CN110835389A - Pyridine styrene butadiene rubber latex and preparation method thereof - Google Patents
Pyridine styrene butadiene rubber latex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses pyridine styrene butadiene rubber latex which is prepared from the following raw materials: butadiene, styrene, 2-vinylpyridine, emulsifier, initiator, molecular weight regulator, diffusant, deoxidant, terminator, electrolyte and soft water; wherein, the emulsifier is: sodium dodecyl sulfate, potassium stearate, disproportionated potassium rosinate and fatty alcohol-polyoxyethylene ether; the initiator is as follows: p-menthane hydroperoxide, sodium formaldehyde sulfoxylate and ferrous sulfate. The preparation method comprises the following steps: (1) weighing the raw materials; (2) adding soft water, an emulsifier, a dispersing agent, an electrolyte, sodium formaldehyde sulfoxylate, ferrous sulfate and a deoxidant, uniformly stirring and vacuumizing; (3) adding styrene, butadiene and p-menthane hydroperoxide for reaction; (4) supplementing 2-vinylpyridine; (5) adding a molecular weight regulator; (6) adding a terminating agent to obtain the product. The invention combines the redox initiation system with the quaternary composite emulsification system, thereby greatly improving various performances of the pyridine styrene-butadiene latex.
Description
Technical Field
The invention relates to the technical field of high molecular compounds, in particular to pyridine styrene butadiene latex and a preparation method thereof.
Background
The pyridine ring of the styrene-butadiene-pyridine latex can react with organic groups on RF resin and fibers to form a combination of hydrogen bonds and dipoles, so that the adhesion of the styrene-butadiene-pyridine latex and synthetic fibers is remarkably superior to that of natural latex and other synthetic latex, and the styrene-butadiene-pyridine latex is widely used as a framework material of rubber products such as tires, rubber tubes, adhesive tapes and the like, becomes a key material for bonding rubber and fibers which is generally adopted in the world, and has irreplaceability. The quality of the pyridine styrene butadiene latex determines the bonding performance of the gum dipping framework material and the rubber product.
The styrene-butadiene-pyridine latex (VPL) comprises polymerized monomers, an emulsifier, inorganic salt, a molecular weight regulator, an initiator and desalted water. Polymerized monomers, namely butadiene (Bd), styrene (St), 2-vinylpyridine (2-VP); the emulsifier usually uses anionic emulsifier such as disproportionated potassium rosinate, fatty acid potassium, and nonionic emulsifier alkylphenol polyoxyethylene, and uses auxiliary emulsifier such as diffusant NF; inorganic salts such as potassium chloride and potassium phosphate; the molecular weight regulator is tert-dodecyl mercaptan. The polymerization reaction can be divided into a hot method reaction and a cold method reaction according to the type of the initiator, the initiator used for the hot method polymerization is mostly persulfate, and the cold method polymerization is mostly initiated by an initiation system consisting of organic peroxide-reducing agent, such as p-menthane peroxide-ferrous sulfate. The method can be divided into high-temperature polymerization and low-temperature polymerization according to the reaction temperature, wherein the reaction temperature of the high-temperature polymerization is 50-60 ℃, and the reaction temperature of the low-temperature polymerization is 6-10 ℃, so that compared with the high-temperature polymerization and the low-temperature polymerization, the reaction time of the high-temperature polymerization is shorter, the monomer conversion rate is higher, but the rubber performance of the polymer is inferior to that of a cold-process polymer; the reaction time of the low-temperature polymerization is longer, but the rubber property of the polymer is better, and the difference is shown in the aging resistance of the fiber cord, the cord fabric and the cord.
The nonionic emulsifier Alkylphenol Polyoxyethylene (APEO) is widely used for textile auxiliaries, including pretreatment agents, dyeing, printing and after-finishing agents, due to the characteristics of stable property, acid and alkali resistance, low cost and the like, and the APEO is used as an important raw material for wetting, penetrating, emulsifying, solubilizing and washing. However, due to the toxicity, irritation, biodegradability and toxicity to aquatic organisms of APEO, european union 2003/53/EC regulations stipulate that the use of alkylphenol ethoxylates is limited in textiles since 1/17 th 2005, which has attracted considerable attention from the auxiliaries community, and adjuvants free of APEO are also continuously introduced by various auxiliaries.
However, most of the currently proposed APEO-free auxiliary agents for preparing pyridine styrene butadiene rubber latex have the disadvantages of high gel rate and relatively high cost, and the produced pyridine styrene butadiene rubber latex has the defects of insufficient binding power, easy decomposition and poor mechanical stability.
Therefore, how to improve the comprehensive performance of the pyridine styrene butadiene rubber latex is a problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a pyridine styrene butadiene latex and a preparation method thereof, so as to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the pyridine styrene-butadiene latex is prepared from the following raw materials in parts by weight: 50-80 parts of butadiene, 15-30 parts of styrene, 5-20 parts of 2-vinylpyridine, 1.3-8.5 parts of emulsifier, 0.16-1.50 parts of initiator, 0.1-1.0 part of molecular weight regulator, 0.1-1.0 part of dispersing agent, 0.05-1.0 part of deoxidant, 0.05-1.0 part of terminator, 0.05-0.6 part of electrolyte and 140-150 parts of soft water; wherein the emulsifier is prepared from the following raw materials in parts by weight: 0.3-2.0 parts of sodium dodecyl sulfate, 0.5-2.5 parts of potassium stearate, 0.5-2.5 parts of disproportionated rosin potassium and 0-1.5 parts of fatty alcohol-polyoxyethylene ether; the initiator consists of the following raw materials in parts by weight: 0.05-0.40 part of p-menthane hydroperoxide, 0.1-0.8 part of sodium formaldehyde sulfoxylate and 0.01-0.30 part of ferrous sulfate.
Preferably, 60-70 parts of butadiene, 15-20 parts of styrene, 10-20 parts of 2-vinylpyridine, 2.8-5.5 parts of emulsifier, 0.41-0.95 part of initiator, 0.2-0.4 part of molecular weight regulator, 0.3-0.8 part of dispersing agent, 0.05-0.08 part of deoxidant, 0.05-1.0 part of terminator, 0.2-0.5 part of electrolyte and 143-148 parts of soft water; wherein the emulsifier is prepared from the following raw materials in parts by weight: 0.8-1.0 part of sodium dodecyl sulfate, 1.0-2.0 parts of potassium stearate, 0.5-1.5 parts of disproportionated rosin potassium and 0.5-1.0 part of fatty alcohol-polyoxyethylene ether; the initiator consists of the following raw materials in parts by weight: 0.2-0.4 part of p-menthane hydroperoxide, 0.2-0.5 part of sodium formaldehyde sulfoxylate and 0.01-0.05 part of ferrous sulfate.
More preferably, 70 parts of butadiene, 15 parts of styrene, 15 parts of 2-vinylpyridine, 4.0 parts of emulsifier, 0.95 part of initiator, 0.3 part of molecular weight regulator, 0.5 part of dispersing agent, 0.08 part of oxygen scavenger, 0.05 part of terminator, 0.4 part of electrolyte and 145 parts of soft water; wherein the emulsifier is prepared from the following raw materials in parts by weight: 0.8 part of sodium dodecyl sulfate, 1.5 parts of potassium stearate, 1.0 part of disproportionated potassium rosinate and 0.7 part of fatty alcohol-polyoxyethylene ether; the initiator consists of the following raw materials in parts by weight: 0.4 part of p-menthane hydroperoxide, 0.5 part of sodium formaldehyde sulfoxylate and 0.05 part of ferrous sulfate.
The invention has the beneficial effects that:
the quaternary composite emulsifying system composed of synthetic anionic emulsifier sodium dodecyl sulfate, anionic carboxylate emulsifier potassium stearate, disproportionated rosin potassium and nonionic emulsifier fatty alcohol-polyoxyethylene ether (FEO) is adopted to replace the original emulsifier, and the initiation system composed of hydrogen peroxide p-menthane, sodium formaldehyde sulfoxylate and ferrous sulfate is adopted to replace the original single persulfate initiator, so that the chemical stability and the mechanical stability of the pyridine styrene-butadiene latex are greatly improved.
Further, the molecular weight regulator is any one or a mixture of several of n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan and n-tetradecyl mercaptan.
The molecular weight regulator can effectively control the molecular weight of latex, reduce side reactions such as chain transfer, branching and the like, avoid forming more crosslinking structures and improve the performance of polymers.
Further, the above-mentioned dispersing agent is a sodium salt obtained by condensing naphthalene sulfonic acid with formaldehyde or a sodium salt obtained by condensing alkyl naphthalene sulfonic acid with formaldehyde, and is preferably sodium methylene dinaphthalene sulfonate.
The dispersing agent can assist the emulsifier to perform solubilization, so that latex particles can be stably dispersed in the solution, and large particles are avoided.
Further, the oxygen scavenger is sodium hydrosulfite.
The oxygen scavenger of the present invention has the further beneficial effect of eliminating the polymerization inhibiting effect of oxygen brought into the polymerization system during compounding and polymerization of the assistant.
Further, the terminator is a mixture of isopropyl hydroxylamine acetate and sodium polysulfide; furthermore, the mass ratio of the isopropyl hydroxylamine acetate to the sodium polysulfide in the mixture was 2: 1. .
The terminating agent of the invention does not produce nitrosamine, and is more environment-friendly.
Further, the electrolyte is potassium chloride or potassium phosphate, preferably potassium chloride.
The electrolyte has the further beneficial effects that the critical micelle concentration CMC of the emulsifier can be reduced, the latex viscosity is reduced, the fluidity of the latex is improved, and the heat dissipation is facilitated.
The invention also provides a preparation method of the pyridine styrene-butadiene latex, which comprises the following steps:
(1) weighing the raw materials according to the parts by weight of the pyridine styrene butadiene rubber latex;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, a dispersing agent, an electrolyte, sodium formaldehyde sulfoxylate, ferrous sulfate and an oxygen scavenger into a polymerization kettle, uniformly stirring (more than 30 min), and vacuumizing;
(3) continuously adding styrene and butadiene, and then adding p-menthane hydroperoxide at one time to start reaction;
(4) when the solid content of the system reaches 8-12 percent (preferably 10 percent), continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 32-36% (preferably 35%), adding a molecular weight regulator, and continuing the reaction;
(6) when the solid content of the system reaches 40-43 percent (preferably 42 percent), adding a terminator to obtain the pyridine styrene butadiene latex.
Further, in the steps (3) - (5), the reaction temperature is 10-40 ℃, preferably 15-25 ℃, and more preferably 15 ℃; the reaction pressure is 0.20-0.25 MPa.
The further beneficial effect of the adoption of the method is that the higher the reaction temperature is, the higher the reaction pressure is, and the faster the reaction speed is, but all indexes and performance of the latex are deviated; although the reaction time of the low-temperature polymerization is longer, the rubber properties of the polymer are better. Tests show that the rubber latex can obtain better rubber performance in a shorter reaction time when the polymerization temperature is 15 ℃, the mechanical stability and the chemical stability of the latex are improved, and the adhesive force of the pyridine styrene butadiene latex is greatly improved.
According to the technical scheme, compared with the prior art, the styrene-butadiene pyridine latex and the preparation method thereof have the following beneficial effects:
1. the invention adopts a quaternary composite emulsifying system consisting of a synthesized anionic emulsifier sodium dodecyl sulfate, an anionic carboxylate emulsifier potassium stearate, disproportionated rosin potassium stearate and a nonionic emulsifier fatty alcohol polyoxyethylene ether (FEO) to replace the original emulsifier, and uses nontoxic fatty alcohol polyoxyethylene ether (FEO) to replace toxic Alkylphenol Polyoxyethylene Ether (APEO), thereby ensuring the production process and the safety of products;
2. the invention adopts an initiation system consisting of the hydrogen peroxide p-menthane, the sodium formaldehyde sulfoxylate and the ferrous sulfate to replace the original single persulfate initiator, reduces side reactions such as chain transfer, branching and the like, improves the performance of the polymer and is beneficial to the improvement of the bonding force of the pyridine styrene butadiene latex;
3. the redox initiation system is matched with the quaternary composite emulsification system, and other auxiliaries are combined, so that the stability of the pyridine styrene-butadiene latex and the stability of the pH value of the pyridine styrene-butadiene latex are greatly improved;
4. the invention uses the combination of isopropyl hydroxylamine acetate and sodium polysulfide as the terminator, does not generate nitrosamine, and is more environment-friendly;
5. the product is prepared by adopting a semi-continuous process under a medium-low temperature condition, the reaction speed is improved, the chemical stability and the mechanical stability of the pyridine styrene-butadiene latex can be improved, and the improvement of the bonding force of the pyridine styrene-butadiene latex is facilitated.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 50kg of butadiene, 30kg of styrene, 20kg of 2-vinylpyridine, 1.3kg of an emulsifier (0.3 kg of sodium dodecyl sulfate, 0.5kg of potassium stearate and 0.5kg of disproportionated potassium rosinate), 0.16kg of an initiator (0.05 kg of p-menthane peroxide, 0.1kg of sodium formaldehyde sulfoxylate and 0.01kg of ferrous sulfate), 0.1kg of tert-dodecyl mercaptan, 0.1kg of sodium methylenedinaphthalenesulfonate, 0.05kg of sodium dithionite, 0.05kg of a mixture of isopropyl hydroxylamine acetate and sodium polysulfide, 0.05kg of potassium chloride and 140kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, sodium methylene dinaphthalene sulfonate, potassium chloride, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium hydrosulfite into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature to be 20 ℃ and the pressure to be 0.22MPa, and then adding hydrogen peroxide to p-menthane for starting reaction;
(4) when the solid content of the system reaches 8%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 32 percent, adding tert-dodecyl mercaptan, and continuing the reaction;
(6) when the solid content of the system reaches 40%, adding a mixture of isopropyl hydroxylamine acetate and sodium polysulfide to obtain a finished product of the butadiene-styrene-pyridine latex.
Example 2
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 60kg of butadiene, 25kg of styrene, 15kg of 2-vinylpyridine, 4.2kg of emulsifier (wherein, 1.6kg of sodium dodecyl sulfate, 1.3kg of potassium stearate, 1.0kg of disproportionated rosin potassium, 0.3kg of fatty alcohol-polyoxyethylene ether), 0.27kg of initiator (wherein, 0.13kg of p-menthane hydroperoxide, 0.13kg of sodium formaldehyde sulfoxylate, 0.01kg of ferrous sulfate), 0.2kg of octyl mercaptan, 0.3kg of methylene dinaphthyl sodium sulfonate, 0.05kg of sodium hydrosulfite, 0.05kg of a mixture of isopropyl hydroxylamine acetate and sodium polysulfide, 0.2kg of potassium chloride and 143kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, sodium methylene dinaphthalene sulfonate, potassium chloride, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium hydrosulfite into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature to be 20 ℃ and the pressure to be 0.22MPa, and then adding hydrogen peroxide to p-menthane for starting reaction;
(4) when the solid content of the system reaches 8%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 32 percent, adding octyl mercaptan and continuing to react;
(6) when the solid content of the system reaches 40%, adding a mixture of isopropyl hydroxylamine acetate and sodium polysulfide to obtain a finished product of the butadiene-styrene-pyridine latex.
Example 3
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 70kg of butadiene, 15kg of styrene, 15kg of 2-vinylpyridine, 4.4kg of emulsifier (wherein, 1.3kg of sodium dodecyl sulfate, 1.1kg of potassium stearate, 1.5kg of disproportionated rosin potassium and 0.5kg of fatty alcohol-polyoxyethylene ether), 0.75kg of initiator (wherein, 0.35kg of p-menthane hydroperoxide, 0.35kg of sodium formaldehyde sulfoxylate and 0.05kg of ferrous sulfate), 0.3kg of n-dodecyl mercaptan, 0.5kg of methylene dinaphthyl sodium sulfonate, 0.08kg of sodium hydrosulfite, 0.05kg of a mixture of isopropyl hydroxylamine acetate and sodium polysulfide, 0.4kg of potassium chloride and 145kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, sodium methylene dinaphthalene sulfonate, potassium chloride, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium hydrosulfite into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature at 15 ℃ and the pressure at 0.20MPa, and then adding hydrogen peroxide p-menthane to start reaction;
(4) when the solid content of the system reaches 10%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 35 percent, adding n-dodecyl mercaptan and continuing the reaction;
(6) when the solid content of the system reaches 42%, adding a mixture of isopropyl hydroxylamine acetate and sodium polysulfide to obtain a finished product of the butadiene-styrene-pyridine latex.
Example 4
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 70kg of butadiene, 20kg of styrene, 10kg of 2-vinylpyridine, 4.6kg of an emulsifier (wherein, 1.1kg of sodium dodecyl sulfate, 0.6kg of potassium stearate, 2.1kg of disproportionated rosin potassium, 0.8kg of fatty alcohol-polyoxyethylene ether), 0.95kg of an initiator (wherein, 0.4kg of p-menthane hydroperoxide, 0.5kg of sodium formaldehyde sulfoxylate, 0.05kg of ferrous sulfate), 0.4kg of n-tetradecyl mercaptan, 0.8kg of sodium methylene dinaphthalene sulfonate, 0.08kg of sodium hydrosulfite, 1.0kg of a mixture of isopropyl hydroxylamine acetate and sodium polysulfide, 0.5kg of potassium phosphate and 148kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, sodium methylene dinaphthalene sulfonate, potassium phosphate, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium hydrosulfite into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature at 25 ℃ and the pressure at 0.20MPa, and then adding hydrogen peroxide p-menthane to start reaction;
(4) when the solid content of the system reaches 8%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 32 percent, adding n-tetradecyl mercaptan and continuing to react;
(6) when the solid content of the system reaches 40%, adding a mixture of isopropyl hydroxylamine acetate and sodium polysulfide to obtain a finished product of the butadiene-styrene-pyridine latex.
Example 5
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 80kg of butadiene, 10kg of styrene, 10kg of 2-vinylpyridine, 7.0kg of an emulsifier (wherein, 1.5kg of sodium dodecyl sulfate, 2.0kg of potassium stearate, 2.0kg of disproportionated rosin potassium, 1.5kg of fatty alcohol-polyoxyethylene ether), 1.50kg of an initiator (wherein, 0.4kg of p-menthane hydroperoxide, 0.8kg of sodium formaldehyde sulfoxylate, 0.30kg of ferrous sulfate), 1.0kg of n-tetradecyl mercaptan, 1.0kg of sodium methylene dinaphthalene sulfonate, 1.0kg of sodium hydrosulfite, 1.0kg of a mixture of isopropyl hydroxylamine acetate and sodium polysulfide, 0.6kg of potassium phosphate and 150kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, sodium methylene dinaphthalene sulfonate, potassium phosphate, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium hydrosulfite into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature at 40 ℃ and the pressure at 0.25MPa, and then adding hydrogen peroxide p-menthane to start reaction;
(4) when the solid content of the system reaches 12%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 36 percent, adding n-tetradecyl mercaptan and continuing to react;
(6) when the solid content of the system reaches 43 percent, adding a mixture of isopropyl hydroxylamine acetate and sodium polysulfide to obtain a finished product of the butadiene-styrene-pyridine latex.
Comparative example
The pyridine styrene butadiene rubber latex is prepared from the following raw materials in parts by weight: 70kg of butadiene, 15kg of styrene, 15kg of 2-vinylpyridine, 4.0kg of emulsifier (wherein, 0.8kg of sodium dodecyl sulfate, 1.5kg of potassium stearate, 1.0kg of disproportionated rosin potassium, and 100.7 kg of nonylphenol ethoxylate NP-100.7 kg), 0.4kg of initiator (potassium persulfate), 0.3kg of n-dodecyl mercaptan, 0.5kg of methylene dinaphthalene sodium sulfonate, 0.05kg of sodium dimethyldithiocarbamate, 0.6kg of potassium chloride and 150kg of soft water.
The preparation method comprises the following steps:
(1) weighing the raw materials according to the weight;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, nonylphenol ethoxylate NP-10, sodium methylene dinaphthalene sulfonate and potassium chloride into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, controlling the temperature at 50 ℃ and the pressure at 0.40MPa, and then adding potassium persulfate to start reaction;
(4) when the solid content of the system reaches 10%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 35 percent, adding n-dodecyl mercaptan and continuing the reaction;
(6) when the solid content of the system reaches 42%, adding sodium dimethyldithiocarbamate to obtain the finished styrene-butadiene-pyridine latex.
Performance detection
According to the specification of SH/T1149-, mechanical stability (SH/T1151-.
Table 1 results of performance test of styrene-butadiene-pyridine latex finished products in examples 1-5 and comparative examples
As can be seen from table 1, the finished fenpyrad-styrene-butadiene latex products prepared in examples 1-5 of the present invention are superior to comparative examples (prior art) in TSC, pH, viscosity, surface tension, mechanical stability, chemical stability, adhesion, etc., wherein example 3 is the most preferred example.
The above tests illustrate that:
1. the invention adopts a quaternary composite emulsifying system consisting of a synthesized anionic emulsifier sodium dodecyl sulfate, an anionic carboxylate emulsifier potassium stearate, disproportionated rosin potassium stearate and a nonionic emulsifier fatty alcohol polyoxyethylene ether (FEO) to replace the original emulsifier, and uses nontoxic fatty alcohol polyoxyethylene ether (FEO) to replace toxic Alkylphenol Polyoxyethylene Ether (APEO), thereby ensuring the production process and the safety of products;
2. the invention adopts an initiation system consisting of the hydrogen peroxide p-menthane, the sodium formaldehyde sulfoxylate and the ferrous sulfate to replace the original single persulfate initiator, reduces side reactions such as chain transfer, branching and the like, improves the performance of the polymer and is beneficial to the improvement of the bonding force of the pyridine styrene butadiene latex;
3. the redox initiation system is matched with the quaternary composite emulsification system, and other auxiliaries are combined, so that the stability of the pyridine styrene-butadiene latex and the stability of the pH value of the pyridine styrene-butadiene latex are greatly improved;
4. the invention uses the combination of isopropyl hydroxylamine acetate and sodium polysulfide as the terminator, does not generate nitrosamine, and is more environment-friendly;
5. the product is prepared by adopting a semi-continuous process under a medium-low temperature condition, the reaction speed is improved, the chemical stability and the mechanical stability of the pyridine styrene-butadiene latex can be improved, and the improvement of the bonding force of the pyridine styrene-butadiene latex is facilitated.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The pyridine styrene butadiene rubber latex is characterized by being prepared from the following raw materials in parts by weight: 50-80 parts of butadiene, 15-30 parts of styrene, 5-20 parts of 2-vinylpyridine, 1.3-8.5 parts of emulsifier, 0.16-1.50 parts of initiator, 0.1-1.0 part of molecular weight regulator, 0.1-1.0 part of dispersing agent, 0.05-1.0 part of deoxidant, 0.05-1.0 part of terminator, 0.05-0.6 part of electrolyte and 140-150 parts of soft water;
the emulsifier is prepared from the following raw materials in parts by weight: 0.3-2.0 parts of sodium dodecyl sulfate, 0.5-2.5 parts of potassium stearate, 0.5-2.5 parts of disproportionated rosin potassium and 0-1.5 parts of fatty alcohol-polyoxyethylene ether;
the initiator consists of the following raw materials in parts by weight: 0.05-0.40 part of p-menthane hydroperoxide, 0.1-0.8 part of sodium formaldehyde sulfoxylate and 0.01-0.30 part of ferrous sulfate.
2. The pyridine styrene butadiene rubber latex according to claim 1, which is prepared from the following raw materials in parts by weight: 60-70 parts of butadiene, 15-20 parts of styrene, 10-20 parts of 2-vinylpyridine, 2.8-5.5 parts of emulsifier, 0.41-0.95 part of initiator, 0.2-0.4 part of molecular weight regulator, 0.3-0.8 part of dispersing agent, 0.05-0.08 part of deoxidant, 0.05-1.0 part of terminator, 0.2-0.5 part of electrolyte and 143-148 parts of soft water;
the emulsifier is prepared from the following raw materials in parts by weight: 0.8-1.0 part of sodium dodecyl sulfate, 1.0-2.0 parts of potassium stearate, 0.5-1.5 parts of disproportionated rosin potassium and 0.5-1.0 part of fatty alcohol-polyoxyethylene ether;
the initiator consists of the following raw materials in parts by weight: 0.2-0.4 part of p-menthane hydroperoxide, 0.2-0.5 part of sodium formaldehyde sulfoxylate and 0.01-0.05 part of ferrous sulfate.
3. The pyridine styrene butadiene rubber latex according to claim 2, which is prepared from the following raw materials in parts by weight: 70 parts of butadiene, 15 parts of styrene, 15 parts of 2-vinylpyridine, 4.0 parts of emulsifier, 0.95 part of initiator, 0.3 part of molecular weight regulator, 0.5 part of dispersing agent, 0.08 part of deoxidant, 0.05 part of terminator, 0.4 part of electrolyte and 145 parts of soft water;
the emulsifier is prepared from the following raw materials in parts by weight: 0.8 part of sodium dodecyl sulfate, 1.5 parts of potassium stearate, 1.0 part of disproportionated potassium rosinate and 0.7 part of fatty alcohol-polyoxyethylene ether;
the initiator consists of the following raw materials in parts by weight: 0.4 part of p-menthane hydroperoxide, 0.5 part of sodium formaldehyde sulfoxylate and 0.05 part of ferrous sulfate.
4. The pyridine styrene butadiene latex according to any one of claims 1 to 3, wherein the molecular weight regulator is any one or a mixture of n-dodecyl mercaptan, tert-dodecyl mercaptan, octyl mercaptan and n-tetradecyl mercaptan.
5. The pyridine styrene-butadiene latex according to any one of claims 1 to 3, wherein the dispersing agent is a sodium salt obtained by condensing naphthalene sulfonic acid and formaldehyde or a sodium salt obtained by condensing alkyl naphthalene sulfonic acid and formaldehyde.
6. The pyridine styrene-butadiene latex according to any one of claims 1 to 3, wherein the oxygen scavenger is sodium hydrosulfite.
7. The pyridine styrene butadiene latex according to any one of claims 1 to 3, wherein the terminator is a mixture of isopropyl hydroxylamine acetate and sodium polysulfide.
8. Pyridine styrene butadiene latex according to any of claims 1 to 3, characterized in that the electrolyte is potassium chloride or potassium phosphate.
9. The preparation method of pyridine styrene butadiene latex is characterized by comprising the following steps:
(1) weighing the raw materials according to the parts by weight of the pyridine styrene-butadiene latex of any one of claims 1 to 8;
(2) adding soft water, sodium dodecyl sulfate, disproportionated potassium rosinate, potassium stearate, fatty alcohol-polyoxyethylene ether, a dispersing agent, an electrolyte, sodium formaldehyde sulfoxylate, ferrous sulfate and an oxygen scavenger into a polymerization kettle, uniformly stirring and vacuumizing;
(3) continuously adding styrene and butadiene, and then adding p-menthane hydroperoxide to start reaction;
(4) when the solid content of the system reaches 8-12%, continuously and uniformly supplementing 2-vinylpyridine, and continuing to react;
(5) when the solid content of the system reaches 32-36%, adding a molecular weight regulator, and continuing to react;
(6) and when the solid content of the system reaches 40-43%, adding a terminator to obtain the pyridine styrene butadiene latex.
10. The method for preparing pyridine styrene butadiene latex according to claim 9, wherein in the steps (3) to (5), the reaction temperature is 10 to 40 ℃ and the pressure is 0.20 to 0.25 MPa.
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| CN116199834B (en) * | 2023-04-03 | 2023-07-18 | 淄博奥固特科技有限公司 | Preparation method and application of modified butadiene-styrene-pyridine latex |
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