BLOW-MOLDABLE RIGID THERMOPLASTIC POLYURETHANE RESINS

Abstract: A rigid thermoplastic polyurethane with improved melt strength can be prepared by deactivating the catalyst for the polymer subsequent to the onset of urethane bond formation. Catalyst deactivation is accomplished either with a latent deactivator for the catalyst, or an active deactivator. The further addition of a crosslinker to the reaction mixture can provide an even greater improvement of melt strength.

Description: 96/23826 BLOW-MOLDABLE RIGID THERMOPLASTIC POLYURETHANE RESINS This invention relates to a blow-moldable rigid thermoplastic polyurethane resin and a method for preparing same. There is a potentially large market for blow-molded grade rigid thermoplastic polyurethane resins (RTPUs), such as ISOPLAST 7 " engineering thermoplastic resins, if such resins could be obtained with sufficiently increased melt strength over current resins. Catalysts which are typically used to promote polymerization to form RTPUs also contribute to depolymerization at temperatures where blow-molding is ordinarily carried out. This depolymerization results in a reduction in melt strength, which is undesirable for blow-molded grade RTPUs. Laughner, in U.S. Patent No. 5,094,806, describes a method of improving melt strength of a variety of thermoplastic polyurethane resins through addition of a small amount of a fluorinated olefinic polymer or copolymer and, optionally, an impact modifier. Unfortunately, these f luorinated polymers are expensive and somewhat difficult to handle. It would be desirable, therefore, to provide a blow-moldable RTPU which is inexpensive and easy to scale up. The present invention is a blow-moldable rigid thermoplastic polyurethane composition comprising a thermoplastic polyurethane resin having a T g of greater than 50°C, a deactivatable catalyst, and a deactivator for the deactivatable catalyst. In another aspect, the present invention is a process for preparing a blow- -moldable rigid thermoplastic polyurethane resin having a T g of greater than 50°C, which process comprises reacting together a diol chain extender having a molecular weight of not more than 300; optionally a high molecular weight glycol having a molecular weight in the range of 500 to 8000; a diisocyanate, wherein the NCO/OH equivalence ratio ranges from 0.95: 1 to 1.05: 1 ; a sufficient quantity of a deactivatable catalyst to catalyze the reaction between the NCO groups and the OH groups to form urethane groups; and in the presence of a sufficient quantity of a latent deactivator for the catalyst to inhibit a depolymerization of the urethane groups. In yet another aspect, the invention is a process for preparing a blow-moldable rigid thermoplastic polyurethane resin having a T g of greater than 50°C which comprises the steps of: a) reacting together a diol chain extender having a molecular weight of not more than 300; optionally a high molecular weight glycol having a molecular weight in the range of 500 to 8000; a diisocyanate, wherein the NCO/OH equivalence ratio ranges from 0.95: 1 to 1.05: 1 ; a sufficient quantity of a deactivatable catalyst to catalyze the reaction between the NCO groups and the OH groups to form urethane groups; and b) adding a sufficient quantity of an active deactivator for the catalyst to inhibit a depolymerization of the urethane groups. The blow-moldable compositions of the present invention are useful in the production of a variety of molded or shaped articles, such as bottles and other containers, and components for use in the transportation and appliance industries. The term RTPU is used herein to refer to a rigid thermoplastic polyurethane which has a T g (glass transition temperature) of at least 50°C. The RTPU contains a hard segment derived from the reaction of a diisocyanate and a diol chain extender having a molecular weight of not more than 300. The hard segment content of the RTPU is sufficiently high to o produce a resin having a T g of greater than 50°C, and preferably constitutes from 75, more preferably from 90, to 100 weight percent of the RTPU. Preferred diisocyanates include aromatic, aliphatic, and cycloaliphatic diisocyanates and combinations thereof. Representative examples of these preferred diisocyanates can be found, for example, in U.S. Patent Nos. 4,385,133; 4,522,975; and 5 5,167,899. More preferred diisocyanates include 4,4'-diisocyanatodiphenylmethane, p-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, and 2,4-toluene diisocyanate, or mixtures thereof. More preferred are 4,4'-diisocyanatodicyclohexylmethane and 0 4,4'-diisocyanatodiphenylmethane. Most preferred is 4,4'-diisocyanatodiphenylmethane. Preferred chain extenders are ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, diethylene glycol, tetraethylene glycol, neopental glycol, 1 ,4-cyclohexanedimethanol, 1 ,4-bishydroxyethylhydroquinone, and mixtures thereof. More preferred chain extenders are 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, 5 and mixtures thereof. The RTPU may optionally contain blocks derived from a high molecular weight glycol having a molecular weight from 500, preferably from 1000, and more preferably from 1500, to 8000, preferably to 6000, and more preferably to 5000. These high molecular weight glycol blocks constitute a sufficiently low fraction of the RTPU such that the T g of the RTPU is 0 above 50°C. Preferably, the high molecular weight glycol blocks constitute from 25, and more preferably from 10, to 0 weight percent of the RTPU. The high molecular weight glycol is preferably a polyester glycol or a polyether glycol or a combination thereof. Examples of preferred polyester glycols and polyether glycols include polycaprolactone glycol, polyoxyethylene glycol, polyoxypropylene glycol, 5 polyoxytetramethylene glycol, polyethylene adipate, polybutylene adipate, polyethylene- -butylene adipate, and poly(hexamethylene carbonate glycol), or combinations thereof. The NCO/OH ratio varies from 0.95: 1, pre erably from 0.975 : 1 , and more preferably from 0.985: 1 , to 1.05: 1 , preferably to 1.025: 1, and more preferably to 1.015: 1. The process of the present invention is carried out in the presence of a deactivatable catalyst. The term deactivatable catalyst is used to refer to any catalyst that can promote the reaction of the isocyanate and OH groups to form urethane linkages, and one that can be quenched or rendered inactive by a deactivator for the catalyst, so that depolymerization of the urethane linkages is suppressed, and, consequently, melt strength is improved. Examples of deactivatable catalysts include Sn+ 2 and Sn + 4 based organotin catalysts, such as stannous octoate and dimethyltin dimercaptide, with stannous octoate being especially preferred. The catalyst is used in sufficient quantities to catalyze the reaction between the o NCO groups from the polyisocyanate and the OH groups from the chain extender or the high molecular weight glycol. Preferably, the amount of catalyst ranges from 0.01 , more preferably 0.02, and most preferably 0.05 to 2, more preferably 1 , and most preferably 0.5 weight percent based on the weight of polyisocyanate, chain extender, and high molecular weight glycol. The deactivator for the catalyst may be added to a mixture containing the 5 reactants, (that is, the diisocyanate, the chain extender, the deactivatable catalyst, and optionally the high molecular weight diol) or a polymer, or a prepolymer formed therefrom, under such conditions to produce an RTPU with improved melt strength. Preferably the deactivator for the catalyst is added in a latent form to a mixture containing the reactants. The term latent is used herein to refer to a deactivator that is initially protected from deactivating 0 the catalyst. This latent or delayed deactivation can be achieved, for example, by granular encapsulation of the deactivator in a soft polymeric protective medium, such as a thermoplastic polyurethane having a T g less than 25 G C. The latent deactivator is preferably fed, along with the reactants, through a reactive zone, preferably a reactive extruder, more preferably a co-rotating, self-wiping twin 5 screw extruder, where the deactivator is released when the reaction has proceeded to such a degree that the exotherm and high viscosity of the reacting polymer cause the soft polymeric coating to melt. The blow-moldable RTPU pellets thusly formed contain deactivated catalyst. Alternatively, latent catalyst may also be dry-blended, preferably as pellets, with already extruded RTPU polymer or prepolymer. When a dry-blending process is used, the 0 deactivatable catalyst is still active until the mixture of the RTPU polymer or prepolymer and latent catalyst is blow-molded. The deactivator may also be added in active form subsequent to the onset of polymerization, for example, downstream of the reactive extruder through a vent port. The deactivator is used in a sufficient quantity to suppress a depolymerization of 5 urethane linkages, consequently improving the melt strength of the resin. Preferably, the amount of deactivator for the catalyst ranges from 0.05, more preferably 0.1 , and most preferably 0.3, to 5, more preferably 2, and most preferably 1 weight percent based on the weight of polyisocyanate, chain extender, and high molecular weight glycol. Examples of deactivators for the catalyst include acids, such as phosphoric acid; phosphites, such as poly(dipropylene glycol) phenyl phosphite, diisooctyl phosphite, distearyl phosphite, trilauryl phosphite, trisnonylphenyl phosphite, and trisphenyl phosphite; and antioxidant metal deactivators, such as hindered phenolic polyamines, hindered phenolic hydrazines, and hindered phenolic oxamides. Representative examples of metal deactivators include 1 ,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazine (also known as IRGANOX'" MD-1024 metal deactivator, Trademark of Ciba-Geigy) and 2,2'-oxamido-bis-ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate (also known as NAUGARD'" XL-1 high performance phenolic antioxidant/metal deactivator, Trademark of Uniroyal Chemical). 1 ,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazine is a preferred deactivator. A crosslinker can be advantageously added to the mixture to further improve melt strength. The crosslinker is a high molecular weight polyol or polyamine having a functionality of greater than 2, preferably a functionality of 3 or 4. Examples include polypropylene oxide based polyether triol, polypropylene oxide based polyether tetraol, and polypropylene oxide based polyether triamine. The crosslinker is added at a sufficiently high level to improve melt strength, but sufficiently low to avoid gelling, preferably at a concentration ranging from 0.005, more preferably from 0.01 , to 0.1 , more preferably to 0.05 equivalent per equivalent of chain extender. The molecular weight of the crosslinker is typically in the range of 250, more preferably 500, to 1000, more preferably 750. A preferred crosslinker is a polypropylene oxide based polyether triol, such as VORANOL'" 2070 triol and VORANOL" 2025 triol (Trademark of The Dow Chemical Company). The RTPU of the present invention can be prepared by any suitable process, but is most preferably prepared by a continuous one-shot process wherein the diisocyanate, the chain extender, the deactivatable catalyst, the latent deactivator for the catalyst, the crosslinker, and optionally the high molecular weight glycol are first fed into and mixed in a mixing device, such as a co-rotating, self-wiping twin screw extruder. After a short period, typically less than one minute, the feed material is then delivered through a heated zone and polymerized. The invention disclosed herein suitably may be practiced in the absence of any component not specifically disclosed herein. Procedure for Determining Melt Strength of an ISOPLAST'" Engineering Thermoplastic Resin ISOPLAST'" 101 E engineering thermoplastic resin is evaluated for blow-moldability by a melt strength test, wherein a dried tensile bar of the resin is suspended in an oven at 200°C for 5 minutes. A weight is attached to the bar and a change in length (the percent elongation) is measured as a function of the suspended weight. Samples with the smallest percent elongation demonstrate the greatest melt strength, and therefore, the best blow-moldability. Table I illustrates the affect of a deactivator for a catalyst (IRGANOX'" MD- 1024), a crosslinker (VORANOL'" 2070 triol), or the combination, on the melt strength of the resin prepared with either a Sn + 2 based catalyst (stannous octoate), or a Sn + 4 based catalyst (dimethyltin dimercaptide). The deactivator is 30 percent active, and encapsulated in a PELLETHANE™ polyurethane elastomer (Trademark of The Dow Chemical Company). Table I Melt Strength Test of ISOPLAST 1 " 101E Engineering Thermoplastic Resin at 200°C Load Elongation Example Catalyst* Deactivator2 Crosslinker3 (g) (%) 1 0.06Z 0.6% - 4 16 UL-22 14 44 2 0.062 0.02 34 13 stannous 84 31 octoate 114 50 3 0.06% 0.3% 0.015 65 0 stannous 115 6 octoate 165 6 4 0.06% 0.1% 66 7 stanndus 116 13 octoate 166 24 Comparative 0.06% - - 4 100 A UL-22 Comparative 0.062 4 0 B stannous 34 16 octoate 64 34 iFOMREZ™ UL-22 (Trademark of itco Corp.) is a dimethyltin dimercaptide based catalyst. 2 Weight percent IRGANOX™ MD-1024 based on weight of the resin. 3Equivalents of VORANOL™ 2070 triol per equivalent of hexanediol in the resin.

Claims: CLAIMS: 1. A blow-moldable rigid thermoplastic polyurethane comprising a thermoplastic polyurethane resin having a T g of greater than 50°C, a deactivatable catalyst, and a deactivator for the deactivatable catalyst. 2. The blow-moldable rigid thermoplastic polyurethane according to Claim 1 wherein the deactivator for the catalyst is selected from hindered phenolic hydrazines and hindered phenolic oxamides. 3. The blow-moldable rigid thermoplastic polyurethane as in Claim 1 or 2 o which contains at least one block derived from a polypropylene oxide triol, a polypropylene oxide tetraol, a polypropylene oxide triamine, or a polypropylene oxide tetraamine. 4. The blow-moldable rigid thermoplastic polyurethane resin as in one of Claims 1-3 which comprises 0.005 to 0.1 equivalent of blocks derived from a polypropylene oxide based polyether triol having a molecular weight in the range of 250 to 1000 per 5 equivalent of diol chain extender blocks in the rigid thermoplastic polyurethane. 5. The blow-moldable rigid thermoplastic polyurethane resin as in one of Claims 1-4 wherein the deactivatable catalyst is stannous octoate. 6. The blow-moldable rigid thermoplastic polyurethane resin according to Claim 5 wherein the concentration of the stannous octoate is 0.01 to 1 weight percent based on o the weight of the resin. 7. The blow-moldable rigid thermoplastic polyurethane resin as in any of Claims 1-6 wherein the concentration of the deactivator for the catalyst is 0.1 to 5 weight percent based on the weight of the resin. 8. The blow-moldable rigid thermoplastic polyurethane resin as in any of 5 Claims 1-7 wherein the deactivator for the catalyst is 1 ,2-bis(3,5-di-tert-butyl- -4-hydroxy-hydrocinnamoyl)hydrazine or 2,2'-oxamido-bis-ethyl 3-(3,5-di-tert-butyl-4- -hydroxyphenyl)proprionate. 9. A process for preparing a blow-moldable rigid thermoplastic polyurethane resin having a T g of greater than 50°C, which process comprises reacting together a diol chain 0 extender having a molecular weight of not more than 300; up to 25 weight percent based on the weight of total reactants of a high molecular weight glycol having a molecular weight of 500 to 8000; a diisocyanate, wherein the NCO/OH equivalence ratio ranges from 0.95: 1 to 1.05: 1 ; and a sufficient quantity of stannous octoate to catalyze the reaction between the NCO groups and the OH groups to form urethane groups; and in the presence of a sufficient 5 quantity of a latent deactivator for the catalyst to inhibit a depolymerization of the urethane groups. 10. A process for preparing a blow-moldable rigid thermoplastic polyurethane resin having a T g of greater than about 50°C which comprises the steps of: a) reacting together a diol chain extender having a molecular weight of not more than 300; optionally a high molecular weight glycol having a molecular weight in the range of about 500 to about 8000; a diisocyanate, wherein the NCO/OH equivalence ratio ranges from 0.95: 1 to 1.05: 1 ; in the presence of a sufficient quantity of a deactivatable catalyst to catalyze the reaction between the NCO groups and the OH groups to form urethane groups; and b) adding a sufficient quantity of an active deactivator for the catalyst to inhibit a depolymerization of the urethane groups.

Inventors: EHRLICH BENJAMIN S, MISTRY GARY S, ORIANI STEVEN R, WANG KUAN J, EHRLICH, BENJAMIN, S., MISTRY, GARY, S., ORIANI, STEVEN, R., WANG, KUAN, J.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1996
Main classification: C08G18
IPC codes: B29C49, B29K75, C08G18