NORYL™ AP2001G POLYOL

IN POLYURETHANE CAST
FORMULATIONS
PROCESSING GUIDELINES

SABIC’s Specialties Business

July 2022
Classification: General Business Use

CONTENTS

Page

NORYL™ AP2001G Polyols in Cast Formulations 3

NORYL AP2001G Polyol – How to use in Cast Formulations 4

Formulation Space Considerations 5

Reactivity Considerations 6

Preparing NORYL AP2001G Polyol / Polyol Blends 7

Preparing Prepolymer and Castings using TDI 12

Preparing Quasi-prepolymer and Castings using MDI 16

Note: The experimental data contained in this document reflect the

processing conditions used by SABIC.

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Classification: General Business Use

NORYL™ AP2001G POLYOLS IN

CAST FORMULATIONS
NORYL AP2001G polyol is a low molecular weight di-functional hydroxyl-
terminated polyol based on polyphenylene ether (PPE). Incorporating NORYL
AP2001G polyol into a solid elastomer matrix may demonstrate the following
structure-property benefits* in traditional cast polyurethane formulations:

- Improved toughness and reduced abrasion

- Increased tensile strength
- Improved strain modulus and elongation
- Retained physical properties at elevated temperatures
- Retained physical properties after aging in hot, wet environments
- Improved resistance to alkaline, acid, water and oil
- Improved adhesion to steel

Potential applications include: coatings, adhesives, sealants, elastomers, foams

and composites.

NORYL AP2001G polyol has the following characteristics:

* Enhancing TDI Cast Elastomers

* Enhancing MDI-BDO Cast Elastomers

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Classification: General Business Use

USING NORYL™ AP2001G POLYOL IN

CAST POLYURETHANE FORMULATIONS

NORYL AP2001G polyol is compatible with a range of polyether polyols and can be blended with
other diols or triols to achieve desired product properties. Since the terminal phenolic hydroxyl
end-groups have a slower reactivity than the aliphatic hydroxyl in the polyether polyol, a
prepolymer should be considered. This document will outline process conditions in the following
stages:

Preparing NORYL Preparing

Processing cast
AP2001G / polyol prepolymers or
formulations
blends quasi-prepolymers

Process Step Considerations

Preparing NORYL AP2001G polyol / polyol blends

+ Polyether polyols used:

→
NORYL AP2001G NORYL AP2001G
PPG polyol / polyol
polyol
PTMG blend

Preparing prepolymer or quasi-prepolymer

+ Diisocyanate
→
NORYL AP2001G
polyol / polyol Prepolymer (TDI)
blend Quasi-prepolymer (MDI)

Processing cast formulations using prepolymer (or quasi-prepolymer)

+ Curative
+ → Cast
Prepolymer (TDI) NORYL AP2001G polyol / polyurethane
Ethacure 300
Quasi-prepolymer (MDI) 1,4-BDO polyol blend

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Classification: General Business Use

FORMULATION SPACE CONSIDERATIONS

NORYL™ AP2001G polyol is compatible with a range of polyether polyols and can be blended
with other diols or triols to achieve desired product properties. Since the terminal phenolic
hydroxyl end-groups have a slower reactivity than the aliphatic hydroxyl in the polyether polyol, a
prepolymer should be considered. This document will outline process conditions in the following
stages:

Preparing NORYL Preparing

Processing cast
AP2001G / polyol prepolymers or
formulations
blends quasi-prepolymers

Formulation Considerations

NORYL AP2001G Polyol blend Prepolymer or Formulating &

polyol Preparation Quasi prepolymer Casting
Preparation

PPG TDI Ethacure®

NORYL AP2001G
polyol Polyether polyols Diisocyanate Curative

TDI Ethacure

PTMG
Polyol blend
MDI
with 1,4 BDO

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Classification: General Business Use

REACTIVITY CONSIDERATIONS
NORYL™ AP2001G polyol has phenol end groups. Phenols react more slowly than alcohols with
isocyanates. Therefore, it is important to carefully design the reaction stoichiometry and
sequence of additions to ensure full bonding of the AP2001G polyol into the urethane
backbone. The relative rates of reaction at 20 C are approximately 300:1, which leads to full
reaction of the polyol first and NORYL AP2001G polyol second. This is demonstrated by the
modelling of the reaction shown in Figure 1.

Figure 1. Relative concentrations for a 2.05:1 TDI:-OH reaction

There needs to be enough NCO in the original formulation to react with all of the AP2001G end
groups. SABIC employed a 2.05:1 stoichiometry in our tests to allow for the presence of
extraneous moisture in the reagents and ensure full capping of the AP2001G. We monitored the
FTIR signal for NCO until it remained constant. Titration of the NCO content of the final
prepolymer was also performed.

An approach to a low free NCO prepolymer is to ensure a full reaction of AP2001G with
isocyanate by employing a higher initial concentration of AP2001G (eg. 40%), followed by dilution
with additional polyol (PPG or PTMG) to achieve the desired final concentration.

In MDI formulations, when making a quasi-prepolymer, the large excess of NCO to –OH should
overcome the kinetic limitation. SABIC did not experience issues in the AP2001G incorporation
with MDI quasi-prepolymers. When making true MDI prepolymers, the same kinetic limitations as
TDI would apply.
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PREPARING NORYL™ AP2001G
POLYOL / POLYOL BLENDS

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Classification: General Business Use

PREPARING NORYL™ AP2001G POLYOL /

POLYOL BLENDS
Preparing NORYL Preparing
Processing cast
AP2001G polyol / prepolymers or
formulations
polyol blends quasi-prepolymers

Preparing NORYL AP2001G polyol/ polyol blends

+ →
NORYL AP2001G Polyether polyols used: NORYL AP2001G
Polyol PPG Polyol blend
PTMG

Key Considerations:

• NORYL AP2001G polyol is soluble in polyether polyols, thus both PPG and PTMG were
considered. NORYL AP2001G polyol is less soluble in polyester polyols, so these were not
considered.

• Polyether polyols (PPG or PTMG) should be de-moisturized for 24 hours at 75-80 °C under
vacuum of 1-3 mmHg with continuous mixing prior to use.

• Consider viscosity data when determining NORYL AP2001G polyol loading level (see Figures
1 and 2 for PPG1000 and PTMG1000 solutions). When using higher molecular weight polyols,
consider lower loading levels of NORYL AP2001G polyol to achieve desired viscosity.

Blending Procedure:

The blends of NORYL AP2001G polyol (in solid particle form) with PTMG or PPG were prepared
using the following procedure:

1. Preheat polyol (PTMG or PPG) at 100 °C under nitrogen sweep and agitation.
2. Add NORYL AP2001G polyol in small portions to avoid agglomeration.
3. Continue agitation and maintain nitrogen sweep for 2 hours at 100 °C.
4. Transfer to storage container if necessary.

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Classification: General Business Use

VISCOSITY DATA:
NORYL™ AP2001G POLYOL / POLYOL BLENDS
2000

80 °C
1600
100 °C
Viscosity, mPa.s

1200

800

400

0
10% 20% 30% 40%
Weight Percent of NORYLTM AP2001G Polyol

Figure 1: Trend in viscosity vs concentration of NORYL AP2001G polyol in

PPG1000 at 80 °C and 100 °C.
6000
80 °C
5000
100 °C
Viscosity, mPa.s

4000

3000

2000

1000

0
10% 20% 30% 40%
Weight Percent of NORYLTM AP2001G Polyol

Figure 2: Trend in viscosity vs concentration of NORYL AP2001G polyol in

PTMG1000 at 80 °C and 100 °C.

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Classification: General Business Use

TYPICAL PROPERTIES:
NORYL™ AP2001G POLYOL / POLYOL
BLENDS

Preparing NORYL Preparing

Processing cast
AP2001G polyol / prepolymer or quasi-
formulations
polyol blends prepolymer

Preparing NORYL AP2001G / polyol blends

+ →
NORYL AP2001G Polyether polyols used: NORYL AP2001G
polyol PPG polyol / polyol
PTMG blend

Typical Properties of NORYL AP2001G polyol in PPG1000:

Test Limits Results Test Method

NORYL AP2001G polyol loading (wt. %) 40

Hydroxyl Value, mg KOH/g - 87.4 Internal Method

Water (wt%) <0.06 0.03 Karl Fischer Titration
Viscosity at 80 °C, cP - 5260 Brookfield Viscometer

Viscosity at 100 °C, cP - 1210 Brookfield Viscometer

Appearance at 50 °C - Reddish colored viscous liquid

Typical Properties of NORYL AP2001G polyol in PTMG1000:

Test Limits Results Test Method

NORYL AP2001G polyol loading (wt. %) 40
Hydroxyl Value, mg KOH/g - 86.9 Internal Method
Water (wt%) <0.06 0.05 Karl Fischer Titration

Viscosity at 80 °C, cP - 6410 Brookfield Viscometer

Viscosity at 100 °C, cP - 1578 Brookfield Viscometer

Appearance at 50 °C - Reddish colored viscous liquid

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PREPARING PREPOLYMER AND
CASTINGS USING TDI

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Classification: General Business Use

PREPARING PREPOLYMERS WITH TDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
prepolymer with TDI formulations
polyol blends

Preparing prepolymer

+ →
NORYL AP2001G Diisocyanates used: Prepolymer (TDI)
polyol / polyol TDI
blend

Key Considerations:

Matching solution viscosities of all components by preheating may improve mixing

characteristics. Gentle heating (40-100 °C) of the resins may be required to obtain a uniformly
mixed system.

• To identify highest workable concentrations in an overall formulation, consider the viscosity

trend.
• Achieving a homogeneous solution will depend on solution temperature, time and overall
formulation.
• To avoid potential phase separation with the polyol components, add polyol blend with NORYL
AP2001G polyol in stages.

Ensure polyol water content is less than or equal to 0.06%. At lab scale, consider the following
procedure:

• Homogenous polyol blends can be dehydrated under vacuum of ~3 mmHg at 70 °C for at

least 24 hours with continuous mixing in a round bottomed flask.
• Confirm water content after drying using ASTM D4672 (SABIC used Karl Fisher Titration).

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Classification: General Business Use

PREPARING PREPOLYMERS WITH TDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
prepolymer with TDI formulations
polyol blends

Preparing prepolymer based on TDI

+ →
NORYL AP2001G Diisocyanate used: Prepolymer (TDI)
polyol / polyol blend TDI

Prepolymer should be prepared using an NCO:OH molar ratio of 2.05:1

Prepolymer procedure:

1. Charge TDI in a 1 L glass reactor equipped under N2 sweep and agitation.

2. Heat reactor to an internal temperature of 70 °C with a mantle and proportional heat control.
3. Slowly add the polyol blend to maintain the reactor temperature at 70-75 °C.
4. Monitor reaction by following the NCO% using the di-n-butylamine method (ASTM D-5155).
5. Once the reaction reaches the theoretical NCO%, cool the mixture to room temperature.
6. Store the prepolymer in a glass jar under N2 at room temperature.

Table 1: Prepolymer preparation considerations

Prepolymer Preparation PPG2000 PTMG2000

NORYL™ AP2001G polyol (wt. %) 0 8.30% 16% 0 8.30% 16%
Temperature of reaction, °C 70 75 75 75 75 75
Duration of reaction, hr 6 4.5 3.5 3.5 3.2 3.2
Theoretical NCO% 3.5 3.54 3.57 3.58 3.52 3.59
Final NCO% 3.54 3.5 3.6 3.54 3.51 3.52
Viscosity at 70°C, mPa·s 580 2400 15400 3340 5400 32400
Viscosity at 80°C, mPa·s 320 1200 5050 1700 3900 15100
Transitions via DSC (Cooling), °C -59.4 -56.1 -49.3 -1.7 -72 -67.5
Transitions via DSC (Heating), °C -55.7 -50.1 -46.9 21.6, 24.8 -67.5, -21.1, 23.3 -60.8, -0.1, 22.3

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Classification: General Business Use

PREPARING CAST FORMULATIONS:

PPG BASED PREPOLYMER WITH TDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
prepolymer with TDI formulations
polyol blends

Processing cast formulations using prepolymer

+ Curatives
→ Cast
Prepolymer
used: polyurethane
PPG / AP2001G / TDI
Ethacure®

Key Considerations:

• Cast elastomers were prepared by reaction of NCO-prepolymers with Ethacure 300 at an

isocyanate index of 1.05 (see Table 2).
• The cast elastomers, sheets and buttons, were cured for one hour at 80 °C in a Carver
hydraulic press.
• After demolding, the samples were conditioned for seven days at room temperature prior
to testing.

Table 2: Formulation and casting considerations: PPG based prepolymers with TDI

Casting A Casting B Casting C

Ingredient (g) (Control) (90/10 blend) (80/20 blend)

PPG-TDI prepolymer 55.25

PPG-AP2001G-90/10 prepolymer 55.30

PPG-AP2001G-80/20 prepolymer 55.18

Ethacure 300 4.75 4.70 4.82

Temperature of component, °C 80 80 80

Gel time, s >375 622 514

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Classification: General Business Use

PREPARING CAST FORMULATIONS:

PTMG BASED PREPOLYMER WITH TDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
prepolymer with TDI formulations
polyol blends

Processing cast formulations using prepolymer

+ → Cast
Prepolymer Curatives used:
PTMG / AP2001G / TDI Ethacure® polyurethane

Key Considerations:

• Cast elastomers were prepared by reaction of NCO-prepolymers with Ethacure® 300 at an

isocyanate index of 1.05 (see Table 3).
• The cast elastomers, sheets and buttons, were cured for one hour at 80 °C in a Carver
hydraulic press.
• After demolding, the samples were conditioned for seven days at room temperature prior
to testing.

Table 3: Formulation and casting considerations: PTMG based prepolymers with TDI

Casting A Casting B Casting C

Ingredient (g) (Control) (90/10 blend) (80/20 blend)

PTMG-TDI prepolymer 55.25

PTMG-AP2001G-90/10 prepolymer 55.29

PTMG-AP2001G-80/20 prepolymer 55.28

Ethacure® 300 4.75 4.71 4.72

Cure Temperature, °C 80 80 80

Gel time, s 360 344 304

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PREPARING QUASI-PREPOLYMER AND
CASTINGS USING MDI

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Classification: General Business Use

PREPARING QUASI-PREPOLYMERS WITH MDI

Preparing NORYL™
Preparing quasi- Processing cast
AP2001G polyol /
prepolymer with MDI formulations
polyol blends

Preparing quasi-prepolymer

+ →
Polyol blend with Diisocyanates used: Quasi-prepolymer (MDI)
NORYL AP2001G polyol MDI

Key Considerations:

Matching solution viscosities of all components by preheating may improve mixing

characteristics.

• To identify highest workable concentrations in an overall formulation, consider the viscosity

trend.
• Achieving a homogeneous solution will depend on solution temperature, time and overall
formulation.
• To avoid potential phase separation with the polyol components, add polyol blend with
NORYL AP2001G polyol in stages.

Ensure polyol water content is less than or equal to 0.06%. At lab scale, consider the following
procedure:

• Homogenous polyol blends were dehydrated under vacuum of ~3 mmHg at 70 °C for at

least 24 hours with continuous mixing in a round bottomed flask.
• Confirm water content after drying using ASTM D4672 (SABIC used Karl Fisher Titration).

Gentle heating (40-100 °C) of the resins may be required to obtain a uniformly mixed system.

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Classification: General Business Use

PREPARING QUASI PREPOLYMER WITH MDI

Preparing NORYL™
Preparing quasi- Processing cast
AP2001G polyol /
prepolymer with MDI formulations
polyol blends

Preparing prepolymer or quasi-prepolymer

+ →
Polyol blend with Diisocyanates used: Quasi-prepolymer (MDI)
NORYL AP2001G polyol MDI

Prepare MDI quasi-prepolymers using an NCO:OH ratio of 1.05:1

Quasi-Prepolymer Procedure

1. Charge MDI to a 1L glass reactor equipped with mechanical agitator under N2 sweep.
2. Slowly add the polyol blend as to maintain the reactor temperature at room temperature.
3. Flush with N2 then close and store at room temperature overnight.
4. Monitor reaction by following the NCO % by the di-n-butylamine method (ASTM D-5155).
5. Determine final NCO % by the di-n-butylamine method (ASTM D-5155).
6. Store the quasi-prepolymer in a glass jar under N2 at room temperature.

Table 4: Prepolymer formulations

Ingredient Qty. (g) Measurement Value

Polyol blend with PTMG 2000 1000.00 OH value 50.9
NORYL AP2001G NORYL AP2001G 250.17 (Troy Polymer Inc.
(20% AP2001G) method)
Reference PTMG 2000 61.34 Theoretical NCO% 23.03
prepolymer Lupranate® 81 300.76 Final NCO% 22.73
20% AP2001G Polyol blend 55.41 Theoretical NCO% 23.03
prepolymer Lupranate 81 234.66 Final NCO% 21.59
10% AP2001G Polyol blend 27.83 Theoretical NCO% 23.03
prepolymer PTMG 2000 27.80 Final NCO% 21.92
Lupranate 81 234.63

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Classification: General Business Use

PREPARING CAST FORMULATIONS WITH MDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
quasi-prepolymer formulations
polyol blends

Processing cast formulations using quasi-prepolymer

Quasi-prepolymer
+ Curative used:
+ Polyol blend with
→ Cast
polyurethane
(MDI) 1,4-BDO NORYL AP2001G plaques
Part A Part B polyol

Key Considerations

• To maximize loadings of NORYL AP2001G polyol in the formulation, the polyol may be
used in both the part A (quasi-prepolymer) and part B of the final formulation.
• The part B solution is a blend of the PTMG polyol and NORYL AP2001G polyol (see
“Preparing NORYL AP2001G Polyol / Polyol Blends” section) plus curative.
• Polyurethane cast elastomers are prepared by compression molding of the reactive
mixture in a Carver press. Part A and Part B components are preheated at 40 °C and cured
for 30 minutes at 80 °C as shown in the next page.

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Classification: General Business Use

PREPARING CAST FORMULATIONS WITH MDI

Preparing NORYL™
Preparing Processing cast
AP2001G polyol /
quasi-prepolymer formulations
polyol blends

CAST formulation and processing considerations

Casting D Casting E Casting F

Formulation
(control) (10% AP2001G-QPP) (20% AP2001G-QPP)

% AP2001G polyol in total

- 5.6 11.0
system

Part B Ingredients (g)

PTMG 2000 28.88 14.17 -

20% AP2001G polyol in

- 14.16 27.63
PTMG 2000

1,4 Butanediol 4.55 4.49 4.53

Dabco T12 0.008 0.008 0.008

Part A Ingredients (g)

Part A NCO%

Reference prepolymer 22.73 26.18 - -

10% AP2001G
21.59 - 26.80 -
prepolymer

20% AP2001G
21.92 - - 27.45
prepolymer

Sheet Synthesis Details

Part B and Part A, temp., °C 40 40 40

Mold and Carver press, temp. °C 80 80 80

Speed mix time, s 20 20 20

Gel time (avg), s 67 ± 12 80 ± 9 87 ± 12

De-mold time, min 30 30 30

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Classification: General Business Use

CONTACT US

AMERICAS ASIA PACIFIC

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Suite 100 2550 Xiupu Road, Pudong
Houston, Texas 77042 Shanghai 201319
USA China

T +1 800 845 0600 T: +86-21-2037-8188

E [email protected] E: [email protected]

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T2 00 36 1 288 3040
E [email protected]

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