TWO COMPONENT POLYURETHANE COMPOSITION

Abstract

A two-component polyurethane composition including of a polyol component and a polyisocyanate component, wherein the polyol component includes at least one reaction product of castor oil with ketone resins A1, at least one aliphatic triol A2, preferably an aliphatic diol A3, a polybutadiene polyol A4 and at least one hydroxylated polyester polyol A5 based on tall oil. The polyurethane composition has high strength and only a minor dependence of mechanical properties, especially of strength, on temperature. Moreover, the composition is capable of curing without blistering under ambient conditions, even in the presence of substrates that typically promote foaming reactions owing to the presence of residual moisture, for example glass fiber weave.

Claims

1. A two-component polyurethane composition consisting of a polyol component K1 and a polyisocyanate component K2; wherein the polyol component K1 comprises at least one reaction product of castor oil with ketone resins having an OH number of 110 to 200 mg KOH/g A1; and at least one aliphatic triol having an average molecular weight of 170-500 g/mol and an OH number of 400-1100 mg KOH/g, which is polyether polyols based on 1,1,1-trimethylolpropane A2; and optionally at least one aliphatic diol having a molecular weight of 90-146 g/mol A3; and at least one polybutadiene polyol having an average OH functionality of 2.1 to 2.9, and having an average molecular weight in the range from 2000 to 4000 g/mol, and an OH number of 40-100 A4; and at least one hydroxylated polyester polyol A5 based on tall oil; and wherein the polyisocyanate component K2 comprises at least one aromatic polyisocyanate B1, where the ratio of the OH groups of (A1+A4+A5)/(A2+A3) is from 0.25-5; and where the ratio of all NCO groups of the aromatic polyisocyanates B1:all OH groups of the polyol component K1=0.95:1-1.25:1.

2. The two-component polyurethane composition as claimed in claim 1, wherein the at least one aliphatic diol A3 is selected from the list consisting of butane-1,4-diol, 2-ethylhexane-1,3-diol, 3-methylpentane-1,5-diol and pentane-1,5-diol.

3. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of all NCO groups of the aromatic polyisocyanates B1:all OH groups of the sum total of (A1+A2+A3+A4+A5)=0.95:1-1.25:1.

4. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of the OH groups of (A1+A4+A5)/(A2+A3) is 0.3-1.4.

5. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of the OH groups of (A1+A2+A4+A5)/(A3) is 0.4-5.

6. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of the OH groups of (A1+A5)/(A4) is 2-15.

7. The two-component polyurethane composition as claimed in claim 1, wherein the sum total of all OH groups of (A1+A2+A3+A4+A5) is 90%, of the sum total of all OH groups of the two-component polyurethane composition.

8. The two-component polyurethane composition as claimed in claim 1, wherein the aromatic polyisocyanate B1 is monomeric MDI or oligomers, polymers and derivatives derived from MDI.

9. The two-component polyurethane composition as claimed in claim 1, wherein the aromatic polyisocyanate B1 is oligomers, polymers and derivatives derived from MDI.

10. The two-component polyurethane composition as claimed in claim 1, wherein the aromatic polyisocyanate B1 is polymers derived from MDI.

11. The two-component polyurethane composition as claimed in claim 1, wherein the sum total of the NCO groups that do not originate from B1 is 5%, based on the sum total of all NCO groups of the two-component polyurethane composition.

12. A method of bonding a first substrate to a second substrate, comprising the steps of: mixing the polyol component (K1) and the polyisocyanate component (K2) of a two-component polyurethane composition as claimed in claim 1, applying the mixed polyurethane composition to at least one of the substrate surfaces to be bonded, joining the substrates to be bonded within the open time, curing the polyurethane composition.

13. A bonded article obtained from a method as claimed in claim 12.

14. A method comprising bonding two substrates together, using a two-component polyurethane composition as claimed in claim 1 as structural adhesive.

Description

EXAMPLES

Substances Used:

[0144]

TABLE-US-00002 Setathane 1150 Reaction product of castor oil with ketone resin, Setathane 1150, OH number of 155 mg KOH/g, OH equivalent weight of about 360 g/eq, Nuplex Resins GmbH, Germany Desmophen T Propoxylated 1,1,1-trimethylolpropane, Desmophen 4011 4011 T, OH number of 550 25 mg KOH/g, average molecular weight of about 300 20 g/mol, Covestro AG, Germany Polybd 45 Polybutadiene polyol having primary OH groups, OH HTLO functionality 2.4-2.6, average molecular weight about 2800 g/mol, OH number 47 mg KOH/g (Poly bd R- 45HTLO from Total Cray Valley, USA) REAGEM REAGEM 5006, OH number of 75 mg KOH/g, CAS 5006 number 92128-24-0, Granel S. A., France Zr catalyst Zirconium chelate complex, Zr content 3.5% by weight (K-Kat A-209 from King Industries Inc., USA) Sylosiv Zeolite (Sylosiv A3 from W. R. Grace & Co., USA) Desmodur VL Polymeric MDI, average NCO functionality of 2.5, Desmodur VL, Covestro AG, Germany Isonate M 143 Modified diphenylmethane diisocyanate containing MDI carbodiimide adducts, average NCO functionality of 2.2, NCO content 29.4% by weight, Isonate M 143 from Dow Desmodur Monomeric MDI, average NCO functionality of 2.0, 44MC Desmodur VL, Covestro AG, Germany

[0145] Production of Polyurethane Compositions

[0146] For each composition, the ingredients specified in tables 1 to 5 were processed in the specified amounts (in parts by weight) of the polyol component K1 by means of a vacuum dissolver with exclusion of moisture to give a homogeneous paste, and stored. The ingredients of the polyisocyanate component K2 specified in tables 1 to 5 were likewise processed and stored. Subsequently, the two components were processed by means of a SpeedMixer (DAC 150 FV, Hauschild) for 30 seconds to give a homogeneous paste and immediately tested as follows:

[0147] To determine the mechanical properties, the adhesive was converted to dumbbell form according to ISO 527, Part 2, 1B, and stored for 7 days under standard climatic conditions (23 C., 50% relative humidity) or stored under standard climatic conditions for 12-24 h and then cured for 3 h at 80 C. Thereafter, at room temperature, modulus of elasticity in the range from 0.05% to 0.2% elongation (Modulus of elasticity, Em 0.05-0.25%), modulus of elasticity in the range from 0.5% to 5% elongation (Modulus of elasticity, Em 0.5-5%), tensile strength (TS) and elongation at break (EB) of the test specimens thus produced were measured to ISO 527 on a Zwick Z020 tensile tester at a testing rate of 10 mm/min.

[0148] Glass transition temperature, abbreviated in the tables to T.sub.g, was determined from DMTA measurements on strip samples (height 2-3 mm, width 2-3 mm, length 8.5 mm) which were stored/cured at 23 C. for 12-24 h and then at 80 C. for 3 h, with a Mettler DMA/SDTA 861e instrument. The measurement conditions were: measurement in tensile mode, excitation frequency 10 Hz and heating rate 5 K/min. The samples were cooled down to 70 C. and heated to 200 C. with determination of the complex modulus of elasticity E* [MPa], and a maximum in the curve for the loss angle tan was read off as T.sub.g.

[0149] The results are reported in tables 1 to 5.

TABLE-US-00003 TABLE 1 OHN E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 Polyol comp. K1 Reagem 5006 75 30 30 30 30 30 30 30 30 30 30 30 30 30 (A5) Setathane 1150 155 34 32 44 42 31 30 29 28 28 27 26 25 24 (A1) Polybutadiene 45 48 30 30 20 20 30 30 30 30 28 27 26 25 24 HTLO (A4) Desmophen 550 4 4 4 4 4 4 4 4 4 4 4 4 4 T 4011 (A2) Butane-1,4-diol 1245 0 2 0 2 3 4 5 6 8 10 12 14 16 (A3) Catalyst 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.06 0.06 0.06 0.06 0.06 Sylosiv 2 2 2 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 100 100 100 100 Mixing ratio 27.9 33.4 30.6 36 36.2 38.8 41.6 44.2 50.4 56 61.8 67.4 73.2 NCO/OH ratio 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A4 + A5)/ 4.07 1.84 4.56 2.07 1.43 1.16 0.97 0.83 0.65 0.53 0.44 0.37 0.32 (A2 + A3) (A1 + A2 + 4.36 4.79 2.86 2.12 1.67 1.37 1.02 0.80 0.65 0.55 0.47 A4 + A5)/(A3) (A1 + A5)/(A4) 5.2 5.0 9.4 9.1 4.9 4.8 4.7 4.6 4.9 5.0 5.0 5.1 5.2 Gelation time 53 14 47 16 12 10 7 8 9 7 7 8 6 [min] 3 h at 80 C. TS [MPa] 9.7 12.4 12 13.7 10.6 12.7 13.9 13.2 14.1 14.7 12.9 12.1 11.8 EB [%] 119 76 85 68 94 92 91 81 71 60 43 32 21 Em0.05-0.25% 98 283 223 395 204 225 253 231 304 272 192 180 278 [MPa] Em 0.5-5% 58 174 133 240 91 115 129 130 162 151 105 99 155 [MPa] 1st Tg ( C.) 60 60 60 60 60 60 60 60 60 60 60 60 60 2nd Tg ( C.) 60 78 67 76 76 84 92 102 108 118 120 125 127 7 d RT TS [MPa] 13.6 13.6 14.1 11.8 10.4 10.7 EB [%] 92 70 61 43 31 22 Em0.05-0.25% 218 225 255 190 165 246 [MPa] Em 0.5-5% 114 130 145 112 102 133 [MPa]

TABLE-US-00004 TABLE 2 OHN E1 E14 E15 E16 E17 E18 E19 E20 E21 E22 E23 Polyol comp. K1 Reagem 5006 (A5) 75 30 30 30 30 30 30 30 30 30 30 30 Setathane 1150 (A1) 155 34 32 31 30 29 28 28 27 26 25 24 Polybutadiene 45 48 30 30 30 30 30 30 28 27 26 25 24 HTLO (A4) Desmophen T 4011 (A2) 550 4 4 4 4 4 4 4 4 4 4 4 Pentane-1,5-diol 1077 2 3 4 5 6 8 10 12 14 16 Catalyst 0.1 0.1 0.1 0.1 0.1 0.1 0.06 0.06 0.06 0.06 0.06 Sylosiv 2 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 100 100 Mixing ratio 27.9 32.6 34.8 37.2 39.4 41.8 47 51.8 56.8 61.6 66.4 NCO/OH ratio 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A4 + A5)/ 4.07 1.99 1.56 1.28 1.08 0.93 0.73 0.60 0.50 0.42 0.37 (A2 + A3) (A1 + A2 + A4 + 5.04 3.31 2.45 1.93 1.58 1.18 0.92 0.75 0.63 0.54 A5)/(A3) (A1 + A5)/(A4) 5.2 5.0 4.9 4.8 4.7 4.6 4.9 5.0 5.0 5.1 5.2 Gelation time [min] 53 17 15 11 7 8 8 7 6 6 6 3 h at 80 C. TS [MPa] 9.7 9.6 11 12.2 12.8 12.9 13.1 11.5 9.6 7.5 7.3 EB [%] 119 120 110 99 91 91 79 39 31 30 27 Em0.05-0.25% [MPa] 98 125 153 221 251 258 329 332 217 74 87 Em 0.5-5% [MPa] 58 48 81 106 123 127 161 183 121 47 54 1st Tg ( C.) 60 60 60 60 60 60 60 60 60 60 60 2nd Tg ( C.) 60 67 73 78 87 93 103 108 113 116 115 7 d RT TS [MPa] 11.9 13 10.7 7.3 6.4 7.2 EB [%] 92 70 20 20 29 25 Em0.05-0.25% [MPa] 262 358 354 197 51 118 Em 0.5-5% [MPa] 125 180 189 108 33 70

TABLE-US-00005 TABLE 3 OHN E24 E25 E26 E27 E28 E29 E30 E31 E32 E33 Polyol comp. K1 Reagem 5006 (A5) 75 30 30 30 30 30 30 30 30 30 30 Setathane 1150 (A1) 155 34 32 30 28 28 27 26 25 24 23 Polybutadiene 45 HTLO (A4) 48 30 30 30 30 28 27 26 25 24 23 Desmophen T 4011 (A2) 550 4 4 4 4 4 4 4 4 4 4 Butane-1,4-diol (A3) 1245 0 2 4 6 8 10 12 14 16 18 Catalyst 0.1 0.1 0.1 0.1 0.06 0.06 0.06 0.06 0.06 0.06 Sylosiv 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Isonate M143 100 100 100 100 100 100 100 100 100 100 Mixing ratio 33.4 36.3 42.3 48.2 54.7 60.9 67.2 73.4 79.6 85.2 NCO/OH ratio 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A4 + A5)/(A2 + A3) 4.07 1.84 1.16 0.83 0.65 0.53 0.44 0.37 0.32 0.28 (A1 + A2 + A4 + A5)/(A3) 4.36 2.12 1.37 1.02 0.80 0.65 0.55 0.47 0.41 (A1 + A5)/(A4) 5.2 5.0 4.8 4.6 4.9 5.0 5.0 5.1 5.2 5.3 Gelation time [min] 11 9 7 5 4 6 3 3 3 2 3 h at 80 C. TS [MPa] 10.9 9.2 11.5 13.7 17 18.2 19.5 21.3 23 22.2 EB [%] 128 108 86 80 89 88 79 71 69 34 Em0.05-0.25% [MPa] 163 236 306 425 536 497 574 641 738 745 Em 0.5-5% [MPa] 68 96 153 179 223 259 309 335 392 378 1st ( C.) 60 60 60 60 60 60 60 60 60 60 2nd Tg ( C.) 63 71 82 91 98 96 103 105 104 105 7 d RT TS [MPa] 9.8 8.6 10.5 12.8 15.4 15.6 16.3 18.2 20.4 18.7 EB [%] 123 116 103 105 111 77 45 25 28 4 Em0.05-0.25% [MPa] 110 162 294 372 432 514 597 668 761 751 Em 0.5-5% [MPa] 57 80 141 172 208 251 295 329 380 n.d.

TABLE-US-00006 TABLE 4 highly exothermic reaction OHN E34 E35 E36 E37 E38 E39 E40 E41 E42 E43 Polyol comp. K1 Reagem 5006 (A5) 75 30 30 30 30 30 30 30 30 30 30 Setathane 1150 (A1) 155 34 32 30 28 28 27 26 25 24 23 Polybutadiene 45 HTLO (A4) 48 30 30 30 30 28 27 26 25 24 23 Desmophen T 4011 (A2) 550 4 4 4 4 4 4 4 4 4 4 Butane-1,4-diol (A3) 1245 0 2 4 6 8 10 12 14 16 18 Catalyst 0.1 0.1 0.1 0.1 0.06 0.06 0.06 0.06 0.06 0 Sylosiv 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur 44MC 100 100 100 100 100 100 100 100 100 100 Mixing ratio 26.6 31.8 37 42.2 47.9 53.3 58.8 64.2 69.7 75.1 NCO/OH ratio 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A4 + A5)/(A2 + A3) 4.07 1.84 1.16 0.83 0.65 0.53 0.44 0.37 0.32 0.28 (A1 + A2 + A4 + A5)/(A3) 4.36 2.12 1.37 1.02 0.80 0.65 0.55 0.47 0.41 (A1 + A5)/(A4) 5.2 5.0 4.8 4.6 4.9 5.0 5.0 5.1 5.2 5.3 Gelation time [min] 16 8 7 5 4 4 3 3 2* 4 3 h at 80 C. TS [MPa] 7.6 8.6 9.8 10.9 13.2 12 12.9 12.6 8.8 7.1 EB [%] 162 120 116 103 90 57 36 12.1 5 6.8 Em0.05-0.25% [MPa] 41 145 155 242 297 321 384 450 365 322 Em 0.5-5% [MPa] 13.7 73 76 106 141 148 177 201 164 119 7 d RT TS [MPa] 7.9 8.6 10.3 10.4 12.4 11 13 12.3 9.2 7.8 EB [%] 158 134 136 107 101 53 38 8 4 4 Em0.05-0.25% [MPa] 57 137 156 239 289 322 426 461 422 382 Em 0.5-5% [MPa] 15 66 74 95 135 142 191 211 n.d. 160 1st Tg ( C.) 60 60 60 60 60 60 60 60 60 60 2nd Tg ( C.) 55 65 66 68 72 74 76 78 82 78

TABLE-US-00007 TABLE 5 OHN R1 R2 R3 R4 R5 R6 Polyol Comp. K1 Reagem 5006 (A5) 75 0 98 94 64 30 30 Setathane 1150 (A1) 155 64 0 0 0 64 62 Polybutadiene 45 HTLO (A4) 48 32 0 0 30 0 0 Desmophen T 4011 (A2) 550 4 0 4 4 4 4 Butane-1,4-diol (A3) 1245 0 0 0 0 0 2 Catalyst 0.3 0.1 0.1 0.1 0.1 0.1 Sylosiv 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 Mixing ratio 34.4 18 22.7 21.1 35.9 41.4 NCO/OH-ratio 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A4 + A5)/(A2 + A3) 5.21 3.20 2.84 5.53 2.53 (A1 + A2 + A4 + A5)/(A3) 5.65 (A1 + A5)/(A4) 6.5 3.3 Gelation time [min] 30 49 52 21 43 26 3 h at 80 C. TS [MPa] 9.5 3.8 6 4.6 12.6 12.3 EB [%] 122.3 67 57 86 96 55 Em0.05-0.25% [MPa] 32 20 65 16 139 352 Em 0.5-5% [MPa] 7 13 40 11 74 192 1st Tg ( C.) 60 38 38 53 2nd Tg ( C.) 52 50 62 53 57 67 7 d RT TS [MPa] 7.76 EB [%] 101.1 Em0.05-0.25% [MPa] 15.4 Em 0.5-5% [MPa] 5

[0150] Tables 1 to 5 specify the components of the polyol comp. K1, or of the polyisocyanate comp. K2, in parts by weight.

[0151] The figures (A1+A4+A5)/(A2+A3) and (A1+A2+A4+A5)/(A3) and also (A1+A5)/(A4) in tables 1 to 5 relate to the ratio of the OH groups of A1 Setathane 1150, A2 Desmophen T 4011, A3 aliphatic diol, A4 Polyvest HT and A5 Reagem 5006, respectively.

[0152] The term NCO/OH ratio indicates the ratio of all NCO groups of the aromatic polyisocyanates B1 to all OH groups of the sum total of (A1+A2+A3+A4+A5).

[0153] The term Mixing ratio indicates the proportion of component K2 in parts by weight that has been added to 100 parts by weight of the appropriate component K1.

[0154] The term OHN represents the hydroxyl number (OH number) of the polyols used.

[0155] Gelation time [min] as a measure of open time was determined the tack-free time. For this purpose, a few grams of the adhesive were applied to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, the time until, when the surface of the adhesive was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette was determined.

[0156] E1 to E43 are inventive examples. R1 to R6 are comparative examples.