JPH03504740A - Solvent-resistant polyether urethane products and their manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Solvent resistant polyether urethane products and its manufacturing method The present invention relates to polyurethanes having hydrocarbon resistance and products made therefrom. do.

Conventional polyurethanes generally have poor hydrocarbon resistance. i.e. dove Most polyurethanes degrade, swell, or dissolve in the presence of hydrocarbons. As a result, they generally cannot be used appropriately when exposed to hydrocarbons. I can't. This issue has been discussed, for example, in U.S. Patent 4.713.399. Here, we will discuss poly(alkylene carbonate) used in the production of urethane foam. ) The use of polyols improves the solvent stability of the foam. is reported. However, in U.S. Patent 4.728.711, the use The solvent swells the polyurethane, and the swelling seals the fuel tank.

Some solvent-resistant polyurethane compositions are made from Contains aliphatic or cycloaliphatic polyisocyanates. For example, U.S. Patent 4.668.5 In No. 35, an aliphatic polyisocyanate is dissolved in a solvent to form a certain aliphatic polyisocyanate. The company manufactures polyurethane used as a "cement" component. methylenebis(4-iso Cyanatocyclohexane) is used in polyurethane to achieve fuel oil resistance. That is taught in U.S. Patent 4.247.678 and 4.487.913. ing.

Producing hydrocarbon-resistant polyurethane using a certain polyester polyol has also been carried out. For example, polyester polyols are used in polyurethane. is disclosed in US Pat. No. 4,247.678.

Hydrocarbon resistance is often determined by the use of certain polyurethanes in combination with certain other polymers. This has been achieved by being present. For example, in U.S. Patent 4.522.979 is a urethane prepolymer mixed with polyester and polycarbonate resins. It is used for profit.

Various other means have been used in attempts to achieve solvent resistance. US patent 4 ．． 404.498, in producing the polyurethane having solvent resistance, Discloses the use of specific long chain diols and short chain triols used in specific proportions. ing.

U.S. Pat. No. 4,146,723 describes a polyurethane polyester with improved chemical resistance. Discloses the use of urea diisocyanate, which is an odor for producing urea. . Introducing some unsaturation into a polyurethane, which in turn introduces through the unsaturation It has also been reported that solvent resistance is improved by being able to be crosslinked. .

Shows hydrocarbon resistance from aromatic polyisocyanates and polyether polyols. It would be desirable to produce a polyurethane with a polyurethane. Polyether polyol is Polyester resists hydrolysis more favorably than polyols and is widely available. be.

Advantageously, the polyether urethane is hydrocarbon resistant without the use of other polymers. .

According to one feature, the invention provides: (a) polyisocyanate component; and (bHi) a small amount relative to the total active hydrogen component; at least about 50% by weight, at least about 50% by weight oxyethylene units , at least one polyether polyester having an average nominal functionality of at least about 3. [The polyether polyol is capped with ethylene oxide] [contains a secondary hydroxyl group] Active hydrogen component containing A urethane polymer produced from a reaction mixture containing It is a hydrocarbon elastomer.

According to another feature, the invention provides: (a) a polyisocyanate component: m and (bHi); ) at least about 50% by weight, based on the total active hydrogen component; % of oxyethylene units. formed from a urethane polymer prepared from a reaction mixture containing an active hydrogen component. Hydrocarbon-resistant seals, conduits, vessel linings, rolls, mechanical parts, and machinery Including target belt.

Furthermore, according to other features, the present invention provides for the following components; (i) with respect to the total active hydrogen component; at least 50% by weight, at least about 50% by weight of oxyethylene units. at least one polyether having an average nominal functionality of at least about 3, comprising: Polyol [The polyether polyol is capped with ethylene oxide] (ii) 0 to 45% by weight of the total active hydrogen component; at least one polyester having a nominal functionality and a molecular weight of 1000 to 5000; Ether polyol; (iii) 5 to 30% by weight of the total active hydrogen component, a molecular weight of about 400 or less; an active hydrogen-containing composition comprising: at least one diol having

The urethane polymer of the present invention exhibits very little swelling in which the polymer Therefore, it is suitable for use in environments where the polymer is exposed to hydrocarbons.

FIG. 1 shows a perspective view of the filtration device.

2 shows a perspective view of the cap of the filtration device of FIG. 1; FIG.

FIG. 3 shows a perspective view of the gasket.

FIG. 4 shows a cutaway perspective view of the line chute.

FIG. 5 shows a perspective view of the roll.

FIG. 6 shows a perspective view of the mechanical belt.

FIG. 7 shows a perspective view of the gear.

FIG. 8 shows a partially sectional perspective view of a gear with an outer layer.

FIG. 9 shows a perspective view of the conduit.

FIG. 10 shows a perspective view of the container.

The urethane polymer of the present invention is produced by a reaction between a polyisocyanate component and an active hydrogen component. to form. The active hydrogen component predicts the tendency of hydrogen-containing groups to react with isocyanates. By Kohler, the Journal of the Ameri can Chemical 5ocity, νo1.49゜p, 3181 ( Isocyanene as shown by the Zelewitinoff test described in (1927) is one or more compounds that are active in reaction with ato groups.

In the practice of this invention, the active hydrogen composition comprises at least also about 50% by weight, at least about 50% by weight of oxyethylene units. Both contain one relatively high equivalent weight polyether polyol. polyether polio is a relatively high equivalent active hydrogen moiety having at least two hydroxyl groups. It is. The oxyethylene group is a divalent -0-CH, -CH, - group. "Comparison" The term "high equivalent weight" is used to indicate an equivalent weight of at least about 400. Main departure Relatively high equivalent weight polyether polyols for use in the present practice are advantageous. 500-2500. Preferably 800-2300, more preferably 1000 It has an average equivalent weight of ~2000.

The oxyethylene group containing the polyether polyol is converted into at least one type of initiator. Manufactured by polymerizing or copolymerizing ethylene oxide in the presence of a compound. be able to. Boron trifluoride, potassium hydroxide, tributylamine, tributyl Catalysts such as amines and the like are generally preferred. The initiator compound may be, for example, water, about 2 Polyhydric alcohols having ~8 hydroxyl groups, and amines. Echi Ren oxide is preferably used in the production of polyether polyols. Used in combination with at least one alkylene oxide. other alkylenes The oxide is preferably propylene oxide or butylene oxide or , more preferably propylene oxide.

Ethylene oxide and other alkylene oxides may be added sequentially or simultaneously (different The latter is preferred.

When alkylene oxides react simultaneously, random copolyethers are formed . If the oxides react continuously, block copolyethers are formed.

Broth produced continuously using ethylene oxide as the final alkylene ether. copolyethers have oxyethylene units on the ends of the polyether chains, It is called an ethylene oxide capped polyether polyol. Echire The carbon oxide cap is a polyether with a very high proportion of primary hydroxyl groups. Reacts extremely quickly to produce polyols and, as a result, to form polyurethanes do. A block of oxyethylene units is placed inside the polyether chain rather than at the end. Random copolyethers and block copolyethers with It is called an unpolluted polyol. These uncapped polyols are , a higher proportion of internal oxide than ethylene oxide-capped polyethers ethylene units and a low proportion of terminal oxyethylene units, resulting in monohydroxyl) slower than ethylene oxide-capped polyols It has more secondary hydroxyl groups than primary hydroxyl groups to react with. This low response Because of its properties and utility, uncapped polyols are preferred in the practice of this invention. More preferable. Most preferably, the polyol contains at least about 25% secondary hydroxyl. It has a syl group. Slower reaction times are desirable in the hydrocarbon resistant products of the present invention. manufactured and shaped (e.g., by molding) engineered elastomers with new physical properties. Allow time to do so.

For use in the practice of this invention, polyether polyols advantageously contain less than at least 50% by weight of oxyethylene units, preferably from 50 to 90, more preferably contains 60-85, most preferably 65-75% by weight oxyethylene units.

Achieving a given weight percent of oxyethylene units depends on the total alkyl used in the polymerization. The weight percent of ethylene oxide in the ethylene oxide is It is often necessary to be somewhat larger than the For example, about 80% by weight About 75% by weight using both tyrene oxide and 20% by weight propylene oxide of oxyethylene units can be produced.

The nominal functionality of the polyether polyol is determined by the starting compound. nominal Polyethers contain as many hydroxyl groups as the starting compound has active hydrogen groups. have Alcohol suitable for initiating the formation of polyalkylene polyethers Examples are ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol lene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-bentanediol, 1,7-heptanediol ol, glycerol, 1,1.1-) listyrol brova 7.1.1.1-t Limethylolethane, hexane-1゜2.6-driol, α-methylglucosylene pentaerythritol, erythritol, and pentatols and hexa Contains satols. Sugars, i.e. glucose, sucrose, fructose Compounds derived from toses, and aldoses, and phenols, viz. , e.g. (4,4'-hydroxyphenyl)-2,2-propane, may also be used in the practice of the invention. is a polyhydric alcohol suitable for forming polyether polyols useful in .

At least about 50% by weight of oxyethylene units used in the practice of this invention Advantageously, the polyether polyol comprising at least about 3, preferably from 3 to It has a nominal functionality of 8, more preferably 3-4. The polyol is advantageously 20 00~7500, preferably 2500~7G(to, more preferably 3000~ 6500, most preferably 4000-6000.

A polyether polyol containing at least about 50% by weight oxyethylene units , in the practice of the invention, at least 2 as determined by the Zerewitinoff method. It is advantageously used with other organic compounds containing active hydrogen-containing groups. suitable active hydrogen The compounds were described in U.S. Pat. No. 4,394,491, particularly in columns 3-5 thereof. The production of polyurethanes such as compounds (where the compounds are called polyals) It is commonly used in construction.

These active hydrogen compounds preferably contain relatively high equivalent weights of polyols. this Examples of such polyols are generally known, such as 5unders and Old gh Polymers by Fr 1sch.

Vol, XVl, Po1urethanes, Chemistry and "Technology".

Interscience Publishers, New York, V ol, 1. p, 32-42.44-54 (1962> and Vow, IN p, 5-6.198-199 (1964); Kunststoff-Han dbuch, Vol, VII, Vieweg-t(ochtlen, 　Cari) Ianser-Verlag.

Munich, p. 45-71 (1966); rs, Chapman Op., 1-76.0.

In addition to the polyether polyol as previously described, less than about 50% by weight Polyesters with strong oxyethylene groups but also hydroxyl-terminated chains are also active. preferred for use as a hydrogen-containing compound. Examples of polyols are hydroxy Functional acrylic acid polymer, hydroxyl-containing epoxy resin, polyhydroxy terminated Urethane polymers, polyhydroxyl-containing phosphorus compounds, and polythioethers , alkylene oxides of polyvalent thioethers, including acetals, including polyacetals. Also includes side adducts. These polyols preferably contain at least about 50% by weight Polyether polyols with oxyethylene groups have a smaller nominal functionality than more preferably a nominal functionality of less than about 3, most preferably a nominal functionality of about 2. It has functionality.

Polymer polyols introduce generally undesirable hardness into the elastomers of the present invention. Because of this, polymer polyols are preferably avoided in the practice of this invention. Po If remer polyols are present, they may cause undesirable polyurethane hardness. should have an insufficient amount to affect the In particular, the active hydrogen component is a polymer than the hardness of a similar polyurethane made from the same formulation without the presence of polyol. is also higher than about 5 Shore A units, and polyurethane elastomers made therefrom Does not contain enough polymer polyol to increase the Shore hardness of the polymer.

Preferably, the active hydrogen component is combined with at least one chain extender and one or more ratios. Contains a relatively high equivalent amount of active hydrogen components.

The term "chain extender" refers to an active hydrogen source suitable for reaction with a useful isocyanate group. at least 2 functional groups having children, advantageously up to about 400, preferably Active hydrogen having an equivalent weight of less than about 200, more preferably less than about 100 Used here to refer to compounds. The chain extender is preferably difunctional. i.e., they contain exactly two functional groups containing active hydrogen atoms per molecule. have Mixtures of difunctional and trifunctional compounds are also useful. A suitable chain extender is , primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, containing alcohols, glycols or mixtures thereof. Examples of compounds are ethylenediamine, Hydroxyamines, such as ethanolamine, propatoolamine, and Contains tanolamine. Chain extenders are used as pre-selected physical are generally chosen to achieve physical properties such as hardness and strength.

Useful chain extenders include primary and secondary diamines that readily react with isocyanates. including. Such chain extenders are disclosed, for example, in U.S. Pat. No. 4,526,905. phenylene diamine, bis(3-chloro-4-aminophenylene), such as ) Methane, 2,4-diamino-3,5-diethyltoluene, 2゜6-diamine -3,5-diethyltoluene, trisec-butanolamine, isodiisopropaz amine, diisopropanolamine, N-(2-hydroxypropyl)ethylamine Diamine, N,N'-di(2-hydroxypropyl)ethylenediamine and Contains di-alkyldiaminobenzene. Aniline is condensed with formaldehyde A liquid mixture of polyphenylpolymethylene polyamines obtained by suitable, as well as e.g. glycol-initiated polyalkylene ethers and and those formed by aminating polyoxypropylene. Oxyalkylene polyamines are also suitable. Amine chain extenders are generally RIM be sufficiently sterically hindered or oxidized to allow sufficient processing time in the equipment. scientifically delayed. Among diamine chain extenders, aromatic dicarbonate having a linear alkyl substituent having 1 to 3 carbon atoms in the ortho position; Amines are generally preferred.

Chain extenders with hydroxyl groups are preferred; low molecular weight aliphatic alcohols, For example, 1,4-butanediol, ethylene glycol, trimethyl dipropane, diethylene glycol, and 1,4-cyclohexane dimeta-2 aromatic ring-containing diols, i.e., for example, bis-hydroxyethyl hydroxyl; non-, bisphenol, catechol, and resorcinol; amide or Contains diol-containing diols as well as amino alcohols. Aliphatic diol chain extender More preferred, generally having a backbone having 2 to 6 carbon atoms; 1.4-butane Diols are most preferred.

Aminated polyalkylene polyethers, i.e. aminated polyoxy Propylene glycol is also useful as a chain extender. Such polyalkylene The polyethers preferably have an average amino hydrogen equivalent weight of 60 to 110.

Different types of chain extenders may be used in combination if desired. For example, 2-cyano-p -Mixtures of fluorinated diamines and aliphatic mono- or dicarboxylic acids are patented in the United States 3.839.292. as desired Enamines and aromatic diamines with polydiols are disclosed in U.S. Pat. 45. The preferred chain extender mixture is , for example, as disclosed in U.S. Pat. No. 4,269,945, Mixture of amines; aminated polyalkylene polyethers and aromatic diamines mixtures; and mixtures of glycols and aminated polyalkylene polyethers including.

The chain extender advantageously has a relatively high equivalent weight relative to the total weight of the active hydrogen-containing compound. 2.5-100% by weight, preferably 5-50% by weight, more preferably 12-50% by weight Used in amounts of % by weight. Those skilled in the art will understand that pre-selected physical properties, e.g. It is well known to adjust the amount of chain extender to achieve flexibility, flexibility, etc. Ru.

Active hydrogen compounds useful in the practice of this invention preferably include (j) total active hydrogen components; at least about 50% by weight of oxyethylene At least one polyether polyol containing units [the polyether polyol] The ol has a nominal functionality of at least about 3 and is capped with ethylene oxide. Not included]; (ii) from 0 to 45% by weight, but less than about 50% by weight, based on the total active hydrogen component; containing oxyethylene units, an average nominal functionality of about 2 and 1000 to 5000 at least one polyether polyol having a molecular weight; (iii) 5 to 30% by weight of the total active hydrogen component, a molecular weight of about 400 or less; at least one diol having

Component (jj) is more preferably present in an amount of 20-45% by weight.

The isocyanate index is the isocyanate group and active water in the total isocyanate component. This is 100 times the ratio of the number of active hydrogen groups in the elementary components. Therefore, the index of 100 is Stoichiometric amounts of isocyanate and active hydrogen compound (if present, chain extender and (including water). An isocyanate index of 85 to 125 is used in the practice of this invention. preferred for As the index increases, the hardness of the reactive polyurethane elastomer generally increases. degree increases.

The molecular weight per crosslink is the theoretically useful active hydrogen for crosslinking the total weight of the materials used. Calculated by dividing by the equivalent weight of the compound. Active hydrogen compounds theoretically useful for crosslinking The equivalent weight of the compound exceeds that required for the stoichiometric reaction with the isocyanate compound. It is understood that it is the total number of equivalents of all active hydrogen compounds.

For example, an index of 95 is: 5% excess of active hydrogen groups) and 2 excess of nominally reactive active hydrogen groups per molecule. That proportion of groups (for example, a triol has a nominal functionality of 3, which is 1/3 excessive). If 300 equivalents of triol are used with an index of 100, then There will be an excess of 100 equivalents. The total excess of these two components over the stoichiometry The total weight is divided into the total weight of the isocyanate component and the active hydrogen component used at that time. . of polyisocyanate reacted with polyol and 1,4-butanediol An illustrative calculation for a mixture is shown in Inventive Example 12.

Generally speaking, a relatively high equivalent amount of active hydrogen compounds when incorporated into polyurethane. The company manufactures a segment of polymer called a soft segment, and this segment has a relatively low glass transition temperature. Relatively low glass transition temperatures are generally The temperature is below the intended use temperature of the polyurethane.

Chain extenders in polyurethanes generally extend the segment called the hard segment. manufactured, which is arranged in the polymer and exceeds polymers without hard segments. It is believed that this increases hardness. The amount and type of chain extender generally Preselected hardness and other preselected properties in the final polyurethane selected to achieve specific physical properties.

The use of an isocyanate index greater than about 100 increases the hard segment content and therefore It also increases hardness. The percentage of hard segments is The weight of the chain extender in the inocyanate used to react with the chain extender. Weight and total hard segment weight (ASTM 1638-74 dibutyl active hydrogen and polyisocyanate (determined by amine back titration procedure) Calculated by dividing by the total weight of the ingredients.

In the practice of this invention, the polyurethane preferably has good hydrocarbon resistance as well as The combination of hard segment content and molecular weight per crosslink that produces elastomeric properties. It has a combination.

The molecular weight per crosslink is preferably at least about It is 2700. The preferred maximum molecular weight per crosslink is the increases in proportion to the amount of component. For example, the hard segment content is approximately 35 wt. %, the molecular weight per crosslinked segment is preferably about 7000 It is smaller than, more preferably 2,700 to 7,000.

However, if the hard segment content is 70% by weight, the molecular weight per crosslink is preferably less than about 12,000, more preferably between 2,700 and 1,200 It is 0.

3 inches (3 inches) of the urethane polymer of the present invention having a thickness of 0.2 inches (5 mm). 76 mm) diameter disc preferably at 250'F for at least about 10 hours. 100 ps ig (690 KPa gauge) with 100 cycles/s at (121 °C) withstands pulses of

Polyisocyanate components suitable for use in the practice of this invention include at least two It is an organic compound containing isocyanate groups. Such compounds are well known It is easily commercially available. The polyisocyanate starting compounds are aromatic, Includes aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Polyiso Examples of cyanates are diisocyanates, i.e. for example m-phenylene diiso Cyanate, toluene-2,4-diisocyanate, toluene-2,6-diiso Cyanate, hexamethylene diisocyanate, tetramethylene diisocyanate cyclohexane-1,4-diisocyanate, hexahydrotoluene diiso Cyanate (and its isomers), naphthylene-1,5-diisocyanate, 1-Medoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4 '-diisocyanate, diphenylmethane-2,4'-diisocyanate, 4. 4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-bi Phenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diiso cyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate. Anate; triisocyanate, i.e., for example, 4.4', 4"-1- Liphenylmethane triisocyanate and toluene-2,4,6-dolyisocyanate Anate; tetraisocyanate, i.e., e.g. 4,4'-dimethyl diphthyl phenylmethane-2,2', 5゜5'-tetraisocyanate, 4,4'-disic Lohexane diisocyanate, isophorone diisocyanate, and their derivatives. as well as other polyisocyanates, i.e. polyphenylisocyanate; nates, and mixtures thereof.

Aromatic polyisocyanates are preferably prepared therefrom according to the practice of the present invention. The present invention is advantageous because the polymers shown in this invention exhibit little swelling when exposed to hydrocarbons. Used in implementation. properties imparted to elastomers made therefrom and Because of its usefulness, toluene diisocyanate, diphenylmethane-4,4'- Diisocyanate, diphenylmethane-2,4'-diisocyanate and poly More preferred are rimethylene polyphenylisocyanate and mixtures thereof: poly Methylene polyphenylisocyanate and diphenylmethane-2,4'-diisocyanate Mixture of anate and/or diphenylmethane-4,4'-diisocyanate most preferred.

The mixture preferably contains at least about 25% by weight polymethylene polyphenyliso Contains cyanate.

Polyisocyanates are typically produced by phosgenation of polyamine precursors be done. For example, polyphenylpolymethylene polyisocyanate is an aniline/polymethylene polyisocyanate. Produced by phosgenation of formaldehyde condensates. Unrefined polyisocyanate Also suitable for use in the practice of this invention. Such unpurified isocyan nate is the crude toluene obtained by phosgenation of a mixture of toluene diamines. For phosgenation of diisocyanate or crude diphenylmethylene diamine. Contains unpurified diphenylmethylene diisocyanate obtained from Unrefined isosome Anate is disclosed in US Pat. No. 3,215,652.

Polyisocyanates useful in the practice of this invention may optionally be prepolymers or pseudopolymers. induced to form a prepolymer. In general, modifications useful in the practice of the present invention The polyisocyanates have a free isocyanate content of 1 to 40% by weight.

The diisocyanate starting compound is added in stoichiometric amounts to form the prepolymer. React with active hydrogen-containing compounds with low oxidation. Suitable active hydrogen-containing compounds are e.g. For example, dipropylene glycol, propylene glycol, hydroxy ester, Amines, amino alcohols, triols, thioesters, and polypropylene Contains glycol.

In the practice of the present invention, when an ordered structure polymerization reaction is desired, the prepolymer shape is Preferably. One method for prepolymers involves competitive reactions such as isocyanate and water and and the control of the reaction between the hydroxyl groups of the polyol is difficult to achieve. In the process, it is used to achieve more uniform chain extension of the polymer. child Under these circumstances, the prepolymer or pseudo-prepolymer is generally combined with the polyol. Formed by reacting excess polyisocyanate. At that time, pre-poly The mer is reacted with a chain extender, preferably in the presence of a catalyst. Prepolymer type polyisocyanate and active hydrogen in undesirable or similar amounts When using the preferred equipment, the use of components directly is called the one-shot method. To cause a reaction in something.

One or more catalysts are advantageously used in producing polyurethanes. appropriate touch The medium is a tertiary amine, i.e., triethylenediamine, N-methyl mol. Holin, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine 1-methyl-4-dimethylaminoethylpiperazine, 3-ethoxy-N-di Methylpropylamine, N,N-dimethyl-N',N'-methylisopropyl propylene diamine, N,N-diethyl-3-diethylaminopropylamine, Dimethylbenzylamine, triethylamine, tributylamine, bis(N,N -diethylaminoethyl)adipate, 2-methylimidazole and 1,4- Contains diazabicyclo-2°2.2-octane. Other suitable catalysts are tin compounds, Thus, for example, stannous chloride, tin salts of carboxylic acids, such as dibutyltin di-2- Ethyl hexoate, dibutyltin dilaurate, dibutyltin diacetate, and di-2-ethylhexyltin oxide, as well as other organometallic compounds, i.e. For example, compounds of lead, arsenic, antimony, mercury, and bismuth, and 2.846.408.

Silamines with carbon-silicon bonds, i.e., e.g. 2°2.4-)rifthyl - as disclosed in German Patent 1,229.290 containing 2-silamorpholine, as well as basic nitrogen compounds such as tetraalkyl ammonium hydroxide, alkalis Metal hydroxides, e.g. sodium hydroxide, alkali metal phenolates, e.g. thorium phenolate, and alkali metal alcoholade, i.e. Sodium methylate, and hexahydrotriazine are also useful catalysts. catalyst Mixtures are also suitable.

The metal atom-containing catalyst generally has a molecular weight of 0.0025 to 0 relative to the active hydrogen-containing starting compound. ．． It is used in an amount of 5% by weight. Amine catalysts generally react with active hydrogen-containing starting compounds. 0.001 to 5% by weight of Special Table Sen3-504740 (7) used in quantity. Those skilled in the art will know the appropriate catalyst composition to promote the reaction between the starting compounds. And you can choose the quantity. Examples of catalysts and details regarding their use can be found in V. Kunstoff-H, published by ieweg and I (ochtlen) andbuch, Vol, νII, Carl-Hanser-Verlag , Munich, 1966, p. 9E+~102.

Additives, i.e. surfactants, antistatic agents, plasticizers, fillers, flame retardants, Pigments and stabilizers such as antioxidants, fungicides and bacteriostatic agents are optionally added to the polyester. Used in urethane.

The active hydrogen component and polyisocyanate component are reacted to form a hydrocarbon-resistant material. Form a urethane polymer. Resistance is extremely low when immersed in hydrocarbons. Confirmed by no swelling. Examples of hydrocarbons are SAE AMS 302 2 Diesel fuel # as specified as A-87. place the sample on the edge It measures 3X3X1/8 inches (76X 76X 3.2 mm). Place a rectangular sample in a container and adjust the volume so that most of the sample surface area is exposed. It was supported by the side of the vessel. At least enough diesel fuel to completely submerge Add #2.

Heat the fuel to 158″F (70°C) for 70 hours. Remove swelling after soaking before soaking. The original weight increased by soaking is determined by the weight of the sample after soaking. Express as a percentage. The practice of the present invention preferably provides less than about 15% by weight. preferably less than about 10% by weight, most preferably less than about 5% by weight. A urethane polymer exhibiting moisture content is produced.

The produced urethane polymer advantageously has an elastomer that can recover its shape after deformation. It's Tomah. The deformation is preferably greater than about 100% at 75″F (24°C). Preferably, as shown by elongation measurements of about 100% to about 400% at 75″F (24°C). It will be done. More preferably, the elastomer has a temperature of at least 250"F (121C). It also has an elongation of about 40%, most preferably between 40% and 150%. preferred rubbery The elasticity is at least about 1000 psi (6900 KPa) at 75″F (24°C). ), preferably 1000 to 3000 ps i (690 0 to 20.700 KPa), more preferably at 250″F (121°C) Both are approximately 300 ps i (2070 KPa), preferably 3000 (2070 KPa). 0) to 1000 ps i (6,900 KPa). tension Both elongation and elongation are determined by ASTM 0638-84 or [1412-84 Measured according to the following. When using a sample of polymer long enough to meet the requirements of the test ASTM 0412-84 is preferably used. For smaller samples , using ASTM 0638-84. The numerical results of the two tests are considered equivalent. It will be done.

60-90 Shore A, measured according to ASTM 02240-84 procedure. A Shore A hardness of 100% is also more preferably achieved.

The urethane polymer elastomers produced in the practice of this invention preferably include Not an open cell foam, more preferably no foam, most preferably a cell It's not quality.

Preferably, the elastomer has a molecular weight greater than about 30, more preferably between 50 and 90, Most preferably 60-80 pounds per cubic foot (71!b, / ft') (PCF), i.e.; preferably greater than about 480, more preferably 800-1440, most preferably 960-1280 kg/m3 <kg/m').

When tested according to the procedure of ASTM D395-85, Method B at 250'F. More preferably, the polymer is less than about 40%, preferably less than about 20%. It is also desirable to have a compression set of less than about 10%.

The urethane polymers of the invention are preferably suitable for use in hydrocarbon resistant conduits, containers, systems, etc. used as wheels, mechanical belts, linings, coatings, rolls, and machine parts It is suitable for applications where the polymer is exposed to hydrocarbons. A conduit is an example Examples include pipes, hoses, tubes, and gasoline lines. The container is, for example , including tanks, bottles, flasks and pans. Mechanical belts are e.g. from energy sources such as engines and turbines to other movable equipment, e.g. Belts that carry energy to the fan and other engine parts, i.e. Vehicle belts, truck belts, and pump belts, as well as transportation belts, e.g. This includes, for example, conveyor belts. Seals include, for example, gaskets; fuel fillers; Adhesive systems that perform adhesive functions such as hydrocarbon filter sheets, including router caps. pipe seals; and adhesive construction seals; gap-filling seals, i.e. , such as construction seals, door seals, window seals and roof seals, and O-lin as well as any polyurethane material that separates other products and fills gaps between said products. Including tan products. Linings include, for example, conduit and vessel linings, i.e. , for example, hoses, pipes, tubes, tanks, bolts, boilers and pans. Including lining for. Coatings are suitable for use on surface coverings and any other objects. preferably objects that come into contact with or are immersed in hydrocarbons, i.e., e.g. conduits, containers; , rolls, and coatings on machine parts. Mechanical parts include gears, oil field equipment, etc. installations, parts of equipment such as downhole equipment, engine parts, and pump parts ( In particular, pump parts for petroleum and petroleum products). The roll can be, for example, a textile roll. , including printing rolls, paper kneading rolls, and metal working rolls.

An example of a particular type of use for a seal is a filter cap for a hydrocarbon filter. filter A filter cap is something on one or more ends of a hydrocarbon filter. Advantageously, filtration The vessel cap fits between the filter and the filter jacket. Preferably, the filter key The cap also restricts the flow of hydrocarbons so that they flow through the filter. do. Hydrocarbons which are suitably filtered include petroleum products, i.e. fuels and and feedstocks, lubricating oils, i.e., oils and other hydrocarbon materials, This includes, for example, solvents and cleaning fluids. Filter person with two caps A typical outline of one is shown in Figure 1. In FIG. 1, the first cap 11 and the There is a cylindrical filter 12 with two caps 13. The filter 12 shown has cylindrical pleats. It is a paper filter.

Other filter shapes, e.g. generally tubular, but with any cross-section, i.e. Square, rectangular, triangular or other polygonal cross-sections are also suitable. Also, the substance , any porosity suitable to pass the desired hydrocarbons while leaving behind the undesired substances. It may be a sexual substance. Such materials are known to those skilled in the art. The filter is It doesn't have to be scalloped, but it exposes more surface area to hydrocarbons than other useful ones. Arrangements such as pleated, folded, or helical arrangements are generally preferred. Each key The cap is preferably molded onto the end of the filter. A person skilled in the art would understand that such a cap can be molded onto the filter without unnecessary experimentation. Advantageously, a filter The formulation is preferably introduced into the mold before the capping formulation is fully cured. It is then introduced into a mold for capping before being soldered.

As shown in FIG. 2, the cap 11 has a hole 15 generally through the center. Generally has a disc shape. The cap also has an outer surface 14. in the manner shown In this case, the second cap 13 has a disc shape without a hole. cap 11 and 13 are preferably filtered so that the hydrocarbons entering at 15 pass through filter 12. is adapted to the filter 12. Preferably there is a jacket around the filter. outer covering If so, the incoming hydrocarbon stream passes through hole 15 and then through filter 12 and is filtered. including means for introducing hydrocarbons such that the hydrocarbons are The outer covering is preferably is a filtered system where the filtered hydrocarbons are not mixed with the incoming hydrocarbons. Includes means to limit hydrocarbons. The jacket preferably filters the filtered hydrocarbons. It also includes means for leading from the vessel.

FIG. 3 shows a perspective view of a gasket 30 suitably formed from the urethane polymer of the present invention. A view is shown. Gasket 30 has a generally rectangular shape and is an example of a seal of the present invention. Ru. Those skilled in the art will be able to form the seals of the present invention without undue experimentation.

Preferably the seal is cast or molded.

FIG. 4 shows a cutaway perspective view of the line chute 40. Shu) 40 is the substance It has a self-shaped structural member 41 suitable for guiding.

Structural member 41 is suitably any material, preferably of structural form and integrity. and the weight of the chute and the material being led, e.g. metal or plastic. Manufactured from something strong enough to support it. The chute 40 further includes the urea of the present invention. It has a lining 42 suitably formed from a tan polymer. The lining 42 , preferably in close contact with the structural member 41. The lining 42 is a liner of the present invention. This is an example of Those skilled in the art will be able to construct conduits, containers, and similar materials without undue experimentation. It can form a lining for the product.

FIG. 5 shows a roll 50 having a shaft 51, an inner cylinder 52, and an outer cylinder 53. A perspective view is shown. Shirt 1-51 and inner cylinder 52 are designed for structural integrity and mechanical Suitably formed from any material suitable for preserving the properties of the material. Such substances are including metals and plastics. External part 53 and optionally shaft 51 and/or the inner cylinder 52 is suitably formed from the urethane polymer of the present invention. Ru. Roll 50 is an example of a roll of the present invention. Advantageously, the roll has an internal cylinder 52 and the outside 53, said member is a member of the present invention. Formed from urethane polymer. Those skilled in the art will be able to utilize the present invention without undue experimentation. can be formed. Preferably the roll is cast or formed. suitable In fact, the exterior designated by 53 in FIG. 5 is designated by 52 in FIG. Can be applied onto the inner cylinder.

FIG. 6 shows a perspective view of mechanical belt 60. Mechanical belt 60 is suitably shown. As is, as shown, or as a belt more oblong than shown It may have other configurations suitable for use. The belt suitably comprises the belt of the present invention. Formed from urethane polymer. Those skilled in the art will be able to ascertain the scope of the invention without undue experimentation. can be formed. Preferably the belt is cast or molded.

FIG. 7 shows a perspective view of a gear 70 suitably formed from the urethane polymer of the present invention. show. Preferably the gear is cast or molded.

FIG. 8 shows a perspective view of a gear 80 having an inner layer 81 and an outer layer 82. FIG. teeth Wheel 80 is a partial cutaway showing the composition of layer 82 on cutout 84 as metal. , shows the outer layer 830 composition as a plastic. Outer layer 82 may suitably be of the present invention. urethane polymer. In other embodiments of the invention, the inner layer is Any material with sufficient strength, hardness, and wear resistance suitable for the function of gears, e.g. Constructed from abrasive metal or plastic. Those skilled in the art will understand that unnecessary experimentation The gear of the present invention can be formed without any process. The inner and outer layers of the gear If so, the gears are preferably formed by compression molding or extrusion.

FIG. 9 shows a perspective view of a conduit 90 suitably formed from the urethane polymer of the present invention. show. FIG. 10 shows a container 100 suitably formed from the urethane polymer of the present invention. A perspective view of the figure is shown. Those skilled in the art will be able to utilize the conduits and containers of the present invention without undue experimentation. can be formed. Preferably, the conduits and containers are cast or molded.

Those skilled in the art will appreciate that polymers do not suffer from similar swelling that normally occurs with hydrocarbons or polyurethanes. The urethane polymers of the invention are particularly suitable for other applications where the urethane polymers are exposed to other substances that You will understand that. However, the urethane polymer of the present invention generally , where swelling upon exposure to water is desirable, e.g. to prevent water leakage or flow. It is preferably used in environments with little exposure to water, except in rare cases. soak in water If necessary, reduce the poly to the minimum level necessary to achieve hydrocarbon resistance. By reducing the oxyethylene content of the ether polyol, the polymer It is generally preferred to balance the swelling tendencies of water and hydrocarbons.

The following examples are provided to illustrate the invention but are not intended to limit its scope. Unintentional. All parts and percentages are by weight unless otherwise specified.

Example 1: Preparation of hydrocarbon-resistant polyurethane Stoichiometric amounts of polyol A, i.e. D About 75% of the commercially available 5000 molecules containing oxyethylene groups and 25% by weight oxypropylene groups amount of triol "Voranol" CP-1421 to isocyanate A, i.e. Dow Chemical Compan under the trade name PAPI-94. a high molecular weight diisocyanate having a molecular weight of about 300, commercially available from React at 80°C for 2 hours and back titrate dibutylamine of ASTl 1638-74. having an unreacted free isocyanate content of approximately 11.5% as determined by the method A prepolymer was formed.

Then, 400 parts by weight of prepolymer and 47 parts of 1,4-butanediol were added. 0.1 parts by weight of bismuth neodecanoate catalyst [under the trade name C03CAT-83] It is commercially available from Osan Chemical Corp. (hereinafter referred to as Catalyst A)] is added to the prepolymer to form a mixture. blend was stirred vigorously for 1 minute. The mixture was then preheated (105°C) 10.5 It is measured as x 7.5 x O01 inch (265 x 190 x 2.5 M). 10,000 I for 1 hour in a hydraulic press at 105°C. t bs, (127 psi or 875 KPa) compression to cure the molded product. formed.

The molded article was then removed from the press and cured in an oven at 100° C. for 16 hours.

The cured product is then completely immersed in a hydrocarbon solvent (diesel fuel #2), which is then refluxed. It was heated to a temperature of 158° C. (70° C.). The weight of the part before soaking is 5.08g. It was. After 70 hours of soaking, the weight of the part is 5.43g and 6.990% by weight of solvent absorption was obtained.

Examples 2-4: Comparison of properties of different formulations The urethane polymer of Example 2 is shown in Table 1 (where polyol A, isocyanate A1 and Catalyst A are as shown in Example 1). Ta. Surfactant A is manufactured by Union Carbide under the trade name L-5304. An organosilane surfactant degassing agent commercially available from Co., Ltd. stomach Socynate B is now Chemical under the trade name 1sonate 181 methane, having an average molecular weight of 364, commercially available from Al Company. Diphenyl diisocyanate and tripropylene glycol and dipropylene It is a mixture of glycols. Polyol B has the trade name Polyglycol 15-2 5, commercially available from Dow Chemical Company under 00 Different supplies of 0% by weight ethylene oxide and 50% by weight propylene oxide A 2600 molecular weight polyether triol was formed from the feed mixture. Po Liol C has approximately 100% by weight oxyethylene groups and a nominal functionality of 2. It is a polyether with a molecular weight of 400. The mixture was degassed under vacuum for 2 minutes.

Pour the mixture into an open mesh mold and keep it at a temperature of 50°C for 8 hours. Placed in a 180'F oven for 24 hours. , Shore A hardness was measured according to ASTM 2240-84 procedure. elongation and Tensile was measured according to ASTM 638-84 procedure. Fuel swelling is described in Example 1 I decided to do so.

Isocyanate B 140.6 153 Polyol C 15 Polyol B150 Polyol A 150 1351.4-butane Diol 29.4 29.4 29.4 Surfactant A O, 40, 40, 4 Catalyst A O, 20, 2 0,2 index 　　　　　　　　104　　104　　104 Hardness, Shore A 89 83 89 Table 1 (continued) Example: 2 3 4 Tensile, psi (KPa) 409 438 [2 (2800) (3000) Fuel Swelling (wt%) at 50″F (121°C) ) 3.59 4.64 3.75 Molecular weight/crosslinking 1478 4850 5644 Hard segment (wt%) 46.0 62.0 60.29 Sample crumbles.

The data in Table 1 shows that the hydrocarbon fuel swelling is kept below 10% on each side. to show that A range of molecular weights/weight percentages of cross-linked and hard segments are low Produce polyurethane with fuel swelling. Molecules larger than 2700 per crosslink Examples 3 and 4 have a pull force greater than 300 ps i (2070 KPa). Tension measurements and elongation greater than 100 at 250″F (121°C).

Examples 5-8: Use of various formulations Example 20 The procedure was repeated using the amounts of materials shown in Table 2.

Isocyanate C is manufactured by Dow Chemical under the trade name PAPI 901. Polymethylene with an average molecular weight of 400, commercially available from It is polyphenylisocyanate. Chain extender A has the trade name 1sonal 9 27, commercially available from the now Chemical Company under 3 0 molecular weight poly(ethylene oxide) triol.

In the high temperature bending test, 8 x 8 x 1/8 inch (203 x 203 x 3 ．． 2 mm) of cured polymer black is heated to 250″F (121°C) in an oven. and equilibrated at that temperature for 1 hour. Then remove the black from the furnace and bent. Decomposition or lack of decomposition was noted.

Table 2 Example: 5678 Isocyanate A 64.2 0 0 0 Isocyanate G8 0 0 68 105 Isocyanate CO147,4 5125 Polyol A 75 150 150 150 po Lior B 81 0 0 0 Polyol c 　　　　oo　　　　　　　　　　　　　

Chain extender A 29 0 0 0 01.4-butanedi All-29,429,429,4 index 1.07 1. 09 1.04 1.04 Hardness, Shore A ---75A 80A molecular weight/crosslinking 992 3072 2750 3746 Fuel Swelling 53.8 The data in Table 2 is based on Polyurethane formed using a molecular weight of 2750 to 3746 per bridge has high temperature resistance. did not decompose in the bend test, whereas Example 5 had a molecular weight per crosslink of 992 and This indicates that it was decomposed during the experiment. Furthermore, Examples 7 and 8 have the desired elastomeric properties. showed tensile and elongation.

Examples 9-13: Use of different formulations The procedure of Example 2 was repeated using the amounts of the substances indicated in Table 3. Isoshi Anate D is sold under the trade name 1sonate' 125M by Dow Chemical. methylene diisocyanate, commercially available from Al Company.

The properties were measured as in the previous example and the results are recorded in Table 3. Additionally, add the sample to water. It was immersed at a temperature of 70°C for 7 days. The weight percent obtained was determined.

Hard segment content and molecular weight per crosslink were calculated as specified. . For example, the calculation of molecular weight per crosslink for Example 10 is shown in the table.

Table 3 Example: 9 10 11 12 13 Isocyanate A 102 51 25 --- Isocyanane) 8 68 106 141 Isocyanate [) 66 Boliol A 150 150 150 1 50 1501.4- Butanediol 29.4 29.4 29.4 29.4 ], 8.3 total parts by weight 281.4 298.4 310.4 320 ．． 4 234.3 Fuel swelling (wt%) 5 4 5 4 15 Elongation (%) (at 250″F > 33 51 73 127 -Molecular weight/crosslinking 1800 2750 3740 4850 3930 hard segment (wt%) 42.1 54.0 57.2 62.0 31.1 Table 3 (continued) Example: 9 10 11 12 13 The total is for each side. Refers to the total parts by weight of all ingredients.

The data in Table 3 shows that each side has low fuel swelling. increasing molecules The amount/crosslinking improves the elastomer properties as measured by tensile and elongation. Extremely low flame Maintaining the material swelling value increases the molecular weight/crosslinking (compare Examples 11 and 13). ), preferably by increasing the hard segment content. moreover , polyurethane absorbs very little water.

The molecular weight/crosslinking calculation for Example 10 is as follows.

Polyol A3. O16701500,090,03-0,030 theory or call Nominal functionality was used.

Therefore, the molecular weight/crosslinking is 298.410.108 = 2750.

FIG.2 FIG.4 FIG.5 FIG.6 FIG.7 FIG.8 FIG.9 FIG, I○ Uml cross investigation report mvy+<ha1^”””””’()Pgo-1-T-/l1QQn/nl’il Q

Claims (14)

[Claims] 1. (a) polyisocyanate component; and (b) (i) total active hydrogen component. at least about 50% by weight, at least about 50% by weight of oxyethylene units at least one polyether having an average nominal functionality of at least about 3, comprising: [The polyether polyol is capped with ethylene oxide] [contains secondary hydroxyl groups] Active hydrogen component containing A urethane polymer produced from a reaction mixture containing [the urethane polymer is It is a hydrocarbon-resistant elastomer]. 2. The polyisocyanate component is diphenylmethane-2,4'-diisocyanate. , diphenylmethane-4,4'-diisocyanate, polymethylene polyphenylene is an aromatic cyisoanate selected from isocyanates and mixtures thereof. , the urethane polymer according to claim 1. 3. The polyisocyanate component is (a) methylene diphenyl diisocyanate and tripropylene glycol and Isocyanate containing a mixture of dipropylene glycol and having a molecular weight of 364 (b) polymethylene polyphenylisocyanate having an average molecular weight of 400; to; (c) methylene diisocyanate; (d) isocyanate (a) and a high molecular weight diisocyanate having a molecular weight of about 300; a formulation of anate; and (e) isocyanate (a) and a polymethylene polymer having an average molecular weight of 400; A urethane polyurethane according to claim 1, selected from: a blend of liphenyl isocyanate; Rimmer. 4. The active hydrogen content is determined by the procedure of ASTM 2240-84, A hardness compared to similar polymers made from the same components without the presence of polymer polyol. Sufficient polyurethane to increase the hardness by about 5 Shore A units higher than that of the urethane. 4. The urethane polymer of claim 1, 2, or 3, which does not contain a mer polyol. 5. The urethane polymer has a 75 Tensile strength of at least about 6900 KPa (1000 psig) at °F (24 °C) and an elastomer having an elongation of at least about 100% at 75°F (24°C) The urethane polymer according to claim 1, 2, or 3, which is. 6. Polyether polyol (b)(i) has a molecular weight of 3000 to 6500 The urethane polymer according to claim 1, 2, or 3. 7. The active hydrogen component further comprises (b)(ii) at least one chain extender. , the urethane polymer according to claim 1, 2, or 3. 8. Claim 1, 2, or having a density greater than about 480 kg/m3. Urethane polymer according to 3. 9. Claim 1, 2, or 3 having a molecular weight/crosslinks of at least about 2700. urethane polymer. 10. When immersed in Diesel Fuel #2 at 158°F (70°C) for 70 hours: Hydrocarbon-resistant elastomers that do not increase in weight by more than about 10% of their original weight, 9 Claim 1, 2, or having a density of 60 kg/m2 to 1280 kg/m2. Urethane polymer according to 3. 11. The following ingredients: (i) at least about 50% by weight, based on the total active hydrogen component; % of oxyethylene units, having an average nominal functionality of at least about 3. At least one polyether polyol [the polyether polyol is not capped with ren oxide]; (ii) 0 relative to total active hydrogen content; ~45% by weight, an average nominal functionality of 2 and a molecular weight of about 1000 to about 5000 at least one polyether polyol having; and (iii) total activated water. 5 to 30% by weight based on the elementary components, at least one having a molecular weight of about 400 or less An active hydrogen-containing composition comprising: a diol. 12. Seals, linings, conduits, containers, mechanical belts, mechanical parts and rolls A hydrocarbon-resistant product selected from; A hydrocarbon-resistant product that is formed from a hydrocarbon polymer. 13. Hydrocarbon-resistant water formed from the urethane polymer according to claim 1, 2, or 3. Original fuel filter cap. 14. (a) polyisocyanate component; and (b) (i) total active hydrogen component. At least about 50% by weight of oxyethylene monomers at least one polyether having an average nominal functionality of at least about 3, Terpolyol [The polyether polyol is capped with ethylene oxide. [contains secondary hydroxyl groups] Active hydrogen component containing A method for producing a hydrocarbon-resistant urethane polymer, the method comprising reacting a hydrocarbon-resistant urethane polymer.