silicone surfactants reactivity analysis - concentrol

UTECHNorthAmerica2016

RIGID FOAM ADDITIVES

Effect of the silicone surfactant reactivity on the properties of rigid polyurethane foams

JosepNadalTechnicalManagerforPUAdditives

1.- INTRODUCTION

2.- EXPERIMENTALS AND RESULTS

3.- CONCLUSIONS


Rigidpolyurethane (PU)foamisoneofthebestthermalinsulationmaterial

Applicationsarewide:

- Appliances:Domesticrefrigeratorsandfreezers,hotwatertanks- Building industry:Sandwichpanels(wallsandroofing panels), insulatingboards,

slabstock or2Ksprayinplace.- Industrial:tanksandcontainersinsulation, pipelines

Besidesthermalinsulationperformance, otherrequirementshavetobetakenintoaccount:

- flammabilityperformance- adhesion todifferent facingmaterials- dimensional stability


1.- INTRODUCTION

Siliconesurfactantsplayasubstantialroleonthefoamproperties

Siliconesurfactantsaresilicone-polyethercopolymers


1.- INTRODUCTION

EO

PO

PDMS


reactivity(R)ofsomesurfactants

1.- INTRODUCTION



Non-capped: -OH

Capped: -OCH3

Capped: -OCOCH3

1.- INTRODUCTION


reactivity(R)ofsomesurfactants


CAPPED OHnumber(mgKOH/g)

ISOREACTIVITY

COST HYDROLITICSTABILITY

-OH varied ü $ ü

-OCH3 ü <10 $ $ $ ü

-OCOCH3 ü <10 $ $ $


APPLICATIONS

-OH varied General purpose: lamination,appliances,spray,block,highdensity,etc.

-OCH3 ü <10 Specific:OCF, spray,lamination

-OCOCH3 ü <10 Veryspecific: lamination

1.- INTRODUCTION

Isreactivityimportant(COST,ISOREACTIVITY,etc.)?



APPLICATIONS

-OH varied General purpose: lamination,appliances,spray,block,highdensity,etc.

-OCH3 ü <10 Specific:OCF, spray,lamination

-OCOCH3 ü <10 Veryspecific: lamination

1.- INTRODUCTION

HASTHEREACTIVITYOFSILICONESURFACTANTSAMAJORIMPACTINA

PUR/PIRFORMULATIONFORLAMINATION?

1.- INTRODUCTION

2.- EXPERIMENTALS AND RESULTS

3.- CONCLUSIONS



ü In the first part we will present new surfactants where the only difference is thecapping group (synthesis and characterization).

Polarity (cloud point analysis)Infrared spectraMolecular Weight by SEC1H-NMR

ü In the second part, physical analysis of the foams prepared with the previouslysynthesized surfactants will be shown. The aim is to establish trends which link thechemical structure with the physical parameters analyzed.

Lambda valuesFire propertiesDimensional stability measurementsGeneral appearance

2.- EXPERIMENTALSANDRESULTS



SYNTHESISand

CHARACTERIZATIONof

NEW SURFACTANTS


POLYSILOXANE POLYETHER(EO %)MW RAMIFICATION VERYHIGHEO HIGHEO MEDIUMEO

LOWMEDIUM

HIGH

MEDIUMLOW

MEDIUM

HIGH LOW


TABLEOFCOMPOSITIONS

Usualstructuresofsurfactantsforlamination


POLYSILOXANE POLYETHER(EO %)MW RAMIFICATION VERYHIGHEO HIGHEO MEDIUMEO

LOWMEDIUM

U-110U-111U-112

HIGHU-120U-121U-122

MEDIUMLOW

U-210U-211U-212

MEDIUMU-220U-221U-222

HIGH LOWU-310U-311U-312

OHhydroxyl OCH3 methoxy OCOCH3 acetoxy


TABLEOFCOMPOSITIONS(15EXPERIMENTALNEWSURFACTANTS)


SURFACTANT CLOUDPOINT(4%water)

U-110 158ºF(70ºC)

U-111 100ºF(38ºC)

U-112 129ºF(54ºC)

U-120 187ºF (86ºC)

U-121 124ºF (51ºC)

U-122 145ºF(63ºC)

HIGH EO%


U-210 104ºF(40ºC)

U-211 77ºF(25ºC)

U-212 88ºF(31ºC)

U-220 140ºF(60ºC)

U-221 127ºF(53ºC)

U-222 114ºF(46ºC)

MEDIUMEO%


U-310 100ºF(38ºC)

U-311 100ºF(38ºC)

U-312 97ºF(36ºC)

LOWEO%


SURFACTANTANALYSIS (POLARITY– CLOUDPOINT)


0

10

20

30

40

50

60

70

80

90

100

CP(ºC)

EO %



- +

REMARKS

1)CAPPEDsurfactantsshowlowerCP

2)Higheristheramification,higheristheCP

3)NomeasuredrelationbetweensurfactantMWandCP

SURFACTANTANALYSIS (POLARITY– CLOUDPOINT)


OHhydroxyl

OCH3 methoxy

OCOCH3 acetoxy


SURFACTANTANALYSIS (INFRAREDSPECTROSCOPY)



OHhydroxyl

OCH3 methoxy

OCOCH3 acetoxy

SURFACTANTANALYSIS (INFRAREDSPECTROSCOPY)



SURFACTANTANALYSIS (MWMEASUREMENTS– SEC)

Low MW

MediumMW

HighMW



SURFACTANTANALYSIS

(1H-NMR)

OCH3 methoxy



OCOCH3 acetoxy

SURFACTANTANALYSIS

(1H-NMR)


ü first part summary.

Using 4 different analytical techniques, accurate characterization can be obtainedof all the 15 new surfactants

Polarity (cloud point analysis)Infrared spectraMolecular Weight by SEC1H-NMR


RIGID PU FOAM

ANALYSIS



FORMULATION

PUR/PIRformulationwithpentaneasblowingagent



% pphp

Polyester-polyol 23 90,2Polyetherpolyol(long chain) 2,5 9,8

PMDI 64 251

TCPP 4 15,7SURFACTANT 1 3,92K-octoate catalyst 1,3 5,1Aminecatalyst(DMCHA) 0,3 1,18Water 0,5 1,96Pentane(iso 75%- n25%) 3,8 14,9

FOAMMEASUREMENTS (GENERALASPECT)



-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)



-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)

Low MW surfactants with very high EO content

Bad performance

Capping group has no clear effect

Ramification Medium High




-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)

-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)

Medium MW surfactants with high EO content

Acceptable performance


No benefit is observedRamification Low Medium




-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)

-OHHYDROXYL

U-110(2) U-120(5) U-210(8) U-220(11) U-310(14)

-OCH3METHOXY

U-111(3) U-121(6) U-211(9) U-221(12) U-311(15)

-OCOCH3ACETOXY

U-112(4) U-122(7) U-212(10) U-222(13) U-312(16)

High MW surfactants with medium EO content

Very good performance


No benefit is observedRamification Low


FOAMMEASUREMENTS (DIMENSIONALSTABILITY)




0,00

0,50

1,00

1,50

2,00

2,50

3,00

3,50

compression(Kg/cm2)

parallelcompression

verticalcompression




0,00

0,50

1,00

1,50

2,00

2,50

3,00

3,50

compression(Kg/cm2)

parallelcompression

verticalcompression





0,00

0,50

1,00

1,50

2,00

2,50

3,00

3,50

compression(Kg/cm2)

Compressionvaluesaremorerelatedtosurfactantcomposition(EO,PO,Siloxane%)

Ratherthatinfluenceofcapping

parallelcompression

verticalcompression





26

27

28

29

30

31

32

33

34

density(Kg/m3)density

Highdegreeofvariability

D(OH)=1,86lb/ft3 (29,8kg/m3)

D(OCH3)=1,89lb/ft3 (30,2kg/m3)

D(OCOCH3)=1,87lb/ft3 (29,9kg/m3)

Notendencyisobserved

FOAMMEASUREMENTS (DENSITY)

average



0,00

1,00

2,00

3,00

4,00

5,00

6,00

inches B2test(DIN4102)

In all cases, flammabilityresults are well above themaximum established by B2Test (DIN 4102)

PIR formulation

15,7 pphp TCPP

FOAMMEASUREMENTS (FLAMMABILITY– B2TEST)



10,00

15,00

20,00

25,00

30,00

35,00

U-110

U-111

U-112

U-120

U-121

U-122

U-210

U-211

U-212

U-220

U-221

U-222

U-310

U-311

U-312

mW/mK Lambdavalue/thermalconductivity (λ)

Thermal conductivitydecreases with higher MWsurfactants with lower EOcontent

No direct relation with thecapping group

AGED

RECENT

FOAMMEASUREMENTS (THERMALCONDUCTIVITY-LAMBDA)


3.- CONCLUSIONS

INTHECHOSENPUR/PIRFORMULATIONFORLAMINATION,BIGGER

DIFFERENCESINPERFORMANCEHADBEENSEENRELATEDTO

THECHEMICALCOMPOSITIONOFTHESURFACTANT

(EO,PO,SILOXANE%) RATHERTHANTHEEFFECTOFTHECAPPINGGROUP

HASTHEREACTIVITYOFSILICONESURFACTANTSAMAJORIMPACTINA

PUR/PIRFORMULATIONFORLAMINATION?


Thankyouforyourtime.

www.concentrol.com

silicone surfactants reactivity analysis - concentrol

Engineering