rate of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer obtained in the embodiment is 33.96%, and the grafting efficiency is 50.94%.
In the first step and the second step of this embodiment, the initiator may also be cumene hydroperoxide-ferrous sulfate composite initiator; the emulsifier in step one of this embodiment may be one or more of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and abietic acid alkyl salt other than disproportionated abietic acid potassium soap; the chelating agent in step two of this embodiment may also be sodium pyrophosphate, or a combination of sodium pyrophosphate and potassium pyrophosphate, the reducing agent may also be ferrous phosphate, or a combination of ferrous sulfate and ferrous phosphate, and the reducing agent may also be one or more than two of glucose other than glucose, sodium hydrogen phosphite, and sodium sulfite.
Example 4
The embodiment comprises the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding 121g of styrene monomer A, 170g of isoprene monomer A, 193g of butadiene monomer A, 650g of soft water, 2.0g of potassium persulfate and 21g of disproportionated potassium rosinate soap into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, introducing nitrogen, and stirring and polymerizing for 30 hours at the constant temperature of 50 ℃ and the stirring speed of 250r/min by adopting nitrogen replacement protection to obtain terpolymer seed emulsion;
102, supplementing 110g of soft water, 19g of disproportionated potassium rosinate soap, 2.0g of potassium persulfate, 96g of styrene monomer B, 135g of isoprene monomer B and 154g of butadiene monomer B into the terpolymer seed emulsion obtained in the step 101, continuing stirring and polymerizing, dropwise adding a mixture of 51g of styrene monomer C, 71g of isoprene monomer C and 82g of butadiene monomer C at a constant speed within 8h of stirring and polymerizing, and polymerizing and aging at the temperature of 80 ℃ for 20h under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex;
through detection, the average particle size of the styrene-isoprene-butadiene terpolymer integrated latex is 500nm, the gel content is 60.38%, and the glass transition temperature T isgAt-54.8 ℃ and a monomer conversion of 93.66%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding 763g of styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, 152g of soft water, 2.95g of cumene hydroperoxide, 4g of potassium pyrophosphate, 0.763g of ferrous sulfate and 7.63g of sodium hydrogen phosphite into a 2L four-neck flask with a reflux condenser, a thermometer, a pressure balance dropping funnel and magnetic stirring, introducing nitrogen for protection, stirring for 15min at a constant temperature of 60 ℃ and a stirring speed of 100r/min, then dropwise adding 156g of styrene monomer and 53g of acrylonitrile monomer into a grafting monomer within 5h at a constant speed, stirring and polymerizing for 3h at a constant temperature of 60 ℃ and a stirring speed of 400r/min under the protection of nitrogen, and obtaining a polymerization product system;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
In the first step and the second step of this embodiment, the initiator may also be cumene hydroperoxide-ferrous sulfate composite initiator; the emulsifier in step one of this embodiment may be one or more of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and abietic acid alkyl salt other than disproportionated abietic acid potassium soap; the chelating agent in step two of this embodiment may also be sodium pyrophosphate, or a combination of sodium pyrophosphate and potassium pyrophosphate, the reducing agent may also be ferrous phosphate, or a combination of ferrous sulfate and ferrous phosphate, and the reducing agent may also be one or more than two of glucose, sodium hydrogen phosphite and sodium sulfite other than sodium hydrogen phosphite.
Through detection, the grafting rate of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer obtained in the embodiment is 37.93%, and the grafting efficiency is 56.08%.
Comparative example 1
This comparative example comprises the following steps:
step one, preparing polybutadiene latex by seed emulsion polymerization method
Step 101, adding 483g of butadiene monomer A, 680g of soft water, 1.5g of potassium persulfate and 21g of disproportionated potassium rosinate soap into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, introducing nitrogen, and stirring and polymerizing for 30 hours at the constant temperature of 65 ℃ and the stirring speed of 250r/min by adopting nitrogen replacement protection to obtain terpolymer seed emulsion;
102, supplementing 107g of soft water, 19g of disproportionated potassium rosinate soap, 2.0g of potassium persulfate and 386g of butadiene monomer B into the terpolymer seed emulsion obtained in the step 101, continuing stirring polymerization, dropwise adding 204g of butadiene monomer C at a constant speed within 8h of stirring polymerization, and polymerizing and aging at the temperature of 65 ℃ for 20h under the protection of nitrogen to obtain polybutadiene latex;
through detection, the polybutadiene latex has the average particle diameter of 313.0nm, the gel content of 84.71 percent and the glass transition temperature TgAt-76.5 ℃ and a butadiene monomer conversion of 93.18%;
step two, preparing polybutadiene latex rubber graft copolymer by emulsion grafting method
Step 201, adding 763g of polybutadiene latex obtained in the step one, 95g of soft water, 1.75g of cumene hydroperoxide, 1g of sodium pyrophosphate, 0.021g of ferrous sulfate and 1.27g of glucose into a 2L four-neck flask with a reflux condenser, a thermometer, a pressure balance dropping funnel and magnetic stirring, introducing nitrogen protection, stirring for 15min at a constant temperature of 60 ℃ and a stirring speed of 100r/min, then dropwise adding 156g of a styrene monomer and 53g of an acrylonitrile monomer into the mixture at a constant speed within 4h, and stirring and polymerizing for 3h at a constant temperature of 60 ℃ and a stirring speed of 400r/min by adopting nitrogen protection to obtain a polymerization product system;
step 202, sequentially filtering, condensing and vacuum drying the polymerization product system obtained in the step 201 to obtain the polybutylene rubber graft copolymer.
Through detection, the graft ratio of the polybutene rubber graft copolymer obtained in the comparative example is 34.22%, and the graft efficiency is 51.33%
Comparative example 2
This comparative example comprises the following steps:
step one, referring to the method disclosed in the patent with the publication number of CN102924840A, 1600g of soft water, 37.33g of disproportionated rosin potassium, 37.56g of sodium stearate, 0.64g of potassium hydroxide, 5.36g of potassium carbonate, 5.36g of tertiary dodecyl mercaptan, 3.23g of potassium persulfate, 1.6g of ammonium persulfate, 215g of styrene, 429g of isoprene and 429g of butadiene are added into a 2L polymerization kettle provided with a stirrer, an air inlet and a constant temperature controller, nitrogen is introduced for replacement protection, stirring and polymerization are carried out for 20 hours at the constant temperature of 65 ℃ and the stirring speed of 250r/min, and the ternary integrated latex is obtained by cooling and discharging;
through detection, the average particle size of the ternary integrated latex is 94.6nm, the gel content is 64.89%, and the glass transition temperature T isgAt-53.28 ℃ and a monomer conversion of 93.5%;
step two, adding a polymer agglomerating agent butyl acrylate/methacrylic acid copolymer into the ternary integrated latex obtained in the step one, and agglomerating for 60min at 65 ℃; the mass of the polymer agglomerant is 1.1 times of that of the ternary integrated latex, and the average particle size of the agglomerated ternary integrated latex is 337.9 nm;
and step three, adding 600g of the ternary integrated rubber latex agglomerated in the step two, 100g of acrylonitrile, 300g of styrene, 3.1g of tert-dodecyl mercaptan, 30g of disproportionated potassium rosinate and 2.2g of sodium pyrophosphate into a 2L polymerization kettle, then stirring and heating to raise the temperature, adding 2.9g of cumene hydroperoxide, 0.045g of ferrous sulfate, 2.7g of glucose and 0.9g of sodium dimethyldithiocarbamate when the temperature reaches 65 ℃, carrying out graft polymerization reaction for 3 hours, and then carrying out coagulation, washing, dehydration and drying to obtain the ternary integrated rubber graft copolymer.
The styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared in the examples 1 to 4 of the invention, the polybutylene rubber graft copolymer prepared in the comparative example 1 and the ternary integrated rubber graft copolymer prepared in the comparative example 2 are used as raw materials, the ABS resin is prepared by a blending granulation method respectively, and the mechanical properties of the ABS resin are tested according to the ASTM D638 and 2014 standards, and the results are shown in the table 1.
TABLE 1
As can be seen from Table 1, the impact strength of the ABS resin prepared from the styrene-isoprene-butadiene terpolymer integrated rubber emulsion graft copolymer prepared in the embodiment 1-embodiment 4 of the invention is more than 300J/m, and the tensile strength is more than 50MPa, which are higher than those of the comparative example 1 and the comparative example 2, which shows that the size-controllable styrene-isoprene-butadiene terpolymer integrated latex prepared by the method of the invention does not need to adopt an agglomeration process, and the impact strength and the tensile strength of the ABS resin are obviously improved.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer is characterized by comprising the following steps:
step one, preparing styrene-isoprene-butadiene terpolymer integrated latex by seed emulsion polymerization method
Step 101, adding a styrene monomer A, an isoprene monomer A, a butadiene monomer A, soft water, an initiator and an emulsifier into a polymerization kettle, and then polymerizing for 20-40 h at the temperature of 50-80 ℃ by adopting nitrogen replacement protection to obtain a terpolymer seed emulsion;
the adding mass of the soft water is 0.5-1.5 times of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A, the adding mass of the emulsifier is 0.01-0.05 time of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A, and the adding mass of the initiator is 0.001-0.004 time of the total mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A;
the mass of the styrene monomer A, the isoprene monomer A and the butadiene monomer A is 45% of that of the styrene monomer, the isoprene monomer and the butadiene monomer added in the preparation process;
102, supplementing soft water, an emulsifier, an initiator, a styrene monomer B, an isoprene monomer B and a butadiene monomer B into the terpolymer seed emulsion obtained in the step 101 for polymerization, dropwise adding the remaining mixture of the styrene monomer C, the isoprene monomer C and the butadiene monomer C within 6-8 h, and polymerizing for 20-40 h at the temperature of 50-80 ℃ under the protection of nitrogen to obtain styrene-isoprene-butadiene terpolymer integrated latex; the average particle size of the styrene-isoprene-butadiene terpolymer integrated latex is 400-500 nm, the gel content is 60-80%, and the monomer conversion rate is 92-95%;
the supplementary mass of the soft water is 0.1-1 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B, the supplementary mass of the emulsifier is 0.01-0.05 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B, and the supplementary mass of the initiator is 0.002-0.008 times of the total mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B;
the mass of the styrene monomer B, the isoprene monomer B and the butadiene monomer B is 36 percent of that of the styrene monomer, the isoprene monomer and the butadiene monomer added in the preparation process;
the styrene monomer added in the preparation process comprises a styrene monomer A, a styrene monomer B and a styrene monomer C, the isoprene monomer added in the preparation process comprises an isoprene monomer A, an isoprene monomer B and an isoprene monomer C, and the butadiene monomer added in the preparation process comprises a butadiene monomer A, a butadiene monomer B and a butadiene monomer C;
the mass content of the styrene monomer in the total mass of the styrene monomer, the isoprene monomer and the butadiene monomer is 20-30%, the mass content of the isoprene monomer is 30-40%, and the mass content of the butadiene monomer is 30-40%;
step two, preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer by emulsion grafting method
Step 201, adding the styrene-isoprene-butadiene terpolymer integrated latex obtained in the step one, soft water, an initiator, a chelating agent, a reducing agent and an auxiliary reducing agent into a reaction kettle, then dropwise adding a grafting monomer styrene monomer and an acrylonitrile monomer within 4-6 h, and polymerizing for 2-5 h at the temperature of 50-80 ℃ under the protection of nitrogen to obtain a polymerization product system;
the adding mass of the soft water is 10-20% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the initiator is 0.1-0.4% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the chelating agent is 0.1-0.5% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, the adding mass of the reducing agent is 0.001-0.1% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex, and the adding mass of the auxiliary reducing agent is 0.1-1% of the mass of the styrene-isoprene-butadiene terpolymer integrated latex;
the mass of the dropwise addition of the styrene monomer is 10-30% of that of the styrene-isoprene-butadiene terpolymer integrated latex, and the mass of the dropwise addition of the acrylonitrile monomer is 5-10% of that of the styrene-isoprene-butadiene terpolymer integrated latex;
and step 202, sequentially filtering, condensing and vacuum-drying the polymerization product system obtained in the step 201 to obtain the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer.
2. The method for preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer according to claim 1, wherein the initiator in the first and second steps is potassium persulfate or cumene hydroperoxide-ferrous sulfate composite initiator.
3. The method for preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer according to claim 1, wherein the emulsifier in step one is one or more selected from the group consisting of free alkyl aryl sulfonate, methyl alkyl alkali metal sulfate, sulfonated alkyl ester, fatty acid salt and rosin acid alkyl salt.
4. The method for preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer according to claim 1, wherein the chelating agent in step two is sodium pyrophosphate or/and potassium pyrophosphate.
5. The method for preparing the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer according to claim 1, wherein the reducing agent in step two is ferrous sulfate or/and ferrous phosphate.
6. The method for preparing styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer according to claim 1, wherein the reducing agent in step two is one or more of glucose, sodium hydrogen phosphite and sodium sulfite.
7. Use of the styrene-isoprene-butadiene ternary integrated rubber emulsion graft copolymer prepared by the method according to any one of claims 1 to 6 in the synthesis of ABS resin.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
| CN105732908A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A preparing method of a rubber graft copolymer and applications of the rubber graft copolymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
| CN105732908A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A preparing method of a rubber graft copolymer and applications of the rubber graft copolymer |
Non-Patent Citations (1)
| Title |
|---|
| KAIHUA SHEN 等: "Poly(styrene–isoprene–butadiene-g-SAN) graft copolymers:Size-controllable synthesis and their toughening properties" * |
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