CN110172114B - High-quality chloridizable PVC special resin and preparation method and application thereof - Google Patents
High-quality chloridizable PVC special resin and preparation method and application thereof Download PDFInfo
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- CN110172114B CN110172114B CN201910550853.5A CN201910550853A CN110172114B CN 110172114 B CN110172114 B CN 110172114B CN 201910550853 A CN201910550853 A CN 201910550853A CN 110172114 B CN110172114 B CN 110172114B
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- 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
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- C08F114/06—Vinyl chloride
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-quality chloridizable PVC special resin, and further discloses a preparation method and application thereof in processing CPVC resin. The invention relates to a preparation method of high-quality chloridizable PVC special resin, which combines the existing suspension method PVC polymerization production, wherein a PVC wet material with the water content of 25-40% is sealed and packaged, then is frozen in a low-temperature environment below 0 ℃, and is thawed after the resin is completely frozen, the internal structure of PVC resin particles can be changed like the formation of frozen bean curd in the freezing process, loose network channels can be formed in the PVC resin particles, so that chlorine can smoothly pass through the network channels when the PVC special resin is chloridized, the chloridization pressure can be greatly reduced, and the chloridization uniformity can be greatly improved because the network channels are uniformly and smoothly distributed, thereby the processability and the physical and mechanical properties of chloridized products are improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-quality chloridizable PVC special resin, and further discloses a preparation method and application thereof in processing CPVC resin.
Background
Polyvinyl chloride resin (PVC resin for short) is a thermoplastic polymer compound obtained by polymerizing vinyl chloride monomer. Because of its excellent flame retardancy, wear resistance, chemical resistance, transparency, electrical insulation and other characteristics, PVC resin is widely used in industry, building, agriculture, packaging, electric power and other fields, and has become one of the most widely used plastic varieties in the world. Along with the rapid expansion of the yield of the PVC resin in China, the production technology of the suspension PVC resin in China also makes great progress in recent years. However, compared with the foreign advanced technology, the method still has certain gaps in the aspects of production scale, production technology, resin quality, modification technology, resin application and the like. Although the yield of PVC resin in China exceeds that of the United states and becomes the largest PVC resin producing country in the world, the products still account for most of the PVC resin by the general suspension method, and other special and special resins still have the defects of few varieties and small yield.
Chlorinated polyvinyl chloride (CPVC) resin is a resin material obtained by further chlorinating and modifying PVC resin serving as a base material, and is a novel plastic material with a high development speed in the application field in recent years due to excellent performances such as high mechanical strength, heat resistance, flame retardance, chemical medium corrosion resistance and the like. The chloridizable PVC special resin is used as a PVC special resin for producing CPVC, and has the characteristics of loose structure, little or no skin, high porosity, uniform internal structure and the like.
In the prior art, in order to keep technical monopoly and high profit, the production of CPVC resin abroad adopts a vinyl chloride polymerization-chlorination integrated technology, and no company sells special chlorinated resin as an intermediate product. However, the production of domestic CPVC resins is mainly based on the aqueous suspension chlorination process, and the demand for chlorinatable PVC-specific resins is large. In 2012, medium petrochemical Qilu division successfully developed chlorinatable PVC resin QS-C62 produced by a suspension method, and became the only one production and sale enterprise of chlorinatable PVC resin at home and abroad at that time. At present, the domestic PVC resin grades suitable for producing CPVC resin are still limited to QS-C62/C65/C60 products developed by Qilu petrochemical industry, and although the grade of chlorinatable PVC special resin has the characteristics of less coating, large plasticizer absorption amount and easy chlorination compared with general resin, the problem of poor chlorination uniformity still exists in the chlorination process due to the existence of the coating, and further the chlorinated products are difficult to process.
Therefore, the development of a high-quality chloridized PVC special resin with little or no skin membrane and loose and uniform internal network structure is imperative.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a preparation method of high-quality chlorinatable PVC special resin, so as to solve the problem that CPVC resin has poor chlorinatability due to more membranes in the chlorinatable PVC special resin in the prior art;
the second technical problem to be solved by the invention is to provide a high-quality chloridizable PVC special resin with little or no skin and loose and uniform internal network structure, thereby improving the processing performance and physical and mechanical properties of chloridized products.
In order to solve the technical problems, the preparation method of the high-quality chloridizable PVC special resin comprises the following steps:
(1) Taking a chloridizable PVC special resin wet material prepared by a PVC polymerization production process for sealing and packaging for later use;
(2) And (3) freezing the sealed chloridized PVC special resin wet material at the temperature below 0 ℃, thawing the sealed PVC resin after the PVC resin is completely frozen, and filtering water to obtain the required high-quality chloridized PVC special resin.
Specifically, in the step (1), the water content of the chloridizable PVC special-purpose resin wet material is controlled to be 25-40%.
Specifically, in the step (1), the PVC polymerization production process comprises a PVC polymerization production process by an aqueous phase suspension method.
Specifically, in the PVC polymerization production process by the water phase suspension method, the water-oil ratio is controlled to be 1.20-1.60, the polymerization temperature is controlled to be 55-64 ℃, and after the polymerization is finished, the monomers are fully recovered and the resin wet material special for chloridizable PVC is obtained through centrifugal dehydration treatment. The wet material monomer residual quantity is not more than 5mg/kg PVC resin, the coating coverage rate is less than 85%, and the plasticizer absorption capacity of 100g resin after drying can reach 27g.
The invention also discloses the high-quality chloridizable PVC special resin prepared by the method.
The invention also discloses application of the high-quality chloridizable PVC special resin in preparation of chlorinated polyvinyl chloride resin.
The invention also discloses a chlorination process of the high-performance chlorinated polyvinyl chloride resin, which comprises the following steps:
(1) Adding 100 parts by weight of the chloridizable PVC special resin into a reaction kettle, adding 400-600 parts by weight of water and 0.010-0.020 part by weight of initiator, and fully stirring for later use;
(2) Sealing the reaction kettle, heating to 50-80 ℃, and introducing chlorine to start chlorination reaction;
(3) Stopping the reaction when the chlorine consumption reaches a specified value to obtain chlorinated product slurry, and filtering, washing, neutralizing, dehydrating and drying to obtain the required CPVC resin product.
Specifically, the initiator comprises bis (2-ethylhexyl) peroxydicarbonate.
Specifically, the chlorination process of the high-performance chlorinated polyvinyl chloride resin further comprises the step of preparing the high-quality chlorinatable PVC special resin according to the method.
The invention also discloses the high-performance chlorinated polyvinyl chloride resin prepared by the chlorination process.
The preparation method of the high-quality chloridizable PVC special resin combines the existing suspension method PVC polymerization production, the PVC wet material which is produced by polymerization and has 25 to 40 percent of water content after monomer recovery and centrifugation is sealed and packaged, then is frozen in a low-temperature environment below 0 ℃, and is unfrozen after the resin is completely frozen, and the internal structure of PVC resin particles can be changed like frozen bean curd in the freezing process: the PVC wet material freezes the back promptly, and the moisture between the inside hole of loose granule freezes and forms the ice crystal body, this moment because water freezes the back volume increase, and the structure is drawn together around the oppression, and the ice crystal between hole and the hole can be connected to each other, then after unfreezing and moisture volatilize, can form loose network channel in the inside of the special resin of PVC, makes special resin of PVC can make the network channel that chlorine passes through smoothly when carrying out chlorination, can greatly reduced chlorination pressure, simultaneously because network channel distributes evenly and unobstructed, can improve the chlorination homogeneity greatly to the processability and the physical mechanical properties of chlorination product have been improved.
The preparation method of the high-quality chloridizable PVC special resin is simple and easy to implement in process, and is particularly suitable for being used in winter and severe cold areas with the temperature lower than 0 ℃.
Detailed Description
Example 1
The polymerization formula and the process of the QS-65 resin special for chloridized PVC of Qilu Miner company are used, the water-oil ratio is controlled to be 1.26, the polymerization temperature is 58.1 ℃, and the conversion rate is controlled to be 80 percent; and (3) after the reaction is ended, recycling, centrifuging and dehydrating the VCM to obtain a CPVC production raw material-PVC wet material, wherein the water content of the PVC wet material is controlled to be 25%.
Packaging and sealing the PVC wet material by using a packaging bag with an inner liner, wherein each bag is filled with 25-50kg; and then freezing the mixture in a low-temperature environment below 0 ℃, thawing the mixture after the resin is completely frozen, and removing water after the thawing is completely carried out to obtain the required high-quality chloridizable PVC special resin.
Example 2
The polymerization formula and the process of the PVC special resin QS-65 which can be chlorinated by the Qilu division company are used, the water-oil ratio is controlled to be 1.26, the polymerization temperature is 58.1 ℃, and the conversion rate is controlled to be 80%; and (3) after the reaction is ended, recycling, centrifuging and dehydrating the VCM to obtain a CPVC production raw material-PVC wet material, wherein the water content of the PVC wet material is controlled to be 30%.
Packaging and sealing the PVC wet material by using a packaging bag with an inner liner, wherein each bag is filled with 25-50kg; and then freezing the mixture in a low-temperature environment below 0 ℃, thawing the mixture after the resin is completely frozen, and removing water after the thawing is completely carried out to obtain the required high-quality chloridizable PVC special resin.
Example 3
The polymerization formula and the process of the PVC special resin QS-65 which can be chlorinated by the Qilu division company are used, the water-oil ratio is controlled to be 1.26, the polymerization temperature is 58.1 ℃, and the conversion rate is controlled to be 80%; and (3) after the reaction is finished, recovering, centrifuging and dehydrating the VCM to obtain a CPVC production raw material-PVC wet material, wherein the water content of the PVC wet material is controlled to be 40%.
Packaging and sealing the PVC wet material by using a packaging bag with an inner liner, wherein each bag is filled with 25-50kg; and then freezing the mixture in a low-temperature environment below 0 ℃, thawing the mixture after the resin is completely frozen, and removing water after the thawing is completely carried out to obtain the required high-quality chloridizable PVC special resin.
Comparative example 1
The polymerization formula and the process of the QS-65 resin special for chlorinatable PVC of the Qilu division company are used, the water-oil ratio is controlled to be 1.26, the polymerization temperature is 58.1 ℃, the conversion rate is controlled to be 80%, VCM is recycled and discharged after the polymerization reaction is ended, and the resin special for chlorinatable PVC is prepared by the working procedures of steam stripping, centrifugation, drying and the like. The detection shows that the water content in the chloridizable PVC special resin is lower than 0.30 percent.
Comparative example 2
The polymerization formula and the process of the PVC special resin QS-65 which can be chlorinated by the Qilu division company are used, the water-oil ratio is controlled to be 1.26, the polymerization temperature is 58.1 ℃, and the conversion rate is controlled to be 80%; and (3) after the reaction is ended, recycling, centrifuging and dehydrating the VCM to obtain a CPVC production raw material-PVC wet material, wherein the water content of the PVC wet material is controlled to be 30%.
Application example 1
Based on the existing CPVC aqueous phase suspension method production formula and process, 100kg of the special PVC resin (the mass of the wet PVC material without water) prepared in the embodiment 1 is added into a reaction kettle, 467kg of process water and 0.020kg of initiator bis (2-ethylhexyl) peroxydicarbonate are added, and the reaction kettle is closed; controlling the stirring speed to be 80r/min, heating to 70 ℃, and then introducing chlorine and starting to react; in the process, the chlorine introducing speed is controlled, and the pressure and the temperature in the reaction kettle are observed and recorded, so that the pressure in the reaction kettle does not exceed the safe operation value; and (3) finishing the reaction after reaching the specified chlorine flux to obtain chlorinated product slurry, and filtering, washing, neutralizing, dehydrating, drying and packaging the slurry to obtain the chlorinated product. The chlorine content of the CPVC chlorinated product is detected to be about 65-70%.
Application example 2
Based on the existing CPVC aqueous phase suspension method production formula and process, 100kg of the special PVC resin (the mass of the wet PVC material without water) prepared in the embodiment 2 is added into a reaction kettle, 557kg of process water and 0.020kg of initiator bis (2-ethylhexyl) peroxydicarbonate are added, and the reaction kettle is closed; controlling the stirring speed to be 80r/min, heating to 70 ℃, and then introducing chlorine and starting to react; in the process, the chlorine introducing speed is controlled, and the pressure and the temperature in the reaction kettle are observed and recorded, so that the pressure in the reaction kettle does not exceed the safe operation value; and (3) finishing the reaction after reaching the specified chlorine flux to obtain chlorinated product slurry, and filtering, washing, neutralizing, dehydrating, drying and packaging the slurry to obtain the chlorinated product. The chlorine content of the CPVC chlorinated product is about 65-70% by detection.
Application example 3
Based on the existing CPVC aqueous phase suspension method production formula and process, 100kg of the special PVC resin (mass of PVC wet material without water) prepared in the embodiment 3 is added into a reaction kettle, 533kg of process water and 0.020kg of initiator bis (2-ethylhexyl) peroxydicarbonate are added, and the reaction kettle is closed; controlling the stirring speed to be 80r/min, heating to 70 ℃, and then introducing chlorine and starting to react; in the process, the chlorine introducing speed is controlled, and the pressure and the temperature in the reaction kettle are observed and recorded, so that the pressure in the reaction kettle does not exceed the safe operation value; and (3) finishing the reaction after reaching the specified chlorine flux to obtain chlorinated product slurry, and filtering, washing, neutralizing, dehydrating, drying and packaging the slurry to obtain the chlorinated product. The chlorine content of the CPVC chlorinated product is detected to be about 65-70%.
Comparative application example 1
Based on the existing CPVC aqueous phase suspension method production formula and process, 600kg of process water is added into an infiltration kettle, 100kg of PVC QS-C65 resin powder prepared in the comparative example 1 and 0.020kg of dispersing agent PVA80 (polyvinyl alcohol with alcoholysis degree of about 80%) are added, and the mixture is conveyed to a reaction kettle after being soaked; adding 0.020kg of initiator bis (2-ethylhexyl) peroxydicarbonate into the reaction kettle, and sealing the reaction kettle; stirring at the rotation speed of 80r/min, heating to 70 ℃, and introducing chlorine to start reaction; controlling the chlorine introducing speed, and observing and recording the pressure and the temperature in the reaction kettle to ensure that the pressure in the reaction kettle does not exceed the safe operation value; finishing the reaction after reaching the specified chlorine flux to obtain chlorinated product slurry; and filtering, washing, neutralizing, dehydrating and drying the slurry to obtain the CPVC chlorinated product.
Comparative application example 2
Based on the existing CPVC aqueous phase suspension method production formula and process, taking 100kg of PVC resin prepared in comparative example 2 (calculated by the mass of moisture removed from a PVC wet material), adding 600kg of process water (including the moisture in the PVC wet material) and 0.020kg of initiator bis (2-ethylhexyl) peroxydicarbonate into a reaction kettle, and sealing the reaction kettle; stirring at the rotation speed of 80r/min, heating to 70 ℃, and introducing chlorine to start reaction; controlling the chlorine introducing speed, and observing and recording the pressure and the temperature in the reaction kettle to ensure that the pressure in the reaction kettle does not exceed the safe operation value; finishing the reaction after reaching the specified chlorine introducing amount to obtain chlorinated product slurry; and filtering, washing, neutralizing, dehydrating and drying the chlorinated product slurry to obtain the CPVC chlorinated product.
Examples of the experiments
The CPVC chlorinated products prepared in the application examples 1-3 and the comparative application examples 1-2 are respectively subjected to performance detection, and the process parameters and performance test results of all samples are shown in the following table 1.
TABLE 1 Process parameters and Performance test results for each sample
As can be seen from the data in the table, the chloridizable PVC special resin prepared by the method can greatly improve the chloridization uniformity during chloridization treatment, thereby improving the processability and physical and mechanical properties of chlorinated products.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A preparation method of high-quality chloridizable PVC special resin is characterized by comprising the following steps:
(1) The water phase suspension method PVC polymerization production process is adopted to prepare a chloridizable PVC special resin wet material with the water content of 25-40 percent, and the chloridizable PVC special resin wet material is hermetically packaged for later use;
in the water phase suspension method PVC polymerization production process, a polymerization formula and a process of chloridizable PVC special resin QS-65 are used, the water-oil ratio is controlled to be 1.20-1.60, the polymerization temperature is controlled to be 55-64 ℃, and after polymerization is finished, monomers are fully recovered and centrifugal dehydration treatment is carried out to obtain the required chloridizable PVC special resin wet material; the wet monomer residue is not more than 5mg/kg PVC resin, the film coverage rate is less than 85%, and the plasticizer absorption capacity of 100g resin after drying can reach 27g;
(2) And (3) freezing the sealed chloridized PVC special resin wet material at the temperature below 0 ℃, thawing the sealed PVC resin after the PVC resin is completely frozen, and filtering water to obtain the required high-quality chloridized PVC special resin.
2. A high quality chlorinatable PVC specialty resin made by the process of claim 1.
3. Use of the high quality chlorinatable PVC specialty resin described in claim 2 for the preparation of chlorinated polyvinyl chloride resin.
4. A chlorination process of high-performance chlorinated polyvinyl chloride resin is characterized by comprising the following steps:
(1) Adding 100 parts by weight of the chloridizable PVC special resin as described in claim 2 into a reaction kettle, adding 400-600 parts by weight of water and 0.010-0.020 part by weight of initiator, and fully stirring for later use;
(2) Sealing the reaction kettle, heating to 50-80 ℃, and introducing chlorine to start chlorination reaction;
(3) Stopping the reaction when the chlorine consumption reaches a specified value to obtain chlorinated product slurry, and filtering, washing, neutralizing, dehydrating and drying to obtain the required CPVC resin product.
5. The process for chlorinating the high performance chlorinated polyvinyl chloride resin of claim 4, wherein said initiator comprises bis (2-ethylhexyl) peroxydicarbonate.
6. The process for chlorinating the high-performance chlorinated polyvinyl chloride resin according to claim 4 or 5, further comprising a step of preparing the high-quality chlorinatable PVC specialized resin.
7. A high performance chlorinated polyvinyl chloride resin prepared by the chlorination process as claimed in any one of claims 4 to 6.
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| CN112029138A (en) * | 2020-09-09 | 2020-12-04 | 金川集团股份有限公司 | Preparation method of polyvinyl chloride resin special for chlorination |
| CN113583524A (en) * | 2021-09-16 | 2021-11-02 | 金川集团股份有限公司 | Preparation method of coating-grade chlorinated polyvinyl chloride resin |
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| CN106574000A (en) * | 2014-07-22 | 2017-04-19 | 瑞来斯实业公司 | A process for manufacturing chlorinated polyvinylchloride |
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| CN102443085A (en) * | 2011-10-31 | 2012-05-09 | 河北盛华化工有限公司 | Method for preparing polyvinyl chloride resin used for chlorination |
| CN106574000A (en) * | 2014-07-22 | 2017-04-19 | 瑞来斯实业公司 | A process for manufacturing chlorinated polyvinylchloride |
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