Tri-Rez™ Polyol · 2011. 12. 21. · Tri-Rez™ Polyol 1020-37 - Technical Datasheet All information and data, including the formulations and procedures discussed herein, are believed

GEO Specialty Chemicals, Inc.

Paints & Coatings Group

▪ Customer Service (USA)

340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424

E-mail: [email protected]

GEO Specialty Chemicals, Ltd.

▪ Customer Service (Europe)

Suite 4, Fairview Court

Fairview Road

Cheltenham, Glos. GL52 2EX

UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303


Website: www.geosc.com

Tri-Rez™ Polyol 1020-37 is a highly crystalline

saturated linear polyester polyol designed for use in

polyurethane based coatings and adhesives.

The hydrophobic crystalline structure of Tri-Rez™

Polyol 1020-37 makes it an ideal polyol for

formulating high solids and water-borne

polyurethane resins for heat activated laminating

adhesives.

TRI-REZ™ POLYOL 1020-37 TECHNICAL DATA SHEET

Tri-Rez™ Polyol 1020-37 Polyester Resin

Product Data

Technical Data Typical Properties

Appearance @ 25°C Solid opaque resin

Acid value (as supplied), mg KOH/g 0.8 max

Hydroxyl number (as supplied), mg KOH/g 34 - 40

Non-volatile % 98 min

Brookfield viscosity @ 60°C (as supplied) 15 - 30 poise

Colour, APHA 250 max

Density

Pounds / Gallon @ 25°C

Grams / Litre @ 25°C

8.9 +/- 0.3

1060 +/- 40

Moisture, % 0.05 max

Tri-Rez™ Polyol 1020-37 - Technical Datasheet

All information and data, including the formulations and procedures discussed herein, are believed to be correct. However, this should not

be accepted as a guarantee of their accuracy, and confirming tests should be run in your laboratory or plant. No statement should be

construed as a recommendation for any use which would violate any patent rights. Sales of all products are pursuant to terms and

conditions included in GEO Specialty Chemicals sales documents. Nothing contained therein shall constitute a guarantee or warranty with

respect to the products described or their use. Safety information regarding these products is contained in their Material Safety Data

Sheets. Users of these products are urged to review and use this information.

Created: February 2011

Handling & Storage

Tri-Rez™ Polyol 1020-37 is a hygroscopic material; contamination from atmospheric moisture

will cause undesirable side reactions in urethane formulations.

Container should be sealed at all times unless discharging.

If pre-heating is required, a maximum temperature of 70°C is recommended.

Tri-Rez™ Polyol 1020-37 can be stored for up to 30 days at 70°C with no adverse reactions.

The shelf-life of the material is 12 months after receipt if stored in the original container

at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303



Tri-Rez™ Polyol 1030-35 is a non-crystalline low

viscosity saturated linear polyester polyol designed

for polyurethane based coatings, adhesives and

foams.

The hydrophobic flexible structure of Tri-Rez™



polyurethane resins.



Product Data


Appearance Clear viscous liquid






Density



9.1 +/- 0.3

1100 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303






foams.







Product Data








Density



9.1 +/- 0.3

1100 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303






foams.







Product Data








Density



9.0 +/- 0.3

1100 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303



Tri-Rez™1220-35 is a semi-crystalline saturated

linear polyester polyol designed for polyurethane

based coatings, adhesives and foams.







Product Data








Density



9.0 +/- 0.3

1050 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303



Tri-Rez™ Polyol 1220-120 is a semi-crystalline

saturated linear polyester polyol designed for

polyurethane based coatings, adhesives and

foams.







Product Data








Density



9.3 +/- 0.3

1115 +/- 40










Handling & Storage

Tri-Rez™ Polyol 1220-120 is a hygroscopic material; contamination from atmospheric

moisture will cause undesirable side reactions in urethane formulations.





at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303



Tri-Rez™ Polyol 1230-35 is a non-crystalline



foams.







Product Data








Density



9.3 +/- 0.3

1115 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303



Tri-Rez™ Polyol 1230-60 is a non-crystalline



foams.







Product Data








Density



9.3 +/- 0.3

1115 +/- 40










Handling & Storage







at 0-50°C

2




340 Mathers Road

Ambler PA 19002

USA

Tel: +1 215 773 9280

(Toll Free 888 519 3883)

Fax:+1 215 773 9424





Fairview Road


UK

Tel: +44 1242 255 772

Fax: +44 1452 450 303






foams.







Product Data








Density



9.3 +/- 0.3

1115 +/- 40










Handling & Storage







at 0-50°C

2

GEO Specialty Chemicals, Inc. Paints & Coatings Group ▪ Customer Service (USA) 340 Mathers Road Ambler PA 19002 USA Tel: +1 215 773 9280 (Toll Free 888 519 3883) Fax:+1 215 773 9424 E-mail: [email protected] GEO Specialty Chemicals, Ltd. ▪ Customer Service (Europe) Unit C, Pate Court, North Place Cheltenham, Glos. GL50 4DY UK Tel: +44 1242 255 772 Fax: +44 1242 262 804 E-mail: [email protected] Website: www.geosc.com

DICAP® 2020 is a linear saturated polyester diol with a pendant carboxylic functional group.

The OH terminated polyester chains are DMPA®

Dimethylolpropionic acid initiated polycaprolactone.

The combination of both hydroxyl and carboxyl functionalities produces unique benefits and versatility.

The acid group promotes water dispersability of the resin after neutralisation with a base or can improve adhesion to difficult substrates.

DICAP® 2020 TECHNICAL DATA SHEET

DICAP® 2020 Acid Functional Saturated Polyester Polyol

Product Data


Appearance Waxy solid

Melting point (DSC), °C 58.3

Non-volatile content, wt. % 99 min

Hydroxyl number, mgKOH / g 50 - 60

Acid number, mgKOH / g 25 - 30

Hydroxyl equivalent weight, g / eqv. (as supplied) 935 - 1122

Acid equivalent weight, g / eqv. 1870 - 2244

Water content wt., % < 0.2

Colour, Gardner 2 max

Viscosity @ 60°C, cP 800 - 1000

DICAP® 2020 - Technical Datasheet

Applications

DICAP® 2020 can be used in combination with polyester, polyether, acrylic or polycarbonate polyols to formulate pre-polymers for polyurethane dispersions without DMPA.

Since no DMPA is required to formulate water dispersible pre-polymers, NMP may be reduced or eliminated from the formulations. Pre-polymers formulated with DICAP® products have very good solubility in monomers for hybrid applications and in acetone for solvent-free PUDs.

Depending on the molecular weight of the DICAP® polyol and the formulating technique, hard films can be formulated for durable coatings or soft urethane polymers can be formulated for coating textiles and leathers.

DICAP® products can be used in compliance with 21CFR 175.105 for indirect contact with food.

Solubility

DICAP® 2020 is soluble in aromatic hydrocarbons, esters, ether esters, ketones and TBAC. It is insoluble in aliphatic hydrocarbon solvents. Most solutions will stay liquid at 25°C at 50% solids. Higher concentrations require gentle heating to remain liquid.

Packaging

DICAP® products are available in 200kg open head lined steel drums.

Shipping, Storage & Handling

DICAP® 2020 is supplied as a waxy solid that can be easily melted with steam or in a hotbox for easy handling.

DICAP® products should be melted at 55-75°C 48 to 72 hours before use. It is not recommended to leave DICAP® products at elevated temperature for extended periods of time.

Not DOT regulated. Store products in airtight containers in a cool, dry ventilated area.

NPFA rating: Health: 1, Flammability: 1, Reactivity: 0.

Please refer to the product MSDS for more information.

O CH3 O || | || H[O(CH2)5C]mO-C-C-C-O-[C(CH2)5O]n H | COOH

CAS Registry No. 72018-10-1 Exempt Under EINECS Polymer Exemption

2

All information and data, including the formulations and procedures discussed herein, are believed to be correct. However, this should not be accepted as a guarantee of their accuracy, and confirming tests should be run in your laboratory or plant. No statement should be construed as a recommendation for any use which would violate any patent rights. Sales of all products are pursuant to terms and conditions included in GEO Specialty Chemicals sales documents. Nothing contained therein shall constitute a guarantee or warranty with respect to the products described or their use. Safety information regarding these products is contained in their Material Safety Data Sheets. Users of these products are urged to review and use this information.

Revised: May 2010


DMPA® Brand of Dimethylolpropionic Acid PRODUCT TECHNICAL GUIDE

DMPA® Dimethylolpropionic Acid

DMPA® Dimethylolpropionic Acid, C5 H10 O4

CH2OH |

CH3 — C — COOH | CH2OH

CAS Registry No. 4767-03-7

EINECS Registry No. 2253063

DMPA® Brand of Dimethylolpropionic Acid - Product Technical Guide

Introduction

DMPA® Brand of Dimethylolpropionic Acid is a unique and versatile hindered diol molecule with both hydroxyl and carboxyl functionality.

The neopentyl structure of this trifunctional compound, having two primary hydroxyl groups and one tertiary carboxylic group, permits simplified processing by allowing the combining of all reactants in a single kettle charge. Good control of the reaction is possible due to the slower esterification rate of the tertiary carboxyl, assuring a uniform distribution of carboxyl groups along the resin backbone.

The free acid group actively promotes resin water solubility or water dispersability after neutralization with a base, easily introduces a polar group to improve coating adhesion and synthetic fibre dye receptivity, and increases the alkali solubility of deposited films.

DMPA is an odourless, free flowing white crystalline solid which provides superior advantages in the formulation and processing of water soluble resins.

Uses

DMPA is widely used in:

• Aqueous urethane dispersions, resulting in fast air-drying, high gloss waterborne coatings with superior toughness and flexibility.

• Water soluble alkyd and polyester resins for improved hydrolytic stability, minimal coupling solvent and improved early water spot resistance in air dried resins.

• Powder coatings as a modifier for improved gloss, impact resistance and flow properties in epoxy-polyester systems. In polyester blocked isocyanate systems, DMPA imparts a high melting point hydroxyl functional reactive diluent for improved coating flexibility.

2

Specifications Hydroxyl Content, wt % 24.0 min

Neutralization Equivalent , g / eq. 141.0 max

Ash as Na2O, wt % 0.03 max

Moisture, wt % 0.3 max

Water Insolubles, ppm 50.0 max


Typical Properties

Molecular Weight 134.13

Acid Number, mg KOH / g 410 - 415

Melting Point, °C 170 - 180

Flashpoint (Cleveland Open Cup), °C 220

Decomposition Temperature, °C 230

Bulk Density, lbs / ft3 52.4

Water 11

Acetone 2.3

Ethanol insoluble

Solubility, g / 100g solvent @ 25°C

DMPA® Brand of Dimethylolpropionic Acid - Product Technical Guide

• Epoxy ester coatings to permit resin formulating flexibility for improved cure response or larger oil strengths, to make resins water soluble, and for electrodeposition resins.

• Urethane elastomers as a modifier for improved adhesion to plastics, glass and steel.

• Electrodeposition coatings as a high performance neutralizing acid for cathodic electro deposition and as a source of free acid groups in formulating anodic electrodeposition resins.

• Nylon / polyester fibre blends for improved compatibility and tear resistance.

• Lubricating oil additives as a carrier for thiophosphates or in rust inhibiting derivatives.

• Photo resists / photo print plates as a modifier of phenolic and urethane resists for improved alkali solubility and improved resolution in aqueous development systems.

Additional data on uses of DMPA and patent references may be found in “A Complete Guide to the DMPA® Brand of Dimethylolpropionic Acid” which can be obtained from your GEO Specialty Chemicals, Paints & Coatings Group customer service representative.

Toxicity

DMPA is essentially non-toxic. Tests with white mice indicate an LD50 for oral ingestion of greater than 5000mg / kg. No data is available on inhalation of DMPA dust; no problems have been reported. DMPA is not irritating to intact skin but may be slightly irritating to abraded skin. It is moderately irritating to the eyes with the irritation limited to the conjunctival area.

First aid: for skin contact, wash thoroughly with mild soap and water; for eyes, flush with water for at least fifteen minutes. See an ophthalmologist if irritation persists. Contaminated clothing should be laundered before re-use.

Refer to the product MSDS for all safety and first aid information.

Shipping, Handling and Storage DMPA is packaged in 250lb fibre drums, 50lb and 25kg multi-wall paper bags with HDPE liners and

500kg super sacks with LDPE liners.

DMPA is classified as “DOT not regulated” by the US Department of Transportation and requires no special labelling for shipment. The Harmonized Tariff Code is 2918.19.9000.

DMPA should be stored in a clean, dry area, following good warehousing practices.

The NFPA Hazardous Materials Identification System rating for DMPA is: Health Hazard - 0; Flammability: - 1; Reactivity: - 0. This rating indicates that DMPA is a minimal hazard substance.

Dimethylolpropionic acid is listed on the Chemical Substance Inventory under the US Toxic Substances Control Act, on the Canadian DSL and in the European Inventory of Existing Chemical Substances. The US and Canadian CAS Registry Number is 4767-03-7 and the European EINECS Registry Number is 2253063.

The REACH pre-registration number for GEO Specialty Chemical’s DMPA® Dimethylolpropionic acid is 05-2114683901-42-0000.

3


Revised: October 2009


DMPA® Brand of Dimethylolpropionic Acid TECHNICAL BULLETIN #7

DMPA® Dimethylolpropionic Acid Hydrolytic Stability vs.

Trimellitic Anhydride (TMA)

DMPA® Brand of Dimethylolpropionic Acid - Technical Bulletin # 7

Introduction

This bulletin summarizes the processing and evaluation of DMPA® Brand of Dimethylolpropionic Acid versus Trimellitic Anhydride (TMA) in isophthalic acid polyesters for water borne baking enamels.

Table 1 - Polyester Starting Point Formulation

Procedure: Equipment:

• Round bottom four neck flask • J-Kem temperature controller • Nitrogen sparge tube • Overhead mechanical stirrer • Vigoreaux column • Reflux condenser • Water trap

1. Charge dipropylene glycol and TME to a reactor set up for fusion processing.

2. Heat glycol solution to 160 - 170°C with low nitrogen sparge and moderate agitation.

3. At 160 - 170°C, charge isophthalic acid and set the temperature to 200 - 205°C.

4. At 205°C, hold for 2 hours, then continue heating to 230°C at a rate of 5 - 10°C per hour with low nitrogen sparge.

5. Hold at 230°C until one half of the theoretical water is collected, then cool to 190°C and charge DMPA.

6. Reheat to 205 - 210°C and hold for acid value of 34 - 38.

7. Cool batch and discharge to container

Polyester Formulations EX1013-60 EX1013-62 Supplier

Raw materials

Dipropylene glycol 459 497 Aldrich

Trimethylolethane® 58.5 56.6 GEO

Isophthalic acid 546 528.7 Flint Hills

DMPA 55 0 GEO

TMA 0 32.5 Flint Hills

Total parts 1118.5 1114.8

Water Loss -118.5 -114.8

Yield 1000 1000

2


Table 2 - Typical Resin Properties

Table 3 - Solvent Free Water Borne Baking Enamel Formulation

Procedure:

1. Warm polyester and Cymel® 303 to 50 - 60°C then charge to vessel and begin mixing at moderate shear.

2. When resin blend is homogeneous, charge the DMEA and continue to mix at moderate shear.

3. Warm de-ionized water to 40 - 45°C.

4. Increase the shear and begin charging the de-ionized water at an even rate.

5. When the viscosity has decreased to the minimum, reduce the shear and adjust pH and viscosity as needed.

3

Non Volatile content, % (Method 24)

98 min

Acid Value on solids, mgKOH /g 34 - 38

Hydroxyl Number, mgKOH /g 155 - 170

Viscosity, Gardner - Holt @ 70% in butyl cellosolve

X - Z

Colour, Gardner @ 70% in butyl cellosolve

2 - 4

Properties Results

Raw Materials Parts

Polyester polyol 238

Cymel® 303 * 102

Dimethylethanol amine (DMEA) 14.3

De-ionized water 645.7

Total parts 1000

* Cytec Industries



Created: March 2010

Table 4 - Typical Coating Properties

Table 5 - Stability Study @ 120°F

Conclusion

It can be concluded that DMPA gives greater hydrolytic stability

4

Properties Results

Non-Volatile content, % 33 - 35

Viscosity, cP 100 - 150

pH 7.7 - 8.0

Time 0 week 1 week 2 weeks 3 weeks

DMPA Polyester

pH 7.95 7.55 7.33 7.31

* pH adjusted to 7.5 with DMEA and solution cleared

** TMA control was prepared using standard TMA polyester processing

Visual opaque separated - -

pH 8.2 7.54 - -

Visual clear clear clear slight haze *

TMA Control **

GEO Specialty Chemicals, Inc. Paints & Coatings Group ▪ Customer Service (USA) 340 Mathers Road Ambler PA 19002 USA Tel: +1 215 773 9280 (Toll Free 888 519 3883) Fax:+1 215 773 9424 E-mail: [email protected] GEO Specialty Chemicals, Ltd. ▪ Customer Service (Europe) Unit C, Pate Court, North Place Cheltenham, Glos. GL50 4DY UK Tel: +44 1242 255 772 Fax: +44 1242 262 804 E-mail: [email protected]


DMPA® Polyol HA-0135 is a linear polyester polyol that contains both hydroxyl and acid functionality.

The structure of DMPA® Polyol HA-0135 has been specifically designed to achieve maximum hydrolytic stability in water-borne applications.

DMPA® Polyol HA-0135 can be used to formulate high solids and NMP free polyurethane dispersions.

DMPA® Polyol HA-0135 TECHNICAL DATA SHEET

DMPA® Polyol HA-0135 Product Data

Technical Data Properties

Appearance Clear / lightly hazy viscous liquid

Acid Value, mgKOH / g (as supplied) 100 - 115

Hydroxyl Number, mgKOH / g (as supplied) 100 - 115

Non-volatile, % 98 min

Brookfield Viscosity @ 100% NV

@ 25°C 4000 - 8000 P @ 55°C 150 - 350 P @ 75°C 60 - 80 P

Density @ 25°C, grams / litre 1200 - 1235


Moisture, % 0.5 max

DMPA® Polyol HA-0135 - Technical Datasheet


Revised: May 2010

Applications

• Source of acid functionality for water-borne applications.

• Co-resin to improve pigment wetting, dispersing and stabilising.

• Pendant acid group can be used to improve adhesion in baking enamels and 2K urethanes.

• Acid groups can react with epoxy functional monomers to add acrylate functionality for UV / EB applications.

• Hydroxyl groups can be reacted with isocyanate functional acrylates to produce UV / EB cured water-borne coatings.

Storage

DMPA® Polyol HA-0135 is very hygroscopic. Container should be sealed at all times unless discharging. Due to the reactive nature of the material, containers should be tightly sealed and stored at 0-30°C. If preheating is required for discharging, DMPA® Polyol HA-0135 should be heated to a maximum temperature of 70°C for no longer than 48 hours. If the material is exposed to >70°C for extended periods of time, undesirable side reactions could occur that could cause variations in the properties of the prepared formulations. The shelf life of the material is twelve months after receipt of the material if stored in a sealed container at 0-30°C.

2



DMPA® Polyol HA-0135 is a low molecular weight linear polyester polyol that contains primary hydroxyl and tertiary carboxyl groups in the terminal positions.

The fact that the DMPA is built into a polymeric polyol eliminates the crystalline properties associated with pure DMPA and as a result, formulating low VOC PUDs with a solvent-free process is much easier.

At 25°C, DMPA® Polyol HA-0135 is a viscous liquid; however, when mild heat is applied, the viscosity of the resin decreases rapidly. DMPA®

Polyol HA-0135 has a unique structure that provides excellent hydrolytic stability in PUD formulations.

To illustrate the benefits and properties of DMPA® Polyol HA-0135 in PUD formulations, a low VOC PUD formulation utilizing a solvent-free process is provided.

DMPA® Polyol HA-0135 TECHNICAL BULLETIN #6

DMPA® Polyol HA-0135 Low VOC PUDs for Heat Activated

Laminated Adhesives

DMPA® Polyol HA-0135 - Technical Bulletin #6

Part I - Synthesis of the NCO terminated pre-polymer

(parts by weight)

1. Charge Diexter G6600-37 and DMPA® Polyol HA-0135 to a reactor equipped with agitator, inert gas sparging tube, a temperature controller and a water-cooled condenser.

2. Heat the contents to 80°C and hold until the solution is homogeneous. Add isocyanate (Desmodur® I or TMXDI®), then reheat the batch to 80°C and hold for 1 hour. After one hour, charge N2220 and solvent (DPG-DME) if needed, heat to 90°C and hold for the NCO end point. Note: % NCO is determined by the di-n-butylamine titration method.

3. When the anticipated percent NCO is obtained, prepare for "Neutralization", “Dispersion” and “Chain Extension".

4. Determine and record the final properties of the pre-polymer solution, such as % non-volatile, vis-cosity, and % NCO.

2

05000

100001500020000250003000035000400004500050000

40 50 60 70 80 90

visc

cps

temp °C

DMPA® Polyol HA-0135

Pre-Polymer Formulation EXP 1025-35 EXP 1025-42

Diexter-G 6600-37 * 256.4 273.4

DMPA® Polyol HA-0135 51.3 54.7

TMXDI **** 0 79.2

Acclaim® Polyol N2220 ** 51.3 54.7

Total parts 449.8 462

Desmodur® I ** 68.4 0

Dipropyleneglycol DME *** 22.4 0

EXP 1025-2

269.2

64.7

58.8

0

0

69.3

462

* Coim USA Inc. *** Clariant Corporation

** Bayer MaterialScience LLC **** Cytec Industries


Part II - Neutralization, Dispersion & Chain Extension

(parts by weight)

Dispersion Procedure

Neutralization and dispersing pre-polymer:

1. At 75°C, begin transferring pre-polymer solution to dispersing vessel equipped with high-speed dispersing agitator. Begin agitation on low to medium speed and charge triethylamine (TEA). Allow time for TEA to mix in, typically 3-5 minutes for a 1000g lab batch.

2. Increase agitator speed to 800-1000 rpm and begin charging de-ionized water at a rate sufficient to maintain a vortex. Once water is in and the resin is dispersed, reduce agitator speed and rapidly cool to 25-30°C.

3

Pre-Polymer Properties EXP 1025-35 EXP 1025-42

Non-Volatile, % 95 100

Viscosity @ 75°C, Brookfield #5 spindle @ 20 rpm, cP 10000 13500

NCO : OH 1.93 1.90

Free NCO, % 2.90 2.80

Acid Value on solids, mgKOH / g 13.5 13.3

EXP 1025-2

85

7500

1.77

1.90

18.5

Dispersion Formulation EXP 1025-35 EXP 1025-42

Pre-Polymer 449.8 462

Triethylamine (TEA) 9.3 9.2

Di-ionized Water * 394.8 378.6

Ethylene Diamine 7.7 8

De-ionized Water 138.4 142.2

Total parts 1000 1000

EXP 1025-2

462

12

384

5.7

136.3

1000

* Note: for lab reactions the pre-polymer was charged to the dispersing vessel and neutralized before adding first charge of water. The water was heated to 35-40°C prior to charging. For production, TEA and water are first charged to the dispersing vessel followed by the pre-polymer.


Chain Extension:

3. While dispersion is cooling, pre-mix ethylene diamine (EDA) and second charge of water.

4. Once the dispersion is below 30°C, begin agitation of EDA and water. Note: it is best to start addition slowly then gradually increase rate if viscosity is stable. If viscosity increases, stop addition until viscosity reduces. If viscosity does not reduce after 1- 2 minutes, add more de-ionized water in small increments until it does. Repeat process if viscosity continues to increase during chain extension.

5. Once all the EDA water pre-mix is in, reduce agitator speed to 300-400 rpm and continue mixing for approx. 20 minutes.

4

Dispersion Properties EXP 1025-35 EXP 1025-42

Non-volatile, % 44 47


KU-2 Viscometer

pH 7.5 7.5

Density lbs/gallon, grams/litre 8.76 / 1050 8.78 / 1050

VOC (as supplied), g / l 77 21

Kreb units 57 83.8

cP 292 917

EXP 1025-2

41.1

2200

67

2260

7.54

8.75 / 1050

156

Minimum activation temperature, °C 45 - 55 45 - 55 45 - 55



Created: May 2010 5

OH – HA‐0135‐OH

OCN‐Isocyanate‐NCO

HO‐Polyester‐OH HO‐Polyester‐OH

OCN‐Isocyanate‐NCO OCN‐Isocyanate‐NCO OCN‐Isocyanate‐NCO

OCN‐Isocyanate‐NCO OH – HA‐0135‐OH HO‐Polyester‐OH HO‐Polycarbonate‐OH HO‐Polyether‐OH Chain Extending Diols

Pre‐polymer reactor: Nitrogen sparge, agitator, Temperature controller, condenser.

• Once pre‐polymer is in and all resin is dispersed, begin addition of EDA/water pre‐mix

• Water and TEA already in reactor • Increase agitator speed and begin

charging pre‐polymer

NCO Terminated Pre‐polymer

Finished Polyurethane Dispersion (PUD) Ready for pH adjustment and filtration

Dispersing vessel with high speed mixer and dispersing blade

Note: for lab batches charge pre‐polymer, neutralize with TEA then add water

Note: for commercial scale isocyanates are metered in to control exotherm. For lab scale isocyanate can be added all at once after polyols are homogeneous

Commercial Process for PUD Synthesis



DMPA® Polyol HA-0135 is a low molecular weight linear polyester polyol that contains primary hydroxyl and tertiary carboxyl groups in the terminal positions.

The fact that the DMPA is built into a polymeric polyol eliminates the crystalline properties associated with pure DMPA and as a result, formulating low VOC PUDs with a solvent-free process is much easier.

At 25°C, DMPA® Polyol HA-0135 is a viscous liquid; however, when mild heat is applied, the viscosity of the resin decreases rapidly. DMPA®

Polyol HA-0135 has a unique structure that provides excellent hydrolytic stability in PUD formulations.

To illustrate the benefits and properties of DMPA® Polyol HA-0135 in PUD formulations, a low VOC PUD formulation utilizing a solvent-free process is provided.

DMPA® Polyol HA-0135 TECHNICAL BULLETIN #7

DMPA® Polyol HA-0135 Solvent-Free PUD Process

For Soft-Feel Coatings


Part I - Synthesis of the NCO terminated pre-polymer

1. Charge Terathane™ 650 and DMPA® Polyol HA-0135 to a reactor equipped with agitator, inert gas sparging tube, a temperature controller and a water-cooled condenser.

2. Heat the contents to 80°C and hold until the solution is homogeneous. Add isocyanate (Desmodur® I or TMXDI® ), then reheat the batch to 80°C and hold for 1 hour. After one hour, increase the temperature to 90ºC and hold for the NCO end point. Note: % NCO is determined by the di-n-butylamine titration method.

3. When the anticipated percent NCO is obtained, prepare for "Neutralization", “Dispersion” and “Chain Extension".

4. Determine and record the final properties of the pre-polymer solution, such as % non-volatile, viscosity, and % NCO.

2

05000

100001500020000250003000035000400004500050000

40 50 60 70 80 90

visc

cps

temp °C

DMPA® Polyol HA-0135

Pre-Polymer Formulation EXP 1025-54 EXP 1025-48

Terathane™ 650 * 168 174.2

DMPA® Polyol HA-0135 84.6 87.1

TMXDI ** 159.4 0

Desmodur® I *** 0 150.7

Total 412 412

* DuPont

** Cytec Industries

*** Bayer MaterialScience LLC


Part II - Neutralization, Dispersion & Chain Extension

(parts by weight)

Neutralization and Dispersion Procedure:

1. At 75°C, begin transferring pre-polymer solution to dispersing vessel equipped with high-speed dispersing agitator. Begin agitation on low to medium speed and charge triethylamine (TEA). Allow time for TEA to mix in, typically 3-5 minutes for a 1000g lab batch.

2. Increase agitator speed to 800-1000 rpm and begin charging de-ionized water at a rate sufficient to maintain a vortex. Once water is in and the resin is dispersed, reduce agitator speed and rapidly cool to 25-30°C.

3

Pre-Polymer Properties EXP 1025-54 EXP 1025-48



NCO : Hydroxyl 1.9 1.9

Free NCO, % 6.30 6.60

Acid Value, mgKOH / g 23 24

Dispersion Formulation EXP 1025-54 EXP 1025-48

Pre-Polymer 412 412

Triethylamine (TEA) 15.4 15.5

De-ionized Water * 417.5 417.5

Ethylene Diamine 18 18

De-ionized Water 137.1 137

Total parts 1000 1000

* Note: for lab reactions the pre-polymer was charged to the dispersing vessel and neutralized before adding first charge of water. The water was heated to 35-40°C prior to charging. For production, TEA and water are first charged to the dispersing vessel followed by the pre-polymer.


Chain Extension:

3. While dispersion is cooling, pre-mix ethylene diamine (EDA) and second charge of water.

4. Once the dispersion is below 30°C, begin addition of EDA / water mixture. Note: it is best to start addition slowly then gradually increase rate if viscosity is stable. If viscosity increases, stop addition until viscosity decreases. If viscosity does not decrease after 1-2 minutes, add more de-ionized water in small increments until it does. Repeat process if viscosity continues to increase during chain extension.

5. Once all the EDA / water mixture is in, reduce agitator speed to 300-400 rpm and continue mixing for approx. 20 minutes.

6. After 20 minutes, stop agitation and transfer dispersion to a new container and hold for one day before adjusting pH and characterizing dispersion. Note: the one day hold is to allow for entrained air to escape.

4

Dispersion Properties EXP 1025-54 EXP 1025-48


Viscosity, Brookfield , cP 350 280

KU-2 Viscometer

pH 7.5 8.13

Density, lbs / gallon grams / litre 8.67 / 1040 8.67 / 1040

VOC (as supplied), g / l 36 36

Kreb units 64.2 63

cP 387 367

Film Properties EXP 1025-48 * % CoatOSil 2287 Silane** on TW 0.00% 0.60% 0.80% 1.00 %

Sunscreen 0 2 4 4

DEET, insect repellent 0 2 3 4

Isopropyl alcohol 0 4 5 5

10% Ammonium hydroxide 3 5 5 5

10% Hydrochloric acid 5 5 5 5

10% Sulfuric acid 5 5 5 5

10% Acetic acid 2 4 5 5

* 3 mils / 70 µm wet film baked 5 minutes @ 90°C, 30 minute exposure @ 25°C.

** Momentive Performance Materials

Chemical Resistance



Created: May 2010 5

OH – HA‐0135‐OH

OCN‐Isocyanate‐NCO

HO‐Polyester‐OH HO‐Polyester‐OH

OCN‐Isocyanate‐NCO OCN‐Isocyanate‐NCO OCN‐Isocyanate‐NCO

OCN‐Isocyanate‐NCO OH – HA‐0135‐OH HO‐Polyester‐OH HO‐Polycarbonate‐OH HO‐Polyether‐OH Chain Extending Diols

Pre‐polymer reactor: Nitrogen sparge, agitator, Temperature controller, condenser.

• Once pre‐polymer is in and all resin is dispersed, begin addition of EDA/water pre‐mix

• Water and TEA already in reactor • Increase agitator speed and begin

charging pre‐polymer

NCO Terminated Pre‐polymer

Finished Polyurethane Dispersion (PUD) Ready for pH adjustment and filtration

Dispersing vessel with high speed mixer and dispersing blade

Note: for lab batches charge pre‐polymer, neutralize with TEA then add water

Note: for commercial scale isocyanates are metered in to control exotherm. For lab scale isocyanate can be added all at once after polyols are homogeneous

Commercial Process for PUD Synthesis



DMPA® Polyol HA-0135LV2 is a low crystalline polyester polyol with both acid and hydroxyl functionality.

Like DMPA® Polyol HA-0135, this resin is designed to eliminate the need for NMP as a processing solvent in the manufacturing of polyurethane dispersions.

DMPA® Polyol HA-0135LV2 TECHNICAL DATA SHEET

DMPA® Polyol HA-0135LV2 Product Data


Hydroxyl Value, mgKOH / g 330 - 345

Acid Value, mgKOH / g 80 - 95

Acid Eq. Wt., g / eqv. 590 - 700

Hydroxyl Eq. Wt., g / eqv. 162 - 170

Colour, APHA < 250 max

Density @ 25°C, grams / litre 1170 - 1200

Moisture, % < 0.5

Viscosity @ 25°C, poise 172

DMPA® Polyol HA-0135LV2 - Technical Datasheet


Revised: May 2010

Increased Hydroxyl Concentration Increased coating hardness

Chemical resistance

Low Crystallinity Allows for ease of handling at lower temperatures

Insert table with Viscosity graph

0

50

100

150

200

250

50 55 60 65 70 75 80 85

Vis

c P

oise

Temperature C

VIscosity HA-0135 vs HA-0135LV2

HA-0135

HA-0135LV2

2

Storage

DMPA® Polyol HA-0135LV2 is very hygroscopic. Container should be sealed at all times unless discharging. Due to the reactive nature of the material, containers should be tightly sealed and stored at 0-30°C. If preheating is required for discharging, DMPA® Polyol HA-0135LV2 should be heated to a maximum temperature of 50°C for no longer than 48 hours. If the material is exposed to >50°C for extended periods of time, undesirable side reactions could occur that could cause variations in the properties of the prepared formulations. The shelf life of the material is six months after receipt of the material if stored in a sealed container at 0-30°C.


DCPD and DCPD resins are common raw materials to both coatings and composite resin formulators. DCPD resins are recognised for a variety of properties such as tackifying, pigment dispersing and moisture / corrosion resistance. Most DCPD based resins are used in non-aqueous applications due to their limited functionality and extremely hydrophobic character. Through a unique process, a hydroxyl functional polymeric DCPD polyol - DMPA® Polyol HC-0123 - is now available. This resin allows formulators to take advantage of the properties of DCPD in a variety of resin formulations through the reactivity of the hydroxyl groups. DMPA® Polyol HC-0123 can be used to prepare both solvent-borne and water-borne resins, including polyurethane dispersions.

DMPA® Polyol HC-0123 TECHNICAL DATA SHEET

DMPA® Polyol HC-0123 Product Data

Technical Data Properties Appearance Amber Resin

Acid value (as supplied), mgKOH / g 5.0 max

Hydroxyl number (as supplied), mgKOH / g 60 - 80


Brookfield viscosity @ 25°C, cP 5000 - 8000

80% in NMP 350 - 450

80% in acetone 50 - 100

80% in mineral spirits 300 - 400

Density, grams / litre 980 - 1020

Colour, Gardner (as supplied) 12 max

Hydroxyl equiv. weight (as supplied), g / eqv. 700 - 935

Iodine value 140 - 155

DMPA® Polyol HC-0123 - Technical Datasheet



Applications

• Polyurethane dispersions for direct to metal application can be prepared with excellent early water spot, wet adhesion and corrosion resistance properties (Refer to DMPA® Polyol HC-0123 Technical Bulletins #1 and #2).

• Solubility in water miscible and low boiling aprotic solvents allows PUD chemists to formulate zero VOC or NMP free polyurethane dispersions for adhesive applications.

• The combination of DCPD and linear aliphatic hydrocarbons in the same molecule can be an advantage in formulating low HAPS UPR for composite applications.

• Moisture curable urethane pre-polymers can easily be prepared with aromatic or aliphatic isocyanates for direct to metal primer or adhesive applications.

• Water-borne and solvent-borne alkyd resins with improved moisture and corrosion resistance can be prepared by replacing a portion of the oil and polyol with DMPA® Polyol HC-0123.

2


DMPA® Polyol BA-0132 is a low colour solid resin prepared through a unique process that combines DMPA® Dimethylolpropionic Acid with bis-phenol A epoxy resins.

The result is an aromatic polymeric polyol with a high concentration of primary hydroxyl groups that can be utilised in a variety of applications.

DMPA® Polyol BA-0132 TECHNICAL DATA SHEET

DMPA® Polyol BA-0132 Product Data


Appearance Clear solid resin

Acid value (as supplied), mgKOH / g 10.0 max

Hydroxyl number (as supplied), mgKOH / g 400 - 450


Weight per gallon N/A

Colour, Gardner @ 60% nvm 3 max

Hydroxyl Equivalent Weight, g / eqv. (as supplied) 125 - 140

Melt Point DSC, °C 60 - 70

DMPA® Polyol BA-0132 - Technical Datasheet


Created: August 2010

Applications

• Co-resin for blending with polyesters, alkyds and acrylic in baking or ambient cure enamels for improved adhesion, corrosion resistance and tack-free time.

• Excellent cross-linking resin for two components urethanes and powder coatings.

• Reaction with unsaturated fatty acids will produce high solids air cured and forced cure one component epoxy primers. Further reactions with trimellitic anhydride (TMA) or acrylic acid will produce water-reducible epoxy esters or epoxy ester dispersions.

• The high concentration of primary hydroxyls makes DMPA® Polyol BA-0132 an excellent building block for epoxy modified alkyd dispersions.

• DMPA® Polyol BA-0132 can be easily acrylated due to the high concentration of primary hydroxyl groups. Acrylated DMPA® Polyol BA-0132 can be used in combination with low viscosity acrylated polyethers and polyesters to produce high solids UV cure coatings with excellent hardness, chemical and scratch resistance.

2


TRIMET® Brand of Trimethylolethane (TME) PRODUCT TECHNICAL GUIDE

TRIMET® Trimethylolethane

TRIMET® Trimethylolethane (TME), C5H12O3

CH2OH | CH3 — C — CH2OH | CH2OH

CAS Registry No.77-85-0

EINECS Registry No. 2010639

TRIMET® Brand of Trimethylolethane (TME) - Product Technical Guide

Introduction

TRIMET® Brand of Trimethylolethane (TME), manufactured by GEO Specialty Chemicals, Inc., Paints & Coatings Group, is a high performance polyol containing three primary hydroxyl groups. Its compact neopentyl structure provides high hydroxyl content and excellent resistance to the effects of heat, light, hydrolysis and oxidation.

Typical TRIMET® TME applications include premium quality alkyd and polyester resins for paints, powder coating resins, polyol ester synthetic lubricants, plasticizers, stabilizers for plastics and titanium dioxide pigment coatings. The nitrate ester is used in explosives and propellants. TME may also be used as a solid phase heat storage medium. Resins prepared with trimethylolethane are noted for their superior weatherability and excellent colour, heat and alkali resistance.

TME is available in two grades: Technical and Pure, and in two forms: briquettes and granular. TME Tech is most often supplied in cake resistant briquettes. Granular TME Tech can be shipped on request. TME Pure is available in granular form only.

TME Technical is a high quality product widely used in the manufacture of alkyd and polyester liquid and powder coating resins. TME Pure is a special grade that has been processed to a higher purity.

Specifications Tech Pure Hydroxyl Content, wt % 41.0 min 41.75 min

Ash as NA2O, wt % 0.01 max 0.01 max

Moisture, wt % (Karl Fisher Method)

0.3 max 0.3 max

Water Insoluble, ppm 50 max 50 max

Colour, APHA 250 max 100 max

2

Typical Properties Tech Pure Appearance White Crystalline Solid

Melting Point, °C 185 - 195 199 - 203

Density, Briquettes lbs / ft3 47.1 -

Density, Granular lbs / ft3 46.4 48.6

Combining Weight 41.0 40.5

Combining Weight, theory 40.05

Molecular Weight 120.15

Flashpoint, Cleveland open cup, °C 160

Solubility, g / 100g solvent @ 25°C Water 40

Methanol 75.2

Ethanol 27.9


Uses

TRIMET® TME is widely used as a raw material for alkyd and polyester resins. Because of their stable neopentyl structure, TME-based resins offer superior resistance to the destructive influences of heat, moisture and light. TME-based alkyds also exhibit faster drying times and better hardness than corresponding alkyds prepared with other polyols. Trimethylolethane has been shown to provide superior corrosion protection, improved gloss retention, better abrasion resistance, reduced discolouration and improved temperature resistance in coating resins compared to those made with trimethylolpropane (TMP).

Oil-free polyester resins made with TME are noted for their excellent colour retention. Siliconized polyesters made with TME offer improved heat resistance and weather resistance compared to other polyols. Both alkyd and polyester resins may be advantageously combined with melamine resins to produce outstanding baking enamels. Those made with TME retain their white colour and gloss exceedingly well even when subjected to severe overbake.

TME esters may be used as lubricant base stocks of plasticizers. Short chain aliphatic esters may be used in polyols ester synthetic lubricants that must withstand high temperatures. Small amounts of antioxidants and corrosion inhibitors are incorporated in the finished lubricant. TME esters are also of value as textile lubricants and are reportedly useful as non-caloric shortenings for food. Due to improved stability, TME triacetate is preferred over triacetin as a specialty plasticizer. TME tribenzoate has been cleared by the US Food and Drug Administration as an additive for adhesives in contact with food.

TME is a preferred surface treatment for titanium dioxide and other inorganic pigments. Use of TME as a solid phase energy storage medium was studied. Typical applications include solar energy storage devices, insulating fabrics, heat storing building products and food warming devices.

Additional data on uses of TME and patent references can be found in “A Complete Guide to TRIMET® Brand of Trimethylolethane” which can be obtained through your GEO Specialty Chemicals, Paints & Coatings Group customer service representative.

Toxicity

TME is essentially non-toxic. The LD50 in mice is greater than 5000mg / kg. TME is mildly irritating to abraded skin with a score of 0.6 in the Draize test. TME is not irritating to the eye with a score 0.0 in the Draize test. No toxicological or allergenic problems have been noted during our many years of production experience.

Shipping, Handling & Storage

TRIMET® TME is packaged in 50lb and 25kg multi-wall paper bags with HDPE liners. Super sacks containing 500kg / 1102lb and lined with antistatic LDPE are also available.

TME is a combustible solid with a flashpoint (Cleveland open cup) of 160°C. Store in a cool, dry area. Do not store near oxidizers.

Briquetted TME Tech and TME Pure granular can be stored indefinitely without change provided the packaging remains intact and is protected from water damage. The moisture content of TME may increase slowly with extended storage.

3


Granular TME Tech storage should be limited to 6 months or less due to a tendency of the product to cake. To minimize caking, pallets should not be stacked on top of each other and storage temperatures should be minimized. High humidity conditions may accelerate caking especially if packaging has been opened.

The NPFA Hazardous Materials Identification System rating for TME is: Health Hazard - 0; Flammability - 1; Reactivity - 0. This rating indicates that TME is a minimal hazard substance.

Due to its granular nature, TME is not likely to form explosive dusts. Care should be taken to avoid accumulation of dusts.

Trimethylolethane is classified as “DOT not regulated” by the US Department of Transportation. No special labelling is required for shipment. The Harmonized Tariff Code is 2905.49.

TME may be disposed of in an approved disposal facility in accordance with applicable federal, state and local regulations. The nature and extent of contamination, if any, may require the use of specialized disposal methods.

Consult the Material Safety Data Sheet for current information on this product. Copies may be obtained through your Paints & Coatings Group customer service representative.

Trimethylolethane is listed on the Chemical Substance Inventory of Existing Chemicals Substances . The US and Canadian CAS Registry Number is 77-85-0 and the European EINECS Registry Number is 2010639. The REACH pre-registration number for GEO Specialty Chemicals’ TRIMET® Trimethylolethane is 05-2114684052-52-0000.

4




TRIMET® Brand of Trimethylolethane (TME) TECHNICAL BULLETIN #10

TRIMET® Trimethylolethane in Silicone Modified Polyester

TRIMET® Brand of Trimethylolethane (TME) - Technical Bulletin #10

Trimethylolethane CH2OH | CH3 — C — CH2OH | CH2OH

CAS Registry No.77-85-0 EINECS Registry No. 2010639

Introduction

TRIMET® Brand of Trimethylolethane (TME), manufactured by GEO Specialty Chemicals Inc., Paints & Coatings Group, is a polyol useful in the preparation of polyester resins for a variety of applications.

TME’s favourable properties arise from its neopentyl structure. The three hydroxyls of TME are primary, and therefore highly reactive. In addition, the central carbon of TME, which is beta to all the hydroxyls, has no hydrogens. The absence of beta hydrogens blocks the elimination process, a common mode of thermal decomposition in polyols. Also, the hydrogens in the alpha position relative to the hydroxyls are adjacent to the highly branched central carbon atom, therefore they are highly hindered and protected from free radical attack. The combination of these factors makes TME a very desirable component of coating compositions where good thermal resistance properties are required.

This Technical Bulletin illustrates the use of TME in the preparation of silicone modified polyesters intended for high temperature resistant industrial and bake ware coating applications.

Table 1 - Preparation of Silicone Modified Polyester

Processing: 1. In a reactor set up for resin processing, charge DI water, TME, isophthalic acid and dibutyltin

oxide.

2. Heat slowly to 150-160°C under low nitrogen sparge and begin agitation as soon as TME becomes molten.

Components kg litre

De-Ionized Water 22.0 22.0

TME 211.5

Isophthalic Acid 162.0

Dibutyltin Oxide 0.1

Subtotal 338.6 PM Acetate 293.0 302.3

SILRES® SY231 * 396.4 347.0

Tyzor® TBT ** 0.2

Subtotal 1028.2

Methanol-off -44.7

n-Butanol 16.5 20.0

Total 1000.0 893

2

* Product of Wacker

** Product of DuPont

TRIMET® Brand of Trimethylolethane (TME) - Technical Bulletin #10

2. Slowly heat reaction to 220°C over a five hour period while continuously removing water. Hold reaction temperature at 220°C for an acid value of less than 10 mgKOH / gram resin.

3. Once the acid value is below 10, begin cooling the reaction down to 120°C, then charge PM acetate solvent, SILRES® SY231 silicone resin and Tyzor® TBT catalyst.

4. Reheat batch to 120°C and hold for final viscosity of 120-160 P as is.

5. Once viscosity is within the desired range, begin cooling down to 80°C and charge n-Butanol.

Table 2 - Resin Properties

Table 3 - Film Properties

3

Physical Properties Typical Values Acid Value, mgKOH / g < 5.0 as supplied

Non-Volatile, % 68 - 72

Brookfield Viscosity @ 25°C, P 120 - 160

Colour, Gardner 1.0

Density, lb / gal g / l

9.2 - 9.5 1100 - 1300

Appearance Clear

Properties Bake schedule 20 minutes @ 250°C

Substrate CRS *

Film thickness, dry mil / µm 1.2 / 30

MEK double rubs 200+

Impact resistance, ft / lbs

Direct 20

Reverse 40

Mandrel, inch / mm ¼ / 6.35 mm

Cross-cut adhesion, dry 5B

Cross-cut adhesion, wet ** 4B

* Untreated cold rolled steel ** Panels were cut then exposed to boiling water for 30 minutes.

5B = no loss 4B = very slight loss


Created: May 2010

Tri-Rez

Documents

Tri-Rez™ Polyol · 2011. 12. 21. · Tri-Rez™ Polyol 1020-37 - Technical Datasheet All information and data, including the formulations and procedures discussed herein, are believed