FORMULATION

Presentation Outline

Research Research
Introduction Background Gap

Research
Case Study Scope
Objective

Conclusion
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 Introduction
➢Formulated product
➢Widely used in daily life
➢Paint
➢Detergent
➢Pesticides
➢Pharmaceuticals
➢Personal care products

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 Introduction
➢ Formulated product design
➢ process of designing a product to fulfil the consumer needs
of a specific application.

➢ Consumer needs of a product

➢ product functionality properties
➢ sensorial properties
➢ safety and health properties

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Current health issues in formulated
product

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Process design VS Product Design

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Process design VS Product
Design

Process Design Product Design

Batch vs Continuous process Identify customer needs
Inputs and outputs Generate ideas to meet
needs
Reactors and recycles Select among ideas
Separation and heat Manufacture products
integration

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Case study
 Case Study 1 : Paint formulation

 Case Study 2 :Detergent formulation

 Case Study 3 :Personal care products formulation

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 Case Study 1:
Paint Formulation Design

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Step 1 :
Identification of product attributes

 Solvent-based paint formulation

 Protection from weather
 White colour for decoration
 Waterproof
 Good spread ability
 Excellent adhesion

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 Safe and less harmful
Exposure route

Eye Ingestion

Spillage of paint Paint flakes

Dermal
Inhalation

Paint 12
Painting a wall
Step 2:
Conversion of product attributes
to property constraints
Product attributes Target Properties

Protection from weather Selection of pigment

Decoration Selection of pigment

Water proof All ingredient must be oil soluble

Spread ability Dynamic viscosity

Adhesion Surface tension

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Step 3:
Determination of product form

 Design of solvent-based paint

 form of a liquid

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Step 4:
Generation of ingredient candidate

Type of Function
ingredient
Pigment • Provide colour
• Protection
• Decoration
Binder • Bind insoluble pigment particles
• Coat the surface
Solvent • Deliver paint on surface
• Expected to vaporize thereafter
Additive Improve some properties
• drying properties
• storage properties
• spread ability
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Step 4:
Generation of ingredient candidate

 Regulation relating to paint formulation

 No specific legislation to control the use of any pigment
and solvent in decorative paint
 No concentration limit for the amount of lead in paint
for household and decorative use
 Ministry
of Domestic Trade, Co-operatives and
Consumerism, Malaysia (MDTCC)
 Safety standard for toys intended for children below
14 years old
 concentration limit of lead in paint ≤ 90 ppm
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 Step 4:
Generation of ingredient candidate
Paint formulation is based on Conte et al. (2011)
Type of Selection Source of ingredient
ingredient
Pigment Titanium dioxide (TiO2) Search from existing
Common white pigment database of paint
formulation
Binder Poly(3-hydroxylalkanoates) (PHAs) Search from existing
Common biodegradable polymers database of paint
formulation
Solvent Design new solvent candidate using Design new solvent
Computer aided molecular design candidate using CAMD
(CAMD)
Additive Sodium dioctyl sulfosuccinate (SDS) Search from existing
as wetting agent database of paint
formulation
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 Design of solvent
 Computer-aided molecular design (CAMD) technique is applied:
 design of molecules that possess desirable functionalities
 identificationof molecule that meets the desired target
properties from a given set of molecular blocks
 the physicochemical properties of the designed molecule is
based on property prediction model

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 Model development

 Property prediction models

 Group contribution method (GCM), UNIFAC model,
etc
 Discrepancies between experimental value and
prediction values

Estimate

Physicochemical
Target properties
properties
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 Many CAMD problems involve multiple design objectives:
 Multi-objective optimisation problem
 Product functionality properties
 Safety and health properties
 Fuzzy optimisation formulation can be adopted:
 solves a design problem with conflicting objectives
 applied max-min aggregation method (Zimmermann, 1978)

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Scope 2 : Optimisation model

 Optimal molecules with respect to target properties are

generated:
 apply integer cuts to obtain multiple solutions
 may be similar with the one available in the market

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Design of solvent
Design criteria Target property Lower Upper
bound bound
Less odours Evaporation time, T90 (s) 250 500
Low VOC content Boiling point (Tb) 50 -
Solubility Solubility, () 17 23

Dynamic viscosity, η
0.5 1
(mPa.s)
Good spread ability Surface tension, σ

(mN/m) 26 30

Molar volume, mv (l/kmol) 100 150

Safety -
Flammability Flash point (Fp) -
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-
- -
 Product functional properties
Eg: less odours, low VOC

Safety property
Design • Flammability (flash point
objective and boiling point)

Health properties
CH3 CH2
• Toxicity (LD50 )
• Permissible exposure limit,
PEL OH CH2

Molecular building blocks

Eg: CH3, CH2, CH, OH, CH2COO
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Design of solvent

 Selection of molecular building blocks

 Solventmixtures candidates: hydrocarbons,
cyclohydrocarbons, alcohol and derivatives
 Exposure to benzene, toluene, ethylbenzene and xylene
isomers (BTEX)
 Health risks: respiratory and reproductive development
 These compounds were not considered in solvent mixtures
candidates
 Molecular building blocks: CH3, CH2, CH, CHO, OH etc.

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 Case study 1 : Result
Solvent mixture Solvent A Solvent B

Solvent mixture 1

Solvent mixture 2

Solvent mixture 3

Solvent mixture 4

Solvent mixture 5

Solvent mixture 6

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The IUPAC name of the solvent

Solvent ID Name
Solvent 1A Octane
Solvent 1B Propanol
Solvent 2A Heptane
Solvent 2B Butanol
Solvent 3A Hexane
Solvent 3B Pentanol
Solvent 4A Pentane
Solvent 4B Hexanol
Solvent 5A Hexane
Solvent 5B 3-methoxy propanol
Solvent 6A Heptane
Solvent 6B Pentanol
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 The properties of the generated
solvent mixture
Solvent Mixture x1  µ σ ρ T90 mv LD50 PEL
Octane /
0.6 18.60 1.08 30.23 0.66 497.12 134.73 154.32 190094.4
propanol
Heptane /
0.7 18.14 1.01 29.44 0.68 332.75 139.38 149.81 260848.4
Butanol
Hexane /
0.8 17.74 0.86 28.39 0.67 348.02 129.30 145.28 351533.3
Pentanol
Pentane /
0.9 17.53 0.70 27.34 1.19 500 102.16 141.95 452904.6
Hexanol

Hexane /
3- 0.8 17.80 0.99 28.62 0.68 281.64 127.38 141.36 350994.8
methoxypropanol

Heptane /
0.9 17.15 0.64 28.15 0.68 385.67 149.76 140.80 334226.3
Pentanol
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 Step 6:
Determination of composition
 composition of each ingredient:
 based on paint formulation presented by Conte et al. (2011).
Concentration of ingredient candidates in paint formulation

Type of ingredient Ingredient candidate % Wi

Pigment TiO2 3.38
Binder PHA 34.95
Solvent mixture 1 Octane 44.91
Propanol 15.75
Additive SDS 1.01
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Step 7:
Product Quality Model
 Two main factors
 Product functionality performances Relevant physico-
 Spread ability chemical properties
quantified using
 Adhesion property prediction
 Sensorial properties model

 Nice colour coating

Test panel
 Less pungent smell of paint

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 Formulation of paint with safer
and healthier ingredients

Type of ingredient Ingredient candidate % Wi

Pigment TiO2 3.38

Binder PHA 34.95
Solvent mixture 1 Octane 44.91
Propanol 15.75
Additive SDS 1.01

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 Case Study 2:
Detergent
Formulation Design
• Emulsified handwash laundry
detergent formulation

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 Step 4:
Generation of candidates (Zhang et al. 2017)

Type of Desired function Ingredients

ingredient
Surfactant • Good cleaning power Anionic
• Wetting of the surface C11-13 Linear alkyl benzene
• Dissolution of the dirt sulfonate (LAS)
• Avoid re-deposition of the dirt itself C14-15 Alkyl sulfate
Non-ionic
Novel ingredient
Solvent • Prevent separation or deterioration Novel ingredient
Builder • Enhance cleaning efficiency of Oleic acid
surfactant Citric acid
Additive • Antimicrobial Protease prills
Water • Dissolve water -soluble substances Water
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 Design of non-ionic surfactant

Product attributes Target property Lower Upper bound

bound
Cleaning Power Critical micelle concentration - 0.01
(CMC)
No degradation Cloud point (CP) 55 -
Non-irritable Hansen solubility Dispersion (D) - 20.9
Polar (P) - 8.3
H2 - bond (H) - 13.4
Good solubility in Hydrophilic lipophilic balance 13 15
water (HLB)
Safety - Flammability Flash point (Fp) - -

Acute toxicity (LD50) - -

Health 34

Permissible exposure limit (PEL) - -

Properties of generated non-ionic surfactant
branched alkyl ethoxylate (BAE)
Surfactant Molecule Fp Tm Tb Mw LD50 PEL

BAE1 HO(CH2CH2O)8(CH)5(CH2)3(CH3)6 469.36 99.08 482.23 566.82 74.42 2312.49

BAE2 HO(CH2CH2O)7(CH)4(CH2)2(CH3)5 396.78 79.07 445.75 480.68 86.14 1021.13

BAE3 HO(CH2CH2O)8(CH)4(CH2)(CH3)5 429.69 88.22 458.34 510.71 76.88 120.64

BAE4 HO(CH2CH2O)8(CH)4(CH2)2(CH3)5 441.21 91.64 465.38 524.74 76.91 102.04

BAE5 HO(CH2CH2O)8(CH)4(CH2)3(CH3)5 452.73 94.99 472.22 538.76 76.93 86.31

BAE6 HO(CH2CH2O)8(CH)4(CH2)5(CH3)5 475.77 101.45 485.35 566.82 76.99 61.76

BAE7 HO(CH2CH2O)7(CH)3(CH2)4(CH3)4 403.19 81.79 449.36 480.68 89.10 27.27

BAE8 HO(CH2CH2O)6(CH)2(CH2)4(CH3)3 342.14 63.20 415.79 408.58 103.16 10.19

BAE9 HO(CH2CH2O)8(CH)3(CH2)5(CH3)5 482.19 103.79 488.43 566.82 79.64 1.65

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 Properties of generated non-ionic
surfactant alkyl methyl glucamide
(AMG)
Surfactant Molecule LD50 CMC Tm Tb Mw HLB

AMG1 CONHCH2(OH)10(CH)9(CH2)9(CH3) 1572.44 1.90x10-3 250.72 576.40 485.61 14.18

AMG2 CONHCH2(OH)9(CH)8(CH2)11(CH3) 1221.27 3.3x10-4 241.55 569.16 483.63 13

AMG3 CONHCH2(OH)9(CH)9(CH2)9(CH3)2 1180.62 4.1x10-4 240.66 566.96 483.63 13

AMG4 CONHCH2(OH)9(CH)10(CH2)7(CH3)3 1141.33 4.80x10-4 239.77 564.73 483.63 13

AMG5 CONHCH2(OH)9(CH)11(CH2)5(CH3)4 1103.36 5.8x10-4 238.86 562.48 483.64 13

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 Properties of generated solvent

Solvent Molecule LD50 η  Fp Tm Tb Mw PEL

S1 OHCH2N(CH3)(CH2)2OH 335.75 31.38 24.17 99.52 18.23 193.59 105.14 195.42
S2 OHCH2N(CH3)OH 335.53 20.52 24.48 76.48 6.47 147.32 77.08 273.14
S3 OHCH3NOH 268.59 32.55 26.58 54.73 15.75 135.90 63.06 46.14
S4 OH(CH2)2CH3N(CH2)7(CH3) 202.27 21.37 20.69 101.56 17.51 272.33 187.33 1393.73
S5 OH(CH2)2CH3N(CH2O)(CH2)3(CH3) 180.30 16.87 21.22 88.40 9.08 234.75 161.25 321.65

S6 OHCH2CH2NH(CH2)2(CH2O) 180.18 13.20 21.52 65.36 19.35 207.91 133.19 449.55

(CH3)
S7 OH(CH2)(CH2O)(OH)(CH2)2CH3N 180.18 11.03 21.52 65.36 -3.49 196.24 133.19 449.55
(CH3)
S8 NH2CH2CH(OH)(CH2)3(CH3) 140.88 10.09 23.20 78.84 19.55 184.69 103.17 241.15

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 Formulation of detergent with
safer and healthier ingredients

Type Ingredient Concentration (%w)

Surfactant MES 42
BAE1 3
AMG1 2
Solvent S4 29.2
Builder Oleic acid 3.4
Citric acid 5.4
Additive Violacein pigment 1
Water Water 14

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• Case Study 3:
Personal Care Products Formulation
Design

• Sunscreen formulation

• Eye cream formulation

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 Sunscreen formulation
 Step 4: Generation of candidates (Conte et al. 2012)

Type of ingredient Desired function Ingredients

UV-A blocker • Protection from sunburns Avobenzone
• Protection from skin cancer Octyl salicylate
UV-B blocker
Vitamin E acetate
Inorganic pigment • Provide white colour Zinc oxide
Antioxidant • Prevent skin aging Vitamin A
Vitamin E acetate
Surfactant • Emulsifier to stabilize formulation Novel ingredient
Solvent • Dispersed phase Novel ingredient
• Continuous phase Water
Additive • Antimicrobial Propyl paraben
• Augment product stability Octocrylene
• Pleasant smell Linalool
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Formulation of sunscreen with safer
and healthier ingredients
Type Ingredient Concentration
(%w)
Active ingredient UV- A blocker : avobenzone 4
UV-B blocker : octyl salicylate 4
Butylated hydroxyltoluene 4
Zinc oxide 10
Vitamin E acetate 4
Dispersed phase solvent S7 6.5
Continuous phase solvent Water 60.4
Emulsifier SF1 2
Additive Octocrylene 1.7
Propyl paraben 1.7
Linalool 1.7

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 Eye cream formulation

 Step 4: Generation of candidates

(www.makingcosmetics.com)

Type of ingredient Desired function Ingredients

Solvent • Diluent Water

Surfactant • Emulsifier Sodium Polyacryloyldimethyl

Taurate, Hydrogenated Polydecene,
Capryl Glucoside
Humectant • Retain moisture Glycerin
• Dry and aged skin Sodium Hyaluronate
Emollient • Improve spreading of Dicaprylyl Carbonate
cream
Additive • Prevent wrinkles Argan oil
• Lifting effect Hydrolyzed Pea Protein
• Enhances penetration Sodium Acrylates Copolymer,
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Lecithin
• Preservative Novel ingredient
Step 10 :
Verification and experimental iteration
 Product functionality performances verification

Product functionality Data

properties
Colour Yellowish

Odour Salty

Texture Smooth and slippery

Viscosity @25 ◦C (mPas) 11493.26

pH value @25 ◦C 6.45

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 Design of formulated product

CAMD

Functionality Safety &

Optimal health
performance
molecules
generated

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Thank You 45