CN115109197A - High-performance conductive degradable carboxylic styrene-butadiene latex as well as preparation method and application thereof - Google Patents

High-performance conductive degradable carboxylic styrene-butadiene latex as well as preparation method and application thereof Download PDF

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CN115109197A
CN115109197A CN202210833199.0A CN202210833199A CN115109197A CN 115109197 A CN115109197 A CN 115109197A CN 202210833199 A CN202210833199 A CN 202210833199A CN 115109197 A CN115109197 A CN 115109197A
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styrene
degradable
butadiene latex
performance conductive
butadiene
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CN115109197B (en
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李鹏宇
刘方冰
禚振友
周海涛
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Xingyu New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

The invention discloses high-performance conductive degradable carboxylic styrene-butadiene latex as well as a preparation method and application thereof, and relates to the technical field of emulsion polymerization in high polymer materials. The preparation method comprises the following steps: the preparation method comprises the steps of pre-emulsifying deionized water, an emulsifier, nano-graphene micro-sheets and other auxiliary agents, adding a styrene monomer, a butadiene monomer, methacrylic acid and mercaptan which are dissolved with degradable high polymer materials, uniformly stirring, adding an initiator to initiate polymerization when the temperature is raised to a reaction temperature, finishing the reaction when the conversion rate is more than 98%, and synthesizing the high-performance conductive degradable carboxylated styrene-butadiene latex. The high-performance conductive degradable carboxylic styrene-butadiene latex provided by the application greatly improves the mechanical property of styrene-butadiene rubber, and the nano graphene nanoplatelets used as the emulsifier increase the conductivity, the mechanical property and the like of the composite material, so that the application range of the product is further expanded.

Description

High-performance conductive degradable carboxylic styrene-butadiene latex as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of emulsion polymerization in high polymer materials, and particularly relates to high-performance conductive degradable carboxylic styrene-butadiene latex as well as a preparation method and application thereof.
Background
The carboxylic styrene-butadiene rubber is a random copolymer generated by emulsion polymerization of butadiene, styrene, a small amount of carboxylic acid and other auxiliary agents. The carboxylic styrene-butadiene latex has the advantages of higher adhesive force and conjunctival strength, good mechanical and chemical stability, good fluidity and storage stability, large filling amount and the like. The method is widely applied to industries such as gum dipping gloves, carpet back coating, back coating of artificial turf, papermaking, building and the like.
With the increasing awareness of social environment, the treatment of solid waste with low carbon, environmental protection and harmlessness is certainly expected by the masses. The styrene butadiene rubber produced by the traditional process is not degradable, so that a large amount of resources are wasted, and the environment is not friendly. Therefore, it is imperative to develop a styrene-butadiene latex which has good performance, conductivity and natural degradation.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide high-performance conductive degradable carboxylic styrene-butadiene latex as well as a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, the present invention provides a preparation method of a high-performance conductive degradable carboxylated styrene-butadiene latex, which comprises: the preparation method comprises the steps of pre-emulsifying deionized water, an emulsifier, nano-graphene micro-sheets and other auxiliary agents, adding a styrene monomer, a butadiene monomer, methacrylic acid and mercaptan which are dissolved with degradable high polymer materials, uniformly stirring, adding an initiator to initiate polymerization to form latex when the temperature is raised to a reaction temperature, finishing the reaction when the conversion rate is more than 98%, and synthesizing the high-performance conductive degradable carboxylated styrene-butadiene latex.
In an optional embodiment, by mass percentage of the high-performance conductive degradable carboxylic styrene-butadiene latex, 35% to 65% of the deionized water, 1% to 10% of the emulsifier, 0.1% to 0.5% of the nano graphene nanoplatelets, 0.01% to 8% of the other auxiliary agents, 1% to 10% of the degradable high polymer material, 10% to 50% of the styrene monomer, 10% to 50% of the butadiene monomer, 1% to 3% of the methacrylic acid, 0.1% to 0.3% of the thiol, and 0.1% to 1% of the initiator.
In an alternative embodiment, the degradable polymeric material comprises one or more of polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol in combination.
In an optional embodiment, the nano graphene nanoplatelets have a plate diameter ranging from 0.03 to 1 μm and 5 to 30 layers.
In an optional embodiment, the pre-emulsification comprises stirring at 100-200 r/min for 20-60 min;
preferably, the reaction temperature is 40-70 ℃.
In an optional embodiment, when the conversion rate is more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator, reducing the temperature of the latex to 38-42 ℃, degassing the latex, adding a terminator and an anti-aging agent after degassing is finished, and finishing the reaction.
In alternative embodiments, the emulsifier comprises a combination of one or more of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, and potassium disproportionate rosinate soap.
In an alternative embodiment, the initiator comprises a combination of one or more of potassium persulfate and ammonium persulfate.
In alternative embodiments, the other adjuvants include one or a combination of more of diffusant-N, potassium oleate, casein, potassium pyrophosphate, and sodium bicarbonate.
In a second aspect, the present invention provides a high performance conductive degradable carboxylated styrene-butadiene latex, which is prepared by the preparation method of the high performance conductive degradable carboxylated styrene-butadiene latex according to any one of the previous embodiments.
In a third aspect, the present invention provides a use of the high performance conductive degradable carboxylated styrene-butadiene latex according to any one of the previous embodiments in the preparation of latex gloves, carpets or artificial lawns.
The invention has the following beneficial effects:
the application provides a high performance electrically conducts degradable carboxylic styrene-butadiene latex is through adding the natural degradable material in the synthetic stage in advance in the styrene-butadiene latex system for degradable macromolecular material disperses more evenly, and the condition of layering split phase that easily follow-up appearance leads to because of the dispersion inequality appears. Further, in the application, nano-graphene micro-sheets with a specific sheet diameter and layer number are selected as a conductive material and used as an emulsifier, so that a Pickering emulsion is formed between the nano-graphene micro-sheets and a subsequent monomer, the nano-graphene micro-sheets are adsorbed on an interface between a water phase and a monomer oil phase, and the oil phase is wrapped to form a stable emulsion. Because the monomer oil phase of the composite material has the degradable high polymer material, the degradable high polymer material is harder, the styrene-butadiene latex is softer, and the styrene-butadiene latex fully wraps the degradable high polymer material, so that the composite material has a stable core-shell structure, the mechanical property of the styrene-butadiene rubber is greatly improved, the nano graphene microchip used as an emulsifier increases the conductivity, the mechanical property and the like of the composite material, the application range of the product is further expanded, and the composite material can be widely applied to preparation of gum dipping gloves, carpets or artificial lawns.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of high-performance conductive degradable carboxylic styrene-butadiene latex, which comprises the following steps:
s1, preparing styrene monomer dissolved with degradable high molecular material.
In the present application, a degradable polymer material is pre-dissolved in a styrene monomer, wherein the degradable polymer material includes, but is not limited to, one or a combination of more of polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol. In the application, the addition amount of the degradable high polymer material accounts for 1% -10% of the high-performance conductive degradable carboxylic styrene-butadiene latex, and the addition amount of the styrene monomer accounts for 10% -50% of the high-performance conductive degradable carboxylic styrene-butadiene latex.
S2, pre-emulsifying the deionized water, the emulsifier, the nano graphene micro-sheets and other auxiliary agents.
In the application, the nano graphene nanoplatelets with the conductive performance are pre-emulsified with the emulsifier and other auxiliaries by stirring at a speed of 100-200 r/min for 20-60 min, so that the good dispersion of the nano graphene nanoplatelets can be ensured.
The addition amount of the deionized water accounts for 35-65% of the high-performance conductive degradable carboxylic styrene-butadiene latex, the addition amount of the emulsifier accounts for 1-10% of the high-performance conductive degradable carboxylic styrene-butadiene latex, the addition amount of the nano graphene micro-sheets accounts for 0.1-0.5% of the high-performance conductive degradable carboxylic styrene-butadiene latex, and the addition amount of other auxiliary agents accounts for 0.01-8% of the high-performance conductive degradable carboxylic styrene-butadiene latex. Wherein, the emulsifier includes but is not limited to one or more combination of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and disproportionated potassium abietate soap. Other adjuvants include, but are not limited to, one or a combination of more of diffusant-N, potassium oleate, casein, potassium pyrophosphate, and sodium bicarbonate.
Specifically, in the application, the appropriate nano graphene nanoplatelets are screened to ensure the emulsifying effect, so that subsequent monomers (styrene monomers, butadiene monomers and methacrylic acid) can be dispersed into Pickering emulsion, the stability of subsequent synthetic latex is ensured, and the conductivity of the styrene-butadiene latex can be improved. The particle size of the solid particles has a certain influence on the stability of the Pickering emulsion. Generally, the smaller the particle size, the better the stability of the Pickering emulsion obtained. However, considering the brownian motion, the particle size has a critical dimension, and below the critical dimension, the brownian motion seriously affects the distribution of the particles at the oil/water interface, so that the stability of the emulsion is rather reduced with the decrease of the particles; above the critical size, the stability of the emulsion increases as the particle size decreases. The critical size of the brownian motion generated by the particles is generally small, the emulsion stability increases rapidly when the solid particle diameter is less than a few microns, and the particles must be smaller than the dispersed phase droplets to effectively stabilize the emulsion. Preferably, the nano graphene nanoplatelets used in the application have a sheet diameter ranging from 0.03 to 1 μm and 5 to 30 layers. Further research in the application finds that when nano graphene micro-sheets with other sheet diameters or layers are adopted, the situation of poor emulsifying property or poor conductivity can occur.
S3, adding styrene monomer, butadiene monomer, methacrylic acid and mercaptan dissolved with degradable high polymer material, and stirring uniformly.
And (3) after the pre-emulsification of the material in the step (S2) is finished, adding the styrene monomer dissolved with the degradable high polymer material obtained in the step (S1), uniformly stirring, and then adding a butadiene monomer, methacrylic acid and mercaptan, wherein the adding amount of the butadiene monomer accounts for 10% -50% of the high-performance conductive degradable carboxylic styrene-butadiene latex, the adding amount of the methacrylic acid accounts for 1% -3% of the high-performance conductive degradable carboxylic styrene-butadiene latex, and the adding amount of the mercaptan accounts for 0.1% -0.3% of the high-performance conductive degradable carboxylic styrene-butadiene latex, and uniformly stirring again after the materials are added.
S4, when the temperature is raised to the reaction temperature, adding an initiator to initiate polymerization.
The reaction temperature is 40-70 ℃, and when the temperature is raised to 40-70 ℃, an initiator is added to initiate polymerization, wherein the initiator comprises but is not limited to one or more of potassium persulfate and ammonium persulfate. The addition amount of the initiator accounts for 0.1 to 1 percent of the high-performance conductive degradable carboxylic styrene-butadiene latex.
And S5, when the conversion rate is more than 98%, ending the reaction to synthesize the high-performance conductive degradable carboxylic styrene-butadiene latex.
And when the conversion rate is more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator, reducing the temperature of the latex to 38-42 ℃, degassing the latex, adding a terminator and an anti-aging agent after degassing is finished, and finishing the reaction.
In this application, through adding the natural degradable material in the synthetic stage in advance in the butylbenzene latex system for degradable macromolecular material disperses more evenly, and the condition that the layering split phase that easily follow-up appearance leads to because of dispersion inequality appears. Furthermore, in the application, nano graphene micro-sheets with a specific sheet diameter and layer number are selected as a conductive material and used as an emulsifier, so that a Pickering emulsion can be formed with a subsequent monomer, the nano graphene micro-sheets are adsorbed on an interface between a water phase and a monomer oil phase, and the oil phase is wrapped to form a stable emulsion. Because the monomer oil phase of the composite material has the degradable high polymer material, the degradable high polymer material is harder, the styrene-butadiene latex is softer, and the styrene-butadiene latex fully wraps the degradable high polymer material, so that the composite material has a stable core-shell structure, the mechanical property of the styrene-butadiene rubber is greatly improved, the nano graphene microchip used as an emulsifier increases the conductivity, the mechanical property and the like of the composite material, the application range of the product is further expanded, and the composite material can be widely applied to preparation of gum dipping gloves, carpets or artificial lawns.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 60g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene nanoplatelets (the diameter of each nanoplatelet is 0.2 mu m, the number of layers is 5-10) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Wherein, the other auxiliary agents comprise 20g of dispersing agent-N, 10g of potassium pyrophosphate and 8g of sodium bicarbonate. Other auxiliaries used in subsequent examples 2 to 4 and comparative examples 1 to 6 are the same as in example 1, and are not described again.
Example 2
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 100g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene nanoplatelets (the diameter of each nanoplatelet is 0.03 mu m, the number of layers is 20-30) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after carrying out air replacement on the polymerization reaction kettle, adding the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan;
4. the reaction system was heated to 70 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Example 3
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 60g of polycaprolactone, 20g of polyglycolic acid and 20g of polyvinyl alcohol into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 15g of nano graphene micro-sheets (the sheet diameter is 0.5 mu m, the number of layers is 5-15 layers) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 55 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Example 4
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 140g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene micro-sheets (the sheet diameter is 0.3 mu m, the number of layers is 10-20) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Example 5
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 40g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 1700g of deionized water, 50g of emulsifier (sodium dodecyl sulfate and disproportionated potassium rosinate soap in a mass ratio of 1: 1), 8g of nano graphene micro-sheets (the sheet diameter is 0.05 mu m, the number of layers is 5-10) and 4g of other additives into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. carrying out air replacement on a polymerization reaction kettle, and then adding the styrene solution prepared in the step 1, 1600g of butadiene, 120g of methacrylic acid and 12g of mercaptan;
4. the reaction system was warmed to 70 ℃ and 15g of initiator (ammonium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished, thereby obtaining the high-performance conductive degradable carboxylated styrene-butadiene latex.
Wherein, the other auxiliary agents comprise 3g of potassium pyrophosphate and 1g of sodium bicarbonate.
Example 6
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 200g of polylactic acid and 200g of polyglycolic acid into 1200g of styrene monomer for uniform dissolution;
2. adding 1500g of deionized water, 400g of emulsifier (sodium dodecyl sulfate and disproportionated potassium rosinate soap in a mass ratio of 1: 1), 20g of nano graphene micro-sheets (the sheet diameter is 1 mu m, the number of layers is 5-10) and 200g of other additives into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, adding the styrene solution prepared in the step 1, 425g of butadiene, 45g of methacrylic acid and 10g of mercaptan;
4. the reaction system is heated to 45 ℃, and 15g of initiator (potassium persulfate and ammonium persulfate with the mass ratio of 1: 1) is added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Wherein, the other auxiliary agents comprise 160g of diffusant-N, 30g of potassium pyrophosphate and 10g of sodium bicarbonate.
Comparative example 1
This comparative example is essentially the same as example 1, except that no polycaprolactone and nanographene nanoplatelets are added to this comparative example. The method specifically comprises the following steps:
1. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
2. after air replacement is carried out on a polymerization reaction kettle, 500g of styrene solution, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
3. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
4. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
5. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like after degassing to finish the reaction to obtain the carboxylic styrene-butadiene latex.
Comparative example 2
This comparative example is substantially the same as example 1 except that nano-graphene nanoplatelets are not added to the comparative example. The method specifically comprises the following steps:
1. adding 60g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance degradable carboxylated styrene-butadiene latex.
Comparative example 3
This comparative example is essentially the same as example 1 except that no polycaprolactone was added to this comparative example. The method specifically comprises the following steps:
1. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene micro-sheets and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
2. after air replacement is carried out on a polymerization reaction kettle, 500g of styrene solution, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
3. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
4. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
5. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive carboxylated styrene-butadiene latex.
Comparative example 4
This comparative example is substantially the same as example 1 except that the nanographene nanoplatelets of example 1 are replaced with carbon black in this comparative example.
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 60g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of carbon black and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Wherein, the other auxiliary agents comprise 20g of dispersing agent-N, 10g of potassium pyrophosphate and 8g of sodium bicarbonate.
Comparative example 5
The comparative example is substantially the same as example 1 except that the nano-graphene nanoplatelets in the comparative example have a sheet diameter of 3 μm and a number of layers of 40.
The embodiment provides a high-performance conductive degradable carboxylic styrene-butadiene latex, and a preparation method thereof comprises the following steps:
1. adding 60g of polycaprolactone into 500g of styrene monomer for uniform dissolution;
2. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene nanoplatelets (the diameter of each nanoplatelet is 3 mu m, the number of layers is 40) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
3. after air replacement is carried out on the polymerization reaction kettle, the styrene solution prepared in the step 1, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
4. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
5. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
6. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Wherein, the other auxiliary agents comprise 20g of diffusant-N, 10g of potassium pyrophosphate and 8g of sodium bicarbonate.
Comparative example 6
The comparative example is basically the same as the example 1, except that polycaprolactone is not dissolved in advance in the comparative example, and the polycaprolactone is directly added when a styrene monomer is added, and the method specifically comprises the following steps:
1. adding 2500g of deionized water, 120g of emulsifier (sodium dodecyl benzene sulfonate), 8g of nano graphene nanoplatelets (the diameter of each nanoplatelet is 0.2 mu m, the number of layers is 5-10) and 38g of other auxiliary agents into a 10L stainless steel polymerization reaction kettle, and stirring at a high speed for pre-emulsification;
2. after air replacement is carried out on a polymerization reaction kettle, 60g of polycaprolactone, 500g of styrene monomer, 1000g of butadiene, 80g of methacrylic acid and 12g of mercaptan are added;
3. the reaction system was heated to 60 ℃ and 15g of initiator (potassium persulfate) was added to initiate the reaction.
4. Controlling the temperature of the polymerization reaction, and periodically detecting the reaction progress. And when the conversion rate reaches more than 98%, adjusting the pH value of the latex to 7-8 by using a pH regulator.
5. And (3) reducing the temperature in the reaction kettle to about 40 ℃, transferring the substances in the reaction kettle to a degassing kettle for degassing operation, and adding a terminator, an anti-aging agent and the like to finish the reaction after the degassing is finished to obtain the high-performance conductive degradable carboxylated styrene-butadiene latex.
Examples of the experiments
The carboxylated styrene-butadiene latex provided in the above examples 1 to 6 and comparative examples 1 to 6 is vulcanized and mixed to prepare a glue film, and the mechanical property and the conductivity of the glue film are tested. The test results are shown in Table 1.
TABLE 1 Performance test Table for carboxylated styrene-butadiene latex provided in different examples
Figure BDA0003746360050000131
Figure BDA0003746360050000141
As can be seen from the above table, in the case of adding polycaprolactone and nano graphene nanoplatelets, the conductivity and mechanical properties are improved in example 1; the performance of the embodiment 5 is best, the emulsifying performance is good, and the stability of the final latex is good; the properties of example 3 are inferior; example 4 the amount of polycaprolactone is increased on the basis of example 2, the elongation at break and tensile strength are slightly reduced, which indicates that the use of excessive amount of polycaprolactone has a bad influence on the performance of the material; in example 6, graphene nanoplatelets having a large sheet diameter were used, and the conductivity was improved to some extent, but the emulsification effect was slightly poor and the emulsion stability was slightly lowered.
The comparative examples 1-3 show that the mechanical property of styrene butadiene rubber can be improved by adding the nano graphene nanoplatelets and the degradable material polycaprolactone, the mechanical property and the synergistic effect are achieved, and meanwhile, the conductivity of the material can be endowed by adding the graphene; comparative example 4 small-sized conductive carbon black is used as a stabilizer of Pickering emulsion, the emulsification effect is relatively poor, the reverse effect is exerted on the mechanical property of the material, and the conductivity is poor; comparative example 5 the graphene nanoplatelets with large sheet diameters cannot be used as a stabilizer of Pickering emulsion, and finally most of the graphene nanoplatelets cannot be kept at a two-phase interface, so that the graphene nanoplatelets are separated out from a system and lose effect, and the performance of the material is not greatly improved; comparative example 6 because of the difference of the adding mode, the produced emulsion has phase splitting phenomenon, part of polycaprolactone is separated out, the reinforcing function is lost, and uniform emulsion can not be formed, so that the performance of the final composite material is poor.
To sum up, the high-performance conductive degradable carboxylic styrene-butadiene latex provided by the application is added with a natural degradable material into a styrene-butadiene latex system in a synthesis stage in advance, so that the degradable high polymer material is more uniformly dispersed, and the condition of layering and phase splitting caused by uneven dispersion is easy to follow-up. Further, in the application, nano-graphene micro-sheets with a specific sheet diameter and layer number are selected as a conductive material and used as an emulsifier, so that a Pickering emulsion is formed between the nano-graphene micro-sheets and a subsequent monomer, the nano-graphene micro-sheets are adsorbed on an interface between a water phase and a monomer oil phase, and the oil phase is wrapped to form a stable emulsion. Because the monomer oil phase of the composite material has the degradable high polymer material, the degradable high polymer material is harder, the styrene-butadiene latex is softer, and the styrene-butadiene latex fully wraps the degradable high polymer material, so that the composite material has a stable core-shell structure, the mechanical property of the styrene-butadiene rubber is greatly improved, the nano graphene microchip used as an emulsifier increases the conductivity, the mechanical property and the like of the composite material, the application range of the product is further expanded, and the composite material can be widely applied to preparation of gum dipping gloves, carpets or artificial lawns.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of high-performance conductive degradable carboxylic styrene-butadiene latex is characterized by comprising the following steps: the preparation method comprises the steps of pre-emulsifying deionized water, an emulsifier, nano-graphene micro-sheets and other auxiliary agents, adding a styrene monomer, a butadiene monomer, methacrylic acid and mercaptan which are dissolved with degradable high polymer materials, uniformly stirring, adding an initiator to initiate polymerization to form latex when the temperature is raised to a reaction temperature, finishing the reaction when the conversion rate is more than 98%, and synthesizing the high-performance conductive degradable carboxylated styrene-butadiene latex.
2. The method for preparing the high-performance conductive degradable carboxylated styrene-butadiene latex according to claim 1, wherein the deionized water is 35% to 65%, the emulsifier is 1% to 10%, the nano graphene micro-sheets are 0.1% to 0.5%, the other additives are 0.01% to 8%, the degradable high polymer material is 1% to 10%, the styrene monomer is 10% to 50%, the butadiene monomer is 10% to 50%, the methacrylic acid is 1% to 3%, the mercaptan is 0.1% to 0.3%, and the initiator is 0.1% to 1% by mass.
3. The method for preparing the high-performance conductive degradable carboxylated styrene-butadiene latex according to claim 1, wherein the degradable polymer material comprises one or more of polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol.
4. The method for preparing the high-performance conductive degradable carboxylated styrene-butadiene latex according to claim 1, wherein the nano graphene micro-sheets have a sheet diameter of 0.03 to 1 μm and 5 to 30 layers.
5. The preparation method of the high-performance conductive degradable carboxylic styrene-butadiene latex according to claim 1, wherein the pre-emulsification comprises stirring at 100-200 r/min for 20-60 min;
preferably, the reaction temperature is 40-70 ℃.
6. The method for preparing high-performance conductive degradable carboxylated styrene-butadiene latex according to claim 1, wherein when the conversion rate is more than 98%, the pH value of the latex is adjusted to 7-8 by using a pH regulator, the temperature of the latex is reduced to 38-42 ℃, the latex is subjected to degassing operation, and a terminator and an anti-aging agent are added after degassing is completed to finish the reaction.
7. The method for preparing high performance conductive degradable carboxylated styrene-butadiene latex according to any of the claims 1 to 6, wherein the emulsifier comprises one or more of sodium dodecylbenzene sulfonate, sodium dodecylsulfate and disproportionated potassium rosinate soap;
preferably, the initiator comprises one or a combination of more of potassium persulfate and ammonium persulfate.
8. The method for preparing high performance conductive degradable carboxylated styrene-butadiene latex according to any of claims 1-6, wherein said other additives include one or more of diffusant-N, potassium oleate, casein, potassium pyrophosphate and sodium bicarbonate.
9. A high performance conductive degradable carboxylic styrene-butadiene latex, which is prepared by the preparation method of the high performance conductive degradable carboxylic styrene-butadiene latex according to any one of claims 1 to 8.
10. Use of the high performance conductive degradable carboxylated styrene-butadiene latex of claim 9 in the preparation of latex gloves, carpets or artificial turf.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130017402A1 (en) * 2010-03-31 2013-01-17 Jsr Corporation Copolymer latex and composition containing the same and application product therof
CN104098795A (en) * 2013-04-12 2014-10-15 中国石油化工股份有限公司 Conductive thermoplastic elastomer and preparation method thereof
CN104592447A (en) * 2015-01-12 2015-05-06 浙江天晨胶业股份有限公司 Preparation method of carboxylic butadiene-styrene latex

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130017402A1 (en) * 2010-03-31 2013-01-17 Jsr Corporation Copolymer latex and composition containing the same and application product therof
CN104098795A (en) * 2013-04-12 2014-10-15 中国石油化工股份有限公司 Conductive thermoplastic elastomer and preparation method thereof
CN104592447A (en) * 2015-01-12 2015-05-06 浙江天晨胶业股份有限公司 Preparation method of carboxylic butadiene-styrene latex

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