750 likes | 2.12k Views
PRIPOL dimerised fatty acids. Large hydrocarbon part (C36) hydrophobic hydrolytic resistance of derivatives affinity for non-polar matrices and surfaces. Irregular non-crystalline structure flexibility low Tg flow, wetting. Di-functional constituent for: polyamides polyesters
E N D
PRIPOL dimerised fatty acids • Large hydrocarbon part (C36) • hydrophobic • hydrolytic resistance of derivatives • affinity for non-polar matrices and surfaces • Irregular non-crystalline structure • flexibility • low Tg • flow, wetting • Di-functional constituent for: • polyamides • polyesters • polyurethanes
Different forms of PRIPOL dimer technology PRIPOL dimer acid PRIPOL dimer diol PRIPLAST polyesters made with PRIPOL dimer acid or dimer diol HO---- E-E ----- OH
A unique performance effect • PRIPOL and PRIPLAST technology provide • a unique combination of resistance against : • Moisture • Chemicals • Heat • Oxidation • Radiation
Supportive data Polyurethane samples were prepared from a range of Priplast polyols and competitive technologies (hexane diol adipate, polycaprolacton, hexane diol carbonate, PTMEG, PPG, and polybutadiene diol) All polyols used had molecular weight of 2000, except Priplast 3196, which is 3000 All recipes were identical in molecular ratio: one part polyol, 2 parts of butane diol, 3.1 parts of pure MDI All polyurethanes were made via the prepolymer route: first a prepolymer of polyol and MDI, followed by chain extension with butane diol
Moisture uptake of PRIPLAST dimerate and other polyurethanes Moisture uptake at 23 C, % Recipe : 1 Polyol 2 Butanediol 3.1 MDI Conditions : 1 week in H2O dist.
Hydrolysis of PU from PRIPLAST dimerate and other polyols Retention of tensile strength, % Recipe : 1 Polyol 2 Butanediol 3.1 MDI Conditions : 1 week in H2O (dist.) at 90 C
Effect of UV-radiation on PU from PRIPLAST dimerate and other polyols Retention of tensile strength, % Recipe : 1 Polyol 2 Butanediol 3.1 MDI Conditions : 2 weeks exposure to UV-B
Effect of oxidation on PU from PRIPLAST dimerate and other polyols Retention of tensile strength / elongation, % Recipe : 1 Polyol 2 Butanediol 3.1 MDI Conditions : Exposure to 140 C for 4 weeks
PRIPLAST versus other diols : stability of TPU Retention of tensile strength, % Recipe : 1 Polyol 2 Butanediol 3.1 MDI Exposure for 2 weeks
Weather resistance Retention of tensile strength, %
Hydrolytic stability of PU in boiling water Retention of tensile strength, %
Mechanical properties of PU from PRIPLAST dimerate and other polyols crystalline adipate Recipe: 1 polyol 2 BDO 3.1 MDI PTMEG strain hardening Priplast 3192 HDO dimerate/adipate Stress Priplast 1838 HDO dimerate no strain hardening Poly BD/rubber Strain
Effect of polyol on modulus and tensile strength Recipe 1 Polyol 2 BDO 3.1 MDI
Elongation of PU made with PRIPLAST dimerate and other polyols Elongation at break, % Recipe : 1 Polyol 2 BDO 3.1 MDI differences only for different MW (3196 is mw 3000, all others 2000) and functuionality (poly-BD)
Shore-A hardness of PU made with PRIPLAST dimerate and other polyols Shore A Recipe : 1 Polyol 2 BDO 3.1 MDI
T(g) of PU made with PRIPLAST dimerate and other polyols Glasstransition temp., °C Recipe : 1 Polyol 2 BDO 3.1 MDI P1838 (*) = 1-1-2.1
PRIPLAST polyols for elastomers A unique combination of thermo-oxidative and hydrolysis resistance Low-temperature flexibility and flex fatigue resistance Low-modulus and soft-touch applications
Elastomers by one-shot processing of PRIPLAST polyols - Priplast polyols do not mix well with many other polyols (especially adipates), chain extenders and isocyanates - one-shot processing without precautions may cause difficulty: very brittle product, or very sticky product - good one-shot processing is possible by making a blend of PRIPLAST polyol and chain extender (like butane diol), and convert this blend in a one-shot process - if for some reason (cost, performance) it is considered to blend PRIPLAST polyol with other polyester polyols, we recommend to NOT make a physical blend, but instead work with one single PRIPLAST polyol made with a mixture of acids
Blending polyols - very careful when mixing partially crystalline polyols disturbance of crystallinity kills hydrolytic stability, green strength and tensile strength. Acceptable combinations: 3192 with hexane diol adipate, 3195 with butane diol adipate - only recommended for the propolymers, for reasons of limited compatibility
PRIPLAST polyols for coatings - for exceptional weatherability and protection (anticorrosive applications) - for exceptional flexibility, flex fatigue resistance - for adhesion to low-energy substrates like plastics - for 2K, moisture cure and aqueous dispersion type
PRIPLAST technology for polyurethane coatings: benefits hydrocarbon character, strength (preservation of hydrogen bonds) hydrophobicity durability (hydrolytic resistance) substrate protection (moisture barrier) adhesion to low energy substrates non-crystallinity, strength (flow, substrate wetting) low glass transition long open time durability (low-temperature flexibility, stress absorption)
PRIPLAST technology for PU coatings: conditions No NMP or other cosolvents solids content at least 35% particle size max. 500 nm aliphatic diisocyanates for colour stability reasons
PRIPLAST technology in aqueous polyurethane dispersions recipe: 44g Priplast 3195, 6.0g DMPA at 130C/10 mbar for 30 minutes break vacuum with N2, cool to 110C, add 38.9g IPDI in 10 minutes, react for 1 hour cool to 60C and add 35g acetone, stir until a clear solution is obtained cool to 50C, add 6g BDO** and 25g acetone slowly, then another 10g of acetone react to NCO-number 1.8 (20 hours without catalyst, about 8 hours with catalyst) add 140g acetone add mix of 3.1g IPDA+0.3g NH4OH (25%)+20g water, react for 5 hours add 1.8g NH4OH (25%), stir for half an hour add 100g water while intensively stirring, until phase inversion (CRITICAL step) add 50g of water, then remove acetone at 50C under gradually increased vacuum (down to 450 mbar, to prevent foaming) ** to increase crosslinking: use 5.5g BDO with 0.5g TMP
Formulations Priplast 3195 (2000 MW) Priplast 3195, with TMP crosslinker hexane diol/neopentylglycol (1/1 molar basis) adipate, 1700 MW (Fomrez ER 191) hexane diol/neopentylglycol (1/1 molar basis) adipate/dimerate (1/1 weight basis), 1700 MW Reference: Commercially available benchmark (aliphatic polyester polyol, 4% NMP, 40% solids, sold at about Euro 7/kg dispersion)
PRIPLAST technology in aqueous polyurethane dispersions - resulting white dispersions have 40% solids and 100-200 nm particles, and give clear transparent film - film blocking of Priplast-based materials exceeds that of commercial PU dispersions - freeze thaw stability: >1 month at -5/+40C
Properties of coatingsbased on PRIPLAST and other polyols Polyol % water uptake adhesion cross cut 24h/23° 24h/50° alufoil steel acryl PVC ABS PRIPLAST 3195 2 8 0 0 0 0 0 slight haze PRIPLAST 3195/TMP 3 7 0 0 0 0 0 slight haze HDO/NPG adipate 9 14 0 0 5 0 0 white HDO/NPG 3 8 0 0 5 0 0 adipate/dimerate slight haze Commercial PUD 8 15 4 0 0 1 1 white
Chemical resistance of coatingsbased on PRIPLAST and other polyols Polyol ethanol butter desin- coffee water ethyl aceton (50%) fectant acetate 1 h 24h 10 min 24h 16 h 10 sec 10 sec PRIPLAST 3195 1 0 1 0 0 5 5 PRIPLAST 3195/TMP 3 0 1 0 0 4 5 HDO/NPG adipate 0-1 0 1 0 0 5 5 HDO/NPG/AA/C36 0-1 0 1 0 0 5 5 Commercial PUD 5 1 5 2 5 4 4
Properties of coatingsbased on PRIPLAST and other polyols Polyol Elongation Hardness Impact Gloss (%) König pencil (cm.kg) (20°) (60°) (85°) PRIPLAST 3195 290 108 4B > 200 135 137 113 PRIPLAST 3195 with 3% TMP 300 114 B > 200 166 141 118 HDO/NPG adipate 170 101 HB > 200 152 125 113 HDO/NPG adipate/ dimerate 180 101 F > 200 149 135 111 Commercial PUD 273 120 B > 200 158 138 114 Gloss measured in gloss units
Stability of PU dispersions based on PRIPLAST polyols kept at 50C
Benefits of PRIPLAST technology for PU dispersion coatings outstanding dispersion stability outstanding weatherability and low moisture absorption outstanding chemicals resistance good flexibility, hardness and gloss readily manufacturable
PRIPLAST polyols for adhesives For hot melts, reactive hot melts, polyurethane dispersions for thermo-oxidative and hydrolytic resistance for flexibility, also at low temperatures for adhesion to low-energy substrates for universal adhesion on a variety of substrates
Polyol effect of adhesion to steel final strength of moisture cured adhesive PRIPLAST products
Polyol effect on adhesion to plastic final strength of moisture cured adhesive Untreated polyethylene 2.5 MDI/1 polyol PRIPLAST products
Advice on PRIPLAST polyols for adhesives Specially recommended for applications with long open time. Green strength is typically low because of non-crystalline character, but specialist advice is available to overcome this moisture curing is slower because of hydrophobicity
PRIPLAST 3191 in water repellent, flexible PU sealant foam • Low water absorption, hence good water sealing properties • Good hydrolytic resistance and compression set over conventional polyester foams, hence improved life cycle • Low fogging • Low air permeability, hence improved sealing properties
Compression set of PU foam from PRIPLAST dimerate vs. other polyols Compression set after hydrolysis, %
Acrylic plates PU foam sealant (dyecut, 50% compressed) Water Water seal test 100 mm Water seal properties Leaking of water after : - PU from Priplast 3191 : > 24 hrs - Conventional PU : < 10 min
Acrylic plates, clamped PU foam sealant (dyecut, 50% compressed) Water Water absorption test Water absorption properties - PU from Priplast 3191 : < 1% V/V - Conventional PU : 20 % V/V 24 hrs. immersion in water
Physical properties Characteristic Priplast 3191 Conventional polyester polyester foam foam (low fogging grade) Density, kg/m3 50 50 Water absorption (ASTM D 994) < 1% > 20% Water seal properties > 24 hrs < 10 min. Air permeability, litre / min < 15 50 Non fogging properties : - Reflectrometric method 96.6 % 85.1 % (3 hrs / 100 °C) - Gravimetric method 0.70 mg 0.95 mg (16 hrs / 100 °C)
Application of PRIPLAST 3191 based foams • Automotive industry, sealants for : • Airconditioning systems • Windows • Head and tail lamps • Mirrors • Door locks • Sun roofs • General industry, sealants for : • Airconditioning and ventilation • Roof windows • Refrigerators
Starting formulation (a) : Tegostab B-8002, ex. Th. Goldschmidt (b) : Dispersant ex. Uniqema (c) : Tertiary amine catalyst ex. Osi Specialities
Choosing the PRIPLAST polyol that is required 2 categories: partially crystalline products: 3192, 3195 amorphous products: 3190, 3196, 3197, 3198, 1838, 1839 partially crystalline: crystallinity gives additional tensile strength (esp. 3192) crystallinity gives green strength in adhesives crystallinity is good for hydrolytic stability crystallinity comes with lower ingredient cost (because of adipic) amorphous: for adhesion to non-polar substrates and compatibilizing with non-polar matrices for low glass transition temperatures (pressure sensitive adhesives, very flexible coatings)
PRIPOL 2033 , dimerdiol Specifications : • acid value max. 0.20 mg KOH/g • saponification value max. 2.0 mg KOH/g • hydroxyl value 202 - 212 mg KOH/g • colour APHA max. 50 Hazen • moisture max. 0.10 % • monomer alcohol max. 2.0 % • dimer alcohol min. 96.5 % • trimer alcohol max. 1.5 % • viscosity typically 2500 mPa.s at 25 °C MW = approx. 540
PRIPLAST polyester polyols:portfolio 3192 semi-crystalline best hydrolytic stability (like polycarbonate diol), MW 2000 best tensile strength (similar to PTMEG), best green strength. for coatings, elastomers, adhesives 3195 semi-crystalline, cheaper alternative to 3192 (slightly less for MW 2000 hydrolytic stability, green strength, tensile strength) 3190 amorphous, MW 2000 adhesives and coatings for low-energy substrates applications that require a very low Tg (-20C and lower) users that require a low-viscosity liquid 3196 amorphous, MW 3000 compatibilizing, pressure sensitive adhesives 3197 amorphous compatibilizing 3198 amorphous, MW 1300 coloured, for adhesives, primer coatings 1838 amorphous, MW 2000 pressure sensitive adhesives, compatibilizing 1839 amorphous, MW 2000 coloured cost-effective alternative to 1838 3191 amorphous, MW 1700 water-repellant foam
PRIPLAST polyester polyols:specifications PRIPLAST acid value OH-value Colour Moisture mg KOH/g mg KOH/g Gardner % 3192 max. 0.5 52-60 max. 2 max. 0.1 3195 max. 1.0 52-60 max. 2 max. 0.10 3190 max. 1.0 52-60 max. 2 max. 0.08 3196 max. 0.5 34-40 max. 2 max. 0.1 3197 max. 0.5 52-60 max. 2 max. 0.08 3198 max. 1 78-88 max. 6 max. 0.01 1838 max. 1.0 52-60 max. 2 max. 0.08 1839 max. 1.0 52-60 max. 6 max. 0.08 3191 0.7-1.5 68-73 - max. 0.07