WO2020073156A1 - Prépolymère de polyuréthane et composition adhésives contenant ce dernier - Google Patents

Prépolymère de polyuréthane et composition adhésives contenant ce dernier Download PDF

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Publication number
WO2020073156A1
WO2020073156A1 PCT/CN2018/109291 CN2018109291W WO2020073156A1 WO 2020073156 A1 WO2020073156 A1 WO 2020073156A1 CN 2018109291 W CN2018109291 W CN 2018109291W WO 2020073156 A1 WO2020073156 A1 WO 2020073156A1
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Prior art keywords
isocyanate
weight
prepolymer
terminated prepolymer
polyurethane
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PCT/CN2018/109291
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English (en)
Inventor
Jiawen Xiong
Xiangyang Tai
Ruizhuan WANG
Original Assignee
Dow Global Technologies Llc
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Priority to PCT/CN2018/109291 priority Critical patent/WO2020073156A1/fr
Publication of WO2020073156A1 publication Critical patent/WO2020073156A1/fr

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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • This invention relates to polyurethane prepolymers and adhesive compositions that contain the prepolymer.
  • Polyurethane coatings, sealants, adhesives, and elastomers are often formulated with a “soft-segment” polyurethane prepolymer.
  • the prepolymer is made by reacting an excess of a polyisocyanate with a polyol that has a low glass transition temperature. It is normally a liquid material that is subsequently cured to form the final product.
  • the prepolymer cures through reaction with a curing agent that has two or more isocyanate-reactive groups.
  • the curing agent is water, which may be atmospheric moisture.
  • the polyol most commonly used to make the prepolymer is a polyether.
  • Polyether polyols have the advantage of being widely available and inexpensive; having good resistance to hydrolysis; and good elasticity.
  • Polyester polyols are an alternative to the polyethers.
  • Polyurethanes made using polyester polyols tend to have greater mechanical strength and abrasion resistance, but these advantages are offset by poor resistance to hydrolysis and high prepolymer viscosities.
  • An excellent combination of properties can be obtained using a polycarbonate as the polyol, but polycarbonate polyols are too expensive to be used economically in most applications.
  • a preferred solution would be to obtain the mechanical performance obtained with polyester and polycarbonate polyols using a polyether polyol instead. Such a solution would take advantage of the lower costs and excellent hydrolytic stability provided by the polyethers.
  • This invention in one aspect is an isocyanate-terminated prepolymer prepared by reacting an excess of at least one organic polyisocyanate having an isocyanate equivalent weight of up to 350 with a polyol mixture, the polyol mixture containing at least 50 weight percent, based on the weight of the polyol mixture of at least one polymer of propylene oxide having a hydroxyl equivalent weight of 500 to 3000 and a nominal hydroxyl functionality of at least 1.8, and 5 to 50 weight percent, based on the weight of the polyol mixture, of at least one bisphenol compound having a hydroxyl equivalent weight of up to 150, wherein the isocyanate-terminated polyurethane prepolymer has an isocyanate content of 2 to 10%by weight.
  • the invention is also a polyurethane or polyurethane-urea produced by curing the isocyanate-terminated prepolymer of the invention by reacting the isocyanate-terminated prepolymer with a curing agent.
  • polyurethanes and polyurethane-ureas of the invention have unexpectedly good mechanical properties, particularly high tensile strength, tensile modulus and tear strength, compared to polyurethanes made by curing a like prepolymer made without the bisphenol compound.
  • the polyurethanes exhibit other advantages of polyether-based polyurethanes such as low cost, low viscosity and good hydrolytic stability.
  • the invention is an adhesive comprising the isocyanate-terminated prepolymer of the invention.
  • the invention is a method of bonding two substrates, comprising forming a layer of the adhesive of the invention at a bondline between two substrates and curing the adhesive at the bondline to form a cured adhesive layer bonded to the two substrates at the bondline.
  • the prepolymer is made in a reaction of one or more organic polyisocyanates with a polyol mixture.
  • Each organic polyisocyanate has at least two isocyanate groups per molecule and an isocyanate equivalent weight of up to 350, such as 80 to 250, 80 to 200, or 80 to 180. If a mixture of such polyisocyanate compounds is present, the mixture may have, for example, an average of 2 to 4 or 2.3 to 3.5 isocyanate groups per molecule.
  • polyisocyanate compounds include aromatic polyisocyanates such as m-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, naphthylene-1, 5-diisocyanate, methoxyphenyl-2, 4-diisocyanate, diphenylmethane-4, 4'-diisocyanate, diphenylmethane-2, 4’-diisocyanate, 4, 4'-biphenylene diisocyanate, 3, 3'-dimethoxy-4, 4'-biphenyl diisocyanate, 3, 3'-dimethyl-4-4'-biphenyl diisocyanate, 3, 3'-dimethyldiphenyl methane-4, 4'-diisocyanate, 4, 4', 4"-triphenyl methane triisocyanate, polymethylene polyphenylisocyanate (PMDI) , tol poly
  • Modified aromatic polyisocyanates that contain urethane, urea, biuret, carbodiimide, uretoneimine, allophanate or other groups formed by reaction of an isocyanate group are also useful.
  • a preferred aromatic polyisocyanate is MDI or PMDI (or a mixture thereof that is commonly referred to as “polymeric MDI” ) , and so-called “liquid MDI” products that are mixtures of MDI and MDI derivatives that have biuret, carbodiimide, uretoneimine and/or allophanate linkages.
  • polyisocyanate compounds having an isocyanate equivalent weight of up to 350 include one or more aliphatic polyisocyanates. Examples of these include cyclohexane diisocyanate, 1, 3-and/or 1, 4-bis (isocyanatomethyl) cyclohexane, 1-methyl-cyclohexane-2, 4-diisocyanate, 1-methyl-cyclohexane-2, 6-diisocyanate, methylene dicyclohexane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, any of which may be modified to contain urethane, urea, biuret, carbodiimide, uretoneimine, allophonate or other groups formed by reaction of an isocyanate group.
  • the mixture of polyols includes at least 50 weight percent, based on the weight of the polyol mixture, of at least one polymer of propylene oxide having a hydroxyl equivalent weight of 500 to 3000 and an average nominal functionality of at least 1.8.
  • the equivalent weight may be at least 700 or at least 900, and may be up to 2500, up to 2000, up to 1750, up to 1500 or up to 1200.
  • the polymer of propylene oxide may be a propylene oxide homopolymer or a random and/or block copolymer of propylene oxide and one or more copolymerizable alkylene oxides such ethylene oxide and/or butylene oxide. If a copolymer, it is preferred that at least 50%, at least 70%, at least 80%or at least 90%, and up to 99.5%, of the total weight of the copolymer is oxypropylene units formed in the ring-opening polymerization of propylene oxide. In some embodiments, at least 50%, at least 70%or at least 90%of the hydroxyl groups of the polymer of propylene oxide are secondary hydroxyl groups.
  • the polymer (s) of propylene oxide may constitute at least 50%, at least 75%, at least 80%or at least 85%of the total weight of the polymer mixture.
  • the polymer mixture contains 5 to 50 weight percent, based on the weight of the polyol mixture, of at least one bisphenol compound having a hydroxyl equivalent weight of up to 150.
  • the bisphenol compound may include one or more of resorcinol, catechol, hydroquinone, biphenol, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane) , bisphenol AP (1, 1-bis (4-hydroxylphenyl) -1-phenyl ethane) , bisphenol AF (2, 2-bis (4-hydroxyphenyl) hexafluoropropane) , bisphenol B (2, 2-bis (4-hydroxyphenyl) butane) , bisphenol C (2, 2-Bis (3-methyl-4-hydroxyphenyl) propane) , bisphenol E (1, 1-bis (4- hydroxyphenyl) ethane) , bisphenol F (bis (4-hydroxyphenyl) methane) , bisphenol S (bis (4-hydroxyphenyl) sulfone) , bis (4-hydroxy
  • the bisphenol compound (s) constitute at least 9%, at least 12%, at least 15%or at least 20%of the weight of the polyol mixture and, in some embodiments, the bisphenol compounds constitute up to 40%or up to 30%of the weight of the polyol mixture.
  • the polyol mixture may contain one or more polyols in addition to the bisphenol and the polymer of propylene oxide.
  • examples of such other example of such an additional polyol is a polyether different from the polymer of propylene oxide.
  • a polyether may be, for example, a polymer of ethylene oxide, a polyether having a hydroxyl equivalent weight of 175 to less than 500, a polyether polyol, compounds having hydroxyl equivalent weights of less than 175 and exactly 2 hydroxyl groups per molecule (such as 1, 2-ethane diol, 1, 2-or 1, 3-propane diol, 1, 4-butane diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol and alkoxylates of any of the foregoing having a hydroxyl equivalent weight of less than 175) , and compounds having three or more hydroxyl groups and hydroxyl equivalent weights of less than 175 (such as gly
  • Such additional polyols if present at all, preferably are present in amounts no greater than 5%, especially no greater than 3%of the total weight of the polyol mixture. They may be absent so that the polymer (s) of propylene oxide and bisphenol compound constitute 100%of the weight of the polyol mixture.
  • the polyol mixture is reacted with an excess of the polyisocyanate (s) to produce the prepolymer. At least one mole of the polyisocyanate (s) is reacted per equivalent of hydroxyl groups in the polyol mixture. A greater excess can be used.
  • the prepolymer-forming reaction can be performed under vacuum or in an inert atmosphere such as nitrogen, preferably with the exclusion water, at an elevated temperature and in the presence of a urethane catalyst such as a tertiary amine, tin, zinc or other metallic catalyst.
  • a urethane catalyst such as a tertiary amine, tin, zinc or other metallic catalyst.
  • the reaction is generally continued until the hydroxyl groups have been consumed, as indicated by a constant isocyanate content in the reaction mixture.
  • the resulting prepolymer may have an isocyanate content of, for example, at least 2 weight percent, at least 3 weight percent or at least 4 weight percent and up to 10 weight percent, up to 8 weight percent or up to 7 weight percent.
  • isocyanate content is conveniently determined using well-known titration methods.
  • the resulting prepolymer may have a number average isocyanate functionality of at least 1.8 and up to 4, preferably up to 3, up to 2.5 or up to 2.2, isocyanate groups per molecule.
  • the “prepolymer” includes reaction products of the polyol mixture with the polyisocyanate, plus any unreacted starting polyisocyanate that may be present at the end of the reaction with the polyol mixture.
  • the prepolymer is useful for making a variety of polyurethane and/or polyurea products. These include, for example, coatings, adhesives, sealants and elastomers, as well as flexible foams.
  • polyurethane products are made by curing the prepolymer with one or more hydroxyl-containing curing agents.
  • Polyurethane-urea products are made by curing the prepolymer with a curing agent that includes water and/or a primary or secondary amine curing agent.
  • Hydroxyl curing agents include a wide range of polyols.
  • the polyol curing agents can have hydroxyl equivalent weights of, for example, 30 to 3000 or more. They may contain 2 to 16 or more hydroxyl groups per molecule.
  • Examples of polyol curing agents include polyether polyols, polyester polyols, polyalkylene carbonate polyols, hydroxyl-terminated diene rubbers, polyvinyl alcohols.
  • at least a portion of the hydroxyl curing agent has a hydroxyl equivalent weight of less than 175. In such a case, chain extenders and crosslinkers useful components of the hydroxyl curing agent, and may even constitute the entirety of the hydroxyl curing agent.
  • hydroxyl-containing chain extenders examples include, for example, 1, 2-ethane diol, 1, 2-or 1, 3-propane diol, 1, 4-butane diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol and alkoxylates of any of the foregoing having a hydroxyl equivalent weight of less than 175.
  • hydroxyl-containing crosslinkers examples include glycerin, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, diethanolamine and alkoxylates of any of the foregoing having a hydroxyl equivalent weight of less than 175.
  • amine curing agents can have an equivalent weight per primary and/or secondary amino group of 30 to 3000 or more and may contain 2 to 16 or more primary and/or secondary amino groups.
  • the amino groups may be bonded directly to an aliphatic (including cycloaliphatic) or aromatic carbon atom.
  • Aminated polyethers are examples of useful amine curing agents.
  • the amine curing agent has an equivalent weight per primary and/or secondary amino group of less than 175.
  • low equivalent weight amine curing agents include, for example, aliphatic polyamines such as ethylene diamine, piperazine, diethylene triamine, triethylene tetraamine, tetraethylenepentaaminepiperazine, N- (2-aminoethyl) piperazine, N, N’-bis (2-aminoethyl) piperazine, cyclohexane diamine (including any one or more of the 1, 2-, 1, 3-and 1, 4-isomers) , bis (aminomethyl) cyclohexane (including any one or more of the 1, 2-, 1, 3-and 1, 4-isomers) and bis (2-aminoethyl) cyclohexane, and aromatic polyamines such as toluene diamine, diethyltoluenediamine, methylenediphenyldiamine phenylene diamine, bis (aminomethyl) benzene and aromatic amine-terminated polyethers.
  • aliphatic polyamines such as
  • Aminoalcohols such as ethanolamine and diethanolamine are also useful curing agents.
  • the invention is a sealant or adhesive comprising the prepolymer of the invention.
  • a sealant or adhesive may be a one-component type in which all the ingredients of the composition are blended and packaged together, except for water when the sealant or adhesive is a moisture-curing type (i.e., one that cures at least partially via a water/isocyanate reaction) .
  • a curing agent is present in such a one-component sealant or adhesive, it is preferably a blocked, encapsulated or otherwise latent type that requires an elevated temperature of at least 50°C to become activated and reactive toward the isocyanate groups of the prepolymer.
  • a one-component sealant or adhesive may consist entirely of the prepolymer (and curing agent if not moisture-curable) .
  • the sealant or adhesive may contain other ingredients such as, for example, one or more curing catalysts; one or more viscosity and/or rheology modifiers such as thickeners, diluents and thixotropic agents; particulate fillers and/or pigments such as carbon black, ochre, titanium dioxide, clay, calcium carbonate, calcium oxide, iron oxide and the like; adhesion promoters; coupling agents; dyes or other colorants; preservatives; antioxidants and surfactants.
  • an adhesive or sealant of the invention can be used in the same manner as conventional polyurethane or polyurethane-urea sealants or adhesives. No special handling or curing conditions are needed.
  • an adhesive of the invention is used to bond two substrates in a process that includes forming a layer of the adhesive of the invention at a bondline between the two substrates and curing the adhesive at the bondline to form a cured adhesive layer bonded to the two substrates at the bondline. If the adhesive is moisture-curing, the adhesive layer is exposed to a source of water. The water can be supplied as liquid water and/or in the form of atmospheric moisture.
  • the prepolymer can be used as a component of a polyurethane or polyurethane-urea coating composition.
  • the prepolymer may be dispersed into an aqueous phase that includes water and preferably one or more external surfactants, and then reacted with a chain extender, preferably a diamine chain extender, to form polyurethane particles dispersed in the aqueous phase.
  • the coating composition may further contain other useful ingredients such as described above with respect to sealants and adhesives.
  • the prepolymer of the invention is also useful to make polyurethane or polyurethane-urea elastomers.
  • Such elastomers are conveniently made in a molding process in which the prepolymer and a curing agent are combined and cured in an open or closed mold.
  • the reaction mixture may be frothed by whipping in air, and/or can be foamed slightly, to produce a microcellular structure.
  • various optional ingredients may be included in the reaction mixture as desired.
  • Polyol A is a 2000 number average molecular weight poly (propylene oxide) diol.
  • the MDI is a mixture of approximately 50%2, 4’-diphenylmethane diisocyanate and approximately 50%4, 4’-diphenylmethane diisocyanate (with small quantities of the 2’2-isomer) .
  • the ingredients to make the prepolymers are as indicated in Table 1, as are the isocyanate contents of the prepolymers.
  • Comparative prepolymers A and B are made in the same general manner from the formulations set forth in Table 2.
  • Polyurethane-urea films are made from each of Examples 1-6 and Comparative Samples A and B. In each case, 10 grams of the prepolymer are applied to one surface of a 300 mm ⁇ 200 mm ⁇ 0.1 mm polypropylene film using a coating machine, and scraped down to form a 50 ⁇ m film. The film is moisture-cured under ambient temperature and humidity conditions for three days, and then at 50°C for one day and for one additional day at 80°C. The film is then removed from the polypropylene substrate and cooled to room temperature (23 ⁇ 2°C) for physical property testing according to ASTM D412-15a (tensile, tensile modulus and elongation) and ASTM D624-00 (tear strength) . Results are as indicated in Table 3.
  • Comparative Sample A represents the case in which no bisphenol compound is present in the making of the prepolymer.
  • a very high elongation polymer with low tensile modulus and low tear strength is formed when this prepolymer is moisture-cured.
  • Example 1 exhibits an increase of about 25%in tear strength compared to Comparative Sample A, even though the bisphenol A constitutes less than 10%of the polyol mixture used to make the prepolymer.
  • Examples 2-6 show that further increases in tear strength are obtained with increasing levels of bisphenol A in the polyol mixture.
  • tensile modulus increases with increasing levels of bisphenol A in the polyol mixture.
  • the bisphenol A constitutes more than 16%of the weight of the polyol mixture (Ex. 5 and 6)
  • the tear strength even exceeds that of the polyester polyol-based sample (Comp. B) , at a much higher tensile modulus.
  • Example 7-11 Prepolymer Synthesis : Polyol A is dried under vacuum. Bisphenol A is added to the dried Polyol A at 110°C and the mixture is further dehydrated at that temperature under vacuum. The dehydrated polyol mixture is cooled to 70-75°C and isophorone diisocyanate (IPDI) is added under nitrogen, followed by a tin catalyst. The resulting reaction mixture is maintained at 70-75°C with stirring for an hour and then heated to 80-85°C for an additional 2-3 hours to produce the prepolymer.
  • IPDI isophorone diisocyanate
  • the ingredients to make the prepolymers are as indicated in Table 4, as are the isocyanate contents of the prepolymers.
  • Comparative prepolymers C and D are made in the same general manner from the formulations set forth in Table 5.
  • Polyurethane-urea films are made from each of Examples 7-11 and Comparative Samples C and D, as described in the previous examples, and tested as described before. Results are as indicated in Table 6.

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

Abstract

L'invention concerne un prépolymère à terminaison isocyanate, qui est préparé par mise en réaction d'un excès d'au moins un polyisocyanate organique présentant un poids équivalent d'isocyanate allant jusqu'à 350 avec un mélange de polyols. Le mélange de polyols contient au moins 50 pour cent en poids d'au moins un polymère d'un oxyde de propylène présentant un poids équivalent hydroxyle de 500 à 3000 et une fonctionnalité hydroxyle nominale d'au moins 1,8, et 5 à 50 pour cent en poids, sur la base du poids du mélange de polyols, d'au moins un composé bisphénol présentant un poids équivalent hydroxyle allant jusqu'à 150. Le prépolymère est avantageux comme constituant d'un adhésif durcissable à l'humidité.
PCT/CN2018/109291 2018-10-08 2018-10-08 Prépolymère de polyuréthane et composition adhésives contenant ce dernier WO2020073156A1 (fr)

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CN1608089A (zh) * 2002-01-18 2005-04-20 塞卡施韦茨股份公司 聚氨酯组合物
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