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United States Patent (19) 11 Patent Number: 5,821,316
Quay et al. (45) Date of Patent: Oct. 13, 1998
54 POLYURETHANE PREPOLYMERS FOR FOREIGN PATENT DOCUMENTS
MAKING ELASTOMERS HAVING
IMPROVED DYNAMIC PROPERTIES 0573206 12/1993 European Pat. Off..
OTHER PUBLICATIONS
75 Inventors: Jeffrey Raymond Quay, Kutztown;
Edwin Lee McInnis. Allentown, both Chen, et al. “Proceedings Polyurethane World Congress
of Pa. s s 1993–Oct. 10–13, 1993, pp. 388-399.
Cliff, Susan M., “Designing Polyurethane Elastomers for
73 Assignee: Air Products and Chemicals, Inc., Dynamic Applications' presented at the PMA Meeting, Oct.
Allentown, Pa. 1991.
Primary Examiner John M. Cooney, Jr.
21 Appl. No.: 788,308 Attorney, Agent, or Firm Michael Leach
22 Filed: Jan. 24, 1997 57 ABSTRACT
51 Int. Cl. ........................ C08G 18/10; CO7C 261/00 An isocyanate-terminated polyurethane prepolymer com
52 U.S. Cl. ................................. 528/64; 560/25; 560/26; prising the reaction product of a polyisocyanate and a polyol
560/115; 560/158; 560/330; 560/355; 560/358; composition consisting essentially of a polyether polyol of
560/359; 560/360 350-2000 equivalent weight and a low molecular weight
58 Field of Search ................................. 528/64; 560/25, polyol of 62 to<300 molecular weight, in an equivalent ratio
560/26, 115, 158,330, 355, 358, 359, 360 of low molecular weight polyol to polyether polyol of
0.25-2.7:1. A polyurethane-urea elastomer having good
56) References Cited dynamic properties can be prepared by reacting the
U.S. PATENT DOCUMENTS isocyanate-terminated prepolymer with aromatic amine
chain extender at an equivalent ratio of 0.9–1.1:1.
3,963,681 6/1976 Kaneko et al..
4,786,703 11/1988 Starner et al. ............................ 528/64 19 Claims, 2 Drawing Sheets
U.S. Patent Oct. 13, 1998 Sheet 1 of 2 5,821,316
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TABLE 1.
EXAMPLES 1. 2 3 4 5 6 7
65
5,821,316
S 6
Tripropylene glycol (TPG)-Mw. 192, Dow Chemical Co. which is Surprising Since one would expect the performance
Arcol PPG-1025-OHit 112.4, Arco Chemical Co., 1000 to be between that of Example 4 (PPG) and Example 3
mol wt PPG diol (PTMEG). Examples 6 and 7 show a further reduction in the
Arcol PPG-2025-OHif 55.6, Arco Chemical Co., 2000 mol peak loSS compliance and remain low throughout the region.
wt PPG diol Chen et. al Show that dynamic properties can be obtained
FormreZ ET-3500–OHit 46.7, Witco Chemical Co., 3500 with PPG systems which are comparable to PTMEG by
mol wt PPG triol using a higher molecular weight PPG polyol and increasing
PTMEG-1000–1000 mol wit poly(tetramethylene ether) the amount of unreacted isocyanate in the System. They
glycol (diol), OH# 114.3) indicate the higher the molecular weight of the PPG polyol,
PTMEG-2000–2000 mol wit poly(tetramethylene ether) the better the dynamic properties. The present invention
glycol (diol), OHH 56.0) shows that dynamic performance can be had which is
AcclaimTM 3201-3000 mol wit poly(ethylene oxide)-co Superior to all PTMEG systems and the Chen et. al systems
by using a specific range of low molecular weight polyol.
poly(propylene oxide) diol, OH# 37.8 There is no need to resort to higher levels of unreacted
AcclaimTM 4200-4000 mol wit poly(propylene oxide) diol, diisocyanate monomer in the prepolymer in order to obtain
OHit 28.1 15 the good properties. The present invention also shows that
Elastomer Preparation by going too high in PPG molecular weight or adding too
The prepolymer was heated to 75 C. and degassed. much low molecular weight polyol, the dynamic properties
Methylenebisorthochloroaniline MOCA was melted at of the system will suffer.
120° C. and added at 95% stoichiometry. The material was STATEMENT OF INDUSTRIAL APPLICATION
hand mixed and degassed. The mixture was poured into a
/16th inch (0.16 cm) mold which had been preheated to 100° The invention provides for the production of lower cost
C. Plaques were post cured at 100° C. for 16 hours. The polyurethane elastomers which can be used for tire, wheel,
plaques were then placed in a constant temperature and roller, belting, and other applications which require good
humidity room for 2 weeks before testing. Dynamic dynamic properties.
Mechanical Spectroscopy DMS was obtained using a 25 We claim:
Rheometrics Solids Analyzer in tensile configuration. All 1. An isocyanate-terminated polyurethane prepolymer
measurements were performed at a frequency of 1 Hz. The comprising the reaction product of a polyisocyanate and a
Samples were quenched to -150° C. and measured isother polyol composition having a hydroxyl functionality of at
mally in 8 C. increments with a 1 minute Soak time at each least 1.9 and consisting essentially of a polyether polyol of
step. Table 1 shows the Shore A and D hardness values for 350-2000 equivalent weight prepared from ethylene oxide
the elastomers of Examples 1-7. or propylene oxide, or blends thereof, and a low molecular
FIGS. 1 and 2 present the loss compliance data for the weight polyol of 62 to <300 molecular weight, which is
elastomers of Examples 1-7 with Examples 5, 6 and 7 being Selected from the group consisting of ethylene glycol, pro
within the scope of the invention. Table 2 presents loss pylene glycol, butane diol, trimethylol propane,
compliance data at 0°C., 25° C. and 130° C. Note that Table 35 pentaerythritol, poly(tetramethylene oxide) oligomer, dieth
1 shows all of the elastomers have approximately the same ylene glycol, triethylene glycol, dipropylene glycol and
hardness and %NCO content as these variable often effect tripropylene glycol, in an equivalents ratio of low molecular
the DMS performance. weight polyol to polyether polyol of 0.25-2.7:1.
2. The prepolymer of claim 1 in which the equivalents
TABLE 2 40 ratio of low molecular weight polyol to polyether polyol is
1-2.5:1.
LOSS COMPLIANCE D" x 10' 3. The prepolymer of claim 1 in which the equivalents
EXAMPLE O C. 25° C. 130° C. ratio of low molecular weight polyol to polyether polyol is
1.8-2.4:1.
1. 4.OO 3.89 8.83 45 4. The prepolymer of claim 1 in which the polyol com
2 4.90 4.54 12.8
3 13.6 13.7 1.77 position contains up to 70 wt % poly(tetramethylene ether)
4 7.75 31.9 2.57 based polyol of 300-2000 equivalent weight.
5 10.2 7.82 1.32 5. The prepolymer of claim 1 in which the polyether
6
7
6.39
6.49
6.30
6.38
2.33
3.93
polyol is a poly(ethylene oxide) glycol, a poly(propylene
50 oxide) glycol, a poly(propylene oxide)-co-poly(ethylene
oxide) glycol, a poly(propylene oxide) tipped with poly
Example 4 has a very large loSS compliance peak which (ethylene oxide), or mixtures thereof.
indicates that it will have a high heat build up upon dynamic 6. The prepolymer of claim 1 in which the polyether
loading. This is typical of PPG based prepolymers. Example polyol is a poly(ethylene oxide) glycol or a poly(propylene
3, based on PTMEG, has a much lower loss compliance peak 55 oxide) glycol.
and is lower throughout the temperature range of interest. 7. The prepolymer of claim 1 in which the polyether
Example 3 is typical of a prepolymer with good dynamic polyol is a poly(ethylene oxide) glycol or a poly(propylene
properties and is the best polyether System currently avail oxide) glycol and the polyol composition also comprises up
able. Examples 1, 2, 5, 6 and 7 all have lower loss compli to 70 wt % poly(tetramethylene ether) glycol of 300–2000
ance peaks than Example 3 which would not be predicted. 60 equivalent weight.
However, Examples 1 and 2 have additional peaks in the 8. The prepolymer of claim 7 in which equivalents ratio
higher temperature (higher frequency) regions of the curve. of the low molecular weight polyol to polyether polyol is
Since the tendency is for the part to heat up under dynamic 1-2.5:1 and the low molecular weight polyol is diethylene
loads which will shift the response toward this area of glycol, triethylene glycol, dipropylene glycol or tripropylene
increased heat loSS, these Systems are not Suitable for most 65 glycol.
dynamic applications. Example 5 shows a slight improve 9. The prepolymer of claim 8 in which the polyisocyanate
ment (improvement in loss compliance) over Example 3 is toluene diisocyanate, the low molecular weight polyol is
5,821,316
7 8
tripropylene glycol and the polyol composition comprises 16. A polyurethane-urea elastomer prepared by reacting
less than 60 wt % of the poly(tetramethylene ether) glycol. an isocyanate-terminated prepolymer of claim 1 with an
10. A method for preparing an isocyanate-terminated aromatic amine chain extender at an equivalent ratio of
polyurethane prepolymer having an NCO content of 3–7 wt prepolymer to chain extender of 0.9-1.1:1, the chain
% by reacting a polyisocyanate and a polyol composition in extender being 4,4'-methylene-bis(o-chloroaniline); 4,4'-
an NCO: OH equivalent ratio of 1.5 and removing the methylene-bis-(3-chloro-2,6-diethylaniline); dimethylthio
exceSS unreacted polyisocyanate to <1 wt %, characterized in toluenediamine, trimethyleneglycol di-p-aminobenzoate;
that the polyol composition consists essentially of a poly 1,2-bis(2-amino-phenylthio)ethane; 4,4'-methylene-bis
ether polyol of 350-2000 equivalent weight prepared from aniline; diethyltoluene diamine; 5-tert-butyl-2,4-
ethylene oxide or propylene oxide, or blends thereof, and a toluenediamine, 3-tert-butyl-2,6-toluenediamine; 5-tert
amyl-2,4-toluenediamine, 3-tert-amyl-2,6-toluenediamine,
low molecular weight polyol of 62 to <300 molecular weight, or chlorotoluenediamine.
which is Selected from the group consisting of ethylene 17. A polyurethane-urea elastomer prepared by reacting
glycol, propylene glycol, butane diol, trimethylolpropane, an isocyanate-terminated prepolymer of claim 7 with an
pentaerythritol, poly(tetramethylene oxide) oligomer, dieth aromatic amine chain extender at an equivalent ratio of
ylene glycol, triethylene glycol, dipropylene glycol and 15
tripropylene glycol, in an equivalents ratio of low molecular prepolymer to chain extender of 0.9-1.1:1, the chain
weight polyol to polyether polyol of 0.25-2.7:1. extender being 4,4'-methylene-bis(o-chloroaniline); 4,4'-
11. The method of claim 10 in which the polyether polyol methylene-bis-(3-chloro-2,6-diethylaniline); dimethylthio
is a poly(ethylene oxide) glycol or a poly(propylene oxide) toluenediamine, trimethyleneglycol di-p-aminobenzoate;
glycol and the polyol composition comprises 0 to 70 wt % 1,2-bis(2-amino-phenylthio)ethane; 4,4'-methylene-bis
poly(tetramethylene ether) glycol of 300-2000 equivalent aniline; diethyltoluene diamine; 5-tert-butyl-2,4-
weight. toluenediamine, 3-tert-butyl-2,6-toluenediamine; 5-tert
12. The method of claim 11 in which the polyisocyanate amyl-2,4-toluenediamine, 3-tert-amyl-2,6-toluenediamine,
or chlorotoluenediamine.
is toluene diisocyanate, diphenylmethane diisocyanate, 18. A polyurethane-urea elastomer prepared by reacting
polymeric diphenylmethane diisocyanate, cyclohexane 25
an isocyanate-terminated prepolymer of claim 8 with an
diisocyanates, isophorone diisocyanates, naphthalene
diisocyanate, phenylene diisocyanate or mixtures thereof. aromatic amine chain extender at an equivalent ratio of
13. A method for preparing an isocyanate-terminated prepolymer to chain extender of 0.9-1.1:1, the chain
polyurethane prepolymer having an NCO content of 3–7 wt extender being 4,4'-methylene-bis(o-chloroaniline); 4,4'-
% by reacting toluene diisocyanate and a polyol composition methylene-bis-(3-chloro-2,6-diethylaniline); dimethylthio
in an NCO:OH equivalent ratio of 3-10:1 and removing the toluenediamine, trimethyleneglycol di-p-aminobenzoate;
exceSS unreacted toluene diisocyanate to <0.25 wt %, char
1,2-bis(2-amino-phenylthio)ethane; 4,4'-methylene-bis
acterized in that the polyol composition consists essentially aniline; diethyltoluene diamine; 5-tert-butyl-2,4-
of a polyethylene or polypropylene glycol of 500-1000 toluenediamine; 3-tert-butyl-2,6-toluenediamine; 5-tert
equivalent weight and a low molecular weight polyol of 62 35
amyl-2,4-toluenediamine, 3-tert-amyl-2,6-toluenediamine,
or chlorotoluenediamine.
to-200 molecular weight, which is Selected from the group 19. A polyurethane-urea elastomer prepared by reacting
consisting of ethylene glycol, propylene glycol, butane diol, an isocyanate-terminated prepolymer of claim 9 with an
trimethylolpropane, pentaerythritol, poly(tetramethylene aromatic amine chain extender at an equivalent ratio of
oxide) oligomer, diethylene glycol, triethylene glycol, dipro prepolymer to chain extender of 0.9-1.1:1, the chain
pylene glycol and tripropylene glycol, in an equivalents ratio 40
extender being 4,4'-methylene-bis(o-chloroaniline); 4,4'-
of low molecular weight polyol to polyether glycol of methylene-bis-(3-chloro-2,6-diethylaniline); dimethylthio
1-2.5:1, the polyol composition containing 0 to less than 60 toluenediamine, trimethyleneglycol di-p-aminobenzoate;
wt % poly(tetramethylene ether) based polyol of 300–2000 1,2-bis(2-amino-phenylthio)ethane; 4,4'-methylene-bis
equivalent weight. aniline; diethyltoluene diamine; 5-tert-butyl-2,4-
14. The method of claim 13 in which the low molecular 45
weight polyol is diethylene glycol, triethylene glycol, dipro toluenediamine, 3-tert-butyl-2,6-toluenediamine; 5-tert
pylene glycol or tripropylene glycol. amyl-2,4-toluenediamine, 3-tert-amyl-2,6-toluenediamine,
or chlorotoluenediamine.
15. The method of claim 14 in which the polyol compo
Sition contains a poly(tetramethylene ether) polyol. k k k k k