CN112409543B - Preparation method of vinyl chloride and acrylate copolymer emulsion - Google Patents

Preparation method of vinyl chloride and acrylate copolymer emulsion Download PDF

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CN112409543B
CN112409543B CN202011157574.1A CN202011157574A CN112409543B CN 112409543 B CN112409543 B CN 112409543B CN 202011157574 A CN202011157574 A CN 202011157574A CN 112409543 B CN112409543 B CN 112409543B
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CN112409543A (en
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张林松
吕马德
刘刚
程传政
虞群峰
裴美芳
夏爱华
陈明凤
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China Salt Anhui Tianchen Chemical Co.,Ltd.
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

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Abstract

The invention discloses a preparation method of vinyl chloride and acrylate copolymer emulsion, which is a polymerization method for preparing polyvinyl chloride seed emulsion and externally connecting an acrylate polymer by using a two-step method. The invention adopts a two-step method to prepare the copolymer emulsion of vinyl chloride and acrylic ester (referred to as chloropropyl emulsion for short), namely, firstly, vinyl chloride monomer is used to prepare polyvinyl chloride seed emulsion, and then acrylic ester polymer is externally connected on the surface of the seed particle to prepare the emulsion particle which is emulsion with a core-shell structure with polyvinyl chloride as a core and polyacrylate as a shell. And because of the existence of the polyvinyl chloride, the coating has certain flame retardant property, self-extinguishing property and corrosion resistance.

Description

Preparation method of vinyl chloride and acrylate copolymer emulsion
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of vinyl chloride and acrylate copolymer emulsion.
Background
The emulsion paint is a paint which takes polymer synthetic resin emulsion as a main film forming substance, the finer the particle size of the emulsion is, the higher the gloss is, and when the particle size of the emulsion is finer and the distribution is wider, the emulsion paint with better gloss and high shear fluidity can be obtained. The emulsion for the coating, which is commonly used in the market at present, is styrene-acrylate copolymer emulsion (styrene-acrylic emulsion for short), has high manufacturing cost, contains benzene series, has large smell, is not environment-friendly, and is not suitable for preparing water-based coating with low VOC requirement.
Acrylic acid and its ester are one of the important industrial raw materials, the acrylic emulsion obtained by polymerizing acrylic acid and its ester has wide application, and the acrylic emulsion with different functions can be synthesized by different proportions, different monomers and different polymerization modes, and can be used in various industries such as building, printing ink, coating, leather, paper making, rubber and plastic, and the like. In the prior art, the acrylic emulsion has general film-forming glossiness and is lack of flame retardant property and waterproof effect, the acrylic emulsion is usually prepared into cheap comprehensive resin emulsion for use, and the main coating component is widely polyurethane, casein emulsion and the like, so that the application of the acrylic emulsion is greatly limited.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a preparation method of a vinyl chloride and acrylate copolymer emulsion.
In order to achieve the above object, the present invention provides the following technical solutions:
a process for preparing the copolymer emulsion of chloroethylene and acrylate includes such steps as preparing the seed emulsion of PVC from chloroethylene monomer, and polymerizing with acrylate polymer.
Further, the preparation method of the polyvinyl chloride seed emulsion specifically comprises the following steps:
(1) preparation before polymerization: spraying a certain amount of formaldehyde and 1-naphthol copolymer aqueous solution into a polymerization kettle from a kettle top condenser of the polymerization kettle, then adding deionized water at 50 ℃, adding lauric acid and potassium hydroxide aqueous solution under stirring, then adding NAOH aqueous solution, keeping the alkaline environment of the system, then adding ferrous sulfate, rongalite and EDTA, uniformly stirring, vacuumizing to-0.07 MPa, and adding liquid VCM monomer at one time;
(2) polymerization: heating the polymerization kettle to 50-60 ℃, controlling the pressure to be 0.065-0.09MPa, starting to dropwise add potassium persulfate to initiate VCM polymerization, continuously dropwise adding sodium dodecyl benzene sulfonate in the polymerization process, and finishing the reaction when the reaction conversion rate reaches 75-85 percent and all monomer droplets disappear;
(3) degassing: after the reaction is finished, removing residual monomers in the polymerization kettle through a kettle top condenser, introducing the removed gas into a recovery system, and adding a certain amount of emulsified silicone oil according to the condition in the degassing process to prevent the kettle top condenser from being blocked due to excessive foam generated by the system;
(4) post-stabilization treatment: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, then sodium dodecyl benzene sulfonate is added, the stirring is carried out for 30min, and the stabilizing treatment is finished;
(5) discharging: pumping the materials in the polymerization kettle into a latex storage tank by a pump to obtain the polyvinyl chloride seed emulsion for later use.
Furthermore, the solid content of the polyvinyl chloride seed emulsion is 35-45%, the average particle size is 0.10-0.12 μm, and the pH is 9-10.
Further, the method for externally connecting the acrylate polymer comprises the following specific steps:
(1) preparation before polymerization: adding deionized water into a charging tank, adding 2-allyl ether-3-hydroxy propane sodium sulfonate and sodium dodecyl sulfate while stirring, then adding butyl acrylate, methyl methacrylate, acrylic acid and cross-linking agent hydroxyethyl ester, uniformly stirring to obtain a pre-emulsified monomer for later use, adding deionized water with the temperature of 30 ℃ into a polymerization kettle, adding the polyvinyl chloride seed emulsion prepared in the first step while stirring, heating to the temperature of 80-85 ℃, and keeping the pressure at normal pressure;
(2) polymerization: adding potassium persulfate into a polymerization kettle, stirring uniformly, continuously dropwise adding a pre-emulsified monomer, starting a polymerization reaction, controlling the dropwise adding speed to be completed within 2 hours, controlling the polymerization temperature to be 80-85 ℃ until the pre-emulsified monomer is completely dropwise added, then preserving the temperature for 1-2 hours, condensing a gas phase part in the polymerization kettle into a liquid phase through a condenser at the top of a normal pressure kettle, and continuing the reaction, so that the conversion rate of the acrylate monomer is improved;
(3) and (3) post-treatment: cooling to 70-75 deg.C after heat preservation, adding sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide, stirring for 30min, and stabilizing;
(4) degassing: after the post-stabilization treatment is finished, removing the residual monomers in the polymerization kettle through a kettle top condenser, and allowing the removed gas to enter a recovery system;
(5) discharging: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, the pressure is recovered to normal pressure after the degassing is finished, the temperature is reduced to 45 to 55 ℃, the PH of the emulsion is regulated to 7.5 to 8.5 by ammonia water, the temperature is reduced to below 40 ℃, the materials in the polymerization kettle are pumped into a latex storage tank by a pump to be stored, and the chloroethylene-acrylate copolymer emulsion is obtained.
Furthermore, the average particle diameter of the chloroethylene-acrylate copolymer emulsion is between 0.15 and 0.20 mu m.
Further, the ratio of the vinyl chloride monomer to the acrylate polymer is controlled to be (55-60): (40-45).
Preferably, the acrylate polymer consists of the following monomer components: methyl methacrylate, butyl acrylate, crosslinking monomer hydroxyethyl ester and acrylic acid.
More preferably, the acrylic polymer comprises 7 to 8 parts by weight of methyl methacrylate, 20 to 25 parts by weight of butyl acrylate, 2.5 to 3 parts by weight of crosslinking monomer hydroxyethyl ester and 9.5 to 10 parts by weight of acrylic acid.
The invention has the advantages that:
the invention adopts a two-step method to prepare the copolymer emulsion (chloropropane emulsion for short) of chloroethylene and acrylic ester, namely, firstly, chloroethylene monomer is used to prepare polyvinyl chloride seed emulsion, and then acrylic ester polymer is externally connected to the surface of the seed particle, and the prepared emulsion particle is core-shell emulsion taking polyvinyl chloride as a core and polyacrylate as a shell. And because of the existence of the polyvinyl chloride, the coating has certain flame retardant property, self-extinguishing property and corrosion resistance.
The invention is based on MSP-3 technology, and has good controllability and high safety in the production process. The two-step method of preparing the polyvinyl chloride seed emulsion and externally connecting the polyvinyl chloride seed emulsion with the acrylic ester polymer, wherein the former polymerization step and the later polymerization step avoid the defect that the polymerization process is difficult to control due to different reactivity ratios of two types of monomers; also overcomes the contradiction that the seed emulsion needs to be polymerized in an alkaline environment, and the acrylic ester needs to be polymerized in an acidic environment. At the later stage of the polymerization reaction, the monomer conversion rate is improved and unreacted monomers are removed by technologies such as condensation, vacuum residue removal and the like, the VOC content of the product is obviously reduced, and the emulsion is an environment-friendly emulsion product. And the vinyl chloride is used for replacing styrene, so that the production cost of the emulsion is obviously reduced, and the emulsion is an economic environment-friendly emulsion product.
The invention solves the problems of high price, large emulsion smell, environmental pollution and the like of styrene-acrylic emulsion products commonly used in the current market, reduces the production cost, is very suitable for preparing the low-VOC water-based paint, further ensures that the paint has certain effects of fire resistance and self-extinguishing property, and improves the covering power of the paint because the emulsion particles have a core-shell structure.
Drawings
FIG. 1 is a graph showing the particle size distribution of the polyvinyl chloride seed emulsion obtained in example 1.
FIG. 2 shows the particle size distribution of the chloropropane emulsion obtained in example 2.
FIG. 3 is a diagram showing a finished chloropropane emulsion obtained in example 2.
FIG. 4 shows the particle size distribution of the chloropropane emulsion obtained in example 3.
FIG. 5 is a schematic diagram showing a finished chloropropane emulsion obtained in example 3.
FIG. 6 shows the particle size distribution of the chloropropane emulsion obtained in example 4.
FIG. 7 is a diagram showing a finished chloropropane emulsion obtained in example 4.
FIG. 8 shows the particle size distribution of the chloropropane emulsion obtained in example 5.
FIG. 9 is a diagram showing a finished chloropropane emulsion obtained in example 5.
FIG. 10 is a graph showing the effects of the chloropropane emulsion obtained in example 4 in the production of an anticorrosive paint.
FIG. 11 is a graph showing the effects of the chloropropane emulsion obtained in example 6 on rust inhibitive coatings.
FIG. 12 is a graph showing effects of a rust inhibitive coating prepared from the chloropropane emulsion obtained in example 7.
FIG. 13 is a schematic structural diagram of a vinyl chloride/acrylate copolymer emulsion of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A preparation method of vinyl chloride and acrylate copolymer emulsion comprises the following two steps:
the first step is as follows: preparation of polyvinyl chloride seed emulsion (design according to 30L polymerizer)
Deionized water: 10Kg of water
Lauric acid and potassium hydroxide aqueous solution: 35g of
Ferrous sulfate: 0.25g
Hanging white blocks: 2.4g
EDTA：1g
VCM：10Kg
Potassium persulfate solution (concentration: 3-8 g/Kg): 0.3Kg
Sodium dodecylbenzenesulfonate: 10Kg of water
Sodium dodecylbenzenesulfonate (added for post-stabilization): 1Kg
Polymerization temperature: 50-60 deg.C
(1) Preparation before polymerization: spraying a certain amount of formaldehyde and 1-naphthol copolymer aqueous solution into a polymerization kettle from a kettle top condenser of the polymerization kettle, then adding deionized water at 50 ℃, adding lauric acid and potassium hydroxide aqueous solution under stirring, then adding NAOH aqueous solution, keeping the alkaline environment of the system, then adding ferrous sulfate, rongalite and EDTA, uniformly stirring, vacuumizing to-0.07 MPa, and adding liquid VCM monomer at one time;
(2) polymerization: heating the polymerization kettle to 50-60 ℃, controlling the pressure to be 0.065-0.09MPa, starting to dropwise add potassium persulfate to initiate VCM polymerization, continuously dropwise adding sodium dodecyl benzene sulfonate in the polymerization process, and when the reaction conversion rate reaches 75-85%, completely eliminating monomer liquid drops and finishing the reaction;
(3) degassing: after the reaction is finished, removing residual monomers in the polymerization kettle through a kettle top condenser, allowing the removed gas to enter a recovery system, and adding a certain amount of emulsified silicone oil according to conditions during the degassing process to prevent the kettle top condenser from being blocked due to excessive foam generated by the system;
(4) post-stabilization treatment: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, then sodium dodecyl benzene sulfonate is added, the stirring is carried out for 30min, and the post-stabilization treatment is finished;
(5) discharging: pumping the materials in the polymerization kettle into a latex storage tank by a pump to obtain polyvinyl chloride seed emulsion for later use.
Materials not listed in the formula are added according to the actual condition during polymerization, and no specific addition amount is needed.
The indexes of the finished product are as follows:
solid content of 35-40%, pH: 9-11, average particle diameter: 0.10-0.12 μm (as shown in FIG. 1), pH: 9-10.
The second step: preparation of chloropropane emulsion (design according to 30L polymerization vessel)
Seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 180-230g
Butyl acrylate: 0.8-3Kg
Methyl methacrylate: 300-800g
Acrylic acid: 0.6-1.0Kg
Crosslinking agent hydroxyethyl ester: 180-220g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg of
Polymerization temperature: 80-85 deg.C
(1) Preparation before polymerization: adding deionized water into a charging tank, adding 2-allyl ether-3-hydroxy propane sodium sulfonate and sodium dodecyl sulfate while stirring, then adding butyl acrylate, methyl methacrylate, acrylic acid and cross-linking agent hydroxyethyl ester, uniformly stirring to obtain a pre-emulsified monomer for later use, adding deionized water with the temperature of 30 ℃ into a polymerization kettle while stirring, adding the polyvinyl chloride seed emulsion prepared in the first step while stirring, heating to the temperature of 80-85 ℃, and keeping the pressure at normal pressure;
(2) polymerization: adding potassium persulfate into a polymerization kettle, stirring uniformly, continuously dropwise adding a pre-emulsified monomer, starting a polymerization reaction, controlling the dropwise adding speed to be completed within 2 hours, controlling the polymerization temperature to be 80-85 ℃ until the pre-emulsified monomer is completely dropwise added, then preserving the temperature for 1-2 hours, condensing a gas phase part in the polymerization kettle into a liquid phase through a condenser at the top of a normal pressure kettle, and continuing the reaction, so that the conversion rate of the acrylate monomer is improved;
(3) and (3) post-treatment: cooling to 70-75 deg.C after heat preservation, adding sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide, stirring for 30min, and stabilizing;
(4) degassing: after the post-stabilization treatment is finished, removing residual monomers in the polymerization kettle through a kettle top condenser, and allowing the removed gas to enter a recovery system;
(5) discharging: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, the pressure is recovered to normal pressure after the degassing is finished, the temperature is reduced to 45 to 55 ℃, the PH of the emulsion is regulated to 7.5 to 8.5 by ammonia water, the temperature is reduced to below 40 ℃, materials in the polymerization kettle are pumped into a latex storage tank by a pump to be stored, and the chloroethylene-acrylate copolymer emulsion (chloropropane emulsion) is obtained.
Materials not listed in the formula are added according to the actual condition during polymerization, and no specific addition amount is needed.
The indexes of the finished product are as follows:
solid content: 45-50%, pH: 7.5-8.5, average particle diameter: 0.15-0.20 μm.
Example 2
Compared with the example 1, the formula of the core structure in the first step is fixed, and the polymerization formula in the second step is adjusted to control the shell structure of the chloropropane emulsion so as to control the particle size of the final emulsion and the softness, hardness and adhesive force of the emulsion after film forming.
(according to a 30L polymerization kettle design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 180g
Butyl acrylate: 800g
Methyl methacrylate: 300g
Acrylic acid: 600g
Crosslinking agent hydroxyethyl ester: 180g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg
Polymerization temperature: 80 deg.C
The indexes of the finished product are as follows:
solid content: 45.3%, pH: 7.8, average particle size: 0.151 μm (as shown in FIG. 2).
The performance of the finished product is as follows:
the emulsion has poor film forming property, cracked film layer, high hardness, no elasticity and insufficient adhesive force, and powder can be removed by scraping (as shown in figure 3).
Example 3
Compared with the example 1, the formula of the core structure in the first step is fixed, and the polymerization formula in the second step is adjusted to control the shell structure of the chloropropane emulsion so as to control the particle size of the final emulsion and the softness, hardness and adhesive force of the emulsion after film forming.
(according to a 30L polymerization kettle design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 190g of
Butyl acrylate: 1.2Kg
Methyl methacrylate: 500g
Acrylic acid: 800g
Crosslinking agent hydroxyethyl ester: 200g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg of
Polymerization temperature: 82 deg.C
The indexes of the finished product are as follows:
solid content: 46.1%, pH: 7.8, average particle diameter: 0.163 μm (as shown in FIG. 4).
The performance of the finished product is as follows:
the emulsion has poor film forming property, a film layer is cracked, the hardness is high, the adhesion force is insufficient, and small cracks (shown in figure 5) appear around the scraped film layer when a sharp tool is used for scraping.
Example 4
Compared with the example 1, the formula of the core structure in the first step is fixed, and the polymerization formula in the second step is adjusted to control the shell structure of the chloropropane emulsion so as to control the particle size of the final emulsion and the softness, hardness and adhesive force of the emulsion after film forming.
(according to a 30L polymerization kettle design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 195g
Butyl acrylate: 1.8Kg
Methyl methacrylate: 600g
Acrylic acid: 800g
Crosslinking agent hydroxyethyl ester: 210g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg
Polymerization temperature: 84 deg.C
The indexes of the finished product are as follows:
solid content: 46.9%, pH: 7.8, average particle diameter: 0.178 μm (as shown in FIG. 6).
The performance of the finished product is as follows:
the emulsion has good film forming property, no cracking of the film layer, moderate film hardness, good adhesive force and no cracking by scraping with a sharp tool (as shown in figure 7).
Example 5
Compared with the example 1, the formula of the core structure in the first step is fixed, and the shell structure of the chloropropane emulsion is controlled by adjusting the polymerization formula in the second step so as to control the particle size of the final emulsion and the softness, hardness and adhesive force of the emulsion after film formation.
(according to a 30L polymerizer design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 210g
Butyl acrylate: 2.5Kg
Methyl methacrylate: 600g
Acrylic acid: 800g
Crosslinking agent hydroxyethyl ester: 220g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg of
Polymerization temperature: 85 deg.C
The indexes of the finished product are as follows:
solid content: 47.3%, pH: 7.8, average particle size: 0.210 μm (as shown in FIG. 8).
The performance of the finished product is as follows:
the emulsion has good film forming property, no cracking of the film layer, moderate film hardness, good adhesion, and no cracking by scraping with a sharp tool (as shown in figure 9). However, the average particle size is larger than 0.2. mu.m.
From the test results of the above examples, the emulsion prepared by polymerization of the formulation in example 4 was selected to be tested, and after the emulsion is prepared into the antirust coating, the antirust capacity is found to be not up to standard, flash rust is easy to appear, more rust points appear after the paint film is dried (as shown in fig. 10), and the amount of the emulsifier is considered to be caused by hydrophilic sodium dodecyl sulfate, so that the amount of the emulsifier is adjusted on the basis of the formulation in example 4.
Example 6
The amount of emulsifier used was adjusted based on the formulation of example 4 as compared to example 4.
(according to a 30L polymerization kettle design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 150g
Fatty alcohol polyoxyethylene ether (AES-9) 45g
Butyl acrylate: 1.8Kg
Methyl methacrylate: 600g
Acrylic acid: 800g
Crosslinking agent hydroxyethyl ester: 210g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg of
Polymerization temperature: 84 deg.C
The performance of the finished product is as follows:
after the prepared antirust coating is prepared, the antirust capacity is obviously improved, flash rust is not easy to appear, but rust points appear after a paint film is dried for 24 hours (as shown in figure 11).
Example 7
The amount of emulsifier used was adjusted based on the formulation of example 4 as compared to example 4.
(according to a 30L polymerization kettle design):
seed emulsion: 14.4Kg
Deionized water: 4Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 20g of
Sodium lauryl sulfate: 135g
Fatty alcohol polyoxyethylene ether (AES-9) 60g
Butyl acrylate: 1.8Kg
Methyl methacrylate: 600g
Acrylic acid: 800g
Crosslinking agent hydroxyethyl ester: 210g
Potassium persulfate solution (concentration: 3-8 g/Kg): 18g of
Hanging white blocks: 0.8 Kg
T-butyl hydroperoxide: 1Kg of
Polymerization temperature: 84 deg.C
The performance of the finished product is as follows:
after the antirust paint is prepared, the antirust capacity is further improved, flash rust does not occur, and rust spots do not occur after a paint film is dried for 48 hours (as shown in figure 12).
Example 8
An engineering scale-up to 0.5m was carried out on the basis of the formulation of example 73And (5) performing trial production in a kettle.
(in terms of 0.5 m)3Polymeric kettle design):
seed emulsion: 240Kg
Deionized water: 67Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 500g
Sodium lauryl sulfate: 2.25Kg
Fatty alcohol polyoxyethylene ether (AES-9): 830g
Butyl acrylate: 30Kg
Methyl methacrylate: 10Kg of water
Acrylic acid: 13.3Kg
Crosslinking agent hydroxyethyl ester: 3.5Kg
Potassium persulfate solution (concentration: 3-8 g/Kg): 300g
Hanging white blocks: 13.3Kg
T-butyl hydroperoxide: 16.6 Kg
Polymerization temperature: 84 deg.C
The performance of the finished product is as follows:
after amplification, the polymerization reaction rate is not easy to control, the rate is too high, and the emulsion contains slag after the reaction is finished. Considering the overdose of the initiator, the amount of the initiator is adjusted.
Example 9
The initiator amount was adjusted based on the formulation of example 8.
(in terms of 0.5 m)3Polymeric kettle design):
seed emulsion: 240Kg
Deionized water: 67Kg
Sodium 2-allyl ether-3-hydroxypropanesulfonate: 500g
Sodium lauryl sulfate: 2.25Kg
Fatty alcohol polyoxyethylene ether (AES-9): 830g
Butyl acrylate: 30Kg
Methyl methacrylate: 10Kg of water
Acrylic acid: 13.3Kg
Crosslinking agent hydroxyethyl ester: 3.5Kg
Potassium persulfate solution (concentration: 3-8 g/Kg): 220g
Hanging white blocks: 13.3Kg
T-butyl hydroperoxide: 16.6 Kg
Polymerization temperature: 84 deg.C
The performance of the finished product is as follows:
the reaction rate is controlled smoothly, the emulsion has no slag after the reaction, and the performance of the coating and the preparation of the antirust paint are equivalent to the results in example 4 and example 7.
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 (1)

1. A preparation method of vinyl chloride and acrylate copolymer emulsion is characterized in that the preparation method is carried out by a two-step method, namely, a polyvinyl chloride seed emulsion is prepared by using a vinyl chloride monomer, and then an acrylate polymer is externally connected;
the preparation method of the polyvinyl chloride seed emulsion specifically comprises the following steps:
(1) preparation before polymerization: spraying a certain amount of formaldehyde and 1-naphthol copolymer aqueous solution into a polymerization kettle from a kettle top condenser of the polymerization kettle, then adding deionized water at 50 ℃, adding lauric acid and potassium hydroxide aqueous solution under stirring, then adding NaOH aqueous solution, keeping the alkaline environment of the system, then adding ferrous sulfate, rongalite and EDTA, vacuumizing to-0.07 MPa after uniformly stirring, and adding liquid VCM monomer at one time;
(2) polymerization: heating the polymerization kettle to 50-60 ℃, controlling the pressure to be 0.065-0.09MPa, starting to dropwise add potassium persulfate to initiate VCM polymerization, continuously dropwise adding sodium dodecyl benzene sulfonate in the polymerization process, and when the reaction conversion rate reaches 75-85%, completely eliminating monomer liquid drops and finishing the reaction;
(3) degassing: after the reaction is finished, removing residual monomers in the polymerization kettle through a kettle top condenser, introducing the removed gas into a recovery system, and adding a certain amount of emulsified silicone oil according to the condition in the degassing process to prevent the kettle top condenser from being blocked due to excessive foam generated by the system;
(4) post-stabilization treatment: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, then sodium dodecyl benzene sulfonate is added, the stirring is carried out for 30min, and the stabilizing treatment is finished;
(5) discharging: pumping the materials in the polymerization kettle into a latex storage tank by a pump to obtain polyvinyl chloride seed emulsion for later use, wherein the solid content of the polyvinyl chloride seed emulsion is 35-45%, the average particle size is 0.10-0.12 mu m, and the pH is 9-10;
the method for externally connecting the acrylate polymer comprises the following specific steps:
(1) preparation before polymerization: adding deionized water into a charging tank, adding 2-allyl ether-3-hydroxy propane sodium sulfonate and sodium dodecyl sulfate while stirring, then adding butyl acrylate, methyl methacrylate, acrylic acid and cross-linking agent hydroxyethyl ester, uniformly stirring to obtain a pre-emulsified monomer for later use, adding deionized water with the temperature of 30 ℃ into a polymerization kettle while stirring, adding the polyvinyl chloride seed emulsion prepared in the first step while stirring, heating to the temperature of 80-85 ℃, and keeping the pressure at normal pressure;
(2) polymerization: adding potassium persulfate into a polymerization kettle, stirring uniformly, continuously dropwise adding a pre-emulsified monomer, starting a polymerization reaction, controlling the dropwise adding speed to be completed within 2 hours, controlling the polymerization temperature to be 80-85 ℃ until the pre-emulsified monomer is completely dropwise added, then preserving the temperature for 1-2 hours, condensing a gas phase part in the polymerization kettle into a liquid phase through a condenser at the top of a normal pressure kettle, and continuing the reaction, so that the conversion rate of the acrylate monomer is improved;
(3) and (3) post-treatment: cooling to 70-75 deg.C after heat preservation, adding sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide, stirring for 30min, and stabilizing;
(4) degassing: after the post-stabilization treatment is finished, removing the residual monomers in the polymerization kettle through a kettle top condenser, and allowing the removed gas to enter a recovery system;
(5) discharging: when the pressure in the polymerization kettle reaches-0.05 to-0.07 MPa in the degassing process, the degassing is finished, the pressure is recovered to normal pressure after the degassing is finished, the temperature is reduced to 45 to 55 ℃, the pH value of the emulsion is adjusted to 7.5 to 8.5 by ammonia water, the temperature is reduced to below 40 ℃, materials in the polymerization kettle are pumped into a latex storage tank by a pump to be stored, and the chloroethylene-acrylate copolymer emulsion is obtained;
the average grain diameter of the chloroethylene-acrylate copolymer emulsion is between 0.15 and 0.20 mu m;
the ratio of the vinyl chloride monomer to the acrylate polymer is controlled to be (55-60): (40-45);
the acrylic ester polymer comprises the following monomer raw materials of 7-8 parts of methyl methacrylate, 20-25 parts of butyl acrylate, 2.5-3 parts of crosslinking monomer hydroxyethyl ester and 9.5-10 parts of acrylic acid in sequence.
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