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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
  • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
  • B01F27/05—Stirrers
  • B01F27/11—Stirrers characterised by the configuration of the stirrers
  • B01F27/116—Stirrers shaped as cylinders, balls or rollers
  • B01F27/1161—Stirrers shaped as cylinders, balls or rollers having holes in the surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0053—Details of the reactor
  • B01J19/006—Baffles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0053—Details of the reactor
  • B01J19/0066—Stirrers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/18—Stationary reactors having moving elements inside
  • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
• • 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
  • C08F14/00—Homopolymers and copolymers 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
  • C08F14/18—Monomers containing fluorine
  • C08F14/26—Tetrafluoroethene
• • 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
  • C08F214/00—Copolymers 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
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
  • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00162—Controlling or regulating processes controlling the pressure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00189—Controlling or regulating processes controlling the stirring velocity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00761—Details of the reactor
  • B01J2219/00763—Baffles
  • B01J2219/00765—Baffles attached to the reactor wall
  • B01J2219/00768—Baffles attached to the reactor wall vertical
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00761—Details of the reactor
  • B01J2219/00763—Baffles
  • B01J2219/00779—Baffles attached to the stirring means
• • 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
  • C08F216/00—Copolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/08—Allyl alcohol
• • 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
  • C08F216/00—Copolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
  • C08F216/18—Acyclic compounds
• • 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
  • C08F218/00—Copolymers 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
  • C08F220/64—Acids; Metal salts or ammonium salts thereof

Definitions

• the present invention is in the field of polymer compounds, and is specifically a method for preparing an organic fluoropolymer using a polymerizable compound. Background technique
• the resin for fluorocarbon polymer coating is synthesized by a copolymerization reaction.
• Its copolymerization composition includes a fluorine monomer and a fluorine- or non-fluorine-containing functional group carboxyl group, a hydroxyl group, an ester group, and an ether group. Since the component with a functional group is present, the coating prepared therefrom imparts its solubility in the medium, crosslinkability, adhesion to the substrate, dispersibility to the filler, transparency and gloss.
• the fluorine atom is highly electronegative, the atomic radius is small, the carbon-fluorine bond is short, the bond energy is as high as 500 KJ / mol, and the adjacent fluorine atoms are mutually exclusive.
• the distribution of fluorine atoms is not in the same plane, and the structure is spirally distributed along the carbon chain.
• the fluorine-containing coating resin is particularly outstanding in weather resistance, salt spray resistance and chemical corrosion resistance, and its excellent performance is mainly determined by the fluorine content, and high fluorine content and polyfunctional groups are prepared.
• the resin for coatings can be used to develop a resin for fluorine-containing coatings which is cured at room temperature, has long-lasting weather resistance, and has outstanding chemical resistance.
• fluorocarbon coatings including an amorphous copolymer in which a hydroxyvinyl ether copolymer, a fluoroolefin structural unit and a different hydrocarbyl vinyl ether structure are alternately arranged.
• the main varieties appearing in the domestic market are the fluorochemical coating resin of Sugamoto Asahi Glass Co., Ltd. and the fluorochemical coating resin of PTFE of Sakamoto Daikin Co., Ltd.
• the fluorine content of the tetrafluoroethylene monomer accounts for 76% of the molecular weight of the monomer. It is the first choice compared with other fluorine-containing monomers.
• the tetrafluoroethylene monomer is used to synthesize a high-fluorination coating resin, which is the preferred monomer.
• Synthesis The component has alkenyl alcohol to participate in copolymerization and thus can be combined with HDI (hexamethylene diisocyanate), N75 (hexamethylene diisocyanate biuret), N3375 (hexamethylene diisocyanate trimer) and other organic compounds. Crosslinking occurs at room temperature to cure.
• the fluorine-containing coating resin can be cured into a new type of fluorocarbon resin in a normal temperature environment, most of which are in a solvent to have good solubility, and products producing low VOC (volatile organic compound) content are still developed.
• the main difficulty The domestic research and development of resins for fluorocarbon coatings is in its infancy, especially the synthesis of fluorocarbon resins for room temperature curing of tetrafluoroethylene coatings. Summary of the invention
• an object of the present invention is to provide a method for preparing a resin containing a polytetrafluoroethylene coating, and to provide a vertical reactor for use in the preparation method.
• a preparation method of a polytetrafluoroethylene-containing resin comprising the steps of:
• the reaction pressure is controlled in the range of 1.0 ⁇ 2.0MPa, preferably 1.9 ⁇ 0.05MPa, in the polymerization process, continuous or intermittent addition of four Fluoroethylene monomer, initiator;
• the pressure in the autoclave is restored to 0.03 ⁇ 0.1MPa with nitrogen, and the obtained polymerization liquid is the product.
• the time of the polymerization reaction is controlled to be 17 to 21 h, preferably 18 to 19 h.
• liquid non-fluoro comonomer is vinyl acetate, methyl vinyl ether, undecylenic acid and allyl alcohol; the added gaseous tetrafluoroethylene monomer and vinyl acetate, methyl vinyl ether
• the mass ratio of undecylenic acid to allyl alcohol is 56: 29: 0.6: 1.4: 5.5 to 6.5.
• the initiator is azobisisobutyronitrile, and in step 1), an initiator having a mass of 1/3 of the total mass of the initiator is added; and in step 3), the remaining 2/3 initiator is added.
• the oxygen content of the oxygen control system is 30 ppm.
• the initiator solution in the step 3) is added continuously or intermittently in a mass ratio of 5%, and the solvent is a mixed solvent of butyl acetate and methyl isobutyl ketone, and the mass ratio of the two solvents is 2.9:1. .
• the obtained polytetrafluoroethylene-containing resin is used in a room temperature curing coating.
• the agitator type of the vertical reaction kettle of the present invention a simple agitator. This type of agitation differs from a typical anchor agitator as well as a typical turbine agitator.
• the viscosity of the material increases as the solid content of the polymerization reaction increases, and it has a medium viscosity material, so the stirring speed is generally selected in the range of 80 to 150 rpm. At this agitation speed, the high-efficiency three-phase dispersion of the polymerization medium is maintained, and a dedicated stirring device is designed to achieve the best results.
• An agitator for carrying out the preparation method comprises a simplified body, and a plurality of streamlined blades are mounted on the simplified wall, and the line connecting the blade and the simplified wall is parallel to the central axis of the agitator, and the tangent and the starting point of the blade are simplified.
• the normal angle of the body is 15 ⁇ 60°. Simplifiedly there are several slots that are evenly distributed. The blades and slots are preferably spaced apart.
• the slot length of the agitator is 0.7 ⁇ 0.9 of the height of the agitator and the width is 10 ⁇ 15mm.
• the number of slots is 2 ⁇ 10.
• the agitator has a simplified height H 2 : the agitator diameter 0 2 is 1.00: 1.05-1.20, and is generally selected to be 1.00: 1.10, preferably 1.00: 1.05.
• the inner diameter of the reactor is 1:0.5 ⁇ 0.6, preferably 1:0.55; the height of the reactor H1 : the outer diameter of the reactor D l.05 ⁇ 1.25: 1.00, generally selected 1.10: 1.00, preferably 1.05: 1.00.
• the reaction device proposed by the invention is suitable for medium-viscosity medium. Under the condition of limited stirring speed, the special simple agitator is used, and the special design of the aspect ratio of the kettle body can better prepare the tetrafluoroethylene with high fluorine content. Resin for coating at room temperature.
• FIG. 1 is a schematic view showing the structure of an agitator in a vertical reaction vessel of the present invention.
• Figure 2 shows the A-A cross-sectional view.
• 1 is a slot
• the width of the slot is W
• 2 is the central axis of the agitator
• 3 is simplified
• 4 is a streamlined blade
• 5 is a rib.
• the angle between the starting point of the streamlined blade and the tangent to the center point is ⁇ , and the arrow outside the axis indicates the direction of rotation of the agitator.
• the initial polymerization temperature was controlled at 65 ⁇ 1 °C, and the polymerization temperature at the termination was controlled at 70 ⁇ 1 °C.
• 56.0 Kg of tetrafluoroethylene monomer was charged into the gas phase, and the polymerization pressure in the reactor was controlled at 1.9 ⁇ 0.05 MPa.
• a 5% (wt) initiator solution was added for a total of about 32 kg.
• the reaction becomes very slow or does not react, that is, the feed is stopped.
• the residual gaseous phase tetrafluoroethylene monomer was recovered and evacuated to a pressure of -0.095 MPa in the autoclave. Finally, the pressure in the autoclave was restored to 0.05 MPa with nitrogen, and the polymerization liquid was poured into a closed discharge chute.
• the polymerization time was 19.5h.
• the initial polymerization temperature was controlled at 65 ⁇ 1 °C, and the polymerization temperature at the termination was controlled at 70 ⁇ 1 °C.
• 56.0 Kg of tetrafluoroethylene monomer was charged into the gas phase, and the polymerization pressure in the reactor was controlled to 1.9 ⁇ 0.05 MPa.
• a 5% (wt) initiator solution was continuously added for a total of about 32 kg.
• the reaction becomes very slow or does not react, that is, the feed is stopped.
• the residual tetrafluoroethylene monomer was recovered and evacuated to a pressure of -0.095 MPa in the autoclave.
• the pressure in the autoclave was restored to 0.05 MPa with nitrogen, and the polymerization liquid was poured into a closed discharge tank.
• the polymerization time was 19 h.
• the initial polymerization temperature was controlled at 65 ⁇ 1 °C, and the polymerization temperature at the termination was controlled at 70 ⁇ 1 °C.
• 56.0 Kg of tetrafluoroethylene monomer was charged into the gas phase, and the polymerization pressure in the reactor was controlled at 1.9 ⁇ 0.05 MPa.
• 5% (wt) of the initiator solution was added in portions, totaling about 32 kg.
• the reaction becomes very slow or does not react, that is, the feed is stopped.
• the residual tetrafluoroethylene monomer was recovered and evacuated to a pressure of -0.095 MPa in the autoclave.
• the pressure in the autoclave was recovered to 0.05 MPa with nitrogen, and the polymerization liquid was poured into a closed discharge chute.
• the polymerization time was 18h.
• the metering pump is used to supplement, and the control of the additional flow rate depends on the actual reaction rate.
• a vertical reactor used in Example a height of 0.80111 reactor, reactor 01 is 0.75M outer diameter, an inner diameter of 0.70m.
• the vertical reactor was equipped with a simple stirrer. The height of the stirrer was 11 2 and the diameter D 2 of the stirrer was 0.45 m.
• the agitator has a round shape, and the simplified body 3 is designed to install four streamlined blades 4 on the wall of the simplified body 3 at a certain angle.
• Four regular slots 1 are uniformly distributed on the simplified body 3, and the width W of the slot 1 is 12 mm. , slot 1 is 0.35m high.
• the blades and slots are spaced apart. Depending on the amount of material being processed, the slots can be machined to a width of 10 to 15 mm.
• the ribs 5 on the simplified side serve as a support. From a top-down perspective, the point of attachment) can be machined to an angle of 15 to 60° depending on the viscosity of the material being processed.
• the line connecting the blade 4 to the simplified wall is parallel to the central axis 2 of the agitator.
• the pressure in the simple one is reduced, and the fluid enters the inner simplified along the upper and lower ends of the simplified body 3, forming a mixed flow pattern mainly composed of axial flow, having a high axial flow and a radial flow, so that
• the components of the whole reaction system can be uniformly stirred and rapidly polymerized, and the dispersion of the copolymer component of the polymer tends to be uniform, so that the quality of the film-forming material (including the fluorine content) is greatly improved.
• the copolymerization components were added in the same amount, and the process control conditions were the same.
• the resin yield, resin solid content, solid resin fluorine content, color grade, and hydroxyl content of the composites obtained in Examples 1 to 3 were large. Improvement. Comparative Example 1, 2 Using an anchor stirrer, under the same formulation and process conditions, the control stability is poor. Although the weight of the obtained product is the same, the quality index value is highly dispersed.
• the hydroxyl value of Examples 1 to 3 fluctuated within a suitable range, indicating that the product quality was stable.
• the hydroxy value of the resin for the room temperature curing tetrafluoroethylene coating is different according to the conditions of the comonomer allyl alcohol and the hydroxy monomer.
• the resin film forming process of the present invention is more elastic.
• the preparation method of the high fluorine content polytetrafluoroethylene-containing resin disclosed in the invention is to add a solvent and a liquid non-fluorinated comonomer and an initiator to the reaction kettle, and evacuate the oxygen to the reaction system, and the polymerization temperature is controlled at 60 ⁇ . At 75 ° C, the tetrafluoroethylene monomer is charged into the gas phase. During the polymerization, the tetrafluoroethylene monomer and the initiator are continuously or intermittently added, and the reaction time is 17 to 21 hours.
• the present invention also proposes a reaction vessel for carrying out the production method.
• the invention is suitable for medium viscosity medium. Under the condition of limited stirring speed, the reactor containing a special simple stirrer can be used to prepare a room temperature curing resin having a high fluorine content of tetrafluoroethylene.

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