Styrenefree unsaturated polyester resin compositions.docx

Styrenefree unsaturated polyester resin compositions.docx

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Styrenefreeunsaturatedpolyesterresincompositions

UnitedStatesPatent

7,396,882

Hewitt, etal.

July8,2008

Styrene-freeunsaturatedpolyesterresincompositions

Abstract

Styrene-freeunsaturatedpolyesterresincompositionsareprovidedwhichhavelowvolatileorganiccompoundsandhazardousairpollutantsemissionswhentheseresincompositionsareusedinopenmoldingapplications.Aprocessforthemanufactureoftheseresincompositionsisprovided.

Inventors:

Hewitt;JohnC.（Collierville,TN）,McAlvin;JohnE.（Collierville,TN）,Hutson;PaulTaylor（Memphis,TN）,Craig;AmberE.（Collierville,TN）,Krantz;Marjorie（Byhalia,MS）,Rivers;DerekK.（Memphis,TN）

Assignee:

AOC,LLC（Collierville,TN）

Appl.No.:

10/440,610

Filed:

May19,2003

RelatedU.S.PatentDocuments

ApplicationNumber

FilingDate

PatentNumber

IssueDate

60382038

May.,2002

CurrentU.S.Class:

525/290;525/192;525/193;525/207;525/263;525/278;525/286;525/312;525/445;525/75;526/283;526/290

CurrentInternationalClass:

C07C13/61 （20060101）;C08F299/02 （20060101）;C08L67/07 （20060101）

FieldofSearch:

526/229,317.1,303.1,283,290525/290,75,278,445,312,263,286,192,193,207

ReferencesCited[ReferencedBy]

U.S.PatentDocuments

4390662

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October1988

Hefner,Jr.

5739240

April1998

Smith

5747597

May1998

Fujitaetal.

5773531

June1998

Smith

5908875

June1999

Smith

6037385

March2000

Smith

6277939

August2001

Smith

6468662

October2002

Nava

6646057

November2003

Andersetal.

6808821

October2004

Fujitaetal.

6884841

April2005

Nava

6992140

January2006

Kosonoetal.

PrimaryExaminer:

Gulakowski;Randy

AssistantExaminer:

Bernshteyn;MichaelM

Attorney,AgentorFirm:

BakerDonelsonBearmanCaldwell&BerkowitzPC

ParentCaseText

ThisapplicationclaimsthebenefitofU.S.ProvisionalApplicationSerialNo.60/382,038,filedMay20,2002.

Claims

Whatisclaimedis:

1.Astyrene-freeunsaturatedpolyesterresincompositionconsistingessentiallyof

（1）adicyclopentadiene-basedunsaturatedpolyester;

（2）aurethane（meth）acrylate;（3）amultifunctional（meth）acrylatemonomerand（4）from5-60percentbyweightofahydroxyl-functionalized（meth）acrylatemonomer,whereintheresincompositionaftercurehasaheatdistortiontemperature（ASTMD-648）ofatleast65.degree.C.

2.Aresincompositionasdefinedbyclaim1whereintheconcentrationoftheunsaturatedpolyesterisfrom15-70percentbyweight.

3.Aresincompositionasdefinedbyclaim1whereintheunsaturatedpolyesterhasaweightaveragemolecularweightof800-10,000.

4.Aresincompositionasdefinedbyclaim1whereintheunsaturatedpolyesteristhereactionproductofdicyclopentadienewithcompoundsofcarboxylicacidsand/oranhydridesandalcohols.

5.Aresincompositionasdefinedbyclaim1whereintheunsaturatedpolyesterismodifiedwithglycidylmethacrylateataleveluptoabout20percentbyweightoftheunsaturatedpolyester.

6.Aresincompositionasdefinedbyclaim1whereintheunsaturatedpolyesterismodifiedwithanallyletherfunctionalizedalcoholorepoxyataleveluptoabout20percentbyweightoftheunsaturatedpolyester.

7.Aresincompositionasdefinedbyclaim1whereintheconcentrationoftheurethane（meth）acrylateisfrom15-70percentbyweight.

8.Aresincompositionasdefinedbyclaim1whereintheurethane（meth）acrylateisareactionproductofahydroxyl-functionalized（meth）acrylatewithadiisocyanateorpolyiisocyanate.

9.Aresincompositionasdefinedbyclaim1whereintheconcentrationofthemultifunctional（meth）acrylateisfrom5-60percentbyweight.

10.Aresincompositionasdefinedbyclaim1thatcontainsuptoabout60percentbyweightofafiller.

11.Aresincompositionasdefinedbyclaim10whereinthefilleriscalciumcarbonate,calciumsulfate,aluminumtrihydrate,clayoracombinationthereof.

12.Aresincompositionasdefinedbyclaim1thatcontainsuptoabout5percentbyweightofathixotropicagent.

13.Aresincompositionasdefinedbyclaim12whereinthethixotropicagentisfumedsilica,organoclaysoracombinationthereof.

14.Aresincompositionasdefinedbyclaim1thatcontainsuptoabout2percentbyweightofabarrierformingagent.

15.Aresincompositionasdefinedbyclaim1thatiscuredwith1-3percentbyweightofadiacylperoxide,hydroperoxide,ketoneperoxide,peroxyester,peroxyketal,dialkylperoxide,alkylperester,percarbonate,azocompoundoracombinationthereof.

16.Aresincompositionasdefinedbyclaim1thatisformulatedwithaderivativeofaniline,anamide,anaromaticamineoranaliphaticamineataleveluptoabout1percentbyweight.

17.Aresincompositionasdefinedbyclaim1thatisformulatedwithacobaltcarboxylate,vanadium,potassium,zincorironcompoundataleveluptoabout1percentbyweight.

18.Aresincompositionasdefinedbyclaim1thataftercurehasatensilestrength（ASTMD-638）andtensilemodulus（ASTMD-638）ofatleast7,000psiand350,000psi,respectively.

19.Aresincompositionasdefinedbyclaim1thataftercurehasaflexuralstrength（ASTMD-790）andflexuralmodulus（ASTMD-790）ofatleast10,000psiand350,000psi,respectively.

20.Aresincompositionasdefinedbyclaim1thatcontainsatleasttwomultifunctional（meth）acrylatemonomers.

21.Aresincompositionasdefinedbyclaim1thatcontainsatleasttwohydroxyl-functionalized（meth）acrylatemonomers.

22.Aresincompositionasdefinedbyclaim14whereinthebarrierformingagentisaparaffin,polyester,polysiloxaneoracombinationthereof.

Description

TECHNICALFIELD

Thepresentinventionrelatestopolyesterresincompositions.Inamorespecificaspect,thisinventionrelatestostyrene-freeunsaturatedpolyesterresincompositions.

BACKGROUNDOFTHEINVENTION

Thermosetresins,includingunsaturatedpolyesters,arecommonlyemployedinavarietyoffabrications,suchascastingmaterials,fiberreinforcedmaterialsandcoatings.Unsaturatedpolyesterresinsmaybedefinedasthecondensationproductsofdicarboxylicacidsoranhydrideswithdifunctionalalcohols,typicallydissolvedinareactivediluentsuchasstyrene.Sincethecommercialinceptionofunsaturatedpolyesterresins,styrenehasbeenaprimaryreactivediluentduetoitslowcost,availability,easeofuseandresultingexcellentmechanicalproperties.However,inrecentyears,governmentregulationshaverestrictedstyreneemissionsinopenmoldingfacilitiesduetoharmfulenvironmentalandhealtheffects.

Anumberofalternativeshasbeensoughttoreduceemissionsandassubstitutesforstyrene.Highermolecularweightderivativesofstyrene,suchasvinyltolueneandt-butylstyrene,havebeenutilizedasreactivediluentsandresultedindecreasedemissions.However,emissionsarestillsignificantintheseresins,andsuchalternativestyreneanalogsarevolatileorganiccompounds.Theadditionofparaffinstounsaturatedpolyesterresinshasbeenshowntoreduceemissionsbyformingathinfilmontheresinsurface.Whilesuitableforsomeapplications,thissolutionisunacceptableforotherapplicationsduetoadecreasedinterlaminateadhesion.

Inmostcases,lowvolatileacrylateandmethacrylatemonomershavebeeninadequateasreplacementsforstyreneinunsaturatedpolyesterresinssinceatmosphericoxygenseverelyretardspolymerization,resultinginanunder-cured"tacky"surface.Furthermore,thepoorcopolymerizationofmostacrylatesandmethacrylateswithmaleateandfumaratemoietiesinthepolyesterbackboneoftenresultsininferiormechanicalpropertiescomparedtostyrenatedunsaturatedpolyesterresins.

Inthisapplication,theterm（meth）acrylatewillbeunderstoodtoincludebothacrylateandmethacrylatecompounds.

Previouspatentshavedescribednon-styrenatedunsaturatedpolyesterresincompositions.

U.S.Pat.No.5,747,597describesacurableresincomprisedofanunsaturatedpolyester,epoxymethacrylateand/orurethanemethacrylate,combinedwitholigoalkylether-monoalkoxymethacrylates.Theresinwasdescribedinmanycasestoairdry"dry-to-touch"aftertheadditionofwax,free-radicalinitiator,catalystandexposuretoelevatedtemperatures（130-145.degree.F.）.Tensiletestingofthecastresinrevealedhighelongationandlowstrengthproperties,whichisinsharpcontrasttodatausingthesamepolymersdissolvedinstyrenethatdemonstratedconsiderablyhighertensilestrengths.

InternationalPatentPublicationNo.WO99/23122describestheuseofhydroxyethylmethylmethacrylate,hydroxyethylpropylmethacrylateand/orurethanehydroxyethylmethacrylatewithpolyestersandvinylesters.Theresultingtensileandflexuralpropertiesofthecuredproductswerecomparabletostyrenatedunsaturatedpolyesterresins,buttack-freecureinthinfilmsandthinlaminatestendstobeaproblemwiththeseresins.Additionally,basedonourevaluation,thestoragestabilityofresinsdescribedinthispublicationisverypoor.

AdditionalU.S.patentswhichdescribenon-styrenatedunsaturatedpolyesterresincompositionsareU.S.Pat.No.5,908,875,U.S.Pat.No.5,739,240,U.S.Pat.No.6,277,939,U.S.Pat.No.5,773,531andU.S.Pat.No.6,037,385.

Anongoinggoalintheunsaturatedpolyesterindustryhasbeentodevelopimprovednon-styrenated,free-radicalcurableresinswhichhaveprocessingsimilartocurrentstyrenatedresins,benefitsinmechanicalandphysicalpropertiesandtack-freecureinthinfilms.

SUMMARYOFTHEINVENTION

Brieflydescr