Functional Acrylic Monomer PLACCEL F-Series

Transcription

1 Functional Acrylic Monomer PLACCEL F-Series Organic Chemical Products Company

2 PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylates) O O C H 2 R O CH 2 CH 2 O C (CH 2 ) 5 O H n R=H PLACCEL FA ; Acrylate derivatives R=CH 3 PLACCEL FM ; Methacrylate derivatives Table. Relation of between Tg and adding caprolacton mol number Adding mol number (n) Product name FA1 FA2 FA3 FA4 FA5 Tg of Homopolymer ( o C) Product name FM1 FM2 FM3 FM4 FM5 Tg of Homopolymer ( o C)

3 PLACCEL F series (epsilon-caprolactone-modified hydroxyalkyl(meth)acrylates) Table. Typical properties of PLACCEL F series Product Name FM1D FM2D FM3 FM5 FA1DDM FA2D FA10L 1 Acrylate hydroxyethylmethacrylate (HEMA) hydroxyethylacrylate (HEA) Apearance Liquid Liquid Partially Partially Paste Liquid Liquid crystalline crystalline Mol. Wt ,256 Value (Kmg/g) 220~ ~ ~120 74~ ー Acid Value (Kmg/g) < 3.0 Viscosity 120~140 20~40 65~85 120~145 (mpa s/25 ) (40 o C) 35 70~90 44~55 Color (APHA) Stabilizer (ppm) :Diluted in Toluene (28~32%). Crystals can be precipitated. May be clouded in low temperature. 2:Calculated value.

4 Cross linking reaction of PLACCEL F copolymer resin Copolymer with PLACCEL F Polymer main chain Polycaprolactone chain Ordinary acryl polyol Polymer main chain Crosslinked NCO HO NCO HO Polyisocyanate hardener Side chain NCO HO Polyisocyanate hardener HO NCO Strong Tough Flexible Higher reactivity Hard Fragile

5 The reaction transition is traced by measuring of NCO-Value. Isocyanate Cross linking of PLACCEL F copolymer NCO reactivity of PCL FM copolymer is faster than HEMA. Residual NCO consentration/% NCO reactivity comparison of PCL-FM and HEMA in urethane-acrylates synthesizing PCL-FM as comonomer HEMA as comonomer Reaction time/days

6 Toughness of PCL-F co-polymerized urethane-acrylate coating film Toughness of films measured by tension tester. Urethane-acrylate coatings of PCL- FM delivered copolymers are excellence at elongation after yielding. Strength(Kgf/cm2) SS curve of cured film PCL-308 blend polymer PCL-F Copolymer HEMA Copolymer Elongation(%)

7 Properties of Urethane-acrylates from PLACCEL In the following points, Urethane-acrylates(UAs) made from PLACCEL have the characteristic superior to HEA, non-cl polyesterpolyol. Low-viscosity Low-temperature storage stability (PCL 200 vs 16HD-AD polyester) High-reactivity at UV irradiation (PCL FA vs HEA) Ex. No. Ex1 Ex2 Ex3 Ex4 Composition of UA PCL 205U /IPDI/HEA PCL 205U /IPDI/FA2D PCL 210N /IPDI/HEA 16HD-AD* 1 /IPDI/HEA Molecular weight(calculated value) 1,200 1,700 1,700 1,700 Viscosity(mPa s, 75 o C) 6,200 1,900 3,300 4,900 Appearance(r.t.)* 2 clear clear clear cloudy Appearance(-5 o C)* 2 clear clear clear Crystallization *1 16HD-AD:Polyesterdiol consisted by 1,6-Hexanediol and Adipic-acid. (calculated Mn:1,000) *2 Samples were diluted with ethyl acetate to 50wt%, and after keeping it for two weeks in room temperature or a -5 o C refrigerator, appearance was checked visually.

8 UV reactivity The reaction transition is traced by measuring of acrylic-derived peak by a certain amount of UV irradiation using FT-IR. (catalyst-free system) Acrylate reactivity of PCL FA2D is faster than HEA in the IPDI urethane acrylate system. 100 Correlation between the UV irradiation quantity and Reactivity Experimental method Reactivity (%) FA2D HEA Mol Ratio: IPDI / PCL205U / FA2D or HEA = 2 / 1 / 2 Catalyst:DBTDL Additive:MEHQ UV irradiation quantity (mj/cm2)

9 Viscosity of UA from PLACCEL By including PLACCEL in composition, viscosity decreases and handling becomes easy. 7,000 Relation between NCO Contents and viscosity of UAs Viscosity of UAs (mpa s, 75 o C) 6,000 5,000 4,000 3,000 2,000 :HEA terminated UAs :FA2D terminated UAs :FA5 terminated UAs HEA/16HD-AD/IPDI Calc.Mn:1,700 HEA/210N/IPDI Calc.Mn:1,700 FA2D/205U/IPDI Calc.Mn:1,700 HEA/205U/IPDI Calc.Mn:1,200 1,000 FA5/IPDI Calc.Mn:1,600 FA2D/IPDI Calc.Mn: % 20% 30% 40% NCO contents(wt%)

10 Mechanical properties of UA from PLACCEL Mechanical properties of hardened UA including PLACCEL are as follows. Low modulus (flexible) Equivalent elongation to HEA terminated UAs Good compression repairability Ex. No. Ex1 Ex2 Ex3 Ex4 Composition of UA PCL 205U /IPDI/HEA PCL 205U /IPDI/FA2D PCL 210N /IPDI/HEA 16HD-AD /IPDI/HEA Elongation at Break(%)* Modulus(MPa)* Hardness(N/mm 2 )* Modulus (N/mm 2 )* Compression repairability* 3 (%) *1:As sheet(about 1mm thickness), measured by Tension tester. *2:As coated films on ABS plates(about 20μm thickness), measured by Nanoindentation. ( ENT 1100a made by ELIONICS Corp.) *3:The degree of restoration / displacement at maximum load ratio, measured by Nanoindentation. ( ENT 1100a made by ELIONICS Corp.)

11 Mechanical properties of UA from PLACCEL UAs containing PLACCEL shows pliability and good stability at measuring Nanoindentation 1.press Load (mn) Correlation of load and displacement 2.unloading 1.press Ex1 Ex2 Ex3 Ex Displacement (nm) stress 2.unloading UAs base(abs) UAs base(abs)

12 Self-repairable UA materials from PLACCEL F Using isocyanurate and PLACCEL F, self-repairable UA materials is obtained.the properties of UAs and their hardened is as follows. Ex. No. Ex5 Ex6 Ex7 Ex8 Formulation UAs - structure HEA/ D-170N *1 4HBA/ D-170N *1 FA2D/ D-170N *1 FA2D/ D-170N *1 Crosslinker PETIA * mol% 60mol% Properties of hardened UAs Tg o C Pencil hardness *3-3H 3H F 3H Elongation at break * 4 % *5 * Modulus* 4 MPa *5 * Compression repairability* 6 % *1: HDI-nulate, Takenate D-170N by Mitsui Chemicals, Inc. *2: Pentaerythritol triacrylate *3: Based on JIS K *4: As sheet(about 1mm thickness), measured by Tension tester. *5: Brittle, test pieces weren t obtained. *6: The degree of restoration / displacement at maximum load ratio, measured by Nanoindentation. ( ENT 1100a made by ELIONICS Corp.)

13 Self-repairable UA materials from PLACCEL F The self- repairability of UAs are estimated by the brass brush scraping method. FA2D-derived UAs with HDI-nulate are support hardness and selfrepairability at the same time by adding PETIA. 110% Gross repairing trend of injured UA films Restoration of scratches Ex5 After 60 2hr 100% 20 Gross repairability /% 90% 80% 70% 60% 50% 40% Ex5 Ex6 Ex7 Ex8 blank immediate 1hr 3hr 60 2hr Ex6 Ex8 After 60 2hr After 60 2hr Immediately after scratch, Ex8 is maintaining higher gloss than the other hard examples(ex5, Ex6). It is guessed that a broad Tg domain is produced by including FA2D, so the hardened UA coat has the soft domain that is repairable at room temperature.