compositionstructure
polyvinylchlorideisapolymermaterialthatusesachlorineatomtoreplaceahydrogenatominpolyethylene.Itisanamorphouspolymerwithasmallamountofcrystallinestructure.Thestructureofthismaterialisasfollows:-(CH2-CHCl)n-.PVCisalinearpolymerinwhichmostVCMmonomersareconnectedinahead-to-tailstructure.Thecarbonatomsarearrangedinazigzagpattern,andallatomsareconnectedbysigmabonds.Allcarbonatomsaresp3hybrids.
ThereisashortsyndiotacticstructureonthePVCmolecularchain.Asthepolymerizationtemperaturedecreases,thesyndiotacticityincreases.Themacromolecularstructureofpolyvinylchloridehasthedisadvantagesofheadstructure,branchedchain,doublebond,allylchloride,tertiarychlorineandotherunstablestructures,whichmakeheat-resistantdeformationandpooragingresistance.Afterpretendingtobecross-linked,suchshortcomingscanbeeliminated.
Crosslinkingisdividedintoradiationcrosslinkingandchemicalcrosslinking.
1.Radiationcrosslinking.High-energyraysareused,generallyraysproducedbyacobalt60radiationsourceorelectronraysproducedbyelectronacceleration,andthelatterismainlyused.Addcrosslinkingaids(twoormorecarbon-carbondoublebondmonomers)forcrosslinking.However,theoperationisdifficultandrequireshighequipment.
2.Chemicalcross-linking.Triazoledimercaptoaminesalt(FSH)isusedforcross-linking.Thecross-linkingmechanismisthatamineandsulfhydrylcombinetoattackthecarbon-chlorinepolarbondtoperformsubstitutionreaction.Aftercross-linking,theperformanceoftheproduct,suchasUVresistance,solventresistance,temperatureresistance,impacttoughening,etc.,willbecomprehensivelyimproved.
Historicalevolution
Asearlyas1835,polyvinylchloridewasdiscoveredbyV·LeñointheUnitedStates.Whenitisirradiatedwithsunlight,itproducesawhitesolid,namelypolyvinylchloride.
PVCwasdiscoveredtwiceinthe19thcentury,oncebyHenriVictorRegnaultin1835andtheotherbyEugenBaumannin1872.Onbothoccasions,thepolymerappearedinabeakerofvinylchlorideplacedunderthesunlightasawhitesolid.Atthebeginningofthe20thcentury,RussianchemistIvanOstromislenskyandGermanGriesheim-ElektronchemistFritzKlattesimultaneouslytriedtousePVCforcommercialpurposes,butthedifficultywashowtoprocessthishardandsometimesbrittlepolymer.
In1912,theGermanFritzKlattesynthesizedPVCandappliedforapatentinGermany,butfailedtodevelopasuitableproductbeforethepatentexpired.
In1926,WaldoSemonofB.F.GoodrichCompanyintheUnitedStatessynthesizedPVCandappliedforapatentintheUnitedStates.WaldoSemonandB.F.GoodrichCompanydevelopedamethodofplasticizingPVCbyaddingvariousadditivesin1926,makingitamoreflexibleandeasier-to-processmaterial,andsoonitwaswidelyusedincommercialapplications.
In1914,itwasdiscoveredthatorganicperoxidescouldacceleratethepolymerizationofvinylchloride.In1931,theGermanmethodusedemulsionpolymerizationtorealizetheindustrialproductionofpolyvinylchloride.In1933,W.L.SimonproposedtousehighboilingpointsolventandtricresylphosphatetoheatandmixwithPVC,whichcanbeprocessedintosoftpolyvinylchlorideproducts,whichmadearealbreakthroughinthepracticalityofPVC.BenemenChemicalIndustries,UnitedKingdom,UnionCarbideCorporation,andGoodrichChemicalCompanydevelopedthesuspensionpolymerizationofvinylchlorideandtheprocessingandapplicationofPVCalmostsimultaneouslyin1936.Inordertosimplifytheproductionprocessandreduceenergyconsumption,theFrenchSaint-Gobaincompanydevelopedthebulkpolymerizationmethodin1956.In1983,theworld'stotalconsumptionwasabout11.1Mt,andthetotalproductioncapacitywasabout17.6Mt;itwasthesecondlargestplasticvarietyafterpolyethyleneproduction,accountingforabout15%ofthetotalplasticproduction.China'sself-designedPVCproductionequipmentwasputintotrialproductioninLiaoningJinxiChemicalPlantin1956.The3ktunitwasofficiallyindustrializedin1958,andtheoutputin1984was530.9kt.
PVCwasindustrializedintheearly1930s.Sincethe1930s,foralongperiodoftime,theoutputofPVChasbeenrankedfirstintheworld'splasticconsumption.Inthelate1960s,polyethylenereplacedpolyvinylchloride.AlthoughPVCplasticsrankssecond,buttheoutputstillaccountsformorethanaquarterofthetotaloutputofplastics.
Beforethe1960s,theproductionofmonomervinylchloridewasbasicallybasedoncalciumcarbideacetylene.Theproductionofcalciumcarbiderequiredalotofelectricityandcoke,andthecostwashigh.Aftertheindustrializationofethyleneoxychlorinationtoproducevinylchlorideintheearly1960s,countriesturnedtocheaperpetroleumasrawmaterials.Inaddition,becausealargepartoftherawmaterialofpolyvinylchloride(about57%byweight)istheby-productofthesodaindustry,itisnotonlyarichsourceofrawmaterials,butalsooneofthemostimportantproductsforthedevelopmentofthechlor-alkaliindustryandthebalanceofchlorine.Therefore,althoughtheproportionofPVCinplasticshasdeclined,itstillmaintainsarelativelyhighgrowthrate.
PVCplasticproductsarewidelyused,butinthemid-1970s,peoplerealizedthattheresidualmonomervinylchloride(VCM)inPVCresinandproductsisaseriouscarcinogen.Undoubtedly,itwillaffectthedevelopmentofPVCtoacertainextent.However,peoplehavesuccessfullyreducedtheresidualVCMthroughvehiclesandothermeans,sothatthecontentofVCMinthepolyvinylchlorideresinislessthan10ppm,whichmeetstherequirementsofsanitaryresinandexpandstheapplicationrangeofpolyvinylchloride.ItcanevenmaketheVCMcontentintheresinlessthan5ppm,andtheresidualVCMafterprocessingisextremelysmall.Basicallyharmlesstothehumanbody,itcanbeusedasfoodmedicinepackagingandchildren'stoys.
Mainclassification
Accordingtothedifferentapplicationscope,PVCcanbedividedinto:general-purposePVCresin,highpolymerizationdegreePVCresin,andcross-linkedPVCresin.Thegeneral-purposePVCresinisformedbythepolymerizationofvinylchloridemonomerundertheactionofaninitiator;thehighdegreeofpolymerizationPVCresinreferstotheresinpolymerizedbyaddingachainextendertothevinylchloridemonomerpolymerizationsystem;thecross-linkedPVCresinisAresinpolymerizedbyaddingacrosslinkingagentcontainingdieneandpolyenetothevinylchloridemonomerpolymerizationsystem.
Accordingtothemethodofobtainingvinylchloridemonomer,itcanbedividedintocalciumcarbidemethod,ethylenemethodandimported(EDC,VCM)monomermethod(theethylenemethodandimportedmonomermethodarecommonlyreferredtoasethyleneLaw).
Accordingtothepolymerizationmethod,polyvinylchloridecanbedividedintofourcategories:suspensionpolyvinylchloride,emulsionpolyvinylchloride,bulkpolyvinylchloride,andsolutionpolyvinylchloride.Suspensionprocesspolyvinylchlorideisthelargestvarietyinoutput,accountingforabout80%ofthetotaloutputofPVC.SuspensionmethodPVCisdividedintosixmodelsaccordingtoabsoluteviscosity:XS-1,XS-2……XS-6;XJ-1,XJ-2……,XJ-6.Themeaningofeachletterinthemodel:X-suspensionmethod;S-loosetype;J-compacttype.
Accordingtotheplasticizercontent,PVCplasticolefinplasticsareoftendividedinto:non-plasticizedPVC,plasticizercontentis0;rigidPVC,plasticizercontentislessthan10%;semi-rigidForhigh-qualityPVC,theplasticizercontentis10-30%;forsoftPVC,theplasticizercontentis30-70%;forpolyvinylchloridepasteplastic,theplasticizercontentismorethan80%.
Preparationmethod
Polyvinylchloridecanbemadebysubstitutionreactionofethylene,chlorineandcatalyst.Duetoitsfireandheatresistance,polyvinylchlorideiswidelyusedinvariousproductsinallwalksoflife:wiresheaths,fiberopticsheaths,shoes,handbags,bags,accessories,signsandbillboards,architecturaldecorationsupplies,furniture,ornaments,Rollers,hoses,toys,doorcurtains,rollingdoors,auxiliarymedicalsupplies,gloves,somefoodwraps,somefashions,etc.
Polymerizationmethod
PVCispreparedbyfreeradicaladditionpolymerizationmethod.Thepolymerizationmethodismainlydividedintosuspensionpolymerizationmethod,emulsionpolymerizationmethodandbulkpolymerizationmethod.Suspensionpolymerizationisthemainmethod,whichaccountsforabout80%ofthetotaloutputofPVC.Purewater,liquefiedVCMmonomer,anddispersantareaddedtothereactor,andtheninitiatorandotheradditivesareadded.Afterthetemperatureisraisedtoacertaintemperature,theVCMmonomerundergoesfreeradicalpolymerizationtoformPVCparticles.Continuousstirringmakestheparticlesizeuniformandsuspendstheresultingparticlesinwater.Inaddition,thereisalsoamicro-suspensionmethodtoproducePVCpasteresin,whichhasgoodproductpropertiesandpaste-formingproperties.
①Suspensionpolymerizationmethod:themonomerissuspendedanddispersedinthewaterphaseintheformofdroplets,theselectedoil-solubleinitiatorisdissolvedinthemonomer,andthepolymerizationreactionproceedsinthesedroplets.Theheatofreactionisabsorbedbywaterintime.Inordertoensurethatthesedropletsaredispersedinwaterasbeads,suspensionstabilizerssuchasgelatin,polyvinylalcohol,methylcellulose,andhydroxyethylcelluloseneedtobeadded.Initiatorsmostlyuseorganicperoxidesandazocompounds,suchasdiisopropylperoxydicarbonate,dicyclohexylperoxydicarbonate,diethylhexylperoxydicarbonate,andazobisisoheptonitrile,azoNitrogentwoisobutyronitrileandsoon.Thepolymerizationiscarriedoutinapolymerizationvesselequippedwithastirrer.Afterpolymerization,thematerialflowsintothemonomerrecoverytankorstrippertorecoverthemonomer.Thenitflowsintothemixingkettle,washedwithwater,dewateredbycentrifugation,anddriedtoobtainthefinishedresinproduct.Vinylchloridemonomershouldberemovedfromtheresinasmuchaspossible.ForPVCusedforfoodpackaging,thefreemonomercontentshouldbecontrolledbelow1ppm.Inordertoensurethattheresinwiththespecifiedmolecularweightandmolecularweightdistributionrangeandpreventexplosionduringpolymerization,thetemperatureandpressureofthepolymerizationprocessmustbecontrolled.Theparticlesizeandparticlesizedistributionoftheresinarecontrolledbythestirringspeedandtheselectionanddosageofthesuspensionstabilizer.Thequalityofresinischaracterizedbyparticlesizeandparticlesizedistribution,molecularweightandmolecularweightdistribution,apparentdensity,porosity,fisheye,thermalstability,color,impuritycontentandpowderfreeflowability.Thepolymerizationreactoristhemainequipment.Itismadeofsteelreactorliningstainlesssteelorenamel.Itisequippedwithastirrerandaheattransferjackettocontrolthetemperature,oraninternalcoolingpipe,arefluxcondenser,etc.Inordertoreducetheproductioncost,thevolumeofthereactorhasgraduallydevelopedfromafewcubicmeterstoadozencubicmeterstoalargescale,andthemaximumhasreached200cubicmeters(kettlereactor).Thepolymerizershouldbedescaledafterrepeateduse.PVCmadewithpolyvinylalcoholandcelluloseethersassuspensionstabilizersisgenerallylooser,hasmanypores,andhasalargesurfacearea,whichiseasytoabsorbplasticizersandplasticize.
②Emulsionpolymerization:oneoftheearliestindustrialproductionmethodsofPVC.Inemulsionpolymerization,inadditiontowaterandvinylchloridemonomers,surfactantssuchassodiumalkylsulfonatearealsoaddedasemulsifierstodispersethemonomersinthewaterphasetoformanemulsion,usingwater-solublepotassiumpersulfateorAmmoniumpersulfateistheinitiator,and"oxidation-reduction"initiationsystemcanalsobeused,andthepolymerizationprocessandsuspensionmethodaredifferent.Therearealsoaddedpolyvinylalcoholasanemulsionstabilizer,dodecylmercaptanasaregulator,andsodiumbicarbonateasabuffer.Therearethreepolymerizationmethods:batchmethod,semi-continuousmethodandcontinuousmethod.Thepolymerizedproductislatex-like,theparticlesizeoftheemulsionis0.05-2μm,anditcanbedirectlyappliedorspray-driedintoapowderedresin.Theemulsionpolymerizationmethodhasashortpolymerizationperiodandiseasiertocontrol.Theobtainedresinhasahighmolecularweightandarelativelyuniformpolymerizationdegree.Itissuitableformakingpolyvinylchloridepaste,makingartificialleatherorimpregnatingproducts.Theformulationofemulsionpolymerizationiscomplex,andtheproducthasahighimpuritycontent.
③Bulkpolymerizationmethod:Thepolymerizationdeviceisrelativelyspecial,mainlycomposedofaverticalpre-polymerizationtankandahorizontalpolymerizationtankwithaframestirrer.Theaggregationiscarriedoutintwostages.Monomersandinitiatorsarepre-polymerizedinthepre-polymerizationkettlefor1hourtogenerateseedparticles.Atthistime,theconversionratereaches8%to10%,andthenflowsintothesecond-stagepolymerizationkettletoaddprepolymers,etc.Theamountofmonomercontinuestopolymerize.Aftertheconversionratereaches85%to90%,theresidualmonomersaredischarged,andthencrushedandsievedtoobtainthefinishedproduct.Theparticlesizeandshapeoftheresinarecontrolledbythestirringspeed,andthereactionheatistakenoutbythemonomerrefluxandcondensation.Theproductionprocessofthismethodissimple,theproductqualityisgood,andtheproductioncostislow.
PVCmodificationmethod
PVCresinisapolarnon-crystallinepolymer,density:1.38g/cm3,glasstransitiontemperature:87°C,soithaspoorthermalstabilityandisnoteasytoprocess.Itcannotbeuseddirectly,itmustbemodifiedandcompounded,andrelatedadditivesandfillerscanbeaddedbeforeitcanbeused.However,duetothedifferenttypesandfractionsofrelatedadditivesandfillersadded,thisdeterminesthatthepropertiesandrequirementsofthepreparedPVCmaterialsaredifferent.WeusuallycallitPVCformula,strictlyspeaking,itisPVCmodifiedformula,andPVCcanonlybeusedaftermodification.Thiscategoryisoftenclassifiedaspolymermodifiedmaterials.Themodificationofpolymermaterialsmainlyfocusesonresearchonthehighperformanceofgeneral-purposeplastics,theconversionofsingle-componentmaterialstomulti-componentcompositematerials(alloys,blends,andcomposites),functionalizationofmaterials,andoptimizationofperformanceandprice.Modificationmethodsaremainlychemicalmodification,fillingmodification,reinforcementmodification,blendingmodificationandnano-compositemodification.Thebasicprincipleofmodificationistogivematerialsfunctionsorimprovecertainpropertiesthroughadditives.Therefore,thelevelofPVCformulationtechnologydeterminestheleveloftechnologyandproductioncapacityofafactory.
PVCgenerallyneedstobemodifiedandpelletizedfirst.Afterbeingpreparedintopelletswithascrewextruderunit,itwillbemorefullyplasticizedandeasiertoprocess,especiallyforproductswhoseprocessisinjectionmolding.Screwextruderisoneofthemostimportantequipmentforplasticmoldingandprocessing.Itusesexternalpowertransmissionandheattransferfromexternalheatingelementstocarryoutplasticsolidtransportation,compaction,melting,shearing,mixing,andextrusionmolding.Thescrewextruderoccupiesanimportantpositionwhetherasaplasticizinggranulatingmachineoraformingprocessingmachine.Strictlyspeaking,PVCproductswithspecialrequirementsandPVCmodifiedformulasaretailor-madeaccordingtocustomerrequirements.ThereisalsoacopolymerizationderivativeinthePVCproductionprocess.Suchmodifiedvarietiesincludevinylchloridecopolymers,polyvinylchlorideblends,andchlorinatedpolyvinylchloride.
Colorability
Polyvinylchloridehaspoorthermalstabilityandlightresistance.Hydrogenchloridebeginstodecomposeat150°C,andadversereactionsoccurwiththecontentofplasticizer.Inaddition,theeffectofpigmentsonPVCisreflectedinwhetherthepigmentsreactwithPVCandothercomponentsthatmakeupPVCproducts,aswellasthemigrationresistanceandheatresistanceofthepigmentitself.Certaincomponentsinthecolorantmaypromotethedegradationoftheresin.Forexample,ironionsandzincionsarecatalystsforthedegradationreactionofPVCresin.Therefore,theuseofironoxide(red,yellow,brownandblack)pigmentsorwhitepigmentssuchaszincoxide,zincsulfideandlithoponewillreducethethermalstabilityofPVCresins.CertaincolorantsmayinteractwiththedegradationproductsofPVCresin.Forexample,ultramarinepigmentshavepooracidresistance,sointheprocessofPVCcoloring,theywillinteractwiththehydrogenchloridegeneratedbythedecompositionofPVCandlosetheirpropercolor.Therefore,asfarasPVCcoloringisconcerned,takingintoaccountthecharacteristicsoftheresinandrelatedadditivesused,combinedwiththecharacteristicsofthepigment.Thefollowingissuesshouldbepaidattentiontowhenchoosingcolorants.
1.CertainmetalionsinthepigmentwillpromotethethermaloxygendecompositionofPVCresin.
Themeasuringmethodisthehuechangeofpigmentedpolyethylenewhenheatedto180℃.ThepigmentcontainsmetalionstoacceleratethedecompositionofPVC,resultinginahuechange.Atthesametime,itshouldbenotedthatthesameadditionoflakeredcanmakePVCproducedifferentcolordifferences.Ifcalciumiscontained,thecolordifferenceissmall;ifmanganeseiscontained,thecolordifferenceislarge.ThisisduetothepromotionofdehydrochlorinationofPVCbymetalssuchasmanganese.
Sulfidecolorants(suchascadmiumred,etc.)areusedtocolorPVC,andhydrogensulfidemaybeliberatedduetotheseparationofthecolorant.Suchcolorantsshouldnotbemixedwithleadstabilizerstoavoidtheformationofblackleadsulfide.
2.TheeffectofpigmentsontheelectricalinsulationofPVC
Asthecablematerial,PVCisthesameaspolyethylene,andtheelectricalpropertiesaftercoloringshouldbeconsidered.Inparticular,polyvinylchlorideitselfislessinsulatingthanpolyethylene,sotheinfluenceofpigmentsisevengreater.ItshowsthatchoosinginorganicpigmentstocolorPVCisbetterforitselectricalinsulationthanorganicpigments(exceptforfurnaceblackandanatasetitaniumdioxide).
Migration
MigrationonlyoccursinplasticizedPVCproducts,andwhenusingdyesororganicpigments.Theso-calledmigrationisthatthepartiallysolubledyesororganicpigmentsinthesurroundingsolventpenetrateintothesurfaceofthePVCproductthroughtheplasticizer,andthedissolveddye(pigment)particlesarealsobroughttothesurfaceoftheproduct,whichleadstodissolution.Bleeding,solventbleedingorblooming.
Anotherproblemis"scaling".Itmeansthatthecolorantisreleasedfromthesystemduetopoorcompatibilityorincompatibilityofthecoloringmaterialduringcoloringprocessing,andisdepositedonthesurfaceoftheprocessingequipment(suchastheinnerwalloftheextruderbarrel,theinnerwallofthediehole).
Weatherresistance
referstotheabilityofthepigmenttowithstandvariousweathers.Theseincludevisibleandultravioletlight,moisture,temperature,atmosphericchlorination,andchemicalsencounteredduringproductuse.Themostimportantweatherresistanceincludescolorfastness,chalkingresistanceanddurabilityofphysicalproperties.However,organicpigmentsaredifferentduetotheirdifferentstructures.Inaddition,intheformulationscontainingwhitepigments,theweatherresistanceofthepigmentswillbemoreseverelyaffected.
Thefading,darkeningorhuechangeofthepigmentisgenerallycausedbythereactiongeneofthepigment.Thesereactivegenescaninteractwithmoistureorchemicalsintheatmosphere-acidsandalkalis.Forexample,cadmiumyellowwillfadeundertheactionofmoistureandsunlight.Litholredhasgoodlightresistanceandissuitableformostindoorapplications.However,itwillfadeseverelywhenusedoutdoorswithacidandalkalicomponents.
ThemeasuringmethodofdehydrochlorinationisaccordingtoJIS-K-6723,andthemeasuringtemperatureis180℃.Basedonthetimeofdechlorinationoftheuncoloredpolyvinylchloridecompound,theextensionorretardationtimeiscalculatedat5%and10%intervals.Anegativevalueindicatesaccelerateddecomposition.
Stability
Thesofteningpointofpolyvinylchlorideresinislow,about75-80℃,andtheembrittlementtemperatureislowerthan-50~-60℃.Mostproductsarenotsuitableforlong-termuse.Above55℃,itcanreach90℃withspecialformula.Ifthepolyvinylchlorideresinispurelyalinearstructurewithahead-to-sexinterface,therearenobranchesandunsaturatedbondsinside,althoughtheC-Clbondenergyisrelativelysmall,thestabilityofthepolyvinylchlorideresinshouldberelativelyhigh..However,evenwithhigh-puritypolyvinylchlorideresin,hydrogenchloridegaswillbegintoescapewhenitisabove100°Corexposedtoultravioletradiationforalongtime.Itshowsthattherearesharpgroupsorunstablestructuresinitsmolecularstructure.Thelongerthetime,themoredegradation,andthehigherthetemperature,thefasterthedegradationrate,andthefasterthedegradationrateinthepresenceofoxygenorair.
Electricalproperties
Polyvinylchlorideisapolarpolymerandhasagreateraffinityforwaterandotherconductivematerials,soitsresistanceislowerthanthatofnon-polarpolyolefins,butitstillHighervolumecathodeandbreakdownvoltage.Thepolargroupsofpolyvinylchloridearedirectlyattachedtothemainchain.Belowtheglasstransitiontemperature,thedipolarsegmentisrestrictedbythemainchainatomsofthefrozenstructureandcannotbemoved,soitdoesnotproducedipolarizationandcanbeusedatroomtemperature.Ofhigh-frequencyinsulationmaterials.Whenusedaswireinsulation,theelectricalinsulationofsuspensionresinis10-100timeshigherthanthatoffloatingresin.Thepresenceofchlorideionsproducedbydegradationwillreduceelectricalinsulation.
ThedevelopmentstatusofPVC
PVCmaterialswithspecialrequirementsgenerallyneedtobeimportedfromabroad.ThemorefamousforeigncompaniesincludeUnionCarbideCorporationandBorealis.WiththecontinuousR&Dandtechnologyaccumulationoflargescientificresearchinstitutesandproductionunits,theformulationdesignandmanufacturingofdomesticPVCmodifiedmaterialshavereachedtheinternationaladvancedlevel,whichhascompletelyreplacedforeignimportedmaterials,andmanyproductshavebeenexportedabroad.
Developmentprospects
1DevelopmenttrendofPVCresinindustry
China'sPVCresinconsumptionismainlyconcentratedinSouthandEastChinaInthetworegions,theconsumptionofGuangdong,Zhejiang,Fujian,ShandongandJiangsuaccountsforabout70.0%ofthetotalconsumptionofthecountry.Amongthem,GuangdongandFujianprovinceshavethelargestmarketdemand,buttheirproductioncapacityisinsufficient.ImportedPVCresinTheproportionisrelativelyhigh;thePVCresinprocessingindustryinJiangsu,ShandongandZhejiangisrelativelydeveloped,andtheconsumptionofthethreeprovincesaccountsforabout34.0%ofthetotaldomesticconsumption;theproductionandsalesofNorthChinaarebasicallybalanced.Withthestrengtheningofdevelopmenteffortsinthecentralandwesternregionsandtheconstructionoflarge-scaleinfrastructure,theconsumptionofPVCresininthecentralandwesternregionswillgraduallyincrease.
2Demandforecast
Thepolyvinylchlorideresinindustryisabasicandenergy-intensiveindustry,whichisgreatlyaffectedbydemandandenergyprices.Basicchemicalrawmaterialsarethereforeverycloselyrelatedtoeconomicdevelopment.Judgingfromthesituationin2012,thedomesticPVCresinproductioncapacityisstilldeclining,whiledownstreamdemandgrowthisrelativelyslow,coupledwithblockedexportsandincreasedimports,theoveralloperatingrateofdomesticPVCresincompaniesisnothigh,andthenumberofidlecapacityisrelativelyhigh.Themarketpricehasalwaysremainedlowandmedium,andthepricefluctuationrangehasbeenreduced.Inaddition,thelistingofPVCresinfutureshasincreasedtheuncertaintyofthepricefluctuationofthePVCresinmarkettoacertainextent.mycountry'sPVCresinindustrywillstillbeinarelativelydifficultperiodofintegration,andtherewillbemanyfactorsthatwillaffectthefuturedevelopmentofmycountry'sPVCresin.
3Exportissues
①Costbarriers
PVCisabasicchemicalrawmaterialwithsmallproductdifferentiation,anditiscompletelycompetitiveinChinaUnderthecurrentmarketstructure,costisthemostimportantfactoraffectingthecompetitivenessofenterprises.Duetoindustrycharacteristics,rawmaterialsandenergyaccountforarelativelyhighproportionofproductcosts.Thecostofthepetroleumethylenemethodismainlyaffectedbythepriceofoil;theproductioncostofthecalciumcarbidemethodismainlyaffectedbythecostofcalciumcarbide.Generallyspeaking,thecostofcalciumcarbideaccountsforabout70%ofthecostofPVC,andthecostofelectricityaccountsforabout60%ofthecostofcalciumcarbide.Westernmycountryhasabundantpowerresourcesandrelativelylowelectricityprices.Comparedwitheasterncalciumcarbidemanufacturingenterprises,westerncalciumcarbidemanufacturingenterpriseshavecertainadvantagesintermsofcost.Andenterpriseswithresourceendowmentandsupportingcalciumcarbideproductionwillbuildamoresolidcostbarrier.
②Industrialpolicybarriers
Inordertopromotetheupgradingoftheindustrialstructureofthechlor-alkaliindustryandstandardizethedevelopmentoftheindustry,follow"Technicalprogress",theNationalDevelopmentandReformCommissionformulatedandissuedthe"Chlor-Alkali(CausticSoda,PVC)IndustryAccessConditions",andithasbeenimplementedsinceDecember1,2007:Intermsofindustriallayout,newchlor-alkaliproductionisrequiredEnterprisesshouldbeclosetoresourcesandenergysources.Inprinciple,nonewcalciumcarbide-basedPVCprojectsandsupportingcausticsodaprojectswillbebuiltintheeasternregionexceptfortherelocatedenterprises;technologicalaspectsrequirethatnewandexpandedcalciumcarbide-basedPVCprojectsmustbeconstructedatthesametimeCalciumcarbideslagisacomprehensiveutilizationdeviceforcementandothercalciumcarbideslag;theaccessconditionsalsosetstandardsfornewprojectsintermsofenergyconsumptionindicatorsandenvironmentalprotection.Theadjustmentofindustrialpolicieshasgreatlyraisedthethresholdofcapital,technology,talents,andresourcesforthechlor-alkaliindustry.
③Scalebarriers
ThescaleofinvestmentrequiredtoproducePVCisrelativelylarge,thefixedcostsarerelativelyhigh,andthescalebenefitsarerelativelyobvious.Large-scaleenterprisesareinamoreadvantageouspositioninnegotiationswithsuppliers,whichisconducivetoreducingrawmaterialcosts.Companieswithlargeproductionandsaleshaveacorrespondinglyhighermarketshare,havegreatermarketinfluence,andarerelativelyeasiertoacquirecustomers.OnceaPVCmanufacturerreachesalargescaleofproductionandsales,themarginalcostwillgraduallydecreaseandtheabilitytoresistriskswillbeenhanced.
④Financialbarriers
Atthesametime,withthecountry’sincreasinglystrictsafetyandenvironmentalprotectionsupervision,theconstructionofchlor-alkaliproductionequipmentmustbeequippedwithcorrespondinglarge-scaleenvironmentalprotectionequipment(suchascalciumcarbidelinemustbeequippedwithcalciumcarbideslagCementequipment,etc.),thecapitalinvestmentisrelativelylarge,andmostsmallandmedium-sizedenterprisesgenerallycannotaffordit.
Therefore,manufacturersinvestinginthisindustrymusthavestrongfinancialstrengthandtherearecertainfinancialbarriers.
ThedemandforPVCintheIndiandomesticmarkethasincreasedyearbyyear,frommorethan1.7milliontonsin2009tomorethan2.2milliontonsin2012;however,therewereonlyfivePVCmanufacturersinIndiawithadomesticproductioncapacityof1.25milliontons./year.IndiaFinolexIndustriesisthelargestproducerofPVCpipesinIndia.Duetotheimbalancebetweensupplyanddemand,thereisalargegap,sotheaverageannualPVCimportvolumeinIndiareaches950,000tons.Atthesametime,India'svinylrawmaterialgapisalsoincreasingyearbyyear.In2011,itwas722,000tons,in2012itwas976,000tons,andin2013itwillreach1.12milliontons.Accordingtostatistics,fromApriltoSeptember2012,India'sPVCimportsweremainlyfromSouthKorea,Taiwan,Germany,theUnitedStates,Mexicoandothercountriesandregions.Amongthem,PVCimportsfromSouthKoreaandTaiwanbothexceeded200,000tons.
RajeshDeshpandesaidthatIndia’sPVCdownstreamproductsaremainlyPVCpipesandaccessories,accountingfor43%ofthecountry’stotalPVCdownstreamproducts.Inthefirstsixmonthsofthe2012-2013fiscalyear,downstreamdemandincreasedby20%,andimportsincreasedby50%.Accordingtothedevelopmentspeed,byMarch2013,thedomesticmarketdemandinIndiawillreach2.2milliontons,andthedevelopmentspeedofPVCpipeswillalsoreachdoubledigits.
AsthedownstreamconsumermarketforPVCisexpandingyearbyyear,India'sPVCindustryhasagreateropportunityfordevelopment.AccordingtoRajeshDeshpande'sforecast,thegrowthofthedownstreamconsumermarketforPVCproductsinIndiastemsfrommanyaspects.Thegovernment'sinvestmentininfrastructureconstructionhasincreasedyearbyyear.Statisticsshowthatduringthe"TwelfthFive-YearPlan"period,theIndiangovernment'sinvestmentininfrastructureconstructionwillreach890billionUSdollars;theruralinfrastructureconstructionanddevelopmentfundwillincreaseto3.5billionUSdollars;theruraldrinkingwaterandenvironmentalsanitationinvestmentbudgetwillreach2.5billionUSdollars;US$53millionwillbeinvestedintheconstructionofirrigationsystems;intheDelhi-MumbaiIndustrialCorridor,US$90billionwillbeinvestedintheconstructionoflarge-scaleinfrastructure,ofwhichtheJapanesegovernmentsponsoredUS$4.5billion.
Despitethelargegapbetweensupplyanddemand,theIndianPVCindustryfacescertainchallengesduetothegreatercompetitiveadvantagesofimportedproducts.RajeshDeshpandesaidfranklythattherearestillcertainproblemsinthedevelopmentofthePVCindustryinIndia:forexample,usershavenotyetseentheadvantagesofplasticpipesovertraditionalpipes;environmentalistsandnon-governmentalorganizationshaveexplainedtheharmsofplasticpipesfromtheperspectiveofenvironmentalhazards;relevantproductioncompanieshavenotPayattentiontothequalitycontroloftheirownproducts.Therefore,iftheIndianPVCindustrywantstoachievesustainabledevelopment,itmustcontinuetodevelopnewproductsandnewtechnologies,andatthesametimepayattentiontotherecyclingandreuseofPVCproducts.
AlthoughChinahastheworld’slargestPVCproductioncapacity,duetothedeclineinethyleneprices,theimportvolumeofethylene-basedPVCsetanewrecordin2009.Ontheotherhand,China’sPVCmarkethasalwaysbeenatalowstart.Ratestatus.Inthefirsthalfof2009,Chinaimportedabout1.2milliontonsofpolyvinylchloride,whichis1milliontonsmorethanthetotalimportvolumein2008.Withthesoaringpriceofethylene,thecompetitiveadvantageofChina'scalciumcarbideprocessPVCproductionhasemerged.Inthesecondhalfof2009,China'sPVCimportsdeclinedsteadily.AccordingtoChinaCustomsdata,importsinNovemberwereonly60,646tons.
Inthefirsthalfof2013,affectedbymanyunfavorablefactorssuchasovercapacityintheindustryandweakdownstreamdemand,theoverallperformanceofthepolyvinylchloride(PVC)industrywaspoor,andcompanieswereinadifficultsituation.However,theperformanceofthePVCforeigntrademarketiseye-catching,andanumberofdatahaveobviousrecoveryadjustmentscomparedwiththesameperiodinpreviousyears.However,industryinsiderspointedoutthatwiththeincreaseintheoperatingrateofPVCplantsintheUnitedStates,mycountry'sPVCforeigntradeisexpectedtoshowarecoverygrowthinimportsandasteadydeclineinexports.
AccordingtothestatisticsofChinaChlor-AlkaliIndustryAssociation,asoftheendofJune2013,thedomesticproductioncapacityofPVC(vagueresin)was23.92milliontonsperyear.Amongthem,inthefirsthalfof2013,thenewlyaddedproductioncapacityofPVCwas860,000tons/year,with350,000tons/yearexited,andanetincreaseof510,000tons/year,allwithdrawnproductioncapacitywascalciumcarbideproductionequipment.Theoverallproductioncapacityexpansionrateoftheindustryhassloweddownsignificantly,butthetrendofsteadyincreaseinproductioncapacitycontinues.
Intermsofexports,mycountry’scumulativeexportsofPVCfromJanuarytoMayincreasedsignificantlyby152.4%overthesameperiodlastyear.Fromtheperspectiveofflow,thelargestexportconsumermarketisIndia;thenumberofsourcesexportedtoRussiahassloweddown,rankingsecond.
Inaddition,sincetheoutbreakofthefinancialcrisis,greatchangeshavetakenplaceintheglobalmarketandtradeenvironment.Tradeprotectionisminvariouscountrieshasrisen,andtradefrictionsagainstChineseenterprises’productshaveincreasedsignificantly.
PhysicalandchemicalpropertiesofPVC
Thenaturalcolorisyellowishtranslucentandshiny.Transparencyisbetterthanpolyethyleneandpolypropylene,butworsethanpolystyrene.Dependingontheamountofadditives,itcanbedividedintosoftandhardpolyvinylchloride.Softproductsareflexibleandtough,andfeelsticky.Thehardnessofhardproductsishigherthanthatoflowdensitypolyethylene.However,ifitislowerthanpolypropylene,whiteningwilloccurattheinflection.Stable;noteasilycorrodedbyacidandalkali;relativelyresistanttoheat.
PVChasflameretardant(flameretardantvalueabove40),highchemicalresistance(resistanttoconcentratedhydrochloricacid,90%sulfuricacid,60%nitricacidand20%Sodiumhydroxide),theadvantagesofgoodmechanicalstrengthandelectricalinsulation.
Polyvinylchloridehaspoorstabilitytolightandheat.Thesofteningpointis80°C,anditstartstodecomposeat130°C.Withoutheatingthestabilizer,polyvinylchloridestartstodecomposeat100°C,anddecomposesfasterabove130°C.Whenheated,itdecomposesandreleaseshydrogenchloridegas(hydrogenchloridegasisatoxicgas)tochangeitscolorfromwhite→lightyellow→red→brown→black.Ultravioletraysandoxygeninthesunwillcausethephoto-oxidationanddecompositionofpolyvinylchloride,whichwillreducetheflexibilityofpolyvinylchlorideandeventuallybecomebrittle.ThisisthereasonwhysomePVCplasticsturnyellowandbecomebrittleovertime.
Ithasstablephysicalandchemicalproperties,isinsolubleinwater,alcohol,gasoline,andhaslowgasandwatervaporleakage;itcanwithstandanyconcentrationofhydrochloricacid,lessthan90%sulfuricacid,50-60%atroomtemperatureThenitricacidandcausticsodasolutionbelow20%havecertainresistancetochemicalcorrosion;itisquitestabletosalts,butitcanbedissolvedinorganicsolventssuchasethers,ketones,chlorinatedaliphatichydrocarbonsandaromatichydrocarbons.
Industrialpolyvinylchlorideresinismainlyamorphousstructure,butalsocontainssomecrystallineregions(about5%),sopolyvinylchloridehasnoobviousmeltingpoint,anditstartstosoftenatabout80°C,andtheheatdistortiontemperature(Under1.82MPaload)itis70-71°C,itstartstoflowat150°Cunderpressure,andslowlyreleaseshydrogenchloride,causingPVCtochangecolor(fromyellowtored,brown,orevenblack).
Theweight-averagerelativemolecularmassofindustrialpolyvinylchlorideisintherangeof4.8-48,000,andthecorrespondingnumber-averagerelativemolecularmassis2-19.5million.Theweight-averagerelativemolecularmassofmostindustrialresinsisbetween100,000and200,000,andthenumber-averagerelativemolecularmassisbetween45,000and64,000.Rigidpolyvinylchloride(withoutplasticizer)hasgoodmechanicalstrength,weatherresistanceandflameresistance,andcanbeusedaloneasastructuralmaterialforthemanufactureofpipes,platesandinjectionmoldedproductsinthechemicalindustry.Rigidpolyvinylchloridecanbeusedasareinforcingmaterial.
Materialproperties
Density:1380kg/m3
Young’smodulusofelasticity(E):2900-3400MPa
Tensilestrength(σt):50-80MPa
Elongationatbreak:20-40%
Glasstransitiontemperature:87℃
Meltingpoint:212℃
Softeningtemperature:85℃
(λ):0.16W/(m·K)
Coefficientofthermalexpansion(α):8×10-5/K
Heatcapacity(c):0.9kJ/(kg·K)
Waterabsorption(ASTM):0.04-0.4
Refractiveindex:1.52~1.55
ThebiggestfeatureofPVCisflameretardant,soitiswidelyusedinfireprotectionapplications.Butpolyvinylchloridewillreleasehydrogenchlorideandothertoxicgasessuchasdioxinsduringthecombustionprocess.
ThecombustionofPVCisdividedintotwosteps.First,thehydrogenchloridegasandthedienecontainingdoublebondsaredecomposedbyburningat240°C-340°C,andthencarboncombustionoccursat400-470°C.
Itisoneofthelargestplasticproductsintheworld.Itischeapandwidelyused.PVCresiniswhiteorlightyellowpowder.Differentadditivescanbeaddedaccordingtodifferentpurposes,andPVCplasticscanpresentdifferentphysicalandmechanicalproperties.Addinganappropriateamountofplasticizertothepolyvinylchlorideresincanbemadeintoavarietyofhard,softandtransparentproducts.
Thedensityofpurepolyvinylchlorideis1.4g/cm3,andthedensityofpolyvinylchlorideplasticpartsaddedwithplasticizersandfillersisgenerally1.15-2.00g/cm3.
Rigidpolyvinylchloridehasgoodtensile,bending,compressionandimpactresistance,andcanbeusedasastructuralmaterialalone.
Theflexibility,elongationatbreak,andcoldresistanceofsoftPVCwillincrease,butthebrittleness,hardness,andtensilestrengthwilldecrease.
Polyvinylchloridehasgoodelectricalinsulationproperties,canbeusedaslow-frequencyinsulationmaterials,anditschemicalstabilityisalsogood.Duetothepoorthermalstabilityofpolyvinylchloride,long-termheatingwillcausedecomposition,releaseHCLgas,andmakepolyvinylchloridediscolor,soitsapplicationrangeisnarrow,andtheusetemperatureisgenerallybetween-15and55℃.
TheconversionofPVChardnessvaluePa(Pa)andShore(shore)hardnessisasfollows:
Pa(Pa(Pa)) | Shorehardness(Shorehardness) |
45 | 89±2,87~91A |
50 | 86±2,84~88A |
55 | 83±2,81~85A |
60 | 80±2,78~82A |
65 | 78±2,76~80A td> |
70 | 75±2,73~77A |
75 | 72±2,70~74A |
80 | 69±2,67~71A |
PVChardnesscomparisontable | |||
Panelhardness | Thickness | Shorehardnesstestvalue | Averagehardnessvalue |
30P | 6mm | 93-96° | 94.5° |
35P | 6mm | 87-93° | 90° |
38P | 6mm | 89-90° | 89.5° |
40P | 6mm | 88-90° | 89° |
45P | 6mm | 84-90° | 85° |
50P | 6mm | 82-83° | 82.5° |
55P | 6mm | 70-80° | 79° |
60P | 6mm | 74-76° | 75° |
65P | 6mm | 73-75° | 74° |
70P | 6mm | 72-74° | 73° |
75P | 6mm | 70-70.5° | 70° |
80P | 6mm | 67-68° | 67.5° |
85P | 6mm | 64-66° | 65° |
90P | 6mm | 63-64° | 63.5° |
95P | 6mm | 58-60° | 59° |
100P | 6mm | 57-59° | 58° |
110P | 6mm | 54-56° | 55° |
Anotherhardnesscomparisontable | |
Pa | Shorehardness |
30 | 95±2 |
45 | 90±2 |
50 | 88±2 |
60 | 84±2 |
70 | 80±2 |
80 | 76±2 |
90 | 72±2 |
95 | 68±2 |
105 | 64±2 |
Note:Shorehardnessvalueis15secondsreading |
Moldingconditions
RigidPVC
Barreltemperature:160-190℃
Moldtemperature:40-60℃
Dryingtemperature:80℃×2h
Pressure:700-1500kg/cm2
Density:1.4g/cm3
Moldingshrinkage:0.1-0.5%
Meatthickness:2.0-50.mm
Waterabsorption(24h):0.1-0.4%
Meltingsofteningpoint:89℃
Heatdistortiontemperature:70℃
SoftPVC
Materialtubetemperature:140-170℃
Moldtemperature:40-60℃
Dryingtemperature:80℃×2h
Injectionpressure:600-1500kg/cm2
Density:1.4g/cm3
Moldingshrinkage:0.1-0.5%
Meatthickness:2.0-50.mm
Waterabsorption(24h):0.1-0.4%
Meltingsofteningpoint:85℃
Heatdistortiontemperature:55℃
Materialprocessing
PolyVinylchlorideplasticshavedifferentforms,withgreatdifferences,andvariousprocessingmethods,suchaspressing,extrusion,injection,coatingandsoon.Theparticlesize,fisheyes,bulkdensity,purity,foreignimpurities,andporosityofpolyvinylchlorideresinhaveanimpactonprocessability;forpasteresin,theviscosityandgellingpropertiesofthepasteshouldbeconsidered.
Polyvinylchlorideisanamorphouspolymerwithlowshrinkage.Thepowdershouldbepreheatedbeforeprocessingtoremovemoisture,enhancetheplasticizingeffect,andpreventbubbles.Moreover,PVCiseasytodecompose,especiallywhenitcomesincontactwithsteelandcopperathightemperatures(decompositiontemperature200degrees).Themoldingtemperaturerangeissmall,andthematerialtemperaturemustbestrictlycontrolled.Whenusingascrewinjectionmachineandastraight-throughnozzle,theapertureshouldbelargetopreventdeadendsfromstagnating.Themoldpouringsystemshouldbethick,thegatesectionshouldbelarge,themoldshouldbecooled,themoldtemperatureis30-60℃,andthematerialtemperatureis160-190℃.
Belowtheglasstransitiontemperature(Tg,80°C),polyvinylchlorideisglassy;atTg→viscousflowtemperature(Tf,about160°C),itisahighlyelasticrubberwithplasticity;atTf→Thethermaldecompositiontemperature(Td)isaviscousfluidstate,thehigherthetemperature,theeasiertheflow.WhenthetemperatureexceedsTd,PVCdecomposesalargeamountofhydrogenchloride(HCl),andthemateriallosesitschemicalstabilityandphysicalproperties.Therefore,Tdistheupperlimittemperatureforprocessingandmolding.DuetothelargeforcebetweenthepolyethylenemoleculesandthehighTf,evenclosetothedecompositiontemperature,itisnecessarytoaddaplasticizertoreducetheTf.Ontheotherhand,itisalsonecessarytoaddstabilizerstoincreasetheTdofPVCinordertobeprocessedandformed.
Theglasstransitiontemperature(Tg)isonlyrelatedtothemolecularchainsegmentstructure,andhaslittletodowiththemolecularweight.Theviscousflowtemperature(Tf)isthetemperatureatwhichmacromoleculesstarttomove,andisrelatedtothemolecularweight.Larger,thehigherTf.Therefore,forsomeprocessingmolding(suchasinjectionmolding),itisnecessarytoappropriatelyreducethemolecularweightoftheresin.Accordingtothedifferentmolecularweight,domesticsuspensionPVCresinisdividedinto1-7grades,thelargertheserialnumber,thesmallerthemolecularweight.XJ-4(XS-4)toXJ-7(XS-7)resinsareoftenusedinthemanufactureofhardpipes,hardboards,etc.OtherresinswithlowermodelsandlargermolecularweightsneedtobeaddedinlargeamountsduetohigherTf.TheagentreducesTf,soitisoftenusedinthemanufactureofsoftproducts.Polyvinylchloridewithanaveragedegreeofpolymerizationbelow1000iscalledlow-polymerizationdegreepolyvinylchloride,whichhasgoodprocessingproperties,andlessplasticizerscanbeaddedduringprocessing,sothattheproductwillnotbeacceleratedduetothemigrationofplasticizersAgeing.Polyvinylchlorideproductswithlowdegreeofpolymerizationhavegoodtransparencyandarewidelyusedinbuildingmaterials,foodandpharmaceuticalpackagingmaterialsandtoreplaceorganicglassproducts.
Polyvinylchloridemeltisanon-Newtonianpseudo-fluid.Thehighertheshearrate,thesmallertheapparentviscosity,andthechangeisquitesensitive.Increasingthetemperaturewillnotreducetheviscositymuch.Eveniftheplasticisbelowthedecompositiontemperature,itwillcauseheatandoxidativedegradationduetothehightemperatureforalongtime,whichwillaffectitsperformance.Therefore,toimprovethefluidityofPVCmelt,themainconsiderationshouldbetoincreasetheshearrate(increasethepressure).Infact,increasingtheexternalforcewillhelpthemovementofthemacromolecules,sothattheTfwillbereduced,andthemacromoleculescanflowatalowertemperature.
Mainuses
1.PVCprofile
ProfilesandprofilesarethelargestconsumptionofPVCinmycountry.Itaccountsforabout25%ofthetotalconsumptionofPVC.Itismainlyusedtomakedoorsandwindowsandenergy-savingmaterials.Itsapplicationvolumeisstillincreasingsignificantlyacrossthecountry.Indevelopedcountries,themarketshareofplasticdoorsandwindowsisalsothehighest,forexample,Germanyis50%,Franceis56%,andtheUnitedStatesis45%.
2.Polyvinylchloridepipes
Amongmanypolyvinylchlorideproducts,polyvinylchloridepipesarethesecondlargestconsumptionarea,accountingforabout20%ofitsconsumption.Inmycountry,polyvinylchloridepipesaredevelopedearlierthanPEpipesandPPpipes,withmorevarieties,excellentperformance,andawiderangeofapplications,andoccupyanimportantpositioninthemarket.
3.Polyvinylchloridefilm
TheconsumptionofPVCinthefieldofPVCfilmranksthird,accountingforabout10%.AfterPVCismixedwithadditivesandplasticized,athree-rollorfour-rollcalenderisusedtomakeatransparentorcoloredfilmwithaspecifiedthickness.Thefilmisprocessedinthiswaytobecomeacalenderedfilm.Itcanalsobecutandheat-sealedtoprocesspackagingbags,raincoats,tablecloths,curtains,inflatabletoys,etc.Thewidetransparentfilmcanbeusedforgreenhouses,plasticgreenhousesandmulchfilms.Thebiaxiallystretchedfilmhasthecharacteristicsofheatshrinkageandcanbeusedforshrinkpackaging.
4.PVChardmaterialsandplates
Stabilizers,lubricantsandfillersareaddedtoPVC.Aftermixing,itcanbeextrudedwithanextruder.Hardpipes,special-shapedpipesandcorrugatedpipesofvariouscalibersareusedassewerpipes,drinkingwaterpipes,wirecasingsorstaircasehandrails.Thecalenderedsheetsareoverlappedandhotpressedtomakehardplatesofvariousthicknesses.Theplatecanbecutintotherequiredshape,andthenweldedwithhotairwithPVCweldingrodtoformvariouschemicalresistantstoragetanks,airductsandcontainers.
5.GeneralsoftPVCproducts
Usinganextruder,itcanbeextrudedintohoses,cables,wires,etc.;usinganinjectionmoldingmachinetomatchvariousMoldscanbemadeintoplasticsandals,shoesoles,slippers,toys,autoparts,etc.
6.Polyvinylchloridepackagingmaterials
PVCproductsaremainlyusedforpackagingvariouscontainers,filmsandrigidsheets.PVCcontainersmainlyproducebottlesofmineralwater,beverages,andcosmetics,aswellaspackagingforrefinedoil.PVCfilmcanbeusedtoco-extrudewithotherpolymerstoproducelow-costlaminatesandtransparentproductswithgoodbarrierproperties.Polyvinylchloridefilmcanalsobeusedforstretchorheatshrinkpackagingforpackagingmattresses,cloth,toysandindustrialgoods.
7.Polyvinylchloridewallpanelsandfloors
PVCwallpanelsaremainlyusedtoreplacealuminumwallpanels.ExceptforapartofPVCresin,theothercomponentsofPVCfloortilesarerecycledmaterials,adhesives,fillersandothercomponents.Theyaremainlyusedonthegroundofairportterminalbuildingsandotherhardground.
8.Polyvinylchloridedailyconsumergoods
Luggagebagsaretraditionalproductsmadeofpolyvinylchloride,andpolyvinylchlorideisusedtomakeAllkindsofimitationleather,usedinluggage,sportsproducts,suchasbasketball,footballandrugby,etc.Itcanalsobeusedtomakebeltsforuniformsandspecialprotectiveequipment.Polyvinylchloridefabricsforclothingaregenerallyabsorbentfabrics(noneedtobecoated),suchasponchos,babypants,imitationleatherjacketsandvariousrainboots.Polyvinylchlorideisusedinmanysportsandentertainmentproducts,suchastoys,records,andsportsgoods.Polyvinylchloridetoysandsportsgoodshavealargegrowthrate.Theyhaveanadvantageduetotheirlowproductioncostandeasymolding.
9.PVCcoatedproducts
TheartificialleatherwithabackingismadebycoatingPVCpasteonclothorpaper,andthenplasticizingitatatemperatureabove100℃.化成。ItcanalsobeformedbycalenderingPVCandadditivesintoafilm,andthenpressingitwiththesubstrate.Artificialleatherwithoutasubstrateisdirectlycalenderedbyacalenderintoasoftsheetofacertainthickness,andthenthepatterncanbepressed.Artificialleathercanbeusedtomakesuitcases,purses,bookcovers,sofasandcarcushions,etc.,aswellasfloorleather,usedasfloorcoveringsforbuildings.
10.PVCfoamproducts
WhensoftPVCismixed,addanappropriateamountoffoamingagenttomakeasheet,whichisfoamedintofoamPlastic,canbeusedasfoamslippers,sandals,insoles,andshock-proofcushioningpackagingmaterials.Theextrudercanalsobeusedtoformlow-foamedhardPVCboardsandprofiles,whichcanreplacewoodandisanewtypeofbuildingmaterial.
11.PVCtransparentsheet
TheimpactmodifierandorganotinstabilizerareaddedtothePVCtobecometransparentaftermixing,plasticizingandcalenderingSheet.Thermoformingcanbemadeintothin-walledtransparentcontainersorusedforvacuumblisterpackaging.Itisanexcellentpackagingmaterialanddecorativematerial.
12.Others
Doorsandwindowsareassembledwithhardspecial-shapedmaterials.Insomecountries,ithasoccupiedthedoorandwindowmarkettogetherwithwoodendoors,windows,aluminumwindows,etc.;wood-likematerials,steel-basedbuildingmaterials(northern,seaside);hollowcontainers.
Virtualcircuitisoneoftheservicesprovidedbypacketswitchingnetwork(theotherisdatagramservice).Simplyput,itistoestablishavirtuallogicalconnectionbetweenuserhoststhroughthecontrolmechanisminsidethenetwork,Andtoensurethecorrectnessandsequenceofthetransmissionoftheenvelope,theestablishmentandremovalofthevirtualcircuitbeforeandafterthecommunication.Apermanentvirtualcircuitisavirtualcircuitthatisestablishedwhenthenetworkisinitialized,andthevirtualcircuitisalwaysmaintained.BothX.25networkandB-ISDNprovidePVCservices.PVCplasticbagsaregenerallyprohibited.
Researchonnewmaterials
Currently,thetotalannualdemandformodifiedplasticsinmycountryisabout5milliontons,accountingforabout10%oftotalplasticconsumption,anditsproportionisfarlowerthanthatoftheworld.Theaveragelevel.Comparedwiththedevelopedcountriesintheworld,mycountry'spercapitaplasticconsumptionstillhasabiggap.Inordertorealizetherapidandstabledevelopmentofmycountry'smodifiedplasticsindustry,innovativetechnologyisthekeytofuturedevelopment.
Chemicalindustryanalystsbelievethatthecurrentoveralldevelopmentlevelofmycountry’smodifiedplasticsindustryisnotveryhigh.Theproductionscaleofenterprisesintheindustryisgenerallysmall,theproductmarketproducesmanyprimaryproducts,andthequalityofintermediateproductsisnotstableenough.,Thelackofhigh-endproductsisfarfrommeetingtheneedsofmycountry’scurrentsocialandeconomicdevelopment.Asanimportantcomponentinthefieldofnewchemicalmaterials,modifiedplasticshavebeenlistedasoneofthekeyscientificandtechnologicalfieldsfordevelopmentbythecountry.Thesuccessiveintroductionofvariouspoliciesinmycountrywillfurtherpromotethedevelopmentofthemodifiedplasticsindustry.Theautomobileandhomeapplianceindustriesarehotspotsforthedevelopmentofmodifiedplastics,andbothaccountformorethan50%.
Theapplicationofplasticsintheautomotiveindustryhasahistoryofmorethan50years.Withthedevelopmentofautomobilesinthedirectionoflightweightandenergysaving,higherrequirementsareputforwardformaterials.Because1kgofplasticcanreplace2-3kgofsteelandotherheaviermaterials,andevery10%reductionintheweightofthecar,fuelconsumptioncanbereducedby6%-8%.Therefore,increasingtheamountofmodifiedplasticsusedinautomobilescanreducethecostandweightoftheentirevehicle,andachieveenergy-savingeffects.Theamountofdifferentplasticsusedinpassengercarsandcommercialvehiclesisalsodifferent.ThedemandformodifiedPP,PCalloyandmodifiedABSwasapproximately114.63,15.13and149,700tonsrespectivelylastyear.Themodifiedplasticsmarketforhouseholdappliancesinmycountryismainlyoccupiedbyforeigncompanies,anddomesticmodifiedplasticscompaniesaccountforlessthanone-thirdofthemarketshare.Sincetheproductsofdomesticcompaniesaremostlylimitedtolow-techandlow-standardlevels,theabilitytodevelopfieldswithhigh-performancerequirementsisobviouslyinsufficient.
Accordingtothe"2009-2012ChinaModifiedPlasticIndustryMarketAnalysisandInvestmentValueResearchReport",withthesubstantialimprovementofpeople’slivingstandardsandtheimprovementoftechnicalmeans,domestic"plasticsinsteadofsteel","Plasticinsteadofwood"willbecomeatrend.Themodifiedplasticsindustry,asasub-industrywiththefastestgrowthandgreatpotentialintheplasticsprocessingindustry,isexpectedtomaintainagrowthrateofmorethan10%inmycountry'stotalmarketdemandinthenextfiveyears.
1.PVCisusedtoreplacesteelmaterialwithplastic
ThroughtheresearchonPVCmodificationtechnology,theuseofforeignadvancedinternalplasticizationtechnologyandadditiveformulaensuresthemechanicalperformanceofPVCplasticsteel.,Electricalperformance,improvedflameretardantperformance,sothattheproducthastheadvantagesofhighstrength,corrosionresistance,flameretardant,goodinsulationperformance,lightweight,andconvenientconstruction.Itcancompletelyreplacesteelpipesinelectricalwiringsystems.
2.PVCisreplacedbywoodwithplastic
PVCwood-plasticcompositeisthemainrawmaterialofwastewoodfiberandplastic,supplementedbyappropriateprocessingaids,andispreparedbyhotpressing.Preparedintoanewtypeofcompositematerial.Itsproductsfullyreflecttheconceptofrecyclingofrenewableresourcesandpetroleumproducts,andareofgreatsignificancetoalleviatingthecurrentshortageofwoodandpetroleumresourcesandseriousenvironmentalpollution.
HomebuildingmaterialsproductsusingPVCasthemainrawmaterialhavebecomethesecondpillarofmycountry'splasticsindustry,withanaverageannualgrowthrateofmorethan15%.Inthenext10years,thecountryisexpectedtoincreasethebuildingareaof30billionsquaremeters.Ifthesebuildingsachieve50%energysavingontheexistingbasis,themarketdemandforenergy-savingbuildingmaterialscanreachtrillionsofyuan,whichisanindoorenergy-savingdecorationmaterial.Thereisahugeroomfordevelopment.Foralongtime,thebuildingmaterialsindustryhasalwaysappearedintheimageofhighenergyconsumptionandhighpollution.Inordertomeettherequirementsofthelow-carboneconomy,afteryearsofresearchanddevelopment,householdbuildingmaterialscompanieshavedevelopedabatchofPVChigh-simulationbuildingmaterialsthatuseplasticinsteadofwood,whichhavebecomeaperfectcombinationoflow-carbonandpracticalhouseholdproducts.
IndustryexpertspointedoutthattheuseofplasticinsteadofwoodforPVCbuildingmaterialsnotonlysavescosts,butisalsorecyclable,inlinewiththegeneraltrendofenvironmentalsustainabilityandcirculareconomy.
14.Syntheticmaterials
Polyvinylchloride,orPVCforshort,isathermoplasticresin.Polyvinylchloridefuturesarealsofuturesvarietieswithpolyvinylchlorideasthesubjectmatter.
Plastics:polyethylene;polyvinylchloride;polystyrene;polyvinylalcohol;polypropylene;polyacrylicacid;polybutene;polyisobutylene;polysulfone;polyoxymethylene;polyamide;polycarbonate;Polylacticacid;polytetrafluoroethylene;polyethyleneterephthalate;epoxyresin;phenolicresin;polyurethane
Syntheticrubber:butadienerubber;styrenebutadienerubber;nitrilerubber;neoprene
Syntheticfibers:polypropylene;polyester;nylon;acrylic;spandex;vinylon;nylon;dacron;Keflon
Identificationmethod
PVCConventionTheidentificationmethodsaregenerallysummarizedintothefollowingthreecategories,namely:
(1)Combustionmethodidentification:
Softeningormeltingtemperaturerange:75~90°C;
Combustionstatus:self-extinguishingafterbeingignited;
Combustionflamestatus:upperyellowandgreenwithsmoke;afterleavingthefire:leavingthefireextinguished;smell:pungentsour.
Thismethodistheeasiestandmostdirect,andisgenerallythefirstchoice.
(2)Solventtreatmentidentification:
Solvent:tetrahydrofuran,cyclohexanone,ketone,dimethylformamide;
Non-solvent:methanol,Acetone,heptane.
ByaddingthesuspectedPVCplastictotheabovesolvent,observethedissolutionoftheplastictodeterminewhetheritisPVC.Afterthesolventisheated,thedissolvingeffectwillbemoreobvious.
(3)Specificgravitymethod:
ThespecificgravityofPVCis1.35~1.45,generallyaround1.38.ThedifferenceinspecificgravityorthemethodofdeterminingspecificgravitycanbeusedtodistinguishPVCfromotherplastics.ButbecausePVCcanaddplasticizers,modifiersandfillerstomakethePVCbecomeverydifferentinspecificgravity,thedifferenceinsoftnessandhardnessisverylarge,andatthesametime,duetotheadditionofsomeingredients,manypropertiesofPVCplasticwillchange,resultinginOurcommonlyusedidentificationmethodsarenoteffective,andeventhephenomenonhaschanged,makingitimpossibletomakeaccuratejudgments.Forexample,intermsofdensity,plasticizedpolyvinylchloride(containingapproximately40%plasticizer)is1.19~1.35;whilePVChardproductshaveincreasedto1.38~1.50.IfitisahighlyfilledPVCproduct,thedensitysometimesexceeds2.
Inaddition,itcanalsobedeterminedbymeasuringwhetherthematerialcontainschlorine,butbecausevinylchloridecopolymers,neoprenerubber,polyvinylidenechloride,chlorinatedpolyvinylchloride,etc.allcontainahigherproportionofchlorine,Butalsothroughthepyridinecolorreactiontoidentify.Notethatbeforethetest,thesamplemustbeextractedwithethertoremovetheplasticizer.Testmethod:Dissolvethesampletakenfrometherwithbenzeneintetrahydrofuran,filterouttheinsolublecomponents,addmethanoltomakeitprecipitate,andextractthesamplebefore75Belowthedegreeofdryness.Donotneed1mLofpyridinetoreactwithasmallamountofdriedsample.Afterafewminutes,add2dropsofmethanolsolutionof5%sodiumhydroxide(1gsodiumhydroxideisdissolvedin20mLmethanol),andobservethecolorimmediately,5minAndobserveagainafter1h.Differentchlorine-containingplasticscanbeidentifiedbasedonthecolor.
Indailylife,PVCandPEplasticfilm(bag)needtobedistinguishedfrommorecontact.Simplemethod:
(1)Touchmethod
Itfeelslubricioustothetouch,andthesurfacelookslikealayerofwax(chemicallycalledwaxfeel).Thisisanon-toxicpolyethylenefilmbag,whilethePVCfilmfeelsalittlesticky.
(2)Shakingmethod
Whenshakingwithhands,thesoundisbrittle,andthethingthatfloatseasilyisapolyethylenefilmbag.Andthelowsoundofshakingwithhandsisapolyvinylchloridefilmbag.
(3)Combustionmethod
Incaseoffire,itisflammable,theflameisyellow,andthereisparaffin-likeoildrippingwhenburning,andthereisgasfromcandleburning.Itisanon-toxicpolymer.Vinylfilmbag.Ifitisnoteasytoburn,itwillbeextinguishedafterleavingthefire,theflamewillbegreen,anditwillbeapolyvinylchloridefilmbag.
(4)Immersionmethod
Immersetheplasticbaginwater,pressitintothewaterwithyourhand,theonethatcanrisetothesurfaceispolyethylene,andtheonethatsinksintothewaterispolyvinylchloride(polyvinylchloride).Thedensityofethyleneislessthanthatofwater,andthedensityofpolyvinylchlorideisgreaterthanthatofwater;atroomtemperature,theyareabout0.92g/cm3and1.4g/cm3).
Youcanalsotakeapieceofcopperwireandburnitinthefiretomakeitred.Then,contactthecopperwirewiththetestplasticfilmtocauseachemicalchange,andthenputthecopperwiredippedintheplasticcomponentbackagainIntheflames.Atthistime,youneedtoobservecarefully.Ifthereisacolorful,dazzlinggreenflame,itmeansthatthisplasticmaterialcontainschlorineandbelongstothepolyvinylchloridematerial.
Mainhazards
Polyvinylchlorideisalsoakindofplasticthatisoftenused.Itisaresincomposedofpolyvinylchlorideresin,plasticizerandantioxidant,anditisnottoxic.However,themainauxiliarymaterialssuchasplasticizersandantioxidantsaretoxic.TheplasticizersindailyPVCplasticsmainlyusedibutylterephthalateanddioctylphthalate.ThesechemicalsAllaretoxic,andleadstearate,anantioxidantforPVC,isalsotoxic.Lead-containinganti-agingagentofpolyvinylchloride(PVC)productscontactwithethanol,etherandothersolventswillprecipitatelead.Lead-salt-containingPVCisusedforfoodpackagingandencounterswithfrieddoughsticks,friedcakes,friedfish,cookedmeatproducts,cakesandsnacks,whichwillcauseleadmoleculestodiffuseintothegrease,soPVCplasticbagscannotbeusedContainfood,especiallyfoodcontainingoil.Inaddition,polyvinylchlorideplasticproductswillslowlydecomposehydrogenchloridegasatahighertemperature,suchasabout50°C,whichisharmfultothehumanbody.Therefore,polyvinylchlorideproductsarenotsuitableforfoodpackaging.
Becausemostdisposablemedicaldeviceproductsusemedicalgradepolyvinylchloride(PVC)orpolycarbonate(PC),andthethermaldecompositionproductsinthePVCprocessingprocessarecorrosivetosteel,PCThehardnessishighandtheviscosityishigh.Therefore,thematerialoftheplasticizedpartmustbecorrosion-resistant,wear-resistantandhavehighpolishingperformance.Mostmedicalinjectionmoldingmachinesusehardchromiumplatingonthebarrelscreworusestainlesssteelasthematerialtomakethemachinescrewtomeettheabovespecialrequirements.Inaddition,inordertopreventthermaldecompositionandgasgenerationduringPVCprocessing,itisrequiredtoaluminizethesurfaceofthemovabletemplate,andalsotoaluminizetheoutersheetmetalorusestainlesssteeltomakethesheetmetal,andthesheetmetaljointsaresealedwithnon-toxicsilicagel.Inordertopreventthegasgeneratedduringtheplasticprocessingfromescapingoutside(thegasgeneratedduringtheplasticprocessingcanbecollectedthroughspecialequipmentandthenpurifiedbeforebeingdischargedintotheatmosphere).
PVCisthemainsourceofdioxins.Dioxin(TCDD),thedeadliestsubstanceinthedioxinsfamily,isawell-knowncarcinogenandhormonedecomposer,andatoxiccompound,whichisveryharmfultohumansandanimals.DioxinsareproducedwhenPVCisproduced,recycled,anddestroyedinincinerators,orwhenPVCproductsareaccidentallyburned,suchaswhenburiedingarbage.