CN100558765C - Adopt 70.5m 3Polymeric kettle is produced the method for polyvinyl chloride - Google Patents
Adopt 70.5m 3Polymeric kettle is produced the method for polyvinyl chloride Download PDFInfo
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- CN100558765C CN100558765C CNB2005100458491A CN200510045849A CN100558765C CN 100558765 C CN100558765 C CN 100558765C CN B2005100458491 A CNB2005100458491 A CN B2005100458491A CN 200510045849 A CN200510045849 A CN 200510045849A CN 100558765 C CN100558765 C CN 100558765C
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 36
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 27
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- 238000011010 flushing procedure Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000009466 transformation Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 12
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 12
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- -1 pivalate ester Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000005502 peroxidation Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229950010765 pivalate Drugs 0.000 claims description 3
- HQDAJGNZGNZGCO-UHFFFAOYSA-N (propan-2-ylideneamino)urea Chemical compound CC(C)=NNC(N)=O HQDAJGNZGNZGCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- CXAFSGPCNGYTOZ-UHFFFAOYSA-N chloroethene hydrate Chemical compound O.ClC=C CXAFSGPCNGYTOZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
Adopt 70.5m
3Polymeric kettle is produced the method for polyvinyl chloride, comprises polymerization process, it is characterized by: under the anoxybiotic state, the corresponding opening for feed by setting firmly in the still successively, water flushing still wall is also discharged waste water, by steam with 0.02m
3Still release agent evenly is sprayed at the still wall, and the water flushing is also got rid of it; Add buffer reagent and count 3.92kg with purity 100wt%; Add volume ratio and be the hot water that 1: 1.02 vinyl chloride monomer and temperature are 85-90 ℃, coefficient is 0.8-0.9; Add dispersion agent and judge dispersion effect; Determine that dispersion system is stable, can add composite initiator; Add the chain-transfer agent mercaptoethanol and count 0-4kg with purity 100wt%; After polymerization begins 10 minutes, inject the water that is lower than temperature of reaction with the flow of 1000kg/h in still, polymeric reaction temperature is 49-64 ℃; When reaching transformation efficiency 80%, add the terminator termination reaction; To the slurry tank blowdown, and in slurry tank, reclaim unreacted vinyl chloride monomer; Slurry through stripping, dewater, be drying to obtain product.Advantage of the present invention is: energy-conservation consumption, the good product quality of removing; Save a large amount of unproductive times, and shorten the production time, single still production intensity is improved more than 2 times, have remarkable economic efficiency; Reduce labor strength, basic non-environmental-pollution.
Description
(1) technical field
The present invention relates to a kind of production method of Chemicals, specifically relate to adopt the 70.5m3 polymeric kettle to produce the method for polyvinyl chloride (PVC).
(2) background technology
China is PVC big producing country, and PVC output was 3,000,000 tons in 2002, but the occupancy volume per person only is 2kg/ people, only be developed country the occupancy volume per person 1/20, thereby the PVC import volume is still about 2,000,000 tons, hence one can see that, and the PVC potentiality to be exploited is very big.But the quite a while, domestic PVC producer all adopts 13.5m3 or 30m3 polymeric kettle more than 80%, limited the development of this product economy scale production.And its production method is as follows substantially: with manual type, a uncovered polymeric kettle has been sprayed still release agent, then use deionized water (abbreviation water) to wash out the unnecessary still release agent that does not adhere on the still wall successively, close the still bottom valve and in still, add gauge water, in still, add auxiliary agents such as buffer reagent, dispersion agent, initiator simultaneously; Close kettle cover, vacuumize deoxidation after, in still, add vinyl chloride monomer (VCM), open still and lead to valve on the monomer scale tank equilibration tube, the scale on the sight gauge measuring tank, to determine adding enough VCM amounts, VCM and water volume ratio are 1: 1.6-1.7; To still chuck and the logical 93 ℃ of hot water of baffle plate, material in the still is warming up to 50-65 ℃ by 20 ℃; The initiator decomposes causes VCM and carries out polyreaction.Owing to be to adopt single initiator, thus after existing earlier slowly soon or polyreaction phenomenon first quick and back slow, be subjected to the restriction of specific heat-transfer capability, reaction process more (about 7 hours) consuming time in addition.When reaction reaches predetermined transformation efficiency, in still, add terminator, termination reaction; To the slurry tank blowdown, open the gas holder valve simultaneously, reclaim unreacted VCM; When the still internal pressure drops to certain value, open vacuum pump, will vacuumize in the still, this process will be lost lot of V CM; After this, open kettle cover, begin next still production.
This small-sized still and supporting PVC production method thereof, not only hindered the production development of PVC economic scale, and non-cutting time and production time are all long, consumed the mass efficient production time, cause single still production intensity low excessively, quality product is not high, and the norm quota of consumption is high, labor strength is big, and environmental pollution is serious.
Early 1980s, the domestic 80m3 polymeric kettle of once developing, but, cause its application not become a reality because supporting technology does not catch up with.
In the recent period, Jinxi Chemical Machinery (Group) Co., Ltd. develops the 70.5m3 polymeric kettle, provides the suite of equipment condition for China PVC produces to the economic scale development.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method for adopting the 70.5m3 polymeric kettle to produce PVC, to reach economic scale production, increases effective production time, improves single still production intensity, and is energy-saving and cost-reducing, guarantees the purpose of quality product.
The technical scheme that adopts is:
Adopt the 70.5m3 polymeric kettle to produce the method for polyvinyl chloride, comprise polymerization process, it is characterized by: under the anoxybiotic state, corresponding opening for feed by setting firmly in the still successively, water flushing still wall is also discharged waste water, by steam the 0.02m3 still release agent evenly is sprayed at the still wall, the water flushing is also got rid of it; Add buffer reagent and count 3.92Kg with purity 100wt%; Add volume ratio and be the hot water that 1: 1.02 vinyl chloride monomer and temperature are 85-90 ℃, coefficient is 0.8-0.9; Add dispersion agent and judge dispersion effect; Determine that dispersion system is stable, can add composite initiator; Add the chain-transfer agent mercaptoethanol and count 0-4kg with purity 100wt%; After polymerization begins 10 minutes, inject the water that is lower than temperature of reaction with the flow of 1000kg/h in still, polymeric reaction temperature is 49-64 ℃; (about 5 hours) add the terminator termination reaction when reaching transformation efficiency 80%; To the slurry tank blowdown, and in slurry tank, reclaim unreacted VCM; Slurry through stripping, dewater, be drying to obtain product.
Above-mentioned composite initiator is azo class, superoxide compounds; Azo compound comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile); The superoxide compounds comprises peroxy dicarbonate-2-ethylhexyl (EHP), peroxide tert pivalate ester (TBPP), peroxidation neodecanoic acid cumyl ester (TrigonoX99); It is composite to be respectively 2-13kg, 0-10kg, 0-4kg in the every still consumption of purity 100wt%, is made into concentration of emulsion used when using and is 1-20%.
Above-mentioned dispersion agent comprises PVA-224E, Alcotex72.5 (or claiming L-10), HPMC, KH-20, is respectively 3-11.3kg in the every still consumption of purity 100wt%, is mixed with the aqueous solution of 0.7-6% during use respectively.After above-mentioned dispersion agent adds, judge that dispersion effect is according to C value computing method:
In the formula: C is that particulate material is judged the factor, and unit is a pound/inch
2K; Δ P is a still internal pressure differences before and after dispersion agent adds, and unit is a pound/inch
2K; Δ T is a temperature in the kettle changing value before and after dispersion agent adds, and unit is K; When C 〉=2.0, show that dispersion system is normal in the still, can continue next production process; When C＜1.9, show that dispersion system is undesired in the still, can start reclaimer, stop that the step produces down; Also can in still, add dispersion agent again, dispersion system in the still is transferred to normally, carry out next step production sequence again.
Above-mentioned dispersion agent adds the back dispersion effect and judges, also can adopt polymeric kettle stirrer current curve method to judge, be that reinforced situation all can show dispersion system normal power graphic representation 1 and the undesired powertrace Fig. 2 of dispersion system when statistic data has provided hot feed in each still on stirrer electric current or power.
Above-mentioned terminator comprises acetone semicarbazone thiocarbamide (ATSC), and it is 0.03-0.1kg/tpvc in purity 100wt% usage quantity, is mixed with the aqueous solution of 3-10% during use.
The recovery of above-mentioned unreacted VCM, be in slurry tank, to carry out, undertaken from pushing back receipts by the pressure of self in the slurry tank during beginning, when pressure drops to can not reclaim by the slurry tank internal pressure time, just adopt the compressor recovery of pressurizeing, be pressurised into 0.25-0.35Mpa.
Advantage of the present invention is: energy-saving and cost-reducing, and good product quality; Save a large amount of unproductive times, and shorten the production time, single still production intensity is improved more than 2 times, have remarkable economic efficiency; Reduce labor strength, basic non-environmental-pollution.
Table 1 has been listed former PVC production method and the inventive method production intensity and the norm quota of consumption relatively:
The two kinds of production method production intensities of table 1 and the norm quota of consumption are relatively
(4) description of drawings
Fig. 1 is a dispersion system normal power graphic representation;
Fig. 2 is the undesired power of dispersion system.
(5) embodiment
Embodiment one
With SG-5 type polyvinyl chloride is example:
Under the kettle cover air-tight state, by being installed in the corresponding charging opening in the 70.5m3 polymeric kettle, carry out following program successively: polymeric kettle is washed with deionized water, simultaneously waste water is entered wastewater trough, then carry out steam and be coated with wall, wash then, remove and do not adhere to still release agent and be drained into wastewater trough, the adding solid content is 8% buffer reagent 49kg, and flushing pipeline enters polymeric kettle with the 200kg deionized water; Adding VCM28.68m3 and temperature are 87 ± 2 ℃ deionized water 30.86m3, add water temp with after guaranteeing to add VCM and water, make temperature of reaction reach 57 ℃ and are as the criterion; Adding dispersion agent PVA-224E is 105kg, and solid content is 4%, and adding dispersant A lcotex72.5 and HPMC is 200.7kg, and wherein containing Alcotex72.5 is 5.6%, and containing HPMC is 0.7%; Whether dispersion system in the still is judged normally,, started reclaimer or add dispersion agent again and be transferred to normally as undesired; Normal as dispersion system, then add effective constituent and be 20% initiator; The reaction beginning with flow water filling in still of 1000kg/h, finished up to reaction after 10 minutes; Transformation efficiency reaches 80%, and adding 0.06m3, to contain effective composition be 3.3% the terminator aqueous solution, then blowdown in slurry tank; And reclaim unreacted VCM in this groove: the pressure by slurry tank self reclaims earlier, when pressure in the slurry tank is lower than the required pressure of recovery VCM, and then pressurization, pressure reaches 0.30Mpa; Slurry promptly gets the PVC product after stripping, dehydration and drying; Technical recipe is concluded and is seen Table 2 in the said process:
Table 2SG-5 type Production of PVC technical recipe
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86 28.68 0.02 3.92 3.8 11.238 1.405 10 3 0.05 57。
Embodiment two
Embodiment two and embodiment one are basic identical, and what difference was to produce is SG-3 type polyvinyl chloride, and its technical recipe sees Table 3:
Table 3SG-3 type Production of PVC technical recipe
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
31.86 27.68 0.02 3.92 4.2 11.238 1.405 12 4 0.01 52
Embodiment three
Embodiment three and embodiment one are basic identical, and what difference was to produce is SG-7 type polyvinyl chloride, and its technical recipe sees Table 4:
Table 4SG-7 type Production of PVC technical recipe
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86 28.68 0.02 3.92 3.8 11.238 1.405 3 9 1 4 0.1 60
Embodiment four
Embodiment four and embodiment one are basic identical, and what difference was to produce is SG-8 type polyvinyl chloride, and its technical recipe sees Table 5:
Table 5SG-8 type Production of PVC technical recipe
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86 28.68 0.02 3.92 3.8 11.238 1.405 2 8 4 0.1 64。
Claims (8)
1, adopts 70.5m
3Polymeric kettle is produced the method for polyvinyl chloride, comprises polymerization process, it is characterized by: under the anoxybiotic state, the corresponding opening for feed by setting firmly in the still successively, water flushing still wall is also discharged waste water, by steam with 0.02m
3Still release agent evenly is sprayed at the still wall, and water washes, and removes not adhere to still release agent and be drained into wastewater trough; Add buffer reagent and count 3.92Kg with purity 100wt%; Add volume ratio and be the hot water that 1: 1.02 vinyl chloride monomer and temperature are 85-90 ℃, coefficient is 0.8-0.9; Add dispersion agent and judge dispersion effect; Determine that dispersion system is stable, can add composite initiator; Adding the chain-transfer agent mercaptoethanol is 0-4kg with purity 100wt%; After polymerization begins 10 minutes, inject the water that is lower than temperature of reaction with the flow of 1000kg/h in still, polymeric reaction temperature is 49-64 ℃; When reaching transformation efficiency 80%, add the terminator termination reaction; To the slurry tank blowdown, and in slurry tank, reclaim the reacted vinyl chloride monomer; Slurry through stripping, dewater, be drying to obtain product; Described composite initiator is the superoxide composite initiator, described superoxide is peroxy dicarbonate-2-ethylhexyl, peroxide tert pivalate ester and peroxidation neodecanoic acid cumyl ester, be respectively 2-13kg, 0-10kg, 0-4kg in the every still consumption of purity 100wt%, wherein the consumption of peroxide tert pivalate ester and peroxidation neodecanoic acid cumyl ester is not 0 simultaneously, is made into concentration of emulsion used during use to be＞0-20%.
2, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described dispersion agent comprises PVA-224E, Alcotex72.5, HPMC and KH-20, is 3-11.3kg with the every still consumption of purity 100wt%, is mixed with the aqueous solution of 0.7-6% during use respectively.
3, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described terminator comprises the acetone semicarbazone thiocarbamide, is 0.03-0.1kg/tpvc in purity 100wt% usage quantity, is mixed with the aqueous solution of 3-10% during use.
4, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that the recovery of described unreacted vinyl chloride monomer, be in slurry tank, to carry out, undertaken from pushing back receipts by the pressure of self in the slurry tank during beginning, when pressure drops to can not reclaim by the slurry tank internal pressure time, just adopt the compressor recovery of pressurizeing, be pressurised into 0.25-0.35Mpa.
5, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described SG-5 type Production of PVC prescription is:
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86 28.68 0.02 3.92 3.8 11.238 1.405?10 3 0.05 57。
6, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described SG-3 type Production of PVC prescription is:
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
31.86?27.68?0.02 3.92 4.2 11.238 1.405?12 4 0.01 52
7, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described SG-7 type Production of PVC prescription is:
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86 28.68?0.02 3.92 3.8 11.238 1.405?3 9 1 4 0.1 60
8, employing 70.5m according to claim 1
3Polymeric kettle is produced the method for polyvinyl chloride, it is characterized in that described SG-8 type Production of PVC prescription is:
H2O VCM is coated with wall agent buffer reagent PVA-224E Alcotex72.5 HPMC EHP TBPP Trigonox99 chain-transfer agent terminator temperature of reaction
m
3 m
3 m
3 kg kg kg kg kg kg kg kg m
3 ℃
30.86?28.68?0.02 3.92 3.8 11.238 1.405?2 8 4 0.1 64。
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| CN101665546B (en) * | 2009-09-25 | 2011-06-15 | 四川金路集团股份有限公司 | Feeding device for manufacturing PVC resin by using 70m<3> polymerization kettle and feeding method |
| CN102954923A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Polymerization-kinetic method for detecting vinyl chloride |
| CN103601825B (en) * | 2013-11-27 | 2015-11-18 | 昊华宇航化工有限责任公司 | The antiseized still method of pvc polymerizer |
| CN104371047B (en) * | 2014-11-12 | 2016-09-14 | 天伟化工有限公司 | A kind of method of vinyl chloride polymerization reactor anti-fouling agent spraying |
| CN105622825B (en) * | 2016-04-06 | 2017-11-24 | 辽宁方大工程设计有限公司 | Produce device and its production technology and the application of polyvinyl chloride interpolymer paste resin |
| 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 |
| CN114634588B (en) * | 2022-03-29 | 2023-06-06 | 内蒙古宜化化工有限公司 | Process for producing polyvinyl chloride |
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|---|---|---|---|---|
| CN85107531A (en) * | 1984-07-23 | 1987-01-21 | 信越化学工业株式会社 | The production method of vinyl chloride-base polymer |
| CN1314421A (en) * | 2000-03-21 | 2001-09-26 | 青岛海晶化工集团有限公司 | Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process |
| CN1362423A (en) * | 2002-01-23 | 2002-08-07 | 上海氯碱化工股份有限公司 | Prepn process of polyvinyl chlroide resin with composite initiator system |
| JP4248813B2 (en) * | 2001-08-20 | 2009-04-02 | ボイス ペ−パ− パテント ゲ−エムベ−ハ− | Equipment for processing fibrous webs |
-
2005
- 2005-02-05 CN CNB2005100458491A patent/CN100558765C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107531A (en) * | 1984-07-23 | 1987-01-21 | 信越化学工业株式会社 | The production method of vinyl chloride-base polymer |
| CN1314421A (en) * | 2000-03-21 | 2001-09-26 | 青岛海晶化工集团有限公司 | Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process |
| JP4248813B2 (en) * | 2001-08-20 | 2009-04-02 | ボイス ペ−パ− パテント ゲ−エムベ−ハ− | Equipment for processing fibrous webs |
| CN1362423A (en) * | 2002-01-23 | 2002-08-07 | 上海氯碱化工股份有限公司 | Prepn process of polyvinyl chlroide resin with composite initiator system |
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