CN101528798B - Polyurethaneurea system - Google Patents
Polyurethaneurea system Download PDFInfo
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- CN101528798B CN101528798B CN2007800399683A CN200780039968A CN101528798B CN 101528798 B CN101528798 B CN 101528798B CN 2007800399683 A CN2007800399683 A CN 2007800399683A CN 200780039968 A CN200780039968 A CN 200780039968A CN 101528798 B CN101528798 B CN 101528798B
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- diisocyanate
- polyurethane
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- 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
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
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
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
Multiple adhesive product comprises that polyurethane binder product commerce can buy with as sealing agent or to repair polymer elasticity material, for example tree elastomer, viton, plastifying SE, sovprene etc.
Usually by POLYMETHYLENE POLYPHENYLISOCYANATE, 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 compsn that obtains is called as polyurethane-urea or PUU.Therefore, the polyurethane-type compsn that has urethanum and a urea bonding can be called as polyurethane-urea.
Summary of the invention
The embodiment that the present invention is special comprises and can be used for bonding and/or repair elastomeric polyurethane-urea system.This system comprises reactive component, and said 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 the massfraction with following every kind of reactive component: A partly for comprise about 55 to about 75 weight % molecular-weight average at about oligomeric polyols (serving as primary polyvalent alcohol), about 3 to about 7 weight % aromatic diamine chain extension agent and mixture of about 0.1 to about 1.5% active catalyst more than 1000 in some embodiment; 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 for special embodiment.
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.
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 in solvent.
Special embodiment of the present invention further comprises goods, and said goods comprise the assembly that is bonded to goods with above-mentioned polyurethane-urea system.
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).
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.
Through 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 obvious, and as depicted in the figures, wherein similar reference signs is represented similar portions of the present invention.
Description of drawings
Fig. 1 is different rubber combination of the present invention and the elongation of example polyurethane-urea material and the figure of modulus.
Fig. 2 is the figure of different rubber combination of the present invention and example polyurethane-urea material strain and true stress.
Fig. 3 is different rubber combination of the present invention and the elongation of example polyurethane-urea material and the figure of hysteresis.
Fig. 4 is of the present invention with the stress-at-break of the multiple different rubber combinations of example polyurethane-urea system adherent and the figure of breaking strain.
Embodiment
The present invention includes the polyurethane-urea system, its preparation method and method of use 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.
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 said 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.
In some embodiment, the mixture characteristic 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.
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 more than 1000 or for 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 full text, only if indicate separately.
The oligomeric polyols reactive component characteristic 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.
The characteristic 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.
The 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).Amine-end capped polyvalent alcohol based on its terminal hydroxy groups by uncle or the substituted polyether glycol of secondary amino group functional group.Polyester polyol can comprise, for example, and polyethylene adipate, polyethylene glycol adipate, polycaprolactone glycol and polycaprolactone-polyadipate copolymer diols.
For those embodiments that not only comprises uncle's oligomeric polyols, can comprise that then for example secondary polyvalent alcohol is as the reactive component in the special embodiment.This, oligomeric polyols can comprise second month in a season, for example, and polybutylene oxide glycol (PBO), polypropylene oxide glycol (PPO) and Viscotrol C.
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.
The amount of the oligomeric polyols reactive component that special embodiment comprises (being expressed as in the A part weight % with the total mass of the reactant composition of 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 %.
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 %.
The non-limitative example of aromatic diamine chain extender reaction component comprises 2,4 and 2 of DETDA (diethyl toluene diamine), methylene-bis (N, N-dibutyl pentanoic), IPDA (isophorone diamine); 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 is 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-MEA) is (MCEA); 1, two (2-amino-phenyl sulfo-) ethane of 2-; N, N '-two-alkyl-right-penylene diamines; 4,4 '-industry methyl-two (2, the 6-diisopropyl aniline) are (MDIPA); Dimethyl sulphide for tolylene diamine (dimethylthiotol-uenediamine) (DMTDA) or its mixture.
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.
The aromatic diamine chain extender reaction component amount that special embodiment comprises (being expressed as in the A part weight % with the total mass of the reactant composition of 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 %.
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.
The short aromatic diisocyanate reactive component characteristic 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.
The non-limitative example of suitable short aromatic diisocyanate comprises, for example, and phenylene diisocyanate, right-and-phenylene diisocyanate; Tolylene diisocyanate, XDI, 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 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 that gathers carbodiimide-modification, like the ISONATE 143L available from Dow ChemicalCompany.
The amount of the short aromatic diisocyanate reactive component that special embodiment comprises (being expressed as) in A part weight % with the total mass of the reactant composition of B part be about 0 weight % of total mass to about 25 weight %, or about alternatively 1 weight % about 15 weight % or about 1 weight % about 13 weight % extremely extremely.
Aromatic diisocyanate prepolymer reactive component characteristic in special embodiment of the B partial confounding compound of polyurethane-urea system can be the reaction product between aforesaid short aromatic diisocyanate and the glycol.The characteristic 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.
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.
Usually, 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.
Special embodiment 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, like the VIBRATHANE B836 available from Chemtura.This prepolymer is the reaction product of polyethers and diphenylmethanediisocyanate (MDI).
The amount of the aromatic diisocyanate prepolymer reactive component that special embodiment comprises (being expressed as in the A part weight % with the total mass of the reactant composition of 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 %.
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 is as conventionally known to one of skill in the art.The active catalyst of example is alicyclic (ring-aliphatics) tertiary amine, like triethylenediamine.
Usually 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).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.
Discovery is compared with the material of other embodiments that when adding catalyzer, obtain in special embodiment, omits catalyzer much hard and quite opaque polyurethane-urea material are provided.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.
Also can protective material (protectorant) be joined in the reactive component so that the protection of anti-environmental hazard to be provided.This protective material can comprise for example inhibitor, 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.
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.
Elastomerics-tensio-active agent in the special embodiment can comprise short aromatic diisocyanate (as stated) 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 be solvent-free, and other embodiments comprise solvent.
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, ETHYLE 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.
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 at the oligomeric polyols more than 1000; B) about 3 to about 7% aromatic diamine chain extension agent; And c) 0.1 to 1.5% active catalyst.B part: d) about 1 to about 15% short aromatic diisocyanate; E) about 5 to about 35% prepolymer.
The rigidity that it should be noted that the polyurethane-urea material can be regulated through the ratio that changes aromatic diamine chain extension agent/polyvalent alcohol in the A partial confounding compound.Through increasing the amount of aromatic amine, gained polyurethane-urea material stiffness increases usually.
Randomly, can about 0 to about 5 weight % protective material and/or pigment be joined in the reaction-ure mixture.Special embodiment can comprise about 0.5 these materials to about 2 weight %.Usually can these materials be joined in the A partial confounding compound of reactant composition.In special embodiment, can in these components some or all be joined in the B partial confounding compound of reactant composition.
The special embodiment that is used to make present method of polyurethane-urea compositions comprises through adhesive dispenser and further, distributes this two-partial reaction mixture through 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, the adhesive dispenser proportioning be can manually use and A part and B partial confounding compound mixed.
This divider and be used for 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.
Use the special embodiment of polyurethane-urea system bonding and/or repair surface of elastomer and can comprise with elastomerics-surfactant treatment and treat surface bonding and/or reparation.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 is also treated the surface of bonding and/or reparation with improvement with prime treatment binding property and wettability (wetability).Usually remove the layer of pollution layer or poor adhesion with this prime treatment.The priming paint of example does, for example, and the solution of TCCA (TIC) in solvent, for example, the TIC of 2-6% in ETHYLE ACETATE.
If use priming paint can be brushed priming paint on surface of elastomer, and it is stayed the surface went up about 15 minutes.Then, with solvent (like ETHYLE 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.
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 through before using two-part polyurethane-urea reactive component, using elastomerics-tensio-active agent to improve the bonding of polyurethane-urea material.
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 about 5 crust to adhesive sheet, the time length of wherein under lower pressure, exerting oneself is longer pro rata usually.
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.
Advantageously, the special embodiment of polyurethane-urea system provide have with tire in the rigidity and the comparable rigidity and the material of hysteresis characteristic of lagging behind 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.
Special embodiment of the present invention comprises having the adherent end face that uses the disclosed polyurethane-urea system of this paper and/or the goods of reparation.For example, the special described goods of embodiment according to the present invention comprise the parts that are bonded together in opposing end faces by disclosed polyurethane-urea system, and 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 through 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.
The embodiment that the present invention is special comprises having the tire that is bonded to the elastomerics patch on it through the disclosed polyurethane-urea system of this paper.This elastomerics patch can comprise RF identification (RFID) technology and can this patch be bonded to the internal surface or the outside surface of tire.
Other embodiments comprise the surface that goods is bonded to another goods (like tire).These goods that can be bonded to the surface of another goods (like 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, can its surface that directly is bonded to another goods (like tire) 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 TP.Can be assemblied on the internal surface of tire this device or on the outside surface of tire.Any or Overall Steps during these embodiments can comprise the steps: the surface of cleaning article (like tire); Use (as stated) priming paint (like the solution of TIC in solvent) to the surface; Use (as stated) elastomerics-tensio-active agent to the surface; Electronic package or device are placed on the surface of tyre; On the part at least of electronic package or device, directly use blended A part and B partial reaction component, thereby electronic package or device directly are bonded to the surface.Like what noticed before, in the embodiment that comprises adhesive article to surface of tyre, can be bonded to outside tire or internal surface with goods (like electronic installation or assembly).
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.Can device be placed on the transfer film, part covers (A part and B partial confounding compound) with the polyurethane-urea component at least then.Can the film of attach mark be placed desired position (for example, the surface of tire) then, wherein face is outside.Can film be divested then, remaining assembly is bonded to the surface.
Can be through comprising tire or other goods of surface of elastomer with the disclosed polyurethane-urea system filling of this paper 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 through using.
Special embodiment of the present invention thereby comprise has tire or other goods of the bonding and/or surface of elastomer repaired of polyurethane-urea system for use.For tire, prepare to be repaired zone with the cleaning affected area with interior and peripheral surface through removing loose surfacing usually with otch, crack, hole or ditch.Preparation can comprise through any conventional instrument or handle the inner surface in polishing ditch, otch or crack.
If the cord in the tire (cords) is damaged, can removes the cord that has damaged, and will strengthen the internal surface that patch is applied to tire, as conventionally known to one of skill in the art.This cord can be processed by polyester, nylon, steel, regenerated fiber or the like.Can use the disclosed polyurethane-urea system of this paper will strengthen the internal surface that patch is bonded to tire.Similarly, if the hole that infringement causes penetrating sidewall can be applied to the part of the internal surface of tire as reparation with patch similarly.
The inner face in ditch, crack and/or hole then can be randomly with aforesaid elastomerics-tensio-active agent coating.Affected area is then filled with the polyurethane-urea material through mixing A part and B part material and mixture being applied in to come in crack or the ditch.Material is solidified in envrionment temperature (that is, about 20 ℃ to 40 ℃).As conventionally known to one of skill in the art, if other reparations that tire is done need can place autoclave with material in curing under heating and the pressure.
Because the envrionment temperature that is solidificated in of polyurethane-urea material takes place, polyurethane-urea system of the present invention is for sport (large items), and the original position of (like 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.
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.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.
Renovate method of the present invention comprises from carcass removes old tyre surface, with elastomerics-surfactant treatment carcass, or with elastomerics-surfactant treatment annular tire tread, or with elastomerics-surfactant treatment above-mentioned both.This method further comprises uses the end face that blended polyurethane-urea reactant to annular tire tread or carcass or the two expose, and then annular tire tread is placed on the carcass surface.
The embodiment that the present invention is special 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 at least one end face that comprises crosslinked rubber combination, and said crosslinked rubber combination mainly comprises at least a diene elastomer.
Term " diene elastomer " means at least partly (promptly; Homopolymer or multipolymer) derived from the elastomerics of diene monomers (having two conjugation or non-conjugated carbon-carbon double bond); Particularly: any homopolymer is obtained by the conjugated diene monomers polymerization that contains 4 to 12 carbon atoms; 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 terminal 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 stated by ethene; 1,4-hexadiene, ethylidene norbornene (ethylidenenorbomene) or Dicyclopentadiene (DCPD)) elastomerics that obtains; Or the multipolymer of iso-butylene and isoprene (butyl rubber or IIR), and the halogen of this analog copolymer (particularly chlorine or bromine) modification.
Preferred especially diene elastomer is selected from polyhutadiene (BR), TR 301 (IR) or tree elastomer (NR), styrene-butadiene copolymer (SBR), ethene, propylene and diene terpolymer (EPDM), butyl rubber or chloroprene.
In further embodiment; Treat to comprise crosslinked rubber combination through 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, like steel.
Further the embodiment according to the present invention, an end face comprises crosslinked rubber combination, and other end faces comprise synthetic textiles, like two-stretch knit type fabric, contain the film of the fibrous texture of selling with registered trademark " LYCRA " with formation.
Further the aspect 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).
Through the following embodiment the present invention that further explains, should only it be regarded as explaining, it does not also limit the present invention in any way.
Use reactant composition as shown in table 1 to prepare polyurethane-urea system batch of material.Two-part tackiness agent/repair materials is through mixing the preparation of A part component and B part component.Through filling the gap between two elastomericss, use these polyurethane-urea materials together then with two elastomer bonded with the polyurethane-urea system.Measure the gained bond strength then.Table 1-polyurethane-urea reactant composition
, and B part material mixing is in the same place with A part material mixing together, and with it in tube of each two-part adhesive dispenser rifle of packing into.Then tube is inserted the adhesive dispenser rifle based on two-part tube.To A1 and A2, the ratio that the rifle divider transmits A part and B part to 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 through additional disposable static mixer mixing A part and B partial reaction component.
Also prepare elastomerics-tensio-active agent.Through mix vulcabond and this elastomerics-tensio-active agent of solvent preparation with the amount shown in the table 1.The weight % of every kind of vulcabond shown in the table 1 is all based on the total mass of vulcabond.In solvent, mix vulcabond to form elastomerics-tensio-active agent, this elastomerics-tensio-active agent is processed by the ETHYLE ACETATE of 50 weight % (in the gross weight of solution) or the vulcabond of toluene (as solvent) and 50 weight %
Use well known to a person skilled in the art three kinds of different rubber elastomeric material of method preparation.These three kinds of materials are sidewall type (SW) rubber combination that comprises tree elastomer and cis-polybutadiene rubber, comprise liner type (IL) rubber of butyl rubber and comprise tyre surface type (T) rubber of tree elastomer.These materials further comprise vulcanizing agent or the like, as conventionally known to one of skill in the art.
It is 2.5mm that every kind of compsn is calendered to thickness, and is cut to 15 * 15cm square.In 15 * 15cm 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, fill the volume (this volume causes by cutting out bar) between two portions with the polyurethane-urea material of preparation among the embodiment 1.Some surface is with the elastomerics-surfactant treatment of preparation among the embodiment 1.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 good flow characteristics number hour (4-8) thereafter.
After the polyurethane-urea material is filled the gap between the 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 in mould, takes place: 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.
Embodiment 3
The specimen that test prepares 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) compsn, and table 3 is listed the result to the specimen that comprises liner (IL) compsn, and table 4 is listed the result to the specimen that comprises tyre surface (T) compsn.
Like table 2,3, shown in 4, use some adherent surface of the solution primary coat specimen of TCCA (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, 3 quilts of the specimen shown in the table 2 are with three layers of TIC5 weight % solution paint (brush) primary coat in ETHYLE ACETATE.After primary coat, make sample drying at room temperature 30 minutes, and after drying, wash with ETHYLE ACETATE.
Similarly, these forms show with which specimen of elastomerics-surfactant treatment that comprises the component shown in embodiment 1 table 1.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.Table 2 - sidewall rubber (SW) the composition of the test results
table 3 - lined with rubber (IL) composition of the test results
table 4 - tread rubber (T) the composition of the test results
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.
Embodiment 4
Prepare the sample of 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.
With 10%, 50%, 100%, 200% and 300% measures modulus of stretch according to ASTM D412 (1998) 26 ℃ of temperature on ASTM C testing plate on 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 xsect of testing plate.Also on each testing plate, measure and lag behind.Test procedure moves on the Model 5500R test machine at INSTRON.
Test result is shown in Fig. 1-3.From these figure, can find out that 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 is illustrated in the low hysteresis of material under the 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.
Should think that the term that uses in claims and the specification sheets of this paper " comprises ", " comprising " and " having ", be the open group of expression, it can comprise other unspecified compositions.Should think the term that uses in claims and the specification sheets of this paper " basically 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 novel characteristic of fundamental sum 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 " interchangeable use.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 like " 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 like x to y.
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, should it be interpreted as restriction.Only limit scope of the present invention by following claim literal.
Claims (21)
1. polyurethane-urea system, wherein the reactive component reaction is to form polyurethane-urea, and said reactive component comprises:
The A part, wherein A is partly for comprising the mixture of following component:
The weight-average molecular weight of 55 to 75 weight % is at the oligomeric polyols more than 1000, and said oligomeric polyols is selected from polyether polyol, amine-end capped polyvalent alcohol, polyester polyol, polyester ether type polyvalent alcohol, many cyclopolyols and polycarbonate polyol and composition thereof;
The aromatic diamine chain extension agent of 3 to 7 weight %, said aromatic diamine chain extension agent are selected from 2,4 and 2,6 isomer of diethyl toluene diamine, methylene-bis (N, N-dibutyl pentanoic), isophorone diamine; Methylene dianiline (MDA), 4,4 '-methylene radical-two-3-(chloro-2,6-Diethyl Aniline), 4,4 '-methylene radical-two-(2-ethyl-6-monomethylaniline); 4,4 '-two-(2, the 6-Diethyl Aniline), 4,4 '-methylene radical-two-(2-sec.-propyl-6-monomethylaniline); 4,4 '-two (second month in a season-butyl is amino) ditan, penylene diamines, methylene radical-two-Ortho-Chloro aniline; 4,4 '-methylene radical-two-(2-methyl-aniline), 4,4 '-methylene radical-two-(2-chloro-6-MEA); 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), dimethyl sulphide is for tolylene diamine and composition thereof; 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 %, said short aromatic diisocyanate is selected from phenylene diisocyanate, tolylene diisocyanate, XDI; The methylene diisocyanate of carbodiimide modified, 4,4 '-phenylbenzene-methane diisocyanate; Polymeric 4,4 '-phenylbenzene-methane diisocyanate, 4 of modification; 4 '-phenylbenzene-methane diisocyanate compound, naphthalene diisocyanate, the isomer mixture of above-mentioned various short aromatic diisocyanate and combination thereof; With
The aromatic diisocyanate prepolymer of 5 to 35 weight %, said aromatic diisocyanate prepolymer is for short aromatic diisocyanate with based on the reaction product of uncle's glycol of polyethers or polyester, and said short aromatic diisocyanate is selected from phenylene diisocyanate; Tolylene diisocyanate, XDI, the methylene diisocyanate of carbodiimide modified; 4,4 '-phenylbenzene-methane diisocyanate, polymeric 4; 4 '-phenylbenzene-methane diisocyanate; 4,4 of modification '-phenylbenzene-methane diisocyanate compound, naphthalene diisocyanate; The isomer mixture of above-mentioned various short aromatic diisocyanate and combination thereof, 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 dimethyl sulphide is 3 for tolylene diamine, 5-dimethyl sulphide generation-2,4-tolylene diamine or 3,5-dimethyl sulphide generation-2,6-tolylene diamine.
3. polyurethane-urea system according to claim 1, wherein oligomeric polyols comprises the above uncle's oligomeric polyols of 50 weight %.
4. polyurethane-urea system according to claim 1, wherein oligomeric polyols comprises the above uncle's oligomeric polyols of 95 weight %.
5. 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.
6. polyurethane-urea system according to claim 5, the wherein as claimed in claim 4 at least a second short aromatic diisocyanate is identical with the described at least a short aromatic diisocyanate of claim 1.
7. polyurethane-urea system according to claim 5, wherein elastomerics-tensio-active agent comprises the short aromatic diisocyanate of 5 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, wherein 4,4 of modification '-phenylbenzene-methane diisocyanate compound is the diphenylmethanediisocyanate that gathers carbodiimide-modification.
10. polyurethane-urea system according to claim 1; Its short-and-medium aromatic diisocyanate is selected from 2; 4 and/or 2,6 tolylene diisocyanates, 4,4 '-phenylbenzene-methane diisocyanate, polymeric 4; 4 '-phenylbenzene-methane diisocyanate, modification 4,4 '-phenylbenzene-methane diisocyanate compound, naphthalene diisocyanate or its combination.
11. polyurethane-urea system according to claim 1, wherein the aromatic diisocyanate prepolymer be 4,4 '-phenylbenzene-methane diisocyanate-terminated polyether vulcabond.
12. polyurethane-urea system according to claim 1, wherein the aromatic diisocyanate prepolymer is the reaction product of glycol, and said glycol is selected from glycol based on polyethers, based on glycol or its combination of polyester.
13. polyurethane-urea system according to claim 1, wherein oligomeric polyols is that weight-average molecular weight is 1500 to 4000 polytetramethylene glycol.
14. 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.
15. 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.
16. polyurethane-urea system according to claim 15, 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.
17. a 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 weight-average molecular weight of 55 to 75 weight % is at the oligomeric polyols more than 1000, and said oligomeric polyols is selected from polyether polyol, amine-end capped polyvalent alcohol, polyester polyol, polyester ether type polyvalent alcohol, many cyclopolyols and polycarbonate polyol and composition thereof; With
The aromatic diamine chain extension agent of 3 to 7 weight %, said aromatic diamine chain extension agent are selected from 2,4 and 2,6 isomer of diethyl toluene diamine, methylene-bis (N, N-dibutyl pentanoic), isophorone diamine; Methylene dianiline (MDA), 4,4 '-methylene radical-two-3-(chloro-2,6-Diethyl Aniline), 4,4 '-methylene radical-two-(2-ethyl-6-monomethylaniline); 4,4 '-two-(2, the 6-Diethyl Aniline), 4,4 '-methylene radical-two-(2-sec.-propyl-6-monomethylaniline); 4,4 '-two (second month in a season-butyl is amino) ditan, penylene diamines, methylene radical-two-Ortho-Chloro aniline; 4,4 '-methylene radical-two-(2-methyl-aniline), 4,4 '-methylene radical-two-(2-chloro-6-MEA); 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), dimethyl sulphide is for tolylene diamine and composition thereof; 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 %, said short aromatic diisocyanate is selected from phenylene diisocyanate, tolylene diisocyanate, XDI; The methylene diisocyanate of carbodiimide modified, 4,4 '-phenylbenzene-methane diisocyanate; Polymeric 4,4 '-phenylbenzene-methane diisocyanate, 4 of modification; 4 '-phenylbenzene-methane diisocyanate compound, naphthalene diisocyanate, the isomer mixture of above-mentioned various short aromatic diisocyanate and combination thereof;
The aromatic diisocyanate prepolymer of 5 to 35 weight %, said aromatic diisocyanate prepolymer is for short aromatic diisocyanate with based on the reaction product of uncle's glycol of polyethers or polyester, and said short aromatic diisocyanate is selected from phenylene diisocyanate; Tolylene diisocyanate, XDI, the methylene diisocyanate of carbodiimide modified; 4,4 '-phenylbenzene-methane diisocyanate, polymeric 4; 4 '-phenylbenzene-methane diisocyanate, 4,4 of modification '-phenylbenzene-methane diisocyanate compound; Naphthalene diisocyanate, the isomer mixture of above-mentioned various short aromatic diisocyanate and combination thereof
Use the end face of polyurethane-urea to crosslinked rubber item; With
The end face of crosslinked rubber item is bonded to ground.
18. polyurethane-urea system according to claim 17, wherein dimethyl sulphide is 3 for tolylene diamine, 5-dimethyl sulphide generation-2,4-tolylene diamine or 3,5-dimethyl sulphide generation-2,6-tolylene diamine.
19. polyurethane-urea system according to claim 17, wherein 4,4 of modification '-phenylbenzene-methane diisocyanate compound is the diphenylmethanediisocyanate that gathers carbodiimide-modification.
20. goods comprise:
Be bonded to the assembly of goods with polyurethane-urea system as claimed in claim 5, wherein at least one the adherent end face between assembly and goods is made by crosslinked rubber combination.
21. goods according to claim 20, wherein the end face of assembly comprise synthetic textiles, thermosetting polymer, ferrous metal, based on metal alloy or its combination of iron.
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| USPCT/US2006/042138 | 2006-10-30 | ||
| PCT/IB2007/004648 WO2008149180A2 (en) | 2006-10-30 | 2007-10-30 | Polyurethaneurea system |
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| CN101528798A CN101528798A (en) | 2009-09-09 |
| CN101528798B true 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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| JP (1) | JP5442443B2 (en) |
| CN (1) | CN101528798B (en) |
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| WO2011118910A2 (en) * | 2010-03-23 | 2011-09-29 | Lee Jae-Hoon | Surface coating compound and coating method for a pallet |
| CL2013000959A1 (en) * | 2013-03-15 | 2013-08-23 | Sika Technology Ag | Polyurethane-based composition comprising a polyurethane prepolymer, a curing agent comprising a mononuclear aromatic polyamine, a solvent and a plasticizer; method of repair of defects in elastic substrates; process of joining flexible substrates; and use of said composition. |
| WO2018232239A1 (en) * | 2017-06-15 | 2018-12-20 | Dow Global Technologies, Llc | Compositions containing hydrophobic modified isocyanate functional prepolymer containing adhesives |
| CN107987781B (en) * | 2017-12-06 | 2021-05-18 | 苏州铂邦胶业有限公司 | Polyurethane sealant |
| JP6827977B2 (en) * | 2018-08-06 | 2021-02-10 | 第一工業製薬株式会社 | Two-component curable adhesive |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298701A (en) * | 1979-04-24 | 1981-11-03 | Bayer Aktiengesellschaft | Process for the production of elastic shaped articles |
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4485136A (en) * | 1983-03-21 | 1984-11-27 | The Firestone Tire & Rubber Company | Ambient temperature repair of elastomeric articles having a hollow therein |
-
2007
- 2007-10-30 WO PCT/IB2007/004648 patent/WO2008149180A2/en active Application Filing
- 2007-10-30 JP JP2009535152A patent/JP5442443B2/en not_active Expired - Fee Related
- 2007-10-30 EP EP07874557A patent/EP2111421A2/en not_active Withdrawn
- 2007-10-30 CN CN2007800399683A patent/CN101528798B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298701A (en) * | 1979-04-24 | 1981-11-03 | Bayer Aktiengesellschaft | Process for the production of elastic shaped articles |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2111421A2 (en) | 2009-10-28 |
| CN101528798A (en) | 2009-09-09 |
| JP5442443B2 (en) | 2014-03-12 |
| WO2008149180A2 (en) | 2008-12-11 |
| JP2010508417A (en) | 2010-03-18 |
| WO2008149180A3 (en) | 2009-03-19 |
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