Organic Chemical Products Company · oNCO=10% 80 C*1.5hr B)PLACCEL + 1,4-BG 80oC 80oC Mixing About...

PLACCEL® Polyester polyol

Organic Chemical Products Company

Document No. 20140102

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Key Technology

1. Oxidation reaction with peracetic acid

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

O

O

O

O

CH3CHO

O2

Baeyer-Villiger Reaction

Epoxidizing Reaction

CH3COOH

O

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Table. Typical properties

O

O

PLACCEL M (epsilon-caprolactone monomer)

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

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

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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

Advantages of PLACCEL M using as modifiers

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diol as initiator

triol as initiator

tetraol as initiator

Mw/Mn < 1.4

Liquid

PTMG or PPG co-polymer

PLACCEL 205, 208, 210, 212, 220, 230, 240

PLACCEL 210N, 220N, 230N,

210CP, 220CPB, 220CPT

PLACCEL 205U, L212AL, L220AL

PLACCEL T2205, P3403

We have others basis of Special Molecular design.

PLACCEL 303, 305, 308, 312, 320, L320AL

PLACCEL 410

PLACCEL 220EB Water resistance

PCD co-polymer PLACCEL 220EC

PLACCEL

M

Polycaprolactone Polyol (Oligomer)

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PLACCEL CD 220

modification

to liquid

PLACCEL 220CPT

PLACCEL 220EC PLACCEL CD220PL

PLACCEL T2205

Liquid grade

PLACCEL L220AL

Carbonate diols grade

Co-polymer grade

Narrow

distribution

grade

PLACCEL 220N

PTMG

PLACCEL 220 as Standard grade

Hydrolysis res.

Heat res.

Elastic recovery

Improved solubility

Low acid value

Hydrolysis res.

Abrasion res.

Compression

permanent

Hydrolysis res.

Cold res.

Polycaprolactonediol family with a molecular weight of 2000

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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

PLACCEL general series (Polycaprolactonediol)

OO

O

Hm

O

O

OH n

R


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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

PLACCEL N series (Narrow distribution grade)

PLACCEL N series are characterized for its narrow molecular weight distribution.


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Product Name 210CP 220CPB 220CPT

Molecular weight 1,000 2,000 2,000

Appearance [r.t.] Paste Wax Wax


Viscosity (mPa･s/75oC) - - 244

OH value (KOHmg/g) 112.8 57.2 56.6


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.


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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


PLACCEL polyfunctional series (Polycaprolactonepolyol)

PLACCEL polyfunctional series is completely control of number of functional group according to ring opening polymerization.


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PLACCEL AL series (Liquid types polycaprolactonepolyol)


PLACCEL AL series are amorphous and viscous liquid of polycaprolactonepolyol.

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


Viscosity (mPa･s/25oC) 3,168 8,433 10,831

OH value (KOHmg/g) 90.2 56.8 83.4



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PLACCEL E series are liquid polyester diol with improved hydrolytic stability. PLACCEL 220EB is special adipate polyester. PLACCEL 220EC is co-polymer with polycabonatediol.

PLACCEL E series (Improved hydrolytic stability)

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


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General Grade : CD220

Liquid Grade w/ lower Md. : CD220PL


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


PLACCEL CD series (Polycarbonatediol)


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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

PLACCEL T2205, P3403 (PTMG or PPG initiated polycaprolactone)



*Excellent properties at low temperature *Excellent compression permanent *Improved abrasion resistance

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Note; PBGA: Polybutylenegycoladipate, PTMG: Polytetramethyleneglycol,

PCD: Polycarbonatediol, PLACCEL; Polycaprolactonediol

CP⇒CPT

Other Polyols PLACCEL

Diols PBGA PTMG PCD 220 220N L220AL 220CPT T2205

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

types Standard Mw/Mn <1.4

Liquid Mw/Mn <1.4

modified by ether

Characteristics of the polyurethane elastomers by used several diols

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Preparation of Polyurethane

1) PLACCEL / MDI / 1,4-BG (PLACCEL content : 60.0%)

2) Preparation Process

3) Formulation (ex. Using PLACCEL 220)

A)PLACCEL / MDI Prepolymer NCO=10% 80oC*1.5hr

B)PLACCEL + 1,4-BG

80oC

80oC

Mixing About 1min

Mold 100 or 120oC Reaction 120oC*17hr

Index(NCOpre/OH)=1.04

A) Prepolymer Mn mol weight

PLACCEL 220 2004 1.000 2004

MDI 250 4.820 1205

Total 3209

B) Hardener Mn mol weight

PLACCEL 220 2004 0.138 276

1,4-BG 90 3.498 315

Total 591

Blend ratio A)Prepolymer 100.0 parts B)Hardener 18.4 parts

mol mol ratio

weight

PLACCEL 220 1.138 1.000 60.00

MDI 4.820 4.236 31.71

1,4-BG 3.498 3.074 8.28

Total 100

PLACCEL=60.00%, Index(NCO/OH)=1.040

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Physical properties (1) Formulation

Polyol (PLACCEL) 210 210N 210CP 212 212CP 220

mol ratio

PLACCEL 1.000 1.000 1.000 1.000 1.000 1.000

MDI 2.211 2.219 2.238 2.712 2.702 4.199

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

Tensile properties

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

400%M (MPa) - - - - - 39.0

Tensile strength (MPa)

45.3 47.9 42.4 53.2 40.2 46.6

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

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Physical properties (2) Formulation

Polyol (PLACCEL) 220N 220CPB 230 230CP 240 240CP

mol ratio

PLACCEL 1.000 1.000 1.000 1.000 1.000 1.000

MDI 4.22 4.15 6.084 6.152 8.060 8.124

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

Tensile properties

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

400%M (MPa) 36.3 32.9 30.5 27.1 29.2 25.7

500%M (MPa) - - - 36.5 48.8 -

Tensile strength (MPa)

41.7 40.4 50.8 43.5 52.4 40.4

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

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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

MDI

Mixing Casting

Prepolymerization 80oC*1hr

1st curing；80oC*1.5hr 2nd curing；120oC*20hr Aging；room temp.(25oC)*1week

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Mechanical Properties of Casting Urethane Elastomers (1)

Polyol PLACCEL

220 PLACCEL

220N PLACCEL

220CP PLACCEL L220AL

Hardness (JIS A) 82 84 81 78

Tensile Properties

100%M (MPa) 5.0 5.1 5.3 4.9

300%M (MPa) 11.0 10.5 10.8 9.7

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.

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Mechanical Properties of Casting Urethane Elastomers (2)

Polyol PLACCEL

220EB PLACCEL

220EC PTMG PBGA

Hardness (JIS A) 75 84 84 82

Tensile Properties

100%M (MPa) 4.5 5.7 6.0 5.2

300%M (MPa) 9.7 12.5 10.8 11.7

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.

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R O HC-(CH2)5

O

mf

-O

*Highly crystalline *Low melting point *Flexibility *Good biodegradability *Thermal degradation(>230oC)


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

PLACCEL H1P (High molecular weight polycaprolactone)

The above data are not specifications and may change without any notice. /30

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

Tg of Homopolymer (oC) -28 -40 -46 -51 -53

Product name FM1 FM2 FM3 FM4 FM5

Tg of Homopolymer (oC) -8 -28 -37 -43 -47

PLACCEL F series are macro monomers with a (meth)acrylic double bond.

RCH

2

O

O

CH2CH

2OH O

O

RCH

2

O

O

CH2CH

2O O H

n

(CH2)5

O

+ n

Hydroxymethyl(meth)acrylate epsilon-caprolactone

C

R=H, PLACCEL FA ; Acrylate darivativeR= CH

3, PLACCEL FM ; Methacrylate derivative

PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylate)

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*1:Diluted in Toluene (28~32%). Crystals can be precipitated. May be clouded in low temperature. *2:Calculated value.

Product Name FM1D FM2D FM3 FM5 FA1DDM FA2D FA10L*1

Acrylate Hydroxyethylmethacrylate (HEMA) Hydroxyethylacrylate (HEA)

Appearance [r.t.] Liquid Liquid Partially

crystalline Paste Liquid Liquid

Partially crystalline

Mol. Wt.*2(g/mol) 244 358 472 700 230 344 1,256

OH Value (KOHmg/g)

224.3 154.5 116.2 78.7 244*2 163*2 31*2

Acid Value (KOHmg/g)

3.41 2.44 1.95 1.36 3.48 2.50 0.67

Viscosity (mPa･s/25℃)

31 72 130 121

/40oC 32 78 48

Color (APHA) 25 20 45 40 10 15 35

PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylate)


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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.

PLACCEL HEMAC1 (Hydroxyl functioned carbonate methacrylate)

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.


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Copolymer with PLACCEL F Ordinary acryl polyol

• Toughness • Flexibility • Higher reactivity

• Hardness • Fragility

Cross linking reaction of PLACCEL F co-polymer resin

OH

OH

OH

OCN

OCN

NCO

N

H O

O

N

O H

O

N

HO

O

Crosslinked

Polyisocyanate

hardener

Polymer main chainSide chain

OH

OH

OHOCN

OCNNCO

N

O H

O

N

HO

ON

H O

O

Crosslinked

Polyisocyanate hardener

Polymer main chain

Polycaprolactone chain

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Isocyanate Cross linking of PLACCEL F co-polymer

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

NCO reactivity of PLACCEL FM copolymer is faster than HEMA.

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)

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

hardener：HMDI NCO/OH=1/1 Reaction Temperature： Room Temperature Measurement ： Tension testing machines

Examination Method

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

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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

Composition of UA PLACCEL 205U

/IPDI/HEA

PLACCEL 205U

/IPDI/FA2D

PLACCEL 210N

/IPDI/HEA

1,6HD-AD*1

/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.

Properties of Urethaneacrylates from “PLACCEL”

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Additionally, it accedes to a request and a lot of various pre-production

samples etc. are collected. Please consult readily, and inquire.

Application of PLACCEL

Grade TPU Leathers Adhesives Ink Shoe Soles

Foam Coating

Poly Capro lactone polyols (PCL)

200 (General grade)

+ + + + + ++ ++

200N (Narrow distribution)

++ + + + ++

200CPT (Hydrolysis resistant)

+ ++ + +

L200AL (Liquid grade)

+ + ++ + ++

200EB (Adipate grade)

++ ++

220EC (Carbonate co-polymer)

++ ++

300、400 (Polyfunctional grade)

+ ++ ++

FM,FA (Acryl monomer)

+ + ++

Poly Carbo nate

polyols (PCD)

CD200 (General grade)

+ + + + + +

CD200PL (Liquid grade)

+ ++ ++ +

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Organic Chemical Products Company · oNCO=10% 80 C*1.5hr B)PLACCEL + 1,4-BG 80oC 80oC Mixing About...

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Transcript of Organic Chemical Products Company · oNCO=10% 80 C*1.5hr B)PLACCEL + 1,4-BG 80oC 80oC Mixing About...