CN102532370A - Method for producing high-degree of polymerization polyvinyl chloride resin by using suspension method - Google Patents
Method for producing high-degree of polymerization polyvinyl chloride resin by using suspension method Download PDFInfo
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- CN102532370A CN102532370A CN2012100054888A CN201210005488A CN102532370A CN 102532370 A CN102532370 A CN 102532370A CN 2012100054888 A CN2012100054888 A CN 2012100054888A CN 201210005488 A CN201210005488 A CN 201210005488A CN 102532370 A CN102532370 A CN 102532370A
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Abstract
The invention discloses a method for producing high-degree of polymerization polyvinyl chloride resin by using a suspension method, which comprises the following steps of: step 1, charging by adopting a constant-temperate water feeding technology, a whole-process airtight feeding technology and a DCS (Distributed Control System) automatic control technology; step 2, producing the high-degree of polymerization polyvinyl chloride resin by adopting a low-temperature method; and step 3, obtaining the high-degree of polymerization polyvinyl chloride resin with a degree of polymerization of 1700-3000. With the adoption of the method for producing the high-degree of polymerization polyvinyl chloride resin by using the suspension method, the high-degree of polymerization polyvinyl chloride resin with a degree of polymerization of 1700-3000 can be produced in a 70 m<3> polymerization kettle system, has the advantages of low energy consumption, large batch production and stable quality and can be produced in the whole year.
Description
Technical field
The present invention relates to the working method of polychloroethylene with high polymerization degree resin, especially at 70m
3Adopt a kind of suspension method to produce the method for polychloroethylene with high polymerization degree resin in the polymeric kettle system.
Background technology
SE (PVC) resin is one of five big general-purpose plastics, is widely used in industry, agricultural, building and other fields.SE (PVC) resin is divided into universal PVC RESINS and polychloroethylene with high polymerization degree resin; There are some defectives in universal PVC RESINS; It can't adapt to high-grade and special processed and applied occasion; The polychloroethylene with high polymerization degree resin (typically refer to mean polymerisation degree more than 1700 or its intermolecular PVC RESINS with slight crosslinking structure) then improved the processing characteristics of universal PVC RESINS; The needs that more adapt to goods such as the special soft goods of processing, high resilience, H.T., high imitative rubber-like and inferior finished product make its goods have higher tensile strength, tearing toughness, elongation at break, wear resistance, high temperature resistant and lower temperature resistance, lower compression permanentset, good softening agent retentivity and the hardness characteristics such as rubber elastic little and unique to variation of temperature.The working method of polychloroethylene with high polymerization degree resin mainly contains two kinds of cold method and chainextender methods at present, there is the little and heat transfer difficulty that causes of still internal-external temperature difference in cold method, reacts difficult control, long reaction time, can only be in shortcomings such as low temperature season productions; The chainextender method has overcome the above-mentioned defective of cold method, yet its production equipment is generally 30m
3Still system or more small-sized 13.5m
3And 7m
3The still system, the level of automation of production equipment is lower, the quality product fluctuation is big.Domestic SE industry general polymeric kettle device at present is 70m
3The polymeric kettle system, but generally all produce universal PVC RESINS, in this system, adopt the chainextender method to produce the polychloroethylene with high polymerization degree resin in batches and do not appear in the newspapers.
Summary of the invention
The objective of the invention is to: the method that provides a kind of suspension method to produce the polychloroethylene with high polymerization degree resin, can be at 70m
3The polymeric kettle system production polymerization degree is 1700～3000 polychloroethylene with high polymerization degree resin, and product energy consumption is low, batch output big, steady quality, and all can produce the whole year.
For realizing above-mentioned purpose, the present invention can take following technical proposals:
The method that a kind of suspension method of the present invention is produced the polychloroethylene with high polymerization degree resin may further comprise the steps:
Step 1: employing waits warm water fed technology, omnidistance airtight fed technology and DCS automatic control technology to feed in raw material
With vinyl chloride monomer, vaal water, dispersion agent, initiator, buffer reagent,, under the control of DCS system, add 70m automatically through waiting warm water fed technology and omnidistance airtight fed technology
3In the polymeric kettle;
Step 2: adopt cold method to produce the polychloroethylene with high polymerization degree resin
Adopt cold method to produce the polychloroethylene with high polymerization degree resin; By the cold method production formula, under agitation condition, vinyl chloride monomer, dispersion agent, initiator, buffer reagent carry out the suspension copolymerization reaction in vaal water; Polymerization temperature is between 36～45 ℃, and polymerization time is 10～16 hours;
Step 3: the acquisition polymerization degree is 1700～3000 polychloroethylene with high polymerization degree resin
Under the control of DCS system; When reaction reaches terminal point; In the trend still, add terminator and stop polyreaction; Polymerization obtains the PVC RESINS slurry, after stripping removes unreacted vinyl chloride monomer, centrifugal drying, can obtain the polymerization degree and be 1700～3000 polychloroethylene with high polymerization degree resin.
Under the control of DCS system, when finishing, polymerization charge can reach temperature of reaction, to avoid the disadvantageous effect of conventional cold feed technology to resin quality.
Said initiator is: peroxy dicarbonate two (2-ethylhexyl) (EHP), one or more compound in the peroxo-neodecanoic acid isopropyl benzene ester (CNP), new peroxide tert-butyl caprate (BNP); Said dispersion agent is: polyvinyl alcohol composite dispersing agent, said Z 150PH (PVA) comprise the compound of two or three in high alcoholysis degree Z 150PH (its alcoholysis degree>=80%), middle alcoholysis degree Z 150PH (its alcoholysis degree 60～70%), the polyvinyl alcohol with low alcoholysis level (its alcoholysis degree≤50%); Said buffer reagent is: yellow soda ash or bicarbonate of ammonia; Said terminator is: have the polyenergic compound terminator of potion, both had the effect that stops polyreaction, the effect that improves the resin thermostability is also arranged.
Said terminator can be selected the HER terminator for use.
Compared with prior art the invention has the beneficial effects as follows: owing to adopt method of the present invention, the production equipment of universal PVC RESINS capable of using is produced the polychloroethylene with high polymerization degree resin, and stable polymerization reaction is easy to control, and operating automation degree is high; Product energy consumption is low, and batch output is big, steady quality.Various materials promptly reach temperature of reaction and begin polyreaction behind reinforced finishing, avoided the low temperature polymerization process that cold feed technology is brought in the conventional production technology, have guaranteed to obtain the polychloroethylene with high polymerization degree resin that MWD is concentrated.It is regular, loose that products obtained therefrom has particle form, centralized particle diameter, the characteristics that flake is few, apparent density is high, plasticizer absorption is high, residual quantity is low.
Embodiment
Embodiment 1:
The DCS system is controlled 5kg bicarbonate of ammonia, 32 tons of hot vaal waters, 25 tons of vinyl chloride monomers, 100kgPVA, 12kg BNP and 7kg CNP materials automatically; Through waiting warm water fed technology and omnidistance airtight fed technology; Under the control of DCS system, add 70m automatically
3In the polymeric kettle,, polymerization charge promptly reaches 36 ℃ temperature of reaction when finishing.Under agitation condition, temperature is controlled at 36 ℃, reacts 14～16 hours; Add 25kg HER terminator and stop polyreaction, obtain the slurry of polychloroethylene with high polymerization degree resin, remove unreacted vinyl chloride monomer through stripping; After the centrifugal drying, can obtain finished product.Said HER is the trade(brand)name of terminator, can directly purchase from market, and manufacturer is a Hangzhou permanent letter auxiliary chemicals ltd.
Embodiment 2:
The DCS system is controlled 5kg yellow soda ash, 32 tons of hot vaal waters, 25 tons of vinyl chloride monomers, 90kgPVA, 10kg EHP and 6.5kg CNP materials automatically; Through waiting warm water fed technology and omnidistance airtight fed technology; Under the control of DCS system, add 70m automatically
3In the polymeric kettle,, polymerization charge promptly reaches 38 ℃ temperature of reaction when finishing.Under agitation condition, temperature is controlled at 38 ℃, reacts 13～15 hours; Add 25kg HER terminator and stop polyreaction, obtain the slurry of polychloroethylene with high polymerization degree resin, remove unreacted vinyl chloride monomer through stripping; After the centrifugal drying, can obtain finished product.
Embodiment 3:
The DCS system is controlled 5kg bicarbonate of ammonia, 32 tons of hot vaal waters, 25 tons of vinyl chloride monomers, 80kgPVA, 9kg BNP and 5kg CNP materials automatically; Through waiting warm water fed technology and omnidistance airtight fed technology; Under the control of DCS system, add 70m automatically
3In the polymeric kettle,, polymerization charge promptly reaches 40.5 ℃ temperature of reaction when finishing.Under agitation condition, temperature is controlled at 40.5 ℃, reacts 10～12 hours; Add 20kg HER terminator and stop polyreaction, obtain the slurry of polychloroethylene with high polymerization degree resin, remove unreacted vinyl chloride monomer through stripping; After the centrifugal drying, can obtain finished product.
Embodiment 4:
The DCS system is controlled 5kg yellow soda ash, 32 tons of hot vaal waters, 25 tons of vinyl chloride monomers, 71kgPVA, 5.5kg EHP and 5kg CNP materials automatically; Through waiting warm water fed technology and omnidistance airtight fed technology; Under the control of DCS system, add 70m automatically
3In the polymeric kettle,, polymerization charge promptly reaches 43 ℃ temperature of reaction when finishing.Under agitation condition, temperature is controlled at 43 ℃, reacts 10～12 hours; Add 20kg HER terminator and stop polyreaction, obtain the slurry of polychloroethylene with high polymerization degree resin, remove unreacted vinyl chloride monomer through stripping; After the centrifugal drying, can obtain finished product.
Through the product that the present invention obtained, to test by standard, test result is following:
| Sequence number | Test event test result | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 1 | Viscosity number, ml/g | 222 | 208 | 191 | 177 |
| 2 | Apparent density, g/ml | 0.44 | 0.46 | 0.48 | 0.48 |
| 3 | Flake, (individual/400cm 2) | 6 | 6 | 4 | 8 |
| 4 | The vinylchlorid residual quantity, μ g/g | 0.1 | 0.1 | 0.1 | 0.1 |
| 5 | The thermal ageing whiteness, % | 86 | 85 | 84 | 84 |
| 6 | 100g resin plasticizer absorbed dose, g | 35 | 34 | 33 | 30 |
Claims (3)
1. a suspension method is produced the method for polychloroethylene with high polymerization degree resin, it is characterized in that may further comprise the steps:
Step 1: employing waits warm water fed technology, omnidistance airtight fed technology and DCS automatic control technology to feed in raw material
With vinyl chloride monomer, vaal water, dispersion agent, initiator, buffer reagent,, under the control of DCS system, add 70m automatically through waiting warm water fed technology and omnidistance airtight fed technology
3In the polymeric kettle;
Step 2: adopt cold method to produce the polychloroethylene with high polymerization degree resin
Adopt cold method to produce the polychloroethylene with high polymerization degree resin; By the cold method production formula, under agitation condition, vinyl chloride monomer, dispersion agent, initiator, buffer reagent carry out the suspension copolymerization reaction in vaal water; Polymerization temperature is between 36～45 ℃, and polymerization time is 10～16 hours;
Step 3: the acquisition polymerization degree is 1700～3000 polychloroethylene with high polymerization degree resin
Under the control of DCS system; When reaction reaches terminal point; In the trend still, add terminator and stop polyreaction; Polymerization obtains the PVC RESINS slurry, after stripping removes unreacted vinyl chloride monomer, centrifugal drying, can obtain the polymerization degree and be 1700～3000 polychloroethylene with high polymerization degree resin.
2. a kind of suspension method according to claim 1 is produced the method for polychloroethylene with high polymerization degree resin; It is characterized in that: under the control of DCS system; When finishing, polymerization charge can reach temperature of reaction, to avoid the disadvantageous effect of conventional cold feed technology to resin quality.
3. a kind of suspension method according to claim 2 is produced the method for polychloroethylene with high polymerization degree resin, it is characterized in that:
Said initiator is: peroxy dicarbonate two (2-ethylhexyl) (EHP), one or more compound in the peroxo-neodecanoic acid isopropyl benzene ester (CNP), new peroxide tert-butyl caprate (BNP);
Said dispersion agent is: polyvinyl alcohol composite dispersing agent, said Z 150PH (PVA) comprise the compound of two or three in high alcoholysis degree Z 150PH, middle alcoholysis degree Z 150PH, the polyvinyl alcohol with low alcoholysis level;
Said buffer reagent is: yellow soda ash or bicarbonate of ammonia;
Said terminator is: have the polyenergic compound terminator of potion, both had the effect that stops polyreaction, the effect that improves the resin thermostability is also arranged.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277169A (en) * | 2014-10-21 | 2015-01-14 | 杭州电化集团有限公司 | Production method of special chlorinated polyvinyl chloride (CPVC) resin |
| CN105273111A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for reducing fouling of steam stripping apparatus during polyvinyl chloride production |
| CN106279477A (en) * | 2016-08-08 | 2017-01-04 | 新疆宜化化工有限公司 | The production method of a kind of modified PVC and process units |
| CN106380531A (en) * | 2016-08-30 | 2017-02-08 | 陕西北元化工集团有限公司 | Preparation method of soft product plastic special polyvinyl chloride resin |
| CN106749797A (en) * | 2016-12-14 | 2017-05-31 | 青海盐湖工业股份有限公司 | A kind of preparation method of polyvinyl chloride |
| CN107236065A (en) * | 2017-06-06 | 2017-10-10 | 滁州市宏源喷涂有限公司 | One kind avoids the method that " flake " is produced in PVC Production Process |
| CN113527557A (en) * | 2021-08-30 | 2021-10-22 | 天能化工有限公司 | Method for isothermal horizontal feeding of vinyl chloride monomer through suspension polymerization |
| CN115340616A (en) * | 2022-08-17 | 2022-11-15 | 新疆中泰化学托克逊能化有限公司 | Production method of bulk polyvinyl chloride MG5 type resin, MG5 type resin and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101812149A (en) * | 2009-11-22 | 2010-08-25 | 天津渤天化工有限责任公司 | Method for producing polyvinyl chloride resin special for battery separators with medium-high polymerization degree |
-
2012
- 2012-01-10 CN CN2012100054888A patent/CN102532370A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101812149A (en) * | 2009-11-22 | 2010-08-25 | 天津渤天化工有限责任公司 | Method for producing polyvinyl chloride resin special for battery separators with medium-high polymerization degree |
Non-Patent Citations (1)
| Title |
|---|
| 杨广鑫等: "国产70m3聚合釜PVC树脂质量的优化控制", 《中国氯碱》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273111A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for reducing fouling of steam stripping apparatus during polyvinyl chloride production |
| CN105273111B (en) * | 2014-06-11 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method of stripper plant fouling in reduction Production of PVC |
| CN104277169A (en) * | 2014-10-21 | 2015-01-14 | 杭州电化集团有限公司 | Production method of special chlorinated polyvinyl chloride (CPVC) resin |
| CN104277169B (en) * | 2014-10-21 | 2017-06-13 | 杭州电化集团有限公司 | A kind of production method of polyvinyl chloride resin used for chlorination |
| CN106279477A (en) * | 2016-08-08 | 2017-01-04 | 新疆宜化化工有限公司 | The production method of a kind of modified PVC and process units |
| CN106380531A (en) * | 2016-08-30 | 2017-02-08 | 陕西北元化工集团有限公司 | Preparation method of soft product plastic special polyvinyl chloride resin |
| CN106749797A (en) * | 2016-12-14 | 2017-05-31 | 青海盐湖工业股份有限公司 | A kind of preparation method of polyvinyl chloride |
| CN106749797B (en) * | 2016-12-14 | 2019-03-05 | 青海盐湖工业股份有限公司 | A kind of preparation method of polyvinyl chloride |
| CN107236065A (en) * | 2017-06-06 | 2017-10-10 | 滁州市宏源喷涂有限公司 | One kind avoids the method that " flake " is produced in PVC Production Process |
| CN113527557A (en) * | 2021-08-30 | 2021-10-22 | 天能化工有限公司 | Method for isothermal horizontal feeding of vinyl chloride monomer through suspension polymerization |
| CN113527557B (en) * | 2021-08-30 | 2022-07-12 | 天能化工有限公司 | Method for isothermal horizontal feeding of vinyl chloride monomer through suspension polymerization |
| CN115340616A (en) * | 2022-08-17 | 2022-11-15 | 新疆中泰化学托克逊能化有限公司 | Production method of bulk polyvinyl chloride MG5 type resin, MG5 type resin and application |
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Application publication date: 20120704 |