CN111704686A - Preparation method of high chlorinated polyethylene - Google Patents
Preparation method of high chlorinated polyethylene Download PDFInfo
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- CN111704686A CN111704686A CN202010717829.9A CN202010717829A CN111704686A CN 111704686 A CN111704686 A CN 111704686A CN 202010717829 A CN202010717829 A CN 202010717829A CN 111704686 A CN111704686 A CN 111704686A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C09D123/286—Chlorinated polyethylene
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- 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
- C09D5/08—Anti-corrosive paints
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of high chlorinated polyethylene, which comprises the steps of adding deionized water, low molecular weight polyethylene powder, an emulsifier and a dispersant into a reaction kettle for pre-dispersion and suspension, adding an initiator when the preset temperature is reached, then starting heating up and introducing chlorine, controlling the chlorine introducing speed and the heating up speed, and finally carrying out post-treatment to obtain the high chlorinated polyethylene.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of high chlorinated polyethylene.
Background
The high chlorinated polyethylene is a high molecular material for heavy corrosion prevention and replacing traditional solvent method chlorinated rubber on ship paint, and is obtained by chlorination reaction of low molecular weight polyethylene in water suspension medium, the product is white or yellowish particles, can be dissolved in solvents such as benzene, esters, chlorohydrocarbons and the like at normal temperature, has high chlorine content, high drying speed and excellent corrosion resistance, and can be applied to places such as steel structures, machinery, pipelines, bridges, ships and the like, and has corrosion resistance, rust prevention and salt mist resistance.
At present, the preparation method of high chlorinated polyethylene mainly comprises a solution method, a solid phase method and a water phase suspension method, and the domestic process mainly adopts the water phase suspension method and has been provided with special patents such as CN 1125734A, CN 1230550A, CN 1394887A, CN 1394884A, CN 101608001A, CN 101704911A and the like. The method is a water phase suspension method except CN 1125734A which is a gas-solid phase method, and the method is a process for applying high-viscosity high-chlorinated polyethylene for adhesives in CN 101704911A, and the main defects of other processes are as follows: 1. the initiator causes two types of high and low temperature to be matched for initiating reaction, so that the materials are easy to cohere in the kettle when the reaction is initiated when the reaction is converted to a certain temperature; 2. the multi-element multi-group reaction requires grafting treatment on the raw materials before the reaction, and the chlorine introducing amount and the chlorine introducing uniformity are difficult to realize; 3. the method is divided into three to four sections of multi-stage reaction, the process is difficult to control, and the automatic industrial production cannot be realized.
Disclosure of Invention
The invention mainly aims to provide a preparation method of high chlorinated polyethylene, which solves the problems that high reaction pressure is easy to form a kettle, chlorine is not uniformly introduced, a finished product is not transparent, chlorine introduction amount is not high, a finished product is easy to gel and the like due to the fact that the high chlorinated polyethylene resin produced by an aqueous phase method process in the market at present adopts various initiators for reaction or various groups are introduced into raw material polyethylene to accelerate chlorine introduction by using an auxiliary agent, and multi-stage chlorine introduction reaction is adopted.
The invention provides a preparation method of high chlorinated polyethylene, which comprises the following steps:
adding deionized water, low molecular weight polyethylene powder, an emulsifier and a dispersant into a reaction kettle for pre-dispersion suspension, adding an initiator when the preset temperature is reached, then starting heating up and introducing chlorine, wherein the chlorine introducing speed is 10-20kg/min, the heating up speed is 2-4 ℃/10min, the reaction pressure is controlled to be not more than 0.3Mpa, and the required chlorine introducing amount is more than 80% before the temperature reaches 90 ℃; when the pressure begins to rise to above 0.35MPa, slowing down the chlorine introducing speed to 2-10kg/min, and continuing introducing chlorine to 110-115 ℃ until the pressure is not higher than 0.4 MPa; and finally, carrying out the working procedures of heat preservation, temperature reduction, deacidification, neutralization, water washing, dehydration and drying to obtain a finished product.
Preferably, the molecular weight of the low molecular weight polyethylene powder is 2000-3000, and the fineness is 60-80 meshes.
Preferably, the emulsifier is peregal O or alkylphenol polyoxyethylene, and the using amount of the emulsifier is 2-4% of the weight of the low molecular weight polyethylene powder.
Preferably, the dispersant is sodium polymethacrylate or polyvinylpyrrolidone, and the dosage of the dispersant is 1-3% of the mass of the low molecular weight polyethylene powder.
Preferably, the initiator is dibenzoyl peroxide, and the amount of the initiator is 1.5-2% of the mass of the low molecular weight polyethylene powder.
Preferably, the predetermined starting chlorine introduction temperature is 65 ℃.
Preferably, the required chlorine passing amount is 3.5 to 4.5 times of the mass of the low molecular weight polyethylene powder.
The processes of heat preservation, temperature reduction, deacidification, neutralization, water washing, dehydration and drying are well-known technologies and are not described in detail herein.
The invention takes low molecular weight polyethylene powder as raw material, selects a single initiation chlorination system to react, leads in chlorine quantity which is strictly controlled at uniform speed, and controls the temperature rise speed to achieve the uniform chlorination reaction of the raw material, the chlorine content reaches more than 65 percent, and the high-performance high chlorinated polyethylene resin is uniformly chlorinated.
Advantageous effects
The high chlorinated polyethylene obtained by the invention has good solubility, high transparency, excellent anti-corrosion performance, high drying speed, strong salt mist resistance and low viscosity, and can completely replace chlorinated rubber for heavy corrosion prevention and marine paint; the method adopts a single initiator, has high chlorine flux, uniform chlorine flux, low reaction pressure, no kettle closure at key temperature, high finished product yield, improved product performance and efficiency and very obvious economic benefit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
In order to make those skilled in the art better understand the technical solutions of the embodiments of the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention, 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprising" and "having," as well as any variations thereof, are intended to cover non-exclusive inclusions.
Example 1
3000 kg of deionized water, 200 kg of low molecular weight polyethylene powder, 7 kg of sodium polymethacrylate and 4 kg of alkylphenol polyoxyethylene ether are filled in an enamel reactor with the volume of 5000L for complete pre-dispersion, 3 kg of dibenzoyl peroxide is added, chlorine starts to be introduced after air is replaced by nitrogen when the temperature reaches 65 ℃, the chlorine introduction speed is controlled to be 10-20kg/min, the temperature rise speed is controlled to be 2-4 ℃/10min, the reaction pressure is controlled not to exceed 0.3Mpa, the chlorine introduction amount is reduced when the pressure is exceeded or the temperature rises too fast until about 88 ℃, the total chlorine introduction amount is not less than 650 kg, the chlorine introduction speed is reduced to 2-10kg/min when the pressure rises to be more than 0.35Mpa, the temperature rises without limitation, the pressure is not higher than 0.4Mpa, the chlorine introduction is stopped until the total chlorine introduction amount 820 kg of chlorine introduction is reached at the temperature of 115 ℃, and then the temperature is reduced and water washing is carried out, Neutralizing, centrifuging and drying to obtain the final product.
Example 2
3000 kg of deionized water, 200 kg of low molecular weight polyethylene powder, 7 kg of sodium polymethacrylate and 4 kg of alkylphenol polyoxyethylene ether are filled in an enamel reactor with the volume of 5000L for complete pre-dispersion, 3 kg of dibenzoyl peroxide is added, chlorine starts to be introduced after air is replaced by nitrogen when the temperature reaches 65 ℃, the chlorine introduction speed is controlled to be 10-20kg/min, the temperature rise speed is controlled to be 2-4 ℃/10min, the reaction pressure is controlled not to exceed 0.3Mpa, the chlorine introduction amount is reduced when the pressure is exceeded or the temperature rises too fast until about 88 ℃, the total chlorine introduction amount is not less than 600 kg, the chlorine introduction speed is reduced to 2-10kg/min when the pressure begins to rise to be more than 0.35Mpa, the temperature rises without limitation, the pressure is not higher than 0.4Mpa until the temperature reaches 115 ℃, the chlorine introduction is stopped until the total chlorine introduction amount reaches 750 kg, and then the temperature is reduced and the chlorine introduction is washed by water, Neutralizing, centrifuging and drying to obtain the final product.
Example 3
3000 kg of deionized water, 200 kg of low molecular weight polyethylene powder, 7 kg of sodium polymethacrylate and 4 kg of alkylphenol polyoxyethylene ether are filled in an enamel reactor with the volume of 5000L for complete pre-dispersion, 3 kg of dibenzoyl peroxide is added, chlorine starts to be introduced after air is replaced by nitrogen when the temperature reaches 65 ℃, the chlorine introduction speed is controlled to be 10-20kg/min, the temperature rising speed is controlled to be 2-10kg/min, the reaction pressure is controlled not to exceed 0.3Mpa, the chlorine introduction amount is reduced when the pressure is exceeded or the temperature rises too fast until about 88 ℃, the total chlorine introduction amount is not less than 550 kg, when the temperature reaches 92 ℃, the pressure starts to rise to be more than 0.38Mpa, the chlorine introduction speed is reduced to 2-10kg/min, the temperature rises without limitation and is not higher than 0.4Mpa, the chlorine introduction is stopped until the total chlorine introduction amount reaches 780 kg when the temperature reaches 115 ℃, and then the temperature is reduced through water washing, and the method is applied to, Neutralizing, centrifuging and drying to obtain the final product.
Example 4
3000 kg of deionized water, 200 kg of low molecular weight polyethylene powder, 7 kg of sodium polymethacrylate and 4 kg of alkylphenol polyoxyethylene ether are filled in an enamel reactor with the volume of 5000L for complete pre-dispersion, 3 kg of dibenzoyl peroxide is added, chlorine starts to be introduced after air is replaced by nitrogen when the temperature reaches 65 ℃, the chlorine introduction speed is controlled to be 10-20kg/min, the temperature rise speed is controlled to be 2-10kg/min, the reaction pressure is controlled not to exceed 0.3Mpa, the chlorine introduction amount is reduced when the pressure is exceeded or the temperature rises too fast until about 88 ℃, the total chlorine introduction amount is not less than 680 kg, the chlorine introduction speed is reduced to 2-10kg/min when the pressure starts to rise to be more than 0.35Mpa, the temperature rises without limitation, the pressure is not higher than 0.4Mpa until the temperature reaches 115 ℃, the chlorine introduction is stopped when the total chlorine introduction amount is 900 kg, and then the temperature is reduced and the chlorine introduction is washed by water, Neutralizing, centrifuging and drying to obtain the final product.
Comparative example 1
High and low temperature initiation and staged reaction are adopted to prepare the high chlorinated polyethylene under the condition of the same raw materials.
3000 kilograms of deionized water, 200 kilograms of low molecular weight polyethylene powder, 7 kilograms of sodium polymethacrylate and 4 kilograms of alkylphenol ethoxylates are filled in an enamel reactor with the volume of 5000L, after the pre-dispersion is completed, 0.8 kilogram of lauroyl peroxide and 1.5 kilograms of dibenzoyl peroxide are introduced, the chlorine is introduced in four sections, the chlorine is introduced in the first section after the air is replaced by nitrogen when the temperature reaches 55 ℃, the chlorine introduction amount is about 150 kilograms, and the pressure in the first section is 0.2 MPa; in the second stage, when the temperature is raised to 75 ℃, about 250 kilograms of chlorine gas is introduced, and the pressure in the second stage is 0.3 Mpa; the third stage is that when the temperature is raised to 90 ℃, 300 kg of chlorine is introduced, and the pressure of the third stage is 0.4MPa or above; and the fourth stage is that the chlorine introduction is finished when the temperature is raised to 105 ℃ to 115 ℃, the total chlorine introduction amount is 820 kilograms, the chlorine introduction is stopped, and then the temperature is reduced, and the finished product is obtained after the procedures of water washing, neutralization, centrifugation and drying.
The result of the detection
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Appearance of the product | White or yellowish particles | White near-powder particles | Yellowish bulky granule | Yellowish particles | Yellowish particles |
| Fineness/mesh number | 40 | 60 | 20 | 40 | 40 |
| Content of chlorine/%) | 65% | 64% | 64% | 68% | 64% |
| Solubility (20% toluene solution) | Transparent, non-insoluble particles | White, slightly transparent and insoluble particle-free | Yellow, slightly transparent and insoluble particle-free | Transparent, non-insoluble particles | Opaque with insoluble particles |
| viscosity/T4. s | 13 | 13.5 | 13 | 12 | 13 |
| Moisture content | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Hydrochloric acid residue% | 0.001 | 0.05 | 0.1 | 0.002 | 0.1 |
Compared with the existing high-low temperature staged initiation aqueous phase method process, the detection result shows that the solubility of the product obtained by the method is remarkably improved, and the application of the heavy-duty anticorrosive paint is more facilitated due to low residual quantity of hydrochloric acid. The production process of the embodiment 1 and the embodiment 4 has low reaction pressure, continuous chlorine introducing speed and sufficient chlorine introducing amount, the later-stage flux of chlorine introducing of the embodiment 2 is not enough to influence the performance of the product, and the early-stage insufficient chlorine introducing of the embodiment 3 increases the reaction pressure when the temperature reaches about 90 ℃, so that a agglomeration kettle is easily generated. In the comparative example 1, two initiators of high and low temperature are selected, the chlorine introducing temperature is lower, the chlorine is introduced in sections to obtain the composite reaction of the initiators, the pressure is obviously increased in the third section, the reaction in the kettle is violent, and the production operation difficulty is increased.
Chlorinated rubber performance indexes are as follows:
| project index | Aqueous phase process | Solvent process |
| Appearance of the product | White or yellowish particles | White or yellowish particles |
| Fineness/mesh number | 40 | 20 |
| Content of chlorine/%) | 65 | 63 |
| Solubility (20% toluene solution) | Transparent, non-insoluble particles | Transparent, non-insoluble particles |
| viscosity/T4. s | 13 | 12 |
| Moisture content | 0.1 | 0.1 |
| Hydrochloric acid residue% | 0.001 | 0.001 |
As can be seen from the performance indexes of the chlorinated rubber, the performance indexes of the high chlorinated polyethylene obtained by the method are very close to those of chlorinated rubber by a water phase method and a solvent method.
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 (7)
1. A preparation method of high chlorinated polyethylene comprises the following steps:
adding deionized water, low molecular weight polyethylene powder, an emulsifier and a dispersant into a reaction kettle for pre-dispersion suspension, adding an initiator when the preset temperature is reached, then starting heating up and introducing chlorine, wherein the chlorine introducing speed is 10-20kg/min, the heating up speed is 2-4 ℃/10min, the reaction pressure is controlled to be not more than 0.3Mpa, and the required chlorine introducing amount is more than 80% before the temperature reaches 90 ℃; when the pressure begins to rise to above 0.35MPa, slowing down the chlorine introducing speed to 2-10kg/min, and continuing introducing chlorine to 110-115 ℃ until the pressure is not higher than 0.4 MPa; and finally, carrying out the working procedures of heat preservation, temperature reduction, deacidification, neutralization, water washing, dehydration and drying to obtain a finished product.
2. The method of claim 1, wherein: the molecular weight of the low molecular weight polyethylene powder is 2000-3000, and the fineness is 60-80 meshes.
3. The method of claim 1, wherein: the emulsifier is peregal O or alkylphenol polyoxyethylene, and the dosage of the emulsifier is 2-4% of the weight of the low molecular weight polyethylene powder.
4. The method of claim 1, wherein: the dispersant is sodium polymethacrylate or polyvinylpyrrolidone, and the dosage of the dispersant is 1-3% of the mass of the low molecular weight polyethylene powder.
5. The method of claim 1, wherein: the initiator is dibenzoyl peroxide, and the dosage of the initiator is 1.5-2% of the mass of the low molecular weight polyethylene powder.
6. The method of claim 1, wherein: the predetermined starting chlorine introduction temperature was 65 ℃.
7. The method of claim 1, wherein: the required chlorine flux is 3.5-4.5 times of the mass of the low molecular weight polyethylene powder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527546A (en) * | 2021-08-17 | 2021-10-22 | 上海宝钱新材料技术有限公司 | Method for preparing chlorinated rubber by water phase method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704911A (en) * | 2009-11-14 | 2010-05-12 | 潍坊高信化工科技有限公司 | Method for producing highly-chlorinated polyethylene |
| CN104650473A (en) * | 2013-11-25 | 2015-05-27 | 江苏中煦高分子材料有限公司 | Chlorinated polyethylene rubber produced by water phase suspension method and synthesis technology thereof |
| CN107118290A (en) * | 2017-06-09 | 2017-09-01 | 江苏科利新材料有限公司 | A kind of method that environment-friendly type aqueous phase method prepares haloflex |
| CN110105479A (en) * | 2019-06-06 | 2019-08-09 | 金辉 | A kind of low consumption environment-friendly type water phase suspension chliorinated polyvinyl chloride preparation method |
| KR20200071035A (en) * | 2018-12-10 | 2020-06-18 | 주식회사 엘지화학 | Polyethylene and its chlorinated polyethylene |
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2020
- 2020-07-23 CN CN202010717829.9A patent/CN111704686B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704911A (en) * | 2009-11-14 | 2010-05-12 | 潍坊高信化工科技有限公司 | Method for producing highly-chlorinated polyethylene |
| CN104650473A (en) * | 2013-11-25 | 2015-05-27 | 江苏中煦高分子材料有限公司 | Chlorinated polyethylene rubber produced by water phase suspension method and synthesis technology thereof |
| CN107118290A (en) * | 2017-06-09 | 2017-09-01 | 江苏科利新材料有限公司 | A kind of method that environment-friendly type aqueous phase method prepares haloflex |
| KR20200071035A (en) * | 2018-12-10 | 2020-06-18 | 주식회사 엘지화학 | Polyethylene and its chlorinated polyethylene |
| CN110105479A (en) * | 2019-06-06 | 2019-08-09 | 金辉 | A kind of low consumption environment-friendly type water phase suspension chliorinated polyvinyl chloride preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527546A (en) * | 2021-08-17 | 2021-10-22 | 上海宝钱新材料技术有限公司 | Method for preparing chlorinated rubber by water phase method |
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