WO1998001492A1 - Compositions de polytetramethylene-ether-glycols et polyoxy-alkylene-polyether-polyols presentant un faible degre d'insaturation - Google Patents

Compositions de polytetramethylene-ether-glycols et polyoxy-alkylene-polyether-polyols presentant un faible degre d'insaturation Download PDF

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Publication number
WO1998001492A1
WO1998001492A1 PCT/EP1997/003522 EP9703522W WO9801492A1 WO 1998001492 A1 WO1998001492 A1 WO 1998001492A1 EP 9703522 W EP9703522 W EP 9703522W WO 9801492 A1 WO9801492 A1 WO 9801492A1
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Prior art keywords
polyol
polyol composition
composition according
unsaturation
weight
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PCT/EP1997/003522
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English (en)
Inventor
Thomas L. Fishback
Duane Allan Heyman
Curtis John Reichel
Adam J. Jaglowski
Thomas Bernard Lee
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Basf Corporation
Basf Aktiengesellschaft
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Priority claimed from US08/678,028 external-priority patent/US5998574A/en
Priority claimed from US08/678,001 external-priority patent/US6040413A/en
Application filed by Basf Corporation, Basf Aktiengesellschaft filed Critical Basf Corporation
Priority to AU35409/97A priority Critical patent/AU3540997A/en
Priority to EP97931765A priority patent/EP0850258A1/fr
Publication of WO1998001492A1 publication Critical patent/WO1998001492A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Definitions

  • This invention relates to blends of poly-tetramethylene polyether glycols and polyoxyalkylene polyether polyols having a low degree of unsaturation of 0.04 or less, and to the cast elastomers, spandex fibers, and thermoplastic polyurethanes made therefrom.
  • Polyurethane elastomers often utilize one or more polytetra- ethylene ether glycols (PTMEG's) as a polyol component to react with one or more polyisocyanates such as MDI because they can im- part to the elastomer the high level of mechanical properties required for specific applications.
  • PTMEG's are often used for such applications where high tensile strength, low compression set, high resilience, and/or a high modulus of elasticity are required.
  • PTMEG's can be difficult and expensive to make due to the availability of starting materials and the formation of undesired side-reaction products during synthesis.
  • the polyol compositions according to the present invention can be used for the manufacture of polyurethane elastomers via a one- shot technique or a prepolymer technique.
  • Elastomers based on the polyol compositions of the invention exhibit a good combination of properties such as tensile strength, compression set, resilience, and/or a modulus of elasticity, which often previously required the use pure PTMEG.
  • Other properties, such as elongation and resilience, can often be improved by utilizing the blend compositions of the invention.
  • a prepolymer obtained by reacting a polyol composition comprising at least the above-described PTMEG and a polyoxyalkylene polyether polyol having a degree of unsaturation of 0.04 or less, with an organic polyisocyanate .
  • the prepolymer may be isocyanate terminated by adding a sub-stoichiometric amount of the polyol composition to the isocyanate, or hydroxyl terminated by adding to the isocyanate a molar excess of the polyol composition.
  • an elastomer made by reacting an organic di- or polyisocyanate with the polyol composition, optionally in the presence of a hydroxyl and/or a ine functional chain extender at an equivalent NCO:OH ratio of at least 1.5:1, where the polyol composition is made up of at least PTMEG and a polyoxyalkylene polyether polyol having a degree of unsaturation of 0.04 or less.
  • the polyol composition of the invention may be a principal polyol component of the urethane elastomer-forming reaction mixture (i.e., one-shot method) or it may first be incorporated into a prepolymer prior to incorporation into the urethane elastomer-forming reaction (i.e., prepolymer methods).
  • PTMEG's useful in the practice of the invention generally have a number average molecular weight ranging from 500 to 5000, prefe- rably 800 to 3000, more preferably from 1000 to 2600. Techniques for the manufacture of PTMEG are well-known in the art, such as described in U.S. Patent 4,294,997 and 4,213,000, the disclosures of which are incorporated herein by reference. Examples of useful PTMEG's include POLYTHF® 650, POLYTHF® 1000, POLYTHF® 2000, an POLYTHF® 2900.
  • PTKEG's are generally synthesized by a ring-opening chain extension reaction of the monomeric tetrahydrofuran (THF) .
  • THF monomeric tetrahydrofuran
  • the ring-opening reaction is catalyzed by fluorosulfonic acid, followed by hydrolysis of sulfate ester groups and water extraction of the acid, followed by neutralization and drying.
  • the PTMEG will be solid at room temperature because of its high degree of crystallinity.
  • the THF can be copolymerized with alkylene oxides (also known as cyclic ethers or monoepoxides) as suggested in U.S. Patent 4,211,854, incorporated herein by reference.
  • Such copolymers have an A-B-A block-heteric structure, wherein the A blocks are random copolymers of tetrahydrofuran and alkylene oxides, and the B block is made up of polytetramethylene oxides.
  • the cyclic ethers copolymerizable with tetrahydrofuran are not particularly limited, provided that they are cyclic ethers capable of ring-opening polymerization, and may include, for example, 3-membered cyclic ethers, 4-membered cyclic ethers, cyclic ethers such as tetrahydrofuran derivatives, and cyclic ethers such as 1, 3-dioxolan, trioxane, etc.
  • cyclic ethers include ethylene oxide, 1,2-butene oxide, 1,2-hexene oxide, 1,2-tert-bu- tyl ethylene oxide, cyclohexene oxide, 1,2-octene oxide, cyclone - xylethylene oxide, styrene oxide, phenyl glycidyl ether, allyl glycidyl ether, 1,2-decene oxide, 1, 2-octadecene oxide, epichlorohydrin, epibromohydrin, epiiodohydrin, perfluoropropy- lene oxide, cyclopentene oxide, 1,2-pentene oxide, propylene oxide, isobutylene oxide, trimethyleneethylene oxide, tetramethy- leneethylene oxide, styrene oxide, 1, 1-diphenylethylene oxide, epifluorohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, 1, 1, 1-trifluoro
  • the content of the copolymerized cyclic ether, if present, in a PTMEG may be within the range of from 5 to 95% by weight, but when obtaining a copolymerized polyetherglycol containing oxyte- tra ethylene groups as a main component which is effective as the soft segment in a polyurethane elastomer such as spandex, the amount of the cyclic ether in the A block copolymerizable with THF is generally from 30 to 70 weight %. In the event one choo- ses to randomly copolymerize cyclic ethers with THF across the whole copolymer, the amount of cyclic ether may range from 5 to 60 weight % of the copolymer.
  • a part of the starting THF may be replaced with an oligomer of PTMEG as the starting material.
  • an oligomer of PTMEG or an oligomer of the polyetherglycol to be synthesized may also be added as a part of the starting material to carry out the reaction.
  • the oligomer generally has a molecular weight lower than the polymer to be synthesized.
  • an oligomer separated by fractional extraction or vacuum distillation from the PTMEG or the copolymerized polyetherglycol synthesized may be employed. Such an oligomer may be added in an amount of up to 10% by weight into the starting monomer.
  • the polymerization temperature should preferably be -10° to 120°C, more preferably 30° to 80°C. If the temperature exceeds 120° C, the yield decreases.
  • the time required for the reaction is generally 0.5 to 20 hours, although it may vary depending upon the catalyst amount and the reaction temperature.
  • the reaction may be carried out in any system generally employed such as tank type or tower type vessel. It is also feasible by either batch or continuous system.
  • Catalysts used in the preparation of PTMEG are well known, and include any cationic catalyst, such as strongly acidic cationic exchange resins, fuming sulfuric acids, and boron trifluorides .
  • the polyol blends of the present invention comprise a di- functional active hydrogen compound-initiated polyoxyalkylene polyether polyol.
  • Difunctional active hydrogen compound-initiated polyoxyalkylene polyether polyols useful in the practice of the invention should have number average molecular weights suitable for the particular application, and generally from 400 to 7000, preferably from 1000 to 6500, more preferably from 1500 to 3500, and most preferably from 2000 to 3000.
  • hydroxyl numbers of the polyoxyalkylene polyether polyols used in the invention correspond to the desired number average molecular weight by the formula:
  • suitable hydroxyl numbers for the polyoxyalkylene polyether polyol ranges from 15 to 250, and most often from 25 to 120.
  • the polyoxyalkylene polyether polyols used in the invention have a degree of unsaturation of 0.04 milliequivalents KOH/g of polyol or less, preferably 0.03 or less, more preferably 0.02 or less.
  • the structure of the polyoxyalkylene polyether polyol contains a nucleus of a difunctional and/or trifunctional active hydrogen compound initiator compound containing at least two hydrogen atoms reactive to alkylene oxides. Specifically, the reactive hydrogen atoms on the initiator compound should be sufficiently labile to open up the epoxide ring of ethylene oxide.
  • the initiator compound has a relatively low molecular weight, generally under 400, more preferably under 150.
  • initiator compounds useful in the practice of this invention include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2,3-butylene glycol, 1,3-butylene glycol, 1, 5-pentanediol , 1, 6-hexanediol , glycerin, trimethylol propane and the like.
  • Another class of reactive hydrogen compounds that can be used are the alkyl amines and alkylene polyamines having at least two reactive hydrogen atoms, such as methylamine, ethylamine, propyl - amine, butylamine, hexylamine, ethylenediamine, diethylene- diamine, 1 , 6-hexanediamine, and ammonia, ethanolamin, diethanol- amin, triethanolamin, isopropanolamin, diisopropanolamin, triiso- propanolamin the like. It may be necessary to select catalysts or adjust reaction conditions that would allow both primary and secondary amine hydrogens to ring-open the alkylene oxides in order to render the monoamines difunctional and diamines trifunctional.
  • Cyclic amines such as piperazine, 2 methylpipera- zine, and 2 , 5-dimethylpiperazine can also be used.
  • Amides constitute a further class of such reactive hydrogen compounds, such as acetamide, succinamide, and benzene sulfonamide.
  • a still further class of such reactive hydrogen compounds are the dicarb- oxylic acids, such as adipic acid and the like.
  • the initiator can also be one containing different functional groups having reactive hydrogen atoms, also, such as glycolic acid, ethanol- amine, and the like.
  • the polyoxyalkylene polyether polyols used in the invention contain at least one hydrophobic block made from propylene oxide or a mixture of propylene oxide and other cyclic ethers.
  • Such other cyclic ethers are either of the type that are hydrophobic relative to polyoxyethylene groups; or if of a hydrophilic character, are admixed with propylene oxide only in those relative amounts that will not render the polyol ineffective for its ultimate application.
  • the hydrophobic block may consist of a homoblock of oxypropylene groups or a block of randomly distributed oxypropylene groups and other oxyalkylene groups.
  • butylene oxide may also be used, as it also exhibits hydrophobic properties and yields polyols having a low degree of unsaturation.
  • the polyether of the invention may also be prepared by the addition reaction between a suitable initiator compound directly or indirectly with a defined amount of propylene oxide to form an internal block of oxypropylene groups, followed by further direct or indirect addition of one or more other oxides.
  • Tha polyoxyalkylene polyether polyol may contain only ethylene oxide groups, especially if the molecular weight is below 600. However, it preferably contains from 50 to 100 weight % of oxypropylene groups, preferably from 70 to 96 weight % of oxypropy- lene groups, based on the weight of all of the cyclic ether groups added.
  • propylene oxide is added to and reacted directly with the initiator compounds through the reactive hydrogen atom sites to form an internal block of polyoxypropylene groups.
  • the structure of such an intermediate compound can be represented according to the following formula:
  • R is the nucleus of the initiator
  • w is an integer representing the number of oxypropylene groups in the block such that the weight of the oxypropylene groups is from 50 to less than 100 weight percent, (or 100 weight % if one desires to make a polyol based solely on oxypropylene groups and the initiator) , based on the weight of all alkylene oxides added
  • z represents the number of reactive sites on the initiator molecule onto which are bonded the chains of oxypropylene groups (preferred 2 or 3).
  • the polyether polyol may also comprise more than one internal block of oxypropylene groups.
  • an internal block is meant that the block of oxypropylene groups should be structurally located between the nucleus of the initiator compound and a different block of one or more different kinds of oxyalkylene groups. It is within the scope of the invention to interpose a block of different oxyalkylene groups between the initiator nucleus and the block of oxypropylene groups, especially if the different oxyalkylene groups are also hydrophobic. In one preferred embodiment, however, the internal block of oxypropylene groups is directly attached to the nucleus of the initiator compound through its reactive hydrogen sites.
  • the polyoxyalkylene polyether polyols used in the invention are terminated with isocyanate reactive hydrogens.
  • the reactive hydrogens may be in the form of primary or secondary hydroxyl groups, or primary or secondary amine groups.
  • isocyanate reactive groups which are more reactive than secondary hydroxyl groups.
  • Primary hydroxyl groups can be introduced onto the polyether polyol by reacting the growing polyether polymer with ethylene oxide. Therefore, in one preferred embodiment of the invention, the polyoxypropylene polyether polyol is terminated with a terminal block of oxyethylene groups.
  • the polyether polymer of the invention may be terminated with of a mixture of primary and secondary terminal hydroxyl groups when a mixture of ethylene oxide and, for example, propylene oxide is employed in the manufacture of a terminal cap.
  • Primary and secondary amine groups can be introduced onto the polyether polymer by a reductive amination process as described in U.S. Patent No. 3,654,370, incorporated herein by reference.
  • the weight of the terminal block of oxyethylene groups when employed is at least 4 weight % to 30 weight %, preferably from 10 weight % to 25 weight %, based upon the weight of all compounds added to the initiator.
  • the method of polymerizing the polyether polymers of the invention is not limited and can occur by anionic, cationic, or coordinate mechanisms.
  • an initiator molecule is reacted with an alkylene oxide in the presence of a basic catalyst, such as an alkoxide or an alkali metal hydroxide.
  • a basic catalyst such as an alkoxide or an alkali metal hydroxide.
  • the reaction can be carried out under super atmospheric pressure and an aprotic solvent such as dimethylsulfoxide or tetrahydrofuran, or in bulk.
  • the type of catalyst used to manufacture the polyoxyalkylene polyether polyol is also not limited so long as the catalyst is of the type that will produce polyoxyalkylene polyether polyols having a degree of unsaturation of 0.04 or less at the desired number average molecular weight.
  • Suitable catalysts include the alkali metal compounds, alkali earth compounds, ammonium, and double metal cyanide catalysts as described in U.S. Patent No. 3,1329,505, incorporated herein by reference, as well as the hydroxides and alkoxides of lithium and rubidium.
  • Other useful catalysts include the oxides, hydroxides, hydrated hydroxides, and the monohydroxide salts of barium or strontium.
  • Suitable alkali metal compounds include compounds that contain sodium, potassium, lithium, rubidium, and cesium. These compounds may be in the form of alkali metal, oxides, hydroxides, carbonates, salts of organic acids, alkoxides, bicarbonates, natural minerals, silicates, hydrates, etc. and mixtures thereof.
  • Suitable alkali earth metal compounds and mixtures thereof include compounds which contain calcium, strontium, magnesium, be- rylliurn, copper, zinc, titanium, zirconium, lead, arsenic, antimony, bismuth, molybdenum, tungsten, manganese, iron, nickel, cobalt, and barium.
  • Suitable ammonium compounds include, but are not limited to, compounds which contain ammonium radical, such as ammonia, amino compounds, e.g., urea, alkyl ureas, dicyano- diamide, melamine, guanidine, aminoguanidine; amines, e.g., aliphatic amines, aromatic amines; organic ammonium salts, e.g., ammonium carbonate, quaternary ammonium hydroxide, ammonium silicate, and mixtures thereof.
  • the ammonium compounds may be mixed with the aforementioned basic salt-forming compounds.
  • Other ty- pical anions may include the halide ions of fluorine, chlorine, bromine, iodine, or nitrates, benzoates, acetates, sulfonates, and the like.
  • the polyoxyalkylene polyether polyols are made with a cesium containing catalyst.
  • cesium-containing catalysts include cesium oxide, cesium acetate, cesium carbonate, cesium alkoxides of the Ci C ⁇ lower alkanols, and cesium hydroxide. These catalysts are effective at reducing the unsaturation of high equivalent weight polyols having a large amount of oxypropylene groups.
  • the cesium-based catalysts do not have to be removed from the reaction chamber prior to adding an ethylene oxide cap onto a polyether polyol.
  • the manufacture of a polyoxy- propylene polyether polyol having an ethylene oxide cap can pro- ceed throughout the whole reaction with a cesium based catalyst.
  • the degree of unsaturation can be determined by reacting the polyether polymer with mercuric acetate and methanol in a metha- nolic solution to release the acetoxy ercuric methoxy compounds and acetic acids.
  • Any left over mercuric acetate is treated with 5 sodium bromide to convert the mercuric acetate to the bromide.
  • Acetic acid in the solution can then be titrated with potassium hydroxide, and the degree of unsaturation can be calculated for a number of moles of acetic acid titrated. More specifically, 30 grams of the polyether polymer sample are weighed into a sample 0 flask, and 50 ml of reagent grade mercuric acetate is added to a sample flask and to a blank flask. The sample is stirred until the contents are dissolved. The sample and blank flasks are left standing for thirty (30) minutes with occasional swirling.
  • the acidity correction is made only if the acid number of the c sample is greater than 0.04, in which case it is divided by 56.1 to give milliequivalents/g.
  • the reaction conditions can be set to those typically employed in the manufacture of polyoxyalkylene polyether polyols. Generally, 0 from 0.005 percent to about 5 percent, preferably from 0.005 to 2.0 percent, and most preferably from 0.005 to 0.5 percent by weight of the catalyst relative to the polyether polymer is uti ⁇ lized.
  • c toy catalyst left in the polyether polymers produced according to the invention can be neutralized by any of the well-known processes described in the art, such as by an acid, adsorption, water washing, or ion exchange.
  • acids used in the neutralization technique include solid and liquid organic acids, 0 such as 2-ethylhexanoic acid and acetic acid.
  • phosphoric acid or sulfuric acid may be used.
  • Extraction or adsorption techniques employ activated clay or synthetic magnesium silicates. It is desirable to remove metal cationic contents down to less than 500 ppm, preferably less than 100 ppm, 5 most preferably from 0.1 to 5 ppm.
  • the temperature at which polymerization of the polyether polymers occurs generally ranges from 80°C to 160°C, preferably from 95°C to 115°C.
  • the reaction can be carried out in a columnar reactor, a tube reactor, or batchwise in an autoclave. In the batch process, the reaction is carried out in a closed vessel under pressure which can be regulated by a pad of inert gas and the feed of alkylene oxides into the reaction chamber.
  • the operating pressures produced by the addition of alkylene oxide range from 10 to 50 psig. Generating a pressure over 100 psig increases the risk of a runaway reaction.
  • the alkylene oxides can be fed into the reaction vessel as either a gas or a liquid.
  • the contents of the reaction vessel are vigorously agitated to maintain a good dispersion of the catalyst and uniform reaction rates throughout the mass.
  • the course of polymerization can be controlled by consecutively metering in each alkylene oxide until a desired amount has been added. Where a block of a random or a statistical distribution of alkylene oxides are desired in the polyether polymer, the alkylene oxides may be metered into the reaction vessel as mixtu- res. Agitation of the contents in the reactor at the reaction temperature is continued until the pressure falls to a low value. The final reaction product may then be cooled, neutralized as desired, and removed.
  • the polyol composition of the invention may include additional polyols in addition to the PTMEG and the above-described polyether polyol.
  • polyols of other functionalities i.e., greater than 3, may be included.
  • Such polyols may be prepared as described above, except that an initiator of higher functionality is used, such as pentaerythritol, sorbitol, sucrose, and the like, and amines such as ethylenediamine, tolue- nediamine, and the like.
  • Higher functional polyols may be incorporated either by physical blending of the finished polyols or by including a higher-functional initiator in a mixture with the above-described difunctional initiator prior to reaction with alkylene oxide(s).
  • a mixture of initiator compounds may be used to adjust the functionality of the initiator to a number between whole numbers. If one desires to manufacture an elastomer having only a slight degree of crosslinking, a high proportion of an initiator having a functionality of 2 , to which is added relatively small amounts of tri- or higher functional initiator compounds, may be mixed together to arrive at an initiator having an average functionality close to 2 and up to 2.3. On the other hand, a larger proportion of tri- or higher functio- nal initiator compounds can be mixed with a di-functional initiator compound when a higher degree of crosslinking is desired.
  • Other types of polyol may also be included in the polyol composition of the invention.
  • polyester polyols may be added to improve certain mechanical properties of an elastomer such as tensile strength and modulus of the urethane polymer.
  • polyether polyols For some elastomeric applications, however, it is preferred to use only polyether polyols because they can be more hydrolytically stable than polyester polyols, and they process well due to their lower viscosities.
  • Other polyols that can be employed in addition to the polyoxyalkylene polyether polymers of the invention are hydroxyl terminated hydrocarbons, such as polybutadiene polyols, where a high degree of hydrophobicity is desired. Castor oils and other natural oils may also be employed.
  • polycaprolactones can be used to increase the tensile strengths of elastomers.
  • Other polyether polyols may be added, and it is preferred that these polyether polyols have a low degree of unsaturation to optimize the mechanical properties of the product.
  • ingredients in the polyol composition may include other polyols, chain extenders or curing agents, catalysts, fillers, pigments, UV stabilizers, and the like.
  • the above-described components of the polyol composition can be blended together with standard mixing techniques, preferably in a PTMEG:polyether polyol weight ratio of from 20:80 to 95:5, although ratios of greater than 95:5 may also be usef l.
  • either of the components (A) or (B) are solid, they should be liquified, preferably by melting, prior to mixing.
  • the polyol composition of the invention should form a homogeneous blend without visual phase separation. It may be necessary to adjust the relative molecular weights of either or both of the components (A) and (B) in order to achieve a homogeneous blend.
  • the average actual functionality of the blend should be from 1.5 to 3.0, preferably from 1.95 to 2.6, and as low as 1.95 to 2.1.
  • polyols having functionalities outside of these ranges can be used so long as the average functionality falls within the range.
  • the functionality of the blend should be maintained at 3.0 or less to avoid losing too much elongation, a desirable feature for certain elastomeric applications.
  • the mean number average molecular weight for the polyol composition of the invention can range from 500 to 5000, preferably from 900 to 4500 ard more preferably from 900 to 3000.
  • One-component elastomers can be cured by moisture from the air. Two-component elastomers can be cured along with chain extenders with compounds containing isocyanate reactive hydrogen. These chain extenders may be contained in the polyol composition. Elastomers may be prepared using the one-shot technique or the prepolymer technique. If the prepolymer technique is used, the polyol composition will usually be free of a chain extender during the manufacture of the prepolymer. The prepolymer is then reacted with any remaining polyol composition which at that point contains a chain extender. In the one-shot process, the polyisocyanate is reacted at the outset with a polyol composition con- taining the chain extender.
  • Chain extenders may be, and are typically, employed in the prepa- ra:ion of polyurethane elastomers.
  • the term "chain extender” is used to mean a relatively low equivalent weight compound, usually less than about 250 equivalent weight, preferably less than 100 equivalent weight, having a plurality of isocyanate-reactive hydrogen atoms.
  • Chain-extending agents can include water, hydra- zine, primary and secondary aliphatic or aromatic diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures the- reof .
  • a preferred group of alcohol chain-extending agents includes water, ethylene glycol, 1, 3-propanediol, 1 , 4-butanediol, 1, 10-decanediol, o, -m, -p-dihydroxycyclohexane, diethylene glycol, 1, -hexanediol, glycerine, trimethylol propane, 1,2,4-, 1, _ ⁇ , 5-trihydroxycyclohexane, and bis (2-hydroxyethyl) hydroqui- none.
  • a preferred group of amine chain extenders includes water, ethylene glycol, 1, 3-propanediol, 1 , 4-butanediol, 1, 10-decanediol, o, -m, -p-dihydroxycyclohexane, diethylene glycol, 1, -hexanediol, glycerine, trimethylol propane, 1,2,4-, 1, _ ⁇ , 5-trihydroxycyclohex
  • secondary aromatic diamines include N, N' -dialkyl-sub- stituted aromatic diamines, which may be unsubstituted or substituted on the aromatic radical by alkyl radicals, having 1 to 20, preferably 1 to 4, carbon atoms in the N-alkyl radical, e.g., N,N' -diethyl-, N, N' -di-sec-pentyl-, N, N' -di-sec-hexyl-, N,N'-di- sec-decyl-, and N, ' -dicyclohexyl-p- and m-phenylenediamine, N,N' -dimethyl-, N,N' -diethyl-, N,N' -diisopropyl- , N,N, '-disec- butyl- and N,N' -dicyclohexyl-4 , 4 ' -diaminodipheny
  • the amount of chain extender used may vary depending on the desi- red physical properties of the elastomer. A higher proportion of chain extender and isocyanate provides the elastomer with a larger number of hard segments, resulting in an elastomer having greater stiffness and heat distortion temperature. Lower amounts of chain extender and isocyanate result in a more flexible elastomer. Generally, about 2 to 70, preferably about 10 to 40, parts of the chain extender may be used per 100 parts of poly- ether polymer and PTMEG and any other higher molecular weight isocyanate reactive components.
  • Catalysts may be employed to accelerate the reaction of the compounds containing hydroxyl groups with polyisocyanates.
  • Exam- pies of suitable compounds are cure catalysts which also function to shorten tack time, promote green strength, and prevent shrinkage.
  • Suitable cure catalysts include organometallic catalysts, preferably organotin catalysts, although it is possible to employ metals such as lead, titanium, copper, mercury, cobalt, nickel, iron, vanadium, antimony, and manganese.
  • Suitable organometallic catalysts are represented by the formula: R n Sn [X-R 1 -Y] 2 , wherein R is a Ci-Ca alkyl or aryl group, R 1 is a Co-Cis methylene group optionally substituted or branched with a C ⁇ -C alkyl group, Y is hydrogen or an hydroxyl group, preferably hydrogen, X is methylene, an -S-, an -SR 2 COO-, -SOOC-, an -O 3 S-, or an -OOC- group wherein R 2 is a C 1 -C 4 alkyl, n is 0 or 2, provided that R 1 is Co only when X is a methylene group.
  • tin (II) acetate tin (II) octa- noate, tin (II) ethylhexanoate and tin (II) laurate
  • organotin catalysts are organotin alkoxides and mono or polyalkyl (C ⁇ -C 8 ) tin (IV) salts of inorganic compounds such as butyltin trichloride, dimethyl- and diethyl- and dibutyl- and dioctyl- and diphenyl- tin oxide, dibutyltin dibutoxide, di (2-ethylhexyl) tin oxide, and dibutyltin dichloride.
  • organotin alkoxides and mono or polyalkyl (C ⁇ -C 8 ) tin (IV) salts of inorganic compounds such as butyltin trichloride, dimethyl- and diethyl- and dibutyl- and dioctyl- and diphenyl- tin oxide, dibutyltin dibutoxide, di (2-ethylhexyl) tin oxide, and dibutyltin dichloride
  • tin catalysts with tin-sul- fur bonds which are resistant to hydrolysis such as dialkyl (C ⁇ -Co) tin dimercaptides, including dimethyl-, dibutyl-, and dioctyl-tin dimercaptides.
  • Tertiary amines also promote urethane linkage formation, and inc- lude triethylamine, 3-methoxypropyldimethylamine, triethylene- diamine, tributylamine, dime hylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N,N,N' ,N' -tetramethylethylenediamine, N,N,N' , ' -tetramethylbutanediamine or N,N,N' ,N' -tetramethylhexa- nediamine, N,N,N' -trimethyl isopropyl propylenediamine, pentame- thyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, l-methyl-4- dimethylaminoethylpiperazine, 1,
  • a batch mixture may be subjected to degassing at a reduced pressure once the ingredients are mixed together.
  • the mixed polyurethane formed ingredients can be heated under vacuum to an elevated temperature to react out or volatilize residual water. By heating to an elevated temperature, residual water reacts with the isocyanate to liberate carbon dioxide, which is drawn from the mixture by the reduced pressure.
  • the polyurethane forming ingredients may be diluted with solvents to reduce the viscosity of the polyurethane forming mixture.
  • solvents should be nonreactive and include tetrahydrofuran, ace- tone, dimethylformamide, dimethylacetamide, normal methylpyrro- lidone, methyl ethyl ketone, etc.
  • the reduction in viscosity of polyurethane forming ingredients aid their extrudability.
  • the amount of solvent should be kept as low as possible to avoid deteriorating their adhesion to substrates.
  • Other solvents include xylene, ethyl acetate, toluene, and cellosolve acetate.
  • Plasticizers may also be included in the A- or B-side components to soften the elastomer and decrease its brittleness temperature.
  • plasticizers include the dialkyl phthalates, dibutyl benzyl phthalate, tricresyl phosphate, dialkyl adipates, and tr:.octylphosphate .
  • adhesion promoters such as clay, silica, fume silica, carbon black, talc, phthalocyanine blue or green, titanium oxide, magnesium carbonate, calcium carbonate, UV-absorbers, antioxidants, and HALS may be added in amounts ranging from 0 to 75 weight percent, based upon the weight of the polyurethane.
  • Other fillers include dissolved gels, plasticells, gre.ded and coated calcium carbonate, urea solids, the reaction product of hydrogenated castor oils with amines, and fibers.
  • the polyurethane elastomers of the invention can be prepared by the. prepolymer technique or in a one-shot process.
  • the elastomers of the invention can be prepared by a reaction injection molding technique, or in a cast process wherein the po- lyurethane forming ingredients are mixed together and poured into a heated mold into pressure.
  • Other techniques include conventional hand-mixed techniques and low pressure or high pressure impingement machine mixing techniques followed by pouring polyure- thane forming ingredients into molds.
  • the PTMEG and the polyoxyalkylene polyether polyol of the invention, catalysts, and other isocyanate reactive components forming the polyol composition are simultaneously reacted with an organic isocyanate (“A-side” components) .
  • A-side components organic isocyanate
  • prepolymer technique all or a portion of the PTMEG and the polyoxyalkylene polyether polyol having an end group degree of unsaturation of 0.04 or less, and any other isocyanate reactive polyols in the polyol composition, and usually without any chain extender, are reacted with a stoichiometric excess of the organic isocyanate to form an isocyanate-terminated prepolymer.
  • prepolymers usually have free NCO contents of 0.5 to 30 weight %, and for many elastomeric applications, have free NCO contents of from 1 to 15 weight %.
  • the isocyanate-ter inated prepolymer is then reacted as an A-side component with any remaining B-side components to form a polyurethane elastomer.
  • all of the B-side components are in the form of an active hydrogen- terminated prepolymer.
  • only a portion of the polyol composition is reacted with the stoichiometric excess of organic isocyanate to form an isocyanate terminated prepolymer, which is subsequently reacted with the remainder of the polyol composition, as a two-component elastomer.
  • An isocyanate-terminated prepolymer is usually reacted with the isocyanate reactive functionalities in the polyol composition at an NCO to OH equivalent ratio of at least 1.5:1.
  • an active hydrogen-terminated prepolymer can be prepared if all or a portion of the PTMEG and the polyoxyalkylene polyether polyol having an end group degree of unsaturation of 0.04 or less, and any other isocyanate reactive polyols in the polyol composition, and usually without any chain extender, are reacted with a stoichiometric deficiency of the organic isocyanate to form an active hydrogen-terminated prepolymer.
  • the prepolymer is then reacted as a B-side component with A-side components to form a polyurethane elastomer.
  • Spandex is, by definition, a hard-segment/soft-segment-containing, urethane-con- taining polymer composed of at least 85% by weight of a segmented polyurethane (or urea).
  • segmented polyurethane or urea
  • Spandex is typically produced using one of four different processes: melt extrusion, reaction spinning, solution dry spin- ning, and solution wet spinning. All processes involve differing practical applications of basically similar chemistry.
  • a block copolymer is prepared by reacting a diisocyanate with the polyol composition of the invention in a molar ratio of about 1:2 and then chain extending the prepolymer with a low mo- lecular weight diol or diamine near stoichiometry equivalence. If the chain extension is carried out in a solvent, the resulting solution may be wet- or dry-spun into fiber.
  • the prepolymer may be reaction-spun by extrusion into an aqueous or non-aqueous diamine bath to begin polymerization to form a fiber or the pre- poLymer may be chain extended with a diol in bulk and the resulting block copolymer melt-extruded in fiber form.
  • Melt spinning is conducted in a manner similar to the melt extrusion of poly- olefins. Reaction spinning is typically carried out after reacting the polyol composition with a diisocyanate to form a pre- polymer.
  • the prepolymer is then extruded into a diamine bath where filament and polymer formation occur simultaneously, as described in more detail in U.S. Pat. No. 4,002,711.
  • thermoplastic polyurethane (TPU) elastomer made with the blends of the invention.
  • TPU is made by reacting a polyol composition comprising PTMEG and a polyoxyalkylene polyether diol having a low degree of unsaturation with and organic diisocyanate to form a linear polymer structure. While other polyols with higher functionalities than 2 can be combined with the diol, these should be used in minor amounts if at all. It is preferable that the functionality of the initiators used to make the polyoxyalkylene polyether polyols is 2, and that no initiators having functionalities of over or under 2 are used, in order to make the polymer chain linear. The same type of chain extenders as described above can be used, with the preferable chain extenders being the difunctional glycols.
  • the reaction may be carried out in a one shot process or by the prepolymer technique.
  • the raw ingre- heads are fed into the reaction zone of an extruder, heated at a temperature effective for polymerization to occur, extruded onto a conveyor belt, and pelletized.
  • the prepolymer technique is si- milar except that the prepolymer and chain extender are the materials fed into the reaction zone of the extruder.
  • the type of extruder employed is not limited. For example, either twin or single screw extruders can be used.
  • Polyol A is a propylene glycol adduct of propylene oxide and ethylene oxide having a 20 weight percent terminal cap of polyoxyethylene groups and an internal block of polyoxypropylene groups, having a molecular weight of about 3000, and a degree of unsaturation of 0.069, manufactured using KOH as a polymerization catalyst.
  • Polyol B is a propylene oxide-ethylene oxide adduct of propylene glycol having a terminal cap of 20 weight percent polyoxyethylene groups and a molecular weight of 3000, manufactured using cesium hydroxide as a polymerization catalyst, with a degree of unsaturation of 0.025.
  • Polyol C is a propylene oxide-ethylene oxide adduct of propylene glycol having a 20 weight percent terminal cap of polyoxyethylene groups and a molecular weight of 2500, manufactured using cesium hydroxide as a polymerization catalyst to a degree of unsaturation of 0.016.
  • Polyol D is a propylene oxide-ethylene oxide adduct of propylene glycol having a 20 weight percent terminal cap of polyoxyethylene groups and a molecular weight of 1250, manufactured using cesium hydroxide as a polymerization catalyst to a degree of unsaturation of 0.008 milliequivalents KOH/g polyol.
  • PTMEG is a polytetramethylene ether glycol manufactured from tetrahydrofuran to the designated molecular weight.
  • the compression sets of cast elastomers made using blends of PTMEG and polyether polyols having a high degree of unsaturation exceeding 0.04 were compared against blends of PTMEG and polyether polyols having degrees of unsaturation of 0.04 or less.
  • Diphenylmethane diisocyanate was reacted with the blends of polyether polyols in the kinds and amounts stated in Table 1 below, to a six (6) percent free NCO content.
  • the prepolymers were then reacted with 1, 4-butanediol chain extender and cast into 1/4-inch plaques in a mold. Each plaque was allowed to heat cure and was then subjected to analysis.
  • the modulus was tested according to ASTM D790, the tensile strength and elongation percent according to ASTM D412, the Graves tear according to ASTM 624, using Die C, the resilience percent according to ASTM 2632-79, and a compres- sion set according to ASTM D395 at 25 percent deformation.
  • Table 2 illustrates the physical properties of cast elastomers made by the same process, according to Example 1, also using a PTMEG/ Polyol B blend.
  • Table 3 illustrates the same process, except using PTHF 2500/Polyol C blends.
  • Table 4 illustrates the physical properties of cast elastomers made by the same process, using PTHF 1000/Polyol D blends.
  • a polyol was prepared as an ethylene oxide (10%) /propylene oxide heteric adduct of glycerine having a 5 weight % terminal ethylene oxide cap, a molecular weight of 2854, and a hydroxyl number of 57.0, manufactured using cesium hydroxide as a polymerization catalyst, with a defree of unsaturation of 0.012.
  • This polyol was blended at various levels with 2000 molecular weight PTMEG for use in the preparation of urethane elastomers.
  • a weight of 200 g of 300 molecular weight glycerine- initiated polyoxypropylene polyether polyol having an OH number of 57.0 was mixed with 5 g of antioxidants and 600 g of polytetramethylene ether glycol having a molecular weight of 2000. The mixture was stirred at 60°C for 2 hours in a nitrogen-blanketed vessel, and then allowed to cool to 40°C.
  • a capped prepolymer was prepared by adding 175 g of methylene bis (4 -phenylisocyanate) (MDI) to the polyol mixture and then heating the resulting mixture under vacuum to 90°C for 3.5 hours.
  • MDI methylene bis (4 -phenylisocyanate
  • the resulting prepolymer was allowed to cool to 50°C, and spandex fibers were formed by extruding the prepolymer into a solvent bath containing 2.5% by weight of ethylene diamine viaconventional reaction spinning techniques.
  • the spandex fibers of 840 denier (932 dtex) had the following physical characteristics:

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Compositions de polyol comprenant (A) un polytétraméthylène-éther-glycol et (B) un polyoxyalkylène-polyéther-polyol initié par un composé hydrogène actif difonctionnel et/ou trifonctionnel, dont le degré d'insaturation ne dépasse pas 0,04 milliéquivalents par gramme de ce polyéther-polyol.
PCT/EP1997/003522 1996-07-10 1997-07-03 Compositions de polytetramethylene-ether-glycols et polyoxy-alkylene-polyether-polyols presentant un faible degre d'insaturation WO1998001492A1 (fr)

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AU35409/97A AU3540997A (en) 1996-07-10 1997-07-03 Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having a low degree of unsaturation
EP97931765A EP0850258A1 (fr) 1996-07-10 1997-07-03 Compositions de polytetramethylene-ether-glycols et polyoxy-alkylene-polyether-polyols presentant un faible degre d'insaturation

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US08/678,028 1996-07-10
US08/678,028 US5998574A (en) 1996-07-10 1996-07-10 Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having a low degree of unsaturation
US08/678,001 US6040413A (en) 1996-07-10 1996-07-10 Composition of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having a low degree of unsaturation
US08/678,001 1996-07-10

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EP1090940A2 (fr) * 1999-10-08 2001-04-11 Bayer Corporation Polyuréthane thermoplastique souple transparent et apte à être travaillé
EP1110984A1 (fr) * 1999-03-17 2001-06-27 Asahi Glass Company Ltd. Resine de polyurethanne / polyurethane-uree et son procede de production
EP1367074A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Polyuréthanne-urées pour la fabrication d'élasthane et procédé pour leur production
EP1367073A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Catalyseurs prépolymères pour produire des fibres d'élasthane
EP1489119A1 (fr) * 2002-03-07 2004-12-22 Asahi Glass Company Ltd. Composition thermodurcissable d'elastomere de polyurethane
JP2008533229A (ja) * 2005-03-11 2008-08-21 ビーエーエスエフ ソシエタス・ヨーロピア プレポリマー及び前記プレポリマーから製造された気泡状ポリイソシアナート重付加生成物
EP0964013B2 (fr) † 1998-06-12 2018-08-29 Basf Se Procédé de préparation d' élastomères polyuréthane
CN112608447A (zh) * 2020-12-15 2021-04-06 无锡吉兴木桥高分子材料科技有限公司 一种高透气性半硬质聚氨酯泡沫及其制备方法

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CN103755948A (zh) * 2014-01-17 2014-04-30 金骄特种新材料（集团）有限公司 一种生物基聚亚烷基二醇及其制备方法

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US4985491A (en) * 1989-10-05 1991-01-15 Olin Corporation Polyurethane sealants made using high molecular weight polyols prepared with double metal cyanide catalysts
EP0553848A2 (fr) * 1992-01-29 1993-08-04 Asahi Glass Company Ltd. Méthode pour la préparation de pièces moulées de mousse de polyuréthane à péau integrée
US5340902A (en) * 1993-06-04 1994-08-23 Olin Corporation Spandex fibers made using low unsaturation polyols

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US4985491A (en) * 1989-10-05 1991-01-15 Olin Corporation Polyurethane sealants made using high molecular weight polyols prepared with double metal cyanide catalysts
EP0553848A2 (fr) * 1992-01-29 1993-08-04 Asahi Glass Company Ltd. Méthode pour la préparation de pièces moulées de mousse de polyuréthane à péau integrée
US5340902A (en) * 1993-06-04 1994-08-23 Olin Corporation Spandex fibers made using low unsaturation polyols

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0964013B2 (fr) † 1998-06-12 2018-08-29 Basf Se Procédé de préparation d' élastomères polyuréthane
EP1110984A1 (fr) * 1999-03-17 2001-06-27 Asahi Glass Company Ltd. Resine de polyurethanne / polyurethane-uree et son procede de production
EP1110984A4 (fr) * 1999-03-17 2003-01-02 Asahi Glass Co Ltd Resine de polyurethanne / polyurethane-uree et son procede de production
EP1090940A2 (fr) * 1999-10-08 2001-04-11 Bayer Corporation Polyuréthane thermoplastique souple transparent et apte à être travaillé
EP1090940A3 (fr) * 1999-10-08 2001-10-10 Bayer Corporation Polyuréthane thermoplastique souple transparent et apte à être travaillé
EP1489119A1 (fr) * 2002-03-07 2004-12-22 Asahi Glass Company Ltd. Composition thermodurcissable d'elastomere de polyurethane
EP1489119A4 (fr) * 2002-03-07 2006-03-22 Asahi Glass Co Ltd Composition thermodurcissable d'elastomere de polyurethane
EP1367073A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Catalyseurs prépolymères pour produire des fibres d'élasthane
US6903179B2 (en) 2002-05-30 2005-06-07 Bayer Materialscience Llc Polyurethane/ureas useful for the production of spandex and a process for their production
US6906163B2 (en) 2002-05-30 2005-06-14 Bayer Materialscience Llc Prepolymer catalysts suitable for preparing spandex fibers
EP1367074A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Polyuréthanne-urées pour la fabrication d'élasthane et procédé pour leur production
JP2008533229A (ja) * 2005-03-11 2008-08-21 ビーエーエスエフ ソシエタス・ヨーロピア プレポリマー及び前記プレポリマーから製造された気泡状ポリイソシアナート重付加生成物
KR101304639B1 (ko) * 2005-03-11 2013-09-06 바스프 에스이 예비중합체 및 이로부터 제조된 셀형 폴리이소시아네이트중부가 생성물
CN112608447A (zh) * 2020-12-15 2021-04-06 无锡吉兴木桥高分子材料科技有限公司 一种高透气性半硬质聚氨酯泡沫及其制备方法
CN112608447B (zh) * 2020-12-15 2022-09-09 无锡吉兴汽车部件有限公司 一种高透气性半硬质聚氨酯泡沫及其制备方法

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