CN112194746A - Medical high-polymerization-degree polyvinyl chloride resin and preparation method thereof - Google Patents
Medical high-polymerization-degree polyvinyl chloride resin and preparation method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 109
- 239000011347 resin Substances 0.000 title claims abstract description 109
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 101
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 116
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims description 60
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012934 organic peroxide initiator Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 4
- 230000007613 environmental effect Effects 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 229940127554 medical product Drugs 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- -1 Polyethylene Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WVEYQAAOVYAMDB-UHFFFAOYSA-N OC1=C(CCC(C(Cl)=CC=C2)=C2O)C=CC=C1 Chemical compound OC1=C(CCC(C(Cl)=CC=C2)=C2O)C=CC=C1 WVEYQAAOVYAMDB-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to polyvinyl chloride resin and a preparation method thereof, in particular to medical high-polymerization-degree polyvinyl chloride resin and a preparation method thereof. Uniformly spraying a required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser under an oxygen-free closed condition, then washing the inner walls, adding a required amount of raw materials into the polymerization kettle, controlling the temperature and the pressure to carry out polymerization reaction for 9 to 10 hours to obtain a first polymer, finishing the polymerization reaction after the pressure is reduced, and carrying out steam stripping and drying treatment on the obtained high-polymerization-degree polyvinyl chloride resin slurry to obtain the medical high-polymerization-degree polyvinyl chloride resin. The invention has high polymerization degree, high resin oil absorption rate, excellent processing performance, good chemical inertia and biological safety, and can be widely applied to the field of medical products.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride resin and preparation thereof, in particular to medical polyvinyl chloride resin with high polymerization degree and a preparation method thereof.
Background
Polyvinyl chloride (PVC) resin is widely used due to its excellent mechanical properties, chemical resistance, flame retardancy, electrical insulation properties, etc., and its global usage amount is the second highest among various synthetic materials. Compared with general resin, the performance requirement of the green medical polyvinyl chloride resin is stricter, and the residual quantity of toxic substances such as chloroethylene, bisphenol A, benzene, nitrile, heavy metal and the like in the medical resin is required to be trace or not contained. At present, the resins widely used in the medical industry include polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), engineering plastics and the like. It is estimated by the market that about 28% of medical plastic products are polyvinyl chloride resins. The total demand of domestic medical grade polyvinyl chloride resin is 15 ten thousand tons/year to 30 ten thousand tons/year. At present, medical grade polyvinyl chloride resin with high polymerization degree is produced in China mainly in small kettles with the diameter below 70, the production capacity is low, the cost is high, the medical grade resin mainly depends on imported ethylene resin, and the market demand can not be met.
Disclosure of Invention
The invention provides a medical high-polymerization-degree polyvinyl chloride resin and a preparation method thereof, overcomes the defects of the prior art, provides a green environment-friendly medical high-polymerization-degree polyvinyl chloride resin which does not contain non-environment-friendly substances, has small dissolution and good biocompatibility, and solves the problems of low productivity and high cost.
One of the technical schemes of the invention is realized by the following measures: the medical high-polymerization-degree polyvinyl chloride resin comprises, by weight, 5.5 to 6 parts of an anti-sticking kettle agent, 1 to 1.25 parts of a pH regulator, 18500 to 19000 parts of a vinyl chloride monomer, 20000 to 21000 parts of deoxidized deionized water, 4.65 to 4.9 parts of a first dispersant, 15.65 to 16.1 parts of a second dispersant, 3.72 to 6.42 parts of a third dispersant, 22.5 to 25 parts of an initiator and 22.5 to 26 parts of an environment-friendly terminator, and is obtained by the following steps: firstly, uniformly spraying the required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser by superheated saturated steam under the anaerobic closed condition, and then using 0.3m3To 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding a required amount of pH regulator into a polymerization kettle, simultaneously adding required amounts of deoxidized deionized water and vinyl chloride monomer, mixing for 2min, adding a required amount of No. two dispersant, adding a required amount of No. one dispersant and a required amount of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5-37.5 ℃ and the pressure of 0.40-0.50 MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.04MPa to 0.10MPa, adding a required amount of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; sixthly, performing solid-liquid separation on the stripped polyvinyl chloride resin slurry with high polymerization degree by using a centrifugal machine, and then drying and dehydrating the polyvinyl chloride resin slurry in drying equipment to obtain the medical polyvinyl chloride resin slurryPolyvinyl chloride resin with high polymerization degree.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the anti-sticking agent is a low-polymerization degree phenolic resin aqueous solution with the pH value of 12 to 14.
The pH regulator is ammonium bicarbonate or sodium bicarbonate.
The first dispersant, the second dispersant and the third dispersant are all polyvinyl alcohol, wherein the first dispersant is polyvinyl alcohol with alcoholysis degree of 78.5-80.5 mol%, the second dispersant is polyvinyl alcohol with alcoholysis degree of 71.5-73.5 mol%, and the third dispersant is polyvinyl alcohol with alcoholysis degree of 54.0-57.0 mol%.
The initiator is organic peroxide initiator.
The environment-friendly terminator is a polyvinyl chloride resin high-efficiency water-soluble terminator.
In the first step, the pressure of the supersaturated steam is 0.7MPa to 0.8 MPa.
In the third step, the polymerization time is 9 to 10 hours.
The second technical scheme of the invention is realized by the following measures: a preparation method of medical polyvinyl chloride resin with high polymerization degree is carried out according to the following steps: firstly, uniformly spraying the required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser by superheated saturated steam under the anaerobic closed condition, and then using 0.3m3To 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding a required amount of pH regulator into a polymerization kettle, simultaneously adding required amounts of deoxidized deionized water and vinyl chloride monomer, mixing for 2min, adding a required amount of No. two dispersant, adding a required amount of No. one dispersant and a required amount of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5-37.5 ℃ and the pressure of 0.40-0.50 MPa to obtain a first polymer; fourthly, after the pressure of the polymerization kettle is reduced by 0.04MPa to 0.10MPa, adding the required amount of the first polymerThe polymerization reaction is finished by the environment-friendly terminator to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin.
The medical high-polymerization-degree polyvinyl chloride resin obtained by the invention has high polymerization degree, high resin oil absorption rate, excellent processing performance, good chemical inertia and biological safety, and can be widely applied to the field of medical products.
Drawings
FIG. 1 is a SEM image of the particle morphology of the medical polyvinyl chloride resin 2 with high degree of polymerization obtained by the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the present invention are all mass percentages unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1: the medical high-polymerization-degree polyvinyl chloride resin comprises, by weight, 5.5 to 6 parts of an anti-sticking kettle agent, 1 to 1.25 parts of a pH regulator, 18500 to 19000 parts of a vinyl chloride monomer, 20000 to 21000 parts of deoxidized deionized water, 4.65 to 4.9 parts of a first dispersant, 15.65 to 16.1 parts of a second dispersant, 3.72 to 6.42 parts of a third dispersant, 22.5 to 25 parts of an initiator and 22.5 to 26 parts of an environment-friendly terminator, and is obtained by the following steps: firstly, uniformly spraying the required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser by superheated saturated steam under the anaerobic closed condition, and then using 0.3m3To 0.4m3The mother liquor washes the anti-sticking agent and then the kettle-coating wastewater is washedEmptying; secondly, adding a required amount of pH regulator into a polymerization kettle, simultaneously adding required amounts of deoxidized deionized water and vinyl chloride monomer, mixing for 2min, adding a required amount of No. two dispersant, adding a required amount of No. one dispersant and a required amount of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5-37.5 ℃ and the pressure of 0.40-0.50 MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.04MPa to 0.10MPa, adding a required amount of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin.
The medical high-polymerization-degree polyvinyl chloride resin obtained by the invention has the water content of 0.1-0.2%, high polymerization degree, high oil absorption rate of the resin, excellent processing performance, good chemical inertness and biological safety, and can be widely applied to the field of medical products.
Example 2: the medical high polymerization degree polyvinyl chloride resin comprises, by weight, 5.5 parts or 6 parts of an anti-sticking kettle agent, 1 part or 1.25 parts of a pH regulator, 18500 parts or 19000 parts of a vinyl chloride monomer, 20000 parts or 21000 parts of deoxidized deionized water, 4.65 parts or 4.9 parts of a first dispersant, 15.65 parts or 16.1 parts of a second dispersant, 3.72 parts or 6.42 parts of a third dispersant, 22.5 parts or 25 parts of an initiator and 22.5 parts or 26 parts of an environment-friendly terminator, and is obtained by the following steps: firstly, uniformly spraying the required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser by superheated saturated steam under the anaerobic closed condition, and then using 0.3m3Or 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; in the second step, the required amount of pH regulator is added into the polymerization kettle, and the required amount of deoxygenation agent is added simultaneouslyMixing water and vinyl chloride monomer for 2min, adding a required amount of a second dispersant, adding a required amount of a first dispersant and a required amount of a third dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5 ℃ or 37.5 ℃ and the pressure of 0.40MPa or 0.50MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.04MPa or 0.10MPa, adding a required amount of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin.
At present, the equipment for producing medical polyvinyl chloride resin with high polymerization degree in China is mainly a small polymerization kettle with the size below 70, the capacity is low, the cost is high, and the equipment for producing the medical polyvinyl chloride resin with high polymerization degree is 105m3The outer jacket polymerization kettle effectively solves the problems of low productivity and high cost of medical grade polyvinyl chloride resin with high polymerization degree. The stirring speed of the polymerization kettle in the reaction process is 40r/min to 54 r/min.
Example 3: as an optimization of the above example, the anti-tank agent is a low-polymerization degree phenol formaldehyde resin aqueous solution with a pH value of 12 to 14.
Example 4: as optimization of the above embodiment, the pH regulator is ammonium bicarbonate or sodium bicarbonate.
Example 5: as optimization of the above embodiment, the first dispersant, the second dispersant and the third dispersant are all polyvinyl alcohol, wherein the first dispersant is polyvinyl alcohol with alcoholysis degree of 78.5mol% to 80.5mol%, the second dispersant is polyvinyl alcohol with alcoholysis degree of 71.5mol% to 73.5mol%, and the third dispersant is polyvinyl alcohol with alcoholysis degree of 54.0mol% to 57.0 mol%.
Example 6: in the optimization of the above embodiment, the initiator is an organic peroxide initiator.
Example 7: as the optimization of the embodiment, the environment-friendly terminator is a polyvinyl chloride resin high-efficiency water-soluble terminator.
Example 8: as an optimization of the above embodiment, in the first step, the pressure of the supersaturated steam is in the range of 0.7MPa to 0.8 MPa.
Example 9: as an optimization of the above examples, the polymerization time in the third step was 9 to 10 hours.
In the invention, the vinyl chloride monomer and the deoxidized deionized water are produced by Zhongtai chemical company, and the kettle adhesion preventing agent, the pH regulator, the first dispersant, the second dispersant, the third dispersant, the initiator and the environment-friendly terminator are all commercially available products.
Example 10: the medical polyvinyl chloride resin with high polymerization degree is prepared by the following method: first, 5.5 parts of anti-sticking agent is evenly sprayed on the inner walls of a polymerization kettle and a kettle top condenser by 0.8MPa of superheated saturated steam under the anaerobic and closed conditions, and then 0.3m of anti-sticking agent is sprayed on the inner walls of the polymerization kettle and the kettle top condenser3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding 1 part of pH regulator into a polymerization kettle, simultaneously adding 21000 parts of deoxidized deionized water and 19000 parts of vinyl chloride monomer, mixing for 2min, adding 16.1 parts of No. two dispersant, adding 4.8 parts of No. one dispersant and 3.84 parts of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding 22.5 parts of initiator into the first mixture, and carrying out polymerization reaction for 10 hours at the temperature of 37.5 ℃ and the pressure of 0.45MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.05MPa, 22.5 parts of environment-friendly terminator is added into the first polymer, and the polymerization reaction is finished to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; sixthly, performing solid-liquid separation on the stripped polyvinyl chloride resin slurry with high polymerization degree by using a centrifugal machine, and then drying and dehydrating the polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin slurryPolyvinyl chloride resin with polymerization degree.
Example 11: the medical polyvinyl chloride resin with high polymerization degree is prepared by the following method: first, 6 parts of anti-sticking agent is evenly sprayed on the inner walls of a polymerization kettle and a kettle top condenser by 0.8MPa of superheated saturated steam under the anaerobic and closed conditions, and then the inner walls are sprayed by 0.3m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding 1.25 parts of pH regulator into a polymerization kettle, simultaneously adding 20000 parts of deoxidized deionized water and 18500 parts of vinyl chloride monomer, mixing for 2min, adding 15.65 parts of No. two dispersant, adding 4.65 parts of No. one dispersant and 3.72 parts of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding 24 parts of initiator into the first mixture, and carrying out polymerization reaction for 10 hours at the temperature of 37 ℃ and the pressure of 0.45MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.05MPa, adding 25 parts of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin 1.
Example 12: the medical polyvinyl chloride resin with high polymerization degree is prepared by the following method: first, 6 parts of anti-sticking agent is evenly sprayed on the inner walls of a polymerization kettle and a kettle top condenser by 0.8MPa of superheated saturated steam under the anaerobic and closed conditions, and then the inner walls are sprayed by 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding 1.25 parts of pH regulator into a polymerization kettle, simultaneously adding 20000 parts of deoxidized deionized water and 18500 parts of vinyl chloride monomer, mixing for 2min, adding 15.65 parts of No. two dispersant, adding 4.9 parts of No. one dispersant and 6.42 parts of No. three dispersant, and mixing for 2min to obtain a first mixture; in the third step, 25 parts of a starter is added to the first mixtureA hair agent, which is subjected to polymerization reaction for 10 hours under the conditions that the temperature is 37 ℃ and the pressure is 0.45MPa, so as to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.05MPa, adding 26 parts of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin 2.
In the present invention, the medical high polymerization degree polyvinyl chloride resin 1, and the medical high polymerization degree polyvinyl chloride resin 2 are obtained in example 10, example 11, and example 12, respectively, and each index of the three is superior to the control standard of the superior product. Wherein, the apparent density is higher than 0.42g/ml required by the index, the viscosity number is between 195ml/g and 205ml/g, and the oil absorption value is higher than the index requirement of 36g/100 g. The medical polyvinyl chloride resin 2 with a high degree of polymerization obtained in example 12 was subjected to electron microscope scanning, and the result of the electron microscope scanning is shown in fig. 1. As can be seen from FIG. 1, the medical polyvinyl chloride resin 2 having a high degree of polymerization obtained in example 12 had a regular particle morphology, loose and porous particles, a high oil absorption rate, and a concentrated particle diameter.
In conclusion, the medical high-polymerization-degree polyvinyl chloride resin obtained by the invention has the characteristics of loose and porous particles, regular shape, concentrated particle size, high oil absorption rate and easiness in processing, has good chemical inertia and biological safety, can be widely applied to the field of medical products, has the advantages of high yield and low cost in industrial production of large-scale polymerization kettles, and has better popularization and practicability in the PVC production industry.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
TABLE 1
Claims (9)
1. The medical high-polymerization-degree polyvinyl chloride resin is characterized by comprising, by weight, 5.5-6 parts of an anti-sticking kettle agent, 1-1.25 parts of a pH regulator, 18500-19000 parts of a vinyl chloride monomer, 20000-21000 parts of deoxidized deionized water, 4.65-4.9 parts of a first dispersant, 15.65-16.1 parts of a second dispersant, 3.72-6.42 parts of a third dispersant, 22.5-25 parts of an initiator and 22.5-26 parts of an environment-friendly terminator, and is prepared by the following steps: firstly, uniformly spraying the required amount of anti-sticking agent on the inner walls of a polymerization kettle and a kettle top condenser by superheated saturated steam under the anaerobic closed condition, and then using 0.3m3To 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding a required amount of pH regulator into a polymerization kettle, simultaneously adding required amounts of deoxidized deionized water and vinyl chloride monomer, mixing for 2min, adding a required amount of No. two dispersant, adding a required amount of No. one dispersant and a required amount of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5-37.5 ℃ and the pressure of 0.40-0.50 MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.04MPa to 0.10MPa, adding a required amount of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin.
2. The medical polyvinyl chloride resin having a high degree of polymerization as claimed in claim 1, wherein the tank-releasing agent is an aqueous solution of a phenol resin having a low degree of polymerization and having a pH of 12 to 14.
3. The medical polyvinyl chloride resin with a high degree of polymerization according to claim 1 or 2, wherein the pH adjuster is ammonium bicarbonate or sodium bicarbonate.
4. The medical polyvinyl chloride resin with a high degree of polymerization according to claim 1, 2 or 3, wherein the first dispersant, the second dispersant and the third dispersant are all polyvinyl alcohols, wherein the first dispersant is polyvinyl alcohol with a degree of alcoholysis of 78.5 to 80.5mol%, the second dispersant is polyvinyl alcohol with a degree of alcoholysis of 71.5 to 73.5mol%, and the third dispersant is polyvinyl alcohol with a degree of alcoholysis of 54.0 to 57.0 mol%.
5. The medical polyvinyl chloride resin with a high degree of polymerization according to claim 1, 2, 3 or 4, wherein the initiator is an organic peroxide initiator.
6. The medical polyvinyl chloride resin with high degree of polymerization according to claim 1, 2, 3, 4 or 5, wherein the environmental terminator is a polyvinyl chloride resin high-efficiency water-soluble terminator.
7. The medical high polymerization degree polyvinyl chloride resin according to claim 1, 2, 3, 4, 5 or 6, wherein in the first step, the pressure of the supersaturated steam is 0.7MPa to 0.8 MPa.
8. The medical high-polymerization-degree polyvinyl chloride resin according to any one of claims 1 to 7, wherein in the third step, the polymerization reaction time is 9 to 10 hours.
9. A method for preparing the medical polyvinyl chloride resin having a high degree of polymerization according to any one of claims 2 to 8, which is carried out according to the following method: firstly, uniformly spraying required amount of anti-sticking agent to a polymerization kettle and the kettle top by superheated saturated steam under the condition of oxygen-free sealingAfter the inner wall of the condenser, use 0.3m3To 0.4m3The mother liquor water washes the anti-sticking agent and then empties the coating waste water; secondly, adding a required amount of pH regulator into a polymerization kettle, simultaneously adding required amounts of deoxidized deionized water and vinyl chloride monomer, mixing for 2min, adding a required amount of No. two dispersant, adding a required amount of No. one dispersant and a required amount of No. three dispersant, and mixing for 2min to obtain a first mixture; thirdly, adding the required amount of initiator into the first mixture, and carrying out polymerization reaction at the temperature of 36.5-37.5 ℃ and the pressure of 0.40-0.50 MPa to obtain a first polymer; fourthly, after the reaction pressure of the polymerization kettle is reduced by 0.04MPa to 0.10MPa, adding a required amount of environment-friendly terminator into the first polymer, and finishing the polymerization reaction to obtain polyvinyl chloride resin slurry with high polymerization degree; fifthly, removing the vinyl chloride adsorbed in the high-polymerization polyvinyl chloride resin slurry by using a stripping tower device to obtain stripped high-polymerization polyvinyl chloride resin slurry; and sixthly, performing solid-liquid separation on the stripped high-polymerization-degree polyvinyl chloride resin slurry by using a centrifugal machine, and then, drying and dehydrating the high-polymerization-degree polyvinyl chloride resin slurry in drying equipment to obtain the medical high-polymerization-degree polyvinyl chloride resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634588A (en) * | 2022-03-29 | 2022-06-17 | 内蒙古宜化化工有限公司 | Process and system for the production of polyvinyl chloride |
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| CN1657545A (en) * | 2004-07-30 | 2005-08-24 | 上海天原集团天原化工有限公司 | Process for preparating medical polyvinyl chioride resin with high polymerization |
| KR20080018082A (en) * | 2006-08-22 | 2008-02-27 | 주식회사 엘지화학 | Methods of preparing a vinyl chloride polymer having superior workability |
| CN101921354A (en) * | 2009-06-16 | 2010-12-22 | 中国石油化工股份有限公司 | Preparation method of high transparent polyvinyl chloride resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114634588A (en) * | 2022-03-29 | 2022-06-17 | 内蒙古宜化化工有限公司 | Process and system for the production of polyvinyl chloride |
| CN114634588B (en) * | 2022-03-29 | 2023-06-06 | 内蒙古宜化化工有限公司 | Process for producing polyvinyl chloride |
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