CN101528798A - Polyurethaneurea system - Google Patents
Polyurethaneurea system Download PDFInfo
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- CN101528798A CN101528798A CNA2007800399683A CN200780039968A CN101528798A CN 101528798 A CN101528798 A CN 101528798A CN A2007800399683 A CNA2007800399683 A CN A2007800399683A CN 200780039968 A CN200780039968 A CN 200780039968A CN 101528798 A CN101528798 A CN 101528798A
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- polyurethane
- urea
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/02—Replaceable treads
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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
- 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
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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
- 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
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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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
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
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- 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
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
- B29D2030/544—Applying an intermediate adhesive layer, e.g. cement or cushioning element between carcass and tread
Abstract
The present invention discloses a polyurethaneurea system that includes in some embodiments Parts A and B reaction components for a polyurethaneurea, wherein an exemplary embodiment provides a Part A that comprises between 55 and 75 wt.% of an oligomeric polyol, between 3 and 7 wt.% of an aromatic diamine chain extender, and between 0.1 and 1.5 % of a reactivity catalyst; Part B includes between 1 and 15 wt.% of a short aromatic diisocyanate and between 5 and 35 wt.% of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol. The polyurethaneurea system may further comprise an elastomer-surface activator comprising a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer, wherein at least one of the second diisocyanates may be the same as at least one of the diisocyanates of Part B.
Description
Technical field
[0001] the present invention relates generally to the polyurethane-urea system, relate more particularly to can be used for polyurethane-urea system bonding and filled elastomer (elastomerics that particularly comprises crosslinked rubber).
Background technology
[0002] multiple adhesive product comprises that polyurethane binder product commerce can buy with as sealing agent or to repair polymer elasticity material, for example natural rubber, synthetic rubber, plastifying polyvinyl chloride, sovprene etc.
[0003] usually by polyisocyanates, polyoxyethylene glycol and chain extension agent synthesis of polyurethane.This chain extension agent is selected from low molecular weight diols, diamines, amino alcohol or water usually.When chain extension agent was glycol, the urethane of formation was all set up jointly by urethane bonds.Yet if for example chain extension agent is water, amino alcohol or diamines, urethanum and urea bonding all exist and the composition that obtains is called as polyurethane-urea or PUU.Therefore, the polyurethane-type composition with urethanum and urea bonding can be called as polyurethane-urea.
Summary of the invention
[0004] the special embodiment of the present invention comprises and can be used for bonding and/or repair elastomeric polyurethane-urea system.This system comprises reactive component, and described reactive component reaction is to form polyurethane-urea, and this reactive component comprises A part and B part.These parts can comprise the mixture (in the total mass of A part and B partial reaction component) of massfraction: A with following every kind of reactive component partly for comprise about 55 to about 75 weight % molecular-weight average about more than 1000 oligomeric polyols (serving as primary polyvalent alcohol in some embodiment), about 3 to about 7 weight % aromatic diamine chain extension agent and the mixture of about 0.1 to about 1.5% active catalyst; B is partly for comprising the mixture of the about 1 short aromatics to about 15 weight % (short aromatic) vulcabond and the about 5 aromatic diisocyanate prepolymers to about 35 weight % (it is the reaction product of short aromatic diisocyanate and glycol).The special embodiment of polyurethane-urea system is provided in the mixture of A part and B part, and isocyanate functionality is about 0.8 to about 2 to the ratio of total functionality of amine and hydroxyl.Alternatively, this ratio is provided is about 1 to about 1.07 to special embodiment.
[0005] the polyurethane-urea system can further comprise elastomerics-tensio-active agent, this elastomerics-tensio-active agent comprises the second short aromatic diisocyanate and the second aromatic diisocyanate prepolymer, and wherein at least a second vulcabond can be identical with at least a vulcabond of B part.
[0006] special embodiment of the present invention further provides a kind of method, comprises making the reactive component of above-mentioned polyurethane-urea system react.This method can further comprise polyurethane-urea is applied to the end face (face) of crosslinked rubber item and the end face of crosslinked rubber item is bonded to ground.The special embodiment of this method can further comprise uses the end face of elastomerics-tensio-active agent to crosslinked rubber item, and wherein this elastomerics-tensio-active agent comprises the second short aromatic diisocyanate and the second aromatic diisocyanate prepolymer.Randomly, this method can comprise the end face with the crosslinked rubber item of the solution primary coat (priming) of TCCA (Trichloroisocyanuric acid) in solvent.
[0007] special embodiment of the present invention further comprises goods, and described goods comprise the assembly that is bonded to goods with above-mentioned polyurethane-urea system.
[0008] special embodiment of the present invention provides a kind of method of retreading, comprise the adhesive surface that elastomerics-tensio-active agent is applied to annular tire tread (tread band), the polyurethane-urea material is applied to the adhesive surface of annular tire tread, and this adhesive surface with annular tire tread of polyurethane-urea material is placed on the outer adhesive surface of carcass (tire carcass).
[0009] special embodiment of the present invention further provides the method for repairing elastomeric article, comprise that wherein this perished surface is the hole in the goods, dark crack, ditch (gouge), breach, otch or the exposed surface of tearing with the perished surface of elastomerics-tensio-active agent coating elastomeric article; With with the hole in the above-mentioned polyurethane-urea filled articles, dark crack, ditch, breach, otch or tear.
[0010] by following preferred embodiment of the present invention is described more specifically, aforesaid purpose, the feature and advantage with other of the present invention will be apparent, and as depicted in the figures, wherein similar reference signs is represented similar portions of the present invention.
Description of drawings
[0011] Fig. 1 is different rubber combination of the present invention and the elongation of example polyurethane-urea material and the figure of modulus.
[0012] Fig. 2 is the figure of different rubber combination of the present invention and example polyurethane-urea material strain and true stress.
[0013] Fig. 3 is different rubber combination of the present invention and the elongation of example polyurethane-urea material and the figure of hysteresis.
[0014] Fig. 4 is of the present invention with the rupture stress of the multiple different rubber combinations of example polyurethane-urea system adherent and the figure of breaking strain.
Embodiment
[0015] the present invention includes polyurethane-urea system, its preparation method and using method thereof.This polyurethane-urea system can be used as the various products tackiness agent and/or the repair materials of (comprise elastomeric article and comprise the elastomeric article that comprises crosslinked (solidified) rubber compound (compound)).This polyurethane-urea system can be used as repair materials to fill hole to be repaired, dark crack, ditch (gouge), breach, otch, to tear and/or cause other damages of starting materials loss (comprising elastomer material).The present invention further comprises having the goods of polyurethane-urea as tackiness agent and/or repair materials.
[0016] the polyurethane-urea system of special embodiment provides the polyurethane-urea product that is obtained by A part and B partial reaction component reaction.The A part can comprise the mixture that comprises oligomeric polyols and aromatic diamine chain extender reaction component, and the B part can comprise the mixture that comprises short aromatic diisocyanate and aromatic diisocyanate prepolymer reactive component, and described prepolymer is the reaction product of short aromatic diisocyanate and glycol.Advantageously, special embodiment is included in A part and the B mixture partly and does not comprise solvent and/or filler.
[0017] in some embodiment, the mixture feature of A part and B partial reaction component can be that isocyanate functionality is about 0.9 to about 2 to the ratio of total functionality of amine and hydroxyl in the mixture.Other embodiments have about 1 to about 1.7 ratio.And other embodiments have about 1 to about 1.07, or about 1 to about 1.03 ratio.
[0018] the A partial confounding compound that is used to form the polyurethane-urea system of special embodiment comprises oligomeric polyols and aromatic diamine chain extension agent.This oligomeric polyols reaction is closed with the urethane bonds that forms in the polyurethane-urea compositions.Special embodiment comprises molecular-weight average about 1000 or more or be about oligomeric polyols of 1000 to 4000, and other embodiments comprise that molecular-weight average is about 1500 to 4000 or about 2000 to about 4000 polyvalent alcohol.All molecular weight are represented with weight-average molecular weight in the text, unless indicate separately.
[0019] the oligomeric polyols reactive component feature of special embodiment can be not have molecular weight about below 1000 or alternatively, about below 900 or at about oligomeric polyols below 800.Alternatively, in special embodiment, oligomeric polyols can comprise and be no more than about 5 weight % or be no more than about 10 weight % alternatively, and the molecular weight of 15 weight % or about 25 weight % is respectively about below 1000, about below 900 or at about oligomeric polyols below 800.
[0020] feature of the oligomeric polyols reactive component of special embodiment can further be to be mainly uncle's oligomeric polyols (primary oligomeric polyol).For example, some embodiment can comprise that oligomeric polyols is 100 weight % uncle's oligomeric polyols or is at least 95 weight % uncle's oligomeric polyols or at least 75 weight % uncle oligomeric polyols alternatively.Special embodiment comprises that the OH functionality is about 2 oligomeric polyols reactive component.
[0021] non-limitative example of suitable uncle's oligomeric polyols comprises polyether polyol, amine-end capped (amine-terminated) polyvalent alcohol, polyester polyol, polyester ether type polyvalent alcohol, many cyclopolyols and polycarbonate polyol.Polyether polyol comprises polytetramethylene ether glycol (PTMEG).The polyether glycol that amine-end capped polyvalent alcohol has been replaced by uncle or secondary amino group functional group based on its terminal hydroxy groups.Polyester polyol can comprise, for example, and polyethylene adipate, polyethylene glycol adipate, polycaprolactone glycol and polycaprolactone-polyadipate copolymer diols.
[0022], can comprise that then for example secondary polyvalent alcohol is as the reactive component in the special embodiment for those embodiments that not only comprises uncle's oligomeric polyols.This, oligomeric polyols can comprise second month in a season, for example, and polybutylene oxide glycol (PBO), polypropylene oxide glycol (PPO) and Viscotrol C.
[0023] randomly, the oligomeric polyols reactive component can comprise be selected from above-mentioned those and/or be selected from the mixture of the oligomeric polyols that well known to a person skilled in the art other kinds.
[0024] amount of the oligomeric polyols reactive component that comprises of special embodiment (being expressed as the weight % in the total mass of the reactant composition of A part and B part) is about 50 weight % about 80 weight % extremely of total mass, or about alternatively 55 weight % are to about 75 weight %, or about 60 weight % are to about 72 weight %.
[0025] another reactive component that can comprise in the A partial confounding compound is the aromatic diamine chain extension agent.This aromatic diamine chain extension agent reaction is to form the urea bonding in the polyurethane-urea reaction product.This aromatic diamine chain extension agent can be, for example, and uncle and/or secondary aromatic diamine.Special embodiment only comprises that uncle's aromatic diamine or this aromatic diamine reactive component can comprise, for example uncle's aromatic diamine of at least 75 weight % or at least 95 weight %.
[0026] non-limitative example of aromatic diamine chain extender reaction component comprises DETDA (diethyl toluene diamine), methylene-bis (N, N-dibutyl pentanoic), 2 of IPDA (isophorone diamine), 4 and 2,6 isomer, or 3, the 5-dimethyl sulphide is for-2,4-tolylene diamine, 3,5-dimethyl sulphide generation-2,6-isomers of toluenediamine, or its mixture.Other examples comprise methylene dianiline (MDA) (MDA), 4,4 '-methylene radical-two-3-(chloro-2,6-Diethyl Aniline) (MCDEA); 4,4 '-methylene radical-two-(2-ethyl-6-monomethylaniline) is (MMEA); 4,4 '-two-(2, the 6-Diethyl Aniline) are (MDEA); 4,4 '-methylene radical-two-(2-sec.-propyl-6-monomethylaniline) is (MMIPA); 4,4 '-two (second month in a season-butyl amino) ditan; The penylene diamines; Methylene radical-two-Ortho-Chloro aniline (MBOCA); 4,4 '-methylene radical-two-(2-methyl-aniline) is (MMA); 4,4 '-methylene radical-two-(2-chloro-6-ethylaniline) is (MCEA); 1, two (2-amino-phenyl sulfo-) ethane of 2-; N, N '-two-alkyl-right-penylene diamines; 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline) are (MDIPA); Dimethyl sulphide for tolylene diamine (dimethylthiotol-uenediamine) (DMTDA) or its mixture.
[0027] randomly, the aromatic diamine chain extender reaction component can comprise be selected from above-mentioned those and/or be selected from the mixture of the aromatic diamine chain extension agent that well known to a person skilled in the art other kinds.
[0028] the aromatic diamine chain extender reaction component amount that comprises of special embodiment (being expressed as the weight % in the total mass of the reactant composition of A part and B part) is about 0 weight % about 10 weight % extremely of total mass, or about alternatively 5 weight % are to about 7 weight %, or about 3.5 weight % are to about 5 weight %.
[0029] the B partial confounding compound that is used to form the polyurethane-urea system of special embodiment comprises short aromatic diisocyanate and prepolymer.This prepolymer can be formed by short aromatic diisocyanate and glycol.Short aromatic diisocyanate is generally non-polymeric component.
[0030] the short aromatic diisocyanate reactive component feature that comprises in the special embodiment can be to be under the room temperature easy-to-handle low-viscosity (mobile) liquid; For example, 25 ℃ of viscosity be about 20 to about 30cps short aromatic diisocyanate.The molecular weight of short aromatic diisocyanate reactive component is usually about below 500, and molecular weight is 160 to 500 or alternatively 160 to 300 in the wherein special embodiment.In special embodiment, short aromatic diisocyanate reactive component can have 2 or alternatively, about 1.8 to 2.2 or about 1.9 to about 2.1 isocyanate functionality.
[0031] non-limitative example of suitable short aromatic diisocyanate comprises, for example, and phenylene diisocyanate, right-and-phenylene diisocyanate; Tolylene diisocyanate, Xylene Diisocyanate, 2,4 and/or 2,6 tolylene diisocyanates (TDI), 1,5-naphthalene diisocyanate; The methylene diisocyanate of carbodiimide (carbodimide) modification, 4,4 '-phenylbenzene-methane diisocyanate (MDI) and, if it is suitable, its higher homologue (polymeric MDI), the MDI compound of modification, naphthalene diisocyanate (NDI), the isomer mixture of various aromatic diisocyanate or its combination.The example of MDI compound that can be used as the modification of short aromatic diisocyanate is the diphenylmethanediisocyanate of poly-carbodiimide-modification, as the ISONATE 143L available from Dow ChemicalCompany.
[0032] amount of the short aromatic diisocyanate reactive component that comprises of special embodiment (being expressed as the weight % in the total mass of the reactant composition of A part and B part) be about 0 weight % about 25 weight % extremely of total mass, or about alternatively 1 weight % about 15 weight % or about 1 weight % about 13 weight % extremely extremely.
[0033] the aromatic diisocyanate prepolymer reactive component of the B partial confounding compound of polyurethane-urea system feature in special embodiment can be the reaction product between aforesaid short aromatic diisocyanate and the glycol.The feature of this aromatic diisocyanate prepolymer can further be to have 2 or alternatively, about 1.8 to 2.2 or about 1.9 to about 2.1 isocyanate functionality.
[0034] in special embodiment, reaction serves as uncle's glycol with the glycol that forms the aromatic diisocyanate prepolymer.In special embodiment, the glycol that is used to form prepolymer can be uncle's glycol of 100 weight %, can be the above uncle's glycol of about 95 weight %, can be the above uncle's glycol of about 75 weight % or can be the above uncle's glycol of about 50 weight %.Special embodiment comprises that molecular weight is about 250 to about 3000 or alternatively, about 400 to about 2000 glycol.
[0035] common, suitable prepolymer can have more than 500 or about 500 to about 4000 molecular weight.Other embodiments comprise that molecular weight is about 800 to about 3000 or alternatively, about 850 to about 1500 prepolymer.
[0036] special embodiment be can be short aromatic diisocyanate as the useful prepolymer of reactive component and based on the reaction product of uncle's glycol of polyethers or polyester.The example of useful aromatic diisocyanate prepolymer based on polyethers is based on the end capped prepolymer of the diphenylmethanediisocyanate of polyethers, as the VIBRATHANE B836 available from Chemtura.This prepolymer is the reaction product of polyethers and diphenylmethanediisocyanate (MDI).
[0037] amount of the aromatic diisocyanate prepolymer reactive component that comprises of special embodiment (being expressed as the weight % in the total mass of the reactant composition of A part and B part) is about 0 weight % about 50 weight % extremely of total mass, or about alternatively 5 weight % are to about 45 weight %, or about 10 weight % are to about 35 weight %.
[0038] working life (potlife), or its become viscosity too so that can't sprawl before use the time limitation of polyurethane-urea tackiness agent/repair materials, be after reactive component (A partly and B part) is mixed about 1.5 to about 4 minutes at 40 ℃.The special embodiment of polyurethane-urea system thereby can comprise that (as reactive component) can be used for the active catalyst of regulating working life, as those skilled in the known.The active catalyst of example is alicyclic (ring-aliphatics) tertiary amine, as triethylenediamine.
[0039] can active catalyst be joined in the reactive component with about 0.1 to about 1.5 weight % of total reaction component (A part and B part) usually.In other embodiments, can be with about 0 to about 15 weight %, about 0.05 to about 9 weight % or about 0.4 to about 1 weight % joins active catalyst in the reactive component.
[0040] finds in special embodiment, to compare, omit catalyzer much hard and quite opaque polyurethane-urea material are provided with the material of other embodiments that when adding catalyzer, obtain.The special embodiment that comprises active catalyst advantageously provides usually at physical properties (for example, rigidity, extension at break and hysteresis) the similar polyurethane-urea material of rubber elastomeric material last and bonded and/or that repair.
[0041] also protective material (protectorant) can be joined in the reactive component so that the protection of anti-environmental hazard to be provided.This protective material can comprise for example antioxidant, UV absorption agent, photostabilizer and combination thereof.Reactive polymer pigment also can be used as reactive component and adds to provide painted to the polyurethane-urea material.For example, if rebuild a tyre, black pigment can be used so that repair materials and tire matching in colour.
[0042] the special embodiment of polyurethane-urea system can further comprise, before using A part and B partial confounding compound, is used to be coated with the elastomerics-tensio-active agent of the material surface of bonded or reparation.Material bonding by the polyurethane-urea system of special embodiment and/or that repair can be resilient material and/or crosslinked elastomeric material.In special embodiment, the use of elastomerics-tensio-active agent provides the improved bonding of the polyurethane-urea that formed by A part and the B partial confounding compound surface to bonded or reparation.
[0043] elastomerics-tensio-active agent in the special embodiment can comprise short aromatic diisocyanate (as mentioned above) and prepolymer.This prepolymer can be the reaction product between for example aforesaid short aromatic diisocyanate and the glycol.To special embodiment, the short aromatic diisocyanate of this elastomerics-tensio-active agent can be identical with the short aromatic diisocyanate of the reactive component that is selected as B partial confounding compound, or the short aromatic diisocyanate of elastomerics-tensio-active agent can be different with the short aromatic diisocyanate of the reactive component that is selected as B partial confounding compound.Special embodiment comprises elastomerics-tensio-active agent, and this elastomerics-tensio-active agent only comprises short aromatic diisocyanate and prepolymer and solvent-free, and other embodiments comprise solvent.
[0044] those are comprised the embodiment of solvent in elastomerics-tensio-active agent, solvent is generally about 35 to about 65 weight %, in the total mass of elastomerics-tensio-active agent.Suitable solvent comprises, for example, and toluene, ethyl acetate, methylethylketone (MEK) or its mixture.The special embodiment of elastomerics-tensio-active agent comprises about 0 to about 90 weight %, or about alternatively 0 to about 80 weight % or about 5 short aromatic diisocyanate to about 80 weight %, in the total mass of the vulcabond in elastomerics-tensio-active agent, all the other are prepolymer.Special embodiment comprises, for example, the mixture of short aromatic diisocyanate/aromatic diisocyanate prepolymer of about 50: 50 weight %, or alternatively, the short aromatic diisocyanate/aromatic diisocyanate prepolymer of about 5: 95 weight % ratios in promoting agent.
[0045] special embodiment of the present invention also comprises the method for preparing polyurethane-urea tackiness agent/repair materials.Special embodiment comprises A partial confounding compound and the reaction of B partial confounding compound.In an embodiment, react in following amount (being expressed as weight %) with the reactant composition total mass:
The A part
A) about 55 to about 75% molecular-weight average is at the oligomeric polyols more than 1000;
B) about 3 to about 7% aromatic diamine chain extension agent; With
C) 0.1 to 1.5% active catalyst.
The B part:
D) about 1 to about 15% short aromatic diisocyanate;
E) about 5 to about 35% prepolymer.
[0046] rigidity that it should be noted that the polyurethane-urea material can be regulated by the ratio that changes aromatic diamine chain extension agent/polyvalent alcohol in the A partial confounding compound.By increasing the amount of aromatic amine, gained polyurethane-urea material stiffness increases usually.
[0047] randomly, about 0 to about 5 weight % protective material and/or pigment can be joined in the reaction-ure mixture.Special embodiment can comprise about 0.5 these materials to about 2 weight %.Usually these materials can be joined in the A partial confounding compound of reactant composition.In special embodiment, in these components some or all can be joined in the B partial confounding compound of reactant composition.
[0048] the special embodiment that is used to make present method of polyurethane-urea compositions comprises by adhesive dispenser and further, distributes this two-partial reaction mixture by the divider that can have static mixer.Static mixer (can freely use usually) has guaranteed in allocation step A part and B partial confounding compound thorough mixing.Can manual, pneumatic or electrically operated adhesive dispenser.Selectively, can manually use adhesive dispenser proportioning and mixing A part and B partial confounding compound.
[0049] this divider and using to conventionally known to one of skill in the art, and can be available from, ConProTec for example, Inc. (office being arranged) at New Hampshire, commodity are called the MIXPAC system.The tube volume ratio of adhesive dispenser (cartridge volume ratio) must be compatible with adhesive formula (formulation).For example the MIXPAC system is useful to the model that the blended tackiness agent is provided, and wherein two portions system blending ratio is 1: 1,2: 1,4: 1 or 10: 1.
[0050] use the special embodiment of polyurethane-urea system bonding and/or repair surface of elastomer and can comprise handling and treat surface bonding and/or reparation with elastomerics-tensio-active agent.In the special embodiment of present method, treat that at least one surface bonding and/or that repair comprises surface of elastomer, wherein some can comprise the elastomerics that comprises crosslinked rubber combination.Randomly, but optional, before using elastomerics-tensio-active agent and/or polyurethane-urea reactive component, can clean surface of elastomer and treat the binding property and the wettability (wetability) on the surface of bonding and/or reparation with prime treatment with improvement.Usually remove the layer of pollution layer or poor adhesion with this prime treatment.The priming paint of example is, for example, and the solution of TCCA (Trichloroisocyanuric acid) (TIC) in solvent, for example, the TIC of 2-6% in ethyl acetate.
[0051] if use priming paint, priming paint can be brushed on surface of elastomer, and it be stayed the surface went up about 15 minutes.Then, with solvent (as ethyl acetate) rinsing surface, to remove any excessive TIC.Can repeat these steps also is that elastomerics-surfactant and/or polyurethane-urea reactive component are ready until cleaning surfaces.
[0052] can use brush, scraper, spray gun or well known to a person skilled in the art that additive method is applied to elastomerics-tensio-active agent and treat surface bonding and/or that repair.Can use one layer or more elastomerics-tensio-active agent to obtain required thickness.Special embodiment comprises and is applied to many about 0.5mm or alternatively, the about 0.05 elastomerics-surfactant to about 0.25mm thickness.Usually by before using two-part polyurethane-urea reactive component, using elastomerics-tensio-active agent to improve the bonding of polyurethane-urea material.
[0053] the special embodiment of using the polyurethane-urea system to repair goods and/or adhesive surface can advantageously be carried out at envrionment temperature (that is, about 20 ℃ to about 40 ℃).If opposing end faces (opposing face) is bonded together, can apply the pressure of for example about 0.03 crust to adhesive sheet to about 5 crust, the time length of wherein exerting oneself under lower pressure is longer pro rata usually.
[0054] when bonding and/or repair materials, can use curing time (maturation time) to the polyurethane-urea system of using among the present invention.This curing time can be about 48 hours at ambient temperature usually, or descends for 60 ℃ to 100 ℃ to be several hours in temperature.Advantageously, even the polyurethane-urea system that should be mainly formed by uncle's glycol discussed above is still kept its bonding/reparation state at least when the temperature that stands 130 ℃, wherein 130 ℃ for use bed course natural gum (gum) material with the tire vulcanizing course of processing that tyre surface is attached to carcass in typical solidification value.
[0055] advantageously, the special embodiment of polyurethane-urea system provide have with tire in rigidity and the lag behind comparable rigidity and the material of hysteresis characteristic of the multiple crosslinked rubber elastomer that uses.This polyurethane-urea properties of materials makes it very useful as the tackiness agent and/or the repair materials that are used for tire.
[0056] special embodiment of the present invention comprises having the adherent end face that uses polyurethane-urea system disclosed herein and/or the goods of reparation.For example, comprise the parts that are bonded together in opposing end faces by disclosed polyurethane-urea system according to the described goods of special embodiment of the present invention, wherein at least one end face in the opposing end faces comprises crosslinked rubber combination.After mixing the polyurethane-urea reactive component, usually this polyurethane-urea reactive component is applied to the opposing end faces of parts, for example by using spray gun, brush or two-part adhesive gun (two-part adhesive gun).In special embodiment, before using blended polyurethane-urea reactive component, elastomerics-tensio-active agent is applied to two surfaces of end face.
[0057] the special embodiment of the present invention comprises having the tire that is bonded to the elastomerics patch on it by polyurethane-urea system disclosed herein.This elastomerics patch can comprise RF identification (RFID) technology and this patch can be bonded to the internal surface or the outside surface of tire.
[0058] other embodiments comprise the surface that goods is bonded to another goods (as tire).These goods that can be bonded to the surface of another goods (as tire) comprise, for example, and by the elastomer material manufacturing or by metal or textile letter.Other goods can comprise electronic package (electronic component) or device, its surface that directly is bonded to another goods (as tire) can be need not assembling and maybe this electronic package (electronic component) or device is encapsulated in the patch.The non-limitative example of this device can comprise, for example, and RFID chip, surface acoustic wave (SAW) transmitter, pressure and/or temperature sensor.This device can be assemblied on the internal surface of tire or on the outside surface of tire.Any or Overall Steps during these embodiments can comprise the steps: the surface of cleaning article (as tire); Use (as mentioned above) priming paint (as the solution of TIC in solvent) to the surface; Use (as mentioned above) elastomerics-tensio-active agent to the surface; Electronic package or device are placed on the surface of tyre; Electronic package or device directly use blended A part and B partial reaction component to the small part, thereby with electronic package or install and directly be bonded to the surface.As previously noted, comprising adhesive article to the embodiment of surface of tyre, can be bonded to outside tire or internal surface goods (as electronic installation or assembly).
[0059] randomly, can use and well known to a person skilled in the art that transfer film (transferfilm) comes application component such as RFID device or SAW transmitter.Transfer film can be flexible plastic sheet.Device can be placed on the transfer film, then to small part polyurethane-urea component covering (A part and B partial confounding compound).The film of attach mark can be placed desired position (for example, the surface of tire) then, wherein face is outside.Film can be divested then, remaining assembly is bonded to the surface.
[0060] can be by comprising tire or other goods of surface of elastomer with polyurethane-urea system filling disclosed herein hole, otch, dark crack, ditch or other opening reparations in goods.Can use the tire of polyurethane-urea system of the present invention reparation or patchery tyres for passenger cars, truck tyre, motorcycle tyre, off-the-highway tire (off-road tire) and other types.This material dark crack, hole or ditch on the sidewall that be particularly useful for rebuilding a tyre.In special embodiment, the surface of elastomer promoting agent is used the A part then and B partial confounding compound is repaired goods by using.
[0061] special embodiment of the present invention thereby comprise has tire or other goods of the bonding and/or surface of elastomer repaired of stand-by polyurethane-urea system.For tire, usually by removing loose surfacing and cleaning affected area and prepare zone to be repaired with interior and peripheral surface with otch, crack, hole or ditch.Preparation can comprise the surface by any conventional instrument or processing polishing ditch, otch or inside, crack.
[0062] if the cord in the tire (cords) is damaged, can remove the cord that has damaged, and will strengthen the internal surface that patch is applied to tire, as those skilled in the known.This cord can be made by polyester, nylon, steel, regenerated fiber or the like.Can use polyurethane-urea system disclosed herein will strengthen the internal surface that patch is bonded to tire.Similarly, if the hole that infringement causes penetrating sidewall, the internal surface that can similarly patch be applied to tire is as the part of repairing.
[0063] inner face in ditch, crack and/or hole then can be randomly with aforesaid elastomerics-tensio-active agent coating.Affected area is then by mixing A part and B part material and mixture being applied in to come in crack or the ditch with the filling of polyurethane-urea material.Material is solidified in envrionment temperature (that is, about 20 ℃ to 40 ℃).As those skilled in the known, if other reparations that tire is done need be solidified, material can be placed autoclave under heating and pressure.
[0064] because the envrionment temperature that is solidificated in of polyurethane-urea material takes place, and polyurethane-urea system of the present invention is for sport (large items), the original position of (as off-the-highway tire, travelling belt or the like) is repaired particularly useful.The polyurethane-urea system be can use at the scene, special autoclave, sweating room or or vulcanizable tyre repair equipment need not.
[0065] special embodiment of the present invention further comprises bonding annular tire tread to carcass, and wherein carcass is new or used.Bonding annular tire tread to used carcass is called as retreading.The specific embodiment of the present invention further comprises having uses polyurethane-urea system of the present invention to be bonded to the tire of the tyre surface on it.
[0066] renovate method of the present invention comprises from carcass and removes old tyre surface, handles carcass with elastomerics-tensio-active agent, or handles annular tire tread with elastomerics-tensio-active agent, or with elastomerics-tensio-active agent processing above-mentioned both.This method further comprises uses the end face of blended polyurethane-urea reactant to annular tire tread or carcass or the two exposure, then annular tire tread is placed on the carcass surface.
[0067] the special embodiment of the present invention comprises bonding or repairs the goods with elastomerics end face, especially has those goods of at least one end face that comprises crosslinked rubber combination.Special embodiment has the end face that at least one comprises crosslinked rubber combination, and described crosslinked rubber combination mainly comprises at least a diene elastomer.
[0068] term " diene elastomer " means to the elastomerics of small part (that is, homopolymer or multipolymer) derived from diene monomers (having two conjugation or non-conjugated carbon-carbon double bond), particularly:
Homopolymer is obtained by the conjugated diene monomers polymerization that contains 4 to 12 carbon atoms arbitrarily;
Any multipolymer is obtained by one or more diene (combine (conjugated together) or contain the vinyl aromatic compounds of 8 to 20 carbon atoms with one or more) copolymerization;
Terpolymer, obtain by ethene or alpha-olefin that contains 3 to 6 carbon atoms and the non-conjugated diene monomers copolymerization that contains 6 to 12 carbon atoms, as or (particularly by the non-conjugated diene monomers of propylene and type as mentioned above by ethene, 1,4-hexadiene, ethylidene norbornene (ethylidenenorbomene) or Dicyclopentadiene (DCPD)) elastomerics that obtains; Or
The multipolymer of iso-butylene and isoprene (isoprene-isobutylene rubber or IIR), and the halogen of this analog copolymer (particularly chlorine or bromine) modification.
[0069] particularly preferred diene elastomer is selected from polyhutadiene (BR), polyisoprene (IR) or natural rubber (NR), styrene-butadiene copolymer (SBR), ethene, propylene and diene terpolymer (EPDM), isoprene-isobutylene rubber or chloroprene.
[0070] in further embodiment, treat to comprise crosslinked rubber combination by the end face that polyurethane-urea system tackiness agent is bonded together with the parts that obtain above-mentioned goods, and other end faces comprise ferrous metal or based on the metal alloy of iron, as steel.
[0071] embodiment further according to the present invention, an end face comprises crosslinked rubber combination, and other end faces comprise synthetic textiles, as two-stretch knit type fabric, contain the film of the fibrous texture of selling with registered trademark " LYCRA " with formation.
[0072] aspect further according to the present invention, an end face comprises crosslinked rubber combination, and other end faces comprise rigidity plastics such as heat-curable urethane (for example, with application of decoration to cover tire).
[0073] by the following embodiment the present invention that further explains, should only it is considered as explaining, it also limit the present invention in any way.
[0074] use reactant composition as shown in table 1 to prepare polyurethane-urea system batch of material.Two-part tackiness agent/repair materials is by mixing the preparation of A part component and B part component.By fill the gap between two elastomericss with the polyurethane-urea system, use these polyurethane-urea materials together then with two elastomer bonded.Measure the gained bond strength then.
Table 1-polyurethane-urea reactant composition
[0075] ETHACURE 300 is the short chain aromatic diamine chain extension agent available from Albemarle Corporation.This product is mainly aromatic diamine 3,5-dimethyl sulphide generation-2,4-(with 2,6) tolylene diamine (DMTDA).TERATHANE 2900 is the oligomeric polyols available from DuPont.This product is that molecular-weight average is 2900 polytetramethylene ether glycol (PTMEG).REACTINT BLACK X95AB is the polyvalent alcohol bonded pigment available from Milliken Chemical.TINUVIN B75 is the protective material system available from Ciba Specialty Chemicals.ISONATE 143L is the aromatic diisocyanate based on poly-carbodiimide available from Dow Chemical.The MDI product of this modification is the diphenylmethanediisocyanate of poly-carbodiimide-modification.VIBRATHANE B836 is the aromatic diisocyanate based on polyethers available from Chemtura.This product is MDI-terminated polyether (PTMEG main chain) vulcabond.DABCO33-LV is the active catalyst triethylenediamine available from Air Products.
[0076] together, and B part material mixing is in the same place A part material mixing, and with it in tube of each two-part adhesive dispenser rifle of packing into.Then tube is inserted adhesive dispenser rifle based on two-part tube.To A1 and A2, rifle divider transmission A part and B part to the ratio of static mixer is 4: 1; That is, divider transmits 4 times of A parts to the volume of B part, is 2: 1 to A3.By adhesive dispenser by additional disposable static mixer mixing A part and B partial reaction component.
[0077] also prepares elastomerics-tensio-active agent.By preparing this elastomerics-tensio-active agent with mixing vulcabond of the amount shown in the table 1 and solvent.The weight % of every kind of vulcabond shown in the table 1 is all based on the total mass of vulcabond.Mix vulcabond to form elastomerics-tensio-active agent in solvent, this elastomerics-tensio-active agent is made by the ethyl acetate of 50 weight % (in the gross weight of solution) or the vulcabond of toluene (as solvent) and 50 weight %
[0078] use the method that well known to a person skilled in the art to prepare three kinds of different rubber elastomeric material.These three kinds of materials are sidewall type (SW) rubber combination that comprises natural rubber and cis-polybutadiene rubber, comprise liner type (IL) rubber of isoprene-isobutylene rubber and comprise tyre surface type (T) rubber of natural rubber.These materials further comprise vulcanizing agent or the like, as those skilled in the known.
[0079] every kind of composition being calendered to thickness is 2.5mm, and is cut to the 15x15cm square.In the 15x15cm mould, solidify these squares.From every solidified square, downcut the bar of about 1.25cm, so that remaining part is all separated about 1.25cm in each square.Then, with the volume (this volume causes by cutting out bar) between polyurethane-urea material filling two portions of preparation among the embodiment 1.Handle with the elastomerics-tensio-active agent of preparation among the embodiment 1 on some surface.It should be noted that A part component is heated to 40 ℃ to improve its flow characteristics.Be heated to after 40 ℃, material will be cooled to room temperature, but still keep thereafter good flow characteristics a few hours (4-8).
[0080] after the gap between polyurethane-urea material filling two halves, solidified sample in mould.Die tip applies the pressure of about 1.5 crust on sample when sample solidifies.Following program is used in the curing that takes place in mould: the top is provided with put in place after, with mold heated more than time of 20 minutes so that temperature is risen to 130 ℃ from room temperature; Temperature was kept 100 minutes down at 130 ℃.After the cooling, remove square, and each is cut into 6 to form 6 specimen with it.
[0081] specimen of test preparation in embodiment 2 is to measure its elongation at break properties.Elongation property is determined as extension at break (%), its according to ASTM standard D412 on ASTM C testing plate 23 ℃ of mensuration.Record extension at break % and breaking strain (MPa).Table 2 is listed the result to the specimen that comprises sidewall rubber (SW) composition, and table 3 is listed the result to the specimen that comprises liner (IL) composition, and table 4 is listed the result to the specimen that comprises tyre surface (T) composition.
[0082] specimen 1 shown in each is rubber witness test (witnesstest) in three tables.The test result of rubber witness test provides the extension at break physical properties of not using polyurethane-urea system adherent rubber combination itself of the present invention.
[0083] as shown in table 2,3,4, uses some adherent surface of the solution primary coat specimen of TCCA (Trichloroisocyanuric acid) (TIC) in solvent.Which kind of sample these forms show by primary coat, the number of times that the solvent of use and solution use.For example, the specimen shown in the table 23 is by with three layers of TIC5 weight % solution paint (brush) primary coat in ethyl acetate.After primary coat, make sample drying at room temperature 30 minutes, and after drying, wash with ethyl acetate.
[0084] similarly, these forms show with comprising which specimen the elastomerics-tensio-active agent of the component shown in embodiment 1 table 1 handles.The solution of elastomerics-tensio-active agent also is provided in the form, and before adding the PUU preparation to the surface with sample drying how long.
The test result of table 2-sidewall rubber (SW) composition
The test result of table 3-liner rubber (IL) composition
The test result of table 4-tread-rubber (T) composition
[0085] test result among the table 2-5 is illustrated in Fig. 4.Zone ring selected among Fig. 4 has defined the optimum adhesion condition to every kind of different rubber combination.
[0086] sample of preparation A2 material and it is cured as plate.Every kind of rubber combination of preparation among the preparation embodiment 2 (T, SW, IL) and the ASTM C testing plate of A2 material.
[0087] on testing plate with 10%, 50%, 100%, 200% and 300% measures modulus of stretch according to ASTM D412 (1998) 26 ℃ of temperature on ASTM C testing plate.It is true secant modulus (true secant moduli), and in MPa, that is, in given elongation, the secant modulus that calculates successively decreases to the true cross section of testing plate.Also on each testing plate, measure and lag behind.Test procedure moves on the Model 5500R test machine at INSTRON.
[0088] test result as Figure 1-3.Can find out that from these figure A2 polyurethane-urea material matches with the rigidity and the elasticity measurement of different rubber combinations very much.Fig. 1 and 2 shows A2 material rigidity more under low deformation.Fig. 3 shows the low hysteresis of material under low deformation.Though in Fig. 2, clearly do not show, shown under the height distortion, for example, be higher than 300% strain, the A2 material is softer than T and SW material.
[0089] should think that the term that uses in the claims of this paper and the specification sheets " comprises ", " comprising " and " having ", be the open group of expression, it can comprise other unspecified compositions.Should think the term that uses in the claims of this paper and the specification sheets " substantially by ... constitute " be the open group of expression part, it can comprise other unspecified compositions, as long as those other compositions do not change the characteristic of fundamental sum novelty of the invention of prescription in fact.The singulative of term " " and speech should be understood to include the plural form of this identical word, thereby term means one or more somethings are provided.Term " at least a " and " one or more " are used interchangeably.Term " one " or " single " should be used to refer to and only in the something of planning to refer to.Similarly, other specified round valuess are used when plan refers to the something of specific quantity as " 2 ".Term " randomly ", " can " and similar terms to be used in reference to preferably a certain, conditioned disjunction step be randomly (nonessential) of the present invention technical characterictic.By the scope of representing between two points,, comprise x and y in this scope as x to y.
[0090] should be appreciated that and to carry out multiple improvement and change to the preferred embodiments of the disclosure from above-mentioned explanation, and do not deviate from its real spirit.Provide above-mentioned explanation only to be used for purpose of explanation, it should be interpreted as restriction.Only limit the scope of the invention by following claim literal.
Claims (42)
1, a kind of polyurethane-urea system, wherein the reactive component reaction is to form polyurethane-urea, and described reactive component comprises:
The A part, wherein A is partly for comprising the mixture of following component:
About 55 to about 75 weight % molecular-weight average is at about oligomeric polyols more than 1000;
About 3 aromatic diamine chain extension agents to about 7 weight %; With
About 0.1 to about 1.5% active catalyst; With
The B part, wherein B is partly for comprising the mixture of following component:
About 1 short aromatic diisocyanate to about 15 weight %; With
About 5 aromatic diisocyanate prepolymers to about 35 weight %, described aromatic diisocyanate prepolymer is the reaction product of short aromatic diisocyanate and glycol, wherein the massfraction of every kind of reactive component is in the total mass of A part and B partial reaction component.
2, polyurethane-urea system according to claim 1, wherein oligomeric polyols comprises the above uncle's oligomeric polyols of 50 weight %.
3, polyurethane-urea system according to claim 1, wherein oligomeric polyols comprises the above uncle's oligomeric polyols of about 95 weight %.
4, polyurethane-urea system according to claim 1 further comprises:
Elastomerics-the tensio-active agent that comprises the second short aromatic diisocyanate and the second aromatic diisocyanate prepolymer.
5, polyurethane-urea system according to claim 4, at least a second vulcabond wherein as claimed in claim 2 is identical with the described at least a vulcabond of claim 1.
6, polyurethane-urea system according to claim 4, wherein elastomerics-tensio-active agent further comprises solvent.
7, polyurethane-urea system according to claim 4, wherein elastomerics-tensio-active agent comprises the short aromatic diisocyanate of 0 to 90 weight %, and wherein massfraction is in the vulcabond total mass in elastomerics-tensio-active agent.
8, polyurethane-urea system according to claim 7, wherein elastomerics-tensio-active agent comprises the short aromatic diisocyanate of 5 to 80 weight %.
9, polyurethane-urea system according to claim 1 further comprises the protective material of 2 weight % at the most, and described protective material is selected from antioxidant, UV absorption agent, photostabilizer or its combination.
10, polyurethane-urea system according to claim 1 further comprises reactive polymer pigment.
11, polyurethane-urea system according to claim 1, its short-and-medium aromatic diisocyanate is the diphenylmethanediisocyanate of poly-carbodiimide-modification.
12, polyurethane-urea system according to claim 1, its short-and-medium aromatic diisocyanate is selected from 2,4 and/or 2,6 tolylene diisocyanates (TDI), 4,4 '-MDI compound, naphthalene diisocyanate (NDI) or its combination of phenylbenzene-methane diisocyanate (MDI), polymeric MDI, modification.
13, polyurethane-urea system according to claim 1, wherein the aromatic diisocyanate prepolymer is a MDI-terminated polyether vulcabond.
14, polyurethane-urea system according to claim 1, wherein the aromatic diisocyanate prepolymer is the reaction product of glycol, described glycol is selected from glycol based on polyethers, based on glycol or its combination of polyester.
15, polyurethane-urea system according to claim 1, wherein oligomeric polyols is that molecular-weight average is about 1500 to about 4000 polytetramethylene glycol.
16, polyurethane-urea system according to claim 1, wherein the aromatic diamine chain extension agent is 2,4 and 2,6 mixture of isomers of dimethyl sulphide for tolylene diamine.
17, polyurethane-urea system according to claim 1, wherein in the mixture of A part and B part, isocyanate functionality is 0.8 to 2 to the ratio of total functionality of amine and hydroxyl.
18, polyurethane-urea system according to claim 17, wherein in the mixture of A part and B part, isocyanate functionality is 1.0 to 1.07 to the ratio of total functionality of amine and hydroxyl.
19, a kind of method comprises:
Make following reactive component reaction to form the polyurethane-urea repair materials with massfraction with respect to the reactant total mass:
The A part, wherein A is partly for comprising the mixture of following component:
The molecular-weight average of 55 to 75 weight % is at the oligomeric polyols more than 1000; With
The aromatic diamine chain extension agent of 3 to 7 weight %; With
0.1 active catalyst to 1.5%; With
The B part, wherein B is partly for comprising the mixture of following component:
The short aromatic diisocyanate of 1 to 15 weight %; With
The aromatic diisocyanate prepolymer of 5 to 35 weight %, described aromatic diisocyanate prepolymer is the reaction product of short aromatic diisocyanate and glycol.
20, method according to claim 19 further comprises:
Use the end face of polyurethane-urea to crosslinked rubber item; With
The end face of crosslinked rubber item is bonded to ground.
21, method according to claim 19 further comprises:
Use the end face of elastomerics-tensio-active agent to crosslinked rubber item, wherein said elastomerics-tensio-active agent comprises the second short aromatic diisocyanate and the second aromatic diisocyanate prepolymer.
22, method according to claim 21 further comprises:
Be used in the end face of the crosslinked rubber item of TCCA (Trichloroisocyanuric acid) solution primary coat in the solvent.
23, method according to claim 19, wherein ground is the end face of crosslinked rubber item.
24, a kind of goods comprise:
Be bonded to the assembly of goods with polyurethane-urea system as claimed in claim 4.
25, goods according to claim 24, wherein the adherent end face between assembly and goods is made by crosslinked rubber combination.
26, goods according to claim 25, wherein said goods are tire.
27, goods according to claim 26, wherein said assembly are annular tire tread.
28, goods according to claim 26, wherein said assembly are patch.
29, goods according to claim 26, wherein at least one the adherent end face between assembly and goods is made by crosslinked rubber combination.
30, goods according to claim 29, wherein the end face of assembly comprise synthetic textiles, thermosetting polymer, ferrous metal, based on metal alloy or its combination of iron.
31, goods according to claim 29, wherein the end face of goods comprise synthetic textiles, thermosetting polymer, ferrous metal, based on metal alloy or its combination of iron.
32, goods according to claim 26, wherein assembly is an electronic installation.
33, goods according to claim 32, wherein assembly comprises the RFID chip.
34, goods according to claim 32, wherein goods comprise the SAW transmitter.
35, a kind of method of retreading comprises:
Elastomerics-tensio-active agent as claimed in claim 2 is applied to the adhesive surface of annular tire tread;
Polyurethane-urea material as claimed in claim 1 is applied to the adhesive surface of annular tire tread;
The adhesive surface that has the annular tire tread of polyurethane-urea material on it is placed on the outer adhesive surface of carcass.
36, method according to claim 35 further comprises:
Elastomerics-tensio-active agent as claimed in claim 2 is applied to the outer adhesive surface of carcass;
Polyurethane-urea material as claimed in claim 1 is applied to the outer adhesive surface of carcass;
37, a kind of method of repairing elastomeric article comprises:
With the perished surface of elastomerics as claimed in claim 2-tensio-active agent coating elastomeric article, wherein this perished surface is the surface of the hole in the goods, dark crack, ditch, breach, otch or the exposure of tearing;
With the hole in the polyurethane-urea filled articles as claimed in claim 1, dark crack, ditch, breach, otch or tear.
38, according to the described method of claim 37, wherein goods are tire.
39, according to the described method of claim 37, wherein said hole, dark crack, ditch, breach, otch or tear on the sidewall of tire.
40, according to the described method of claim 37, wherein said hole, dark crack, ditch, breach, otch or tear on the internal surface of tire.
41, a kind of goods of repairing by method as claimed in claim 37.
42, according to the described goods of claim 41, wherein said goods are tire.
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| USPCT/US06/42138 | 2006-10-30 | ||
| USPCT/US2006/042138 | 2006-10-30 | ||
| PCT/IB2007/004648 WO2008149180A2 (en) | 2006-10-30 | 2007-10-30 | Polyurethaneurea system |
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| CN101528798A true CN101528798A (en) | 2009-09-09 |
| CN101528798B CN101528798B (en) | 2012-09-26 |
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| CN2007800399683A Expired - Fee Related CN101528798B (en) | 2006-10-30 | 2007-10-30 | Polyurethaneurea system |
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|---|---|
| EP (1) | EP2111421A2 (en) |
| JP (1) | JP5442443B2 (en) |
| CN (1) | CN101528798B (en) |
| WO (1) | WO2008149180A2 (en) |
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| CN105189593A (en) * | 2013-03-15 | 2015-12-23 | Sika技术股份公司 | Repair liquid for conveyor belts |
| CN107987781A (en) * | 2017-12-06 | 2018-05-04 | 苏州铂邦胶业有限公司 | Polyurethane sealant |
| CN112469799A (en) * | 2018-08-06 | 2021-03-09 | 第一工业制药株式会社 | Two-component curing adhesive |
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| US11732080B2 (en) | 2017-06-15 | 2023-08-22 | Ddp Specialty Electronics Materials Us, Inc. | Compositions containing hydrophobic modified isocyanate functional prepolymer containing adhesives |
| CN114479632A (en) * | 2021-12-30 | 2022-05-13 | 江苏朗科建材科技有限公司 | Solvent-free polyurethane spraying process for steel pipe surface |
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| DE2916485A1 (en) * | 1979-04-24 | 1980-11-06 | Bayer Ag | METHOD FOR PRODUCING ELASTIC MOLDED BODIES |
| US4374210A (en) * | 1981-09-18 | 1983-02-15 | The Upjohn Company | Polyurea-polyurethane from a mixture of a polyol, an aromatic diamine, and an isocyanate-terminated prepolymer |
| US4433067A (en) * | 1982-04-23 | 1984-02-21 | Texaco Inc. | Reaction injection molded elastomers prepared from amine terminated polyethers, amine terminated chain extender and aromatic polyisocyanate |
| US4485136A (en) * | 1983-03-21 | 1984-11-27 | The Firestone Tire & Rubber Company | Ambient temperature repair of elastomeric articles having a hollow therein |
| US5110629A (en) * | 1990-10-05 | 1992-05-05 | Synair Corporation | Method for preparing rubber surface for adhesion to polymeric formulation |
| US5183877A (en) * | 1991-10-25 | 1993-02-02 | H. B. Fuller Company | Polyurea or polyurea-urethane adhesive for bonding elastomers |
-
2007
- 2007-10-30 WO PCT/IB2007/004648 patent/WO2008149180A2/en active Application Filing
- 2007-10-30 CN CN2007800399683A patent/CN101528798B/en not_active Expired - Fee Related
- 2007-10-30 JP JP2009535152A patent/JP5442443B2/en not_active Expired - Fee Related
- 2007-10-30 EP EP07874557A patent/EP2111421A2/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199393A (en) * | 2010-03-23 | 2011-09-28 | 李哉勋 | Surface coating comoound and coating method for a plate |
| CN102199393B (en) * | 2010-03-23 | 2015-02-04 | 李哉勋 | Surface coating comoound and coating method for a plate |
| CN105189593A (en) * | 2013-03-15 | 2015-12-23 | Sika技术股份公司 | Repair liquid for conveyor belts |
| CN105189593B (en) * | 2013-03-15 | 2018-05-15 | Sika技术股份公司 | Reparation liquid for conveyer belt |
| CN107987781A (en) * | 2017-12-06 | 2018-05-04 | 苏州铂邦胶业有限公司 | Polyurethane sealant |
| CN112469799A (en) * | 2018-08-06 | 2021-03-09 | 第一工业制药株式会社 | Two-component curing adhesive |
| CN112469799B (en) * | 2018-08-06 | 2022-09-23 | 第一工业制药株式会社 | Two-component curing adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010508417A (en) | 2010-03-18 |
| CN101528798B (en) | 2012-09-26 |
| WO2008149180A3 (en) | 2009-03-19 |
| WO2008149180A2 (en) | 2008-12-11 |
| JP5442443B2 (en) | 2014-03-12 |
| EP2111421A2 (en) | 2009-10-28 |
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