FLEXIBLE HR FOAM ADDITIVES. New silicone surfactants for low emission HR-foams

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Lesley Hawkins
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2 FLEXIBLE HR FOAM ADDITIVES New silicone surfactants for low emission HR-foams Dr. Josep Nadal Technical Manager for PU Additives Mr. Adrià López Technical responsible for PU Additives

3 1.- INTRODUCTION 3.- CONCLUSIONS

4 1.- INTRODUCTION 3.- CONCLUSIONS

5 1.- INTRODUCTION Flexible polyurethane foam has a long history: 1950s 1960s 1970s first slabstock foams. Some were used in car seats development of hot cure molded foam process development of cold cure molded foam process 1980s emanations control goes into the subsurface materials used, like seat pads. Raw material suppliers were asked to find sources of these emanations and work together with the OEMs to reduce the overall quantity. Catalysts and surfactants included. 1990s first commercial available low emission surfactants. Initially mainly for MDI formulations 2000s - present significant decrease in siloxane emissions. Introduction of thermal desorption methods like VDA278

6 1.- INTRODUCTION VOC / FOG Definition s ºC VVOC: Very Volatile Organic Compounds ºC VOC: Volatile Organic Compounds ºC SVOC: Semi Volatile Organic Compounds VOC FOG

7 1.- INTRODUCTION Direct Thermal Desorption-VDA 278 The European automotive industry, adopts a method to testing emissions from car trim components. Their Method VDA 278 specifies direct desorption of materials, at elevated temperatures, to assess both VOCs and SVOCs (fogging) components. Small section of material placed inside of empty sorbent tube and content thermally extracted. Desorbing for 30 minutes at 90º C - VOC s up to n-c20 Followed by 60 minutes at 120º C SVOC (fogging) n-c16 to n-c32

8 1.- INTRODUCTION Direct Thermal Desorption-VDA 278 Piece of foam in a small tube GC-MS

9 1.- INTRODUCTION Raw Materials to Produce a PU Flexible Foam 100 average % Small contribution 0

10 1.- INTRODUCTION Direct Thermal Desorption-VDA 278 Typical Results of VOC Test MD n M MDM D4 MD2M D5 MD3M D6 MD4M D7 MD5M MD6M MD7M Cyclic and low MW linear polysiloxanes are analyzed by GC-MS

11 1.- INTRODUCTION It is known that the major contribution to VOC is coming from low molecular weight (MW) remains of cyclic and linear polydimethylsiloxanes (PDMS) But also polyether remains become part of the total emissions!! Physical methods like stripping of volatile remains had been widely used to reduce the amount of cyclic and linear low MW PDMS, but they have clear limitations when VDA278 method is used.

12 1.- INTRODUCTION Standard CONCENTROL STB PU-1259 PF Surfactant dosage: 0,6 pphp VOC Maximum value 84 µg/g Second value 82 µg/g Retention Substance CAS-Nr. Area (%) ppm Classification Time(min.) 27,52?,...117,103,59#,45,41,...Glycolether 2,3 2 35,60?,...117,103,59#,45,41,...Glycolether 1,6 1 35,69?,...117,103,59#,45,41,...Glycolether 5,4 5 35,79?,...117,103,59#,45,41,...Glycolether 3,9 3 36,18?,...229, 145, 113, 85, 70, 58#,Amine 1,8 2 38,65?,...85,58#,...Amine 2,0 2 39,29 1,4,7-Trioxacyclotridecan-8,13-dione ,0 2 40,13?,...117,103,59#,45,41,...Glycolether 3,2 3 40,19?,...117,103,59#,45,41,...Glycolether 4,0 3 40,27?,...117,85,59#,58,57,41,... 3,0 3 42,03 alkene,alkanol,cycloalkane 2,5 2 42,91 aliphatic compound 6,3 5 43,18 butyl- alkylated diphenylamine 5,2 4 43,49?,...369,355,295,281,221,207,147,73#,...siloxane 4,0 3 44,78?7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester ,4 2 44,89?,...369,295,281,221,207,147,73#,...siloxane 4,4 4 45,01 alkene,alkanol,cycloalkane 1,4 1 46,46 octyl-diphenylamine 1,8 1 Total amount of individual substances (<1 ppm) above the baseline 42,9 36 Total amount of identified or further named substances 100,0 84

13 1.- INTRODUCTION Standard CONCENTROL STB PU-1259 PF Surfactant dosage: 0,6 pphp FOG Total value 537 µg/g Retention Substance CAS-Nr. Area (%) ppm Classification Time(min.) 11,88?,...58#,...Amine 0,2 1 13,19 1-[Bis(3-dimethylamino)propyl)amino]2-propanol , ,87?,...85,72,58#,...Amine 0,4 2 14,21?,...117,103,59#,45,41,...Glycolether 0,8 4 15,75 alkene,alkanol,cycloalkane 0,6 3 16,22?,...117,103,59#,45,41,...Glycolether 0,4 2 16,39 7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione ,4 2 16,54?,...111,93,81,71,57#,55,43,41,... 0,8 4 16,61?,...94,79#,67,57,41,... 0,2 1 16,86 butyl-alkylated diphenylamine 5, ,98?,...117,103,59#,45,41,...Glycolether 0,3 2 17,69 alkene,alkanol,cycloalkane 1,7 9 18,35 7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester , ,57 7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester , ,68 aliphatic compound 0,3 2 19,35?,...117,103,59#,45,41,...Glycolether 1, ,63 aliphatic compound 0,2 1 19,76?,...369,295,281,221,207,147,73#,... 0,5 3 19,98 octyl-alkylated diphenylamine 5, ,09 di-t-butyl-alkylated diphenylamine 1,3 7 20,70 octyl-diphenylamine + aliphatic compound 1,4 7 21,91 aliphatic compound 0,2 1 22,02?,...112,83,70,57#,43,... 0,4 2 22,16 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,7 4 22,74 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,5 3 22,96 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,1 6 23,10 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 1 23,35 Hexacosane ,7 4 24,53 butyl-octyl-alkylated diphenylamine, Isomere 1,0 5 25,09 aliphatic compound 0,2 1 27,20 aliphatic compound 0,4 2 Total amount of individual substances (<1 ppm) above the baseline 27,6 148

14 1.- INTRODUCTION Standard CONCENTROL STB PU-1259 PF Surfactant dosage: 0,5 pphp VOC Maximum value 131 µg/g Second value 118 µg/g Retention Substance CAS-Nr. Area (%) ppm Classification Time(min.) 21,90 2-Propanol, 1,1'-oxybis , ,71 Propanol, oxybis ,5 2 22,87?,...117,103,59#,45,41,...Glycolether 2,4 3 27,39?,...117,103,59#,45,41,...Glycolether 1,3 2 27,52?,...117,103,59#,45,41,...Glycolether 2,6 3 35,59?,...117,103,59#,45,41,...Glycolether 2,6 3 35,69?,...117,103,59#,45,41,...Glycolether 7, ,79?,...117,103,59#,45,41,...Glycolether 5,4 7 35,93?,...117,103,59#,45,41,...Glycolether 1,0 1 38,65?,...85,58#,...Amine 1,5 2 39,29 1,4,7-Trioxacyclotridecan-8,13-dione ,9 1 40,13?,...117,103,59#,45,41,...Glycolether 2,4 3 40,19?,...117,103,59#,45,41,...Glycolether 3,0 4 40,27?,...117,103,59#,45,41,...Glycolether 2,7 3 42,85 Methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 0,9 1 43,18 butyl- alkylated diphenylamine 5,0 7 43,49?,...369,295,281,221,207,147,73#,... 2,0 3 44,78?7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester ,0 1 44,89?,...369,295,281,221,207,147,73#,...siloxane 2,0 3 46,46 octyl-diphenylamine 1,7 2 Total amount of individual substances (<1 ppm) above the baseline 26,7 35 Total amount of identified or further named substances 100,0 131

15 1.- INTRODUCTION Standard CONCENTROL STB PU-1259 PF Surfactant dosage: 0,5 pphp FOG Total value 632 µg/g Retention Substance CAS-Nr. Area (%) ppm Classification Time(min.) 11,88?,...72,58#,...Amine 0,2 1 13,20 1-[Bis(3-dimethylamino)propyl)amino]2-propanol , ,87?,...102,85,72,58#,...Amine 0,6 4 14,21?,...117,103,59#,45,41,...Glycolether 1,2 7 15,75 alkene,alkanol,cycloalkane 0,4 3 15,84?,...117,103,59#,45,41,...Glycolether 0,3 2 16,22?,...117,103,59#,45,41,...Glycolether 0,3 2 16,36?,...94,79,58#,... 0,5 3 16,53 Methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 0,6 4 16,85 butyl-alkylated diphenylamine 6, ,98?,...117,103,59#,45,41,...Glycolether 0,3 2 17,68 alkene,alkanol,cycloalkane 0,5 3 18,35 7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester , ,57 7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester , ,68 aliphatic compound 0,3 2 19,34?,...117,103,59#,45,41,...Glycolether 0,9 5 19,76?,...369,295,281,221,207,147,73#,...siloxane 0,3 2 19,98 octyl-diphenylamine 5, ,09 di-t-butyl-alkylated diphenylamine 1,4 9 20,70 octyl-diphenylamine + aliphatic compound 1,2 8 21,59?,...376,361,219,147,57#,... 0,2 1 21,65?,...145#,88,69,57,43,... 0,3 2 21,72 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 2 21,99 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,5 3 22,06 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 2 22,16 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate , ,29 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 2 22,43 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,2 1 22,52 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 2 22,74 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate , ,96 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate , ,10 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,1 7 23,35 aliphatic compound 0,5 3 23,50 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ,3 2 24,52 butyl-octyl-alkylated diphenylamine, Isomere 1,3 8 Total amount of individual substances (<1 ppm) above the baseline 17,7 112 Total amount of identified or further named substances 100,0 632

16 1.- INTRODUCTION Silicone surfactants are silicone-polyether copolymers PDMS EO PO

17 1.- INTRODUCTION Silicone surfactants are silicone-polyether copolymers silicone backbone polyether backbone

18 1.- INTRODUCTION New synthetic approaches had been used where the remains of low MW PDMS and polyether are almost negligible a) Synthesis of new surfactants with higher MW Less volatile b) Synthesis of surfactants with very low or without remains of cyclic and linear PDMS

19 1.- INTRODUCTION 3.- CONCLUSIONS

first part: synthesis and characterization of 24 new

Polarity (cloud point analysis) Molecular Weight by SEC Gas

prepared, physical analysis performed and emissions

20 first part: synthesis and characterization of 24 new surfactants specially designed to fulfill low emissions Polarity (cloud point analysis) Molecular Weight by SEC Gas Chromatography second part: foams (MDI and TDI type) had been prepared, physical analysis performed and emissions calculations done. Density General appearance Force to Crush Emissions calculation of the surfactant

21 SYNTHESIS and CHARACTERIZATION of NEW SURFACTANTS

22 TABLE OF COMPOSITIONS POLYETHER SILOXANE SILOXANE POLYETHER WEIGHT % WEIGHT % MX-01 P-A S MX-02 P-B S MX-03 P-C S MX-04 P-D S MX-05 P-E S MX-06 P-F S MX-11 P-A S MX-12 P-B S MX-13 P-C S MX-14 P-D S MX-15 P-E S MX-16 P-F S MX-21 P-A S MX-22 P-B S MX-23 P-C S MX-24 P-D S MX-25 P-E S MX-26 P-F S MX-31 P-A S MX-32 P-B S MX-33 P-C S MX-34 P-D S MX-35 P-E S MX-36 P-F S POLYETHERS P-A P-B P-C P-D P-E P-F 4 POLYSILOXANES S-1 S-2 S-3 S-4

23 TABLE OF COMPOSITIONS POLARITY CLOUD POINT POLYETHER SILOXANE SILOXANE POLYETHER WEIGHT % WEIGHT % CP (4% H 2 O) CP (4% BDG) MX-01 P-A S <25 78 MX-02 P-B S <25 83 MX-03 P-C S <25 87 MX-04 P-D S <25 98 MX-05 P-E S MX-06 P-F S MX-11 P-A S <25 77 MX-12 P-B S <25 83 MX-13 P-C S <25 87 MX-14 P-D S <25 97 MX-15 P-E S MX-16 P-F S MX-21 P-A S <25 77 MX-22 P-B S MX-23 P-C S MX-24 P-D S MX-25 P-E S >100 MX-26 P-F S MX-31 P-A S <25 71 MX-32 P-B S <25 79 MX-33 P-C S <25 83 MX-34 P-D S <25 91 MX-35 P-E S MX-36 P-F S

24 SURFACTANT ANALYSIS (MW MEASUREMENTS SEC)

25 SURFACTANT ANALYSIS (MW MEASUREMENTS SEC)

26 SURFACTANT ANALYSIS (GAS CROMATOGRAPHY) Please contact our company to have the information regarding GC analysis of the surfactants:

27 FOAMS AND EMISSIONS CALCULATION

28 NOT ONLY EMISSIONS ARE IMPORTANT!! SILICONE SURFACTANTS for flexible HR PU foams are additives which basically have two functions in the PU foaming process: - Stabilization: Most polyurethane formulations need an additive which provides stabilizing capacity in the foaming process. - Cell regulation: In many formulations regulation of the size and distribution of the cells originated in the mixing process of the polyol and isocyanate components is needed.

29 TDI FORMULATION Polyether-polyol (OH=30 mg KOH/g) Polymer-polyol (OH=23 mg KOH/g, 32% SAN) TDI (80/20) % pphp 52, , ,7 38 DEOA 85 0,53 0,75 33% triethylenediamine in DPG 0,14 0,2 70% bis(2-dimethylaminoethyl) ether in DPG 0,09 0,13 NE-300 (non-emissive amine) 0,03 0,05 H 2 O 2,30 3,28 Surfactant 0,35-0,70 0,5-1

30 1 PPHP SURFACTANT TDI Lower density Better appearance Good cellular structure

31 0,5 PPHP SURFACTANT - TDI Lower density Better appearance Good cellular structure

32 0,5 PPHP SURFACTANT - TDI 53.0 Density NONE PU-1259 PF MX-01 MX-02 MX-03 MX-11 MX-12 MX-13 d (kg/m3)

33 F (N) PSE Europe ,5 PPHP SURFACTANT TDI Molded (d=40kg/m 3 ) 1400 FTC NONE 1259 PF MX-01 MX-02 MX-03 MX-11 MX-12 MX-13 F F F F Unstable

34 MDI FORMULATION Polyether-polyol (OH=28 mg KOH/g) PMDI (32% NCO) % pphp 59, ,65 61,41 DEOA 85 1, % triethylenediamine in DPG 0,24 0,4 NE-300 (non-emissive amine) 0,20 0,33 H 2 O 2,03 3,4 Surfactant 0,5-1 0,5-1

35 0,5 pphp SURFACTANT - MDI Lower density Better appearance Good cellular structure

36 0,5 pphp SURFACTANT - MDI Blank 1259 PF MX-01 MX-02 MX-03 MX-11 MX-12 MX-13 d (kg/m3)

37 F (N) PSE Europe ,1 pphp SURFACTANT MDI Molded (d=67kg/m 3 ) FTC Blank 1259 PF MX-01 MX-02 MX-03 MX-11 MX-12 MX-13 F F F F

38 GAS CROMATOGRAPHY-EMISSIONS Please contact our company to have the information regarding GC analysis of the surfactants:

39 % PSE Europe 2017 GAS CROMATOGRAPHY-EMISSIONS PF MX-01 MX-02 MX-03 MX-11 MX-12 MX-13 C C Total

40 GAS CROMATOGRAPHY-EMISSIONS Please contact our company to have the information regarding GC analysis of the surfactants: Surfactants like MX-02 and MX-03 show: - Very good performance both in MDI and TDI formulations - Very low MW silicone and polyether remains

41 1.- INTRODUCTION 3.- CONCLUSIONS

42 3.- CONCLUSIONS THE RIGHT CHEMICAL COMPOSITION AND MOLECULAR WEIGHT OF THE SURFACTANT CAN HELP TO REDUCE DRAMATICALLY THE EMISSIONS (VDA-278) ALMOST FREE EMISSIONS (SURFACTANT SIDE) FOAMS COULD BE OBTAINED.

43 Thank you for your time.

Reactive polymer-bound stabilizers for polyols and PU, improving emissions and long term yellowing of foam

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