CN115340616A - Production method of bulk polyvinyl chloride MG5 type resin, MG5 type resin and application - Google Patents
Production method of bulk polyvinyl chloride MG5 type resin, MG5 type resin and application Download PDFInfo
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- CN115340616A CN115340616A CN202210985496.7A CN202210985496A CN115340616A CN 115340616 A CN115340616 A CN 115340616A CN 202210985496 A CN202210985496 A CN 202210985496A CN 115340616 A CN115340616 A CN 115340616A
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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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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/03—Organic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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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
- C08F2/02—Polymerisation in bulk
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/38—Mixtures of peroxy-compounds
Abstract
The invention relates to a production method of a main body polyvinyl chloride MG5 type resin, the MG5 type resin and application, relating to the field of polyvinyl chloride resin and comprising the following steps: step 1: preparing seeds; step 2: adding solid auxiliary agent into a polymerization kettle, vacuumizing to remove oxygen, transferring all seeds into the polymerization kettle, adding 75% of CNP,50% of EHP, nitric acid and VC monomer; and step 3: heating a polymerization kettle, controlling the pressure to be 0.7-0.75 MPa 150 minutes before reaction when the pressure in the polymerization kettle is increased to be 0.7-0.75 MPa, uniformly increasing the pressure to be 0.80MPa after the reaction is carried out for 150 minutes, and controlling the reaction time to be 200-220 minutes to obtain a polymerization product; and 4, step 4: degassing recovery and stripping are carried out in sequence. The conversion rate of the chloroethylene is improved by more than 5%, and the prepared resin has the advantages of good thermal stability, regular product particles, less fine particles and good processability.
Description
Technical Field
The invention relates to the field of polyvinyl chloride resin, and particularly relates to a production method of bulk polyvinyl chloride MG5 type resin, MG5 type resin and application.
Background
Polyvinyl chloride (PVC), which is an initiator for Vinyl Chloride Monomer (VCM), in the presence of peroxides, azo compounds, etc.; or a polymer polymerized by a free radical polymerization mechanism under the action of light and heat. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively referred to as vinyl chloride resins. The product has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like.
In the polymerization of polyvinyl chloride, in order to simplify the production process and reduce energy consumption, a bulk polymerization process was developed by atrox francisco in 1956. At present, a polymerization device of a bulk polymerization method mainly comprises a vertical prepolymerization kettle and a horizontal polymerization kettle with a frame type stirrer; the polymerization is carried out in two stages, the monomer and the initiator are prepolymerized for 1h in a prepolymerization kettle in the first stage of polymerization to generate seed particles, the conversion rate reaches 8-10%, then the seed particles flow into a second stage of polymerization kettle, the monomer with the same amount as the prepolymer is replenished, the polymerization is continued, the residual monomer is discharged when the conversion rate reaches 50-60%, and the finished product is obtained after crushing and sieving. The particle size and particle shape of the resin are controlled by the stirring speed, and the reaction heat is brought out by monomer reflux condensation. However, the polyvinyl chloride bulk polymerization MG5 type resin mainly has the following problems: (1) The initiator is compounded by ACSP (acetyl cyclohexyl sulfonate peroxide) and EHP, and the ACSP initiator is gradually eliminated at present due to low decomposition temperature, high risk and high toxicity; (2) the polymerization time is shorter than 180 minutes, and the conversion rate is lower; (3) The polymerization is controlled by constant pressure of 0.75MPa, the decomposition amount of the initiator is less, the residue is more, and the thermal stability of the product is lower; and (4) the product has more fine particles and poorer particle concentration.
In view of the above problems, the present invention provides a method for producing bulk polyvinyl chloride MG 5-type resin and MG 5-type resin.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing a polyvinyl chloride MG5 type resin, the MG5 type resin and application. Aims to improve the conversion rate of chloroethylene in a bulk polymerization method, and ensure that the prepared polyvinyl chloride MG5 type resin has good thermal stability, regular product particles, less fine particles and good processability.
The present invention has been made to solve the above problems, and a first object of the present invention is to provide a method for producing a bulk polyvinyl chloride MG 5-type resin, comprising the steps of:
step 1: preparing seeds: firstly, vacuumizing a prepolymerization kettle, adding 16500-17500 parts by weight of VC (vinyl chloride) monomer, 7-9 parts by weight of EHP (peroxydicarbonate bis (2-ethylhexyl)) initiator with the mass fraction of 50% and a proper amount of nitric acid, heating the prepolymerization kettle at a stirring speed of 90-120 pmr, starting heat dissipation when the pressure reaches 1.18-1.20 MPa, controlling the pressure at 1.20 +/-0.02 MPa, and performing prepolymerization reaction for 9-12 minutes to complete the preparation of seeds; wherein hot water can be introduced into the prepolymerization kettle through a jacket for heating, heat dissipation is started when the pressure reaches 1.18-1.20 MPa, the jacket of the prepolymerization kettle and a condenser are switched with cold water, and the pressure is controlled at 1.20 +/-0.02 MPa through an adjusting valve;
and 2, step: feeding and filling a polymerization kettle: firstly, adding 1.1-2.2 parts by weight of solid auxiliary agent into a polymerization kettle, vacuumizing to remove oxygen, transferring all the seeds prepared in the step 1 into the polymerization kettle, and then adding 8-10 parts by weight of 75% CNP (initiator cumyl peroxyneodecanoate) initiator and 10500-13500 parts by weight of proper amount of nitric acid and VC monomer into the polymerization kettle, wherein the mass fraction of the CNP initiator is 10-13 parts by weight of 50% EHP, and the mass fraction of the CNP initiator is from 10500-13500 parts by weight to 28000-30000 parts by weight, so as to finish the charging and filling of the polymerization kettle;
and step 3: polymerization reaction: heating a polymerization kettle which is filled with materials, stopping heating when the pressure in the polymerization kettle rises to 0.7-0.75 MPa, starting heat dissipation, performing polymerization reaction under the condition of controlling the pressure of the polymerization kettle, controlling the pressure to be 0.7-0.75 MPa 150 minutes before the first stage of the polymerization reaction, controlling the pressure to rise from 0.7-0.75 MPa to 0.80MPa at a constant speed 150 minutes after the second stage of the polymerization reaction, controlling the polymerization reaction time to be 200-220 minutes, and finishing the polymerization reaction when the pressure of the polymerization reaction is reduced to obtain a polymerization product; wherein hot water with the temperature of 80-85 ℃ is introduced into the polymerization kettle which is filled by the material feeding through the jacket and the condenser jacket for heating, when the pressure in the polymerization kettle rises to 0.7-0.75 MPa, the heating is stopped, the introduction of the hot water is stopped, the heat dissipation is started to be switched into cold water, and the polymerization reaction is carried out under the condition that the pressure of the polymerization kettle is controlled by the polymerization kettle jacket cold water regulating valve and the condenser cold water regulating valve;
and 4, step 4: and (3) degassing, recovering and stripping the polymerization product obtained in the step (3) in sequence to obtain the polyvinyl chloride MG5 type resin.
The invention has the beneficial effects that: compared with the existing bulk polymerization method, the method adopts initiator cumyl peroxyneodecanoate (CNP) and bis (2-ethylhexyl) peroxydicarbonate (EHP) to carry out compounding; the polymerization time is 200 to 220 minutes; constant pressure control is adopted 150 minutes before polymerization, the pressure is uniformly increased to 0.80Mpa 150 minutes later, the conversion rate of the chloroethylene is improved by more than 5 percent, and the prepared polyvinyl chloride MG5 type resin has good thermal stability, regular product particles, less fine particles and good processability.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step 2, 1.3-2.0 parts by weight of solid auxiliary agent is added into a polymerization kettle, after vacuumizing and deoxidizing, all the seeds prepared in the step 1 are transferred into the polymerization kettle, 8.5-9.5 parts by weight of 75% mass of CNP initiator is added, the mass fraction is 50% EHP 11-12 parts by weight, a proper amount of nitric acid and a VC monomer 10500-13500 parts by weight.
Further, if the nitric acid in the step 1 and the step 2 adopts 20% by mass, 1.26-1.89 parts by weight of 20% by mass of nitric acid is added in the step 1, and 0.63-1.26 parts by weight of 20% by mass of nitric acid is added in the step 2; the solid auxiliary agent comprises 1-2 parts by weight of antioxidant and 0.1-0.2 part by weight of thickening agent. The antioxidant can adopt antioxidant BHT, and the thickener can adopt thickener CT5.
Further, heating the polymerization kettle after the feeding and filling in the step 3, stopping heating when the pressure in the polymerization kettle rises to 0.71-0.74 MPa, starting heat dissipation, performing polymerization reaction under the condition of controlling the pressure in the polymerization kettle, controlling the pressure to be 0.71-0.74 MPa 150 minutes before the polymerization reaction, and increasing the pressure to be 0.71-0.74 MPa at a constant speed after the polymerization reaction is carried out for 150 minutes.
Further, the speed is less than or equal to 0.001MPa/min in the pressure increasing process of increasing the pressure to 0.80MPa in the step 3.
The adoption of the further scheme has the beneficial effects that under the optimized conditions, the conversion rate of vinyl chloride is higher, the thermal stability of the prepared polyvinyl chloride MG5 type resin is better, the product particles are more regular, and the fine particles are less.
Further, the specific method for degassing and recycling in the step 4 comprises the following steps: and (3) degassing and recovering the unconverted VC monomer in the polymerization product obtained in the step (3).
Further, the specific method of stripping in step 4 is: introducing water vapor into the polymerization product recovered by degassing, simultaneously adding glycerol with the volume ratio of (3-4.8) and (2-3.2) and ammonia water with the mass fraction of 20 percent by using a metering pump, and then vacuumizing to further remove the residual VC monomer.
The beneficial effect of adopting the further scheme is that: and (3) degassing and recovering the polymerization product obtained in the step (3), and further purifying by steam stripping to obtain the purity of the polyvinyl chloride MG5 type resin meeting the production requirement.
Further, the method also comprises the step 5: and (4) discharging and grading, sucking the polyvinyl chloride MG5 type resin obtained in the step (4) to a product receiving groove through a negative pressure pneumatic conveying system, and conveying, homogenizing and packaging the screened polyvinyl chloride MG5 type resin.
The second purpose is to provide a bulk polyvinyl chloride MG5 type resin, which is prepared by the production method of the bulk polyvinyl chloride MG5 type resin.
The third purpose is to provide the application of the bulk polyvinyl chloride MG5 type resin, and the application of the polyvinyl chloride MG5 type resin in food or medical products.
The beneficial effect who adopts above-mentioned scheme is: because the adopted nontoxic composite initiator (initiator cumyl peroxyneodecanoate (CNP) is compounded with bis (2-ethylhexyl) peroxydicarbonate (EHP)), the product can be directly used for food and pharmaceutical products.
Drawings
FIG. 1 is an electron micrograph of example 1 of the present invention;
FIG. 2 is an electron micrograph of example 6 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The production method of the polyvinyl chloride MG5 type resin comprises the following steps:
first, preparation of seeds
Vacuumizing the prepolymerization reactor, adding 17.0 tons of VC monomer (chloroethylene) and 8Kg 50% EHP initiator, 1.5L 20% nitric acid (density is 1.26 g/ml), introducing hot water into the jacket of the prepolymerization reactor at a stirring speed of 90pmr to heat, switching cold water between the jacket of the prepolymerization reactor and a condenser when the pressure reaches 1.20MPa, controlling the pressure to be constant at 1.20MPa by an adjusting valve, and carrying out prepolymerization reaction for 10 minutes to finish the preparation of seeds
Secondly, the polymerization kettle is filled with materials
And (3) mixing a solid auxiliary agent: adding 2000g of antioxidant BHT and 200g of thickener CT into a polymerization kettle, vacuumizing to remove oxygen, transferring all the seeds prepared in the prepolymerization kettle into the polymerization kettle, adding 75% of initiator CNP 9Kg, adding 1.0L of initiator EHP 50% of 12Kg nitric acid 20, and adding VC monomer to 30 tons to complete the feeding and filling of the polymerization kettle;
third, polymerization
Introducing hot water of 85 ℃ into a polymerization kettle jacket and a condenser jacket for heating, stopping introducing the hot water when the pressure in the polymerization kettle rises to 0.75MPa, and switching to cold water;
controlling the pressure of a polymerization kettle by a polymerization kettle jacket cold water regulating valve and a condenser cold water regulating valve, controlling the constant pressure at 0.75MPa in 150 minutes before polymerization reaction, increasing the pressure from 0.75MPa to 0.80MPa (the pressure increasing speed is 0.001 MPa/min) at a constant speed after 150 minutes, controlling the polymerization reaction time at 220 minutes, and finishing the reaction when the pressure of the polymerization reaction is reduced to obtain a polymerization product;
the fourth step, degassing recovery and stripping
After the reaction is finished, recovering unconverted monomers in the obtained polymerization product through degassing; introducing steam into the powder in the polymerization kettle, simultaneously adding 4.8L of glycerol and 3.2L of ammonia water (20%) by using a metering pump, and vacuumizing to remove residual monomers;
fifthly, discharging and grading; and sucking the obtained polyvinyl chloride MG5 type resin in the polymerization kettle to a product receiving groove through a negative pressure pneumatic conveying system, and conveying, homogenizing and packaging the screened obtained polyvinyl chloride MG5 type resin.
Examples 2 to 5
Examples 2 to 5 were the same as example 1 except that the amounts of the additives and the reaction conditions in Table 1 were different from those in example 1.
Table 1 examples 2 to 3
Table 2 examples 4 to 5
Example 6: comparative example
As compared with example 1, the percentage of the initiator cumene peroxyneodecanoate CNP75% in the second step was replaced by ACSP 75% by 9Kg (acetyl cyclohexylsulfonate peroxide); and (3) carrying out a third polymerization reaction: reacting for 220 minutes under the constant pressure of 0.75 MPa; the remaining parameters and process control were the same as in example 1.
Example 7: detection experiment
The conversion and PVC quality index of the samples of examples 1 to 5 and the control are shown in Table 3 (the PVC quality index is determined according to the national standard HG/T4076-2008).
Table 3 experimental results of examples 1 to 5 and comparative example
As shown in Table 1, the MG5 type resin produced by the invention has the advantages of high conversion rate of more than 5%, complete initiator consumption, good thermal stability, thermal aging whiteness (160 ℃) more than 80%, more than or equal to 63 μm particles reaching 98.5%, regular product particles, less fine particles, good processing performance under the condition that the electron micrographs of figures 1 and 2 are the same magnification, and detailed figures 1 and 2.
In conclusion, the bulk polymerization method adopted by the invention has higher vinyl chloride conversion rate, and the prepared polyvinyl chloride MG5 type resin has good thermal stability, regular product particles, less fine particles and good processability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for producing a bulk polyvinyl chloride MG5 type resin is characterized by comprising the following steps:
step 1: preparing seeds: vacuumizing a prepolymerization kettle, adding 16500-17500 parts by weight of VC monomer, 7-9 parts by weight of EHP initiator with the mass fraction of 50% and proper amount of nitric acid, radiating when the pressure reaches 1.18-1.20 MPa, controlling the pressure to be 1.20 +/-0.02 MPa, and performing prepolymerization reaction for 9-12 minutes to finish the preparation of seeds;
step 2: feeding and filling of a polymerization kettle: firstly, adding 1.1-2.2 parts by weight of solid auxiliary agent into a polymerization kettle, vacuumizing to remove oxygen, transferring all the seeds prepared in the step 1 into the polymerization kettle, adding 8-10 parts by weight of 75% CNP initiator, which is 50% EHP, 10-13 parts by weight of proper amount of nitric acid and 10500-13500 parts by weight of VC monomer, and finishing the charging of the polymerization kettle;
and step 3: polymerization reaction: heating a polymerization kettle which is filled with materials, stopping heating when the pressure in the polymerization kettle rises to 0.7-0.75 MPa, starting heat dissipation, performing polymerization reaction under the condition of controlling the pressure of the polymerization kettle, controlling the pressure to be 0.7-0.75 MPa 150 minutes before the first stage of the polymerization reaction, controlling the pressure to rise from 0.7-0.75 MPa to 0.80MPa at a constant speed 150 minutes after the second stage of the polymerization reaction, controlling the total time of the polymerization reaction to be 200-220 minutes, and finishing the polymerization reaction when the pressure of the polymerization reaction is reduced to obtain a polymerization product;
and 4, step 4: and (4) degassing, recovering and stripping the polymerization product obtained in the step (3) in sequence to obtain the polyvinyl chloride MG5 type resin.
2. The method for producing a bulk polyvinyl chloride MG 5-type resin according to claim 1, wherein in step 2, 1.3 to 2.0 parts by weight of the solid auxiliary is added to a polymerization vessel, vacuum is applied to remove oxygen, the whole seed prepared in step 1 is transferred to the polymerization vessel, 8.5 to 9.5 parts by weight of 75% by weight of the CNP initiator, 11 to 12 parts by weight of EHP, and appropriate amounts of nitric acid and VC monomer are added thereto, 10500 to 13500 parts by weight.
3. The method for producing a bulk polyvinyl chloride MG5 type resin according to claim 2, wherein if 20% by mass of nitric acid is used as the nitric acid in the steps 1 and 2, 1.26 to 1.89 parts by mass of 20% by mass of nitric acid is added in the step 1, and 0.63 to 1.26 parts by mass of 20% by mass of nitric acid is added in the step 2; the solid auxiliary agent comprises 1-2 parts by weight of antioxidant and 0.1-0.2 part by weight of thickening agent.
4. The method for producing a bulk polyvinyl chloride MG5 type resin according to claim 1, wherein in step 3, the polymerization vessel in which the charging is completed is heated, and when the pressure in the polymerization vessel rises to 0.71 to 0.74MPa, the heating is stopped and the heat dissipation is started, and the polymerization is carried out under the condition of controlling the pressure in the polymerization vessel, wherein the pressure is controlled to 0.71 to 0.74MPa 150 minutes before the polymerization, and the pressure is uniformly raised to 0.80MPa from 0.71 to 0.74MPa 150 minutes after the polymerization.
5. The method for producing a bulk polyvinyl chloride MG5 type resin of claim 1 or 4, wherein the pressure raising rate in the step 3 up to 0.80MPa is 0.001MPa/min or less.
6. The method of producing a bulk polyvinyl chloride MG 5-type resin according to claim 1, wherein the degassing recovery in step 4 comprises: and (3) degassing and recovering the unconverted VC monomer in the polymerization product obtained in the step (3).
7. The method for producing bulk polyvinyl chloride MG5 type resin according to claim 1, wherein the specific method of stripping in step 4 is: introducing water vapor into the polymerization product recovered by degassing, simultaneously adding (3-4.8) of glycerol and 20% of ammonia water by mass percentage, and then vacuumizing to further remove the residual VC monomer.
8. The method of producing a bulk polyvinyl chloride MG5 type resin of claim 1, further comprising a step 5 of: and (4) discharging and grading, namely sucking the polyvinyl chloride MG5 type resin obtained in the step (4) to a product receiving groove through a negative pressure pneumatic conveying system, and conveying, homogenizing and packaging the screened polyvinyl chloride MG5 type resin.
9. A bulk polyvinyl chloride MG 5-type resin prepared by the method for producing a bulk polyvinyl chloride MG 5-type resin according to any one of claims 1 to 8.
10. Use of the bulk polyvinyl chloride MG 5-type resin according to claim 9, wherein the polyvinyl chloride MG 5-type resin is used in food or pharmaceutical products.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288476A (en) * | 1998-11-20 | 2001-03-21 | Lg化学株式会社 | Method of preparing vinyl chloride resin having high impact strength and low die swell |
| 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 |
| CN102276774A (en) * | 2011-04-28 | 2011-12-14 | 内江市运通塑料助剂有限公司 | Feeding technology and apparatus used in bulk polymerization method for preparing vinyl chloride and acrylic ester copolymer resin |
| CN102532370A (en) * | 2012-01-10 | 2012-07-04 | 杭州电化集团有限公司 | Method for producing high-degree of polymerization polyvinyl chloride resin by using suspension method |
| CN107056972A (en) * | 2017-05-04 | 2017-08-18 | 宜宾天原集团股份有限公司 | A kind of bulk PVC manufacturing technique method |
| CN107151282A (en) * | 2017-05-04 | 2017-09-12 | 宜宾天原集团股份有限公司 | A kind of bulk PVC manufacturing technique method |
-
2022
- 2022-08-17 CN CN202210985496.7A patent/CN115340616A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288476A (en) * | 1998-11-20 | 2001-03-21 | Lg化学株式会社 | Method of preparing vinyl chloride resin having high impact strength and low die swell |
| 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 |
| CN102276774A (en) * | 2011-04-28 | 2011-12-14 | 内江市运通塑料助剂有限公司 | Feeding technology and apparatus used in bulk polymerization method for preparing vinyl chloride and acrylic ester copolymer resin |
| CN102532370A (en) * | 2012-01-10 | 2012-07-04 | 杭州电化集团有限公司 | Method for producing high-degree of polymerization polyvinyl chloride resin by using suspension method |
| CN107056972A (en) * | 2017-05-04 | 2017-08-18 | 宜宾天原集团股份有限公司 | A kind of bulk PVC manufacturing technique method |
| CN107151282A (en) * | 2017-05-04 | 2017-09-12 | 宜宾天原集团股份有限公司 | A kind of bulk PVC manufacturing technique method |
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