Melt processible polyureas and polyurea-urethanes, method for the production thereof and products made therefrom

Abstract

A polyurea or polyurea-urethane elastomer comprises a soft polymer segment and a hard polymer segment, wherein the hard polymer segment includes polyurea groups in combination with H-bond accepting chain extenders (HACEs) to reduce the flow temperature (T.sub.flow) while maintaining the excellent mechanical properties such that the resulting polyurea elatomer is rendered melt-processable.

Claims

1. A polyurea-urethane elastomer comprising: at least one soft segment selected from polyisobutylene and poly(tetramethylene oxide); and at least two hard segments, wherein at least one hard segment comprises a plurality of urethane groups and an H-bond accepting chain extender, and wherein at least a second hard segment comprises a plurality of urea groups and a chain extender having a M.sub.n of less than 150 g/mol formed from an aliphatic diamine, an aromatic diamine and a combination of aliphatic and aromatic diamines, wherein the urea groups, the urethane groups, and the H-bond accepting chain extender form H bonds, wherein the H-bond accepting chain extender is formed from a 50 mol % blend of hydroxyl-telechelic poly(hexamethylene carbonate) having a M.sub.n of 800 g/mol mixed with hydroxyl-telechelic poly(pentamethylene carbonate) having a M.sub.n of 500 g/mol; wherein the elastomer is melt processible.

2. The polyurea-urethane elastomer according to claim 1, wherein the hard segment content is at least 30% by weight of the elastomer.

3. The polyurea-urethane elastomer according to claim 2, wherein the hard segment content is at least 35% by weight of the elastomer.

4. The polyurea-urethane elastomer according to claim 1, wherein the H-bond accepting chain extender has more nucleophilic groups than are found in ethylene glycol.

5. The polyurea-urethane elastomer according to claim 1, wherein at least 2 percent by weight of the elastomer of the H-bond accepting chain extender is present.

6. The polyurea-urethane elastomer according to claim 1, wherein the elastomer has a T.sub.flow of less than 220 C.

7. The polyurea-urethane elastomer according claim 6, wherein the elastomer has a T.sub.flow of less than 200 C.

8. The polyurea-urethane elastomer according claim 6, wherein the elastomer has a T.sub.flow of less than 190 C.

9. The polyurea-urethane elastomer according claim 6, wherein the elastomer has a T.sub.flow in the range of from 170 C. to 210 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a representative DMTA trace of a poly(tetramethylene oxide)-based polyurea, wherein the arrows indicate T.sub.flow;

(2) FIG. 2 is a graph of tensile strength versus T.sub.flow of conventional (no HACE) poly(tetramethylene oxide)-based polyureas and HACE-containing polyurea-urethanes, wherein a significant shift left indicates lower T.sub.flows of the HACE-containing products;

(3) FIG. 3A is a graph of the effect of BG.sub.9 concentration on mechanical properties, including tensile strength and elongation;

(4) FIG. 3B is a graph of the effect of EG.sub.9 concentration on mechanical properties, including tensile strength and elongation;

(5) FIG. 4 is a TGA trace of Same PIB-4 in air; and

(6) FIG. 5 is a representative idealized micromorphology of conventional (without HACE) polyureas and the HACE-containing polyureas of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(7) As noted hereinabove, the present invention seeks to render polyureas or polyurea-urethanes melt processable. Polyurea can be melt processed only if its flow temperature (T.sub.flow) is reduced sufficiently so that it can flow (i.e., melt) at a temperature lower than the temperature at which it would degrade. As noted above, conventional polyurea degrades at about 240 C., and since the T.sub.flow of conventional polyurea is above that temperature, conventional polyurea does not melt.

(8) In the present invention, polyurea and polyurea-urethane elastomers have been prepared by the use of conventional chain extenders (CEs) in combination with H-accepting chain extenders (HACEs). In one embodiment, at least 2 percent HACEs are preferably employed. In other embodiments, at least 3 percent is employed. In other embodiments, at least 6 percent is employed. In yet other embodiments, amounts up to 15 percent or more HACEs are used, where larger amounts of HACEs are needed to provide flexibility to the hard segments. HACEs have more nucleophilic groups than CEs, can for purposes of this invention, the HACEs used have more nucleophilic groups than found in ethylene glycol, a known conventional chain extender. In one embodiment, less than 10 percent of commercially available polycarbonate- and polyether-based HACEs were used in conjunction with at least urea groups and optionally, urethane groups, to produce polyurea elastomers or polyurea-urethane elastomers, respectively.

(9) In detailed embodiments depicted in this description, the present invention provides for the synthesis of conventional (no HACE) poly(tetramethylene oxide) (PTMO)-based polyurea-urethanes, novel (HACE-containing) PTMO-based polyurea-urethanes, and novel (HACE-containing) polyisobutylene (PIB)-based polyurea-urethanes, the novel compositions exhibiting flow temperatures below 200 C. (T.sub.flow180 C.), while maintaining excellent mechanical properties. Stated differently, in the preparation of the polyureas and polyurea-urethanes the present invention, the combination of CEs and HACEs produce H-bonding of sufficient strength for good mechanical properties together with increased hard segment mobility for melt processing.

(10) In order to demonstrate practice of the invention, various polyureas were synthesized. The following detailed description provides one possible embodiment of the present invention and should not be seen as limited the scope of the invention to the particular components recited therein, the scope of the invention be determined and limited by the claims which follow.

(11) The present invention employed the following materials in the synthesis of the polyureas and polyurea-urethanes of the present invention (and the controls). Amine-telechelic poly(tetramethylene oxide) (H.sub.2N-PTMO-NH.sub.2) of Mn=1,100 g/mol was obtained. Hydroxyl-telechelic PTMO of Mn=650 (referred to herein as BG.sub.9) was obtained. Poly(ethylene glycol) of Mn=400 (referred to herein as EG.sub.9) was obtained. 1,4-hexane diol (HDO), 1,6-hexamethylene diamine (HDA), bis(4-isocyanatocyclohexyl)methane (HMDI), and dibutyltin dilaurate (DBTDL) were purchased from Aldrich and used without further purification. Reagent grade tetrahydrofuran (THF) was purchased form Fisher Chemicals and was freshly distilled before use. Hydroxyl-telechelic poly(hexamethylene carbonate) mixed with hydroxyl-telechelic poly(pentamethylene carbonate), 50 mol %, of Mn=800 and 500 (HOPCOH), was kindly provided by Chori America, Inc. (Jersey City, N.J.). Amine telechelic PIB (H.sub.2N-PIB-NH.sub.2) of Mn-3,500 g/mol was prepared by a well-established method known in the art.

(12) Polyureas and polyurea-urethanes (prepared by using amine-telechelic polyols and chain extenders, and hydroxyl-telechelic HACEs, i.e., BG9 and PC) were synthesized by a two-step pre-polymer method. Representative synthetic procedures follow.

(13) For the synthesis of PTMO-based polylureas (Control Sample C-3 in Table I), H.sub.2N-PTMO-NH.sub.2 (1 g, 0.91 mmol) was dissolved in 3 mL THF in a 20 mL vial equipped with a magnetic stirrer. HMDI (0.462 g, 1.76 mmol) was dissolved in 1.5 mL THF and was added to the solution and stirred at room temperature for 5 minutes to obtain the prepolymer. HDA (0.08 g, 0.691 mmol) was dissolved in 3 mL THF and was added to the prepolymer solution. The system was then stirred for 30 minutes. Progress and completion of the reaction was monitored by IR spectroscopy (disappearance of NCO peaks at 2270 cm.sup.1). The solution was then poured into a 7.5 cm7.5 cm Teflon mold, the solvent was evaporated in air and the sample dried at 70 C. in a convection oven and 40 C. in a vacuum oven, until constant weight. The other samples of PTMO-based (No HACE) polyureas were similarly produced.

(14) For the synthesis of PTMO-based, HACE-containing polyurea-urethanes, H.sub.2N-PTMO-NH.sub.2 was dissolved in 3 mL THF in a 20 mL vial equipped with a magnetic stirrer. HMDI was dissolved in THF and was added to the prepolymer solution. The system was then stirred at room temperature for 5 minutes. Subsequently, HDA and OHPCOH, were added dropwise, DBTDL catalyst was added, and the system was stirred at 60 C. for 3 hours to complete the reaction. Progress and completion of the synthesis was monitored by IR spectroscopy (disappearance of NCO peaks at 2270 cm.sup.1). The solution was poured into a 7.5 cm7.5 cm Teflon mold. The solvent was evaporated in air, and the sample was dried at 70 C. in a convection oven. The sample was dried until constant weight in a vacuum oven at room temperature. The dried sample was stored at 4 C. for a week in a refrigerator, to accelerate the formation of hydrogen bonds in the HACE-containing hard segment. Samples were stored at room temperature in a vacuum oven until characterization.

(15) For the synthesis of PIB-based, HACE-containing polyurea-urethanes (Sample PIB-4 in Table I), H.sub.2N-PIB-NH.sub.2 (1 g, 0.286 mmol), and dissolved in 3 mL THF in a 20 mL vial equipped with a magnetic stirrer. HMDI (0.216 g, 0.823 mmol) was dissolved in 3 mL THF and added to the solution and stirred for 30 minutes to obtain the prepolymer. HDA (0.018 g, 0.154 mmol) and BG.sub.9 (0.201 g, 0.309 mmol) dissolved in 3 mL THF and three drops of DBTDL (0.03 g) were added to the prepolymer solution. The system was stirred at 60 C. for 3 hours. Progress and completion of the synthesis was monitored by IR spectroscopy (disappearance of NCO peaks at 2270 cm.sup.1). The solution was poured into a 7.5 cm7.5 cm Teflon mold. The solvent was evaporated in air, and the sample was dried at 70 C. in a convection oven. The sample was dried until constant weight in a vacuum oven at room temperature. The dried sample was stored at 4 C. for a week in a refrigerator, to accelerate the formation of hydrogen bonds in the HACE-containing hard segment. Samples were stored at room temperature in a vacuum oven until characterization. The other samples of PIB-based, HACE-containing polyurea-urethanes were similarly synthesized.

(16) Melt proccessability was assessed in terms of flow temperature (T.sub.flow) determined by dynamic mechanical thermal analysis (DMTA) using a PerkinElmer dynamic mechanical analyzer. Measurements were made in tensile mode at 1 Hz, between 120 C. and 250 C., under a nitrogen atmosphere, at 3 C./minute heating rate. FIG. 1 shows storage modulus (E), loss modulus (E), and tan 8 together with T.sub.flow of a representative PTMO-based polyurea.

(17) Shore Durometer Hardness (Shore A) was determined by using approximately 5 mm thick films by a Micro-O-Ring Hardness Tester, Model 714 by Instron of the three determinations reported.

(18) Stress-strain behavior was determined by an Instron Model 5543 Universal Tester controlled by Series Merlin 3.11 software. A bench-top die (ASTM 1708) was used to cut dog-bones from 0.25 mm thick films. Samples (25 mm long, 3.18 mm width at the neck) were tested to failure at a crosshead speed of 25 mm/min at room temperature. Averages of two or three determinations are reported.

(19) Thermal gravimetric analysis (TGA) was used to obtain degradation temperatures of 6 mg samples by using a TA Instruments Q500 Series, at 10 C./minute heating rate to 450 C. in air (60 mL/minute).

(20) In light of the foregoing tests and as best shown in Tables I and II and FIGS. 2, 3A and 3B, it will be appreciated that melt processable polyureas can be obtained by combinations of CEs and HACEs used in combination with the requisite polyurea groups and optionally, polyurethane groups. In the first series shown in Table I, conventional PTMO-based polyureas were prepared. The effect of the addition of a HACE (HOPCOH) on mechanical properties and T.sub.flow was studied. In the second series shown in Table II, similarly, PIB-based polyureas was prepared and the effect of two HACEs (BG.sub.9 and EG.sub.9) was investigated on these parameters.

(21) TABLE-US-00001 TABLE I Mechanical Properties and Flow Temperatures of Conventional (no HACE) Polyurea-urethanes Compared to those of PTMO-based Polyurea-urethanes Urethane/urea Tensile Elongation T.sub.flow Sample Composition (mol %/mol %) (MPa) (%) ( C.) Conventional (no HACE) PTMO-based polyureas C-I H.sub.2N-PTM0-NH.sub.2(1.1K, 0/100 31.1 0.1 1000 7 171 75%)/HMDI + HDA = 25% C-2 H.sub.2N-PTM0-NH.sub.2(1.1K, 0/100 51.4 1.6 849 26 183 2 70%)/HMDI + HAD = 30% C-3 H.sub.2N-PTM0-NH.sub.2(1.1K, 0/100 58.2 0.6 744 4 230 2 65%)/HMDI + HAD = 35% PTMO-based HACE-containing polyurea-urethanes PTMO-1 H.sub.2N-PTM0-NH.sub.2(1.1K, 65%)/HMDI + 7/93 55.5 0.1 820 11 193 5HDA + 1HO-PC-OH (500, 3.2%) = 35% PTMO-2 H.sub.2N-PTM0-NH.sub.2(1.1K, 65%)/HMDI + 8/92 56.2 1.3 770 55 203 4HDA + 1 HO-PC-OH (500, 3.8%) = 35% PTMO-3 H.sub.2N-PTM0-NH.sub.2(1.1K, 65%)/HMDI + 10/90 58.4 2.4 910 36 188 3HDA + 1HO-PC-OH (500, 4.5%) = 35% PTMO-4 H.sub.2N-PTMO-NH.sub.2(1.1K, 65%)/HMDI + 12/88 46.5 3.8 910 29 169 2HDA + 1 HO-PC-OH (500, 5.7%) = 35% PTMO-5 H.sub.2N-PTMO-NH.sub.2(1.1K, 65%)/HMDI + 9/91 56.2 + 0.4 866 6 177 3HDA + 1HO-PC-OH (800, 6.3%) = 35%

(22) Table I summarizes compositions, mechanical properties and flow temperatures of representative PTMO-based polyurea-urethanes. Samples C-I through C-3 show data obtained with conventional (no HACE) PTMO-based polyureas containing 25, 30 and 35% hard segments. As anticipated, increasing the hard segment content from 25 to 35% increased the tensile strengths from 31.1 to 58.2 MPa, decreased elongations from 1000 to 740%, and increased flow temperatures from 170 to 230 C. A T.sub.flow of 230 C. may be dangerously high for thermal processing due to possible degradation.

(23) In view of the excellent mechanical properties exhibited by Sample C-3, this sample was selected for experimentation aimed at reducing T.sub.flow. Samples PTMO-1 through PTMO-5 show the effect of the addition of a HACE, a commercially available polycarbonate (HOPCOH), relative to that of Sample C-3. In review of the strong H-bond accepting character of the carbonate (OCOO) group, it was believed that even a small amount of this HACE would suffice to disrupt the H-bridges between urea groups and thus bring about thermal proccessability. Indeed, by increasing the amount of HOPCOH from 3.2 to 6.3% (see PTMO-1 to PTMO-5) T.sub.flow decreased significantly relative to that of Sample C-3, while the tensile strengths remained essentially unchanged. Importantly, T.sub.flow/PTMO-5 dropped about 53 C. (to 177 C.) relative to that of T.sub.flow/C-3=230 C., while the mechanical properties remained essentially unchanged (tensile strengths 58.2 and 56.2 MPa).

(24) FIG. 2 depicts tensile strength vs. T.sub.flow of PTMO-based polyureas relative to polyurea-urethanes. The T.sub.flows of products synthesized with the HACE are significantly lower than those of conventional (no HACE) polyureas, while tensile strengths remain unchanged. According to the T.sub.flows of these polyurea-urethanes, they are thermally processable below 200 C.

(25) Table 2 summarizes compositions, urethane/urea ratios, mechanical properties, and T.sub.flows of PIB-based polyurea-urethanes prepared with two commercially available polyether-based HACEs, BG.sub.9 and EG.sub.9. Samples PIB-1 through PIB-6 show products prepared with BG.sub.9, and PIB-7 through PIB-9 show those made with EG.sub.9. It was decided not to use HOPCOH in conjunction with PIB-based polyurethanes or polyureas because that HACE, while giving similar tensile strengths, reduced the elongation by 50% below that obtained with BG.sub.9.

(26) TABLE-US-00002 TABLE II Mechanical Properties and Flow Temperatures of PIB-based HACE- containing Polyurea-urethanes Urethane/ Tensile Urea strength Sample Composition mol %/mol % (MPa) Elongation(%) HACE = BG.sub.9 PIB-1 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 17/83 13.2 1.9 263 30 HDA + BG.sub.9(0.65K, 7.5%) = 30% PIB-2 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 23/77 23.3 0.7 434 11 HDA + BG.sub.9(0.65K, 9.1%) = 30% PIB-3 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 32/68 22.4 0.3 557 9 HDA + BG.sub.9(0.65K, 11.8%) = 30% PIB- NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 41/59 24.1 0.6 671 9 4.sup.a HDA + BG.sub.9(0.65K, 14.0%) = 30% PIB-5 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 43/57 23.3 0.1 615 7 HDA + BG.sub.9(0.65K, 14.4%) = 30% PIB-6 NH.sub.2-PIB-NH.sub.2(3.5K, 55/45 22.4 1.1 862 42 70%)/HMDI + BG.sub.9(0.65K, 16.1% >= 30% HACE = EG.sub.9 PIB-7 NH.sub.2-PIB-NH.sub.2(3.5K; 70%)/HMDI + 34/66 20.1 0.9 387 21 HDA + EG.sub.9(0.4K, 8.9%) = 30% PIB-8 NH.sub.rPIB-NH.sub.2(3.5K, 70%)/HMDI + 45/55 22.0 0.9 521 27 HDA + EG.sub.9(0.4K,. 10.9%) = 30% PIB-9 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 63/37 20.0 0.3 710 8 EG.sub.9(0.4K, 13.3%) = 30% *T.sub.flow and hardness of PIB-4 are 178 C. and 73 Shore A, respectively.

(27) Products prepared with BG.sub.9 yielded better mechanical properties than those with EG.sub.9. For example, PIB-4 exhibited 24.1 MPa and 671% tensile strength and elongation, respectively, while PIB-9 gave 22.0 MPa and 521%. The superiority of BG.sub.9 may be due to the fact that this HACE is more flexible and thus gives rise to more flexible hard segments than EG.sub.9. Flexible hard segments are believed to be fundamental in providing for improved mechanical properties.

(28) FIGS. 3A and 3B show the effect of the BG.sub.9 and EG.sub.9 concentration on mechanical properties. The figures show a similar trend: increasing HACE concentration, increases tensile strengths and elongations. However, in the absence of the conventional CE (HDA), tensile strengths decreased somewhat (see the last data points in the figures).

(29) Evidently, to obtain optimum mechanical properties the H-donating and H-accepting groups should preferably be balanced. In other words, the number of NH (donating) groups must preferably balance the number of H-accepting sites (-0-, -0-CO-0-) which include those in the HACE.

(30) The data in Table 3 serve to compare the mechanical properties of a representative PIB-based polyurethane and three polyureas, all containing 30% hard segments by varying the nature of the terminal groups of (HO or NH.sub.2), the CEs (HDO or HDA), and the amount of HACE (5.2 or 14% BG.sub.9). Sample 1 contains only ethane linkages. By changing to urea linkages, i.e., by replacing HO-PIB-OH with NH.sub.2-PIB-NH.sub.2 (Sample 2), the tensile strength increases from 17.4 to 19.0 MPa and elongation decreases from 480 to 310%. The addition of a few percent of HACE (5.2% BG.sub.9) increases both tensile strength and elongation to 24.2 MPa and 570%, respectively (Sample 3). Tensile strengths remain the same when HDO is replaced with HAD (Sample 4). Significantly, the amount of a HACE that produces the similar tensile strengths is very different. While Sample 3 contains only 5.2% BG.sub.9, Sample 4 contains 14%. This indicates that a larger amount of HACE is needed to flexibilize, i.e., loosen, the hard segment in the polyurea than in the polyurea-urethane.

(31) TABLE-US-00003 TABLE 3 Comparison of mechanical properties of a PIB-based polyurethane and three polyureas prepared with various chain extenders and amounts of HACE. Tensile Strength Elongation Comparision (MPa) (%) 1a HO-PIB-OH(3.5K, 70%)/HMDI + 17.4 480 HDO = 30% 2a NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 19.0 310 HDO = 30% 3a NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 24.2 570 HDO + BG.sub.9(0.65K, 5.2%) = 30% PIB-4 NH.sub.2-PIB-NH.sub.2(3.5K, 70%)/HMDI + 24.1 671 HDA + BG.sub.9(0.65K, 14.0%) = 30%

(32) The thermal stability of a representative polyurea-urethane was investigated by TGA. FIG. 4 shows the TGA trace of PIB-4 in air indicating 1 and 5% weight loss at 234 and 273 C., respectively. The trace indicates a two step degradation pattern. The first step at 270 C. denotes the degradation of urea and/or urethane linkages, while the second step at 350 C. indicates the degradation of the soft PIB segment. Because the T.sub.flow of PIB-4 is 178 C., this polyurea is expected to be thermally processable in the 178 to 234 C. range without degradation.

(33) FIG. 5 shows idealized micromorphologies of polyureas in the absence and presence of HACE. The conventional polyurea (sketch on the left) contains many strong H-bonds between the urea units and consequently its T.sub.flow is high, which obviates thermal proccessability. In contrast, the H-bond system in polyureas prepared with polycarbonate- or polyether-based HACE is looser (sketch on the right), which lowers the T.sub.flow and leads to thermal proccessability. In the presence of HACEs, H-bonds form not only between the urea groups but also between the urea groups and HACEs, i.e., the HACEs and urea groups compete for H-bonding. The H-bonds due to HACEs help to flexibilize the hard segments, improve mechanical properties, and reduce T.sub.flow (impart thermal proccessability).

(34) The chemical structures of PTMO and BG.sub.9 are essentially identical except the latter is of much lower molecular weight (1000 g/mol vs 650 g/mol). It was shown that the mechanical properties of polyurethanes do not improve with a HACE whose molecular weight is higher than 650 g/mol. Although the structures of BG.sub.9 and the conventional CE, 1,4-butane diol, are quite similar, the latter (with Mn=90 g/mol) does not improve mechanical properties when used as a HACE and is therefore considered only a CE. At the same hard segment content, 1,4-butane diol produces a larger number of urethane linkages than that of the higher molecular weight BG.sub.9. The increased number of urethane linkages produces more H-bonding, which in turn leads to more rigid hard segments, undesirable high phase separation, and thus, to elevated T.sub.flow. It was suggested that for a HACE to be efficient its molecular weight must be higher than 150 g/mol.

(35) The role of HACEs is fundamentally different in PTMO- and PIB-based polyureas: whereas, in PTMO-based polyureas, HACEs loosen the strong H-bonding between the urea units and thus decrease T.sub.flow, in PIB-based polyureas, HACEs flexibilize the hard segments and thus improve mechanical properties.

(36) In light of the foregoing, it should now be evident how polyureas can be rendered melt processable. Heretofore, polyureas were not melt processable because of the presence of strong H bonds in the hard segments which resulted in the thermal degradation of the product upon heating to temperature of 240 C. or more. By adding HACEs to the polyurea groups in the hard segments, either in combination with or separately from conventional CEs, a more flexible hard segment can be attained, or strong H-bond loosened, thus, decreasing T.sub.flow. It has been found that by the addition of 2 to 15 percent of HACEs to the system in polyureas can redistribute the H-bonding patterns such that the T.sub.flow of the elastomer is reduced to about 170 to 200 C., which allows for convenient thermal processing and still maintains excellent mechanical properties similar to those of polyureas produced by solution processing. The beneficial effect of HACEs has been demonstrated with PTMO- and PIB-base polyureas and polyurea-urethanes, both containing at least 30 percent hard segments.

(37) Although the present invention has been described in considerable detail with reference to certain embodiments, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.