'US0103087. 2) United States Patent Gao et al (54) METHOD FOR PREPARING POLYVINYL CHLORIDE. BY SUSPENSION AND. POLYMERIZATION, AND FEEDING DEVICE om Amos Chemicals Ine. Jericho, NY ws) Yuhai Gao, Qingdao (CN); Xianzhen hwo, Qingdao (CN) Applicant (72) Inventors: 3) Amos Chet ws) Assignee: els Ine, Jericho, NY (#) Notice: Subjct to any diselaimer the term of this patent is extended or adjusted under 35 USC. 1540) by 65 days. en Appl. Nos 151593,605 (22) PCT Filed: Reb. 11, 2015 (86) PCT No, § 371 (XI, @) Date: POTICN201 Jun. 6, 2017 PCT Pub, Nos WO2016/106964 PCT Pub, Date: Jul. 7, 2016 @ 63) "lor Publication Data US 2017103496801 Dec. 7,2017 G0) Foreign Application Priority Data Dee. 31,2014 (CN) 2014 1 0853196 Gl) Int, Cos 11806 Bois 00 (2006.01) (2006.01), (Continued) @ v, S.C, oe CORE 11406 (201301); BOLE 4700 (2013.01; Boxy 4001 3013.01); CoBF 201 2013.01); Case 220 (2013.01); COBF 14706 (01301) eae n saad to} és eee | 8 ys Pe _ 31m 2 39) (10) Patent No.: (4s) Date of Patent: US 10,308,739 B2 jun. 4, 2019 (58) Field of Classification Search cre ‘CORP 2/18: COSE 114/06; BOLI 4/001 (Continved) 60) References Cited US. PATENT DOCUMENTS. ATIOSSL A * 121987 Miyata cose 1406 20090292091 AL* 1/2009. Heneta cost 108 526 191 FOREIGN PATENT DOCUMENTS oN torseo069 11/2008 (Continsed) (OTHER PUBLICATIONS Chinese Search Repor for Application No, 2014108531969, "Poly ‘ing ehloide suspension polymerization preparation method and feeding device” dted Apr 5.2017 (Continved) Fred M Teskin Hamilton, Brook, Smith Primary Bvaminer (74) Auornes. Agent, oF Firm & Reynolds, PC on ABSTRACT The present invention provides a production method of polyviny? chloride by suspension polymerization and & feeding apparats. This method comprises: Step 1: injecting a vinyl ebloride monomer and water at 25-08° C. into & reaction vessel (9 oblain a water suspension, closing the reaction kettle, repeatedly and eyelically” performing vacuin-pumping and cleansing with nitrogen, string and ‘evacuating oxygen in the reaction Kettle; Step 2: adling a frst suspension agent and a second suspension agent into the reaction Kettle, and then adding a nanopowder and an initiator composite, to cary out the polymerization reaction: Step 3: adding cold water to terminate the polymerization reattion upon the pressure in the rection kettle is redeed fo 3.5 bar or less; Step 4: evacuating and vacuumizing the (Continved) aw mi faa oh ie ho L sad mieUS 10,308,739 B2 Page 2 reaction kee, and then filtering, washing and drying the resulted polymer, to obtain polyvinyl chloride. The present invention also provides a feeding apparatus used for the ‘above production method, Polyvinyl chloride produced by the method ofthis invention has good performance and can rcet the roquirements of physical and chemical properties and applicability for most applications. 20 Claims, 3 Drawing Sheets (1) eer. COS 201 (2006.01) Cos 220 (2006.01), CORE 408 (2006.01), CoB 4730. (2005.01), CORE 1406 (2006.01) (58) Fleld of Classification Search USPC’ ‘526/84, 202, 344.2, 214 See application fie for complete search history. 66) References Cited POREIGN PATENT DOCUMENTS ow towrsi73 A 92014 cw aosesas0 0D 6201 P ‘0623632 A2* 111994 cose 28 (OTHER PUBLICATIONS International Search Report for Intemational Application No. PCT (CN201S/072812, "Method for Preparing Polyvinyl Chloride by ‘Sspension and Polymerization, and Feeding Device, dated Sep 25,2015. * cited by examinerUS 10,308,739 B2 Sheet 1 of 3 Jun. 4, 2019 U.S. Patent .ayem jeuareu Bulueys V3 a9eid uonz9i}o0 | “uonessupur apyay uopaean ayy yo doyUS 10,308,739 B2 Sheet 2 of 3 Jun. 4, 2019 U.S. Patent Fig.2 — Lo ae =U.S. Patent Jun. 4, 2019 Sheet 3 of 3 US 10,308,739 B2 cee ote Loe : = 7 = of ee = o :US 10,308,739 B2 1 METHOD FOR PREPARING POLYVINYL, ‘CHLORIDE BY SUSPENSION AND POLYMERIZATION, AND FEEDING DEVICE, RELATED APPLICATIONS This application is the U.S. National Stage of Interna tional Application No. PCTICN2015/072812, file on Feb. 11, 2015, which designates the U.S., published in Chinese, and claims provty under 35 U.S.C. § 119 or 365 t0 China, Application No. 2014108531960, filed Dee. 31, 2014. The ‘ati teachings of the above applications are incorporated herein by reference. FIBLD OF TECHNOLOGY “The present invention relates to produetion method of polyvinyl chloride by suspension polymerization and a Jeeding apparatus thereo, belonging tothe technical field oF polyvinyl chloride synthesis BACKGROUND ART In prior an, vinyl chloride is polymerized by using 3 suspension method, and organic catalysts, such as peroxides, zo compounds of peotestive colloids, such as geatis methylcellulose and polyvinyl alcohol, ae commonly used in the process. The quality of the suspension polymer prepared according to the existing technical procedures dacs not sullciently satisfy the production and application engi- neers, especially in tems of the thermal stability, and a lage amount of heat stabilizers required durin the modification process of polyvinyl chloride (PVC), wherein the heat Sabilzer is precominantly a lead-containing product. In fee, the main ingredients (vin chloride VCM, water, ‘uiliaries) addled for he standard suspension PVC polyn: ‘erization process has been foreseen prior tothe start of the polymerization. At the start of the polymerization reaction, 4 slicient amount of initiator is required to be added to fctivate the reaetion and continue #0 be added until the reaction is completed within the predetermined procedure time. The most commonly used initiators are ongsnie per- ‘oxides (different types, various properties) with good effects, but atthe same time, some of the key defects wil also affect the processing performance and quality ofthe finshed PVC. “The suspended polyvinyl chloride (S-PVC) in the indus tty is curently and mainly produced by suspension polym- cerization via a hatch feed process using a stainless stel autoclave. VCM is polymerized in acconlance with the mechanism of fre radical, and monomers ae aed into the reaction autoclave as Figuid form. The water phase includes desalted water, dispersant (protective colloids, surfactants), buffer salts, and usually futher includes defoamers, the ‘water phase are finally dispersed into small droplets by ‘continvous string. After the initiator i added, the polymerization reaction is started, and the initiator is dissolved in the organic VCM phase. During polymerization, the medium must be contin- ‘ously stired, Thus, the polymerization is carried out only between VOM droplets. The reaction is caried out at @ ‘constant temperature of 35-75° C, under sirated vapor pressure of VOM. Eventually, the polymerization of VOM ‘ceases aller the addition of the Killing agent capable of ‘capturing free radicals. In general case, according to the production configuration and operating characteristics, the 0 o 2 average conversion rate hetween VCM and finished PVC is 82-86%, Moreover, killing agents are a class of chemical products at higher prices. "The morphology of suspended PVC and the microstruc- ture of S-PVC panicles depend primarily on the polymer- ination temperature, the types and amounts of dispersant, the type of stimer and string conditions. ‘The types of dispersants used also greatly determine the morphology afthe PVC, because the dispersants ean prevent the aggregation of the monomer VCM droplets during the polymerization reaction. Commonly used dispersamts are partially Water-soluble polymers such as cellulose deriva- tives and partially sleoholized polyvinyl alcohols (com- monly referred to as PVAs). PVAS with different aleoholysis degrees are widely used and commonly can be used for ‘commercial production of S-PVC. The alcoolysis degrees and molecular weights of PVAs determine their protective behaviors and the final sizes, shapes, and pores (morphol- ‘ogy) othe polymer particles. The distribution of PVAS on the surface of VCM droplets depends on their aleoholysis ‘doprees. The “primary” dispersant eontals the size of poly- ‘mc particles, and sich PVAs are block copolymers having high lcobolysis degrees and having mediim and high molecular weights, in general, their aleaholysis degree is saenerlly more than 70%. On the other hand, the “second ay” dispersant mainly controls the pores of the polymer particles. PVAS serving as the secondary dispersant belong {o random copolymers, having medium aleoholysis degrees generally in a range of 20-60%, with lower molecular eights Tnitiators commonly used in VCM polymerization reac- tion are generally different types of organie peroxides and am compounds, soli long-chain hydroxy peroxydicarbon- ate salls, such as diacetoxy dicarbonates or perbi ‘myristtes, which are mainly formulated into water suspen- sions and widely used due 10 the stability and ease of ‘operation, A certin amount of initiator has high repeatab ity/reproducibilty after being added to a reaction kettle, and cate of its very low solubility in water, a hard shell ‘would be formed mostly atthe surface ofthe reaction ket "AL present, an increasing number of sol peroxy dec Donate sas are replaced with liquid peroxy decarbonate salts. Liguid peroxy decarbonate salts are cheaper, and can dissolve in VCM more quiekly. But thee is « high risk of ‘explosion, so the operation must be care, wicks becomes daily problem in the industry ‘The performance of organic peroxides mainly depends on the decomposition rate, Which is expressed by the halflife ata specific temperature. As described above, the tWo oF ‘more initiators of different types ae often used in combi tation due tothe dflerence in polymerization temperature, ‘When PVC having a high K value (K80 fo K100) is to be produced, the polymerization temperature is below 50° C. Rapid initiators such a bisobatyry! peroxides are often used to eahance the slow initiation rates caused by low polymerization temperatures, Such inititors are often used in combination with slightly slower initiators such as bilsobutyryl peroxides. Rapid initiators and peroxy decar- bonate sis are offen used after mixing for the PVC having a K value hetwoen 70-80, S-PVCs of specification between KS0-K70 are produced using peroxy decarbonate salts, noutral reactive porestors and diaeyl peroxides or using these initiators in combina ‘ion. In the inital stage of the initiation phase, the droplets of the initiator rapidly disappeared because the initiator tifsed into the VCM droplets nnd then aggregated. From the intial stage of the polymerization process until theUS 10,308,739 B2 3 ‘conversion rate of 15%, the monomer droplets ae dispersed and aggregated again, sueh that the initiator was evenly isiibured between the VCM droplets, ‘he distribution of the intistor on the VCM droplets would affect the morphology of the finished S-PVC par- tices. I the initiator is not evenly distributed on each VCM ‘droplet, particles with no pores are formed, which are referred to as plasticized particles. These non-porous par- ticles have vitreous properties and high densities, and are almost spherical. Compact vitreous particles are difficult to process, Due tothe lack of pores intakes of plasticizer and Stabilizer ane very litle, resulting in that these particles are not easy to be glatinized and moulded during the process of processing. The presence of these particles leads to visible defects atthe surface of finished S-PVC, i, so-called “ish ee The production of these nonporous vitreous particles “originates from presence of the large amount of initiator ‘dmoplets inside the polymerization resction, replacing the ‘conventional polymerization between VCM droplets, When, the initiator is not sufficiently dispersed in the aqueous medium, the initiator droplets having a wide panicle size distribution are formed. Under normal circumstances, the ‘small initistor droplets will disappear quickly dae to con- 0. In the above production method, the particle sizeof the nanopowder used is preferably in the range of from 60 40 200 nm, In the above production method, preferably, the nanopo= vwder futher contains zine oxide; more preferably, the ratio by mass of zine oxide:magnesium hydroxide and/or al rium hydroxide (i. the sum of the masses of magnesium hydroxide and aluminum hydroxide) is 1:3. According 1o a specific embodiment of the present inven- tion, the proction method may further comprise the steps ‘of adding a primary dispersant and a secondary dispersant ‘wherein, the primary dispersant is a polyvinyl aleobo! ha= ing an aleobolysis deprev of 80-72.5%; and the primary dispersant is added at an amount of 800-1500 ppm, ia relative tothe weight ofthe water suspension; the secondary life ofthe previously added initiator composite fisly adding the remaining ehloroformate and the organi ‘cid ankiydrde, and then adding the remaining peroxide ‘and sodium hydroxide 3. The method seconling to claim 1, wherein the fist suspension agent isa polyvinyl alcohol having an alcaboly- sis degree of 88%, aad the second suspension agent is a polyvinyl sleohol having an alcaholysis degree of 72%. 4. The method according to claim 1, wherein the ehloro- formate, the peroxide, the organic acid anhydride and sium hydroxide inthe initiator composite are in ratio by jp mass of S11:1.53, '. The method acconting to claim 1, wherein the vinyl chloride monomer and water are ina ratio by mass of 1:1 6. The method according to claim 1, wherein the suspen sion stabilizer contains zine oxide, a manopowder and an ‘organic acid sat compound, and the nanopowder contains ‘magnesium hydroxide and aluminum hydroxide 7. The method according (0 claim 6, wherein the amount of magnesium hydroxide is 4-12 wt Y and the amount of ‘aluminum hyeloxide is 2-8 wt %, relative tothe weight of the water suspension, and the zine oxide, the nanopowder and the organi acid salt compound are in a ratio by mass of 133. 8. The method according fo claim 7, wherein the amount of magnesium hydroxide is 7-8, the amount of alumni hydroxide is 4%, relative to weight of the suspension of Water and the monomer '9. The method according to claim 6, wherein the organic acid salt compound has a structural formulas 0 a5 BLN YONDIMAT gO 1M2* represents a divalent metal eaton selected from the group consisting of Mg, Ca, Za, and Co M® represents AI or Bi; AY represents an anion having a valence of 1 to 4 and includes HCO,", Cr, CO, or CH,COO”: ‘cand y are numbers in ihe following ranges: 0,240.33. ‘and y>0. 16, The method aevording fo clan 1, wherein the method further comprises 2 primary dispersant and a soc- 5 ondary dispersant, ‘the primary dispersant is » polyvinyl alcohol having an aleobolysis degree of 80-72.5%: oUS 10,308,739 B2 17 and the primary dispersant is added at an amount of ‘800-100 ppm, relative 10 the weight of the water suspension; the secondary dispersant is. poly aleoholysis degree of 35-55%, 11. The method according to claim 10, wherein the primary dispersant is ade in a), and the secondary disper Santis added in b), 12, The method according to claim 1, wherein the chlo- roformate has a molecular formula of CICOOR, , wherein Ry jis methyl, ethyl, isopropyl, m-propyl or 2-thyl; the onganie acid ankiydride has a molecular Formula of {(RCO},0, wherein R is methyl or ethyl; the peroxide is hydrogen peroxide andior Sodium perox- ide. 18. The method aeeording to claim 12, wherein the ‘onuanie acid anhydride comprises propionic anhydride, and ‘or isopropionic anhydride 14. The method according to claim 12, wherein the yao having an starting materials of the initiator composite comprise ethyl 2 cchloroformate, hyirogen peroxide, propionic anhydride and sodium hydroxide 18. The method according to claim 12, wherein the im-propyl is propyl 16. vacutum-pumping in d) is earied nt at 42-48 mbar, 33-37° C. for 45 minutes, the washing is carried out by using reverse osmosis water, and the temperature for drying is 50-60" C. 17, The method aeconting fo claim 1, wherein an ant- sticking-to-kettle agent is fist acded to the reaction ketle prior to the addition of the vinyl ehloride monomer and 18, A feeding apparatus for producing polyvinyl chloride by suspension polymerization, comprising: a peroxide ves- sel, a peroxide storage tank, a yodium hydroxide solution vessel, sodium hydroxide solution storage tank, a ehloro- omate storage drum, an organic acid anhydride storage drum, a waste liquid tank, washing tower, a box for ‘automat handling of drums contained therein, and an inlet Pipe for starting material water The method according to claim 1, wherein the > 18 the peroxide solution vessel is connected to the peroxide storage fank by frst pump, and the peroxide solution storage tank is connected to the inlet pipe for starting material water by a first feeding pump: the sodium hydroxide solution vessel is connected tthe sodium hydroxide solution storage tank by a second ‘pop, and the sodium hydroxide solution storae tank is connected tthe inlet pipe for starting material water by a second feeding pump: the chloroformate storage drum and the onpanie avid ‘anhydride storage drum are aeranged in the box for tomatic handling of the drums, wherein the box is provided with an exhaust veatilation device, a blower fand a vertical pumps the blower is connected to the ‘washing tower, and the vertical pump is connected to the waste liquid tank; ‘one end of the inlet pipe Tor stating material waters used for inputting the starting material water, andthe other end thereof is connected to the top ofa reaction Kettle: the chloroformate store drum is connected to the inlet pipe for stating material water by a thied feeding Pomp, and the organic acid anhydride storage drum is ‘connected to the inlet pipe for starting material water by o fourth festing pump: the bottom ofthe washing tower is connected tothe waste Figuid tanks ‘the waste liquid! tank is provided witha sodium hydroxide inlet pipes the waste liquid tank is connected (© the outside of the ‘apparatus by a Foust pump, 19, The feeding apparatus according to claim 18, wherein the washing tower has a first pipeline connected to aa incineration collction place outside the feeding apparatus, ‘anda second pipeline connected toa waste liquid treatment Sevice ouside the feeding appara. 20. The feeding apparatus according to claim 18, wherein the waste liquid tank is connected to a prestiter device outside the eeding apparatus by the fourth pump.