JP3326176B2 - Hard thermoplastic polyurethane elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic polyurethane ("TPU") elastomers and polyurea elastomers having high hardness, and more particularly to low unsaturation levels controlled using double metal cyanide complex catalysts. The present invention relates to the production of an elastomer using a polyol mixture containing a polyol.

The use of double metal cyanide (so-called "DMC") catalysts in the preparation of high molecular weight polyols is well established in the art. For example, U.S. Pat. No. 3,829,505, assigned to General Tire & Rubber, discloses the preparation of high molecular weight diols, triols and the like using these catalysts.
Polyols prepared using these catalysts are produced to have higher and lower amounts of terminal unsaturated groups than those prepared using commonly used KOH catalysts. The '505 patent discloses that these high molecular weight polyol products are used to prepare non-ionic surfactants, lubricants and coolants, fabric glues, packaging films, as well as to prepare hard or flexible polyurethanes by reaction with polyisocyanates. It is disclosed that it is effective.

Certain thermoset polyurethane elastomers made with DMC-catalyzed triols are also known. In particular, U.S. Pat. No. 4,242,490 uses a prepolymer process or a "one-shot"
The catalyst is adjusted to react polypropylene ether triol having a molecular weight of 7,000 to 14,000, ethylene glycol and toluene diisocyanate in a specific range of molar ratio,
The preparation of such elastomers is disclosed.

The methodology of TPU elastomer preparation is well established in the art. By way of illustration, U.S. Pat.No. 4,202,957
Discloses a polyether-based polyurethane elastomer made using a selected group of polypropylene oxide-polyethylene oxide block copolymers, which polyurethanes are thermoplastic, recyclable and resistant to high temperature degradation. And enables injection molding.

As another illustration, U.S. Pat. No. 5,096,993 discloses the preparation of a TPU elastomer made using a DMC-modified polyether polyol. These elastomers are disclosed in the '993 patent as having excellent physical and chemical properties.

Hard TPU elastomers have a hardness ranging between 75 Shore A and approximately 75 Shore D, but unfortunately, DMC
-Hard TPU elastomers prepared according to the prior art means using controlled polyols are usually not easily extruded into articles of the desired shape. Therefore, a new methodology for producing hard elastomers having excellent physical and chemical properties produced using DMC-modified polyols as an easily extrudable elastomer-forming composition has been strongly desired by the elastomer manufacturing industry. . The present invention provides such an expected methodology.

In one aspect, the present invention provides a method for preparing a first polyol and a second polyol.
Prepared by reacting a polyol, a mixture of polyether polyols consisting of the following polyols, diisocyanates with a difunctional isocyanate-reactive chain extender in a "one-shot" process, preferably a continuous one-shot process. Thermoplastic polyurethane or polyurea elastomers. First
The polyol is prepared using a double metal cyanide complex catalyst and has a molecular weight of about 1,000 to 5,000 (conveniently, 1,500 to 2,500), and the first polyol has a molecular weight of 0.04 meq / g or less of polyol (preferably, (0.02 or less, more preferably 0.01 or less). The second polyol is a polyether polyol having an average molecular weight of about 1,000 to 20,000 (conveniently 1,000 to 4,000, more conveniently 1,000 to 4,000);
Is present in an amount of about 5 to 50% based on the weight of the polyol mixture. However, the average molecular weight of the second polyol is different from the average molecular weight of the first polyol, and the polydispersity of the polyol mixture is larger than the polydispersity of the first polyol. The polydispersity of the mixture is about 1.05-3.0 (preferably 1.1-1.
5, more preferably 1.1 to 1.2). The equivalent ratio of the NCO group of the diisocyanate to the active hydrogen of the polyol and the chain extender is about 1: 0.7 to 1: 1.3 (preferably 1: 0.9 to
0.9: 1, more preferably 1: 0.95 to 0.95: 19, and the molar ratio of chain extender to polyol is about 0.15: 1 to 75: 1. The elastomer has a hardness of from 75 Shore A (preferably 80 or more) to about 75 Shore D (preferably 65 or less, more preferably 55 or less). Preferably, the first
The polyol and the second polyol are each a polyether diol.

In another aspect, the invention is directed to a thermoplastic polyurethane or polyurea prepared by the reaction of an isocyanate-terminated prepolymer with a bifunctional isocyanate-reactive chain extender. The isocyanate-terminated prepolymer is the reaction product of a polyisocyanate and a polyol mixture of a polyether polyol comprising a first polyol and a second polyol. The first polyol is prepared using a mixture of double metal cyanide complex, and has a
5,000 (1,500-4,000 for convenience, 1,500 for more convenience
2,500) and the first polyol is less than 0.04 milliequivalents per gram of polyol (preferably 0.02
And more preferably 0.01 or less). The second polyol is about 1,000-20,000
(1,000-4,000 for convenience, 1,000-4.0 for more convenience
00), wherein said second polyol is present in an amount of about 5 to 50% based on the weight of said polyol mixture. However, the average molecular weight of the second polyol is different from the average molecular weight of the first polyol, and the polydispersity of the polyol mixture is larger than the polydispersity of the first polyol. The dispersibility is 1.09 to 3.0 (preferably 1.1 to 1.
5, more preferably 1.1 to 1.2). The equivalent ratio of the NCO group of the diisocyanate to the active hydrogen of the polyol and the chain extender is about 1: 0.7 to 1: 1.3 (preferably 1: 0.9 to 0.
9: 1, more preferably 1: 0.95 to 0.95: 1), and the molar ratio of chain extender to polyol is about 0.15: 1 to 75: 1. The elastomer has a hardness of from 75 Shore A (preferably 80 or more) to about 75 Shore D (preferably 65 or less, more preferably 55 or less). Preferably, each of the first polyol and the second polyol is a polyether diol.

In yet another aspect, the present invention is a method for producing a thermoplastic elastomer, comprising: (a) producing a polyol mixture of a polyether polyol comprising a first polyol and a second polyol, wherein the first polyol is a double metal cyanide Prepared using a complex catalyst and having a molecular weight of about 1,000 to 5,000 (conveniently 1,500 to 4,000, more conveniently 1,500 to 2,500), the first polyol is less than 0.04 per gram of polyol (preferably 0.02 to 4,000). Or less, more preferably 0.01 or less), and the second polyol has a level of about 1,000 to 20,000.
(1,000-4,000 for convenience, 1,000-4.0 for more convenience
00), wherein the second polyol is present in an amount of about 5% to 50% based on the weight of the polyol mixture, provided that the average molecular weight of the second polyol is Different from the average molecular weight of the first polyol, the polydispersity of the polyol mixture is greater than the polydispersity of the first polyol, and the polydispersity of the polyol mixture is about 1.05 to 3.0 (preferably 1.1-1.
5, more preferably 1.1 to 1.2), (b) reacting the polyol mixture with diisocyanate to produce an isocyanate-terminated prepolymer, and (c) bifunctional with the isocyanate-terminated prepolymer;
The isocyanate-reactive chain extender is reacted in a mold or in an extruder to have a Shore A hardness of 75 (preferably 80 or more) to 75 (preferably 65 or less, more preferably 55 or less). Produce hard elastomers.

However, when the molecular weight of the polyol is 4,000 or less, the polyol has an ethylene oxide content of 35% or less based on the weight of the polyol. Preferably, the polyol mixture has a maximum of about 0-45%, preferably 5-30%, based on the total weight of the polyol mixture,
More preferably it has an average ethylene oxide ("EO") content of 10-25%. Preferably, each of the first polyol and the second polyol is a polyether diol.

The present invention relates to a method for producing the above-mentioned thermoplastic elastomer, comprising the steps.

These and other aspects will become apparent from the following detailed description of the invention.

According to the present invention, a hard, easily extrudable thermoplastic elastomer having a hardness in the range of 75 Shore A and 75 Shore D and made with one or more polyols made using a DMC catalyst can be properly prepared. The fact that it can be manufactured is a surprising finding. Elastomers are manufactured using a polyol mixture that includes one or more polyols that are conditioned using a double metal cyanide complex catalyst. These elastomers exhibit excellent physical and chemical properties. This elastomer has excellent structural strength and stability. Further, the elastomer is reusable and can be re-extruded if desired.

Past efforts by the present inventors to produce such hard elastomers using DMC catalysts have included "slam-up" in the cold section of the extruder or in the die during the extrusion process.
The present invention is particularly surprising because only poorly extrudable elastomer-forming polymers are obtained, which tend to crystallize. An undesirably cloudy milky film containing irregular pieces of hard material was obtained instead of the desired clear and clear extruded film. While not wishing to be bound by any particular theory, we believe that poor extrusion performance is due to the narrow molecular weight distribution of polyols made using DMC. The present invention provides a solution to this extrudability problem, and it is believed that this solution is due to the expanded molecular weight distribution or polydispersity associated with the polyol used in the present invention.

The thermoplastic elastomer of the present invention can be produced by a prepolymer method or a one-shot method. The polyurethane isocyanate-terminated prepolymer utilized when using the prepolymer method according to the present invention comprises an organic polyisocyanate and a polyalkylene ether polyol having an equivalent ratio of NCO to OH groups of about 1.5: 1 to 1.2: 1 (preferably 7: 1). : 1 to 3: 1) to produce isocyanate-terminated prepolymers of controlled molecular weight in the usual manner. The reaction is promoted by using a catalyst; universal urethane catalysts are known to those skilled in the art and include a variety of organometallic compounds and amines, such as tertiary amines and lead octanoate, mercury succinate Metal compounds such as tin octoate, or dibutyl tin dilaurate can be used. Any amount of catalyst can be used, for example, the amount used can vary from about 0.01 to 2% based on the weight of the polyurethane prepolymer, depending on the particular catalyst used.

The polyol mixture includes at least a first polyol and a second polyol, and additional polyols can be used in the mixture if desired. Essentially, the preferred polyols consist of two or three polyols. Preferred polyol reactants are polyether diols and combinations thereof. Suitable polyether diols are various polyoxyalkylene diols and combinations thereof, preferably comprising ethylene oxide ("EO") in an amount of from about 5 to 40% by weight, more preferably from about 15 to 40% by weight, based on the weight of the polyol. Contains 30% by weight.

Suitable diols have a primary hydroxyl group content of preferably about 30
~ 95%, more preferably about 50-95%. The level of ethylenic unsaturation of the polyol is preferably no greater than 0.04 meq / g, more preferably no greater than 0.025 meq / g of polyol. The alkali metal catalyst residue in the polyol is preferably 25 ppm, more preferably 8 ppm or less, and most preferably 5 ppm. The potential adverse effects of alkali metal catalysts can be counteracted by neutralization with an effective amount of an acid such as phosphoric acid.

The polyols can be prepared in a known manner by random or sequential addition of the alkylene oxides or mixtures thereof and the polyhydric alcohol initiators or mixtures thereof. Representative alkylene oxides are ethylene oxide, propylene oxide,
It includes aralkylene oxides such as butylene oxide, amylene oxide and styrene oxide, and halogenated alkylene oxides such as trichlorobutylene. The most preferred alkylene oxide is propylene oxide or a mixture thereof with ethylene oxide using random or sequential oxyalkylation.

The polyhydric alcohol reaction initiator used when producing the polyether diol reactant includes ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, butanediol, pentanediol, water, and mixtures thereof.

The condensation reaction of the alkylene oxide-polyhydric alcohol reaction initiator is performed in the presence of a double metal cyanide catalyst. Without wishing to be bound by any particular theory, the present inventors speculate that the unsaturated end groups create monofunctional species and act as chain stoppers in the elastomer-forming reaction. In polyol synthesis using a KOH catalyst, the unsaturated bonds formed increase as a direct function of the equivalents. In the end, the condition is satisfied that the addition of polypropylene oxide does not increase the molecular weight. In other words, the use of an alkaline catalyst to produce high molecular weight hydroxy-terminated polyoxypropylene ethers substantially reduces hydroxy functionality. When a double metal cyanide catalyst is used, the generation of unsaturated bonds is reduced, and a high equivalent weight polyol can be produced.

Suitable double metal cyanide catalysts and their preparation are described in US Pat. Nos. 4,472,560 and 4,464 by Shell Petroleum Company.
No. 77,589 and General Tire and Rubber Company U.S. Pat. Nos. 3,941,849, 4,242,490 and 4,335,188.

A particularly suitable double metal cyanide complex catalyst for use is zinc hexacyanometallate of the formula

Zn ₃ [M (CN) ₆ ] ₂ .xZnCl ₂ .yGLYME.zH ₂ O where M is Co (III), Cr (III), Fe (II) or Fe
(III), where x, y and z are fractions, integers or 0 and vary depending on the precise adjustment of the complex.

The second component of the polyol mixture has a different molecular weight,
A mixture of high or low molecular weight, or high and low molecular weight, broadens the molecular weight distribution. Molecular weight distribution and polydispersity measurements are measured on an appropriate GPC or HPSEC column or set of columns, and the ratio of weight average molecular weight to number average molecular weight, Mw / Mn
It is about.

When Mw / Mn is 1.054 or less, formation of a suitable extrusion grade polymer is not recognized, and when Mw / Mn is 1.054 to 3.5 (preferably 1.10 to 3.0, more preferably 1.10 to 2.5), a preferable material is formed. .

Any organic diisocyanate or mixture of diisocyanates can be used in the method for producing an elastomer of the present invention. Typical is the 80: 2 of the 2.4- and 2,6-isomers.
0 and 65:35 mixtures of toluene diisocyanate, ethylene diisocyanate, propylene diisocyanate, methylene-bis (4-phenyl) isocyanate (also referred to as diphenylmethane diisocyanate or DMI), dibenzyl diisocyanate, xylene diisocyanate (XDI), isophorone diisocyanate (IPD
I), 3,3'-bistoluene-4,4'-diisocyanate, hexamethylene diisocyanate (HDI), hydrogenated M
DI, hydrogenated XDI, cyclohexane diisocyanate, paraphenylene diisocyanate, and mixtures and derivatives thereof. In another advantageous example of the present invention, 2,4-
It is appropriate to use a mixture of isomers of 2,6-toluene diisocyanate and 2,4- and 2,6-isomers,
60: 40-90: 10, preferably used at about 65: 35-80: 20,
Or MDI is the same.

Chain extenders useful in the present invention are diols and diamines, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, 3-methylpentane-1,5-diol, hexanediol, Oxyalkylated hydroquinone, resorcinol and bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, or poly-alkylene oxide diol having a molecular weight of 100 to 500, diethyltoluenediamine, ethylenediamine, 4,4′-methylenebis (2 -Chloroaniline) ("MOCA"), hydrazine, substituted aromatic diamines such as UOP products sold as UNILINK 4200, ISONOL 10 manufactured by Dow Chemical Company
Includes N, N-bis (2-hydroxypropyl) -aniline sold as 0, and the like, and mixtures thereof. The chain extender is introduced in situ during the prepolymer formation or in a separate reaction step.

In the production of polyurethane and / or polyurea elastomers, polyether polyols, polyisocyanates, chain extenders and other components are reacted under elevated temperature conditions. The preferred method of producing the desired thermoplastic elastomer is a continuous manufacturing method using an extruder as described in U.S. Pat. No. 3,642,964. Alternative methods, including batch manufacturing, followed by milling and extrusion of the resulting elastomer, are well known in the art. Either the prepolymer method or the one-shot method is used, but the one-shot method is preferred. In the one-shot method, the diisocyanate is added to a small amount of the polyol (that is, about 10
% Or less) and is converted to a quasi-prepolymer.

In the production of elastomers, urethane-forming catalysts are used in the same way as conventional preparations such as antioxidants or other anti-deterioration agents. Representative antioxidants include hindered phenol, butylated hydroxytoluene ("BHT"), and the like. Other optional ingredients include, for example, plasticizers,
Adhesion promoters include clays, silica, fumed silica, carbon black, talc, phthalocyanine blue and green, TiO _2, an ultraviolet absorber, and the like fillers and pigments such as MgCO _3, CaCO _3. Formulations such as fillers are preferably added to the elastomer in an amount of 0 to about 75% by weight, based on the weight of the elastomer. The polymerization reaction is a bulk polymerization or a solution polymerization, and is a single reaction (one-shot process) or one-shot polymerization.
Alternatively, a further continuous step (prepolymer step) is performed.

When employing solution polymerization, tetrahydrofuran (“TH
Polar solvents such as F "), dimethylformamide (" DMF "), and dimethylacetamide (" DMAC ") are typically used. In a one-shot process, all isocyanate-reactive components react simultaneously with the polyisocyanate. In the step, all the components except for the polyisocyanate are mixed to form “B
It is customary to lead to a "side" mixer where it reacts with the polyisocyanate to produce a polyurethane and / or polyurea elastomer.
The order of mixing is not important, unless all components are inadvertently reacted before meeting. The reaction mixture is then usually cast or extruded in an extruder and cured at a suitable temperature. The equipment used for mixing or molding is not particularly critical. Manual kneading, commercial kneading machines and so-called reaction injection molding (RIM) equipment are all suitable.

In the prepolymer step, some or all of the one or more isocyanate-reactive materials react with a stoichiometric excess of polyisocyanate to produce an isocyanate-terminated prepolymer. This prepolymer reacts with the remaining isocyanate-reactive material to form a polyurethane and / or polyurea elastomer. The prepolymer may be formulated with a polyether or chain extender, or a mixture thereof.

The kneading of the reactants is carried out at ambient temperature (level of 25 ° C.)
Next, the obtained kneaded material is about 40 ° C to 130 ° C, preferably about 9 ° C.
The mixture is heated to a temperature of 0 ° C to 120 ° C, and preferably one or more of the reactants is preheated to a temperature in the above range to perform kneading. In the batch method, the heated reaction components are conveniently degassed prior to the reaction to remove air bubbles, water, or other gas inflows. Degassing is performed under reduced pressure,
The components are kept at reduced pressure until no further bubbles are generated. The degassed reaction components are then kneaded, transferred to a suitable mold or extruder, and cured at a temperature on the order of about 20C to 115C.

It is well known in the art that the time required for curing varies with the curing temperature and the properties of the particular composition.

As used herein, the terms "molecular weight" and "average molecular weight" refer to weight average molecular weight. "Polydispersity" is defined as the weight average molecular weight divided by the number average molecular weight.

Although the invention has been described with respect to particular embodiments, it is evident that many alternatives, modifications and changes may be made without departing from the inventive concept disclosed herein. It is therefore intended to cover such replacements, modifications and alterations as fall within the spirit and broad scope of the appended claims.

Specific Examples I. Preparation of high molecular weight polyols with low unsaturation 550 g of POLY-G ^* 20-112, polyoxypropylene diol of 1000 molecular weight and 2.2 g of double metal cyanide catalyst,
A 2 gallon autoclave was filled. The catalyst is a zinc cobalt hexacyanate complex of 1.2-dimethoxyethane (glyme). Close the reaction vessel and flush with nitrogen three times,
Heated to 100 ° C. At this time, a total of 150 g of propylene oxide was added, and the reaction started 20 minutes later, and the pressure dropped. Thereafter, 3850 g of propylene oxide was added at a partial pressure of propylene oxide of 30 psi over 4 hours.

When the pressure dropped to 10 psi, 16 g of KOH was introduced into the reactor, and a further 680 g of ethylene oxide was added to 70 psi.
For 5 hours. Unreacted ethylene oxide was wetted and the reaction vessel was cooled and opened. 100 g of magnesium silicate and 100 g of Supercell filter aid were added to the reaction vessel. The contents of the autoclave were heated to 100 ° C. for 2 hours and then water at a vacuum of 25 ″ was poured for 1 hour. The polyol was extruded at 40 psi and 100 ° C. into a slightly preheated filter press equipped with 5 micron filter paper. Analysis showed that the polyol contained 9% ethylene oxide,
It had 16 mg KOH / g OH and had 70% primary OH. Unsaturation value is 0.0175meq / g, Zm, Co and k content is 2ppm
It was below.

II.4000 molecular weight, low unsaturated polyol (OH ^# 28.3, Mw3
965) Preparation A polyol was prepared by the same preparation method as in the above I, and as a result of analysis, the material contained 20% ethylene oxide, and OH ^#
It was 28.3 mgKOH / g. Unsaturation value is 0.005meq / g, residual KOH
Was 0.0 ppm.

III.2000 molecular weight, low unsaturated polyol (OH ^# 50.1, Mw
Preparation of 2240) A polyol was prepared by the same preparation method as in the above I, and analysis showed that the material contained 24.6% ethylene oxide, 75.6% primary OH and had OH ^# 50.1 mg KOH / g. Unsaturation value is
0.007 meq / g, KOH residue was 0.20 ppm.

[Production of 30% Hard Segment of Thermoplastic Polyurethane] (Comparative Example) (No second polyol is used) 1100 g, 2000 ml of 0.491 mol of polyol (OH ^# 50.1)
Was charged in a resin flask. In addition, 138.8 g, 1.54 mol of 1,4-butanediol, up to 1% by weight of a mixture of phenolic antioxidants, ester release agents and other process aids were added. After dehydrating the mixture at 85 ° C. and 1-2 mm Hg vacuum for 2 hours, 300 g of the bulking agent was weighed and placed in a 90 ° C. oven before mixing with the isocyanate.

(Reaction with diphenylmethane diisocyanate)

125.5 g, 0.502 mol of diphenylmethane diisocyanate, MDI and extender were weighed and kept at 90 ° C. before mixing. 0.14--0.
18 g of stanna octoate was added to the polyol sample and mixed. MDI was then added and the mixture was stirred rapidly until thickened (10-15 seconds), then poured into a Teflon ^* coated pan and allowed to cure. After curing, crush the elastomer,
Dry at 100 ° C., 0.3 mmHg for 14-18 hours.

The dried polymer was compression molded at 420 ° F. 5 at ambient temperature
After holding for days, samples for tensile, punch C and tear were punched from the formed platelets. With a Shore A hardness of 75
An elastomer with a tensile strength of 5512 psi was obtained.

Dry polymer at zone 1, 195 ° C; zone 2, 202
C .; zone 3, 203 ° C .; die, 3 / at 209 ° C. profile
Extruded through a 4 inch die in a 4 inch extruder.
The resulting cloudy tape had a 300% modulus at 1200 psi and a maximum tensile strength of 4500 psi.

[Production of Thermoplastic Polyurethane-35% Hard Segment] Vacuum-dried 1200 g, 0.536 mol of polyol (OH ^# 5
0.1) was charged into a 2000 ml resin flask. In addition, 1
90.2 g, 2.11 mol of 1,4-butanediol and up to 1% by weight of a mixture of phenolic antioxidants, ester release agents and other process aids were added. 85 ° C, vacuum 1-2m
After dehydration at mHg for 2 hours, 300 g of the bulking agent was weighed and placed in a 90 ° C. oven before mixing with the isocyanate.

(Reaction with diphenylmethane diisocyanate)

157.9 g, 0.631 mol of diphenylmethane diisocyanate and the extender were weighed and kept at 90 ° C. prior to mixing. 0.05 to 0.
Add 10 g of stanna octoate to the polyol sample,
Mixed. DMI was then added and the mixture was stirred rapidly until thickened (10-18 seconds), at which point it was poured into a Teflon ^* coated pan and allowed to cure. After curing, the elastomer was pulverized and dried at 100 ° C. and 0.3 mmHg for 14-18 hours.

The dried polymer was compression molded at 420-430 ° F. The platelets were hazy, with areas of transparent polymer and areas of white opaque material, appearing heterogeneous.

The dried polymer was subjected to Zone 1, 190 ° C .;
Zone 3, 195 ° C; Die, 208 ° C profile, 3/4
Extruded through a 4 inch film die on an inch extruder. After a short extrusion time, a cloudy white tape was obtained and the material crystallized in the extruder cylinder. Zone 1,
190 ° C; Zone 2, 200 ° C; Zone 3, 200 ° C; Die, 212
Starting with a ° C profile, the melt viscosity was low and a film could not be formed.

(Production of polyol mixture)

The different polyols were mixed in the indicated parts by weight to form the polyol mixture listed in Table 1 and the hydroxyl number (OH) of the polyol mixture prior to the production of the thermoplastic polyurethane.
^# ), Weight average molecular weight (Mw) and polydispersity (Mw / Mn) were measured. The polydispersity is measured by GPC chromatography, while the molecular weight of the mixture is determined by the individual polyols used in the preparation of the various polyol mixtures (polyols A, B, C;
The polyols A and C correspond to the second polyol).

1100 g of the polyol mixture V was charged into a 2000 ml resin flask, and the polyol was dried under vacuum. In addition, 173.
1 g, 1.92 mol of 1,4-butanediol and up to 1% by weight of a phenolic antioxidant, an ester release agent and other process aids were added. The mixture was cooled to 85 ° C at a vacuum of 1-2 mmHg for 2 hours.
After dewatering for 300 hours, 300 g of the bulking agent was weighed and placed in a 90 ° C. oven prior to mixing with the isocyanate.

(Reaction with diphenylmethane diisocyanate)

143.0 g, 0.571 mol of diphenylmethane diisocyanate and the extender were weighed and held at 90 ° C. prior to mixing. 0.05 to 0.
10 g of stanna octoate was added to the polyol sample and mixed. Then add MDI until thickening (18-26 seconds)
The mixture was stirred rapidly, at which point it was poured into a Teflon ^* coat pan and allowed to cure. After curing, the elastomer was pulverized and dried at 100 ° C. and 0.3 mmHg for 14-18 hours.

The dried polymer was compression molded at 400 ° F. 5 at ambient temperature
After holding for days, samples for tensile, punch C and tearing were punched from the formed platelets. An elastomer having a Shore A hardness of 87 and a tensile strength of 6000 psi was obtained.

Dry polymer at zone 1, 206 ° C; zone 2, 212
3 ° C, zone 3, 212 ° C, die, 215 ° C profile
Extruded through a 4 inch film die on a 4 inch extruder. The resulting clear transparent tape is 1630 psi
Had a 300% modulus and a maximum tensile strength of 5300 psi.

In a similar manner, thermoplastic polyurethanes at the 35% hard segment level were prepared from other polyol mixtures, resulting in clean transparent extruded tapes and clear compression molded platelets. The physical property values are listed in Table 2.

[Proposed embodiment]

Example I. 50 parts of OH ^# 112.7 polyol and OH ^# 50.1 polyol 5
By mixing 0 parts, an OH ^# 81.4 polyol was obtained.

[Production of Thermoplastic Polyurethane-35% Hard Segment] 950 g of a polyol mixture was charged into a 200 ml resin flask, and the polyol was dried under vacuum. In addition, 160.0g, 1.78
Molar 1,4-butanediol and up to 1% by weight of phenolic antioxidant, ester release agent and other processing aids were added. After drying the mixture at 85 ° C. and a vacuum of 1-2 mmHg for 2 hours, 300 g of the bulking agent was weighed and kept in a 90 ° C. oven prior to mixing with the isocyanate.

(Reaction with diphenylmethane diisocyanate)

170.0 g, 0.680 mol of diphenylmethane diisocyanate, MDI and extender were weighed and kept at 90 ° C. prior to mixing. 0.05 to produce thermoplastic polyurethane
0.10.10 g of stanna octoate was added to the polyol sample and mixed. Then MDI was added and the mixture was stirred rapidly until thickening (18-26 seconds), at which point Teflon ^*
Poured into coat pan and allowed to cure. After curing, the elastomer was pulverized and dried at 100 ° C. and 0.3 mmHg for 14 to 18 hours.

The dried polymer was compression molded at 400 ° F. 5 at ambient temperature
After holding for one day, the formed plate was pulled, die C and a sample for tearing were punched out. 6000 psi with Shore A hardness 85-95
This gave an elastomer having a tensile strength of.

Drying polymer at zone 1, 200-210 ° C .;
205-215 ° C; Zone 3, 205-215 ° C; Die, 205-220 ° C
And extruded through a 4 inch film die with a 3/4 inch extruder. The resulting clean transparent tape has a 300% modulus of 1500-2500 psi and 5000-6500
It had a maximum tensile strength of psi.

Example II 50 parts of OH ^* 50.1 polyol and 50 parts of OH ^* 27.9 polyol
The parts were mixed to obtain a polyol of OH ^* 39.

[Production of Thermoplastic Polyurethane-35% Hard Segment] 950 g of a polyol mixture was charged into a 2000 ml resin flask, and the polyol was dried under vacuum. In addition, 147.2g,
1.63 moles of 1,4-butanediol and up to 1% by weight of phenolic antioxidants, ester release agents and other process aids were added. The mixture was dewatered for 2 hours at 85 ° C. under a vacuum of 1-2 mmHg, after which 300 g of the bulking agent was weighed and placed in a 90 ° C. oven prior to mixing with the isocyanate.

(Reaction with diphenylmethane diisoanate)

137.0 g, 0.548 mol of diphenylmethane diisocyanate, MDI, and extender were weighed and held at 90 ° C. prior to mixing. 0.
05-0.10 g of stanna octoate was added to the polyol sample and mixed. Thereafter, MDI was added and the mixture was stirred rapidly until thickened (18-26 seconds), at which point it was poured into a Teflon ^* coated pan and allowed to cure. After curing, the elastomer was pulverized and dried at 100 ° C. and 0.3 mmHg for 14 to 18 hours.

The dried polymer was compression molded at 400 ° F. After holding at the ambient temperature for 5 days, the molded plate was pulled out, and the die C and the sample for tearing were punched out. An elastomer having a Shore A hardness of 80 to 90 and a tensile strength of 5000 to 6000 psi was obtained.

Drying polymer at zone 1, 200-210 ° C .;
205-215 ° C; Zone 3, 205-215 ° C; Die, 205-220 ° C
And extruded through a 4 inch film die with a 3/4 inch extruder. The resulting clean transparent tape has a 300% modulus of 1500-2500 psi and 5000-65
It had a maximum tensile strength of 00 psi.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor O'Connor, James M. United States 06405 Becket Avenue, Branford, CT 107 (56) References JP-A-59-187019 (JP, A) US Patent 3427334 (US, A) U.S. Pat. No. 3,427,335 (US, A) U.S. Pat. No. 4,379,904 (US, A) WO 92/7892 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB names) C08G 18/00-18 / 87

Claims (10)

(57) [Claims] 1. A thermoplastic polyurethane produced by reacting a polyol mixture of a polyether polyol containing a first polyol and a second polyol, a diisocyanate and a bifunctional, isocyanate-reactive chain extender by a "one-shot" method. Or a polyurea elastomer, wherein the first polyol is produced using a double metal cyanide complex catalyst and has a molecular weight of 1,000 to 5,000,
The polyol has an end group unsaturation level of 0.01 meq or less per gram of polyol, and the second polyol is 1,000 to 2
A polyether polyol having an average molecular weight of 0,000, wherein the second polyol is present in an amount of 5% to 50% based on the weight of the polyol mixture, wherein the average molecular weight of the second polyol is the average molecular weight of the first polyol. The conditions are different from the molecular weight, the polydispersity of the polyol mixture is a condition that is greater than the polydispersity of the first polyol, the polydispersity of the polyol mixture is 1.1 to 1.5.
The equivalent ratio of the NCO group of the diisocyanate to the sum of the active hydrogen groups of the polyol and the chain extender is 1:
0.7 to 1: 1.3, and the molar ratio of chain extender to polyol is 0.15: 1 to 75: 1, wherein the elastomer is
The above thermoplastic polyurethane or polyurea elastomer having a hardness of 75 Shore A to 75 Shore D. 2. The elastomer of claim 1 wherein said chain extender is selected from the group consisting of diols, diamines and combinations thereof. 3. The chain extender comprises ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, 3-methylpentane-1,5-diol, hexanediol, oxyalkylated hydroquinone, resorcinol, Bisphenol A, hydrogenated bisphenol A,
1,4-cyclohexaneditamenol, polyalkylene oxide diol having a molecular weight of 100 to 500, diethyltoluenediamine, ethylenediamine, 4,4'-methylenebis (2-chloroaniline) ("MOCA"), hydrazine, substituted aromatic The elastomer of claim 1, wherein the elastomer is selected from the group consisting of diamines, N, N-bis (2-hydroxypropyl) -aniline and combinations thereof. 4. The method according to claim 1, wherein said polyol mixture has an average molecular weight of 4,000 or less,
The elastomer of claim 1 having the following average ethylene oxide content: 5. A thermoplastic polyurethane or polyurea elastomer produced by reacting an isocyanate-terminated prepolymer with a bifunctional, isocyanate-reactive chain extender, wherein the isocyanate-terminated prepolymer comprises a polyisocyanate, a first polyol and a second polyol. A reaction product of a polyol mixture of a polyether polyol containing two polyols, wherein the first polyol is produced using a double metal cyanide complex catalyst and has a molecular weight of 1,000 to 5,000, and the first polyol is per gram of polyol. 0.01
The second polyol is a polyether polyol having an end group unsaturation level of less than or equal to milliequivalents and having an average molecular weight of 1,000 to 20,000, wherein the second polyol is 5% to 50% based on the weight of the polyol mixture. Under the condition that the average molecular weight of the second polyol is different from the average molecular weight of the first polyol, and the polydispersity of the polyol mixture is greater than the polydispersity of the first polyol. The polydispersity of the polyol mixture is 1.1-1.5, the equivalent ratio of the NCO groups of the diisocyanate to the active hydrogen groups of the polyol and chain extender is 1: 0.7-1: 1.3, and the chain extender The thermoplastic polyurethane has a molar ratio of 0.15: 1 to 75: 1, and the elastomer has a hardness of 75 Shore A to 75 Shore D. Tan or polyurea elastomer. 6. An elastomer according to claim 5, wherein said chain extender is selected from the group consisting of diols, diamines and combinations thereof. 7. The chain extender is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, 3-methylpentane-1,5-diol, hexanediol, oxyalkylated hydroquinone, resorcinol, Bisphenol A, hydrogenated bisphenol A,
1,4-cyclohexanedimethanol, polyalkylene oxide diol having a molecular weight of 100 to 500, diethyltoluenediamine, ethylenediamine, 4,4'-methylenebis (2-chloroaniline) ("MOCA"), hydrazine, substituted aromatic diamine The elastomer of claim 5, wherein the elastomer is selected from the group consisting of: N, N-bis (2-hydroxypropyl) -aniline, and combinations thereof. 8. The elastomer according to claim 5, wherein said polyol mixture has an average ethylene oxide content of 35% by weight or less when the average molecular weight of said polyol mixture is 4,000 or less. 9. A method for producing a thermoplastic elastomer, comprising: (a) producing a polyol mixture of a polyether polyol containing a first polyol and a second polyol, wherein the first polyol is produced using a double metal cyanide complex catalyst. And
The first polyol has a molecular weight of 1,000 to 5,000, the first polyol has a terminal group unsaturation level of 0.01 meq or less per gram of the polyol, and the second polyol is a polyether polyol having an average molecular weight of 1,000 to 20,000, 2 The polyol is from 5% to 5% based on the weight of the polyol mixture.
Present in an amount of 50%, wherein the average molecular weight of the second polyol is different from the average molecular weight of the first polyol;
Further, the polydispersity of the polyol mixture is a condition that is larger than the polydispersity of the first polyol, and the polydispersity of the polyol mixture is 1.1 to 1.5. (B) reacting the polyol mixture with diisocyanate (C) reacting the isocyanate-terminated prepolymer with a bifunctional isocyanate-reactive chain extender in a mold or extruder to give a hardness of 75 Shore A to 75 Shore D Producing a hard elastomer having the following formula: wherein the molecular weight of the polyol is less than 4,000 and the polyol mixture has an ethylene oxide content of less than 35% by weight, based on the weight of the polyol. A method for producing the thermoplastic elastomer, which is characterized in that: 10. A "one-shot" preparation of a thermoplastic polyurethane or polyurea elastomer by reacting a polyol mixture of a polyether polyol containing a first polyol and a second polyol, a difunctional isocyanate with a bifunctional, isocyanate-reactive chain extender. Wherein the first polyol is prepared using a double metal cyanide complex catalyst and has a molecular weight of 1,000 to 5,000, and the first polyol has an end group unsaturation level of 0.01 meq or less per gram of polyol. And the second polyol is 1,000 to 20,
A polyether polyol having an average molecular weight of 000, wherein the second polyol is present in an amount of from 5% to 50% based on the weight of the polyol mixture, wherein the average molecular weight of the second polyol is the average molecular weight of the first polyol. The molecular weight is different from that of the first polyol, and the polydispersity of the polyol mixture is 1.1 to 1.5, and the NCO of the diisocyanate is 1.1 to 1.5. The equivalent ratio of the group and the sum of the active hydrogen groups of the polyol and the chain extender is 1: 0.7 to
The thermoplastic polyurethane, wherein the elastomer has a hardness of 75 Shore A to 75 Shore D, the molar ratio of the chain extender to the polyol being 0.15: 1 to 75: 1. Or a "one-shot" production process for polyurea elastomers.