TYTANTM Titanate Coupling Agent

A Quick Overview
on
Calcium Carbonate MB Polyolefin
Applications

June 2018
Compilation SKT
What is TYTAN Titanate Coupling Agent?

Bridging and coupling between inorganic fillers and organic

polymers.
TYTAN titanate coupling agent is to treat the surface of
inorganic fillers like CaCO3 etc in order to improve its
compatibility with the polymers in the system
Hence system properties can be improved as a result of
having better overall compatibility. Applications include
plastic compound, composite material, etc.
 TYTAN Titanate Coupling Agent - How it works?

Organic chain to function

Isopropyl to bond with organic polymer
with inorganic filler
H

iPrOH

OH
Filler OH + iPrO Ti Filler
T °c
OH

Titanate coupling agent Filler coated with

coupling agent
surface with
OH or surface H
 TYTAN Titanate Coupling Agent - How it works?

Polymer Chain Void Polymer Chain

Untreated Filler Treated Filler

Agglomeration creates voids in the polymer, Better dispersion, less void, improved
easily to fracture at the void. property
TYTAN Titanate Coupling Agent - Application Field

CaCO3 PVC
TYTAN Titanate Coupling Agent Success Story

Calcium Carbonate
Customer Application
Masterbatch
Calcium Carbonate,
Filler
uncoated
Polymer PP/PE
TYTAN Product CP-219

The Calcium Carbonate loading 70 – 85 %.

Equipment: High speed mixer, twin screw extruder, dosage
0.5 to 1.0%.
Benefit: improved quality and better processibility
Benefits

Mechanical
Strength

Benefits $
Green Cost Saving
Chemistry

Processability
Benefits – Improve Mechanical Strength (a generic illustration)

Improve mechanical property

Elastic modulus values of PP/CaCO3 composites Percentage strain at break values of PP/CaCO3 composites
EFFECTS OF TITANATE COUPLING AGENTS ON LOW DENSITY
POLYETHYLENE AND POLYPROPYLENE BLENDS AND COMPOSITES
Benefits – Compound showing a better rheolody, example of CCMB making

Reduced extrusion torque and die pressure (illustrated from 50% CaCO3 in PP)

Higher throughput can be achieved or the extrusion temperature can be lowered

to reduce the energy cost
Application, PP weaving

Extrusion Cut into

into film flat yarn

Masterbatch

Weaving Winder Stretching and annealing

GCL PRIVATE LIMITED
Application, PE blow film/bag

http://www.multipakusa.com/
Benefits – Better Properties transferring to CCMB users

50wt% CaCO3 in PP
Tensile Stress at break Elongation at
Coupling agent Dosage Izod impact strength break
used to treat CaCO3 (wt% on CaCO3) 2
strength(J/m ) (MPa)
(MPa) (%)
N/A N/A 1933 21.1 17.4 163.7
Stearic acid 2% 3050 24.1 21.5 305.9
CP-326 1% 3157 23.9 22.0 543.0
CP-317 1% N/A 22.8 21.4 507.1
CP-219 1% N/A 22.7 21.4 497.1
CP-318 1% N/A 24.7 23.5 424.6
PP test slip
Keys:
Titanate coupling agent evidently improve elongation -> very good for flat yarn PP
production owing to reduced breakage of filament.
Benefits:
1. A more smooth downstream process for compounders (PP woven bag)
2. Potential of more loading of calcium carbonate MB.
 Case Study Benefits to PP woven bag makers by using TYTAN modified CCMB

• CaCO3 in the original MB that customer used to use was not treated with titanate coupling agent
• CaCO3 in the modified MB is treated with titanate coupling agent

Case 1 Case 2 Case 3

Addition of original MB 6% Addition of original MB 7% Addition of original MB 13%

Addition of modified MB 6% Addition of modified MB 10% Addition of modified MB 20%

Improved strength Costs saving Costs saving

Good leveling
Speed up the PP drawing film
Improved weave speed
Less dust
Customer knew that dosage of
modified MB can be increased but
chosed not to for now
Improved strength (show by white Original MB was used at max 13%.
yarn sampling) PP flat yarn was easy to break after
Less dust MB dosage higher than 13%
Customer can use modified PP MB
at 20% to produce yarn with the
same strength as that of 13%
original MB.
Case Study Benefits to PP woven bag makers by using TYTAN modified CCMB

Case 4
A new PP woven bag line has been set up, integrated back to a new CCMB facility including
high speed mixer, to take advantage of the benefits that this new approach has been offering
Quality, and process of making, of their final products are more stable in comparison with of
using previous recipe

• CaCO3 in the original MB that customer used to use was not treated with titanate coupling agent
• CaCO3 in the modified MB is treated with titanate coupling agent

Addition of original MB 15%

Addition of modified MB) 18%

Benefits – Cost Saving potential to other applications

Improve filler/pigment dispersion

Enable higher filler loading for cost saving while properties are maintained.
Increase pigment dispersion means increase color intensity -> increase capacity.
Improve recycled plastic properties -> more recycled plastic used, cost saving!

50wt% CaCO3 in PP
Extrusion Coupling agent used to Dosage Tensile strength Stress at break Elongation at break
Cycle treat CaCO3 (wt% on CaCO3) (MPa) (MPa) (%)
x2 N/A N/A 21.1 17.4 163.7
x2 CP-326 1% 23.9 22.1 543.0
x10 N/A N/A 23.4 17.9 101.1
x10 CP-326 1% 24.1 21.6 413.0

Effects of titanate coupling agent on rheological behavior, dispersion characteristics and mechanical properties of talc flled polypropylene
Key Points to Successful Application

Good surface treatment of fillers is obtained via achieving thorough mixing between
titanate coupling agent and fillers above proper temperature
• Dosing by spraying would be ideal
• Direct feeding is acceptable, providing a good mixing
• High speed mixer gives much better results than that from normal mixer
• Liquid dosing is better than dry blend

Proper temperature to active titanate coupling agent bonding to fillers

Above is to make sure that filler surfaces can be properly treated with titanate
coupling agent
 Tytan Titanate Coupling Agent - How to use them?

Liquid coupling agent: Dosing + Mixing + Heating

Dosage: In general 0.2- Coupling Agent
Proper temperature is needed to activate titanate
1.0 % wt uncoated dosing coupling agent bonding to filler.
CaCO3. May reach Mixing to reach min. 80 °C (100+ °C
4.0 +% in treating Mixing preferred). Mixing time could be a few
carbon black minutes to 10+ minutes depending on
Dosing by spraying mixer speed.
would be ideal, though
not essential.
Thorough mixing is Filler
important. Filler coated with coupling agent

Ideally, removing free moisture from filler

prior to mixing is recommended
Tytan Titanate Coupling Agent - How to use them?

Solid coupling agent : Dry Blend

Filler Titanate Coupling Agent

Same comment as in the
liquid case
Same comments as in the liquid case
Mixer

Filler coated with

coupling agent Polymer

Solid-type dosage
0.5 - 5.0 % by weight of filler
Compounding
 Tytan Titanate Coupling Agent

Tytan product Chemistry Appearance Features

Excellent filler dispersion
Isostearyl
CP-317 Reddish liquid Reduce working viscosity
titanate
Increase toughness of polymer

CP-219 Oleyl titanate Reddish liquid Similar effect to CP-317 at a lower cost

Pyrophosphate Moisture resistance

CP-326 Yellowish liquid
titanate Flame retardant and anticorrosion

ALL Tytan Titanate Coupling Agent are REACH pre-registered

 Tytan Titanate Coupling & Dispersing Agent – CP-219

Structure - isopropyl trioleyl titanate, liquid.

Decomposing temperature: 207 C.
Viscosity: 50 cps
Similar effect to CP-317, but lower cost due to the raw material
oleic acid and isostearic acid.
Chemical information:

Borica CAS EC
Tytan CP-219 33485-00-6 251-540-0
 Tytan Titanate Coupling & Dispersing Agent – CP-326

Structure - Isopropyl tris (2-ethylhexyl pyrophosphate) titanate.

Decomposing temperature: 215 C.
Viscosity: 2,200 cps.
Moisture resistance due to the ester structure, suitable for
high moisture content filler.
Chemical information:

Borica CAS EC
Tytan CP-326 68585-78-4 271-587-0
 Tytan Titanate Coupling Agent - Well treated or not?

Qualitative Method – Hydrophobicity Test:

Add treated filler into distilled water and stir it.
If the filler is well treated, it will float in water. If under dosed or poorly treated, it will sink in
water. Please increase dosage until the treated filler floats in water.
This is a preliminary method to verify if filler is well treated with correct dosage of coupling
agent.

Untreated filler Treated filler Untreated filler Treated filler

Tytan Titanate Coupling Agent - How to Determine Dosage?

Quantitative Method – Viscosity Test.

An example of the test: Calcium carbonate filler treated with Tytan CP-219, CP-326 coupling
agent and use hexane as solvent.
To determine the optimal dosage, choose a range of dosages to test, for example: 0.2 %, 0.4
%, 0.6 %, 0.8 % and 1.0 %. Adding treated filler into liquid paraffin at ratio of 60/40
(filler/liquid paraffin). Stir thoroughly and measure the viscosities and chart the data in the
figures in the next slide.
Tytan Titanate Coupling Agent - How to Determine Dosage?

Quantitative Method – Viscosity Test. To determine the optimal dosage.

The viscosity drops sharply from 0.1 % to 0.5 %. It indicates the filler surface is bonded with
the titanate coupling agent and becomes hydrophobic; therefore the viscosity went down
steeply. When the dosage increases from 0.5% to 1.2 %, the viscosity decreases slightly. The
turning point at 0.5 % dosage is the most efficient dosage to be chosen.
THANK YOU