KR100259667B1 - Hard thermoplastic polyurethane elastomers and their preparation method - Google Patents

Abstract

The present invention

(a) a first polyol prepared using a double metal cyanide complex catalyst and having a molecular weight of about 1,000 to about 5,000 and a terminal group unsaturation of no more than 0.04 milliequivalents per gram of polyol and a polyether polyol having an average molecular weight of about 1,000 to about 20,000 Preparing a polyol blend, a diisocyanate, and a bifunctional isocyanato-reactive chain-extender comprising a second polyol and having a desired polydispersity,

(b) reacting the polyol blend with diisocyanate to produce an isocyanate-terminated prepolymer,

(c) reacting the isocyanate-terminated prepolymer with a bifunctional isocyanato-reactive chain extender in a mold or extruder to produce a hard elastomer characterized by a hardness of 75 Shore A to about 75 Shore D. It relates to a method for producing a thermoplastic elastomer, comprising the step of producing. Also claimed is an elastomer made by the method using a one-shot technique.

Description

[Name of invention]

Rigid Thermoplastic Polyurethane Elastomer and Method for Making the Same

Detailed description of the invention

The present invention generally relates to methods for preparing thermoplastic polyurethane ("TPU") elastomers and polyurea elastomers with high hardness, more specifically low-unsaturated polyols prepared using double metal cyanide complex catalysts. It relates to a method for producing an elastomer using a polyol blend containing.

The use of double metal cyanide (aka "DMC") catalysts for the preparation of high molecular weight polyols is well established in the art. For example, US Pat. No. 3,829,505 to General Tire & Rubber Company describes a process for preparing high molecular weight diols, triols and the like using these catalysts. Polyols prepared using these catalysts can be secondarily fabricated to have higher molecular weights and even smaller amounts of terminal group unsaturation than can be prepared using commonly used KOH catalysts. The '505 patent discloses that these high molecular weight polyol products are suitable for the preparation of solid or flexible polyurethanes by reaction with nonionic surfactants, lubricants and coolants, textile sizes, packaging films, and polyisocyanates. It is said to be useful for manufacturing.

Certain thermosetting polyurethane elastomers made using triols made with DMC catalysts are also known. More specifically, US Pat. No. 4,242,490 describes polypropylene ether triols, ethylene prepared from DMC catalysts having molecular weights of 7,000 to 14,000 in a specific molar ratio using the initial polymer method and the "one-shot" method. A process for preparing such elastomers by reacting glycols and toluene diisocyanates is described.

Methodologies for preparing TPU elastomers are well established in the art. As a description of this, U.S. Patent No. 4,202,957 is prepared using a selected group of polypropylene oxide-polyethylene oxide block copolymers, and because the patent is thermoplastic, renewable and resistant to high temperature decomposition, secondary processing by injection molding is not possible. Polyurethane polyether-based elastomers are described that can be described.

As another description, US Pat. No. 5,096,993 describes the preparation of TPU elastomers prepared using DMC prepared polyether polyols. These elastomers are described in the '993 patent as having excellent physical and chemical properties.

Unfortunately, hard TPU elastomers, such as elastomers having a hardness in the range of 75 Shore A to about 75 Sho D, prepared according to the prior art methods using DMC-prepared polyols, generally have the desired moldings. It is not easily extruded into. Thus, there is a great need in the elastomer manufacturing industry for novel methodologies for producing rigid elastomers having excellent physical and chemical properties made using DMC-prepared polyol (s) in easily extrudable elastomeric forming compositions. . The present invention provides this desired methodology.

In one embodiment, the present invention provides a one-shot (preferred) method for polyol blends, diisocyanates, and difunctional isocyanato reactive chain extenders of polyether polyols comprising first and second polyols. Preferably a thermoplastic polyurethane or polyurea elastomer prepared by reaction in a continuous one-shot process, wherein the first polyol is prepared using a double metal cyanide complex catalyst and has a molecular weight of from about 1,000 to about 5,000 (advantageously 1,500 to 4,000, more advantageously 1,500 to 2,500), and terminal group unsaturation of 0.04 milliliters or less per g of polyol (preferably less than 0.02 milliequivalents, more preferably less than 0.01 milliequivalents) and the second polyol has an average molecular weight About 1,000 to about 20,000 (preferably 1,000 to 4,000, more preferably 1,000 to 4,000) polyether polyols and poly Wherein the second polyol has an average molecular weight that is different from the average molecular weight of the first polyol and the polydispersity of the polyol blend is that of the first polyol. The polydispersity is greater than the degree of dispersion and the polydispersity of the polyol blend is from about 1.05 to about 3.0 (preferably 1.1 to 1.5, more preferably 1.1 to 1.2) and the NCO group on the diisocyanate to the active hydrogen group on the polyol and chain extender The equivalent ratio is about 1: 0.7 to about 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 about 75: 1 and the hardness of the elastomer is from Shore A to 75 (preferably 80 or greater) Shore A to about 75 (preferably 65 or less, more preferably 55 or less). Preferably, the first polyol and the second polyol are each polyether diols.

In another aspect, the present invention reacts an isocyanate terminated initial polymer, which is a reaction product of a polyol blend of polyisocyanate with a polyether polyol comprising a first polyol and a second polyol, with a bifunctional isocyanato reactive chain extender To a thermoplastic polyurethane or polyurea elastomer prepared by making a first polyol using a double metal cyanide complex catalyst and having a molecular weight of about 1,000 to about 5,000 (preferably 1,500 to 4,000, more advantageously 1,500). To 2,500), and the terminal group unsaturation is 0.04 milliliter or less (preferably less than 0.02 milliliter equivalents, more preferably less than 0.01 milliliter equivalents) per g of the polyol, and the second polyol has an average molecular weight of about 1,000 to about 20,000 Is a polyether polyol of 1,000 to 4,000, more advantageously 1,000 to 4,000) Present in an amount of about 5 to about 50% by weight of the polyol blend, provided 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 blend is Larger than the degree of dispersion, the polydispersity of the polyol blend is from about 1.09 to about 3.0 (preferably 1.1 to 1.5, more preferably 1.1 to 1.2), the NCO group on the diisocyanate to the active hydrogen group on the polyol and the chain extender The equivalent ratio of is about 1: 0.7 to about 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 about 75: 1, and the hardness of the elastomer is from Shore A to 75 (preferably 80 or more) Shore A to about 75 (preferably 65 or less, more preferably 55 or less). Preferably, the first polyol and the second polyol are each polyether diols.

In another aspect, the invention is prepared using a double metal cyanide complex catalyst and has a molecular weight of about 1,000 to about 5,000 (advantageously 1,500 to 4,000, more advantageously 1,500 to 2,500) and terminal group unsaturation per gram of polyol. A first polyol that is at most 0.04 milliequivalents (preferably less than 0.02 milliequivalents, more preferably less than 0.01 milliequivalents), and an average molecular weight of about 1,000 to about 20,000 (preferably 1,000 to 4,000, more advantageously 1,000 to 4,000) polyether polyol blends comprising a second polyol present in an amount of about 5 to about 50% by weight of the polyol blend, provided that the average molecular weight of the second polyol is the average of the first polyol Different from the molecular weight and the polydispersity of the polyol blend is greater than the polydispersity of the first polyol, the polydispersity of the polyol blend is from about 1.05 to about 3.0 The step (a) to process 1.1 to 1.5, and more preferably 1.1 to 1.2) for the second,

Reacting the polyol blend with diisocyanate to produce an isocyanate terminated initial polymer, (b),

The isocyanate terminated initial polymer is reacted with a bifunctional isocyanato reactive chain extender in a mold or extruder to have a hardness of 75 (preferably 80 or greater) Shore A to about 75 (preferably 65 or less, more preferred) Producing a hard elastomer characterized by Shore D, provided that the polyol has a molecular weight of less than 4,000, wherein the ethylene oxide content of the polyol is less than 35 weight percent based on the weight of the polyol (c) It relates to a method for producing a thermoplastic elastomer comprising a). Preferably, the average ethylene oxide ("EO") content of the polyol blend has an upper limit of 0 to about 45%, preferably 5 to 30%, more preferably 10 to 25%, based on the total weight of the polyol blend. to be. Preferably, the first polyol and the second polyol are each polyether diols.

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

Surprisingly, the present invention contemplates a hard, rapidly extrudable thermoplastic elastomer that has a hardness ranging from 75 Shore A to 75 Shore D and is secondary processed using one or more polyols made using DMC catalysts. It has been found to be suitably produced according to the invention. Elastomers are produced using polyol blends containing one or more polyols prepared using double metal cyanide complex catalysts. These elastomers exhibit excellent physical and chemical properties. The elastomer has excellent structural strength and stability properties. In addition, the elastomer is recyclable and can be reextruded and remolded if necessary.

The present invention is a prior art effort by the inventors of producing such hard elastomers using polyols made with DMC catalysts to provide a "slam-up" at the low temperature of the extruder or die during the extrusion process. "It is particularly surprising because it produces poorly extruded elastomeric forming polymers that tend to crystallize. An undesired opaque film is obtained which may contain any piece of hard material instead of the desired clear, transparent extruded film. Without wishing to be bound by any particular theory, the inventors believe that this poor extrudability is due to the narrow molecular weight distribution of the polyols produced using the DMC catalyst. The present invention provides a solution to this extrudability problem, which solution is believed to be due to the enhanced molecular weight distribution or polydispersity with the polyols used in the present invention.

The thermoplastic elastomer of the present invention can be produced by an initial polymer method or a one-shot method. Polyurethane isocyanate terminated initial polymers used when employing the initial polymer process according to the present invention are prepared using standard methods to convert organic polyisocyanates to the equivalent ratios of polyalkylene ether polyol (s) and NCO to OH groups. Prepared by reaction from 15: 1 to about 1.2: 1 (preferably 7: 1 to 3: 1) to obtain an isocyanate terminated initial polymer of controlled molecular weight. The reaction can be facilitated by the use of catalysts, and conventional urethane catalysts are well known in the art and include many organometallic compounds, such as tertiary amines and metal compounds such as lead octanoate, as well as amines. Mercury succinate, tin octanoate or dibutyltin dilaurate). Any catalytic amount may be used; Specifically, this amount varies from about 0.01 to about 2 weight percent of the polyurethane initial polymer, depending on the particular catalyst used.

The polyol blend includes one or more first polyols and second polyols, and additional polyols may be used in the blend as needed. Preferred polyol blends consist essentially of two or three polyols. Preferred polyol reactants are polyether diols and mixtures thereof. Suitable polyether diols include various polyoxyalkylene diols and mixtures thereof, preferably about 5 to about 40 weight percent, more preferably about 15 to about ethylene oxide ("EO") based on the polyol weight It is contained in an amount of 30% by weight. Suitable diols preferably have a primary hydroxyl content of about 30 to about 95%, more preferably about 50 to about 95%. The ethylenic unsaturation relative to the polyol is preferably less than 0.04 milliequivalents per gram of polyol, more preferably less than 0.025 milliequivalents. It is preferred that any residual alkali metal catalyst in the polyol is 25 ppm or less, more preferably 8 ppm or less, most preferably 5 ppm or less. Potential adverse effects of residual alkali metal catalysts in polyols can be overcome by neutralizing with an effective amount of acid, such as phosphoric acid.

Polyols can be prepared by condensation of alkylene oxide or a mixture of alkylene oxides optionally or stepwise added into a multivalent initiator or initiator mixture according to well known methods. Specific alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides such as styrene oxide and halogenated alkylene oxides such as trichlorobutylene oxide and the like. Most preferred alkylene oxides are propylene oxide or a mixture of ethylene oxide and propylene oxide optionally or stepwise oxyalkylated.

Polyhydric initiators used to prepare polyether diol reactants include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, butane diol, pentane diol, water, mixtures thereof, and the like.

The alkylene oxide-multivalent initiator condensation reaction is preferably carried out in the presence of a double metal cyanide catalyst. Without wishing to be limited to any particular theory, the inventors of the present invention contemplate monofunctional species, which act as chain stoppers in elastomer formation with unsaturated end groups. In polyol synthesis using KOH catalysts, the unsaturation formed increases as a direct action of the equivalents. Eventually a state is established in which additional polyethylene addition does not increase the molecular weight. In other words, the use of an alkali catalyst to produce high molecular weight hydroxy terminated polyoxypropylene ethers substantially loses hydroxy functionality. Using a double metal cyanide catalyst, much less unsaturated groups are formed while producing a high equivalent polyol.

Double metal cyanide complex series catalysts suitable for use and preparation methods thereof are described in US Pat. Nos. 4,472,560 and 4,477,589 to Shell Chemical Company, and US Pat. 3,941,849; 4,242,490 and 4,335,188.

A double metal cyanide complex catalyst found to be particularly suitable for use is zinc hexacyanometallate of the general formula:

Zn ₃ [M (CN) ₆ ] ₂ x ZnCl ₂ yGLYME zH ₂ O

Where

M may be Co (III), Cr (III), Fe (II) or Fe (III), x, y and z may be fractions, integers or zeros and may vary depending on the exact method of preparation of the complex.

The second component of the polyol blends having different molecular weights is a higher or lower molecular weight or a mixture of higher and lower molecular weights in order to broaden the molecular weight distribution. Polydispersity, a measure of molecular weight distribution, is measured on a suitable GPC or HPSEC column or column set and is related to the ratio of weight average molecular weight and number average molecular weight, Mw / Mn. The formation of a suitable extrusion grade polymer is not permitted with Mw / Mn of 1.054 or less, while Mw / Mn of 1.054 to 3.5 (preferably 1.10 to 3.0, more preferably 1.10 to 2.5) yields the desired material. .

Any suitable organic diisocyanate or mixture of diisocyanates may be used in the elastomer formation process of the present invention. For example, toluene diisocyanate (e.g., 80:20 and 65:35 mixtures of 2,4- and 2,6-isomers), ethylene diisocyanate, propylene diisocyanate, methylene-bis (4-phenyl) isocyanate ( Also called diphenylmethane diisocyanate or MDI), dibenzyl diisocyanate, xylene diisocyanate (XDI), isopron diisocyanate (IPDI), 3,3'-bistoluene-4,4'-diisocyanate, hexamethylene di Isocyanate (HDI), hydrogenated MDI, hydrogenated XDI, cyclohexane diisocyanate, paraphenylene diisocyanate, mixtures and derivatives thereof and the like. In another preferred embodiment of the invention 2,4- and 2,4- isomers having a weight ratio of 2,6-isomers are from about 60:40 to about 90:10, more preferably from about 65:35 to about 80:20 Isomer mixtures of 2,6-toluene diisocyanate and MDI are suitably used.

Chain extenders useful in the present invention are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, pentane diol, 3-methylpentane-1,5-diol, hexane diol, oxyalkylated hydroquinone, resorcinol And bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexane dimethanol or polyalkylene oxide diols having a molecular weight of 100 to 500, diethyltoluene diamine, ethylene diamine, 4,4'-methylene bis (2-chloroaniline) ( "MOCA"), hydrazine, substituted aromatic diamines (such as those sold under the trade name UNILINK 4200 manufactured by UOP, Inc.), N, N-bis (2-hydroxypropyl) -aniline (such as Dow Chemical Corp Diols and diamines, and mixtures thereof, such as those sold under the trade name ISONOL 100 manufactured by. Chain extension can be carried out in situ during the initial polymer formation or in a separate reaction step.

In the preparation of polyurethanes and / or polyurea elastomers, polyether polyol (s), polyisocyanate (s), chain extender (s), and other components are typically reacted under elevated temperature. The preferred method of forming the desired thermoplastic elastomer is by a continuous method using an extruder as described in US Pat. No. 3,642,964. Another method involves grinding and extruding the formed elastomer as is well known in the art after batch processing. Although either the initial polymer method or the one-shot method can be used, the one-shot method is preferred. The one-shot method also includes the process of converting the diisocyanate to a pseudo initial polymer by reacting with a small amount (ie less than about 10% based on the equivalent) of the polyol before carrying out the polyurethane formation reaction.

In the preparation of elastomers, urethane forming catalysts and conventional compounding components such as antioxidants or other antidegradants can be used. Typical antioxidants include hindered phenols, butylated hydroxytoluene ("BHT"), and the like. Other optional compounding ingredients include, for example, plasticizers, adhesion promoters, fillers, clays and pigments such as silica, fumed silica, carbon black, talc, phthalocyanine blue or green, TiO ₂ , UV absorbers, MgCO ₃ , CaCO _3, and the like]. Formulation ingredients, such as fillers, are suitably used in amounts of from 0 to about 75 weight percent of the elastomer, based on the weight of the elastomer. The polymerization reaction can be carried out in a single reaction (one-shot method) or in one or more successive steps (initial polymer method) using a bulk polymerization solution or a solution polymerization reaction. When using solution polymerization, polar solvents such as tetrahydrofuran ("THF"), dimethylformamide ("DMF") and dimethylacetamide ("DMAC") are typically used. In the one-shot method, all isocyanate reactive components are reacted simultaneously with the polyisocyanate. It is common practice in this process to blend all components except polyisocyanates into a "B-side" mixture and then react with the polyisocyanate to form polyurethane and / or polyurea elastomers. However, the order of mixing is not critical unless the components react undesirably before all components are present. The reaction mixture is then typically placed in a mold and extruded through an extruder and cured at a suitable temperature. The apparatus used for blending and forming is not particularly important. Manual mixing, conventional mechanical mixing and so-called reactive injection molding (RIM) devices are all suitable. In the initial polymer process, all or part of one or more isocyanate-reactive materials are reacted with stoichiometric excess polyisocyanate to form an isocyanate terminated initial polymer. This initial polymer is then reacted with residual isocyanate reactive materials to produce polyurethane and / or polyurea elastomers. The initial polymer can be made of a polyether or chain extender or a mixture of both.

Mixing of the reactants may be carried out at ambient temperature (about 25 ° C.) and then the resulting mixture is heated to a temperature of about 40 to about 130 ° C., preferably about 90 to about 120 ° C. Alternatively, it is preferable to preheat to said temperature range before mixing at least one reactant. Advantageously, in a batch process, the heated reaction components are degassed to remove entrained bubbles, vapors or other gases before the reaction takes place. Such degassing is typically accomplished conveniently by depressurizing to pressure under conditions where the components are maintained until no further bubble release occurs. The degassed reaction components are then mixed and transferred to a suitable mold or extruder or the like to cure at a temperature of about 20 to about 115 ° C. The time required for curing varies with the curing temperature and the properties of the particular component, as is known in the art.

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

Although the present invention has been described above with regard to specific embodiments thereof, it is apparent that many changes, modifications and variations can be made without departing from the inventive concept described herein. Accordingly, it is intended that such changes, modifications and variations fall within the spirit and broad scope of the appended claims.

Specific Example

I. Preparation of High Molecular Weight Polyols with Low Unsaturation

Two gallons were charged to the autoclave with 550 g of POLY-G ^* 20-112, polyoxypropylenediol of molecular weight 1000 and 2.2 g of double metal cyanide catalyst. The catalyst is a zinc cobaltihexacyanate complex with 1,2-dimethoxyethane (glyme). The reactor is closed, washed three times with nitrogen and heated to 100 ° C. At this point, 150 g of propylene oxide is added and the reaction starts after 20 minutes, which appears as a pressure drop. 3850 g of propylene oxide is then added over 4 hours at a propylene oxide partial pressure of 30 psi.

When the pressure drops to 10 psi, 16 g of KOH is introduced into the reactor, and then 680 g of ethylene oxide is reacted at 70 psi for 5 hours. Release unreacted ethylene oxide and cool and open the reactor. 100 g of magnesium silicate and 100 g of Supercell filter aid are added to the reactor. The contents of the autoclave are then heated to 100 ° C. for 2 hours, vacuumed to 25 ”and water added for 1 hour. The polyol is then passed through a preheated small filter press containing 5 μm filter paper at 40 psi and 100 ° C. Analyzes indicate that a polyol containing 9% ethylene oxide has an OH # of 16 mg KOH / g and a primary OH of 70%, with an unsaturation value of 0.0175 meq / g and a Zn, Co and K content of less than 2 ppm. to be.

II. Preparation of low polyunsaturation polyol (OH # 28.3, MW 3965)

Preparation and analysis of polyols similar to the preparation of I above indicated that they contained 20% ethylene oxide and had an OH # of 28.3 mg KOH / g. The unsaturation value is 0.005 meq / g and the KOH residual is 0.0 ppm.

III. Preparation of low polyunsaturation polyol (OH # 50.1, MW 2240)

Preparation and analysis of polyols similar to the preparation of I above indicated that they contained 24.6% ethylene oxide and 75.6% primary OH and OH # was 50.1 mg KOH / g. The unsaturated value is 0.007 meq / g and the KOH residual is 0.20 ppm.

[Preparation of Thermoplastic Polyurethanes-30% Hard Fragment]

Into a 2000 ml resin flask was charged 1100 g (1.491 mol) of polyol (OH # 50.1). Also, 138.8 g (1.54 mol) of 1,4-butanediol, a mixture of less than 1% by weight of phenolic antioxidants, ester mold release aids and other processing aids are added. The mixture is dehydrated for 2 hours at 1-2 mmHg under vacuum at 85 ° C. and then 300 g of additional portion is weighed and placed in a 90 ° C. oven before mixing with isocyanates.

[Reaction with Diphenylmethane Diisocyanate]

An additional 125.5 g (0.502 mol) of diphenylmethane diisocyanate, MDI is weighed and kept at 90 ° C. before mixing. To prepare the thermoplastic polyurethane, 0.14 to 0.18 g of octosan first tin is added to the polyol sample and mixed. MDI is then added and stirred rapidly until the mixture thickens (10-15 seconds), then poured into a Teflon ^* coated pan and cured. After curing, the elastomer is granulated and dried at 100 ° C. and 0.3 mm Hg for 14-18 hours.

The dry polymer is compression molded at 420 ° F. After standing for 5 days at ambient temperature, the specimens for tension, die C and split tear are die cut from the molded plaque. The hardness of the elastomer is 79 Shore A and the tensile strength is 5512 psi.

Dry polymer was section 1, 195 ° C. in a 3/4 ”extruder through a 4” film die; Section 2, 202 ° C .; Section 3, 203 ° C .; The die is extruded at 209 ° C. The 300% modulus of the opaque tape obtained is 1200 psi and the final tensile strength is 4500 psi.

[Preparation of thermoplastic polyurethane-35% hard fragment]

2000 ml of a resin flask was charged with 1200 g of vacuum dried polyol (OH # 50.1), 0.536 mol. Also added is a mixture of less than 10.2% (1.4-butanediol) by weight of phenolic antioxidant, ester mold release aid and other processing aids. The mixture is dehydrated at 85 ° C. under vacuum at 1-2 mm Hg for 2 hours and then 300 g of additional portion is weighed and placed in a 90 ° C. oven before mixing with isocyanates.

[Reaction with Diphenylmethane Diisocyanate]

An additional 157.9 g (0.631 mol) of diphenylmethane diisocyanate MDI are weighed and kept at 90 ° C. before mixing. To prepare the thermoplastic polyurethane, 0.05 to 0.10 g of octosan first tin is added to the polyol sample and mixed. MDI is then added and stirred rapidly until the mixture thickens (10-18 seconds), then poured into a Teflon ^* coated pan and cured. After curing, the elastomer is granulated and dried at 100 ° C. and 0.3 mm Hg for 14-18 hours.

The dry polymer is compression molded at 420 to 430 ° F. Plaques appear to be heterogeneous with hazy, transparent polymer regions and regions of white opaque material.

Dry polymer was section 1, 190 ° C. in a 3/4 ”extruder through a 4” film die; Section 2, 195 ° C .; Interval 3, 195 ° C .; The die is extruded at 208 ° C. After a short extrusion, an opaque white tape is produced which crystallizes the material in the barrel of the extruder. Interval 1, 190 ° C .; Section 2, 200 ° C .; Section 3, 200 ° C .; When the die starts at 212 ° C., the melt viscosity is too low to form a film.

[Production of Polyol Blend]

The polyol blends listed in Table 1 are prepared by mixing the specified weight parts of different polyols, followed by the hydroxyl number (OH #), weight average molecular weight (Mw) and polyunsaturation of the polyol blend prior to preparing the thermoplastic polyurethane. The degree of dispersion (Mw / Mn) is measured. Polydispersity is measured by GPC chromatography, while the molecular weight of the blend is calculated based on the hydroxyl value of each polyol (polyols A, B, and C) used to prepare the various polyol blends.

* Polyols prepared by conventional (KOH) catalytic cracking rather than DMC catalytic cracking

[Preparation of Thermoplastic Polyurethanes-35% Hard Fragment-Polyol Blend V]

A 2000 ml resin flask is charged with 1100 g of Polyol Blend V and vacuum dried polyol. Also, 173.1 g (1.92 mol) of 1,4-butanediol and less than 1% by weight of a mixture of phenolic antioxidants, ester release aids and other processing aids are added. The mixture is dehydrated at 85 ° C. under vacuum at 1-2 mmHg for 2 hours and then 300 g of additional portion is weighed and placed in a 90 ° C. oven before mixing with isocyanates.

[Reaction with Diphenylmethane Diisocyanate]

A further 143.0 g (0.571 mol) of diphenylmethane diisocyanate, MDI, were weighed and kept at 90 ° C. before mixing. To prepare the thermoplastic polyurethane, 0.05 to 0.10 g of octosan first tin is added to the polyol sample and mixed. Thereafter, MDI is added and stirred rapidly until the mixture thickens (18-26 seconds), then poured into a Teflon ^* coated pan and cured. After curing, the elastomer is granulated and dried at 100 ° C. and 0.3 mm Hg for 14-18 hours.

The dry polymer is compression molded at 400 ° F. After standing for 5 days at ambient temperature, the specimens for tension, die C and split tear are die cut from the molded plaque. The hardness of the elastomer is 87 Shore A and the tensile strength is 6000 psi.

Dry polymer was section 1, 206 ° C. in a 3/4 ”extruder through a 4” film die; Section 2, 212 ° C .; Section 3, 212 ° C .; The die is extruded at 215 ° C. The resulting clear transparent tape has a 300% modulus of 1630 psi and a final tensile strength of 5300 psi.

In a similar manner 35% hard fragment level thermoplastic polyurethane is prepared from other polyol blends to produce clear transparent extruded tape and clear compression molded plaques. Physical property data is summarized in Table 2.

[Suggested Example]

Example I

50 parts of a polyol having an OH # of 112.7 and 50 parts of a polyol having an OH # of 50.1 are blended to obtain a polyol having an OH # of 81.4.

[Preparation of thermoplastic polyurethane-35% hard fragment]

A 2000 ml resin flask is charged with 950 g of polyol blend and vacuum dried polyol. Also, 160.0 g (1.78 mol) of 1,4-butanediol and less than 1% by weight of a mixture of phenolic antioxidants, ester mold release aids and other processing aids are added. The mixture is dehydrated at 85 ° C. under vacuum at 1-2 mmHg for 2 hours and then 300 g additional portion is weighed and placed in a 90 ° C. oven before mixing with isocyanates.

[Reaction with Diphenylmethane Diisocyanate]

An additional portion of 170.0 g (0.680 mol) of diphenylmethane diisocyanate, MDI is weighed and maintained at 90 ° C. before mixing. To prepare the thermoplastic polyurethane, 0.05-0.10 g of octosan first tin is added to the polyol sample and mixed. MDI is then added and stirred rapidly until the mixture thickens (18-26 seconds), then poured and cured in a Teflon ^* coated pan. After curing, the elastomer is granulated and dried at 100 ° C. and 0.3 mm Hg for 14-18 hours.

The dry polymer is compression molded at 400 ° F. After standing for 5 days at ambient temperature, the specimens for tension, die C and split tear are die cut from the molded plaque. The hardness of the elastomer is 85 to 95 Shore A and the tensile strength is 6000 psi.

Dry polymer was section 1, 200-210 ° C. in a 3/4 ”extruder through a 4” film die; Section 2, 205-215 ° C .; Section 3, 205-215 ° C .; Die, extruded at 205-220 ° C. The resulting clear transparent tape has a 300% modulus of 1500 to 2500 psi and a final tensile strength of 5000 to 6500 psi.

Example II

50 parts of a polyol having an OH # of 50.1 and 50 parts of a polyol having an OH # of 27.9 are blended to obtain a polyol having a OH # of 39.

[Preparation of thermoplastic polyurethane-35% hard fragment]

A 2000 ml resin flask is charged with 950 g of polyol blend and vacuum dried polyol. Also added is 147.2 g (1.63 mol) of 1,4-butanediol and less than 1% by weight of a mixture of phenolic antioxidants, ester release aids and other processing aids. The mixture is dehydrated at 85 ° C. under vacuum at 1-2 mmHg for 2 hours and then 300 g additional portion is weighed and placed in a 90 ° C. oven before mixing with isocyanates.

[Reaction with Diphenylmethane Diisocyanate]

An additional portion of 137.0 g (0.548 mol) of diphenylmethane diisocyanate, MDI is weighed and maintained at 90 ° C. before mixing. To prepare the thermoplastic polyurethane, 0.05 to 0.10 g of octosan first tin is added to the polyol sample and mixed. Thereafter, MDI is added and stirred rapidly until the mixture thickens (18-26 seconds), then poured into a Teflon ^* coated pan and cured. After curing, the elastomer is granulated and dried at 100 ° C. and 0.3 mm Hg for 14-18 hours.

The dry polymer is compression molded at 400 ° F. After standing for 5 days at ambient temperature, the specimens for tension, die C and split tear are die cut from the molded plaque. The hardness of the elastomer is 80 to 90 Shore A and the tensile strength is 5000 to 6000 psi.

Dry polymer was section 1, 200-210 ° C. in a 3/4 ”extruder through a 4” film die; Section 2, 205-215 ° C .; Section 3, 205-215 ° C .; Die, extruded at 205-220 ° C. The resulting clear transparent tape has a 300% modulus of 1500 to 2500 psi and a final tensile strength of 5000 to 6500 psi.

[Summary of Physical Properties]

Extrusion:

Polyol 300% final tensile final

Blend Modulus Strength (psi) Elongation (%)

Ⅱ 1575 6557 623

Ⅲ 1540 6140 660

Ⅳ 1597 4238 675

Ⅴ 1631 5307 595

Ⅵ 1675 5871 630

Ⅶ 1529 5201 640

Compression molding:

Polyol 300% Final Tensile Final

Blend Hardness Modulus Strength Elongation (%)

Ⅱ 86A 2010 6117 680

Ⅲ 89A 1876 4957 680

Ⅳ 88A 1991 5766 640

Ⅴ 87A 1916 6011 677

Ⅵ 88A 1863 4696 705

Ⅶ 88A 1792 4556 717

Claims (21)

A first polyol prepared using a double metal cyanide complex catalyst and having a molecular weight of 1,000 to 5,000 and a terminal group unsaturation of 0.04 milliliters or less per gram of polyol and a polyether polyol having an average molecular weight of 1,000 to 20,000, based on the weight of the polyol blend The polyol blends, diisocyanates and difunctional isocyanato reactive chain extenders of polyether polyols comprising a second polyol present in an amount of from 5 to 50% are referred to as "one-shot" methods (" one-shot "process, 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 blend is greater than the polydispersity of the first polyol, The degree of dispersion is from 1.09 to 3.0, and the NCO group present in the diisocyanate to the active hydrogen group present in the polyol and chain extender A thermoplastic polyurethane or polyurea elastomer having an equivalent ratio of 1: 0.7 to 1: 1.3 and a hardness of 75 Shore A to 75 Shore D with a molar ratio of chain extender to polyol of 0.15: 1 to 75: 1. The elastomer of claim 1, wherein the chain extender is selected from the group consisting of diols, diamines, and mixtures thereof. The chain extender of claim 1 wherein the chain extender is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, pentanediol, 3-methylpentane-1,5-diol, hexane diol, oxyalkylated hydroquinone, lesosi Nol and bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexane dimethanol, polyalkylene oxide diols having a molecular weight of 100 to 500, diethyltoluene diamine, ethylene diamine, 4,4'-methylene bis (2-chloroaniline) ("MOCA"), hydrazine, substituted aromatic diamines, N, N-bis (2-hydroxypropyl) aniline, and mixtures thereof. The one or more combinations of claim 1, which is selected from the group consisting of antioxidants, plasticizers, UV stabilizers, adhesion promoters, fillers and pigments and used in an amount of 0 to 75% by weight, based on the total weight of the composition. Elastomers, further comprising components. The elastomer of claim 1 wherein the molecular weight of the first polyol is 1,500 to 4,000 and the polydispersity of the polyol blend is 1.1 to 1.5. The elastomer of claim 1, wherein the average ethylene oxide content of the polyol blend is less than 35% by weight when the average molecular weight of the polyol blend is less than 4,000. A polyisocyanate and a first polyol prepared using a double metal cyanide complex catalyst and having a molecular weight of 1,000 to 5,000 and a terminal group unsaturation of 0.04 milliliters or less per gram of polyol and a polyether polyol having an average molecular weight of 1,000 to 20,000, and a polyol blend Bifunctional isocyanato reactivity of an isocyanate terminated prepolymer which is a reaction product of a polyether polyol with a polyol blend comprising a second polyol present in an amount of 5 to 50%, based on the weight of Prepared by reacting with a chain extender, 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 blend is greater than the polydispersity of the first polyol, and the polydispersity of the polyol blend 1.09 to 3.0, chain extension with the NCO group to polyol present in the diisocyanate A thermoplastic poly having an elastomeric hardness of 75 Shore A to 75 Shore D with an equivalent ratio of active hydrogen groups present in the ratio of 1: 0.7 to 1: 1.3 and a molar ratio of chain extender to polyol of 0.15: 1 to 75: 1 Urethane or polyurea elastomers. 8. The elastomer of claim 7, wherein the chain extender is selected from the group consisting of diols, diamines, and mixtures thereof. The chain extender of claim 7 wherein the chain extender is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, pentane diol, 3-methylpentane-1,5-diol, hexane diol, oxyalkylated hydroquinone, resorcy Nol and bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexane dimethanol, polyalkylene oxide diols having a molecular weight of 100 to 500, diethyltoluene diamine, ethylene diamine, 4,4'-methylene bis (2-chloroaniline) ("MOCA"), hydrazine, substituted aromatic diamines, N, N-bis (2-hydroxypropyl) aniline, and mixtures thereof. The one or more formulations according to claim 7, which is selected from the group consisting of antioxidants, plasticizers, UV stabilizers, adhesion promoters, fillers and pigments and used in an amount of 0 to 75% by weight, based on the total weight of the composition. Elastomers, further comprising components. The elastomer of claim 7 wherein the molecular weight of the first polyol is 1,500 to 4,000 and the polydispersity of the polyol blend is 1.1 to 1.5. 8. The elastomer of claim 7, wherein the average ethylene oxide content of the polyol blend is less than 35 weight percent when the average molecular weight of the polyol blend is less than 4,000. A first polyol prepared using a double metal cyanide complex catalyst and having a molecular weight of 1,000 to 5,000 and a terminal group unsaturation of 0.04 milliliters or less per gram of polyol and a polyether polyol having an average molecular weight of 1,000 to 20,000, based on the weight of the polyol blend Polyether polyol blends comprising a second polyol present in an amount of from 5 to 50%, provided 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 (A) subjecting the polyol blend to diisocyanate to produce an isocyanate terminated initial polymer that is greater than the polydispersity of the polyol and the polydispersity of the polyol blend is from 1.09 to 3.0). Step (b), the isocyanate terminated initial polymer is difunctional isocyanato half in a mold or extruder Hard elastomers characterized by a hardness of 75 Shore A to 75 Shore D when reacted with a chain extender, provided that the ethylene oxide content of the polyol blend is 35 based on the weight of the polyol when the polyol has a molecular weight of less than 4,000. Less than% by weight). The method of claim 13, wherein the chain extender is selected from the group consisting of diols, diamines, and mixtures thereof. 14. The chain extender of claim 13 wherein the chain extender is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, pentane diol, 3-methylpentane-1,5-diol, hexane diol, oxyalkylated hydroquinone, lesosi Nol and bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexane dimethanol, polyalkylene oxide diols having a molecular weight of 100 to 500, diethyltoluene diamine, ethylene diamine, 4,4'-methylene bis (2-chloroaniline) ("MOCA"), hydrazine, substituted aromatic diamines, N, N-bis (2-hydroxypropyl) aniline and mixtures thereof. The method of claim 13 wherein the molecular weight of the first polyol is 1,500 to 4,000 and the polydispersity of the polyol blend is 1.1 to 1.5. The method of claim 13, wherein the elastomer further contains at least one blending component selected from the group consisting of antioxidants, plasticizers, UV stabilizers, adhesion promoters, fillers and pigments. The method of claim 17, wherein the blending component is used in an amount of 0 to 75% by weight, based on the total weight of the composition. The method of claim 13, wherein step (b) and step (c) are performed simultaneously. The method of claim 13 wherein the hardness is between 80 Shore A and 65 Shore D. A first polyol prepared using a double metal cyanide complex catalyst and having a molecular weight of 1,000 to 5,000 and a terminal group unsaturation of 0.04 milliliters or less per gram of polyol and a polyether polyol having an average molecular weight of 1,000 to 20,000, based on the weight of the polyol blend Thereby reacting a polyol blend of a polyether polyol comprising a second polyol present in an amount of 5% to 50%, a diisocyanate and a difunctional isocyanato reactive chain extender, provided that the second polyol The average molecular weight of the polyol blend is different from the average molecular weight of the first polyol and the polydispersity of the polyol blend is greater than that of the first polyol, the polydispersity of the polyol blend is from 1.09 to 3.0, The equivalent ratio of active hydrogen groups present in the polyol and the chain extender is from 1: 0.7 to 1: 1.3, and the chain extender Of the polyol mole ratio of 0.15: 1 to 75: 1, the hardness of the elastomer of 75 Shore A to 75 Shore D of the thermoplastic polyurethane or for the production of urea elastomer "one-shot" method.