Document No. 20140102

PLACCEL® Polyester polyol

Organic Chemical Products Company

Page 1/30 Key Technology

1. Oxidation reaction with peracetic acid

O O O O CH CHO 3 CH3COOH O2 Baeyer-Villiger Reaction

O

Epoxidizing Reaction

2. Ring opening reaction and polymerization of epoxy and epsilon- caprolactone

Page 2/30 PLACCEL M (epsilon-caprolactone monomer) O

O

Table. Typical properties Product Name PLACCEL M Molecular weight 114.14 Appearance [r.t.] Colorless liquid Specific gravity (20 / 4oC) 1.0693 Boiling point (oC) 237.1 Vapor pressure (mmHg / 20oC) 0.02 Viscosity (mPa・s / 20oC) 6.6 Flash points (oC) 118 The above data are not specifications and may change without any notice.

Page 3/30 Advantages of PLACCEL M using as modifiers

Good reactivity with some active hydrogen groups (-OH, -NH groups)

1) Reacting end-functional group has primary hydroxyl group • Reaction with hardener is easily • Crosslinked material is tightly

2) Introducing polycaprolactone moiety • To improve compatibility with some resin • To improve solubility • To improve flexibility at low temperature Page 4/30 Polycaprolactone Polyol (Oligomer)

diol as initiator PLACCEL PLACCEL 205, 208, 210, 212, 220, 230, 240 M Mw/Mn < 1.4 PLACCEL 210N, 220N, 230N, 210CP, 220CPB, 220CPT Liquid PLACCEL 205U, L212AL, L220AL Water resistance PLACCEL 220EB PTMG or PPG co-polymer PLACCEL T2205, P3403 PCD co-polymer PLACCEL 220EC triol as initiator PLACCEL 303, 305, 308, 312, 320, L320AL tetraol as initiator PLACCEL 410

Page 5/30 We have others basis of Special Molecular design. Polycaprolactonediol family with a molecular weight of 2000 Narrow PLACCEL 220N PLACCEL 220CPT distribution grade Abrasion res. Low acid value Compression Hydrolysis res. permanent Liquid grade PLACCEL 220 as Standard grade PLACCEL L220AL Elastic recovery Improved solubility Carbonate diols grade PTMG PLACCEL CD 220 modification Co-polymer grade to liquid PLACCEL CD220PL PLACCEL T2205 PLACCEL 220EC Hydrolysis res. Hydrolysis res. Cold res. Heat res. Page 6/30 PLACCEL general series (Polycaprolactonediol)

O O

O R O H n O O m H

Table. Typical properties Product Name 205 210 220 240 Molecular weight 525 1,000 2,000 4,000 Appearance [r.t.] Paste Wax Wax Wax Color (APHA) 10 10 15 20 Viscosity (mPa･s/75oC) - 120 372 - OH value (KOHmg/g) 213.3 112.8 56.7 28.5 Acid value (KOHmg/g) 0.08 0.09 0.07 0.07

The above data are not specifications and may change without any notice.

Page 7/30 PLACCEL N series (Narrow distribution grade) PLACCEL N series are characterized for its narrow molecular weight distribution.

Table. Typical properties Product Name 210N 220N 230N Molecular weight 1,000 2,000 3,000 Appearance [r.t.] Wax Wax Wax Color (APHA) 10 10 10 Viscosity (mPa･s/75oC) 84 242 - OH value (KOHmg/g) 113.2 56.1 37.1 Acid value (KOHmg/g) 0.13 0.10 0.13 The above data are not specifications and may change without any notice.

Page 8/30 PLACCEL CP series (Narrow distribution and better hydrolysis resistance) PLACCEL CP series are characterized for different initiator. In addition, PLACCEL220 CPT is higher hydrolysis resistance, due to a lower acid value.

Table. Typical properties Product Name 210CP 220CPB 220CPT Molecular weight 1,000 2,000 2,000 Appearance [r.t.] Paste Wax Wax Color (APHA) 10 10 10 Viscosity (mPa･s/75oC) - - 244 OH value (KOHmg/g) 112.8 57.2 56.6 Acid value (KOHmg/g) 0.16 0.16 0.02 The above data are not specifications and may change without any notice.

Page 9/30 PLACCEL polyfunctional series (Polycaprolactonepolyol) PLACCEL polyfunctional series is completely control of number of functional group according to ring opening polymerization. Table. Typical properties Product Name 305 312 320 410 number of functional group 3 3 3 4 Molecular weight 550 1,250 2,000 1,030 Appearance [r.t.] Liquid Wax Wax Liquid Color (APHA) 10 20 20 15 Viscosity (mPa･s) 1,279/25oC 152/75oC 281/75oC 272/60oC OH value (KOHmg/g) 305.6 136.1 85.4 217.8 Acid value (KOHmg/g) 0.50 0.38 0.29 0.56 The above data are not specifications and may change without any notice.

Page 10/30 PLACCEL AL series (Liquid types polycaprolactonepolyol) PLACCEL AL series are amorphous and viscous liquid of polycaprolactonepolyol.

Table. Typical properties Product Name L212AL L220AL L320AL number of functional group 2 2 3 Molecular weight 1250 2,000 2,000 Appearance [r.t.] Liquid Liquid Liquid Color (APHA) 15 10 10 Viscosity (mPa･s/25oC) 3,168 8,433 10,831 OH value (KOHmg/g) 90.2 56.8 83.4 Acid value (KOHmg/g) 0.17 0.20 0.45 The above data are not specifications and may change without any notice.

Page 11/30 PLACCEL E series (Improved hydrolytic stability) PLACCEL E series are liquid polyester diol with improved hydrolytic stability. PLACCEL 220EB is special adipate polyester. PLACCEL 220EC is co-polymer with polycabonatediol.

Table. Typical properties Product Name 220EB 220EC number of functional group 2 2 Molecular weight 2,000 2,000 Appearance [r.t.] Liquid Liquid Color (APHA) 20 45 Viscosity (mPa･s/75oC) 752 1,055 OH value (KOHmg/g) 56.8 56.5 Acid value (KOHmg/g) 0.24 0.02 The above data are not specifications and may change without any notice. Page 12/30 PLACCEL CD series (Polycarbonatediol)

General Grade : CD220 Liquid Grade w/ lower Md. : CD220PL

Table. Typical properties Product Name CD210 CD220 CD205PL CD220PL Molecular weight 1,000 2,000 500 2,000 Appearance [r.t.] Wax Wax Liquid Liquid Color (APHA) 20 10 10 10 Viscosity (mPa･s) 415.4/75oC 2,588/75oC 1,396/25oC 4615/60oC OH value (KOHmg/g) 111.5 55.7 230.6 57.6 Acid value (KOHmg/g) 0.02 0.03 0.05 0.03 The above data are not specifications and may change without any notice.

Page 13/30 PLACCEL T2205, P3403 (PTMG or PPG initiated polycaprolactone)

*Excellent properties at low temperature *Excellent compression permanent *Improved abrasion resistance Table. Typical properties Product Name T2205 P3403 Initiator PTMG PPG number of functional group 2 3 Molecular weight 2000 4000 Appearance [r.t.] Wax Liquid Color (APHA) 25 25 OH value (KOHmg/g) 55.0 42.4 Acid value (KOHmg/g) 0.12 0.26 The above data are not specifications and may change without any notice. Page 14/30 Characteristics of the polyurethane elastomers by used several diols

Other Polyols PLACCEL Diols PBGA PTMG PCD 220 220N L220AL 220CPT T2205 CP⇒CPT Water × ○ ◎ △ △ △ ○ △ resistance poor good excellent fair fair fair good fair

Heat △ × ◎ ○ ○ ○ ○ △ resistance fair poor excellent good good good good fair

Oil × ○ ○ ○ ○ ○ ○ ○ resistance poor good good good good good good good

Cold × ◎ × ○ ○ ○ ○ ◎ resistance poor excellent poor good good good good excellent

Compression × △ × × ○ ○ ○ ◎ permanent poor fair poor poor good good good excellent

Abrasion △ × ○ ○ ◎ △ ○ △ resistance fair poor good good excellent fair good fair

Weather ○ × ○ ○ ○ ○ ○ × resistance good poor good good good good good poor Mw/Mn Mw/Mn modified types Standard Liquid <1.4 <1.4 by ether Note; PBGA: Polybutylenegycoladipate, PTMG: Polytetramethyleneglycol, PCD: Polycarbonatediol, PLACCEL; Polycaprolactonediol Page 15/30 Preparation of Polyurethane 1) PLACCEL / MDI / 1,4-BG (PLACCEL content : 60.0%) 2) Preparation Process

A)PLACCEL / MDI Prepolymer 80oC NCO=10% 80oC*1.5hr Mixing Mold About 1min 100 or 120oC B)PLACCEL + 1,4-BG 80oC Reaction 120oC*17hr

Index(NCOpre/OH)=1.04 3) Formulation (ex. Using PLACCEL 220)

A) Prepolymer Mn mol weight mol mol weight ratio PLACCEL 220 2004 1.000 2004 PLACCEL 220 1.138 1.000 60.00 MDI 250 4.820 1205 MDI 4.820 4.236 31.71 Total 3209 1,4-BG 3.498 3.074 8.28 Blend ratio Total 100 B) Hardener Mn mol weight A)Prepolymer PLACCEL 220 2004 0.138 276 100.0 parts PLACCEL=60.00%, Index(NCO/OH)=1.040 1,4-BG 90 3.498 315 B)Hardener 18.4 parts Total 591 Page 16/30 Physical properties (1) Formulation Polyol (PLACCEL) 210 210N 210CP 212 212CP 220 PLACCEL 1.000 1.000 1.000 1.000 1.000 1.000 mol MDI 2.211 2.219 2.238 2.712 2.702 4.199 ratio 1,4-BG 1.154 1.162 1.179 1.637 1.627 3.071 Index[NCO]pre/[OH] 1.035 1.038 1.039 1.041 1.036 1.035

TPU Hardness (JIS A) 85 85 87 86 86 90 100%M (MPa) 6.3 5.9 7.5 7.2 7.7 8.6 200%M (MPa) 9.8 9.3 11.6 10.9 11.9 13.3 300%M (MPa) 21.3 23.1 26.0 22.0 22.9 21.2 Tensile 400%M (MPa) - - - - - 39.0 properties Tensile strength 45.3 47.9 42.4 53.2 40.2 46.6 (MPa) Elongation (%) 375 370 340 390 360 430 Tearing strength (N/mm) B 81 80 77 86 83 93 Softening point (oC) 209 210 207 209 208 205 Tg (DMS) (1Hz,2oC/min) -18.1 -17.0 -18.9 -28.4 -25.5 -39.1

Page 17/30 Physical properties (2) Formulation Polyol (PLACCEL) 220N 220CPB 230 230CP 240 240CP PLACCEL 1.000 1.000 1.000 1.000 1.000 1.000 mol MDI 4.22 4.15 6.084 6.152 8.060 8.124 ratio 1,4-BG 3.091 3.030 4.888 4.952 6.788 6.850 Index[NCO]pre/[OH] 1.042 1.037 1.048 1.038 1.037 1.043

TPU Hardness (JIS A) 90 90 90 93 93 92 100%M (MPa) 9.0 9.1 7.9 10.5 9.3 6.3 200%M (MPa) 12.9 12.8 12.7 14.3 14.5 11.1 300%M (MPa) 20.0 19.2 19.1 19.2 20.4 16.9 Tensile 400%M (MPa) 36.3 32.9 30.5 27.1 29.2 25.7 properties 500%M (MPa) - - - 36.5 48.8 - Tensile strength 41.7 40.4 50.8 43.5 52.4 40.4 (MPa) Elongation (%) 420 425 495 530 525 490 Tearing strength (N/mm) B 102 98 109 110 125 111 Softening point (oC) 204 202 210 213 212 214 Tg (DMS) (1Hz,2oC/min) -39.2 -38.9 -45.6 -46.4 -31.9 -50.0 Page 18/30 Preparation of Casting Urethane Elastomer Formulation for Polyurethane Solution Isocyanate : 4,4’-Diphenylmethane diisocyanate (MDI) Isocyanate Index : 105 Chain-extender : 1,4-Butanediol (BG) Equivalent ratio of Polyols / MDI / BG : 1.0 / 3.0 / 2.0 Synthesis of Polyurethane

1,4-BG

Polyol Mixing Casting MDI 1st curing；80oC*1.5hr Prepolymerization 2nd curing；120oC*20hr o 80 C*1hr Aging；room temp.(25oC)*1week

Page 19/30 Mechanical Properties of Casting Urethane Elastomers (1)

PLACCEL PLACCEL PLACCEL PLACCEL Polyol 220 220N 220CP L220AL Hardness (JIS A) 82 84 81 78 100%M (MPa) 5.0 5.1 5.3 4.9 Tensile 300%M (MPa) 11.0 10.5 10.8 9.7 Properties Tensile strength (MPa) 44.5 39.9 42.8 38.1 Elongation (%) 536 512 519 614 Tearing strength (N/mm) B 82 75 77 73 Impact Resilience (%) 63 66 60 53 Abrasion per 1000times*1 (mg) 53 49 72 72 Recovery of Elasticity (%) 17 65 79 85 Compression Set (100oC*70hr) (%) 45 48 57 47 *1:Taper method : 1kg weight. H-22 abrasion ring These elastomers were subjected to mechanical tests according to JIS-K 6301, 7311.

Page 20/30 Mechanical Properties of Casting Urethane Elastomers (2)

PLACCEL PLACCEL Polyol PTMG PBGA 220EB 220EC Hardness (JIS A) 75 84 84 82 100%M (MPa) 4.5 5.7 6.0 5.2 Tensile 300%M (MPa) 9.7 12.5 10.8 11.7 Properties Tensile strength (MPa) 22.7 51.6 89 94 Elongation (%) 639 471 591 583 Tearing strength (N/mm) B 51 76 89 94 Impact Resilience (%) 14 52 70 58 Abrasion per 1000times*1 (mg) 97 55 72 60 Recovery of Elasticity (%) 80 80 80 13 Compression Set (100oC*70hr) (%) 54 34 56 51 *1:Taper method : 1kg weight, H-22 abrasion ring These elastomers were subjected to mechanical tests according to JIS-K 6301, 7311.

Page 21/30 PLACCEL H1P (High molecular weight polycaprolactone) *Highly crystalline O *Low melting point *Flexibility R O C-(CH2)5-O H m *Good biodegradability f *Thermal degradation(>230oC) Table. Typical properties Product Name H1P Molecular weight 10,000 Appearance [r.t.] granular Melting point (oC) 60 Tg (oC) -60 OH value(KOHmg/g) 12.3 Acid value(KOHmg/g) 0.18 Color (APHA) 30 The above data are not specifications and may change Page 22/30 without any notice. PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylate) PLACCEL F series are macro monomers with a (meth)acrylic double bond. O O

O CH2CH2OH O H2C + n R Hydroxymethyl(meth)acrylate epsilon-caprolactone O O O CH CH O C (CH ) O H 2 2 2 5 n H2C R R=H, PLACCEL FA ; Acrylate darivative R= CH3, PLACCEL FM ; Methacrylate derivative Table. Relation of between Tg and adding caprolactone mol number Adding mol number (n) 1 2 3 4 5 Product name FA1 FA2 FA3 FA4 FA5 o Tg of Homopolymer ( C) -28 -40 -46 -51 -53

Product name FM1 FM2 FM3 FM4 FM5 o Tg of Homopolymer ( C) -8 -28 -37 -43 -47 Page 23/30 PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylate) Table. Typical properties Product Name FM1D FM2D FM3 FM5 FA1DDM FA2D FA10L*1 Acrylate Hydroxyethylmethacrylate (HEMA) Hydroxyethylacrylate (HEA) Partially Partially Appearance [r.t.] Liquid Liquid Paste Liquid Liquid crystalline crystalline Mol. Wt.*2(g/mol) 244 358 472 700 230 344 1,256 OH Value 224.3 154.5 116.2 78.7 244*2 163*2 31*2 (KOHmg/g) Acid Value 3.41 2.44 1.95 1.36 3.48 2.50 0.67 (KOHmg/g) Viscosity 121 31 72 130 32 78 48 (mPa･s/25℃) /40oC Color (APHA) 25 20 45 40 10 15 35

*1:Diluted in Toluene (28~32%). Crystals can be precipitated. May be clouded in low temperature. *2:Calculated value. The above data are not specifications and may change without any notice.

Page 24/30 PLACCEL HEMAC1 (Hydroxyl functioned carbonate methacrylate)

PLACCEL HEMAC1 is a Hydroxyl functioned carbonate methacrylate newly developed by Daicel. It has a radical polymerizable methacrylic double bond and a highly reactive primary OH group in the molecule. In addition, HEMAC is highly hydrolysis resistant and heat resistant because of its carbonate bond.

Table. Typical properties Product Name HEMAC1 Appearance [r.t.] Liquid OH Value*1 (KOHmg/g) 216 Acid Value (KOHmg/g) 0.12 Viscosity (mPa･s/25℃) 103 Color (APHA) 70 *1:Calculated value. The above data are not specifications and may change without any notice.

Page 25/30 Cross linking reaction of PLACCEL F co-polymer resin Copolymer with PLACCEL F Ordinary acryl polyol

Polymer main chain Side chain Polymer main chain Polycaprolactone chain OH OCN OH OCN NCO HO NCO HO OCN OH OH OCN Polyisocyanate hardener Polyisocyanate hardener Crosslinked Crosslinked

O H O H H O O N O N H O N O N O O N O N O H O H

• Toughness • Hardness • Flexibility • Fragility • Higher reactivity Page 26/30 Isocyanate Cross linking of PLACCEL F co-polymer

The reaction transition is traced by measuring of NCO-Value.

Examination Method hardener：HMDI NCO/OH=1/1

Reaction Temperature：20oC Base Material： cold rolled steel

thickness：25um

Measurement： Tracing NCO remaining by FTIR (2950cm-1、2270cm-1)

NCO reactivity of PLACCEL FM copolymer is faster than HEMA.

Page 27/30 Toughness of PLACCEL F co-polymerized urethane-acrylate coating film Toughness of films measured by tension tester.

Examination Method

hardener：HMDI NCO/OH=1/1

Reaction Temperature： Room Temperature

Measurement ： Tension testing machines

Urethane-acrylate coatings of PLACCEL FM delivered copolymers are excellence at elongation after yielding.

Page 28/30 Properties of Urethaneacrylates from “PLACCEL” In the following points, Urethaneacrylates(UA) made from “PLACCEL” have the characteristic superior to HEA, non-CL polyesterpolyol. *Low-viscosity *Low-temperature storage stability (PLACCEL 200 vs 1,6HD-AD polyester) *High-reactivity by UV irradiation (PLACCEL FA vs HEA)

Ex. No. Ex1 Ex2 Ex3 Ex4 PLACCEL 205U PLACCEL 205U PLACCEL 210N 1,6HD-AD*1 Composition of UA /IPDI/HEA /IPDI/FA2D /IPDI/HEA /IPDI/HEA Molecular weight*2 1,200 1,700 1,700 1,700 Viscosity (mPa･s/75oC) 6,200 1,900 3,300 4,900 Appearance [r.t.]*3 clear clear clear cloudy Appearance [-5oC]*3 clear clear clear Crystallization *1: 1,6HD-AD:Polyesterdiol consisted by 1,6-Hexanediol and Adipic acid. (Calcd. Mn:1,000) *2 :Calculated value *3 :Samples were diluted with ethyl acetate to 50wt%, and after keeping it for two weeks in room temperature or a -5oC refrigerator, appearance was checked visually. Page 29/30 Application of PLACCEL

Shoe Grade TPU Leathers Adhesives Ink Foam Coating Soles 200 + + + + + ++ ++ (General grade) 200N ++ + + + ++ (Narrow distribution) 200CPT + ++ + + (Hydrolysis resistant) Poly L200AL + + ++ + ++ Capro (Liquid grade) lactone 200EB polyols ++ ++ (PCL) (Adipate grade) 220EC ++ ++ (Carbonate co-polymer) 300、400 + ++ ++ (Polyfunctional grade) FM,FA + + ++ (Acryl monomer) Poly CD200 + + + + + + Carbo (General grade) nate CD200PL polyols + ++ ++ + (PCD) (Liquid grade) Additionally, it accedes to a request and a lot of various pre-production samples etc. are collected. Please consult readily, and inquire. Page 30/30