CN115947884B - Synthesis method of large-particle-size polybutadiene latex - Google Patents

Synthesis method of large-particle-size polybutadiene latex Download PDF

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CN115947884B
CN115947884B CN202211636068.XA CN202211636068A CN115947884B CN 115947884 B CN115947884 B CN 115947884B CN 202211636068 A CN202211636068 A CN 202211636068A CN 115947884 B CN115947884 B CN 115947884B
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reaction
particle size
polybutadiene latex
butadiene
chain transfer
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CN115947884A (en
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谢丰鸣
郭凌霄
尚吉国
韩成功
刘永峰
李志康
巴文远
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Shandong Wanda Chemical Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • 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
    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract

The invention relates to the technical field of high polymer material preparation, and provides a method for synthesizing polybutadiene latex with large particle size. According to the invention, butadiene and a chain transfer agent are added into a reaction liquid in batches for polymerization reaction, and polybutadiene obtained in the previous reaction can be used as seeds for the subsequent polymerization reaction, so that multi-step seed polymerization is realized; the method provided by the invention is simple to operate, the reaction time is short, and the obtained polybutadiene latex has narrow particle size distribution; meanwhile, the particle size of the obtained polybutadiene latex can be controlled by controlling the reaction times, and the particle size of the obtained polybutadiene latex is larger when the reaction times are larger under the condition that the total consumption of butadiene and chain transfer agent is the same. In addition, the polybutadiene latex obtained by the synthesis method provided by the invention has low solid content, and is beneficial to control of reaction.

Description

Synthesis method of large-particle-size polybutadiene latex
Technical Field
The invention relates to the technical field of high polymer material preparation, in particular to a method for synthesizing polybutadiene latex with large particle size.
Background
ABS resin is formed by blending and granulating ABS high rubber powder (also called ABS graft copolymer) and SAN resin. ABS high rubber powder is a graft copolymer of polybutadiene rubber (B stands for butadiene) with styrene (S stands for styrene) and acrylonitrile (A or AN stands for acrylonitrile). ABS resin has a complex two-phase structure, polybutadiene rubber is a dispersed phase, SAN is a continuous phase as a matrix resin. The presence of polybutadiene rubber can improve the impact property of the material, so that the ABS resin has excellent performance.
ABS high rubber powder is usually obtained by emulsion polymerization. In order to provide an ABS resin with sufficient impact strength, it is required that the particle size of the polybutadiene rubber emulsion (PBL) is 260nm or more. The synthesis method of the PBL with large particle size mainly comprises a one-step method and a two-step method. The one-step method is to directly synthesize the PBL with large particle size in the polymerization process, the reaction time of the method is long (more than 20 h), the reaction heat release is large, liquid nitrogen is needed to control the temperature, and the operation is difficult. The two-step process is to synthesize PBL with small particle size of about 100nm first and agglomerate to synthesize PBL with large particle size. The two-step process has short reaction time, but the obtained product has wide particle size distribution.
Therefore, there is a need to provide a method for synthesizing large-particle polybutadiene latex with simple operation, short reaction time and narrow particle size distribution of the obtained product.
Disclosure of Invention
In view of this, the present invention provides a method for synthesizing a large particle size polybutadiene latex (PBL). The invention adopts a multi-step seed polymerization method to synthesize the polybutadiene latex with large particle diameter, has simple operation and short reaction time, and the obtained product has narrow particle diameter distribution, and can control the particle diameter of PBL.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for synthesizing polybutadiene latex with large particle diameter, which comprises the following steps:
mixing deionized water, an emulsifying agent, an initiator and electrolyte to obtain a mixed solution;
adding butadiene and a chain transfer agent into the mixed solution in batches for polymerization reaction to obtain polybutadiene latex with large particle size; after each batch of butadiene and chain transfer agent is added, reacting for 1-2 h, and recording each added batch as one reaction, wherein the times of the reactions are more than or equal to 3 times;
the particle size of the large-particle-size polybutadiene latex is 300nm or more.
Preferably, the number of the reactions is 3 to 7.
Preferably, the emulsifier is an anionic emulsifier.
Preferably, the anionic emulsifier comprises one or more of stearic acid soap, oleic acid soap, rosin soap, disproportionated rosin soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the initiator is a persulfate.
Preferably, the electrolyte comprises one or more of potassium carbonate, sodium carbonate and potassium chloride.
Preferably, the chain transfer agent is dodecyl mercaptan.
Preferably, the synthetic raw materials of the polybutadiene latex with large particle diameter comprise, in parts by mass: 45-48 parts of butadiene, 50-52 parts of deionized water, 1.5-30 parts of emulsifying agent, 0.18-0.45 part of initiator, 0.12-0.3 part of electrolyte and 0.1-0.3 part of chain transfer agent.
Preferably, the temperature of the polymerization reaction is 63-67 ℃, and the total time of the polymerization reaction is 5-11 h.
Preferably, the solid content of the large-particle-size polybutadiene latex is 45 to 50wt%.
The invention provides a method for synthesizing polybutadiene latex with large particle size, which comprises the following steps: mixing deionized water, an emulsifying agent, an initiator and electrolyte to obtain a mixed solution; adding butadiene and a chain transfer agent into the mixed solution in batches for polymerization reaction to obtain polybutadiene latex with large particle size; after each batch of butadiene and chain transfer agent is added, reacting for 1-2 h, and recording each added batch as one reaction, wherein the times of the reactions are more than or equal to 3 times; the particle size of the large-particle-size polybutadiene latex is 300nm or more. According to the invention, butadiene and a chain transfer agent are added in batches for polymerization reaction, and polybutadiene obtained in the previous reaction can be used as seeds for the subsequent polymerization reaction, so that multi-step seed polymerization is realized; the method provided by the invention is simple to operate, the reaction time is short, and the obtained polybutadiene latex has narrow particle size distribution; meanwhile, the particle size of the obtained polybutadiene latex can be controlled by controlling the reaction times, and the particle size of the obtained polybutadiene latex is larger when the reaction times are larger under the condition that the total consumption of butadiene and chain transfer agent is the same. Furthermore, the polybutadiene latex obtained by the synthesis method provided by the invention has low solid content, and is beneficial to control of reaction.
Drawings
FIG. 1 is a particle size test result of the large particle size polybutadiene latex prepared in example 1;
FIG. 2 is a particle size test result of the large particle size polybutadiene latex prepared in example 2;
FIG. 3 is a particle size test result of the large particle size polybutadiene latex prepared in example 3.
Detailed Description
The invention provides a method for synthesizing polybutadiene latex with large particle size, which comprises the following steps:
mixing deionized water, an emulsifying agent, an initiator and electrolyte to obtain a mixed solution;
adding butadiene and a chain transfer agent into the mixed solution in batches for polymerization reaction to obtain polybutadiene latex with large particle size; after each batch of butadiene and chain transfer agent is added, reacting for 1-2 h, and recording each added batch as one reaction, wherein the times of the reactions are more than or equal to 3 times;
the particle size of the large-particle-size polybutadiene latex is 300nm or more.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
Deionized water, an emulsifying agent, an initiator and electrolyte are mixed to obtain a mixed solution. In the present invention, the emulsifier is preferably an anionic emulsifier; the anionic emulsifier preferably comprises one or more of stearic acid soap, oleic acid soap, rosin soap, disproportionated rosin soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; in a specific embodiment of the present invention, the emulsifier is preferably a mixture of disproportionated rosin soap, oleic acid soap and sodium dodecyl sulfate, and the mass ratio of disproportionated rosin soap, oleic acid soap and sodium dodecyl sulfate in the mixture is preferably 3:1:1. In the present invention, the initiator is preferably a persulfate, and the persulfate is preferably potassium persulfate; the electrolyte preferably comprises one or more of potassium carbonate, sodium carbonate and potassium chloride. The invention has no special requirement on the mixing of deionized water, an emulsifying agent, an initiator and electrolyte, and the raw materials are added into a reaction kettle and stirred uniformly; the reaction kettle is preferably a pressure-resistant polymerization kettle.
After the mixed solution is obtained, butadiene and a chain transfer agent are added into the mixed solution in batches for polymerization reaction to obtain polybutadiene latex with large particle size; the butadiene and the chain transfer agent are reacted for 1 to 2 hours after each batch is added, and each batch is recorded as one reaction, wherein the times of the reactions are more than or equal to 3 times, preferably 3 to 7 times, and particularly preferably 3, 4, 5, 6 or 7 times; in particular embodiments of the present invention, the mass of butadiene added per batch or chain transfer agent added per batch is preferably equal. In the present invention, the polymerization reaction is preferably carried out at a temperature of 63 to 67 ℃, more preferably 65 ℃, and the polymerization reaction is preferably carried out under a nitrogen atmosphere.
In the present invention, the chain transfer agent is preferably dodecyl mercaptan.
In the present invention, the synthetic raw materials of the large particle size polybutadiene latex preferably include, in parts by mass: 45-48 parts of butadiene, preferably 46-47 parts; 50 to 52 parts of deionized water, preferably 51 to 51.5 parts; 1.5 to 30 parts, preferably 1.5 to 25 parts, more preferably 1.5 to 3 parts of emulsifier; 0.18 to 0.45 part of initiator, preferably 0.2 to 0.4 part; 0.12 to 0.3 part of electrolyte, preferably 0.15 to 0.25 part; 0.1 to 0.3 part of chain transfer agent, preferably 0.15 to 0.25 part; the butadiene and chain transfer agent are used in the total amount of the multi-batch reaction. In the specific embodiment of the invention, butadiene and a chain transfer agent are preferably equally divided into n (n is more than or equal to 3), after deionized water, an emulsifying agent, an initiator and an electrolyte are uniformly mixed, a first batch of butadiene and the chain transfer agent are added into the mixed solution, the temperature is raised to the temperature of polymerization reaction, the reaction is carried out for 1 to 2 hours, then the next batch of butadiene and the chain transfer agent are added, the reaction temperature is kept for continuous reaction for 1 to 2 hours, and then the next batch of butadiene and the chain transfer agent are added until all the addition is completed; after the last batch is added, preferably, the reaction is stopped until the conversion rate of butadiene is more than 98%; all the above processes are carried out under the protection of nitrogen. In the present invention, the total time of the polymerization reaction is preferably 5 to 11 hours, more preferably 6 to 10 hours, and still more preferably 8 to 9 hours.
After the polymerization reaction is finished, the invention preferably reduces the temperature of the obtained product feed liquid to below 40 ℃, and then filters the product feed liquid by a filter screen to obtain polybutadiene latex with large particle size; the mesh number of the filter screen is preferably 100 mesh.
In the present invention, the particle size of the large-particle-size polybutadiene latex is 300nm or more, preferably 300 to 350nm; the Solid Content (TSC) of the large-particle polybutadiene latex is preferably 45 to 50wt%.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
After the pressure-resistant polymerization kettle is cleaned, an experiment is started, and the whole reaction process is performed under the protection of nitrogen, and is specifically as follows:
(1) Adding into a reaction kettle: 3640g of deionized water, 756g of disproportionated rosin soap, 252g of oleic acid soap, 252g of sodium dodecyl sulfate, 16g of potassium persulfate and 16g of potassium carbonate, and adding 630g of butadiene and 3g of dodecyl mercaptan after stirring and mixing uniformly; and (3) heating, namely when the temperature is raised to 65 ℃, reacting for 1h, controlling the temperature to 65+/-2 ℃, and protecting the reaction by nitrogen.
(2) 630g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(3) 630g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(4) 630g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(5) 630g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen. And (3) reacting for 1-2 h until the conversion rate reaches 98%, and ending the reaction.
(6) Cooling to below 40 ℃, and filtering by a 100-mesh filter screen to obtain the polybutadiene latex with large particle size.
The particle size, particle size distribution and solid content of the obtained large-particle-size polybutadiene latex were tested, and the results showed that: particle size d=312.7 nm, particle size distribution: pdi=0.0, solids tsc=47 wt%; FIG. 1 shows the results of particle size measurement of the large particle size polybutadiene latex prepared in this example.
Example 2
After the pressure-resistant polymerization kettle is cleaned, an experiment is started, and the whole reaction process is carried out under the protection of nitrogen, and specifically comprises the following steps:
(1) 3640g deionized water, 756g disproportionated rosin soap, 252g oleic acid soap,
252g of sodium dodecyl sulfate, 16g of potassium persulfate and 16g of potassium carbonate, and after uniformly stirring and mixing, 525g of butadiene and 3g of dodecyl mercaptan are added. And (3) heating, namely when the temperature is raised to 65 ℃, reacting for 1h, controlling the temperature to 65+/-2 ℃, and protecting the reaction by nitrogen.
(2) 525g of butadiene and 3g of dodecyl mercaptan are added into the reaction kettle and reacted for 1 hour. The temperature is controlled to be 65+/-2 ℃, and the reaction needs nitrogen protection.
(3) 525g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for reaction for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(4) 525g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for reaction for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(5) 525g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle for reaction for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(6) 525g of butadiene and 3g of dodecyl mercaptan are added into a reaction kettle, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen. And (3) reacting for 1-2 hours until the conversion rate reaches 98%, and ending the reaction.
(7) Cooling to below 40 ℃, and filtering by a 100-mesh filter screen to obtain the polybutadiene latex with large particle size.
The particle size, particle size distribution and solid content of the obtained large-particle-size polybutadiene latex were tested, and the results showed that: particle size d= 324.2nm, particle size distribution: pdi=0.011, solids tsc=47.2 wt%; FIG. 2 shows the results of particle size measurement of the large particle size polybutadiene latex prepared in this example.
Example 3
After the pressure-resistant polymerization kettle is cleaned, an experiment is started, and the whole reaction process is carried out under the protection of nitrogen, and specifically comprises the following steps:
(1) 3640g deionized water, 756g disproportionated rosin soap, 252g oleic acid soap, 252g sodium dodecyl sulfate, 16g potassium persulfate and 16g potassium carbonate are added into the reaction kettle, and after being stirred and mixed uniformly, 450g butadiene and 2g dodecyl mercaptan are added. And starting to heat, and reacting for 1h when the temperature is raised to 65 ℃. The temperature is controlled to be 65+/-2 ℃, and the reaction needs nitrogen protection.
(2) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(3) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(4) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(5) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(6) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle for 1h, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen.
(7) 450g of butadiene and 2g of dodecyl mercaptan are added into a reaction kettle, the temperature is controlled to be 65+/-2 ℃, and the reaction is protected by nitrogen. And (3) reacting for 1-2 hours until the conversion rate reaches 98%, and ending the reaction.
(8) Cooling to below 40deg.C, and filtering with 100 mesh sieve to obtain polybutadiene latex with large particle diameter.
The particle size, particle size distribution and solid content of the obtained large-particle-size polybutadiene latex were tested, and the results showed that: particle size d= 340.4nm, particle size distribution: pdi=0.07, solids tsc=47.3 wt%; FIG. 3 shows the results of particle size measurement of the large particle size polybutadiene latex prepared in this example.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (5)

1. A method for synthesizing polybutadiene latex with large particle diameter, which is characterized by comprising the following steps:
mixing deionized water, an emulsifying agent, an initiator and electrolyte to obtain a mixed solution;
adding butadiene and a chain transfer agent into the mixed solution in batches for polymerization reaction to obtain polybutadiene latex with large particle size; after each batch of butadiene and chain transfer agent is added, reacting for 1-2 h, and recording each added batch as one reaction, wherein the times of the reactions are more than or equal to 5 times; the mass of butadiene added in each batch is equal to that of chain transfer agent added in each batch;
the particle size of the polybutadiene latex with large particle size is more than 300 nm;
the emulsifier is a mixture of disproportionated rosin soap, oleic acid soap and sodium dodecyl sulfate, and the mass ratio of the disproportionated rosin soap, the oleic acid soap and the sodium dodecyl sulfate in the mixture is 3:1:1;
the temperature of the polymerization reaction is 65+/-2 ℃, and the total time of the polymerization reaction is 5-11 h;
the synthetic raw materials of the polybutadiene latex with large particle size comprise the following components in parts by mass: 45-48 parts of butadiene, 50-52 parts of deionized water, 1.5-30 parts of emulsifying agent, 0.18-0.45 part of initiator, 0.12-0.3 part of electrolyte and 0.1-0.3 part of chain transfer agent.
2. The method of synthesis according to claim 1, wherein the initiator is a persulfate.
3. The method of synthesis according to claim 1, wherein the electrolyte comprises one or more of potassium carbonate, sodium carbonate and potassium chloride.
4. The synthetic method of claim 1 wherein the chain transfer agent is dodecyl mercaptan.
5. The synthetic method according to claim 1, wherein the solid content of the large particle size polybutadiene latex is 45 to 50wt%.
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