CN106749793A - A kind of preparation method of Corvic - Google Patents
A kind of preparation method of Corvic Download PDFInfo
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- CN106749793A CN106749793A CN201610254681.3A CN201610254681A CN106749793A CN 106749793 A CN106749793 A CN 106749793A CN 201610254681 A CN201610254681 A CN 201610254681A CN 106749793 A CN106749793 A CN 106749793A
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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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- 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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- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the field of chemical synthesis, specifically related to a kind of preparation method of Corvic, concretely comprise the following steps in water, VCM, compound dispersing agent, polymerization stabilizer, chain-transferring agent, PH buffers and initiator addition polymeric kettle, in 1.00~1.10 MPa, polymerisation is carried out at 60 DEG C~70 DEG C, when keeping polymerization temperature to polymerization pressure 0.15~0.25MPa of decline, reaction terminating agent is added, the remaining VCM of discharge, then collects target product from product.The advantage of the invention is that it is high to obtain PVC spherical resin circularity using this preparation method, apparent density is high, gas porosity is high, ageing whiteness is high, can be good at meeting the commercial development and production of PVC spherical resin,, for meeting China's economic development, shorten also has great significance with the gap of international advanced technology level for this.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to a kind of preparation method of Corvic.
Background technology
Polyvinyl chloride (PVC) spherical resin, outward appearance is in spherical shape, and particle diameter is more than 105 microns, and average shape factor is more than 0.90, apparent density is high, internal void is uniform, particle surface is smooth, dry good fluidity.In extrusion processing tubing and profile shapes, extruder screw can be filled up rapidly and the effect of height density is reached, in the presence of heat and shearing force, melting speed is fast, and melt viscosity is low, good fluidity, gel degree is high, good processability, it is easy to batch mixing, extrusion frictional heat is low, without heat spot, resulting product quality is high, therefore spherical resin is suitable for high speed extrusion processing request, even if the speed of extrusion molding processing, is also far longer than aspherical resin under same rotating speed.The performance of PVC spherical resins is better than common suspending resin, is mainly manifested in the following aspects：(1) spherical resin particle profile (common PVC resin shape factor 0.76 spherical in shape；And spherical resin>0.90), granule regularizing degree is high.(2)
Spherical resin internal void is uniform, and porosity is about 0.05~0.5 ㎝3/ g, specific surface is big.(3) spherical resin apparent density is high, about 0.5~0.67 ㎝3/ g is higher by 15% or so than same degree of polymerization suspension ordinary resin.(4) the dry good fluidity of spherical resin, easily plastifies during processing, and melt rheological property is good, and heat endurance is good.(5) with antistatic behaviour.Heavy caliber pipe is processed with spherical resin, the rate of extrusion of extruder can be made to improve 15~25%, tubing cost is greatly reduced, and pipe workpiece quality is good；During production PVC spherical resins, because the resin particle for generating keeps spherical, therefore viscous kettle is lighter；Compared with ordinary resin, packing factor is big, can largely save packaging and freight.In addition, PVC spherical resins not only can also act as various profile shapes, clear sheet and packaging material etc. as tubing speciality resin.
The country is mostly PVC-SG4,5 resins for the resin of PVC production, the tubing of small-bore (110mm) can only be produced with this resin, and obtained pipe workpiece quality is not high, low production efficiency, high cost, when especially doing heavy caliber pipe, because of reasons such as resin particle forms, bubble is also easy to produce, plasticizing capacity is low, heat endurance is poor, so as to have a strong impact on quality of item.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Corvic, the defect in currently available technology is can solve the problem that, novel tube is obtained with this resin dedicated.
The preparation method of Corvic of the present invention, comprises the following steps：
（1）By water, VCM, composite dispersing agent, polymerization stabilizer, chain-transferring agent, PH buffers and initiator are added and are provided with the polymeric kettle of agitating device, pressure is evacuated to for 1.0~1.1MPa, wherein, the addition of water is 1.2~2 times of VCM quality, composite dispersing agent is the 0.05~0.07% of VCM quality, polymerization stabilizer is the 0.001%~0.1% of VCM quality, chain-transferring agent is the 0~0.20% of VCM quality, PH buffers addition is so that the PH of reaction system is controlled 5.5~7, initiator is the 0.01~0.20% of VCM quality；
（2）It is warming up to 60 DEG C~70 DEG C, proceed by polymerisation, holding polymerization temperature is when polymerization pressure declines 0.15~0.25MPa, add reaction terminating agent, reaction terminating agent addition is the 0.01~0.05% of VCM quality, the remaining VCM of discharge, then collects target product from product.
Wherein, water is preferably deionized water, and its electrical conductivity is 1~5 μ s/cm.The addition of water is preferably 1.4~1.8 times of VCM quality, and water-oil factor is too small, and polymerisation appearance is unstable, and resin particle distribution broadens, and a large amount of bulky grains and " flake ", the excessive then production efficiency reduction of water-oil factor easily occurs.
Composite dispersing agent is preferably the polyvinyl alcohol of two kinds of partial alcoholysis and the mixture of hydroxypropyl methyl cellulose.
Two kinds of above-mentioned polyvinyl alcohol of partial alcoholysis are alcoholysis degree 70~90%, preferably 78~82%, viscosity is 40~55 mPa.s (at 20 DEG C, during 4% concentration determine) alcoholysis degree high in viscosity PVA I and alcoholysis degree be 40~50%, preferably 42~46%, viscosity is (25 DEG C of 60~120mPa.s, under 35% concentration determine) the high-viscosity PVA II of low alcoholysis level, wherein the consumptions of PVA I are that the consumption of 0.006~0.03%, the PVA II of VCM quality is the 0.02~0.07% of VCM quality.PVA I can reduce the surface tension of system, play a part of the colloid protection ability and dispersibility of coordination system, make polymerization system while certain protection drop ability is kept, and take into account dispersibility, prevent viscous kettle, hang oar.This dispersant of PVA II is in oil-soluble, during chloroethylene polymerization influence can be produced on the primary particle in polyvinyl chloride particles and its aggregation, the porousness of resin particle is improved, resin internal void uniformity is improved, resin particle surfaces epithelium fold situation is reduced.The unit of alcoholysis degree is molar fraction in the present invention, and PVA is the English abbreviation of polyvinyl alcohol.
The methoxyl substitution of above-mentioned hydroxypropyl methyl cellulose is preferably 20~40%, more preferably 25~35%；Hydroxypropyl substitution value is preferably 5~15%, more preferably 5~10%, and viscosity is preferably 30~70mPa.s (20 DEG C, determined during 2% concentration), more preferably 40~60 mPa.s (20 DEG C, determined during 2% concentration).The consumption of hydroxypropyl methyl cellulose is the 0.01~0.05% of VCM quality.Hydroxypropyl methyl cellulose plays the drop effect of dispersion vinyl chloride in system, while having certain protective role to vinyl chloride drop, being attached to vinyl chloride droplet surface can preferably coordinate droplet distribution-coalescence, prevent out coarse fodder.
Polymerization stabilizer is preferably C7~C16Fatty acid zinc heat stabilizer, more preferably C7~C10Fatty acid zinc heat stabilizer.The effect of polymerization stabilizer is in the presence of strong mixing, its colloid protection ability that dispersant can be effectively reduced in polymerization initial stage, the coalescence of drop (particle) is set to be completed compared with early stage in polymerization, at this moment the viscosity of drop (particle) is smaller, the trend of still oriented spherical development after coalescence, final prepared regularity spheroidal particle higher.
In addition, the degree of polymerization of the universal polyvinyl chloride resin of suspension method is controlled by polymerization temperature.When oligomeric resin is produced, it is simple to improve polymerization temperature, resin property can develop to unfavorable direction, as the side chain of resin is more, stability is poor, whiteness is low, so generally requiring to add chain-transferring agent to adjust polymerization temperature when oligomeric resin is produced, it is ensured that produce the resin of same polymeric degree at a lower polymerization temperature.
Chain-transferring agent is preferably mercaptan compound, trichloro ethylene, carbon tetrachloride or the chloro- 1- iodoethane of 1-, wherein with preferable using mercaptan compound, mercaptan compound is preferably 2 mercapto ethanol, thioglycollic acid-2-ethyl hexyl ester, isooctyl thioglycolate or ethylene glycol dimercapto acetate, wherein again with 2 mercapto ethanol as best.Chain-transferring agent consumption is preferably the 0.005~0.15% of VCM quality.Chain-transferring agent can once be added before polymerization, or a part is added before polymerization starts, and another part starts certain hour and adds in polymerization.
PH buffers are preferably NaOH, sodium acid carbonate or ammonium hydrogen carbonate, the still ammonium salt class PH buffer maximum for improving the contribution of resin gas porosity, therefore preferably ammonium hydrogen carbonate, and it can improve resin particle form, improve the regularity of resin particle.
Initiator is preferably organic peroxide initiator or azo-initiator, therefore can be combined for one or more in the new heptanoic acid tert-butyl ester of peroxidating, cumyl peroxyneodecanoate, peroxidating pivalic acid spy pentyl ester, peroxide tert pivalate ester, peroxy dicarbonate pair-initiator such as (2- Octyl Nitrites) or ABVN.
Reaction terminating agent is preferably acetone semicarbazone thiocarbamide, bisphenol-A, diethyl hydroxylamine or natrium nitrosum.
The advantage of the invention is that：Using polyvinyl chloride resin obtained in this preparation method, kettle is not glued in polymerization, gained resin particle form is regular, and fine particle content is less, apparent density is high, dry good fluidity, easily plasticizing, and melt rheological property is good, heat endurance is high, and resin particle size is easily controlled, with larger industrializing implementation prospect.
Specific embodiment
Embodiment 1：
Polymerisation is carried out in 375L polymeric kettles, kettle internal diameter D=700mm, straight tube height H=740mm, the leaf 90 of two-layer two0Flat paddle, four pieces of upright flat baffle plates, speed of agitator is 180r/min.Process conditions and process are summarized as follows：First by II 35.0g of 8.5g, PVA of deionized water 180kg, PVA I, hydroxypropyl methyl cellulose 15.0g, C7~C10Fatty acid zinc heat stabilizer 70.0g, 2 mercapto ethanol 30.0g, ABVN 70.0g, NH4HCO3In 30.0g input kettles, start stirring after pressure testing, VCM 100kg is added after being evacuated to 1.0MPa, pre- stirring 15 minutes is passed through 90 DEG C of hot water to chuck, it is warming up to 65 DEG C and starts polymerization, reaction temperature keeps polymerization temperature to decline 0.25MPa to polymerization pressure by DCS controls, adds 38.0g diethyl hydroxylamine terminating reactions, discharged from after pushing back receipts monomer, polyvinyl chloride resin is obtained after centrifugal drying.
The alcoholysis degree 80% of above dispersant PVA I, the mPa.s of viscosity 48 (20 DEG C, determined under 4% concentration)；The alcoholysis degree of dispersant PVA II is 45%, and viscosity is 90 mPa.s (25 DEG C, determined under 35% concentration)；Dispersant hydroxypropyl methyl cellulose is methoxyl substitution 25%, hydroxypropyl substitution value 6%, the mPa.s of viscosity 50 (20 DEG C, determined under 2% concentration).
Test result is as follows：K values 57, apparent density 0.55g/ml, 100g resin plasticizer absorption 18g, resin whiteness 93%, ageing whiteness (160 DEG C, 10min) 80%, 130.0 microns of average grain diameter, the dispersion of distribution is 1.15, particle circularity 0.93.
Embodiment 2：
Deionized water addition be changed to 200kg, hydroxypropyl methyl cellulose be changed to 21.0g, peroxy dicarbonate it is double-(2- Octyl Nitrites) 60.0g, cumyl peroxyneodecanoate 25.5g, C7~C10Fatty acid zinc heat stabilizer 80.0g, is not added with chain-transferring agent, and VCM addition is 100kg, and reaction temperature is 56.5 DEG C, controls pressure drop for 0.15 MPa, and other process conditions are with embodiment 1, and its test result is as follows：K values 67, apparent density 0.53g/ml, 100g resin plasticizer absorption 19g, resin whiteness 93%, ageing whiteness 83%, 128.0 microns of average grain diameter, the dispersion of distribution is 1.20, particle circularity 0.91.
Embodiment 3：
Dispersant hydroxypropyl methyl cellulose addition is changed to 21.0g, other process conditions are with embodiment 1, and its test result is as follows：K values 57, apparent density 0.55g/ml, 100g resin plasticizer absorption 19g, resin whiteness 93%, ageing whiteness 82%, 125.0 microns of average grain diameter, the dispersion of distribution is 1.15, particle circularity 0.92.
Comparative example 1：
Dispersant hydroxypropyl methyl cellulose addition is changed to 21.0g, polymerization stabilizer is not added with, with embodiment 1, gained resin is general universal resin to other process conditions, and particle is normal, and test result is as follows：K values 57, apparent density 0.53g/ml, 100g resin plasticizer absorption 22g, resin whiteness 93%, ageing whiteness 79%, 105.0 microns of average grain diameter, the dispersion of distribution is 1.25, particle circularity 0.82.
Comparative example 2：
Dispersant hydroxypropyl methyl cellulose addition is changed to 10.0g, polymerization stabilizer is not added with, other process conditions are with embodiment 1, and test result is as follows：K values 57, apparent density 0.53g/ml, 100g resin plasticizer absorption 21g, resin whiteness 94%, ageing whiteness 78%, 110.0 microns of average grain diameter, the dispersion of distribution is 1.30, particle circularity 0.81.
Comparative example 3：
The additions of dispersant PVA I is changed into the addition of 12.75g, PVA II it is changed to 52.5g, hydroxypropyl methyl cellulose addition to be changed to 22.5g, with embodiment 1, gained resin is general universal resin to other process conditions, and particle is normal, and test result is as follows：K values 58, apparent density 0.54g/ml, 100g resin plasticizer absorption 22g, resin whiteness 93%, ageing whiteness 80%, 98.0 microns of average grain diameter, the dispersion of distribution is 1.12, particle circularity 0.85.
Claims (10)
1. a kind of preparation method of Corvic, it is characterised in that comprise the following steps：
（1）By water, VCM, composite dispersing agent, polymerization stabilizer, chain-transferring agent, PH buffers and initiator are added and are provided with the polymeric kettle of agitating device, pressure is evacuated to for 1.00~1.10MPa, wherein, the addition of water is 1.2~2 times of VCM quality, composite dispersing agent is the 0.05~0.07% of VCM quality, polymerization stabilizer is the 0.001%~0.1% of VCM quality, chain-transferring agent is the 0~0.20% of VCM quality, PH buffers addition is so that the PH of reaction system is controlled 5.5~7, initiator is the 0.01~0.20% of VCM quality；
（2）It is warming up to 60 DEG C~70 DEG C, proceed by polymerisation, holding polymerization temperature is when polymerization pressure declines 0.15~0.25MPa, add reaction terminating agent, reaction terminating agent addition is the 0.01~0.05% of VCM quality, the remaining VCM of discharge, then collects target product from product.
2. the preparation method of Corvic according to claim 1, it is characterised in that water is deionized water, its electrical conductivity is 1~5 μ s/cm.
3. the preparation method of Corvic according to claim 1, it is characterized in that composite dispersing agent is the polyvinyl alcohol of two kinds of partial alcoholysis and the mixture of hydroxypropyl methyl cellulose, two kinds of polyvinyl alcohol of partial alcoholysis are alcoholysis degree 70~90%, viscosity be 40~55mPa.s alcoholysis degree high in viscosity PVA I and alcoholysis degree be 40~50%, viscosity is the high-viscosity PVA II of low alcoholysis level of 60~120mPa.s, wherein the consumptions of PVA I are the 0.006~0.03% of VCM quality, the consumption of PVA II is the 0.02~0.07% of VCM quality, the consumption of hydroxypropyl methyl cellulose is the 0.01~0.05% of VCM quality.
4. the preparation method of Corvic according to claim 3, it is characterised in that the methoxyl substitution of hydroxypropyl methyl cellulose is 20~40%, hydroxypropyl substitution value is 5~15%, and viscosity is 30~70mPa.s.
5. the preparation method of Corvic according to claim 1, it is characterised in that polymerization stabilizer is C7~C16Fatty acid zinc heat stabilizer.
6. the preparation method of Corvic according to claim 1, it is characterised in that chain-transferring agent is mercaptan compound, trichloro ethylene, carbon tetrachloride or the chloro- 1- iodoethane of 1-.
7. the preparation method of Corvic according to claim 6, it is characterised in that mercaptan compound is 2 mercapto ethanol, thioglycollic acid-2-ethyl hexyl ester, isooctyl thioglycolate or ethylene glycol dimercapto acetate.
8. the preparation method of Corvic according to claim 1, it is characterised in that PH buffers are NaOH, sodium acid carbonate or ammonium hydrogen carbonate.
9. the preparation method of Corvic according to claim 1, it is characterised in that initiator is organic peroxide initiator or azo-initiator.
10. the preparation method of Corvic according to claim 1, it is characterised in that reaction terminating agent is acetone semicarbazone thiocarbamide, bisphenol-A, diethyl hydroxylamine, dilauryl thiodipropionate or natrium nitrosum.
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| CN201610254681.3A CN106749793A (en) | 2016-04-23 | 2016-04-23 | A kind of preparation method of Corvic |
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| CN201610254681.3A CN106749793A (en) | 2016-04-23 | 2016-04-23 | A kind of preparation method of Corvic |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034015A (en) * | 2017-12-27 | 2018-05-15 | 山西阿科达化工科技有限公司 | A kind of preparation method of polyvinyl chloride |
| CN108659409A (en) * | 2018-06-21 | 2018-10-16 | 江苏新汇烽塑胶有限公司 | A kind of high temperature resistant Corvic and preparation method thereof |
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| CN1389483A (en) * | 2002-06-25 | 2003-01-08 | 上海氯碱化工股份有限公司 | Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight |
| CN1927898A (en) * | 2006-09-13 | 2007-03-14 | 上海氯碱化工股份有限公司 | Preparation method of low polymerization degree and high porosity resin |
| CN102453176A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of PVC (polrvinyl chloride) resin with high porosity and low film coverage rate |
| CN102952220A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of polyvinyl chloride spherical resin |
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2016
- 2016-04-23 CN CN201610254681.3A patent/CN106749793A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389483A (en) * | 2002-06-25 | 2003-01-08 | 上海氯碱化工股份有限公司 | Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight |
| CN1927898A (en) * | 2006-09-13 | 2007-03-14 | 上海氯碱化工股份有限公司 | Preparation method of low polymerization degree and high porosity resin |
| CN102453176A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of PVC (polrvinyl chloride) resin with high porosity and low film coverage rate |
| CN102952220A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of polyvinyl chloride spherical resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034015A (en) * | 2017-12-27 | 2018-05-15 | 山西阿科达化工科技有限公司 | A kind of preparation method of polyvinyl chloride |
| CN108034015B (en) * | 2017-12-27 | 2020-08-04 | 山西阿科达化工科技有限公司 | Preparation method of polyvinyl chloride |
| CN108659409A (en) * | 2018-06-21 | 2018-10-16 | 江苏新汇烽塑胶有限公司 | A kind of high temperature resistant Corvic and preparation method thereof |
| CN108659409B (en) * | 2018-06-21 | 2020-12-15 | 江苏新汇烽塑胶有限公司 | High-temperature-resistant polyvinyl chloride resin and preparation method thereof |
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Application publication date: 20170531 |