EVALUATION OF SUSTERRA®-BASED … CPI Susterra...of 3000 MW were prepared at Troy Polymers, Inc....

198 Blair Bend Drive, Loudon, TN 37774

duponttateandlyle.com

EVALUATION OF SUSTERRA®-BASED PROPANEDIOL POLYESTER POLYOLS IN HOT-MELT ADHESIVES

DuPont Tate & Lyle Bio Products 198 Blair Bend Drive

Loudon, TN 37774

July 2015

Hot-Melt Adhesives DuPont Tate & Lyle Bio Products

SUMMARY OF RESULTS:

Novel polyester polyols based on 1,3-PDO (bio-based) were evaluated in hot melt adhesive application, which included PDO succinate polyester polyols of 2000 MW and 3000 MW and PDO adipate polyester polyols of 2000 and 3000 MW. Novel polyol BD succinate 2000 MW and conventional polyol BD adipate 3000 MW were used as a reference polyols in this study. PDO succinate polyester polyol of 2000 MW and 3000 MW and PDO adipate polyester polyols of 3000 MW were prepared at Troy Polymers, Inc. Reference polyols BD succinate 2000 MW and BD adipate 3000 MW were also prepared at Troy Polymers. PDO succinate of 2000 MW and 3000 MW exhibited glass transition temperature (Tg) at -37°C and -35°C, respectively and did not exhibit crystalline transitions based on DSC-spectra (Table 3). Other polyester polyols in this study exhibited crystalline transitions. The NCO-prepolymers based on 4,4’-MDI and polyester polyols at 2/1 isocyanate to polyol equivalent ratio were prepared (Table 4). The NCO-prepolymers based on PDO succinate of 2000 MW and 3000 MW and PDO adipate polyester polyols of 2000 and 3000 MW were not crystalline, based on DSC analysis. The prepolymer based on BD adipate 3000 MW was crystalline type. The NCO-prepolymer based on BD succinate 2000 was not possible to prepare due to polyol high melting temperature. The NCO-prepolymer based on an equimolar blend of BD succinate 2000 and PDO succinate of 3000 MW was easy to prepare. This prepolymer was crystalline type. Two NCO-prepolymers based on a blend BD succinate 2000 and PDO adipate 3000 were also crystalline type. The curing of NCO-prepolymers with moisture at room temperature was monitored via FTIR. The results indicate that curing of NCO-prepolymer with and without added catalyst was completed in most cases in three days of curing. The adhesives based on crystalline NCO-prepolymers exhibited very good green strength (30 minutes after application) as well as good adhesive strength after 7 days of curing (Table 6).




Hot melt adhesives based on a blend of BD succinate 2000 and PDO succinate 3000 polyols and a blend of BD succinate 2000 and PDO adipate 3000 exhibited very good retention of adhesion properties after humid aging, better than referent adhesive based on BD adipate 3000 polyol (Table 6). In many cases hot melt adhesives are prepared with two types of polyester polyols. One polyol is crystalline polyol and other is non-crystalline liquid polyol that provides wetting of adhesive to the substrate. This is possible way to include non-crystalline 1,3-PDO based polyester polyols into hot melt adhesives formulation. The adhesive based on non-crystalline NCO-prepolymers did not exhibit green strength, as could be expected. The adhesives gained adhesive properties after moisture curing for 3 and 7 days (Table 6). As such, these type of adhesives are suitable for one-component moisture cured adhesives that have variety of applications. OBJECTIVES: The objective of this study is to determine performance of novel PDO succinate polyester polyols and PDO adipate polyester polyols in reactive hot melt adhesives. PDO succinate polyester polyol of 2000 MW and 3000 MW and PDO adipate polyester polyols of 2000 and 3000 MW were evaluated in hot melt adhesive application. Novel polyol BD succinate 2000 MW and commercial polyol BD adipate 3000 MW were used as a reference polyols in reactive hot melt adhesive study. EXPERIMENTAL RESULS: Chemicals Raw materials used in this study are shown in Table 1. Prior to preparation of NCO-prepolymers, polyols were dried for 24 hours at 75 - 80°C under vacuum of 1-3 mm Hg and continuous mixing by magnetic stirrer. The water content after drying was checked by Karl Fisher Titrator. Diphenylmethane diisocyanate (4,4’-MDI) was used as received from the supplier and its isocyanate content was checked by di-n-butylamine titration method (ASTM D-5155). All other chemicals were used as received from the suppliers. Preparation of polyester polyols




The synthesis of polyester polyols of 2000 MW and 3000 MW was carried out using 2-L reaction kettle equipped with a mixer which was assembled of metal rod and paddle. The rate of mixing was kept at ~300 rpm and was checked periodically with Tachometer (5URHO, Grainger). The reactor was equipped with Dean Stark attachment, heating mantle, thermo-couple and temperature controller. The reaction was carried under constant flow of nitrogen at 30 ml/min which was regulated with Rotameter (Ace Glass). The synthesis of polyols was carried out in a temperature range of 120°-180°C. The reaction was carried out at atmospheric pressure in the presence of nitrogen. Preparation of NCO-prepolymers The formulations of NCO-prepolymers and processing conditions are shown in Tables 4. The NCO-prepolymers were prepared utilizing laboratory procedure for the prepolymer preparation, as follows: MDI melted at 44°C, was placed in the heated reaction kettle, which was equipped with a stirrer, thermometer and continuous flow of nitrogen (Figure 2). The isocyanate was heated up to 50°C (or 70°C) and preheated polyol was added slowly to isocyanate under mixing (Table 4). The reaction temperature was adjusted to 70°C (or 110°C) and kept at that temperature during the prepolymer synthesis (Table 4). The NCO% of the prepolymers was checked periodically during the synthesis. Once, when the NCO % reached value close to theoretical, the prepolymer was transferred into glass jars and sealed under dry nitrogen. Curing study 0.15g of preheated NCO- prepolymer was spread over ½ x 1 inch bond area of standardized adhesion test plate (dimensions 1 x 4 x 0.063 inches, AR-14, Q-Lab ). The plate with adhesive was then placed in humid chamber at 23°C and 68% relative humidity. FTIR spectra of the adhesive were taken periodically. Adhesion testing Hot-melt adhesives based on crystalline NCO-prepolymers The NCO-prepolymer was preheated at 120°C in a metal container suited for Speed mixer, additives (adhesion promotor, catalyst and Ortogel 501) were added to the prepolymer and mixed via Speed Mixer for 60 seconds at 2200 rpm. The NCO-prepolymer that contains all additives, conditioned at 120°C, was applied to the substrate which was preheated for short time at 105°C. 0.15g of the prepolymer was spread over ½ x 1 inch bond area (etched surface) of each standardized adhesion test plate (dimensions 1 x 4 x 0.063 inches, aluminum, AR-14, Q-Lab). Two plates were clamped together over bond area and cured at room temperature (Figure 3). The adhesion testing was carried out after 30 minutes,




after 3 days and 7 days of curing. The curing was carried out at 23°C and 68% relative humidity (Figure 4). Moisture-cured adhesives based on non-crystalline NCO-prepolymers The NCO-prepolymer was preheated at 70°C in a plastic container suited for Speed mixer, additives (adhesion promotor, catalyst and Ortogal 501) were added to the prepolymer and mixed via Speed Mixer for 60 seconds at 2200rpm. The NCO-prepolymer that contained all additives, conditioned at 70°C, was applied to the substrate which was kept at room temperature. 0.15g of the prepolymer was spread over ½ x 1 inch bond area (etched surface) of each standardized adhesion test plate (dimensions 1 x 4 x 0.063 inches, aluminum, AR-14, Q-Lab). Two plates were clamped together over bond area and cured at room temperature. The adhesion testing was carried out after 30 minutes, after 3 and 7 days of curing. The curing was carried out at 23°C and 68% relative humidity. RESULTS AND DISCUSSION

a. Polyols The polyols used in this study, their composition and properties are presented in Tables 1 and 3. Based on DSC analysis, PDO Succinate polyols of 2000 MW (PDO-SA-2000) and 3000 MW (PDO-SA-3000) are amorphous polyols (Figures 6a and 6d). These polyols did not exhibit crystalline transition in DSC spectra. Their glass transition temperature was at -37°C and -35°C, respectively. Crystalline polyols (with melting point in parenthesis) used in this study are: BD succinate 2000 (112°C), PDO Adipate 2000 (31.8°C) and PDO Adipate 3000 (33.6°C) (DSC graphs, Figures 6c, 6b and 6e, respectively).

b. NCO-prepolymers The adhesives in this study were based on NCO-prepolymers and cured with moisture. The NCO-prepolymers were prepared using conventional laboratory procedure for preparation of NCO-prepolymers (Figure 2). The formulations of NCO-prepolymers, reaction conditions in their synthesis and properties of final product are presented in Table 4. It was not possible to prepare NCO-prepolymer based on BD Succinate 2000 (BD-SA-2000) polyol due to high melting temperature (112°C) of this polyol. The NCO-prepolymers based on PDO-SA-2000 and PDO-SA-3000 were amorphous due to non-crystalline nature of the polyols (Table 4, Figure 7a




and Figure 7d). The NCO-prepolymers based on crystalline polyols PDO-AA-2000 and PDO-AA-2000, were not crystalline either (Table 4, Figure 7b and Figure 7e). This could be due to hydrogen bonding of ester groups with hydrogen from urethane group which might affect crystallization of polyol side of NCO-prepolymer. The NCO-prepolymer based on referent polyol BD-AA-3000 exhibited crystalline transition at 34-59°C (heating mode) (Table 4 and Figure 7f). NCO-prepolymer PS3-BS2-SA, which is based on blend of crystalline polyol BD-SA-2000 and amorphous polyol PDO-SA-3000, exhibited crystalline transitions at 106°C (heating mode), Figure 7c. Crystalline NCO-prepolymers PA3-BS2-AA-SA and 40PA3-60BS2-AA-SA were prepared by using a blend of BD-SA-2000 and PDO-AA-3000 polyols (Table 4). These NCO-prepolymers exhibited crystalline melt transition at 105°C and 106°C, respectively (Figures 7g and 7h). DSC spectra of NCO-prepolymers have two graphs. One is DSC graph recorded in a heating mode and the other DSC graph in cooling mode. DSC graphs in cooling mode has information on crystallization (temperature and heat of crystallization) of NCO-prepolymer that are relevant to the application of hot melt adhesives. In the application, hot melt adhesive are heated to elevated temperature (e.g. 120°C), applied to the substrate, cooled down and cured at room temperature.

Curing study The reaction of NCO-prepolymers with moisture is a major reaction during curing of hot melt adhesives which is taking place at room temperature. This reaction of isocyanate with moisture is taking place even without catalyst, but it is facilitated with presence of selective catalysts. The curing of NCO-prepolymers with moisture was evaluated at 23°C and controlled humidity of 68%. The reaction of NCO-prepolymers with moisture was monitored via FTIR. The curing reaction of NCO-prepolymers containing Jeffcat DMDEE, amine delayed action moisture curing catalyst, was carried out. As reference, the curing of NCO-prepolymers without added catalyst was studied as well. The curing of NCO-prepolymers was monitored as a decrease of a peak of absorption of isocyanate (NCO) groups at ~2270 cm1 in FTIR spectra (Figures 12a – 15g). The curing of NCO-prepolymers progressed well at room temperature, with and without catalyst present in the system. After 3 days of curing of NCO-prepolymers, there was none or very small peak of isocyanate groups absorption in FTIR spectra. Formulations and properties of adhesives




The adhesive formulations were based on NCO-prepolymer and a package of additives: catalyst Jeffcat DMDEE, Silquest A-187 adhesion promotor and antifoaming agent Ortogel 501 (Table 5). Standardized aluminum plates (dimensions 1 x 4 x 0.063 inches, AR-14, Q-Lab) were used as substrate to prepare adhesion test samples. The adhesives tested in this study are divided in two groups (Table 6):

a. Adhesives based on non-crystalline NCO-prepolymers that include: PDOSA2000, PDOAA2000 and PDOAA3000 adhesive

b. Adhesives based on crystalline NCO-prepolymers that include: PS3-BS2-SA, BDAA3000, PA3-BS2-AA-SA and 40PA3-60BS2-AA-SA adhesive

The adhesives based on non-crystalline prepolymers are one component moisture cured adhesives and did not have significant green strength, as could be expected (Table 6). The adhesive strength of samples cured for seven days at 23°C and 68% relative humidity was 381 psi – 414 psi, which could be expected for moisture cured adhesives (Table 6, Figures 1a and 1b). The adhesives based on crystalline prepolymers are hot melt adhesives. These adhesive include referent adhesive based on BD adipate 3000 polyol and three adhesives based on a blend of polyols. The adhesives based on blend of polyols contain BD Succinate 2000 prepolymer which is highly crystalline and the other NCO-prepolymer which is not crystalline. The following is their composition:

a. PS3-BS2-SA (BS-SA-2000/PDO-SA-3000/MDI, 1.00/1.26/4.62 equivalent ratio) b. PA3-BS2-AA-SA (BS-SA-2000/PDO-AA-3000, 1.00/1.99/6.24 equivalent ratio) c. 4OPA3-60BS2-AA-SA (BS-SA-2000/PDO-AA-3000, 1.00/1.99/6.24 equivalent ratio)

In these adhesives, non-crystalline NCO-prepolymers should help wetting of substrate with adhesive, which is very important for good adhesion properties. All crystalline adhesives exhibited green strength after 30 minutes of curing (Table 6, Figures 1a and 1b. Adhesive samples based on a blend of polyol exhibited very good adhesive strength around 1000 psi after seven days of curing (Table 6, Figures 1a and 1b). The adhesive strength of referent adhesive based on BD-AA-3000 was higher 1540 psi. It appears that adhesive strength correlate with latent heat of crystallization of NCO-prepolymers which was measured via DSC (cooling mode) (Table 4, Figures 7c, 7d, 7e and 7f). The adhesives based on blend of polyols performed very well in the humid aging test at 100% relative humidity and 38°C. The retention of properties of adhesives based on polyol blend was better than that of referent adhesive (Table 6 and Figure 1b).




Table 1. Chemicals Designation Description Supplier

1,3-PDO Susterra 1,3-Propanediol DuPont Tate & Lyle Bioproducts

Succinic Acid Succinic Acid Roquette Adipic Acid Adipic Acid Alfa Aesar Titanium Butoxide

Titanium(IV) Butoxide catalyst; 97% reagent grade Sigma Aldrich

PDO-SA-2000 PDO Succinate 2000 MW Troy Polymers, Inc. Poly S 2000PAR PDO Adipate 2000 MW DuPont Tate & Lyle

Bioproducts BD-SA-2000 BD Succinate 2000 MW Troy Polymers, Inc. BD-AA-3000 3000 MW BD Adipate Troy Polymer, Inc

Mondur M Monomeric diphenylmethane 4,4’-diisocyanate; NCO%: 31.7 Bayer Material Science

Jeffcat® DMDEE

Morpholine, 4,4’-(oxydi-2,1-ethanodiyl) bis- catalyst Huntsman

Silquest A-187® silane

Gamma-Glycidoxypropyltrimethoxysilane; Adhesion promoter Momentive

Ortegol 501 Anti-foaming additive Evonik Industries Aluminum Substrate

Aluminum plates (AR-14, dimensions 1 x 4 x 0.063 inches 1)

Q-Lab

Table 2. The methods used in testing of polyols, NCO-prepolymers and adhesives Property ASTM method Instrument Hydroxyl number ASTM D 4274 – 05 Titration Acid number ASTM D 4662 – 08 Titration Viscosity ASTM 478-08 Brookfield viscometer Moisture content, % ASTM D 4672 Karl Fisher Titrator Isocyanate content ASTM D-5155 Titration Adhesion properties ASTM D 1002, Apparent Shear

Strength of Single-Lap-Joint Adhesively Bonded Metal

Specimens

Instron tester (Instron 5500R, Model 1122)

Humidity resistance of adhesives at 37oC and 100% relative humidity

ASTM D2247 Moisture chamber, HCP108, MEMMERT GmbH

Thermal properties, DSC ASTM D3418 Differential Scanning

Calorimeter, DSC, Q10, TA Instrument)




FTIR Analysis FTIR Spectrometer (Spectrum Two, Perkin Elmer with Pike

Miracle ATR Attachment




Table 3. Properties of polyols Polyol *OH Value,

mg KOH/g Acid Value, mg KOH/g

Moisture content, %

Onset/Peak of melting via DSC, °C

PDO-SA-2000 58.3 1.00 0.020 N/A Poly S 2000PAR 53.4 0.24 0.015 17.6/31.8 BD-SA-2000 55.6 1.25 0.012 93.1/112.1 PDO-SA-3000 42.0 1.40 0.044 N/A PDO-AA-3000 39.8 0.97 0.007 18.1/33.6 BD-AA-3000 39.3 1.8 0.040 35.8/57.3




Table 4. Formulations and properties of NCO- prepolymers

Prepolymer designation: PDOSA2000 PDOAA2000 PS3-BS2-SA Blend PDOSA3000 PDOAA3000 BDAA3000 PA3-BS2-AA-SA

Blend

40PA3-60BS2-AA-SA Blend

Formulation, pbw

TPI PDO-SA-2000 polyol, g 312.1 - - - - - - - Poly S 2000PAR polyol, g - 318.0 - - - - - - TPI BD-SA-2000 polyol, g - - 157.6 - - - 157.6 189.2

TPI PDO-SA-3000 polyol, g - - 166.3 332.5 - - - - TPI PDO-AA-3000 polyol, g - - - - 335.5 - 167.7 133.0

TPI BD-AA-3000 polyol, g - - - - - 336.1 - - Mondur M, g 87.9 82.1 76.1 67.5 64.5 63.9 74.6 77.82

Benzoyl Chloride, drops 6 0 6 0 0 4 6 6 Equivalent ratio of polyol to

isocyanate 1 to 2

Isocyanate index 1.05 Reaction conditions

Pre-temperature of Polyol, °C 44 44 120/44 44 44 65 120/44 120/44 Pre-temperature of Isocyanate, °C 44 44 44 44 44 44 44 44

Initial reaction temperature (beginning of polyol addition), °C 50 50 70 50 50 50 70 70

Final reaction temperature (all components added), °C 70 70 110 70 70 70 110 110

Reaction time, hours 2.25 2.25 0.75 1.75 1.75 2.0 0.75 0.75 Final properties

NCO content, % 3.62 3.33 3.10 2.62 2.67 2.53 2.93 3.01 Viscosity at 120°C, cps 5300 4400 7700 11400 12800 9500 6575 5800

Transitions via DSC, °C -18.5 -39.7 -23.1, 27.9, 75.7, 105.9, 163.7 -20.8 -43.6 -42.8, 34-59 -43.2,

79.0-110.4 -42.2, 83.0-113.9

Latent heat of crystallization (∆Hc), J/g N/A N/A 11.0 N/A N/A 49.3 25.3 29.8




Table 5. Formulations for hot-melt adhesives

Designation: PDOSA2000

adhesive PDOAA2000

adhesive PS3-BS2-SA Blend

adhesive PDOSA3000

adhesive PDOAA3000

adhesive BDAA3000 adhesive

PA3-BS2-AA-SA Blend adhesive

40PA3-60BS2-AA-SA Blend

Adhesive Formulation Prepolymer used: PDOSA2000 PDOAA2000 PS3-BS2-SA PDOSA3000 PDOAA3000 BDAA3000 PA3-BS2-AA-SA 40PA-BS2-AA-SA Prepolymer temperature, °C: 70 70 120 70 70 120 120 120 Prepolymer amount, g: 30 Catalyst used: Jeffcat DMDEE Catalyst amount, %: 0.8 Silquest A-187, %: 1.0 Ortogel 501, %: 1.0 Mix speed, rpm: 2200 Mix duration, seconds: 60 Amount applied to substrate, g: 0.3 Application Temperature of adhesive, °C 70 70 120 70 70 120 120 120 Temperature of substrate° C RT RT 105 RT RT 105 105 105 Curing conditions Temperature, °C: 22-24 Relative humidity, %: 68-69




Table 6. Adhesion properties* of adhesives based on various polyester polyols

Formulation Used: PDOSA2000

adhesive PDOAA2000

adhesive *PS3-BS2-SA

blend adhesive PDOSA3000

adhesive PDOAA3000

adhesive *BDAA3000

adhesive

*PA3-BS2-AA-SA

blend adhesive

*40PA3-60BS2-AA-SA blend

adhesive Substrate Substrate material: Aluminum Green strength Properties (30 minute cure) Maximum load, lbf: - - 68 ± 9 0.5 - 109 ± 22 89 ± 10 70 ± 8 Load at failure, psi: - - 119 ± 14 0.9 - 208 ± 48 178 ± 27 132 ± 15 Strain at failure, % - - 1.5 ± 0.1 3.8 - 2.8 ± 0.7 2.0 ± 0.4 1.5 ± 0.3

Failure type: - - Cohesive/ Adhesive Cohesive - Cohesive Cohesive Cohesive

Strength after 3 days of cure Maximum load, lbf: 141 ± 42 175 ± 21 270 ± 39 104 ± 21 200 ± 49 528 ± 48 270 ± 32 386 ± 66 Load at failure, psi: 250 ± 74 311 ± 37 461 ± 55 194 ± 33 349 ± 88 916 ± 211 525 ± 58 705 ± 77 Strain at failure, % 4.3 ± 0.2 4.3 ± 0.3 4.3 ± 0.1 3.6 ± 0.7 4.4 ± 0.2 7.5 ± 1.7 5.0 ± 0.4 6.1 ± 0.5

Failure type: Adhesive Adhesive Cohesive/ Adhesive Adhesive Adhesive Adhesive Cohesive/

Adhesive Cohesive/ Adhesive

Strength after 7 days of cure Maximum load, lbf: 216 ± 42 220 ± 16 499 ± 94 139 ± 52 215 ± 57 785 ± 88 497 ± 81 605 ± 61 Load at failure, psi: 381 ± 70 414 ± 34 919 ± 136 264 ± 103 402 ± 111 1540 ± 155 999 ± 149 1105 ± 115 Strain at failure, % 4.5 ± 0.4 4.8 ± 0.4 7.6 ± 0.5 4.2 ± 0.8 4.7 ± 0.6 10.4 ± 0.6 7.4 ± 0.7 9.0 ± 0.6 Failure type: Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Strength after aging in 100% humidity at 38°C for 3 days Maximum load, lbf: 78 ± 15 76 ± 17 365 ± 40 69 ± 5 80 ± 16 522 ± 158 454 ± 87 435 ± 74 Load at failure, psi: 153 ± 32 143 ± 32 708 ± 107 127 ± 11 154 ± 28 970 ± 296 799 ± 94 838 ± 190 Strain at failure, % 2.1 ± 0.7 1.9 ± 0.6 5.5 ± 0.5 1.8 ± 0.3 2.2 ± 0.7 7.4 ± 1.8 6.4 ± 0.4 7.2 ± 1.7 Failure type: Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Adhesive Retention of adhesion strength, % 40.0 34.5 77 48 38 62 80 75

*Crystalline formulations applied on substrate preheated to 105°C







Figure 1a. Adhesive strength of various adhesives cured at 23°C and 68-69% relative humidity (Table 6)

Figure 1b. The effect of humid aging on adhesion properties of various adhesives (Table 6)




Figure 2. Reactor set-up for the synthesis of NCO-prepolymers




Figure 3. Assembled adhesion test specimens




Figure 4. Curing of adhesives in a moisture chamber at 22°C- 23°C and 68% relative humidity




Figure 5. Testing of adhesive strength per ASTM D10002 method




Figure 6a. DSC graph of polyol PDO-SA-2000

Figure 6b. DSC graph of polyol Poly S 2000PAR




Figure 6c. DSC graph of polyol BD-SA-2000




Figure 6d. DSC graph of polyol PDO-SA-3000

Figure 6e. DSC graph of polyol PDO-AA-3000




Figure 6f. DSC graph of polyol BD-AA-3000




Figure 7a. DSC graph of NCO-prepolymer PDOSA2000: upper curve- cooling mode; lower curve-

heating mode

Figure 7b. DSC graph of NCO-prepolymer PDO-AA-2000: upper curve- cooling mode; lower curve-

heating mode




Figure 7c. DSC graph of NCO-prepolymer P3-B2-SA prepared with blend of BD-SC-2000 and PDO-

SC-3000 polyols: upper curve- cooling mode; lower curve-heating mode

Figure 7d. DSC graph of NCO-prepolymer PDOSA3000: upper curve- cooling mode; lower curve-heating mode




Figure 7e. DSC graph of NCO-prepolymer PDOAA3000: upper curve- cooling mode; lower curve-

heating mode

Figure 7f. DSC graph of NCO-prepolymer BDAA3000 upper curve- cooling mode; lower curve-heating mode




Figure 7g. DSC graph of NCO-prepolymer PA3-BS2-AA-SA blend; upper curve- cooling mode;

lower curve-heating mode




Figure 7h. DSC graph of prepolymer 40PA3-60BS2-AA-SA blend; upper curve- cooling mode;

lower curve-heating mode

4000 6503500 3000 2500 2000 1500 1000

105

4445

50

55

60

65

70

75

80

85

90

95

100

cm-1

%T 2269.72269.7

Figure 8a. Initial FTIR of adhesive PDOSA2000 (no catalyst)

4000 6503500 3000 2500 2000 1500 1000

107

35

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.3

Figure 8b. FTIR of adhesive PDOSA2000 (without catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

109

35

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2280.42280.4

Figure 8c. FTIR of PDOSA2000 adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

32

40

50

60

70

80

90

100

cm-1

%T

2276.82276.8

Figure 8d. FTIR of PDOSA2000 adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

109

36

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 8e. FTIR of PDOSA2000 adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

110

33

40

50

60

70

80

90

100

cm-1

%T

2276.82276.8




Figure 8f. FTIR of PDOSA2000 adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

110

36

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.3

Figure 8g. FTIR of adhesive PDOSA2000 (with catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

107

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T 22682268

Figure 9a. Initial FTIR of adhesive PDOAA2000

4000 6503500 3000 2500 2000 1500 1000

107

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.3

Figure 9b. FTIR of PDOSA2000 adhesive (without catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

110

4750

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 9c. FTIR of PDOAA2000 adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

46

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8




Figure 9d. FTIR of PDOAA2000 adhesive (without catalyst) after 2 days day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

47

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.3

Figure 9e. FTIR of PDOAA2000 adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

109

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2280.42280.4

Figure 9f. FTIR of PDOAA2000 adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

110

4750

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 9g. FTIR of PDOAA2000 adhesive (with catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

110

33

40

50

60

70

80

90

100

cm-1

%T

2269.72269.7

Figure 10a. Initial FTIR of PS3-BS2-SA adhesive

4000 6503500 3000 2500 2000 1500 1000

105

3335

40

45

50

55

60

65

70

75

80

85

90

95

100

cm-1

%T

2269.72269.72337.52337.5

Figure 10b. FTIR spectra of PS3-BS2-SA adhesive (without catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

108

32

40

50

60

70

80

90

100

cm-1

%T

Figure 10c. FTIR spectra of adhesive PS3-BS2-SA (with catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

107

3740

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 10d. FTIR of PS3-BS2-SA adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

106

41

45

50

55

60

65

70

75

80

85

90

95

100

cm-1

%T

2276.82276.8

Figure 10e. FTIR of PS3-BS2-SA adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

35

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2280.42280.4

Figure 10f. FTIR of PS3-BS2-SA adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

107

35

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

Figure 10g. FTIR of PS3-BS2-SA adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

4345

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 11a. Initial FTIR of PDOSA3000 adhesive




4000 6503500 3000 2500 2000 1500 1000

106

34

40

45

50

55

60

65

70

75

80

85

90

95

100

cm-1

%T

2337.52337.52269.72269.7

Figure 11b. FTIR of adhesive PDOSA3000 (without catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

32

40

50

60

70

80

90

100

cm-1

%T

2280.42280.4

Figure 11c. FTIR of PDOSA3000 adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

111

32

40

50

60

70

80

90

100

cm-1

%T

2276.82276.8

Figure 11d. FTIR of PDOSA3000 adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

32

40

50

60

70

80

90

100

cm-1

%T

2276.82276.8




Figure 11e. FTIR of PDOSA3000 adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

110

34

40

50

60

70

80

90

100

cm-1

%T

2280.42280.4

Figure 11f. FTIR of PDOSA3000 adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

36

40

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 11g. FTIR of adhesive PDOSA3000 (with catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

109

46

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T 22682268

Figure 12a. Initial FTIR of PDOAA3000 adhesive

4000 6503500 3000 2500 2000 1500 1000

107

4345

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.32344.62344.6

Figure 12b. FTIR of PDOAA3000 adhesive (without catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

108

4345

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2269.72269.7

Figure 12c. FTIR of PDOAA3000 adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

4345

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 12d. FTIR of PDOAA3000 adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

107

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 12e. FTIR of PDOAA3000 adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

111

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 12f. FTIR of PDOAA3000 adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

109

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 12g. FTIR of PDOAA3000 adhesive (with catalyst) after 3 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

111

41

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2269.72269.7

Figure 13a. Initial FTIR of sample BDAA3000




4000 6503500 3000 2500 2000 1500 1000

108

57

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2273.32273.3

Figure 13b. FTIR after 1 day of sample BDAA3000 (without catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

108

5455

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2276.82276.8

Figure 13c. FTIR of BDAA3000 adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

102

76

78

80

82

84

86

88

90

92

94

96

98

100

cm-1

%T

2273.32273.3

Figure 13d. FTIR of BDAA3000 adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

103

79

80

82

84

86

88

90

92

94

96

98

100

102

cm-1

%T

2273.32273.3

Figure 13e. FTIR of BDAA3000 adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

102

76

78

80

82

84

86

88

90

92

94

96

98

100

102

cm-1

%T

2276.82276.8

Figure 13f. FTIR BDAA3000 adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

105

64

70

75

80

85

90

95

100

cm-1

%T

2276.82276.8

Figure 13g. FTIR of BDAA3000 adhesive (with catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

117

3740

50

60

70

80

90

100

110

cm-1

%T 22682268

Figure 14a. Initial FTIR of PA3-BS2-AA-SA adhesive

4000 6503500 3000 2500 2000 1500 1000

108

44

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 14b. FTIR of PA3-BS2-AA-SA adhesive (without catalyst) after 1 day of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

110

4750

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2282.22282.2

Figure 14c. FTIR of PA3-BS2-AA-SA adhesive (with catalyst) after 1 day of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

56

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 14d. FTIR of PA3-BS2-AA-SA adhesive (without catalyst) after 2 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

108

4850

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 14e. FTIR of PA3-BS2-AA-SA adhesive (with catalyst) after 2 days of curing at 23°C and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

4850

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22672267

Figure 14f. FTIR of PA3-BS2-AA-SA adhesive (without catalyst) after 3 days of curing at 23°C and 68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

108

4950

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22672267

Figure 14g. FTIR of PA3-BS2-AA-SA adhesive (with catalyst) after 3 days of curing at 23°C and

68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

114

39

45

50

55

60

65

70

75

80

85

90

95

100

105

110

cm-1

%T 22682268

Figure 15a. Initial FTIR of 40PA3-60BS2-AA-SA adhesive




4000 6503500 3000 2500 2000 1500 1000

107

5860

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 15b. FTIR of 40PA3-60BS2-AA-SA adhesive (without catalyst) after 1 day of curing at 23°C

and 68% relative humidity

4000 6503500 3000 2500 2000 1500 1000

109

45

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

2278.62278.6

Figure 15c. FTIR of 40PA3-60BS2-AA-SA adhesive (with catalyst) after 1 day of curing at 23°C and

68% relative humidity




4000 6503500 3000 2500 2000 1500 1000

108

50

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 15d. FTIR of 40PA3-60BS2-AA-SA adhesive (without catalyst) after2 days of curing at 23°C


4000 6503500 3000 2500 2000 1500 1000

109

49

55

60

65

70

75

80

85

90

95

100

105

cm-1

%T

22682268

Figure 15e. FTIR of 40PA3-60BS2-AA-SA adhesive (with catalyst) after2 days of curing at 23°C





4000 6503500 3000 2500 2000 1500 1000

107

6465

70

75

80

85

90

95

100

105

cm-1

%T

22712271

Figure 15f. FTIR of 40PA3-60BS2-AA-SA adhesive (without catalyst) after3 days of curing at 23°C


4000 6503500 3000 2500 2000 1500 1000

107

74

76

78

80

82

84

86

88

90

92

94

96

98

100

102

104106

cm-1

%T

22712271

Figure 15g. FTIR of 40PA3-60BS2-AA-SA adhesive (with catalyst) after 3 days of curing at 23°C





Figure 16a. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PS3-BS2-SA adhesive after 30 minutes cure (green strength)




Figure 16b. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with BDAA3000 adhesive after 30 minutes cure (green strength)

Figure 16c. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PA3-BS2-AA-SA adhesive after 30 minutes cure (green strength)




Figure 16d. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

40PA3-60BS2-AA-SA adhesive after 30 minutes cure (green strength)

Figure 17a. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOSA2000

adhesive after 3 days of curing




Figure 17b. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOAA2000


Figure 17c. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PS3-BS2-SA





Figure 17d. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOSA3000





Figure 17e. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOAA3000 adhesive after 3 days of curing

Figure 17f. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with BDAA3000





Figure 17g. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PA3-BS2-AA-SA adhesive after 3 days of curing

Figure 17h. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

40PA3-60BS2-AA-SA adhesive after 3 days of curing.




Figure 18a. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PDOSA2000 adhesive after 7 days of curing

Figure 18b. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PDOAA2000 adhesive after 7 days of curing











Figure 18e. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOAA3000






after 7 days of curing

Figure 18g. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PA3-BS2-AA-SA adhesive after 7 days of curing




Figure 18h. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with 40PA3-60BS2-AA-SA adhesive after 7 days of curing

Figure 19a. Stress-strain curves (per ASTM D1002 of adhesive sample bonded PDOSA2000 adhesive after aging at 37°C and 100% relative humidity




Figure 19b. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOAA2000

adhesive after aging at 37°C and 100% relative humidity











Figure 19e. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with PDOAA3000 adhesive after aging at 37°C and 100% relative humidity






Figure 19g. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

PA3-BS2-AA-SA adhesive after aging at 37°C and 100% relative humidity

Figure 19h. Stress-strain curves (per ASTM D1002) of adhesive sample bonded with

40PA3-60BS2-AA-SA adhesive after aging at 37°C and 100% relative humidity

Date post:	20-May-2018
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EVALUATION OF SUSTERRA®-BASED … CPI Susterra...of 3000 MW were prepared at Troy Polymers, Inc....

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