CN111363069A - Preparation method of polyvinyl chloride resin composite initiator - Google Patents
Preparation method of polyvinyl chloride resin composite initiator Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyvinyl chloride resin composite initiator, belonging to the technical field of initiator preparation. The preparation method of the composite initiator comprises the following steps: firstly, introducing the raw materials of the composite initiator, alkali liquor and cyclohexane into a pipeline static mixer for reaction to synthesize an organic peroxide ester or peroxide acyl composite initiator, and then adding isododecane into the initiator obtained by the reaction to prepare the solution type mixed initiator. By adopting the technical scheme of the invention, the defects of single synthesis, complex process, longer production period and difficult control of the conventional polyvinyl chloride resin initiator can be effectively overcome, and the yield of the obtained mixed initiator is relatively high.
Description
Technical Field
The invention belongs to the technical field of initiator preparation, and particularly relates to a preparation method of a polyvinyl chloride resin composite initiator.
Background
PVC has been the most widely used plastic in world production and has been widely used in the fields of building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, electric wires and cables, packaging films, bottles, foamed materials, sealing materials, fibers, and the like. The production method of PVC generally includes bulk polymerization, emulsion polymerization, suspension polymerization, microsuspension polymerization, solution polymerization, and the like. With the rapid development of the domestic PVC industry, the varieties and the demand of the initiators for PVC production are also rapidly improved. The initiator is added, so that the polymerization production of PVC has the advantages of stable reaction, stable product quality, quick initiation, uniform heat release and the like.
The initiator, also called as free radical initiator, refers to a kind of compound which is easy to be decomposed into free radicals (i.e. primary free radicals) by heating, and can be used for initiating free radical polymerization and copolymerization of alkene and diene monomers, and also can be used for crosslinking curing and macromolecule crosslinking reaction of unsaturated polyester. At present, the existing PVC polymerization initiator synthesis process is single synthesis, the synthesis period is long, and the synthesis process is not easy to control; the synthesis process needs to be washed repeatedly, and because the initiator is not easy to divide water, a large amount of waste water is generated, the environment is polluted, and the treatment is not easy. In addition, the finished product is also required to be compounded by downstream customers in proportion, which brings great inconvenience to the customers.
For example, the Chinese patent application number is: 201710086687.9, filing date: in 2017, 17.02 month, the name of invention creation is: an emulsion type peroxydicarbonate di (2-ethylhexyl) ester initiator and application thereof. The application discloses a preparation method of a peroxydicarbonate di (2-ethylhexyl) ester initiator, which comprises the following specific steps: dispersing agent, ionic emulsifier, antifreeze and desalted water according to the mass ratio of 1: (1.5-3.0): (12-14): (55-57) uniformly mixing to prepare a homogenized liquid; mixing the peroxydicarbonate di (2-ethylhexyl) ester with the homogenized solution, and then carrying out emulsification treatment to obtain the emulsion type peroxydicarbonate (2-ethylhexyl) ester initiator. However, the synthesis process of the initiator of the application is a single synthesis process, and still has the problems of long synthesis period and difficulty in controlling the synthesis process.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects that the existing polyvinyl chloride resin initiator is mostly synthesized singly, the process is complex, the production period is long and the control is difficult, and provides a preparation method of a polyvinyl chloride resin composite initiator. By adopting the technical scheme of the invention, the defects can be effectively solved, and the yield of the obtained mixed initiator is relatively high.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of a polyvinyl chloride resin composite initiator, which comprises the steps of mixing a composite initiator raw material and alkali liquor for reaction, synthesizing an organic peroxide ester or peroxide acyl mixed initiator, and then adding isododecane into the initiator obtained by the reaction to prepare a solution type mixed initiator; wherein, the raw materials of the composite initiator comprise acyl chloride, chloroformate compounds, organic hydroperoxide and hydrogen peroxide derivatives; cyclohexane is added when the composite initiator raw material and the alkali liquor are mixed for reaction.
Furthermore, the composite initiator raw material and alkali liquor are introduced into the mixer to react, and the temperature of the reactant flow is controlled to be 1-50 ℃.
Furthermore, during preparation, the mixer adopts a pipeline static mixer, the pipeline static mixer comprises three sections, each section of static mixer is provided with a cooling device, and the pipeline static mixer is provided with at least 4 feed inlets.
Furthermore, the prepared composite initiator is any combination of bis (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, cumyl peroxide and bis (3,5, 5-trimethylhexanoyl) peroxide; the preparation process of the composite initiator comprises the following specific steps: firstly, introducing alkali liquor, organic hydroperoxide and derivatives of hydrogen peroxide into a first section of a pipeline static mixer, wherein the feeding speeds are respectively 280-300 mol/min, 50-57.8 mol/min and 55-65 mol/min; then, introducing the chloroformate compound into a second section of the pipeline static mixer at a feeding speed of 60-75 mol/min, and controlling the temperature to be 10-20 ℃; and finally, introducing the acyl chloride organic compound and cyclohexane into a third section of a pipeline static mixer at feeding speeds of 40-50 mol/min and 5-7.5 mol/min respectively, and controlling the temperature to be 20-30 ℃ to obtain the composite initiator.
Further, the acid chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride.
Further, the chloroformate compound is preferably diethylhexyl chloroformate.
Furthermore, the organic hydroperoxide is preferably hydrogen peroxide, and the alkali liquor is preferably 10-50% of potassium hydroxide solution by mass percent.
Further, the derivative of hydrogen peroxide is preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide.
Furthermore, after the reaction is finished, a water distribution device is adopted to distribute water to the prepared composite initiator.
Further, the water diversion device adopts a coalescer, and the coalescer is preferably a corrugated plate type liquid-liquid coalescer.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the polyvinyl chloride resin composite initiator, the raw material of the composite initiator is mixed with alkali liquor to react, so that the organic peroxide ester or peroxide acyl composite initiator is synthesized, and then isododecane is added into the initiator obtained by the reaction to prepare the solution type composite initiator, so that on one hand, compared with the single synthesis of the existing initiator, the synthesis period of the composite initiator is shorter, and the production cost is favorably reduced; on the other hand, by simulating a client system, initiators with equal ratios are directly synthesized according to the compounding ratio of a client finished product, and then a solvent type initiator is prepared and directly used by a client, so that the method is simple and convenient. Meanwhile, in the synthesis process, a specific substance cyclohexane is added into the reactants, so that on one hand, the initiator can react more thoroughly in the synthesis process, the reaction rate is obviously improved, and the production time is reduced; on the other hand, when a plurality of materials are mixed and reacted, the cyclohexane can effectively avoid the generation of byproducts in the system, thereby realizing the mixed synthesis of a plurality of initiators and further improving the yield of the initiators.
(2) According to the preparation method of the polyvinyl chloride resin composite initiator, the pipeline static mixer is adopted and consists of three sections, so that the reaction is carried out in the three sections of static mixers, turbulence and vortex can be formed in the static mixers, the reaction materials are contacted more fully, the reaction is more thorough, and the reaction rate can be remarkably accelerated; meanwhile, each section of static mixer is provided with a respective independent cooling device, and the reaction can be controlled by controlling the reaction temperature of each section, so that on one hand, the full reaction can be effectively ensured, on the other hand, the generation of byproducts can be avoided, and the quality of the obtained composite initiator can be ensured.
(3) According to the preparation method of the polyvinyl chloride resin composite initiator, through specific selection of specific types of acyl chloride, chloroformate compounds, organic hydroperoxide and hydrogen peroxide derivative components, the synergistic cooperation effect among the components can be exerted to a greater extent, and the yield of the obtained composite initiator is further ensured; meanwhile, the addition sequence and the feeding speed among the components are optimally designed, so that the reaction rate is further improved, and the synthesis process is easy to control.
(4) According to the preparation method of the polyvinyl chloride resin composite initiator, the prepared composite initiator is subjected to water diversion by adopting the water diversion device, the corrugated plate type liquid-liquid coalescer with the model of TB 6X 56 is preferably selected, the synthesized initiator product can be effectively subjected to water diversion by adopting the coalescer, the oil-water separation effect is good, the water content of the product can be smaller than 0.1%, and therefore the water diversion requirement can be met.
Detailed Description
The invention relates to a preparation method of a polyvinyl chloride resin composite initiator, which mainly comprises the steps of mixing a composite initiator raw material and alkali liquor for reaction to synthesize an organic peroxide ester or peroxide acyl mixed initiator, and then adding isododecane into the initiator obtained by the reaction to prepare a solution type mixed initiator with the mass percentage of 60-80%.
Specifically, the composite initiator raw material comprises acyl chloride, chloroformate compounds, organic hydroperoxides and hydrogen peroxide derivatives. Among them, the acid chloride is preferably any one of neodecanoyl chloride and isononyl chloride. The chloroformate compound is preferably diethylhexyl chloroformate. The organic hydroperoxide is preferably hydrogen peroxide. The derivative of hydrogen peroxide is preferably any of tert-butyl hydroperoxide and cumene hydroperoxide. The alkali liquor is preferably 10-50% of potassium hydroxide solution by mass percent. The organic peroxide ester or peroxide acyl mixed initiator is specifically any two combinations of bis (2-ethylhexyl) peroxydicarbonate, EHP, tert-butyl peroxyneodecanoate, CNP, cumyl peroxide, TND and bis (3,5, 5-trimethylhexanoyl) peroxide, B355.
The synthesis principle of the organic peroxyester mixed initiator is as follows:
tert-butyl hydroperoxide, cumene hydroperoxide and hydrogen peroxide respectively react with potassium hydroxide to generate tert-butyl potassium peroxide, cumene potassium peroxide and potassium peroxide, then the potassium peroxide reacts with diethylhexyl chloroformate to generate bis (2-ethylhexyl) peroxydicarbonate (EHP), and the tert-butyl potassium peroxide reacts with neodecanoyl chloride to generate tert-butyl peroxyneodecanoate (CNP); reacting the cumyl potassium peroxide with neodecanoyl chloride to generate cumyl peroxide TND.
The synthesis principle of the organic peroxide acyl mixed initiator is as follows:
the hydrogen peroxide reacts with the potassium hydroxide to generate potassium peroxide, and the potassium peroxide reacts with the isononanoyl chloride to generate the bis (3,5, 5-trimethylhexanoyl) peroxide B355.
In the process of the mixed reaction of bis (2-ethylhexyl) peroxydicarbonate EHP, tert-butyl peroxyneodecanoate CNP, cumyl peroxide TND and bis (3,5, 5-trimethylhexanoyl) B355, the chemical properties of the raw materials of the composite initiator are similar, so that the raw materials of the composite initiator are cross-reacted, and other byproducts are easily generated, thereby affecting the quality of the obtained initiator product. Meanwhile, in the existing process for synthesizing the initiator, multiple times of water washing is needed, and the obtained initiator is not easy to divide water, so that a large amount of waste water is easily generated, the environment is polluted, and the treatment is not easy. Through a large amount of experimental researches, on one hand, the applicant can exert the synergistic cooperation effect among the components to a greater extent through specific selection of specific types of acyl chloride, chloroformate compounds, organic hydroperoxides and hydrogen peroxide derivative components; on the other hand, the reaction rate is further improved by optimally designing the adding sequence and the feeding speed among the components. Particularly, when the reactants are subjected to chemical reaction, firstly, the specific substance cyclohexane is added into the reactants, so that the initiator can react more completely in the synthesis process, the reaction rate is obviously improved, and the product synthesis period is shortened. Meanwhile, when various materials are mixed and reacted, the cyclohexane is added, so that the generation of byproducts in the system can be effectively avoided, the mixed synthesis of various initiators is realized, and the yield of the initiators is further improved. Secondly, the composite initiator raw material and alkali liquor are metered by a flow pump and introduced into a pipeline static mixer for reaction, and the temperature of the reactant flow is controlled to be 1-50 ℃. Wherein, the setting of pipeline static mixer can make the reactant form torrent and vortex in static mixer to make the contact of reaction material more abundant, the reaction is more thorough, and then is showing and accelerate reaction rate. Furthermore, the pipeline static mixer consists of three parts: the pipeline static mixer consists of three sections of static mixers, and each section of static mixer is provided with a water-cooling jacket and a cooling device consisting of the water-cooling jacket which are independent from each other, so that the reaction can be controlled by controlling the reaction temperature in each section of static mixer, and the full reaction can be effectively ensured; on the other hand, the generation of byproducts can be avoided, and the quality of the obtained composite initiator is ensured. And finally, at least 4 feed inlets are arranged on the pipeline static mixer and are respectively an A-D feed inlet. When materials are added, the feeding speed of the materials can be respectively controlled, so that the control of the reaction process is realized, the reaction rate is improved, and the synthesis period of the initiator is shortened.
In addition, the prepared composite initiator is subjected to water diversion by adopting a water diversion device, preferably, the type TB 6X 56 corrugated plate type liquid-liquid coalescer is selected, and mutually adjacent fluid channels of coalescer coalescing fillers of the type are communicated in a staggered manner, so that fluid in the fillers flows in a staggered manner, the coalescing probability of oil drops is greatly increased, and the oil-water separation efficiency is improved; especially, the steady flow space is enlarged behind the coalescent filler, so that the separation effect of oil and water phases is further improved, the water content of the initiator after water diversion is within the range of 0.01-0.1%, and the water diversion effect is more obvious compared with a common coalescer.
The preparation method of the polyvinyl chloride resin composite initiator comprises the following specific preparation processes:
(1) 10-50% potassium hydroxide solution is fed from the feed port A, and hydrogen peroxide derivatives (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) are fed from the feed port B while the temperature is controlled at 5-15 deg.C. Then introducing the potassium hydroxide solution, the hydrogen peroxide and the hydrogen peroxide derivative into a first-stage reaction zone (corresponding to a first stage of a pipeline static mixer, wherein the first stage only represents any stage in the pipeline static mixer and has no other specific limitation) at feeding speeds of 280-300 mol/min, 50-57.8 mol/min and 55-65 mol/min respectively for reaction;
(2) introducing a chloroformate compound (preferably diethylhexyl chloroformate) into a second reaction zone from a C feeding port at a feeding speed of 60-75 mol/min, and controlling the temperature at 5-15 ℃;
(3) introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone through a D feeding port at feeding speeds of 40-50 mol/min and 5-7.5 mol/min respectively, controlling the temperature to be 20-30 ℃, cooling the material after the reaction is completed, controlling the temperature of circulating cooling water to be 7-12 ℃, and distributing water to the obtained mixture through a corrugated plate type coalescer so that the water content of the mixture is in the range of 0.01-0.1%, wherein the yield of the obtained mixed initiator is 80-90%.
In addition, by simulating a client system, initiator semi-finished products with equal proportion can be directly synthesized according to the compounding proportion of the client finished products, and then solvent type initiators are prepared and directly used by clients, so that the market demand is met, and the manpower and material resources are saved for the clients. Specifically, 1-10 parts of alkali liquor, 1-10 parts of hydrogen peroxide, 0.5-10 parts of hydrogen peroxide derivative, 1.5-20 parts of chloroformate compound and 0.5-10 parts of acyl chloride organic compound are reacted to form tert-butyl peroxyneodecanoate CNP and bis (2-ethylhexyl) ehP peroxydicarbonate or cumyl peroxide TND and bis (3,5, 5-trimethylhexanoyl) B355 peroxyde; the mixing ratio of the two groups of materials is 1: 1.0-8.0, controlling the flow rate of reactants at 0.1-10L/h, and carrying out water separation treatment to ensure that the water content is in the range of 0.01-0.1 percent and the yield of the obtained mixed initiator is 80-90 percent.
The invention is further described with reference to specific examples.
Example 1
Introducing 45 mass percent of potassium hydroxide solution, hydrogen peroxide and a hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) into a first-stage reaction zone at feeding speeds of 300mol/min, 57.8mol/min and 65mol/min respectively, and controlling the temperature at 10 ℃; then introducing the chloroformate compound into a second reaction zone at a feeding speed of 75mol/min, and controlling the temperature at 10 ℃; finally, introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min respectively, wherein the temperature is controlled to be 20 ℃, and the temperature of circulating cooling water is controlled to be 7 ℃. The mixture obtained after the reaction was passed through a corrugated plate coalescer to separate water to a water content of 0.01%, and the yield of the obtained mixed initiator was 80%.
Example 2
Introducing 45 mass percent of potassium hydroxide solution, hydrogen peroxide and a hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) into a first-stage reaction zone at feeding speeds of 300mol/min, 57.8mol/min and 65mol/min respectively, and controlling the temperature at 15 ℃; then introducing the chloroformate compound into a second reaction zone at a feeding speed of 75mol/min, and controlling the temperature to be 15 ℃; finally, introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min respectively, wherein the temperature is controlled to be 25 ℃, and the temperature of circulating cooling water is controlled to be 10 ℃. The mixture obtained after the reaction was passed through a corrugated plate coalescer to separate water to a water content of 0.1%, and the yield of the obtained mixed initiator was 87%.
Example 3
Introducing 45 mass percent of potassium hydroxide solution, hydrogen peroxide and a hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) into a first-stage reaction zone at feeding speeds of 300mol/min, 57.8mol/min and 65mol/min respectively, and controlling the temperature at 5 ℃; then introducing the chloroformate compound into a second reaction zone at a feeding speed of 75mol/min, and controlling the temperature to be 15 ℃; finally, introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min respectively, wherein the temperature is controlled to be 30 ℃, and the temperature of circulating cooling water is controlled to be 12 ℃. The mixture obtained after the reaction was passed through a corrugated plate coalescer to separate water to a water content of 0.05% and the yield of the obtained mixed initiator was 90%.
Example 4
Introducing 50 mass percent of potassium hydroxide solution, hydrogen peroxide and a hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) into a first-stage reaction zone at feeding speeds of 280mol/min, 50mol/min and 55mol/min respectively, and controlling the temperature at 10 ℃; then introducing the chloroformate compound into a second reaction zone at a feeding speed of 60mol/min, and controlling the temperature to be 5 ℃; finally, introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone at feeding speeds of 40mol/min and 5mol/min respectively, controlling the temperature to be 20 ℃ and controlling the temperature of circulating cooling water to be 8 ℃. The mixture obtained after the reaction was passed through a corrugated plate coalescer to separate water to a water content of 0.02%, and the yield of the obtained mixed initiator was 90%.
Example 5
Introducing 10 mass percent of potassium hydroxide solution, hydrogen peroxide and hydrogen peroxide derivatives (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) into a first-stage reaction zone at feeding speeds of 290mol/min, 55mol/min and 60mol/min respectively, and controlling the temperature at 10 ℃; then introducing the chloroformate compound into a second reaction zone at a feeding speed of 65mol/min, and controlling the temperature to be 10 ℃; finally, introducing acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane into a third reaction zone at feeding speeds of 45mol/min and 6mol/min respectively, controlling the temperature to be 25 ℃ and controlling the temperature of circulating cooling water to be 8 ℃. The mixture obtained after the reaction was passed through a corrugated plate coalescer to separate water to a water content of 0.06% and the yield of the obtained mixed initiator was 85%.
Example 6
3 parts of 45 mass percent potassium hydroxide solution, 1.5 parts of hydrogen peroxide and 1.5 parts of hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) are respectively introduced into a first-stage reaction zone at the feeding speeds of 300mol/min, 57.8mol/min and 65mol/min, and the temperature is controlled at 10 ℃; then 0.9 part of chloroformate compound is introduced into a second reaction zone at a feeding speed of 75mol/min, and the temperature is controlled at 10 ℃; finally, 5 parts of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively led into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min, the temperature is controlled to be 20 ℃, and the temperature of circulating cooling water is controlled to be 7 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 2.0, the flow rate of the mixture was controlled at 0.5L/h, and water was distributed through a corrugated plate coalescer so that the water content was in the range of 0.01%, and the yield of the obtained mixed initiator was 90%.
Example 7
5 parts of 45 mass percent potassium hydroxide solution, 3.5 parts of hydrogen peroxide and 1.5 parts of hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) are respectively introduced into a first-stage reaction zone at the feeding speeds of 300mol/min, 57.8mol/min and 65mol/min, and the temperature is controlled at 15 ℃; then 2.6 parts of chloroformate compound is introduced into a second reaction zone at a feeding speed of 75mol/min, and the temperature is controlled at 15 ℃; finally, 5 parts of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively led into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min, the temperature is controlled to be 25 ℃, and the temperature of circulating cooling water is controlled to be 10 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 5.5, controlling the flow rate of the mixture to be 0.8L/h, and separating water by a corrugated plate type coalescer to ensure that the water content is in the range of 0.01-0.1 percent, wherein the yield of the obtained mixed initiator is 85 percent.
Example 8
5.8 parts of 45 mass percent potassium hydroxide solution, 4.2 parts of hydrogen peroxide and 1.5 parts of hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) are respectively introduced into a first-stage reaction zone at the feeding speeds of 300mol/min, 57.8mol/min and 65mol/min, and the temperature is controlled at 5 ℃; then 3.1 parts of chloroformate compound is introduced into a second reaction zone at a feeding speed of 75mol/min, and the temperature is controlled at 15 ℃; finally, 5 parts of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively led into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min, the temperature is controlled to be 30 ℃, and the temperature of circulating cooling water is controlled to be 7-12 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 7.0, the flow rate of the mixture was controlled at 1.0L/h, and water was distributed through a corrugated plate coalescer so that the water content was in the range of 0.05%, and the yield of the obtained mixed initiator was 90%.
Example 9
1 part of 45 mass percent potassium hydroxide solution, 1 part of hydrogen peroxide and 0.5 part of hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) are respectively introduced into a first-stage reaction zone at the feeding speeds of 300mol/min, 57.8mol/min and 65mol/min, and the temperature is controlled at 10 ℃; then 20 parts of chloroformate compound is introduced into a second reaction zone at a feeding speed of 75mol/min, and the temperature is controlled at 5 ℃; finally, 10 parts of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively led into a third reaction zone at the feeding speeds of 50mol/min and 7.5mol/min, the temperature is controlled to be 20 ℃, and the temperature of circulating cooling water is controlled to be 8 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 8.0, the flow rate of the mixture was controlled at 0.5L/h, and water was distributed through a corrugated plate coalescer so that the water content was in the range of 0.02%, and the yield of the obtained mixed initiator was 87%.
Example 10
Taking 10 parts of 45 mass percent potassium hydroxide solution, 7 parts of hydrogen peroxide and 10 parts of hydrogen peroxide derivatives (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) to be respectively introduced into a first-stage reaction zone at feeding speeds of 280mol/min, 50mol/min and 55mol/min, and controlling the temperature at 10 ℃; then 1.5 parts of chloroformate compound is introduced into a second reaction zone at a feeding speed of 60mol/min, and the temperature is controlled at 10 ℃; and finally, 0.5 part of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively introduced into a third reaction zone at feeding speeds of 40mol/min and 5mol/min, the temperature is controlled to be 25 ℃, and the temperature of circulating cooling water is controlled to be 8 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 1.0, the flow rate of the mixture was controlled at 10L/h, and water was distributed through a corrugated plate coalescer so that the water content was in the range of 0.1%, and the yield of the obtained mixed initiator was 80%.
Example 11
Taking 7 parts of 10-50% by mass potassium hydroxide solution, 10 parts of hydrogen peroxide and 5 parts of hydrogen peroxide derivative (preferably any one of tert-butyl hydroperoxide and cumene hydroperoxide) to be respectively introduced into a first-stage reaction zone at feeding speeds of 290mol/min, 55mol/min and 60mol/min, and controlling the temperature at 10 ℃; then 10 parts of chloroformate compound is introduced into a second reaction zone at a feeding speed of 70mol/min, and the temperature is controlled at 10 ℃; finally, 2 parts of acyl chloride (the acyl chloride is preferably any one of neodecanoyl chloride and isononanoyl chloride) and cyclohexane are respectively led into a third reaction zone at the feeding speeds of 45mol/min and 7mol/min, the temperature is controlled to be 20 ℃, and the temperature of circulating cooling water is controlled to be 6 ℃. The mixing ratio of the mixed initiator obtained after the reaction is 1: 5.0, controlling the flow rate of the mixture at 5L/h, and separating water by a corrugated plate type coalescer to ensure that the water content is in the range of 0.01-0.1 percent, wherein the yield of the obtained mixed initiator is 85 percent.
Claims (10)
1. A preparation method of a polyvinyl chloride resin composite initiator is characterized by comprising the following steps: firstly, mixing a composite initiator raw material and alkali liquor for reaction to synthesize an organic peroxide ester or peroxide acyl composite initiator, and then adding isododecane into the initiator obtained by the reaction to prepare a solution type mixed initiator; wherein, the raw materials of the composite initiator comprise acyl chloride, chloroformate compounds, organic hydroperoxide and hydrogen peroxide derivatives; cyclohexane is added when the composite initiator raw material and the alkali liquor are mixed for reaction.
2. The method for preparing the polyvinyl chloride resin composite initiator according to claim 1, wherein the method comprises the following steps: the composite initiator raw material and alkali liquor are introduced into a mixer for reaction, and the temperature of the reactant flow is controlled to be 1-50 ℃.
3. The method for preparing the polyvinyl chloride resin composite initiator according to claim 2, wherein the method comprises the following steps: during preparation, the mixer adopts a pipeline static mixer, the pipeline static mixer comprises three sections, each section of static mixer is provided with a cooling device, and the pipeline static mixer is at least provided with 4 feed inlets.
4. The method for preparing the polyvinyl chloride resin composite initiator according to claim 3, wherein the method comprises the following steps: the prepared composite initiator is any combination of bis (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, cumyl peroxide and bis (3,3, 5-trimethylhexanoyl) peroxide; the preparation process of the composite initiator comprises the following specific steps: firstly, introducing alkali liquor, organic hydroperoxide and derivatives of hydrogen peroxide into a first section of a pipeline static mixer, wherein the feeding speeds are respectively 280-300 mol/min, 50-57.8 mol/min and 55-65 mol/min; then, introducing the chloroformate compound into a second section of the pipeline static mixer at a feeding speed of 60-75 mol/min, and controlling the temperature to be 10-20 ℃; and finally, introducing the acyl chloride organic compound and cyclohexane into a third section of a pipeline static mixer at feeding speeds of 40-50 mol/min and 5-7.5 mol/min respectively, and controlling the temperature to be 20-30 ℃ to obtain the composite initiator.
5. The method for preparing a polyvinyl chloride resin composite initiator according to any one of claims 1 to 4, wherein: the acid chloride is preferably any one of neodecanoyl chloride and isononyl chloride.
6. The method for preparing the polyvinyl chloride resin composite initiator according to claim 5, wherein the method comprises the following steps: the chloroformate compound is preferably diethylhexyl chloroformate.
7. The method for preparing the polyvinyl chloride resin composite initiator according to claim 6, wherein the method comprises the following steps: the organic hydroperoxide is preferably hydrogen peroxide, and the alkali liquor is preferably 10-50% of potassium hydroxide solution by mass percent.
8. The method for preparing the polyvinyl chloride resin composite initiator according to claim 7, wherein the method comprises the following steps: the derivative of hydrogen peroxide is preferably any of tert-butyl hydroperoxide and cumene hydroperoxide.
9. The method for preparing a polyvinyl chloride resin composite initiator according to any one of claims 1 to 4, wherein: and (3) carrying out water distribution on the prepared composite initiator by adopting a water distribution device.
10. The method for preparing the polyvinyl chloride resin composite initiator according to claim 9, wherein the method comprises the following steps: the water diversion device adopts a coalescer, and is preferably a corrugated plate type liquid-liquid coalescer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2087469C1 (en) * | 1994-06-29 | 1997-08-20 | Институт химических проблем экологии Академии естественных наук РФ | Method of preparing multicomponent peroxide polymerization initiator |
| CN1411439A (en) * | 1998-04-15 | 2003-04-16 | 阿克佐诺贝尔公司 | Peroxides, their preparation and use |
| CN1491210A (en) * | 2001-02-13 | 2004-04-21 | ���з��ɹ�˾ | Peroxyester preparation method |
-
2020
- 2020-03-27 CN CN202010226521.4A patent/CN111363069B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2087469C1 (en) * | 1994-06-29 | 1997-08-20 | Институт химических проблем экологии Академии естественных наук РФ | Method of preparing multicomponent peroxide polymerization initiator |
| CN1411439A (en) * | 1998-04-15 | 2003-04-16 | 阿克佐诺贝尔公司 | Peroxides, their preparation and use |
| CN1491210A (en) * | 2001-02-13 | 2004-04-21 | ���з��ɹ�˾ | Peroxyester preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 聂梅生等: "《水工业工程设计手册 水资源及给水处理》", 31 December 2001, 中国建筑工业出版社 * |
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