Classifications

• • 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
• • 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
• • 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
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
  • C08G18/28—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
  • C08G18/4808—Mixtures of two or more polyetherdiols
• • 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
  • C08G18/70—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
• • 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
  • C08G2190/00—Compositions for sealing or packing joints

Definitions

• Polyurethane prepolymers are widely used in various industries, including coatings, adhesives, sealants, and elastomers. For many adhesive applications it is preferable to provide polyurethane prepolymers with a low viscosity, a high NCO content and a low amount of residual diisocyanate monomers. As used herein, such prepolymers with residual non-reacted diisocyante monomers may be referred to as “low free” or “LF” prepolymers.
• MDI Methylene diphenyldiisocyanate
• pMDI polymeric methylene diphenyldiisocyanate
• pMDI is often used for the production of rigid foam and as a binder in the wood-working industry.
• Reese et al. disclose a low- monomer polymethylenepolyphenylene polyisocyanate mixture formed by stripping a pMDI/MDI mixture alone to form a low-monomer pMDI, and then, in a second step, mixing the “low-monomer” pMDI/MDI mixture with polyurethane prepolymers to provide a foam.
• the present invention relates to an N CO-terminated polyurethane prepolymer composition comprising pMDI.
• the prepolymer composition has a low viscosity and increased NCO content and can be cured to produce a flexible and durable polyurethane adhesive material.
• the invention also provides a process for preparing such polyurethane prepolymers by reacting pMDI and polyols in a specific ratio and under specific reaction conditions or by reacting MDI and polyols in a specific ratio and under specific reaction conditions and admixing pMDI therewith.
• a polyurethane prepolymer composition is prepared by a process comprising the following steps: (1) reacting a pMDI and a polyol to form a polyurethane prepolymer comprising residual monomeric MDI; and (2) reducing the amount of residual monomeric MDI of said polyurethane prepolymer.
• polyurethane prepolymer composition prepared by a process comprising the steps: (1) reacting monomeric MDI and a polyol to form a polyurethane prepolymer; (2) admixing pMDI to the prepolymer thereby forming a prepolymer mixture comprising residual monomeric MDI; and (3) reducing the amount of residual monomeric MDI of said polyurethane prepolymer mixture.
• the polyurethane prepolymer composition in once embodiment has a residual monomeric MDI content of 0.4 wt% or lower, preferably 0.1 wt% or lower, based on the total weight of prepolymers.
• the polyurethane prepolymer composition is formed of a polyether polyol, preferably PPG, more preferably PPG with a molecular weight of 200 to 10,000 g/mol and more preferably 500 to 4000 g/mol and even more preferably 1500- 2500 g/mol.
• the polyurethane prepolymer composition is formed in one embodiment by reducing the content of residual monomeric MDI by means of distillation.
• a process for preparing a polyurethane prepolymer composition comprising the steps of: (1) reacting a pMDI and a polyol to form a polyurethane prepolymer comprising residual monomeric MDI; and (2) reducing the amount of residual monomeric MDI of said polyurethane prepolymer.
• a process for preparing a polyurethane prepolymer composition comprising the steps of: (1) reacting monomeric MDI and a polyol to form a polyurethane prepolymer; (2) admixing pMDI to the prepolymer thereby forming a prepolymer mixture comprising residual monomeric MDI; and (3) reducing the amount of residual monomeric MDI of said polyurethane prepolymer mixture.
• the reducing of the amount of residual monomeric MDI is accomplished by means of distillation.
• polyurethane prepolymer compositions described above are used for the production of adhesives and sealants.
• the polyurethane prepolymer compositions of the invention comprise a prepolymer segment composed of specific diisocyanate units and a specific polyol units.
• the prepolymer segment is formed of the reaction of (A) a methylene diphenyl diisocyanate (MDI) unit, and (B) a polyol unit.
• the prepolymer segment is formed of the reaction of (A) a polyphenylene polydimethylene polyisocyanates diisocyanate (pMDI) unit and (B) a polyol unit.
• the compound A unit in a prepolymer refers to a unit derived from the compound A among the repeat units that constitute the polymer chain. That is, the compound A in the polymerization of a polymer would be one of the repeat units that constitute the polymer chain after a certain component or bond at the terminal is modified by a reaction such as condensation polymerization. The polymer thus produced will thus contain the compound A unit in the main chain or side chain.
• the unit (A) and the unit (B) may be interconnected with each other to form a chain in the prepolymer segment.
• the unit (A) and the unit (B) may be interconnected with each other via an NCO bond.
• the prepolymers of the invention are made using standard reaction processes and conditions as known in the art for the production of prepolymers and polyurethanes generally. Illustrative processes are described by way of example in U.S. Pat. Nos. 4,832,098, 4,934,425, 4,921 ,029, 4,784,201 , and 5,605,657, and U.S. application Ser. No. 09/919,994, filed on Aug. 2, 2001.
• the diisocyanate component for preparation of the prepolymer may include aromatic and aliphatic diisocyanate monomers or polymers.
• Aromatic diisocyanates are well known and are widely used in the preparation of polyurethanes.
• Aliphatic diisocyanate monomers include 1,6-hexane diisocyanate (HDI), dibenzyl-4,4'- diisocyanate, isophorone diisocyanate (IPDI), 1 ,3'- and 1 ,4'-xylene diisocyanates, 1 ,6- hexamethylene diisocyanate, 1 ,3'- and 1,4'-cyclohexyl diisocyanate (CHDI), the three geometric isomers of 1 ,1 '-methylene-bis(4-isocyanatocyclohexane) (H12MDI), and mixtures thereof.
• HDI 1,6-hexane diisocyanate
• IPDI isophorone diisocyanate
• CHDI 1,4-cyclohexyl diisocyanate
• H12MDI the three geometric isomers of 1 ,1 '-methylene-bis(4-isocyanatocyclohexane)
• the diisocyanate monomers are aromatic diisocyanates namely a monomeric MDI.
• Monomeric MDI is, for example, selected from the group of diphenylmethane diisocyanate (MDI) with all its isomers (4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-M DI)).
• the diisocyanate component for preparation of the prepolymer is polymeric isocyanate for example pMDI.
• pMDI is a mixture of monomeric (2-ring) MDI and polyaromatic (3-ring and higher) species of methylene diphenyldiisocyanates.
• These are, for example, the known industrial raw materials "crude MDI” and the “polymeric MDI” obtainable therefrom.
• crude MDI to mean the crude product obtained during the industrial synthesis of MDI after the phosgenation step, which is a mixture of the known binuclear MDI isomers and polynuclear ( ⁇ 3) oligomers. This is worked up by distillation in a further step to give so-called polymeric MDI, which is a crude MDI depleted in binuclear MDI isomers and other low-boiling by-products.
• polyols include compounds having more than one hydroxyl, amino, or thiol functional groups or combinations thereof.
• the formation of such polyols is well known in the art.
• Such polyols may contain ester, ether, amide, aliphatic, acrylic, polylactic acid, polyglycolic acid, metal, metalloid and other functionalities as also known to those skilled in the art.
• the polyol may comprise one or more of polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyacrylate polyols, polylactic acid, polyglycolic acid, and polyols containing blocks of different types of esters, ethers, amides, and/or other repeating groups or segments, and mixtures or combinations thereof.
• the polyols have a molecular weight ranging from 100 to 10,000, in one embodiment , from 225 to 6,000, and in another embodiment from 250 to 3,000.
• molecular weight refers to the number average molecular weight in Daltons which as used herein is calculated via Hydroxyl number measurement by ASTM E222-94 method.
• the polyol may comprise glycols, triols, and/or higher average hydroxyl functionality and having molecular weights ranging, for example those including from 50 to 600, and in another embodiment from 55 to 300, and in another from 60 to 200.
• Such polyols may include in one embodiment lower molecular weight polyols.
• the average hydroxyl functionality can range from about 2 to 8, preferably about 2 to 3 and more preferably from about 2 to 2.5.
• Such glycols or triols may include, for example, ethylene glycol, isomers of propylene glycol, isomers of butane diol, isomers of pentanediol, isomers of hexanediol, trimethylolpropane, pentaerythritol, poly(tetramethylene ether) glycol, poly(trimethylene ether) glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and mixtures thereof.
• the polyols useful for making prepolymer are compounds of the polyester polyol type.
• polyols are prepared by conventional methods using a combination of diacids and diols that are known in the art, for example succinate, adipate or other esters.
• the esters may also be prepared by the condensation reaction of hydroxyl carboxylic acids, for example lactic or glycolic acids. Esters may also be prepared from acyl chlorides.
• polyester polyols are poly(adipate) glycol, poly(hexamethylene adipate) glycol, polyethylene adipate) glycol (PEAG), poly(diethylene adipate) glycol, poly(ethylene/propylene adipate) glycol, poly(trimethylolpropane/hexamethylene adipate) glycol, poly(ethylene/butylene adipate) glycol, poly(butylene adipate) glycol, poly(hexamethylene/neopentyl adipate) glycol, poly(butylene/hexamethylene adipate) glycol (PBHAG), poly(neopentyl adipate) glycol, and mixtures, copolymers (including block and random copolymers) and terpolymers thereof.
• PAG poly(diethylene adipate) glycol
• poly(ethylene/propylene adipate) glycol poly(trimethylolpropane/hexamethylene adip
• PEAG polyol with an aromatic diisocyanate as the isocyanate component.
• the prepolymer segment comprises methylene diphenyl diisocyanate (MDI) as the diisocyanate unit (A). In another embodiment, the prepolymer segment comprises polyphenylene polydimethylene polyisocyanates (pMDI) as the polyisocyanate unit (A).
• MDI methylene diphenyl diisocyanate
• pMDI polyphenylene polydimethylene polyisocyanates
• the prepolymer segment comprises PPG as the polyol unit (B).
• the NCO:OH ratio is from 1 :1 to 10:1, preferably 3:1 to 8:1, more preferably 5:1 to 7:1 and most preferably 7:1.
• the inventive polyurethane prepolymer composition is prepared by a process comprising the following steps: (1) reacting pMDI (A) and a polyol (B) to form a polyurethane prepolymer; and (2) distilling off monomeric MDI from said polyurethane prepolymer.
• inventive polyurethane prepolymer composition prepared by process comprising the following steps: (1) reacting MDI (A) and a polyol (B) to form a polyurethane prepolymer; (2) admixing pMDI to the prepolymer thereby forming a prepolymer mixture; and (3) distilling off the monomeric MDI from said polyurethane prepolymer mixture.
• Any process suitable in reducing the amount of free diisocyanate monomer in the polyurethane prepolymer composition to the low levels of the present invention may be employed.
• a variety of methods is known for reducing the residual isocyanate content of diisocyanate monomers to a minimum such as wiped film evaporation, solvent aided distillation/co-distillation, molecular sieves, and solvent extraction. Distillation under reduced pressure is preferred, in particular thin film or agitated film evaporation under vacuum.
• the NCO-terminated polyurethane prepolymers according to the invention have a content of monomeric, unreacted MDI monomer of less than 1 wt. %, preferably less than 0.5 wt. %, particularly preferably less than 0.2 wt.%, and most particularly preferably less than 0.1 wt.%.
• the number of NCO groups per molecule is between 1 and 5, preferably 2 to 4, and in particular, exclusively reactive aromatic isocyanate groups are contained.
• the reaction products contain at least two urethane groups in the molecule.
• the polyurethane prepolymers of the present invention can be cured with moisture or water.
• Suitable further curatives for the polyurethane prepolymer composition of the present invention include polyamines, polyols, or blends thereof.
• Suitable polyamines for the polyurethane prepolymer composition of the present invention include both aromatic and aliphatic diamines, primary and secondary amine terminated polyether polyols, and difunctional, trifunctional, and polymeric amines.
• Suitable of polyols for the polyurethane prepolymer composition of the present invention include polyester or polyether polyols, which can be diols, triols and tetrols, having primary, secondary and/or tertiary alcohol groups. These polyols may be mixed with diamines. Polyols are typically preferred over polyamines.
• the curative is 1 ,4-Butanediol
• the polyurethane prepolymer composition of the present invention optionally comprises, where appropriate, further additives such as stabilizers, thickening agents, tackifying resins, fillers, plasticizers, thixotropic agents, color agents, pigments, solvents and/or drying agents.
• Stabilizers for the purposes of this invention refers on the one hand to stabilizers which have a viscosity-stabilizing effect on polyurethane prepolymers during production, storage and use. These are for example monofunctional carbonyl chlorides, monofunctional high reactivity isocyanates, but also non-corrosive inorganic acids, examples being benzoyl chloride, toluenesulfonyl isocyanate, phosphoric acid or phosphorous acid.
• Useful stabilizers for the purposes of this invention further include antioxidants, UV stabilizers or hydrolysis stabilizers.
• antioxidants include antioxidants, UV stabilizers or hydrolysis stabilizers.
• the selection of these stabilizers depends not only on the main components of the composition but also on the application conditions and the likely destabilizing stresses on the cured product.
• the polyurethane prepolymer is predominantly constructed from polyether building blocks, there is mainly a need for antioxidants with or without UV protectants. Examples thereof are the commercially available sterically hindered phenols and/or thioethers and/or substituted benzotriazoles or the sterically hindered amines of the HALS (Hindered Amine Light Stabilizer) type.
• HALS Hindered Amine Light Stabilizer
• the low-free pMDI polyurethane prepolymer of the present invention are typically used in applications such as coatings, adhesives, sealants or elastomers. In a preferred embodiment, the low-free pMDI polyurethane prepolymer of the present invention are used for adhesive applications.
• TPG Tripropylene Glycol Regular Grade tri(propylene) glycol isomer mixture
• TPG Tripropylene Glycol Regular Grade tri(propylene) glycol isomer mixture
• CAS No.: 24800-44-0 Tripropylene Glycol Regular Grade tri(propylene) glycol isomer mixture
• the prepolymer was prepared as follows.
• the 4,4’-MDI (68.3%), available from Covestro under the trademark Mondur® M, is agitated and heated to 50°C under a blanket of nitrogen. Thereafter, charges of 26.4% PPG-1100 and 5.4% PPG-500 were added, and the reaction temperature was held at 70 °C for 4 hours.. Finally, excess residual 4,4’-MDI monomer was removed by thin-film distillation under reduced pressure from the reaction mixture to a level of less than 0.1 wt % residual 4,4’-MDI, and total % NCO content of 6.0%.
• the prepolymer was prepared as follows.
• the pMDI (63.4%), available from BorsodChem under the trademark Ongronat® CO 4150, is agitated and heated to 50°C under a blanket of nitrogen. Thereafter, a charge of 36.6% PPG-1100 was added, and the reaction temperature was held at 70 °C for 4 hours. Finally, excess residual 2,4’-M DI and 4,4’-M DI monomer was removed by thin- film distillation under reduced pressure from the reaction mixture to a level of less than 0.1 wt % residual 2,4’-MDI and 4,4’-MDI.
• the prepolymer was prepared as follows.
• the pMDI (48.3%), available from BorsodChem under the trademark Ongronat® CO 4150, is agitated and heated to 50°C under a blanket of nitrogen. Thereafter, a charge of 51.7% PPG-2000 was added, and the reaction temperature was held at 70 °C for 4 hours. Finally, excess residual 2,4’-M DI and 4,4’-M DI monomer was removed by thin- film distillation under reduced pressure from the reaction mixture to a level of less than 0.1 wt % residual 2,4’-MDI and 4,4’-MDI.
• the prepolymer was prepared as follows.
• 70.0% prepolymer was blended with 30.0% pMDI available from BorsodChem under the trademark Ongronat® CO 4150.
• excess residual 2,4’-MDI and 4,4’-MDI monomer was removed by thin-film distillation under reduced pressure from the reaction mixture to a level of less than 0.1 wt % residual 2,4’-MDI and 4,4’-MDI.
• All four resulting prepolymers are stable with a high color (very dark brown), have more than double the target %NCO of 6% and have higher than expected batch yields.
• the prepolymer prepared by using Ongronat® CO 4150 shows the best balance of high NCO and low viscosity.
• Table 6 shows that the resulting LF prepolymers had similar viscosity profiles, however the higher NCO:OH ratio had a higher %NCO.
• Inventive Example 8 a 4,4’-MDI/PPG-2000 prepolymerwas produced in a first step. Then, 30% pMDI were added after the reaction and then finally stripped.

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