KR20080061890A - Process for making microcellular polyurethane elastomers - Google Patents

Abstract

A method for preparing microporous polyurethane elastomers is provided to attain a density less than 0.5 g/cm^3 without sacrificing a good processing range or excellent elastomer characteristics. A method for preparing microporous polyurethane elastomers includes a step of reacting a resin component(B side) with an isocyanate-terminated precursor polymer(A side) in the presence of optionally, a foaming agent, a surfactant, and a catalyst to prepare the microporous polyurethane elastomers having a density of 500 kg/m^3. The resin component comprises a mixture of a first chain extender and a first polyol having a high content of primary hydroxyl groups and a low degree of unsaturation. The precursor polymer is prepared by reacting polyisocyanate, a second polyol having a high content of primary hydroxyl groups and a low degree of unsaturation identical to or different from the first polyol, and a second chain extender identical to or different from the first chain extender. After the reaction, the second chain extender in the A side is contained in an amount of 5-60 equivalent percent of the total chain extenders.

Description

Process for Making Microcellular Polyurethane Elastomers

FIELD OF THE INVENTION The present invention relates to microporous polyurethane elastomers and methods for their preparation, and more particularly, to microporous polyurethane elastomers having a variety of uses, and particularly useful for sports protective articles, automotive articles and footwear.

Microporous polyurethane elastomers are well known. They have fine and evenly distributed bubbles and their density is low compared to solid urethane elastomers and high compared to soft polyurethane foams. Microporous polyurethane elastomers are used in sporting protective articles, automotive parts (eg bumpers and armrests), gaskets, vibration damping devices and shoes.

Many methods of making microporous polyurethane elastomers are known, but most of them fall into two classes, such as the "one-shot" method and the "prepolymer" method. In the one-shot method, all the components (polyol, polyisocyanate, blowing agent, surfactant, catalyst, chain extender) are combined and reacted in a single step. In contrast, the propolymerization method pre-reacts a polyisocyanate with a polyol to produce a "propolymer" ("A" side), which is then combined with the remaining reactants comprising any chain extender ("B" side), Prepare the elastomer in two steps. US Pat. No. 4,559,366 demonstrates that it may be desirable to prepare "similar prepolymers" using reacting polyols with sufficient polyisocyanates to produce mixtures of isocyanate-terminated propolymers and free polyisocyanates. Such pseudoprepolymers are typically used to increase the available NCO content on the "A" side.

It is also known to prepare propolymers (“A” side) from mixtures of isocyanates and polyol-extensions. For example, US Pat. No. 5,658,959 teaches the preparation of isocyanate-terminated propolymers from MDI, dipropylene glycol, polyoxypropylated / ethoxylated glycerin and polyoxypropylated / ethoxylated glycols (Example 1 See).

The polyols in this document have an ethylene oxide content of up to 35% by weight, but do not disclose the degree of "endcapping" or the primary hydroxyl group content (see lines 17-38 of column 5). In addition, the document does not mention the degree of unsaturation of the polyol. U.S. Patent 5,618,967 contains a similar disclosure. In short, these documents suggest that the polyunsaturation or primary hydroxyl content is not critical.

U.S. Pat. No. 5,284,880 also describes propolymers prepared from isocyanates, polyols and chain extenders (dipropylene glycol) (see lines 30-45 of column 13). However, the document teaches that the "A" side polyol should be "polyethers containing predominantly secondary hydroxyl groups" (see lines 4-5 of column 2 and 28-54 of column 4 in the summary). ).

In addition, the document makes no mention of the need for low unsaturation polyols. In general, the advantages of low unsaturation polyols (less than 0.020 meq / g) are known for polyurethanes, in particular microporous polyurethane elastomers. For example, US Pat. Nos. 5,677,413 and 5,728,745 describe microporous polyurethanes made from polyols having an unsaturation of less than about 0.010 meq / g. U. S. Patent No. 5,728, 745 prepares elastomers by the propolymer method (see Example 8 and Table 6 of the literature) or the one-shot method (see Example 9-11 and Table 6 of the literature). The propolymer of Example 8 is the reaction product of polyoxypropylene diol or triol with 4,4'-MDI.

No chain extender was used to prepare the propolymer. In Examples 9 to 11 low polyunsaturations having a high primary content are used. This document teaches several advantages of using low unsaturation polyols, including good elasticity, low compression set and reduced shrinkage, which are particularly important for soles.

US Pat. No. 5,106,874 teaches a propolymer or one-shot process for preparing non-porous elastomers from low unsaturation polyols. Propolymers are typically prepared by reacting polyoxyalkylene polyols with excess polyisocyanates. The document teaches that chain extenders may be included in the propolymer (see lines 49-53 of column 7). However, none of the practical examples contained the chain extender included in response to the "A" side, and no microporous elastomer was produced.

US Pat. No. 5,696,221 teaches the preparation of polyurethane / urea elastomers by reacting propolymers with chain extenders. Propolymers include diols having a molecular weight of less than 400 in addition to low unsaturation polyoxypropylene diols. The document does not disclose microporous elastomers.

Despite the well-known advantages of using low polyunsaturated polyols in the preparation of microporous polyurethane elastomers, some problems remain with conventional one-shot and propolymer processes. As described in US Pat. No. 4,559,366, the one-shot method cannot be readily used with 4,4'-diphenylmethane diisocyanate (4,4'-MDI), a common raw material for shoe elastomers, which is 4, This is because 4'-diphenylmethane diisocyanate does not readily mix with other reactants and solidifies at room temperature (see column 1 of the literature).

The propolymer method also has disadvantages. High quality, low density elastomers, especially those with a density of less than 0.5 g / cm 3, are difficult to manufacture. A sure way to reduce the density is to increase the amount of blowing agent (usually water).

However, this increases the urea content of the elastomer, reduces elongation and decreases flexibility. Adding more chain extenders on the "B" side helps maintain good hardness at low densities, but results in poor processability and early phase separation. As shown in Comparative Example 8 (below), such products often cause undesirable phenomena such as surface defects and internal splitting.

Although it is known to include some chain extender on the "A" side, in relation to the preparation of microporous elastomers based on low unsaturation polyols, especially those having a high content of primary hydroxyl groups, on the "A" side Little is known about the benefits of including some chain extenders.

In short, a better method of producing microporous polyurethane elastomers, in particular low density elastomers, would be advantageous. The preferred method is to use polyunsaturated low unsaturation found in the present invention to give urethane a significant advantage in physical properties. The preferred method is not only easy to perform, but also overcomes the disadvantages of conventional one-shot and propolymer processes, in particular in the production of low density elastomers.

Accordingly, the technical problem to be achieved by the present invention is to provide a radically advanced method which enables manufacturers of microporous elastomers to achieve a density of less than 0.5 g / cm 3 without sacrificing good processing range or good elastomeric properties. .

In order to achieve the above technical problem, the method includes reacting a resin component ("B" side) and an isocyanate-terminated propolymer ("A" side), optionally in the presence of a blowing agent, a surfactant and a catalyst. do.

The resin component includes a first chain extender and a low polyunsaturated first polyol having a high primary content. However, the main component is a propolymer prepared by reacting a polyisocyanate, a high primary content, a low polyunsaturated second polyol and a second chain extender. The second chain extender included in the "A" side in response constitutes about 5 to about 60 equivalent percent of the total chain extender.

The inventors have surprisingly found that as a part of the propolymer, pre-reacting an appropriate amount of chain extender component to the "A" side, which contains a low polyunsaturation polyol having a high primary content, has a low density (0.5 g) without problems associated with poor processability or poor physical properties. / cm 3) microporous elastomers have been found.

The method of the present invention is therefore easy to implement and provides a lighter, higher quality polyurethane product that includes a sporting protective article, an armrest or steering wheel in the automotive industry and a midsole or shoe sole of a shoe.

In the process of the present invention, the resin component ("B" side) comprises a low polyunsaturated first polyol and a chain extender having a high primary content.

Polyols useful in the process of the present invention are prepared by ring-opening polymerization of cyclic ethers and include epoxide polymers, oxetane polymers, tetrahydrofuran polymers and the like. The polyols are prepared by any preferred method, but the final product must have both low unsaturation and high content of primary hydroxyl groups. Especially preferred are propyleneoxide-based polyols capped or tipped with oxyethylene.

Polyols have a high content of primary hydroxyl end groups. Such polyols are typically prepared by tipping or capping the ends of the polyoxypropylene polyols using oxyethylene units. By "high primary content" is meant a polyol having at least about 50% primary hydroxyl groups. More preferably, the primary hydroxyl group of the polyol is at least about 65%, and most preferably the primary hydroxyl group of the polyol is at least about 75%. It is important that the content of primary hydroxyl groups is high, and poor elastomers are obtained when polyols having a low primary content are used in the process of the invention, as shown in Comparative Example 6 below.

In addition, polyols have a low degree of unsaturation. "Low unsaturation" means that the degree of unsaturation is less than about 0.02 meq / g as measured by standard methods such as ASTM D-2849-69, "Test of Urethane Foam Polyol Raw Materials." Preferred polyols have an unsaturation of less than about 0.01 meq / g, and most preferred polyols have an unsaturation of less than about 0.007 meq / g. Polyols having very low unsaturation are simply prepared via double metal cyanide catalysts as described, for example, in US Pat. Nos. 5,470,813 and 5,482,908, the teachings of which are incorporated herein by reference. .

The polyols preferably have an average hydroxyl functionality of less than about 3. A more preferred range is about 1.8 to about 3.0.

In addition, the polyols preferably have a number average molecular weight ranging from about 500 to about 50000. A more preferred range is about 1000 to about 6000, and the most preferred range is about 2000 to about 6000.

The polyols preferably have a content of at least about 5% by weight, more preferably about 10 to about 20% by weight, of oxyethylene which may be present therein in the tip or end cap. Preferably most of the oxyethylene contained is located towards the end of the polyol to provide the desired high content of primary hydroxyl groups.

Low unsaturation polyols having a high primary content are usually the main component on the "B" side. Typically, at least about 40% by weight of the resin component is comprised. The preferred range is about 45 to about 90 weight percent, more preferably about 50 to about 70 weight percent of the resin component.

The resin component also includes a chain extender. Useful chain extenders have two or more active hydrogens and include low molecular weight diols, diamines, aminoalcohols, dithiols and the like. Preferably, the chain extender has a number average molecular weight of less than about 400, more preferably less than about 300. Diols are the preferred chain extenders. Suitable chain extenders include, for example, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl Glycol, cyclohexanedimethanol, 1,6-hexanediol, ethylene diamine, ethanedithiol and the like and mixtures thereof.

Particular preference is given to dipropylene glycol, ethylene glycol and 1,4-butanediol. Chain extenders (eg, glycerin) having a small amount of three or more active hydrogens may optionally be included.

The chain extender is the "B" side accessory. Typically, it constitutes less than about 30% by weight of the resin component. The preferred range is about 1 to about 20% by weight, more preferably about 3 to about 10% by weight of the resin component.

The resin component further includes a polyol, optionally with or without a low unsaturation or high primary content. Preferably, the resin component includes a polymer polyol. Suitable polymer polyols include a variety of well known ones prepared by obtaining a stable dispersion of polymer particles in a base polyol, for example styrene-acrylonitrile (SAN) polymer polyols, by in-situ polymerization of vinyl monomers in a base polyol. Other suitable polymer polyols include commercially available PIPA and PHD polyols (similar to SAN polymer polyols). Such polymeric polyols generally have a polymer solids content in the range of about 5 to about 50 weight percent. When polymeric polyols are included, it is preferred to use amounts ranging from 5 to about 45 weight percent based on the total amount of resin components.

The isocyanate-terminated propolymer ("A" side) reacts with the resin component ("B" side) in the process of the present invention. Propolymers are reaction products of polyisocyanates, high primary content, low polyunsaturated second polyols and second chain extenders.

Polyisocyanates are aromatic, aliphatic or cycloaliphatic isocyanates containing two or more free NCO groups. Suitable polyisocyanates include diphenylmethane diisocyanate (MDI), polymeric MDI, MDI variants, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like and mixtures thereof.

Preferred polyisocyanates are 4,4'-MDI, other MDI blends containing significant amounts of 4,4'-MDI isomers, and MDIs with other components themselves to react carbodiimides, allophanates, ureas, urethanes. , Modified MDIs (MDI variants) prepared by introducing burettes or other bonds into the structure. Especially preferred are 4,4'-MDI, carbodiimide-modified MDI and mixtures thereof.

The amount of polyisocyanate used is preferably the amount necessary to obtain an NCO-terminal propolymer or pseudoprepolymer having a free NCO content in the range of about 15 to about 30% by weight, more preferably in the range of about 20 to about 28% by weight.

The propolymer includes a high primary content, low unsaturation second polyol that may be the same as or different from the high primary content, low unsaturation first polyol. However, the second polyol has the same general properties as the first polyol such as low unsaturation (less than about 0.02 meq / g) and high content of primary hydroxyl groups (at least about 50%). Low unsaturation polyols of high primary content are the "A" side accessory. The isocyanate-terminated propolymer is preferably in the range of about 1 to about 10% by weight of the propolymer component, more preferably in the range of about 2 to about 8% by weight.

Propolymers also include chain extenders. This chain extender ("second" chain extender) may be the same as or different from the chain extender ("first" chain extender) used in the resin component. Alternatively, the second chain extender conforms to the above description for the first chain extender. The second chain extender reacting on the "A" side comprises about 5 to about 60 equivalent percent of total chain extender. Preferably the second chain extender comprises about 10 to about 40 equivalent percent of the total chain extender, with the range of about 15 to about 35 equivalent percent being most preferred.

The amount of chain extender used to prepare the propolymer is important. If present at less than about 5 equivalent percent, foam splitting, surface defects and other problems occur (see Comparative Example 8). In contrast, if more than about 60 equivalent percent of the total chain extender is present on the "A" side, excessive heat may be generated, resulting in undesired gelation of the propolymer.

Most propolymers are simply the reaction products of polyisocyanates and polyols, and the present invention incorporates chain extenders into the propolymers. The inventors have surprisingly found that 5 to 60 equivalent% of the total chain extender is pre-reacted on the "A" side with a high primary content, low unsaturation polyol at low density (0.5 g / cm) without problems of poor processability or poor physical properties. And less than 3) microporous elastomers. This simple step is important for providing lighter, higher quality polyurethane products, in particular the midsole or sole of a shoe.

The propolymers typically combine the second polyol, second chain extender and polyisocyanate in any desired order, and heat the mixture at a temperature and for a time effective to prepare the isocyanate-terminated propolymer. Usually, it is preferable to react the polyisocyanate with a low primary polyunsaturated polyol for a short time before introducing the second chain extender. The heating is then continued until the propolymer reaches the desired free NCO group content. In another preferred form, all or part of the second chain extender is added at the start of the propolymer-forming reaction.

After the propolymer is prepared, the resin component is blended to prepare the microporous elastomer by using conventional techniques. The resin component is a well blended mixture of low polyunsaturated first polyols, first chain extenders and other optional components, such as blowing agents, surfactants, catalysts and the like. Elastomers can be manufactured by hand casting or by machine. The "A" and "B" side components are combined, quickly mixed and injected or poured into an open or closed mold. The compositions described herein are well suited for use in commercially available equipment (eg, Gusbi molding machines) for making midsoles and soles of shoes by hermetic molding techniques.

Preferably, the process of the invention is carried out in the presence of a blowing agent. Suitable blowing agents are those well known in the art of microporous polyurethane elastomer production. These include "physical" blowing agents such as low boiling halocarbons (e.g. CFC, HCFC, methylene chloride) or hydrocarbons (e.g. butane, pentane), inert gases (e.g. nitrogen, argon, carbon dioxide), etc .; “Reactive” blowing agents such as water and other active-hydrogen compounds that react with the NCO group to release the gas are included. Blowing agent mixtures may also be used. Water is a particularly preferred blowing agent. The blowing agent is used in the amount necessary to prepare the microporous elastomer having a density of less than 0.5 g / cm 3. Preferably, the resulting elastomer has a density in the range of about 0.02 to about 0.4 g / cm 3, with the most preferred range being about 0.1 to about 0.3 g / cm 3.

The process optionally includes other conventional urethane foam components such as surfactants, foaming catalysts, urethane-forming catalysts, pigments, UV stabilizers, crosslinking agents, antioxidants, other polyols, and / or other additives. . This optional component is preferably completely mixed with the resin component before the resin component reacts with the "A" side to produce an elastomer.

The method of the present invention provides an advantage in the processing of elastomers. An appropriate amount of chain extender is "migrated" to the "A" side component to obtain improved control over reactivity and flowability during the processing of the elastomer, since much of the total reaction occurs before the elastomer is made. In addition, the method provides a wide processing range. As demonstrated in the examples below, good products can be produced in a wide temperature range (40 to 60 ° C.) and a wide index range (95 to 105) and have a short withdrawal time (less than 7 minutes).

In addition, the present invention provides advantages in physical properties. In the past, it has been difficult to produce microporous elastomers having a density of less than 0.5 g / cm 3 (particularly those having a density of less than 0.3 g / cm 3) without problems related to the quality of the product. Microporous elastomers prepared using the method of the present invention exhibited excellent tensile strength and tear strength, good skin quality and no internal splitting appeared. As shown in the examples below, the process of the present invention can readily prepare good elastomers having a density as low as about 0.26 g / cm 3.

The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

Example

<Examples 1 to 5 and Comparative Example 6>

Preparation of Microporous Polyurethane Elastomers

The reaction injection molding mixtures of the "A" and "B" side components as shown in Table 1 below were molded at 35 ° C using a Gooseby molding machine to form a 10 mm fine elastomeric plate. Molding temperatures ranged from 40 to 60 ° C. The product disappeared in viscosity within 1 minute. Physical properties are shown in Table 2. As shown in Table 2, microporous elastomers having a density of less than 0.27 g / cm 3 and good physical property balance can be obtained by the method of the present invention. In each embodiment of the present invention, the "A" side comprises a chain extender (dipropylene glycol) and a low primary polyunsaturated polyol. Comparative Example 6 shows the importance of using a "high primary content" polyol. Low unsaturation alone is not sufficient to obtain such a low density good product.

Composition Resin composition ("B" side) pbw Low Unsaturation Polyols (see Table 2) 58 Polymer Polyols 1 35 water 1.1 Ethylene glycol 5.2 Dabco EG Catalyst 2 0.2 X-8154 Catalyst 2 1.0 BL-17 Catalyst 2 0.2 T-120 catalyst 0.02 DC-193 surfactant 3 0.25 LK-221 emulsifier 2 0.75 Pigments (eg carbon black or TiO 2) 1.2 B-75 Stabilizer 4 1.0 Propolymer (“A” side; 24 wt.% NCO) 4,4'-MDI 80 Carbodiimide-modified MDI 8 Low Unsaturation Polyols (see Table 2) 5 Dipropylene glycol 7 1: SAN type, 43 weight% solids content, hydroxyl value 20 mg KOH / g 2: Product from Air Products 3: Product from Dow Corning 4: Product Ciba-Geigy Four products

Microporous Polyurethane Elastomer Example One 2 3 4 5 C6 Resin polyol A-4220 A-4220 A-4220 A-2220 A-2220 A-3201 Propolymer Polyols A-4220 A-4220 A-4220 A-2220 A-2220 A-3201 A / B side (w / w) 0.53 0.55 0.58 0.55 0.55 0.55 Index (NCO / OH) 0.95 1.00 1.05 1.00 1.00 1.00 Properties Density (g / cm3) 0.265 0.265 0.265 0.265 0.265 0.265 Hardness (Asker C) 61 62 62 60 58 60 Tensile strength (kg / cm2) 19.4 20.8 23.2 16.4 19.2 * Elongation (%) 307 255 296 319 324 * Split Tear (kg / cm, 10mm) 2.3 2.6 2.6 1.9 2.1 * A-4220 is Accuflex, a polyoxypropylenediol having an oxyethylene content (5% internal, 15% cap) of about 20% by weight and a primary hydroxyl group content of about 85% 4220 polyols. A-2220 is an Acuplex 2220 polyol, a polyoxypropylene diol having an oxyethylene content (5% internal, 15% cap) of about 20% by weight and a primary hydroxyl group content of about 85% . A-3201 is an Acuplex 3201 polyol which is a polyoxypropylene diol having an internal oxyethylene content of Mn = 3000, "about 10% by weight. All products are from ARCO Chemical. * Samples that crack and cannot be tested

<Example 7>

The methods of Examples 1-6 were followed except that the propolymer was prepared using 52 parts of 4,4'-MDI, 4 parts of dipropylene glycol and 3 parts of Accucue 4220 polyol.

The resulting midsole of the resulting shoe, which can be easily molded over a wide temperature range of 40 to 60 ° C., was excellent. Physical property: density: 0.26 g / cm3; Asker C hardness: 60 to 65; Split tear strength: 2.0 kg / cm; Tensile Strength: 19 kg / cm 2. The extraction time was less than 7 minutes and no skin peeling appeared.

<Comparative Example 8>

In this example, all the chain extenders used are included in the resin component ("B" side).

The method of Example 7 was changed as follows. The resin blend contained 1.5 parts of water and 12.5 parts of ethylene glycol. The propolymer was prepared using 81 parts of 4,4'-MDI, 46 parts of Accucux 4220 polyol and without chain extender.

The resulting midsole was poor. Physical property: density: 0.26 g / cm 3; Asker C hardness: 60 to 65; Split tear strength: 1.6 kg / cm; Tensile Strength: 17 kg / cm 2. The extraction time was 7 minutes or more. As apparent from the removal of the molded article, the skin quality of many samples was poor. In addition, internal splitting occurred in a number of components.

This embodiment is for illustrative purposes only, and the scope of the present invention is defined by the following claims.

As described above, the method of the present invention is easy to implement and provides a lighter, high-quality polyurethane product that is lightweight, including sporting protective articles, armrests or steering wheels in the automotive industry, and midsoles or soles of shoes.

Claims (7)

Resin component (“B” side) and isocyanate-terminated propolymer (“A” side) are reacted in the presence of a blowing agent, surfactant and catalyst to produce a microporous polyurethane elastomer having a density of 500 kg / m 3 Include, Wherein the resin component comprises a mixture of a first chain extender and a low polyunsaturation first polyol having a high primary content, The propolymer is reacted with a polyisocyanate, a second polyol having a high primary content, which may be the same as or different from the first polyol, and a second chain extender that may be the same as or different from the first chain extender. Manufacturing, Reacting and wherein said second chain extender comprised on the "A" side constitutes 5 to 60 equivalent percent of total chain extender. The method of claim 1 wherein the second chain extender comprises 10 to 40 equivalent percent of total chain extender. (a) (i) a low polyunsaturated first polyol of high primary content, (ii) a first chain extender, and (iii) optionally blowing agents, surfactants and catalysts A resin component comprising a mixture of ("B" side), and (b) (i) polyisocyanates, (ii) a low polyunsaturation second polyol having a higher primary content, which may be the same or different from the first polyol, (iii) a second chain extender which may be the same as or different from the first chain extender Isocyanate-terminated propolymers containing the reaction product of the "A" side Wherein the second chain extender reacted on the "A" side comprises from 5 to 60 equivalent percent of the total chain extender and the elastomer has a density of less than 500 kg / m 3. Urethane elastomer. The elastomer of claim 3 having a density in the range of 20 to 400 kg / m 3. The elastomer of claim 3 or 4, wherein the “B” side comprises a polymer polyol. Sports protective article comprising the microporous elastomer of any one of the preceding claims. A shoe sole comprising the microporous elastomer of any one of the preceding claims.