CN111848869A - Preparation method of small-particle-size high-crosslinking polybutadiene and copolymer latex thereof - Google Patents
Preparation method of small-particle-size high-crosslinking polybutadiene and copolymer latex thereof Download PDFInfo
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- CN111848869A CN111848869A CN202010727738.3A CN202010727738A CN111848869A CN 111848869 A CN111848869 A CN 111848869A CN 202010727738 A CN202010727738 A CN 202010727738A CN 111848869 A CN111848869 A CN 111848869A
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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
- 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
- C08F236/10—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 with vinyl-aromatic monomers
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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
- 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
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Abstract
A preparation method of small-particle-size high-crosslinking polybutadiene and copolymer latex thereof belongs to the field of synthetic resin. And (2) fully mixing the butadiene monomer with water at the temperature of 30-40 ℃ by using desalted water, an emulsifier, an electrolyte, an initiator, a cross-linking agent, a comonomer and the butadiene monomer, heating to 55-75 ℃, keeping the temperature for 7-12 hours, and reducing the pressure to be below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The invention is characterized in that the cross-linking agent is introduced in the process of synthesizing the butadiene latex with small particle size, and the formation of a cross-linked network structure is promoted by adding the cross-linking agent, so that the problem of low gel content in the process of synthesizing the latex with small particle size is avoided, the elasticity of the synthesized latex particles is increased, and the mechanical property of the synthesized ABS resin is improved.
Description
Technical Field
The invention belongs to the field of synthetic resin, and particularly relates to a method for rapidly preparing small-particle-size high-crosslinking polybutadiene and copolymer latex thereof.
Background
ABS resin as a general engineering plastic has been widely used in the fields of home appliance production, automobile manufacturing, electrical and electronic engineering, aerospace and the like because of its characteristics of good mechanical properties, processability, solvent resistance and the like. At present, the preparation process of ABS resin is divided into two methods, namely a bulk method and an emulsion blending method, wherein the emulsion blending method is most widely applied. The technological route for preparing ABS resin by emulsion blending method can be divided into several sections, firstly polybutadiene latex with large particle size is prepared, then emulsion grafting is carried out on the polybutadiene latex to obtain ABS graft latex, then the ABS graft latex is melt blended with SAN resin prepared by bulk polymerization after flocculation drying, and finally the ABS resin is prepared by granulation.
The most central step in the whole ABS resin synthesis stage is to prepare polybutadiene latex with large particle size. The preparation of the large-particle polybutadiene latex can be divided into two modes, namely a one-step method and a two-step method, for example, the one-step method for preparing the large-particle polybutadiene latex reported in the synthetic rubber industry (1987, 5, 328-332) has the production period of 55 hours, and although the technology for preparing the large-particle polybutadiene latex by the one-step method is rapidly developed in recent years, the polymerization time is as long as nearly 30 hours. Longer polymerization time leads to higher gel content of the polybutadiene latex, generally up to 95%, further reduces the flexibility of the polybutadiene latex and also reduces the crosslinking point in the grafting process of the polybutadiene latex emulsion. In order to avoid excessive crosslinking during the synthesis of polybutadiene latex in one step, it is generally necessary to introduce the molecular weight regulator dodecylmercaptan at the beginning of the polymerization to limit the crosslinking degree of the system. The two-step method for preparing the polybutadiene latex with the large particle size needs to prepare the polybutadiene latex with the small particle size firstly, the preparation time of the polybutadiene latex with the small particle size is usually about 80-12 hours, and then the polybutadiene latex with the particle size of about 300nm is prepared by agglomeration by using methods such as electrolyte, organic acid or acid anhydride, pressure and the like. The advantage of the two-step method for preparing polybutadiene latex is that the polymerization period is short, for example, in the preparation method of polybutadiene latex with small particle size reported in patent CN106866885A, a redox system is used to initiate polybutadiene polymerization, the polymerization period is only 4-8 hours, but the particle size of the prepared latex is too small, and is only about 60 nm. The limitation of the two-step method for preparing polybutadiene latex is that the gel content of the prepared product is too low, the gel content is only 20-40%, the elasticity of latex particles is small, and the toughening efficiency is low in the process of preparing ABS resin.
In the polybutadiene latex emulsion polymerization process, the gel content of the latex particles generally increases gradually with the prolonging of the polymerization reaction time, and the preparation time of the latex with small particle size is short, so the gel content is not required. How to prepare the small-particle size polybutadiene latex with proper gel content in a short time is the key for improving the performance of ABS resin products and saving the production cost.
Disclosure of Invention
The invention aims to develop a method for rapidly preparing polybutadiene with high crosslinking density and a copolymer thereof, and solves the problem of low gel content in the process of preparing polybutadiene latex with large particle size by a two-step method. The preparation method of the small-particle-size high-crosslinking polybutadiene and the copolymer latex thereof comprises the following specific steps:
(1) replacing a pressure reaction kettle with nitrogen for 2 times, vacuumizing, adding 100-200 parts of desalted water, 2-5 parts of emulsifier, 0.2-1 part of electrolyte and 0.15-0.4 part of initiator into the pressure reaction kettle, starting stirring to completely dissolve the materials, adding 1-5 parts of cross-linking agent, 0-10 parts of comonomer and 100 parts of butadiene monomer;
(2) starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 55-75 ℃, preserving heat for 7-12 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex.
The emulsifier used in the invention is one or a mixture of several of disproportionated potassium abietate, potassium oleate, fatty acid polyoxyethylene ether, potassium fatty acid, potassium ricinoleate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkyl naphthalene sulfonate;
the electrolyte used in the invention is one or a mixture of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the initiator used in the invention is potassium persulfate or sodium persulfate;
the cross-linking agent used in the invention is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylpropane trimethacrylate, triallyl isocyanurate and dicyclopentadiene acrylate;
the comonomer used in the invention is one or a mixture of styrene, methyl methacrylate, acrylonitrile and butyl acrylate.
From the aspect of emulsion polymerization kinetics, the cross-linking monomer is introduced in the process of preparing the small-particle-size polybutadiene latex, the self-crosslinking in the butadiene polymerization process is promoted, the elasticity of latex particles is further improved, sufficient grafting points are reserved for the graft polymerization of the latex particles, the problem of preparing the butadiene latex and the copolymer thereof with the small particle size and suitable gel content in a short period is further solved, and the following technical effects are achieved: (1) the small-particle size butadiene latex prepared in a short period has higher gel content; (2) the particle size distribution of the prepared small-particle-size latex shows a monomodal distribution.
Drawings
FIG. 1 is a graph showing the particle size distribution of the polybutadiene latex prepared in example 1 of the present invention.
FIG. 2 is a graph showing the particle size distribution of the polybutadiene latex prepared in example 2 of the present invention.
FIG. 3 is a graph showing the particle size distribution of the polybutadiene latex prepared in example 3 of the present invention.
FIG. 4 is a graph showing the particle size distribution of the polybutadiene latex prepared in example 4 of the present invention.
FIG. 5 is a graph showing the particle size distribution of the polybutadiene latex prepared in example 5 of the present invention.
FIG. 6 is a particle size distribution diagram of the polybutadiene latex prepared in the comparative example.
Example 1:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, desalted water 15KG, potassium oleate soap (dry basis) 200g, disproportionated potassium abietate soap (dry basis) 150g, electrolyte potassium carbonate 50g and initiator potassium persulfate 25g are added into the pressure reaction kettle, the pressure reaction kettle is started to be stirred to be completely dissolved, and crosslinking agent divinylbenzene 100g, comonomer styrene 500g and butadiene monomer 10KG are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving heat for 8 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 1, the final average particle diameter of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 105nm, and the particle size distribution exhibited a monomodal distribution.
Example 2:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, 15KG desalted water, 200g of potassium oleate soap (dry basis), 50g of disproportionated potassium abietate soap (dry basis), 100g of potassium ricinoleate soap (dry basis), 50g of electrolyte potassium bicarbonate, 10g of sodium carbonate and 25g of initiator potassium persulfate are placed in the pressure reaction kettle, the pressure reaction kettle is started to be stirred to be completely dissolved, 80g of crosslinking agent ethylene glycol dimethacrylate, 500g of comonomer methyl methacrylate and 10KG of butadiene monomer are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving the temperature for 9 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 2, the final average particle diameter of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 103nm, and the particle size distribution exhibited a monomodal distribution.
Example 3:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, 15KG desalted water, 150g of potassium aliphatate (dry basis), 50g of disproportionated potassium abietate soap (dry basis), 10g of sodium dodecyl benzene sulfonate, 50g of electrolyte sodium bicarbonate, 10g of sodium carbonate and 25g of initiator potassium persulfate are added to the pressure reaction kettle, stirring is started to completely dissolve the potassium aliphatate, 30g of cross-linking agent ethylene glycol dimethacrylate, 10g of pentaerythritol triacrylate, 500g of comonomer acrylonitrile and 10KG of butadiene monomer are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving the temperature for 9 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 3, the final average particle size of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 110nm, and the particle size distribution exhibited a monomodal distribution.
Example 4:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, desalted water 15KG, fatty acid potassium (dry basis) 200g, sodium dodecyl sulfate 10g, sodium dodecyl benzene sulfonate 10g, electrolyte sodium bicarbonate 50g, sodium carbonate 10g and initiator potassium persulfate 25g are added and placed in the pressure reaction kettle, stirring is started to completely dissolve the potassium dodecyl benzene sulfonate, and crosslinking agent triallyl isocyanurate 30g, pentaerythritol triacrylate 10g, comonomer acrylonitrile 500g and butadiene monomer 10KG are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving the temperature for 9 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 4, the final average particle diameter of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 95nm, and the particle size distribution exhibited a monomodal distribution.
Example 5:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, desalted water 15KG, fatty acid potassium (dry basis) 200g, sodium dodecyl sulfate 10g, sodium dodecyl benzene sulfonate 10g, electrolyte sodium bicarbonate 50g, sodium carbonate 10g and initiator potassium persulfate 25g are added into the pressure reaction kettle, the pressure reaction kettle is started to be stirred to be completely dissolved, and crosslinking agent dicyclopentadiene acrylate 50g, comonomer acrylonitrile 500g and butadiene monomer 10KG are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving the temperature for 9 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 5, the final average particle size of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 98nm, and the particle size distribution exhibited a monomodal distribution.
Comparative example 1:
the pressure reaction kettle is replaced by nitrogen for 2 times, the pressure reaction kettle is vacuumized, desalted water 15KG, potassium oleate soap (dry basis) 200g, disproportionated potassium abietate soap (dry basis) 150g, electrolyte potassium carbonate 50g and initiator potassium persulfate 25g are added into the pressure reaction kettle, the pressure reaction kettle is started to be stirred to be completely dissolved, and crosslinking agent 0g, comonomer styrene 500g and butadiene monomer 10KG are added. Starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 65 ℃, preserving heat for 8 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex. The obtained latex was tested for its particle size distribution using a laser particle sizer and for gel content using an acetone dissolution method.
As can be seen from FIG. 6, the final average particle diameter of the small-particle size butadiene latex after the addition of the crosslinking agent divinylbenzene was 103nm, and the particle size distribution exhibited a monomodal distribution.
Examples and comparative examples preparation of latex Performance tables
| Average particle diameter | Dispersion Index (PDI) | Gel content (%) | |
| Example 1 | 105 | 0.023 | 87.2 |
| Example 2 | 103 | 0.034 | 79.5 |
| Example 3 | 110 | 0.019 | 58.1 |
| Example 4 | 95 | 0.028 | 49.6 |
| Example 5 | 98 | 0.043 | 40.7 |
| Comparative example | 103 | 0.029 | 34.2 |
As shown by the comparison of the above examples, the introduction of the crosslinking agent during the preparation of the small-particle-size polybutadiene latex can increase the crosslinking density of the latex itself, and has no significant influence on the particle size and the particle size distribution of the prepared small-particle-size polybutadiene latex.
Claims (5)
1. A method for preparing small-particle-size high-crosslinking polybutadiene and copolymer latex thereof is characterized by comprising the following steps:
(1) replacing a pressure reaction kettle with nitrogen for 2 times, vacuumizing, adding 100-200 parts of desalted water, 2-5 parts of emulsifier, 0.2-1 part of electrolyte and 0.15-0.4 part of initiator into the pressure reaction kettle, starting stirring to completely dissolve the materials, adding 1-5 parts of cross-linking agent, 0-10 parts of comonomer and 100 parts of butadiene monomer;
(2) starting a stirring device to fully mix butadiene monomers with water at the temperature of 30-40 ℃, then heating to 55-75 ℃, preserving heat for 7-12 hours, and discharging when the polymerization conversion rate reaches more than 97% when the pressure is reduced to below 0.2Mpa to obtain the small-particle-size polybutadiene latex.
2. The process for producing the small-particle size highly crosslinked polybutadiene and its copolymer latex according to claim 1, wherein: the emulsifier is one or more of disproportionated potassium abietate, potassium oleate, polyoxyethylene fatty acid ether, potassium fatty acid, potassium ricinoleate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and alkyl sodium naphthalene sulfonate.
3. The process for producing the small-particle size highly crosslinked polybutadiene and its copolymer latex according to claim 1, wherein: the electrolyte is one or a mixture of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the initiator used is potassium persulfate or sodium persulfate.
4. The process for producing the small-particle size highly crosslinked polybutadiene and its copolymer latex according to claim 1, wherein: the crosslinking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylpropane trimethacrylate, triallyl isocyanurate and dicyclopentadiene acrylate.
5. The process for producing the small-particle size highly crosslinked polybutadiene and its copolymer latex according to claim 1, wherein: the comonomer is one or more of styrene, methyl methacrylate, acrylonitrile and butyl acrylate.
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Cited By (2)
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| CN114031720A (en) * | 2021-11-05 | 2022-02-11 | 北方华锦化学工业股份有限公司 | Preparation method of small-particle-size styrene-butadiene latex |
| CN115838549A (en) * | 2022-11-22 | 2023-03-24 | 南方电网电力科技股份有限公司 | Coal pile surface covering agent and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031720A (en) * | 2021-11-05 | 2022-02-11 | 北方华锦化学工业股份有限公司 | Preparation method of small-particle-size styrene-butadiene latex |
| CN115838549A (en) * | 2022-11-22 | 2023-03-24 | 南方电网电力科技股份有限公司 | Coal pile surface covering agent and preparation method and application thereof |
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