CN111848846A - Preparation method and application of vinyl chloride polymer - Google Patents
Preparation method and application of vinyl chloride polymer Download PDFInfo
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- CN111848846A CN111848846A CN202010630307.5A CN202010630307A CN111848846A CN 111848846 A CN111848846 A CN 111848846A CN 202010630307 A CN202010630307 A CN 202010630307A CN 111848846 A CN111848846 A CN 111848846A
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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
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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Abstract
The invention discloses a preparation method and application of a vinyl chloride polymer, relating to the technical field of vinyl chloride and comprising the following steps: placing chloroethylene and an anti-caking agent into a reactor, vacuumizing the reactor to the pressure of-0.1 to-0.05 MPa, introducing chlorine gas to the reactor to the pressure of 0.2 to 0.6MPa, carrying out chlorination reaction, discharging reaction waste gas after the reaction is finished, and repeating the operations of vacuumizing, introducing chlorine gas to carry out chlorination reaction and discharging waste gas to obtain chlorinated polyvinyl chloride. The method for preparing a vinyl chloride polymer of the present invention, the method for preparing a vinyl chloride polymer by bulk polymerization and the vinyl chloride polymer prepared thereby can be easily applied to industries requiring a vinyl chloride polymer, for example, industries relating to vinyl chloride resins and molded articles thereof.
Description
Technical Field
The invention relates to the technical field of vinyl chloride, in particular to a preparation method and application of a vinyl chloride polymer.
Background
Vinyl chloride polymers are polymers containing more than 50% of vinyl chloride, are inexpensive, have easy control of hardness, are suitable for most processing equipment, and have various application fields. In addition, vinyl chloride polymers can provide molded products having excellent physical and chemical properties such as mechanical strength, weather resistance and chemical resistance, and are widely used in various fields. However, the vinyl chloride polymer causes dehydrochlorination due to defects of a chemical structure generated during a polymerization reaction due to heat or ultraviolet rays applied during processing, and thus may cause discoloration of a resin or deterioration of physical properties.
In particular, in vinyl chloride polymers, there are chemical defects generated in the polymerization reaction, i.e., defects in the chemical structures of chloropropenes and trichloride. Due to the defects of the chemical structure, the binding energy of carbon to chlorine in the vinyl chloride polymer may be much lower than that of carbon to chlorine in a general molecular structure, and the bond between carbon and chlorine may be easily broken due to external radical transfer during the processing of the vinyl chloride polymer. The separate hydrogen chloride from the polymer chain accelerates other side reactions by autocatalytic reactions, thereby continuously generating additional hydrogen chloride. In addition, double bonds may be formed at the positions where the hydrogen chloride is removed, and several double bonds may overlap to cause discoloration of the resin and deterioration of physical properties. That is, in a vinyl chloride polymer or a molded article processed therefrom, a dehydrochlorination reaction occurs due to heat or ultraviolet rays, thereby causing discoloration defects of the vinyl chloride polymer or deterioration or change in physical properties.
In order to improve the limitations of vinyl chloride polymers, organometallic compounds containing metals such as Ba, Zn, Ca and Pb have been mixed with vinyl chloride polymers to inhibit the generation of radicals or ions during thermal decomposition of the vinyl chloride polymers and to control the thermal decomposition rate of the resins. Recently, methods using various types of heat stabilizers such as metal substances or organic compounds have been proposed. However, the use thereof is limited due to environmental problems and high price caused by the use of heavy metal stabilizers.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a vinyl chloride polymer.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a vinyl chloride polymer, comprising the steps of: placing chloroethylene and an anti-caking agent into a reactor, vacuumizing the reactor to the pressure of-0.1 to-0.05 MPa, introducing chlorine gas to the reactor to the pressure of 0.2 to 0.6 MPa, carrying out chlorination reaction, discharging reaction waste gas after the reaction is finished, and repeating the operations of vacuumizing, introducing chlorine gas to carry out chlorination reaction and discharging waste gas to obtain chlorinated polyvinyl chloride.
Preferably, the polymerization degree of the polyvinyl chloride is 500-1300, the water content is less than 0.3 wt%, and the particle size is 100-315 mu m.
Preferably, the anti-bonding agent is silicon dioxide, white carbon black or talcum powder.
Preferably, the particle size of the anti-bonding agent is 5-10 μm.
Preferably, the mass ratio of the anti-bonding agent to the polyvinyl chloride is 0.1-5: 100.
Preferably, the chlorination reaction is carried out in the presence of an initiator or under ultraviolet irradiation, and the initiator is an azo initiator or an organic peroxide initiator.
Preferably, the azo initiator is azobisisoheptonitrile and/or azobisisobutyronitrile, and the organic peroxide initiator is benzoyl peroxide.
Preferably, the mass ratio of the initiator to the polyvinyl chloride is 0.1-1: 100.
Preferably, the rising speed of the pressure in the reactor is 0.01-0.2 MPa/10 min.
Preferably, the temperature of the chlorination reaction is 40-65 ℃ and the time is 10-30 min.
By adopting the technical scheme of the invention, the following beneficial effects can be obtained:
the method for preparing a vinyl chloride polymer of the present invention, the method for preparing a vinyl chloride polymer by bulk polymerization and the vinyl chloride polymer prepared thereby can be easily applied to industries requiring a vinyl chloride polymer, for example, industries relating to vinyl chloride resins and molded articles thereof.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention in further detail.
The method for preparing a vinyl chloride polymer by bulk polymerization according to an embodiment of the present invention is characterized by comprising: prepolymerizing to form core particles (step 1); and adding vinyl chloride monomer and a post-polymerization initiator to the core particles and performing post-polymerization (step 2), wherein during the post-polymerization, 0.001 to 10 parts by weight of a modifier is added with respect to 100 parts by weight of vinyl chloride monomer. Step 1 is a prepolymerization step for forming core particles of a vinyl chloride polymer and may be performed by adding vinyl chloride monomer and a prepolymerization initiator to a reactor and prepolymerization. Specifically, the prepolymerization can be carried out by a conventional method known in the art without particular limitation. For example, the prepolymerization can be performed by adding vinyl chloride monomer and a prepolymerization initiator to a prepolymerization reactor and controlling the reaction pressure and temperature.
The prepolymerization initiator can be used in an amount of 0.05 to 1 part by weight relative to 100 parts by weight of the vinyl chloride monomer, and the kind of the prepolymerization initiator is not particularly limited, but those known in the art can be used. For example, peroxyesters, peroxydicarbonates, and the like can be used. Specifically, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxyneodecanoate, or a mixture thereof may be used.
The vinyl chloride monomer may be vinyl chloride monomer alone or vinyl chloride monomer and may be co-polymerized with the vinyl chloride monomer
Mixtures of poly (vinyl monomers). The vinyl monomer copolymerizable with the vinyl chloride monomer is not particularly limited, but may include olefin compounds such as ethylene, propylene and butane; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; unsaturated nitriles such as acrylonitrile; vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether and vinyl dodecyl ether; vinylidene halides, such as vinylidene chloride; unsaturated fatty acids and anhydrides of fatty acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride and itaconic anhydride; unsaturated fatty acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate and butyl benzyl maleate; crosslinking monomers, such as diallyl phthalate. The vinyl monomer may be used alone or as a mixture of two or more. The reaction pressure and temperature are not particularly limited and may be publicly known conditions. For example, the reaction pressure may be 7.5K/G to 13K/G and the temperature may be in the range of 30 ℃ to 70 ℃.
Step 2 is a step of preparing a vinyl chloride polymer by growing the core particles prepared in the prepolymerization step, and may be performed by adding vinyl chloride monomer and a post-polymerization initiator to the core particles prepared in the prepolymerization step and post-polymerizing. In this case, the post-polymerization may be carried out with the addition of a modifier to impart high thermal stability to the vinyl chloride polymer as above. Specifically, the post-polymerization is not particularly limited, but may be performed by a method well known in the art. For example, the post-polymerization may be performed by transferring the core particles prepared in the pre-polymerization step to a reactor for post-polymerization containing additional vinyl chloride monomer (vinyl chloride monomer added during the post-polymerization), then adding a post-polymerization initiator thereto, and controlling the reaction pressure and temperature of the reactor.
The post-polymerization initiator is not particularly limited, and may be used in an amount of 0.1 to 2 parts by weight with respect to 100 parts by weight of additional vinyl chloride monomer (vinyl chloride monomer added during post-polymerization). The post-polymerization initiator may be added to the reactor for post-polymerization while transferring the core particles or may be added after completing the transfer of the core particles or during the post-polymerization. In particular, the post-polymerization initiator may be added immediately after the completion of the transfer of the core particles or at a point when the post-polymerization conversion rate is 10% to 40% after the completion of the transfer. In this case, the postpolymerization initiator may be added in portions or separately or continuously. The kind of the post-polymerization initiator used for the post-polymerization is not particularly limited, but publicly known substances such as peroxyester, peroxydicarbonate, etc. can be used. Specifically, cumyl peroxide, t-butyl peroxide, octyl peroxydicarbonate, 1, 3, 3-tetramethylbutyl peroxydicarbonate (1, 1, 3, 3-tetramethylbutyl peroxydicarbonate), and the like can be used. The additional vinyl chloride monomer (vinyl chloride monomer added during post polymerization) is the same as described above. The post-polymerization step may be performed by adding a modifier to impart high heat stability to the vinyl chloride polymer thus prepared, and the modifier may be added to the reactor for post-polymerization together with additional vinyl chloride monomer or at any time during the post-polymerization to participate in the polymerization. By adding the modifier, the dehydrochlorination reaction of the thus-prepared vinyl chloride polymer upon exposure to heat or ultraviolet rays can be suppressed, and the thermal stability of the vinyl chloride polymer can be significantly improved. In addition, discoloration of the vinyl chloride polymer caused by heat and ultraviolet rays can be prevented.
Specifically, the modifier may be added to the reactor for post-polymerization together with additional vinyl chloride monomer at a point before or after the post-initiation polymerization when the polymerization conversion rate is 30% or more, preferably 50% to 95%, more preferably 80% to 95%. The modifier according to an embodiment of the present invention may be included in an amount of 0.001 parts by weight to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride monomer, and the amount may vary according to the kind of the modifier. Specifically, the modifier may be at least one selected from the group consisting of a hydroxycarboxylic acid salt, an inorganic phosphate salt, and ethylenediaminetetraacetate.
The salt of the hydroxycarboxylic acid is not particularly limited, but may be citric acid or trisodium citrate. In the case where the modifier is a salt of hydroxycarboxylic acid, the salt of hydroxycarboxylic acid may be contained in an appropriate amount in the range of 0.001 to 10 parts by weight, preferably in an amount of 0.001 to 1 part by weight, relative to 100 parts by weight of the vinyl chloride monomer as described above. If the amount of the hydroxycarboxylic acid salt is less than 0.001 parts by weight, the dehydrochlorination reaction inhibiting effect is very small and the effect of improving the thermal stability of the vinyl chloride polymer is deteriorated, whereas if the amount of the hydroxycarboxylic acid salt is more than 10 parts by weight, the processability of the vinyl chloride polymer containing it is deteriorated and the colorability of the molded article obtained therefrom is deteriorated.
The inorganic phosphate is not particularly limited, but may be disodium diphosphate or tetrasodium diphosphate, and particularly may be tetrasodium diphosphate. In the case where the modifier is an inorganic phosphate, the inorganic phosphate may be included in an appropriate amount ranging from 0.001 parts by weight to 10 parts by weight, preferably may be included in an amount of 0.001 parts by weight to 1 part by weight, relative to 100 parts by weight of the vinyl chloride monomer as described above. If the amount of the inorganic phosphate is less than 0.001 parts by weight, the inhibition effect of dehydrochlorination reaction is very small and the effect of improving the thermal stability of the vinyl chloride polymer is deteriorated, whereas if the amount of the inorganic phosphate is more than 10 parts by weight, the processability of the vinyl chloride polymer including it is deteriorated and the colorability of the molded article thus obtained is deteriorated.
The salt of ethylenediaminetetraacetic acid is not particularly limited, but may be disodium ethylenediaminetetraacetate or tetrasodium ethylenediaminetetraacetate, and particularly may be tetrasodium ethylenediaminetetraacetate. In the case where the modifier is ethylenediamine tetraacetate, the ethylenediamine tetraacetate may be contained in an appropriate amount in the range of 0.001 to 10 parts by weight, preferably in an amount of 0.001 to 1 part by weight, with respect to 100 parts by weight of the vinyl chloride monomer as described above. If the amount of the ethylenediaminetetraacetate is less than 0.001 parts by weight, the dehydrochlorination reaction inhibiting effect is very small and the thermal stability improving effect of the vinyl chloride polymer is deteriorated, whereas if the amount of the ethylenediaminetetraacetate is more than 10 parts by weight, the processability of the vinyl chloride polymer including it is deteriorated and the colorability of the molded article obtained therefrom is deteriorated.
The reaction pressure and reaction temperature in the post-polymerization step are not particularly limited and may be conditions well known in the art. For example, the reaction pressure may be 7.5K/G to 13K/G, and the reaction temperature may be in the range of 30 ℃ to 70 ℃. In the preparation method by bulk polymerization according to the present invention, a polymerization inhibitor may be added at the end of the post-polymerization to eliminate the reactivity of the remaining post-polymerization initiator. The polymerization inhibitor is not particularly limited, but those known in the art may be used. For example, hydroquinone, butylated hydroxytoluene, hydroquinone monomethyl ether, tetrabutyl catechol, diphenylamine, triisopropanolamine, triethanolamine, and the like can be used. The amount of the polymerization inhibitor used may be controlled according to the amount of the post-polymerization initiator, and may be used in an amount of 0.001 to 0.1 parts by weight, relative to 100 parts by weight of the vinyl chloride monomer.
In the production method by bulk polymerization according to the present invention, the reaction medium may be used together with vinyl chloride monomer, and additives such as a molecular weight controlling agent may be used in addition to the above-mentioned effective ingredients.
The reaction medium is not particularly limited and may be a conventional organic solvent. For example, the reaction medium may include aromatic compounds such as benzene, toluene, xylene, methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane, and the like. The molecular weight controlling agent is not particularly limited, but may be, for example, n-butylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, etc. Further, in the present invention, there is provided a vinyl chloride polymer prepared by the preparation method by bulk polymerization.
The present invention has been described in connection with the embodiments, and it is obvious that the specific implementation of the present invention is not limited by the above-mentioned manner, and it is within the protection scope of the present invention as long as various insubstantial modifications are made by using the method concept and technical scheme of the present invention, or the concept and technical scheme of the present invention are directly applied to other occasions without modification.
Claims (10)
1. A method for preparing a vinyl chloride polymer, comprising the steps of: placing chloroethylene and an anti-caking agent into a reactor, vacuumizing the reactor to the pressure of-0.1 to-0.05 MPa, introducing chlorine gas to the reactor to the pressure of 0.2 to 0.6 MPa, carrying out chlorination reaction, discharging reaction waste gas after the reaction is finished, and repeating the operations of vacuumizing, introducing chlorine gas to carry out chlorination reaction and discharging waste gas to obtain chlorinated polyvinyl chloride.
2. The method according to claim 1, wherein the polyvinyl chloride has a polymerization degree of 500 to 1300, a water content of less than 0.3 wt%, and a particle diameter of 100 to 315 μm.
3. The preparation method according to claim 1, wherein the anti-blocking agent is silica, white carbon black or talcum powder.
4. The production method according to claim 1 or 3, wherein the anti-blocking agent has a particle size of 5 to 10 μm.
5. The preparation method according to claim 1 or 3, wherein the mass ratio of the anti-blocking agent to the polyvinyl chloride is 0.1-5: 100.
6. The preparation method according to claim 1, wherein the chlorination reaction is carried out in the presence of an initiator or under ultraviolet irradiation, and the initiator is an azo initiator or an organic peroxide initiator.
7. The method according to claim 6, wherein the azo initiator is azobisisoheptonitrile and/or azobisisobutyronitrile, and the organic peroxide initiator is benzoyl peroxide.
8. The preparation method according to claim 1, 6 or 7, wherein the mass ratio of the initiator to the polyvinyl chloride is 0.1-1: 100.
9. The method according to claim 1, wherein the rate of pressure increase in the reactor during the introduction of the chlorine gas is 0.01 to 0.2 MPa/10 min.
10. The method according to claim 1, wherein the chlorination reaction is carried out at a temperature of 40 to 65 ℃ for 10 to 30 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010630307.5A CN111848846A (en) | 2020-07-03 | 2020-07-03 | Preparation method and application of vinyl chloride polymer |
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| CN202010630307.5A CN111848846A (en) | 2020-07-03 | 2020-07-03 | Preparation method and application of vinyl chloride polymer |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250324A (en) * | 2014-07-16 | 2014-12-31 | 杭州新元化工技术开发有限公司 | Gas-solid phase reaction method for preparation of chlorinated polyvinyl chloride |
| CN110028604A (en) * | 2019-04-24 | 2019-07-19 | 杭州新元化工技术开发有限公司 | A kind of preparation method of chliorinated polyvinyl chloride |
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2020
- 2020-07-03 CN CN202010630307.5A patent/CN111848846A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250324A (en) * | 2014-07-16 | 2014-12-31 | 杭州新元化工技术开发有限公司 | Gas-solid phase reaction method for preparation of chlorinated polyvinyl chloride |
| CN110028604A (en) * | 2019-04-24 | 2019-07-19 | 杭州新元化工技术开发有限公司 | A kind of preparation method of chliorinated polyvinyl chloride |
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