reactive polymer-bound stabilizers for polyols and pu ... · reactive polymer-bound stabilizers for...

Antoni Puig | Sales Manager EMEA

PSE Europe, 28th June 2017, Munich

Reactive polymer-bound stabilizers for polyols and PU,

improving emissions and long term yellowing of foam

© Milliken & Company

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Milliken & Company

More than

Manufacturing facilities

around the world

Headquartered in Spartanburg, SC, USA

associates

world-wide39

7000


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Our Divisions:

Milliken & Company


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Divisions

4

Milliken & Company

Performance and

Protective Textiles

Performance Solutions

Floor Covering

Chemical


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Milliken & Company Divisions

Beautifying offices, hotels,

airports, homes, and

commercial environments

around the world

FloorCovering


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Consisting of 6 businesses : Airbag,

Engineered and Performance Products,

Napery, Nonwovens, Specialty Interiors and

Uniform and Protective

Performance and Protective Textiles


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Assisting organizations to become safer and

more competitive in the marketplace

PerformanceSolutions


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Producing innovative chemical additives

and colorants that help create value for

customers by improving performance,

appearance, productivity and costs

Chemical


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Giving superior protection to polyurethane

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Additives for enhanced quality and protection

Intense Color

Microbial Protection

Reduced Yellowing

Reduced Emissions

Reactint® AlphaSan® Milliguard®


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Intense Color


Reduced Yellowing

Reduced Emissions



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Polymer Bound Chemistry

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Reactint Polymeric Colorants for PU

AOX

Strong chromophores

Effective at low loadings

Liquid

Easy Handling and metering

Miscibility/Compatibility

Chemically bound into the PU matrix

Active Center

Polymeric Tail

Functional Center


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Cost efficient solutions

High Color Strength

Cost effective matches in our

labs or visit web app

Reduce waste from changeover

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Visit our Reactint web app Reactint.millikenchemical.com

Short color transition because

of high polyol solubility of

colorants


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5 Primary Colorants

Wide Color space

Reduced Inventory

Blend on the fly


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Enabling easy dosing of color in polyol manufacturing process

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Color pipe/tubing

Gear pump

Container

Polyol line


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Using deep color for marketing messages

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Branding Differentiation Personalization Highlighting Marketing


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Intense Color


Reduced Yellowing

Reduced Emissions



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Silver based Anti-microbial AlphaSan

Protecting PU against

microbial contamination

Foam Cushions

Footwear

Wound careThermoplastic Polyurethane

Foam Matresses


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Intense Color


Reduced Yellowing

Reduced Emissions



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Unique AO Stabilizer

technology for amine-free Polyol

EuropurInnovation

Award Winner 2016


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Amine-free antioxidant package for improved scorch and post-yellowing performance

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Polymeric, reactive antioxidant Milliguard AOX-1

Polyol Supplier

Polyol Stabilisation with Milliguard AOX

•Scorch protection at lower loadings

•Allowing lower VOC/FOG: VDA278 compliance

•Reduced discoloration after UV light & NOx exposure

Polyurethane Foam Producer

Scorch Prevention with Milliguard AOX

•Reduced thermal degradation in polyurethane

Protected with

Milliguard AOX-1

Protected with

Milliguard AOX-1


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Offering unique value through its unique polymeric structure

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AOX

lactone-based carbon-centered radical scavenger

Liquid

Easy Handling and metering

Miscibility/Compatibility

Chemically bound into the PU matrix

No contributions to emissions

Active Center

Polymeric Tail

Functional Center


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Lactones are uniquely capable of scavenging the carbon centered radicals, providing a superior

performance and efficacy

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Polymer

RH

Free

Radical

R•Photolysis

Thermal

Degradation

Auto-oxidation

cycle

ROO•

CO•

•OH

R•

H2O

Polymer

RH


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Lactones are uniquely capable of scavenging the carbon centered radicals, providing a superior

performance and efficacy

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Milliguard

AOX-1

Polymer

RH

Photolysis

Thermal

Degradation

Free

Radical

R•

Auto-oxidation

cycle

ROO•

CO•

•OH

R•

H2O

Polymer

RH

Lactones prevent the first step of the degradation cycle


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Heat ageing of polyols with different stabilization

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Conventional AO consumption leads to color body formation,

Milliguard AOX-1 has the ability to regenerate hindered phenol antioxidants thus minimizing the color bodies associated with consumption

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31

0

5

10

15

20

25

30

35

Minimum stabilizedPolyol

Milliguard AOX-1Stabilized Polyol

Industry Standard Polyol

Yellow

ness

Index

OVT – Polyol – 18 hrs @ 170°C


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Polyol stabilization | Microwave scorch performance

25


30

10

0

5

10

15

20

25

30

35

Industry Stand @ 4000 ppm

Milliguard AOX-1 package@ 2500 ppm

Yellow

ness

Index

Milliguard AOX-1 stabilization technology outperforms industry standard AO package at reduced loading levels.

Industry standard @ 4000 ppm

Milliguard AOX-1 package @ 2500 ppm


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Milliguard AOX-1 reduces thermal degradation in PU and reduces yellowing caused by NOx exposure even at higher loadings

Industry standard = commercial stabilized polyol

9 9 9

35

28

23

0

5

10

15

20

25

30

35

40

Ind. Standard Minimum Stabilized (MS) MS + 3000 ppm MilliguardAOX-1 package

YI

NOx Exposure

0 hr 2 hr

Industry standard

Minimum stabilized (MS)

MS + 3000 ppm Milliguard AOX-

1 package

Polyol stabilization | NOx Exposure


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63

53

43

0

10

20

30

40

50

60

70

Industry standard Minimum stabilized MS + 0,3phpMilliguard AOX-1

package

YI

Industry standard

Minimum stabilized

MS + 0,3php Milliguard

AOX-1 package

Milliguard AOX-1 reduces yellowing caused by UV exposure

Polyol stabilization | UV Exposure


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69

22

0

10

20

30

40

50

60

70

80

VOC (ppm)

VOC (ppm)

Industry Standard 3000 ppm Milliguard AOX-1 package

Efficiency at low

loadings

Reacts with

Isocyanate

Low VOC/FOG

Industry standard = commercial stabilized polyol

Milliguard AOX-1 meets the stringent automotive VDA 278 requirements for VOC and FOG

Milliguard AOX-1 meets the stringent automotive VDA 278 requirements for VOC and FOG

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60

100

200

300

400

500

600

FOG (ppm)

FOG (ppm)

Industry Standard 3000 ppm Milliguard AOX-1 package


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Milliguard AOX-1 has proven to significantly reduce scorch in flexible polyurethane foams

100

43

22

0

20

40

60

80

100

120

Ind. Standard 0,50 php Ref AO 0,25 php MilliguardAOX-1 package

YI

Industry standard

0,50 php Ref AO

0,25 php Milliguard

AOX-1 package

PU Flexible Foam | Scorch performance


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Benefits from Milliguard AOX-1

• Covalently bound in the PU matrix and does not migrate

• Synergy with traditional primary anti-oxidants

• Regeneration of traditional primary anti-oxidants

• Lower loading of stabilizer in polyols

• Lower contribution to VOC/FOG

Benefits from Eliminating Diphenyl Amine

• Minimal contribution to gas fade & emissions

• Lower toxicity

• Lower color body formation


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Milliguard AOX-1 shows superior yellowing performance in box pour trials

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60

80

100

120

140

160

180

200

0:05 0:55 1:45 2:35 3:25

Box Pour Trial temperature Profile

Milliguard AOX-1 package

Industry Standard AO


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Milliken - PCC Rokita partnership

• Polyols for CME foam

• Hypersoft polyols

• Viscoelastic polyols (MDI)

• Viscoelastic polyols (TDI)

PCC Rokita: innovative polyol manufacturer launching new Premium polyols in the market with superior technology based on Milliguard® AOX-1:

High color stability PU foams, delays yellowing of foams for mattresses & pillows

Reduced scorching of PU foam opens up significant opportunities for the Comfort market

Low emission of VOCs, amine-free polyols, adapting to highest standards


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Foams after suntest 72 h

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Milliken - PCC Rokita partnership

Protected with

Milliguard AOX-1

Protected with

Milliguard AOX-1

Polyol for CME foam| aminic antioxidant new Polyol for CME foam| Milliguard AOX-1

Hypersoft Polyol| aminic antioxidant new Hypersoft Polyol| Milliguard AOX-1


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Superior synergy between Antioxidant and UV absorber for high demanding applications

Reactive Primary hydroxyl, allowing the additive to be chemically bound into the

PU matrix, preventing migration and surface

bloom

Liquid form, allowing ease of handling and metering

Compatible with a variety Polyurethane formulations

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Milliguard AOX-1 and Milliguard UVX-200HF

2 Hr Xenon UV Stability

no added UV Package

24 Hr Xenon UV Stability

with added UV Package (4 php)

Industry Standard AOX-1 Amine Free Industry Standard AOX-1 Amine Free

UVX

200HF


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Intense Color


Reduced Yellowing

Reduced Emissions



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Revised GB/T27630 to become an official regulation Jan 1, 2018

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International Standards for Indoor Air Quality

1Limits of exposure suggested by Ministry of Health, Labor and Welfare of Japan—Sick House Syndrome Research Council2Cal/EPA OEHHA list of chemicals for which non-cancer Chronic Reference Exposure Levels Exist (see http://www.oehha.ca.gov/air/chronic_rels/AllChrels.html)

Harmful Substance(Test Temperature & Time)

Original Chinese

GB/T27630

Standard25⁰ C for 16 Hrs

Proposed

Chinese New

Standard25⁰ C for 16 Hrs

Korea25⁰ C for 2 Hrs

Japan (JAMA)1

23⁰/40⁰ C for 4.5 Hrs

Formaldehyde 100 100 210 100

Benzene 110 60 30 -

Toluene 1,100 1,000 1,000 260

Ethyl Benzene 1,500 1,000 1,000 3,800

Xylene 1,500 1,000 870 870

Styrene 260 260 220 220

Acetaldehyde 50 200 - 48

Acrolein 50 50 50 -

Phenol

Glycol-Ethers-Esters

Maximum allowed levels in µg / m3

http://www.oehha.ca.gov/air/chronic_rels/AllChrels.html


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Environmental Test Chamber

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New Aldehyde Scavenger Technology- Milliguard®

Milliguard Aldehyde Scavenger Technology reduces aldehyde content in molded foam seating systems

407443

9675

379

90

100

200

300

400

500

Formaldehyde Acetaldehyde Acrolein

Aldehyde levels in automotive seating foams made with MDI based system

Control made w/ Standard Polyol System (µg/m3 )

Milliken Scavenger Technology @ 4000 ppm (µg/m3)

1m3 Environmental Test Chamber (VW, PV3942-2000)


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Enhancing and protecting polyurethane : Visit us in Hall 3, stand 420

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Specialty Additives

Intense Color Microbial Protection Reduced Yellowing Reduced Emissions


Reactint Colorants

Alphasan Antimicrobial

Milliguard AOX Antioxidants

Milliguard UVX UV Absorbers


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How can we help you innovate?

Antoni Puig

Market Manager

Product Line Manager Polyurethane Colorants & Ingredients

T +34-93-733.85.83 / C +34-699-96.38.56

[email protected]

www.millikenchemical.com

reactive polymer-bound stabilizers for polyols and pu ... · reactive polymer-bound stabilizers for...

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