CN109081897A - The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application - Google Patents

The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application Download PDF

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Publication number
CN109081897A
CN109081897A CN201810865635.6A CN201810865635A CN109081897A CN 109081897 A CN109081897 A CN 109081897A CN 201810865635 A CN201810865635 A CN 201810865635A CN 109081897 A CN109081897 A CN 109081897A
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polyurethane
urea
weight
component
aqueous dispersion
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Inventor
刘云玲
晋云全
纪学顺
曹玉阳
王震
朱文辉
王晓
邢庆达
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Wanhua Chemical Group Co Ltd
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Shanghai Wan Hua Ke Ju Chemical Technology Development Co Ltd
Wanhua Chemical Group Co Ltd
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Priority to CN201810865635.6A priority Critical patent/CN109081897A/en
Publication of CN109081897A publication Critical patent/CN109081897A/en
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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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Abstract

The present invention relates to the excellent polyurethane of wet-hot aging performance or aqueous dispersion of polyurethane-urea and its preparation method and application, the reaction such as the polyurethane or polyurethane-urea are by least one silicone components containing at least two NCO reactive functional groups, at least one silicone components containing a NCO reactive functional groups, the polyol component that at least one degree of functionality is 2~4, at least one polyisocyanate component, at least one hydrophilic compounds component, at least one NCO are reactive, single functionality non-ionic hydrophilic compound and prepare.The aqueous dispersion wet-hot aging performance of polyurethane or polyurethane-urea of the invention is excellent, is suitable for preparing high quality paint vehicle, sealant especially adhesive.

Description

Aqueous dispersion and its preparation side of the excellent polyurethane of wet-hot aging performance or polyurethane-urea Method and purposes
Technical field
The present invention relates to aqueous dispersion of the excellent polyurethane of wet-hot aging performance or polyurethane-urea and preparation method thereof and Purposes.
Background technique
Due to the aqueous dispersion of polyurethane or polyurethane-urea have excellent brushability, excellent first viscous and peel strength with And patience outstanding, it has been widely used in the fields such as coating, sealant and adhesive.The moisture of polyurethane or polyurethane-urea Granular media activates in adhesive in use, generally requiring in advance.Activation refers to: after aqueous dispersion is applied on substrate, Moisture is removed by the method for heating, while at such a temperature, the activity of polyurethane segment increases, polyurethane or polyurethane-urea It is transformed into viscoelastic state, then carries out the operation such as being bonded again.
In order to improve polyurethane binder performance, US4870129 is pointed out in the aqueous dispersion of polyurethane or polyurethane-urea Hydroxyl is introduced, is then used in compounding again with isocyanates, isocyanates reacts to increase crosslink density with hydroxyl, hence it is evident that improves Adhesive strength and heat resistance.But in this mode, isocyanates can carry out with water anti-in advance in the processes such as ingredient, brushing It answers, causes the construction time of adhesive shorter, general several hours.
The patents such as DE19954500, DE4410557 or EP792908 are proposed in polyurethane or the aqueous dispersion of polyurethane-urea Then middle introducing carboxylate is compounded with carbodiimide again to improve bond properties, this mainly utilizes carboxylic acid therein and carbon two The reaction of imines increases crosslink density, improves the intensity of adhesive.Wherein carboxylate is by polyurethane or polyurethane-urea It is added what then dihydromethyl propionic acid was neutralized with tertiary amine again.But carboxyl and carbon two are sub- in such adhesive complex scheme The reactivity of amine is lower, and final performance is generally inadequate for requirement of the adhesive for heat resistance.
US5066705 is described using the polymer containing carboxyl, the polyurethane containing carboxyl and poly- carbodiimide and is made The weather-proof water paint of standby plastic basis material.But carboxylic polymer and polyurethane used in patent all have it is very high Acid value, this will lead to final film hydrophily with higher, be easy to be influenced by water or other materials, under film performance Drop, service life shorten.In addition, the carboxyl of polyurethane is by using dihydromethyl propionic acid or containing the polyester of carboxyl in patent Come what is introduced, the carboxyl that both incorporation ways obtain all has biggish steric hindrance, drops with the reactivity of carbodiimide Low, the crosslink density of final film is not high, and performance raising is not obvious.
EP1272588 describes a kind of containing at least one crystalline polyester-dispersions of polyurethanes, polyacrylate copolymerization Object, polychloroprene dispersion can be thermally cured resin and the adhesive of stabilizer (amino alcohol, carbodiimide and magnesia) is compound Object, wherein used stabilizer has the function of poly- ester hydrolysis in inhibition system and keeps stable system.But it is such Multicomponent system is expensive, and failure is fast, seriously limits its use in real life.
CN102216359, which is described, has obtained one by the carboxylic acid that mono amino and/or monohydroxy are added in the synthesis process The polyurethane of carboxyl or the aqueous dispersion of polyurethane-urea are contained in kind end, then compound composite adhesives with carbodiimide, due to end With carbodiimide quick cross-linking reaction can occur for the high activity of carboxyl, to significantly improve film performance.But carboxylic acid meeting The stability of polyurethane or polyurethane-urea aqueous dispersion is influenced, while carbodiimide stability itself is bad, these are all unfavorable for The storage of this system.
CN101381451, which is described, obtains the aqueous polyurethane dispersion of self-crosslinkable by the way that steric hindrance type siloxanes is added, Although steric hindrance type siloxane structure, which is added, can guarantee the storage-stable of self-crosslinking dispersion, also results in dispersion and used Cross-linking reaction speed is excessively slow and cannot establish the performance of needs in journey.The patent, which also indicates that use, simultaneously contains methoxyl group or second The dispersion of the silicone cross linking monomer preparation of the groups such as oxygroup is due to being unable to storage-stable, without self-crosslinking energy.
Summary of the invention
The purpose of the present invention is to provide a kind of polyurethane that wet-hot aging performance is excellent or the aqueous dispersions of polyurethane-urea. Contain siloxane group, the number of the polyurethane or polyurethane-urea in the side chain and main chain of the polyurethane or polyurethane-urea Average molecular weight 5000-350000, viscosity range 300-9000cP.Aqueous dispersion is in dry and activation process, side chain and main chain On siloxanes occur between each other hydrolysis, crosslinking, greatly improve adhesive wet-hot aging performance.Aqueous dispersion itself is stable It is good.In addition, the compound system based on it has excellent stability, storage time is long.Be suitable for prepare high quality paint vehicle, Sealant especially adhesive.
Another object of the present invention is to provide the water dispersions of a kind of polyurethane that wet-hot aging performance is excellent or polyurethane-urea The preparation method of body, the method are simple and easy.
In order to realize the above goal of the invention, technical scheme is as follows:
The aqueous dispersion of a kind of polyurethane or polyurethane-urea, wherein the polyurethane or polyurethane-urea are by following components React the reaction product obtained:
A) at least one silicone components, the silicone components contain at least two NCO reactive functional groups, Yi Jiyu Silicon atom key even at least two groups be methoxyl group and/or ethyoxyl,
B) at least one silicone components, the silicone components contain a NCO reactive functional groups, and former with silicon Sub-key even at least two groups be methoxyl group and/or ethyoxyl,
C) polyol component that at least one degree of functionality is 2~4,
D) at least one polyisocyanate component,
E) at least one hydrophilic compounds component, the hydrophilic radical of the hydrophilic compounds include ionic group, latent ion One of group, non-ionic group are a variety of, and the hydrophilic compounds contain 2~3 NCO reactive functional groups；It is described from Preferred carboxylate radical-the COO of subbase group-And/or sulfonate radical-SO3 -；Preferred carboxyl-the COOH of the ionogenic group and/or sulfonic group- SO3H；The preferred polyethoxy structures unit of non-ionic group；The preferred hydroxyl of the NCO reactive group and/or amino；
F) at least one NCO is reactive, non-ionic hydrophilic compound of single functionality, and
G) optional small molecule amine chain extender, and
H) optional other isocyanate-reactive compounds.
The dosage of component a) of the present invention is 0.02~5 weight %, preferably 0.1~3 weight %, more preferable 0.2~2.5 Weight %；The dosage of component b) is 0.1~4 weight %, 0.3~2 weight %, more preferable 0.4~1.5 weight %；Component c's) Dosage is 5~94 weight %, preferably 8~90 weight %, more preferable 70~90 weight %；The dosage of component d) is 5~40 weights Measure %, preferably 8~30 weight %, more preferable 8~20 weight %；The dosage of component e) is 0.2~50 weight %, 0.5~40 weight Measure %, more preferable 1~5 weight %；The dosage of component f) be 0.01~20 weight %, preferably 0.05~10 weight %, more preferably 0.5~3 weight %；The dosage of component g) is 0~10 weight %, preferably 0.5~5 weight %, more preferable 0.5~3 weight %；Group Dividing dosage h) is 0~15 weight %, preferably 0~8 weight % or 0.5~8 weight %；With the polyurethane or polyurethane-urea It is calculated on the basis of solid part weight of aqueous dispersion.
In the application, " optional " indicate presence or absence of component mentioned later, i.e., the component can be 0.
Component a) silicone components of the present invention assign the siloxanes of the polyurethane or polyurethane-urea side chain Base, contains at least two NCO reactive functional groups, and the NCO reactive functional groups are preferably selected from hydroxyl, primary amino group, parahelium One of base is a variety of.At least two NCO reactive functional groups are at least two amino or at least two hydroxyls or at least One amino and a hydroxyl.The component a) is preferably the siloxanes at least two primary amino groups and/or secondary amino group.Properly Example include but is not limited to N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl three Ethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, two silicon of 1,3- bis- (aminopropyl) tetramethyl Oxygen alkane etc., more preferable N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, three ethoxy of N- β-(aminoethyl)-γ-aminopropyl Base silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.
Component b) silicone components of the present invention assign the siloxanes of the polyurethane or polyurethane-urea main chain Base contains a NCO reactive functional groups, and the NCO reactive functional groups are for example in hydroxyl, primary amino group, secondary amino group It is one or more.The component b) the preferably siloxanes at least one primary amino group and/or secondary amino group, such as bis- (3- tri- Triethoxysilyl propyl) amine, bis- (3- trimethoxy-silylpropyl) amine, bis- (3- triethoxysilylethyls) One of amine, bis- (3- trimethoxysilylethylgroup group) amine etc. or a variety of, preferably bis- (3- triethoxysilyls third Base) amine and/or bis- (3- trimethoxy-silylpropyl) amine.
A) two or more active hydrogens in the amino or hydroxyl in component are reacted with isocyanate groups so that silicon oxygen Groups are connected to polyurethane side chain, and the polyurethane of siloxy group is had thus to obtain side chain；B) amino or hydroxyl in component In active hydrogen reacted with isocyanate terminated, polyurethane backbone end is connected to, thus to obtain main chain with the poly- of siloxy group Urethane.
It is (tri- second of 3- that following formulas, which is N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, component b with component a, Oxygroup silylpropyl) for amine, the siloxy group for showing component a) is connected to the siloxanes of polyurethane side chain, component b) It is connected to the mechanism of polyurethane backbone end.
As shown in the above reaction equation, containing there are two amino, can carrying out chain extending reaction in a component, between two amino Segment has been connected on main chain, and remaining siloxane structure is as side chain；In b component after only one amino, with prepolymer reaction Terminal of the silicone components in chain, it is not possible to react again, the NCO of the performed polymer other side it is anti-can to carry out chain growth with a chain extension It answers, can also be reacted with b, the other side is also silicone components as terminal, therefore the siloxanes of b component is all on main chain.
Component c) of the present invention is the polyalcohol that number-average molecular weight is 20~15000, the degree of functionality of the polyalcohol At least 2；The dihydric alcohol and/or trihydroxylic alcohol and/or tetrahydroxylic alcohol that preferred number average molecular weight is 80~5000；More preferably count equal molecule Amount for 400~5000 degree of functionality be 2~3 polyester, polycarbonate, poly-lactone polyol and number-average molecular weight be 80~ One of small molecular alcohol that 400 degree of functionality is 2~4 is a variety of.
Suitable polyester polyol is linear polyesters glycol or micro- branched polyesters dihydric alcohol (containing on a small quantity greater than 3 degrees of functionality Polyester polyol), such as can be by known means by carboxylic acid and/or acid anhydrides such as aliphatic, alicyclic, aromatic series dicarboxyl Acid or polybasic carboxylic acid or its corresponding acid anhydrides etc. and polyalcohol by dehydration contracting and obtain, and the example of the carboxylic acid or acid anhydrides includes But it is not limited to succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, nonane dicarboxyl Acid, decane dicarboxylic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Cyclohexane dicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride or Their mixture；The example of the polyalcohol include but is not limited to ethylene glycol, two-, three-, tetraethylene glycol, 1,2- propylene glycol, Two-, three-, four propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,3 butylene glycol, 2,3- butanediol, 1,5- pentanediol, 1,6- Hexylene glycol, 2,2- dimethyl -1,3- propylene glycol, 1,4- dihydroxy butylcyclohexane, 1,4- hydroxymethyl-cyclohexane, 1,8- ethohexadiol, 1,10- decanediol, 1,12- dodecanediol or their mixture.It is optionally possible to be added with higher functional polyalcohol, Such as trimethylolpropane, glycerol or pentaerythrite.Alicyclic, aromatic series two-and/or polyol also are suitable as using In the polyalcohol for preparing the polyester polyol.It is preferred that containing M-phthalic acid and/or terephthalic acid (TPA) and/or adipic acid, and it is new The polyester polyol of pentanediol, ethylene glycol, butanediol and/or hexylene glycol as structural constituent.
The polyester polyol is also possible to the homopolymer or copolymer of lactone, they can pass through the mixed of lactone or lactone The low molecular weight polyols open loop for closing object and suitable two-and/or higher functional obtains.Wherein lactone such as butyrolactone, ε-are in oneself Ester, methyl-epsilon-caprolactone and their mixture, polyalcohol are used as the structural constituent of polyester polyol as described above Low molecular weight polyols.It is preferable to use 1,4- butanediol, 1,6-HD, 2,2- dimethyl -1,3- propylene glycol or theirs is mixed Close the polyester polyol of the straight chain of object open loop 6-caprolactone.
Polyhydroxy component also is suitable as by using the polycarbonate with hydroxyl of two pure and mild carbonic ester preparations.Glycol It can be 1,4-butanediol, 1,6- hexylene glycol, carbonic ester can be diaryl carbonate, dialkyl carbonate.The carbonic acid two Aryl ester includes diphenyl carbonate, and the dialkyl carbonate includes dimethyl carbonate；It is preferred that passing through 1,6-HD and carbon The polycarbonate of sour dimethyl esters reaction preparation.
The degree of functionality for the small molecular alcohol that component c) middle-molecular-weihydroxyethyl of the present invention is 80~400 is 2~4, suitable small The example of molecule alcohol includes but is not limited to ethylene glycol, two-, three-, tetraethylene glycol, 1,2-PD, two-, three-, four propylene glycol, 1,3-PD, 1,4-butanediol, 1,3-BDO, 2,3-butanediol, 1,5-PD, 1,6- hexylene glycol, 2,2- dimethyl- 1,3-PD (NPG), Isosorbide-5-Nitrae-dihydroxy butylcyclohexane, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, 1,8- ethohexadiol, 1,10- decanediol, 1, 12- dodecanediol, neopentyl glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, Isosorbide-5-Nitrae-, 1,3-, 1,2- dihydroxy benzenes or 2,2- bis--(4- hydroxyphenyl) propane (bisphenol-A), trimethylolpropane, glycerol, pentaerythrite, dipentaerythritol or theirs is mixed Close object, preferably one of 1,4-butanediol, 1,6- hexylene glycol and trimethylolpropane or a variety of.
Component d) polyisocyanates of the present invention is the organic compound at least two isocyanate groups.It is excellent Choosing uses diisocyanate Y (NCO)2, wherein Y represents divalent aliphatic alkyl containing 4-12 carbon atom, containing 6-15 carbon atom Alicyclic divalent hydrocarbon radical, the divalent aromatic hydrocarbon group containing 6-15 carbon atom or the divalent araliphatic hydrocarbon containing 7-15 carbon atom Base.Suitable diisocyanate can be tetramethylene diisocyanate, pentamethylene diisocyanate, two isocyanide of hexa-methylene Acid esters, ten dimethylene diisocyanates, 1,4- hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- dicyclohexyl Methane diisocyanate, 4,4'- dicyclohexyl propane diisocyanate, 1,4- benzene diisocyanate, 2,4- toluene diisocynate, 2,6- first Benzene diisocyanate, 4,4'- diphenylmethane diisocyanate, 2,2'- and 2,4'- diphenylmethane diisocyanate, tetramethyl xylene Phenyl diisocyanate, terephthaldehyde's group diisocyanate and the mixture being made of these compounds.
Component d) of the present invention can also include the polyisocyanate cyanogen of higher functional known per se in a small amount of polyurethane chemistry Acid esters contains such as carbodiimide, allophanate group, isocyanurate group, carbamate groups and/or biuret groups Modified polyisocyanate.
Other than these simple diisocyanate, there is the degree of functionality of more than two isocyanate group in per molecule Polyisocyanates is also suitable.Such as changing by simple aliphatic, alicyclic, araliphatic and/or aromatic diisocyanates Property preparation or by least two diisocyanate (have urea diketone, isocyanuric acid ester, carbamate, allophanate, Biuret, carbodiimide, imino group oxadiazines diketone and/or oxadiazines triketone structure) synthesis polyisocyanates.
Diisocyanate is aliphatic and alicyclic diisocyanate such as two isocyanide of hexa-methylene in preferred component d) Acid esters, 1,4- cyclohexane diisocyanate, isophorone diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate, 4,4'- Dicyclohexyl propane diisocyanate and its mixture.More preferably 1,4- cyclohexane diisocyanate, two isocyanide of isophorone Acid esters, 4,4'- dicyclohexyl methyl hydride diisocyanate and its mixture.
Preferred component d) is the mixture using hexamethylene diisocyanate and isophorone diisocyanate, or Use hexamethylene diisocyanate and 4, the mixture of 4'- dicyclohexyl methyl hydride diisocyanate, wherein two isocyanide of hexa-methylene Acid esters and the mass ratio of isophorone diisocyanate are 1~50:1, preferably 3~10:1, hexamethylene diisocyanate and 4, The mass ratio of 4'- dicyclohexyl methyl hydride diisocyanate is 1~50:1, preferably 3~10:1.
The hydrophilic compounds containing ionic group or ionogenic group are to contain 2~3 in component e) of the present invention NCO reactive group and the simultaneously compound of at least one ion or ionogenic group, wherein the ionogenic group refers to tool There is the functional group of covalent bond, is easy to be converted to corresponding salt with the change of the pH of its solution by addition neutralizer.
Preferred ionogenic group includes acidic group, and the acidic group is selected from carboxyl-COOH and/or sulfonic group-SO3H；Preferably NCO reactive group is selected from hydroxyl and/or amino.
Preferred ionic group includes carboxylate radical-COO‐And/or sulfonate radical-SO3‐。
Preferably as the hydrophilic compounds containing ionic group or ionogenic group in component e) example include two and/or Trihydroxy carboxylic acid and/or two and/or trihydroxy sulfonic acid or two and/or triamido sulfonic acid and/or two and/or three Amino carboxylic acid and their salt etc..
The example of the hydrophilic compounds containing ionic group or ionogenic group includes dihydroxy in particularly preferred component e) Methylpropanoic acid, dimethylolpropionic acid, dihydroxymethyl acetic acid, dihydroxysuccinic acid, N- (2- aminoethyl) -2- aminoethane sulphonic acid, N- (3- aminopropyl) -2-aminoethanesulfonic acid, N- (3- aminopropyl)-Homotaurine, N- (2- aminoethyl) -3- aminopropan Sulfonic acid and its alkali metal salt and/or ammonium salt or acrylic acid, methacrylic acid, maleic acid, fumaric acid add to amine (such as different Buddhist Your ketone diamines, butanediamine, ethylenediamine or 1,6- hexamethylene diamine) on Michael (Michael) addition product etc..
If using latent ionic compound as component e), can before dispersion, among or be added neutralizer later.It is added Neutralizer amount can make ionogenic group it is some or all of become ionic group.Suitable neutralizer is such as primary amine, secondary One of amine, tertiary amine, alkali metal compound, alkaline earth metal compound are a variety of, and the example of suitable neutralizer includes but not It is limited to ammonia, ethanol amine, diethanol amine, triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N- methyl Morpholine, dimethyl isopropyl amine, N methyldiethanol amine, triethylamine, dimethyl cyclohexyl amine, ethyl diisopropylamine, sodium hydroxide, One of potassium hydroxide, lithium hydroxide or calcium hydroxide etc. are a variety of.
In general, enough neutralizers are added, so that the acidic group based on introducing, degree of neutralization is at least 50%, preferably extremely Less it is 75%, and is no more than 150%.When degree of neutralization is more than 100%, other than 100% ionic salt group, there is also trips From neutralizing amine.Particularly preferred degree of neutralization is 95~110%.
The hydrophilic compounds containing non-ionic group can be the polyethers of bifunctionality in component e) of the present invention, such as Styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, the homopolymer of epichlorohydrin, copolymer and grafting produce The dehydrating condensation product of or mixtures thereof object, polyalcohol is obtained by the alkoxylate of dihydric alcohol, diamine and mono amino alcohol Polyether Glycols.Wherein, each molecule ethylene oxide number is 4~200, preferably 12~75.It is also possible to polyfunctionality Polyethoxy ether, such as with pentaerythrite, sugar for initiator, polymerized unit is the one or two of propylene oxide and ethylene oxide, Optimization ethylene oxide.Wherein, each molecule ethylene oxide number is 4~200, preferably 12~75.
Preferred number average molecular weight is 200~8000, the polyethoxy ether that ethylene oxide number is 4~200, and more preferably number is equal Molecular weight 500~3000, the polyethoxy ether for the bifunctionality that ethylene oxide number is 12~75.
Preferred component e) includes N- (2- aminoethyl) -2- aminoethane sulphonic acid salt, dihydromethyl propionic acid salt, Bai Situo (Perstop) one of Ymer 120 of company or a variety of.
Component f) of the present invention is single functionality non-ionic hydrophilic compound component, preferably comprising a hydroxyl or The polyoxyalkylene ether of amino.The example of the initiator of the polyoxyalkylene ether includes but is not limited to saturated monohydroxy alcohol, for example, first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the amylalcohol of isomery, hexanol, octanol, nonyl alcohol, Decanol, N-dodecanol, tetradecanol, positive hexadecanol, cyclohexanol, methylol hexamethylene and 3- ethyl -3- methylol oxa- ring；Insatiable hunger And alcohol, for example, allyl alcohol, 1,1- dimethyl-allyl alcohol or oleyl alcohol；The aromatic alcohol such as cresols of phenol, isomery or methylol benzene Phenol；Aromatic grease group alcohol such as benzylalcohol, anise alcohol or cinnamyl alcohol；Secondary monoamine, such as dimethylamine, diethylamine, di-n-propylamine, diisopropyl Amine, di-n-butylamine, di-iso-butylmanice, bis- (2- ethylhexyl)-amine, N- methyl-and N- Ethylcyclohexylamine or dicyclohexylamine； Secondary amine of heterocycle, such as morpholine, pyrrolidines, piperidinoethyl pyrazoles etc.；Preferred initiator is that have satisfying for most 4 carbon atoms And monohydric alcohol, particularly preferred methanol is as initiator.The polymerized unit of the polyoxyalkylene ether is propylene oxide and/or epoxy second Alkane, optimization ethylene oxide.Wherein, each molecule ethylene oxide number is 4~200, preferably 12~75.
Component f) preferred number average molecular weight of the present invention is 200~8000, single official that ethylene oxide number is 4~200 Energy degree polyethoxy ether, more preferable number-average molecular weight 500~3000, the polyethyleneglycol first that ethylene oxide number is 12~75 Ether.
Component g) of the present invention is such as aliphatic and/or alicyclic uncle and/or secondary monoamine (such as ethamine, diethyl Amine, isopropylamine and butylamine), the aliphatic monoamine of more advanced straight chain, alicyclic monoamine (such as cyclohexylamine).It can also be amino alcohol, That is the compound containing amino and hydroxyl in a molecule, for example, ethanol amine, N- methylethanolamine, diethanol amine, diisopropanolamine (DIPA), 1,3- diamino -2- propyl alcohol, N- (2- ethoxy) ethylene diamine, N, bis- (2- ethoxy) ethylene diamines of N- and 2- propyl alcohol Amine.It can also be diamines and triamine, such as 1,2- ethylenediamine, 1,6- hexamethylene diamine, 1- amino -3,3,5- trimethyl -5- Aminomethyl cyclohexane (isophorone diamine), piperazine, 1,4- diaminocyclohexane, double-(4- aminocyclohexyl) methane and two are sub- Ethyl triamine.It can also be special amine, such as adipic dihydrazide, hydrazine.Also the mixture of above compound can be used.
Component g) can serve as chain extender to reach higher molecular weight and/or serve as monofunctional compound with restriction molecule amount And/or other reactive groups, such as free hydroxyl group are optionally also introduced, as other crosslinking points.
It is sub- that component g) of the present invention is preferably isophorone diamine, N- (2- ethoxy) ethylene diamine, 1,6- six Methanediamine and their mixture.
Component g) of the present invention more preferably molar ratio is 0.5~10:1, the preferably isophorone diamine of 1~5:1 With the mixture of N- (2- ethoxy) ethylene diamine.
The sealer that component h) of the present invention can be commonly used for isocyanates field (can take off at relatively high temperatures Go) such as diacetylmonoxime, dimethyl pyrazole, caprolactam, malonate, triazole, triazol-dimethyl, tert-butyl benzyl amine, cyclopentanone Carboxyl ethyl ester；Unsaturated compound containing polymerization activity group, such as hydroxy-ethyl acrylate, hydroxyethyl methacrylate second Ester, hy-droxybutyl, methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, three propylene of pentaerythrite Acid esters, monoepoxide, di-epoxide and/or polyepoxide react production with the hydroxyl-functional of acrylic or methacrylic acid Object etc..
The aqueous dispersion of polyurethane or polyurethane-urea according to the present invention has 15~70wt%, preferably 30~60wt% Solid content.The pH value of the dispersion is 4~11, preferably 5~10.Average grain diameter is usually 20~750nm, preferably 50~ 450nm。
The present invention also provides the preparation methods of above-mentioned polyurethane or the aqueous dispersion of polyurethane-urea, which is characterized in that (A) with one or more steps reaction make component c), d), f) and optional h) react to form isocyanate terminated prepolymer, (B) with One or two-stage reaction make the prepolymer with component a), b), e) and optional g) react, and (C) by the reaction of step (B) production Object be dispersed in water dissolution or it is water-dispersible, wherein in step (A) and/or (B) optionally use can during dispersion or Pass through distillation fraction or the solvent completely removed later, that is, step (C) can also include by distillation fraction or completely removing The solvent that step (A) and/or (B) are used.The amount of water may be such that the solid content for being formed by dispersion is in step (C) The amount of 15~70wt%, preferably 25-60wt% or 30-60wt%.Step (A) can carry out at 40~150 DEG C, step (B) It can be carried out at a temperature of preferably 25~60 DEG C at 10~100 DEG C.
The preparation of the aqueous dispersion of polyurethane or polyurethane-urea according to the present invention can be by one or more stages equal It is partly carried out in dispersed phase in phase or in the case where multistage reaction.Be after complete or partial polymerization reaction dispersion, Emulsification or dissolving step.Optionally, addition polymerization or modification can be further carried out behind in dispersed phase.
All methods known from the prior art, such as the mixing of emulsifier shearing force, acetone, prepolymer, melt emulsification, ketone Imines and solid thermoplastic polymer method or their deriving method can be used for the water dispersion of above-mentioned polyurethane or polyurethane-urea The preparation of body.The summary of these methods may refer to Methoden der organischen Chemie (Houben-Weyl, Erweiterungs-undZur 4.Auflage rolls up E20, H.Bartl and J.Falbe, Stuttgart, New York, Thieme 1987, the 1671-1682 pages).It is preferred that melt emulsification method, prepolymer mixing method and acetone method.Particularly preferably Acetone method.
Quantitative mixed component c), d), e), f), then carry out at a certain temperature polymerization reaction formed it is isocyanate terminated Then base polyurethane prepolymer for use as makes the base polyurethane prepolymer for use as and component g) carry out chain extending reaction, is then dispersed in water, obtains poly- ammonia The aqueous dispersion of ester or polyurethane-urea, component a) can b) be added in any stage.
Polymerization reaction is to be pre-filled with reactor by all or part of component c), e), f) with optional h), is optionally added into Inert to isocyanate group can dilute with water compatibility solvent, then in room temperature to measuring addO-on therapy d) between 120 DEG C Obtain isocyanate terminated base polyurethane prepolymer for use as.This reaction can be carried out with single phase or with the multistage.Multistage reaction can be with It is following to carry out: to be pre-filled with component c), f e), optional) and add after react with the isocyanate functional component d) the Two component h) then can be reacted with the part isocyanate group still having, and component a) can b) be added in any stage.
Suitable solvent can be acetone, methyl iso-butyl ketone (MIBK), butanone, tetrahydrofuran, dioxanes, acetonitrile, dipropylene glycol Dimethyl ether, 1-Methyl-2-Pyrrolidone etc., they can not only add at the beginning of preparation but also can be in reaction process In or terminate after addition.It can also be added batch-wise.It is preferred that acetone and butanone, more preferable acetone.
For prepare polyurethane or polyurethane-urea of the invention aqueous dispersion isocyanates mole and hydroxyl and The ratio of the sum of the mole of amino can be 1.05-2.5:1, preferably 1.10-1.85:1.
Conversion degree is usually monitored by the NCO content of tracking reaction mixture.It is (such as red that spectroscopic measurements can be carried out thus Outer or near-infrared spectra, refractive index measurement) and chemical potential titration (such as chemistry titration through taking out sample), it is preferably chemical Constant-current titration.
Conventional catalyst can be those of ordinary skill in the art and become known for the catalyst for accelerating NCO to react with OH.Example Such as, triethylamine, Isosorbide-5-Nitrae-diazabicyclo-[2,2,2]-octane, dibutyl tin oxide, two tin octoates or dibutyl tin dilaurate, it is double- (2 ethyl hexanoic acid) tin, bismuth neodecanoate, 2 ethyl hexanoic acid bismuth etc..It is preferred that bismuth neodecanoate, 2 ethyl hexanoic acid bismuth, more preferable neodecanoic acid Bismuth.
Usually at 10~100 DEG C, preferably 25~60 DEG C of temperature carries out chain extension temperature.
The organic solvent optionally employed, such as acetone distillate during dispersion and/or after dispersion.
Preferred preparation method is described as follows:
It is previously added component c), f), d) and optional solvent and be heated to 50~100 DEG C.It stirs simultaneously.It is anti-using heat release It answers, the reaction mixture is stirred at 40~150 DEG C until having reached or slightly less than theoretical isocyanate content, is added optional Component h), the reaction was continued reaches or slightly less than theoretical isocyanate content.Then 25 are diluted to by adding solvent~ 95wt%, the preferably solid content of 40~80wt%, then at 10~100 DEG C, at preferably 25~60 DEG C, solvent is used in addition respectively Diluted component a), b), e) carries out chain extension optionally together with component g).After 2~60 minutes reaction time, by adding Add distilled water or carries out dispersion and during or after dispersion steps by the way that mixture to be transferred in the distilled water being pre-filled with Completely or partially distillate used solvent.Polymerization reaction can optionally add catalyst.
Polyurethane or polyurethane-urea of the present invention have the siloxy group segment of side chain and main chain.The water Dispersion can be with storage-stable, in dry and activation process, and hydrolysis, fast between each other occurs rapidly for the siloxy group on side chain Speed crosslinking, hence it is evident that improve the performances such as the wet-heat resisting of adhesive.
Polyurethane or polyurethane-urea of the present invention also have in addition to the siloxanes segment with side chain and main chain Other than sulfonate radical and/or carboxylate group and/or polyethoxy segment, also with the polyethoxy segment of end.With in chain or Person's side chain introduces polyethoxy segment difference, and end introduces after polyethoxy segment, heavier in addition to existing as hydrophilic radical What is wanted is the molecular weight for being conducive to control polyurethane or polyurethane-urea, and adhesive is made to obtain suitable performance.
Invention further provides the purposes that above-mentioned aqueous dispersion is used to prepare coating agent, adhesive or sealant.
The present invention still further provides a kind of coating agent, adhesive or sealant comprising water dispersion as described above Body and optional emulsifier, light stabilizer (such as UV absorbent and sterically hindered amines (HALS)), there are also antioxidant, filler, Antisettling agent, defoaming and/or wetting agent, flowing regulator, reactive diluent, plasticizer, neutralizer, catalyst, auxiliary are molten One of agent, thickener, pigment, dyestuff, delustering agent, tackifier are a variety of, what these additives can be conventional by this field Dosage is come using and being known to the person skilled in the art.
Compared with existing aqueous polyurethane-polyurea, aqueous dispersion of the present invention is used as adhesive, is had excellent Different wet-heat resisting hydrolysis property, existing aqueous polyurethane-polyurea wet-heat resisting is within for 24 hours, and water dispersion of the present invention Body wet-hot aging performance can achieve 4-5d.
Existing aqueous polyurethane-polyurea dispersion needs to be added before use the crosslinking such as isocyanates or carbodiimide Agent needs to mix according to the ratio before construction, complicated for operation, and the glue prepared must use before the deadline, when open Between it is short, aqueous dispersion of the invention, which does not need additionally to add the crosslinking agents such as isocyanates or carbodiimide, can meet performance need It asks, can be used as the use of one-component product, it is easy to operate, the open hour are long, greatly increase construction efficiency.
The additional amount of aqueous dispersion siloxanes of the present invention is few, and aqueous dispersion itself is stable good.Based on it Compound system has excellent stability, and storage time is long.It is suitable for preparing high quality paint vehicle, sealant especially adhesive.
The aqueous dispersion of polyurethane or polyurethane-urea prepared in accordance with the present invention can be used alone or with coating and bonding Known auxiliary substance is used together with additive in agent technology.Such as emulsifier, light stabilizer (such as UV absorbent and space Bulky amine (HALS)), there are also antioxidant, filler, antisettling agent, defoaming and/or wetting agent, flowing regulator, reactivity it is dilute Release agent, plasticizer, neutralizer, catalyst, secondary solvent, thickener, pigment, dyestuff, delustering agent, tackifier (Tackifier) Deng.
Can before the polymerization/rear additive and/or adjuvant is added.However, it is also possible to which addition is added after dispersion Agent and/or adjuvant.
Can also by the aqueous dispersion of polyurethane prepared in accordance with the present invention or polyurethane-urea and it is other aqueous or contain solvent Oligomer or mixed with polymers use, for example, polyvinylesters, polyvingl ether, polyvinyl alcohol, polyethylene, polystyrene, Polybutadiene, polyvinyl chloride, polyurethane, polyurethane-polyurea, polyurethane-polyacrylate, polyester, polyacrylate and/or altogether Copolymer dispersion or lotion or aqueous solution or organic solution.It must be tested in each case using simple preliminary test such The compatibility of mixture.
The aqueous dispersion of polyurethane or polyurethane-urea prepared in accordance with the present invention and the adhesive based on it or binder group Properly together in any substrate, such as all types of metals, alloy, timber, wood-based material is bonded, particieboard, is made pottery at MDF plate Porcelain, building stones, concrete, pitch, hard fibre, glass, glass fibre, carbon fiber, carbon nanotube, porcelain, plastics, leather, weaving Product and inorganic material.They be equally applicable to for example natural sticking rubber material and synthetic rubber, various plastics such as polyurethane, The polyvinyl chloride of polyvinyl acetate, polyvinyl chloride, especially plasticizer-containing.It is equally applicable to thermoplastic such as ABS (third Olefin(e) acid class-butadiene-styrene), PC (polycarbonate), polyolefin plastics and their mixture.
The adhesive of aqueous dispersion based on polyurethane prepared in accordance with the present invention or polyurethane-urea be equally suitable for by Sole made of these materials, is based especially on polyvinyl chloride, more particularly the sole of the polyvinyl chloride of plasticizer-containing, based on poly- The bonding of the sole of ethylene vinyl acetate or polyurethane elastomer foam, the upper of a shoe made of leather or artificial leather.Also especially It is suitable for film and wood bonding based on the polyvinyl chloride of polyvinyl chloride or plasticizer-containing.
The coverture based on aqueous dispersion of the invention prepared by known technology in coating technology or adhesive techniques/ Sealant can be applied in these areas.
Specific embodiment
The material used:
Polyester I (component c)): polyadipate -1,4-butanediol esterdiol, OH value=56mg KOH/g
Polyester II (component c)): the polyester-diol being made of 1,6- hexylene glycol, neopentyl glycol and adipic acid, OH value=74mg KOH/g
Polyester III (component c)): polyadipate -1,4-butanediol esterdiol, OH value=112mg KOH/g
Polyester IV (component c)): poly- phthalic acid -1,6- hexylene glycol esterdiol, OH value=56mg KOH/g
Polyester V (component c)): polycarbonate glycol, OH value=56mg KOH/g (PCDL T5652, Asahi Kasei Corporation)
Isocyanates I (component d)): hexamethylene diisocyanate (HDI, ten thousand China's chemistry)
Isocyanates II (component d)): isophorone diisocyanate (IPDI, ten thousand China's chemistry)
Polyethers I (component f)): the polyethoxy ether of single functionality has average molecular weight 1200g/mol
Polyethers II (component f)): the polyethoxy ether of single functionality has average molecular weight 520g/mol
In embodiment, GPC test uses Waters liquid chromatograph and Waters2410 differential refraction detector, tetrahydro furan It mutters as solvent, grain diameter measurement uses Malvern Zetasizer Nano ZS90 laser particle analyzer.
Embodiment 1
Polyester I (component c)), 28.35g isocyanates I (component d)), 2g by 210g Jing Guo dehydration is by dehydration Processing polyethers I (component f)), 23g acetone (organic solvent), 0.04g bismuth neodecanoate (catalyst) are added to equipped with import and export of nitrogen 1L four round flask in, the mixture is stirred at 80~90 DEG C until NCO reaches 2.00%.The performed polymer is dissolved in In 400g acetone and it is cooled to 50 DEG C.Will dissolved with 4.63g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium (component e)), 3.26g the 35g aqueous solution of isophorone diamine (component e)), 0.86g hydroxyethyl ethylenediamine (component g)) and be dissolved with 0.5g N- The 5g acetone soln of β-(aminoethyl)-γ-aminopropyltrimethoxysilane (component a)) and be dissolved with bis- (tri- ethoxies of 3- of 1.1g Base silylpropyl) amine (component b)) 6g acetone soln, be respectively added in the acetone soln dissolved with performed polymer simultaneously It is vigorously stirred.20min is stirred, is then dispersed the mixture by addition 238g water.After being separated by distillation out acetone, Add 4g emulsifier Tween 20.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is surveyed through GPC It is set to 86000, there is the solid content of 50wt% and passes through the average grain diameter of the 180nm of laser related assays in dispersed phase, PH value is 7.5, viscosity 4500cP.
Embodiment 2
Polyester II, 28.5g isocyanates I, the 24g of polyester I, 60g Jing Guo dehydration by 150g Jing Guo dehydration Acetone, 0.04g bismuth neodecanoate, 3.15g polyethers II are added in the 1L four round flask equipped with import and export of nitrogen, 80~90 DEG C the mixture is stirred until NCO reaches 1.95%.The performed polymer is dissolved in 405g acetone and is cooled to 50 DEG C.It will dissolution There are 2g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3.42g isophorone diamine, the 10g of 0.41g hydroxyethyl ethylenediamine water-soluble Liquid and dissolved with 2.39g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 20g acetone soln and be dissolved with 1.1g The 6g acetone soln of bis- (3- triethoxysilylpropyltetrasulfide) amine is respectively added in the acetone soln dissolved with performed polymer same When be vigorously stirred.20min is stirred, is then dispersed the mixture by addition 197g water.Be separated by distillation out acetone it Afterwards, 4g emulsifier Tween 20 is added.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is through GPC 90000 are measured as, there is the solid content of 55wt% and in dispersed phase by the average grain of the 220nm of laser related assays Diameter, pH value are 7.2, viscosity 5000cP.
Embodiment 3
Polyester III, the 20g of polyester I, 25g Jing Guo dehydration by 80g Jing Guo dehydration gathers by dehydration Polyethers I, 22g isocyanates I, 18g acetone Jing Guo dehydration of ester IV, 2g, 0.04g bismuth neodecanoate be added to equipped with nitrogen into In the 1L four round flask of outlet, the mixture is stirred at 80-90 DEG C until NCO reaches 2.1%.The performed polymer is dissolved in In 309g acetone and it is cooled to 50 DEG C.4.6g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 1.8g isophorone will be dissolved with Diamines, 1g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.5g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 5g acetone soln and be dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2g 10g acetone soln, be respectively added to It is vigorously stirred simultaneously in acetone soln dissolved with performed polymer.20min is stirred, is then divided the mixture by addition 224g water It dissipates.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane-polyurea Aqueous dispersion, number-average molecular weight have the solid content of 45wt% and pass through laser in dispersed phase through GPC measurement 110000 The average grain diameter of the 150nm of related assays, pH value are 7.5, viscosity 3500cP.
Embodiment 4
Polyester II, the 35g of polyester I, 110g Jing Guo dehydration by 80g Jing Guo dehydration gathers by dehydration Ester III, 28.35g isocyanates I, 2g are added to by dehydration polyethers I, 25g acetone, 0.04g bismuth neodecanoate equipped with nitrogen In the 1L four round flask of inlet and outlet, the mixture is stirred at 80-90 DEG C until NCO reaches 2.00%.The performed polymer is molten Solution is in 405g acetone and is cooled to 50 DEG C.5g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3g isophorone will be dissolved with Diamines, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.72g N- β-(aminoethyl)-gamma-aminopropyl-triethoxy The 5g acetone soln of silane and the 14g acetone soln for being dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2.8g, respectively It is added in the acetone soln dissolved with performed polymer while is vigorously stirred.20min is stirred, is then mixed this by adding 238g water Close object dispersion.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane- The aqueous dispersion of polyureas, number-average molecular weight are measured as 120000 through GPC, have the solid content of 50wt% and in dispersed phase By the average grain diameter of the 180nm of laser related assays, pH value is 7.5, viscosity 3850cP.
Embodiment 5
Polyester II, 28.35g isocyanates I, the 2g of polyester I, 120g Jing Guo dehydration by 150g Jing Guo dehydration It is added in the 1L four round flask equipped with import and export of nitrogen by dehydration polyethers I, the mixture is stirred at 80-90 DEG C Until NCO reaches 2.19%.The performed polymer is dissolved in 424g acetone and is cooled to 50 DEG C.5g N- (2- ammonia second will be dissolved with Base) -2-aminoethanesulfonic acid sodium, 3g isophorone diamine, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.8g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 5g acetone soln and be dissolved with bis- (the 3- triethoxy-silicanes of 3.2g Base propyl) amine 15g acetone soln, be respectively added in the acetone soln dissolved with performed polymer while being vigorously stirred.Stirring Then 20min is dispersed the mixture by addition 558g water.After being separated by distillation out acetone, 4g emulsifier is added Tween 20.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is measured as 110000 through GPC, tool There is the solid content of 30wt% and in dispersed phase by the average grain diameter of the 64nm of laser related assays, pH value is 6.8, viscosity 1500cP。
Embodiment 6
Polyester I, 43g isocyanates I, 2g by 210g Jing Guo dehydration are added to by dehydration polyethers I to be equipped with In the 1L four round flask of import and export of nitrogen, the mixture is stirred at 80-90 DEG C until NCO reaches 4.98%, is then added In 50 DEG C of addition 15.2g diacetylmonoximes, 2.20% is reduced to NCO.The performed polymer is dissolved in 450g acetone and is cooled to 50 ℃.It will be dissolved with 5g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3g isophorone diamine, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and dissolved with 0.58g N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 5g acetone soln and 14g acetone soln dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 3.05g is respectively added to dissolved with performed polymer It is vigorously stirred simultaneously in acetone soln.20min is stirred, is then dispersed the mixture by addition 253g water.Passing through distillation After isolating acetone, 4g emulsifier Tween 20 is added.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, is counted Average molecular weight is measured as 130000 through GPC, has the solid content of 50wt% and in dispersed phase by laser related assays The average grain diameter of 180nm, pH value are 7.8, viscosity 3600cP.
Embodiment 7
Polyester I, 20g isocyanates I, 11.1g isocyanates II, 2g by 210g Jing Guo dehydration pass through dehydration Polyethers I, 24g acetone, 0.04g bismuth neodecanoate are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80-90 DEG C The mixture is mixed until NCO reaches 1.95%.The performed polymer is dissolved in 405g acetone and is cooled to 50 DEG C.It will be dissolved with 4.8g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3.26g isophorone diamine, the 35g of 0.86g hydroxyethyl ethylenediamine are water-soluble Liquid and dissolved with 0.5g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 5g acetone soln and dissolved with 3g it is bis- The 14.5g acetone soln of (3- triethoxysilylpropyltetrasulfide) amine is respectively added in the acetone soln dissolved with performed polymer It is vigorously stirred simultaneously.20min is stirred, is then dispersed the mixture by addition 241g water.It is being separated by distillation out acetone Later, 4g emulsifier Tween 20 is added.Obtain the aqueous dispersion of solvent-free polyurethane-polyurea, number-average molecular weight warp GPC is measured as 110000, the solid content with 50wt% and being averaged by the 176nm of laser related assays in dispersed phase Partial size, pH value are 8, viscosity 3400cP.
Embodiment 8
Polyester I, 35g isocyanates I, 5.8g dihydromethyl propionic acid, 2g by 210g Jing Guo dehydration is by dehydration Reason polyethers I, 24g acetone, 0.04g bismuth neodecanoate are added in the 1L four round flask equipped with import and export of nitrogen, at 80-90 DEG C The mixture is stirred until NCO reaches 2.09%.The performed polymer is dissolved in 419g acetone and is cooled to 50 DEG C, is then added In 4.4g triethylamine and 5 minutes.2g isophorone diamine, the 35g aqueous solution of 0.86g hydroxyethyl ethylenediamine and dissolution will be dissolved with There is 6g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 50g acetone soln and dissolved with bis- (tri- ethoxies of 3- of 0.5g Base silylpropyl) amine 2g acetone soln, be respectively added in the acetone soln dissolved with performed polymer while being vigorously stirred. 20min is stirred, is then dispersed the mixture by addition 300g water.After being separated by distillation out acetone, addition 4g cream Agent Tween 20.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is measured as through GPC 140000, there is the solid content of 40wt% and in dispersed phase by the average grain diameter of the 195nm of laser related assays, pH value It is 7.5, viscosity 800cP.
Embodiment 9
Polyester I, 32g isocyanates I, 4g 1,4- butanediol, 2g by 210g Jing Guo dehydration gather by dehydration Ether I, 24g acetone, 0.04g bismuth neodecanoate are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80-90 DEG C The mixture reaches 1.92% until NCO.The performed polymer is dissolved in 413g acetone and is cooled to 50 DEG C.It will be dissolved with 4.63g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 2.4g isophorone diamine, the 35g of 0.86g hydroxyethyl ethylenediamine are water-soluble Liquid and dissolved with 1.5g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 50g acetone soln and dissolved with g it is bis- The 10g acetone soln of (3- triethoxysilylpropyltetrasulfide) amine is respectively added in the acetone soln dissolved with performed polymer same When be vigorously stirred.20min is stirred, is then dispersed the mixture by addition 300g water.Be separated by distillation out acetone it Afterwards, 4g emulsifier Tween 20 is added.The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is through GPC 105000 are measured as, there is the solid content of 40wt% and in dispersed phase by the average grain of the 195nm of laser related assays Diameter, pH value are 7.5, viscosity 700cP.
Embodiment 10
Polyester V, 20g isocyanates I, the 11g of polyester I, 12g Jing Guo dehydration by 190g Jing Guo dehydration is different Cyanate II, 2g are added to the 1L tetra- equipped with import and export of nitrogen by dehydration polyethers I, 23g acetone, 0.04g bismuth neodecanoate In mouth round-bottomed flask, the mixture is stirred at 80-90 DEG C until NCO reaches 2.15%.The performed polymer is dissolved in 400g acetone In and be cooled to 50 DEG C.Will dissolved with 4.63g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3.26g isophorone diamine, The 35g aqueous solution of 0.86g hydroxyethyl ethylenediamine and be dissolved with 0.5g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 5g acetone soln and the 14g acetone soln for being dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2.7g, are respectively added to It is vigorously stirred simultaneously in acetone soln dissolved with performed polymer.20min is stirred, is then divided the mixture by addition 238g water It dissipates.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane-polyurea Aqueous dispersion, number-average molecular weight are measured as 120000 through GPC, have the solid content of 50wt% and in dispersed phase by swashing The average grain diameter of the 165nm of light related assays, pH value are 7.0, viscosity 3500cP.
Embodiment 11
Polyester V, 20g isocyanates I, the 13g of polyester I, 20g Jing Guo dehydration by 190g Jing Guo dehydration is different Cyanate II, 2g are added to the 1L tetra- equipped with import and export of nitrogen by dehydration polyethers I, 23g acetone, 0.04g bismuth neodecanoate In mouth round-bottomed flask, the mixture is stirred at 80-90 DEG C until NCO reaches 2.05%.The performed polymer is dissolved in 400g acetone In and be cooled to 50 DEG C.Will dissolved with 4.63g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3.26g isophorone diamine, The 35g aqueous solution of 0.86g hydroxyethyl ethylenediamine and be dissolved with 0.5g N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane 5g acetone soln and the 13g acetone soln for being dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2.5g, are respectively added to It is vigorously stirred simultaneously in acetone soln dissolved with performed polymer.20min is stirred, is then divided the mixture by addition 238g water It dissipates.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane-polyurea Aqueous dispersion, number-average molecular weight are measured as 116000 through GPC, have the solid content of 50wt% and in dispersed phase by swashing The average grain diameter of the 178nm of light related assays, pH value are 6.8, viscosity 3300cP.
Embodiment 12
Polyester II, the 30g of polyester I, 120g Jing Guo dehydration by 80g Jing Guo dehydration gathers by dehydration Ester III, 28.35g isocyanates I, 2g are added to by dehydration polyethers I, 25g acetone, 0.04g bismuth neodecanoate equipped with nitrogen In the 1L four round flask of inlet and outlet, the mixture is stirred at 80-90 DEG C until NCO reaches 1.92%.The performed polymer is molten Solution is in 395g acetone and is cooled to 50 DEG C.5g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3g isophorone will be dissolved with Diamines, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.72g N- β-(aminoethyl)-gamma-aminopropyl-triethoxy The 5g acetone soln of silane and the 12g acetone soln for being dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2.3g, respectively It is added in the acetone soln dissolved with performed polymer while is vigorously stirred.20min is stirred, is then mixed this by adding 238g water Close object dispersion.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane- The aqueous dispersion of polyureas, number-average molecular weight are measured as 138000 through GPC, have the solid content of 50wt% and in dispersed phase By the average grain diameter of the 185nm of laser related assays, pH value is 7.2, viscosity 2800cP.
Embodiment 13
Polyester II, the 15g of polyester I, 150g Jing Guo dehydration by 80g Jing Guo dehydration gathers by dehydration Ester III, 28.35g isocyanates I, 2g are added to by dehydration polyethers I, 25g acetone, 0.04g bismuth neodecanoate equipped with nitrogen In the 1L four round flask of inlet and outlet, the mixture is stirred at 80-90 DEG C until NCO reaches 2.03%.The performed polymer is molten Solution is in 415g acetone and is cooled to 50 DEG C.5g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3g isophorone will be dissolved with Diamines, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.72g N- β-(aminoethyl)-gamma-aminopropyl-triethoxy The 5g acetone soln of silane and the 13g acetone soln for being dissolved with bis- (3- triethoxysilylpropyltetrasulfide) amine of 2.5g, respectively It is added in the acetone soln dissolved with performed polymer while is vigorously stirred.20min is stirred, is then mixed this by adding 238g water Close object dispersion.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain solvent-free polyurethane- The aqueous dispersion of polyureas, number-average molecular weight are measured as 110000 through GPC, have the solid content of 50wt% and in dispersed phase By the average grain diameter of the 178nm of laser related assays, pH value is 7.0, viscosity 2900cP.
Comparative example 14
Polyester I, 28.35g isocyanates I, 24g acetone, 2g by 210g Jing Guo dehydration pass through dehydration polyethers I, 0.04g bismuth neodecanoate is added in the 1L four round flask equipped with import and export of nitrogen, and it is straight that the mixture is stirred at 80-90 DEG C Reach 1.72% to NCO.The performed polymer is dissolved in 405g acetone and is cooled to 50 DEG C.5.1g N- (2- ammonia second will be dissolved with Base) -2-aminoethanesulfonic acid sodium, 3.51g isophorone diamine, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution, be added to dissolution Have in the acetone soln of performed polymer while being vigorously stirred.20min is stirred, is then dispersed the mixture by addition 300g water. After being separated by distillation out acetone, 4g emulsifier Tween 20 is added.Obtain the moisture of solvent-free polyurethane-polyurea Granular media, number-average molecular weight are measured as 90000 through GPC, have the solid content of 50wt% and pass through laser phase in dispersed phase The average grain diameter of the 180nm of measurement is closed, pH value is 7.5, viscosity 2500cP.
Comparative example 15
Polyester II, the 15g of polyester I, 150g Jing Guo dehydration by 80g Jing Guo dehydration gathers by dehydration Ester III, 28.35g isocyanates I, 2g are added to by dehydration polyethers I, 25g acetone, 0.04g bismuth neodecanoate equipped with nitrogen In the 1L four round flask of inlet and outlet, the mixture is stirred at 80-90 DEG C until NCO reaches 2.03%.The performed polymer is molten Solution is in 415g acetone and is cooled to 50 DEG C.5g N- (2- aminoethyl) -2-aminoethanesulfonic acid sodium, 3g isophorone will be dissolved with Diamines, 0.86g hydroxyethyl ethylenediamine 35g aqueous solution and be dissolved with 0.72g N- β-(aminoethyl)-gamma-aminopropyl-triethoxy The 5g acetone soln of silane is respectively added in the acetone soln dissolved with performed polymer while being vigorously stirred.20min is stirred, so The mixture is dispersed by addition 238g water afterwards.After being separated by distillation out acetone, 4g emulsifier Tween 20 is added. The aqueous dispersion of solvent-free polyurethane-polyurea is obtained, number-average molecular weight is measured as 100000 through GPC, has 50wt% Solid content and in dispersed phase by the average grain diameter of the 175nm of laser related assays, pH value is 7.1, and viscosity is 3000cP。
The preparation of adhesive
By 100g aqueous dispersion, 0.05g BYK024 (Bi Ke chemistry) mixing, 5min is stirred under the conditions of 500rpm, is being added Enter 0.2g Tego245 (Digao), be stirred for 5min, adds 0.15g Vesmody U604 (ten thousand China's chemistry), then exist 600rpm stirs 10min.
The preparation of sample
Sample is prepared with following composite material:
Composite material Substrate 1 Substrate 2
A Rubber Rubber
B Canvas Canvas
C PVC PVC
Substrate 1 (rubber), substrate 2 (rubber) are handled with inorganic agent first, dried later stand-by.Use brush head First the thin unfertile land of described adhesive dispersion is applied in the substrate strip of 2.5cm wide and 15cm long and is done in 65 DEG C of baking ovens It is dry 5 minutes, rear to take out in 30kg/cm2Composite A is made in pressing 10 seconds.
Composite material B, composite material C are prepared using same method.
Test the peel strength of composite material
Peel strength is measured under the detachment rate of 200mm/min with GOTECH puller system.
Early strength: its peel strength directly is tested to puller system after having pressed.
Later strength: by test specimen after being placed at room temperature for 24 hours, its peel strength is tested.
Test result is shown in Table 1.
The intensity of adhesive on 1 different substrate materials of table
Note: (1) the one-component formula for being added without curing agent is indicated；
(2) it indicates when configuring adhesive, another be added is equivalent to lotion 5wt%'s161 (Yantai Wanhuas Chemistry, NCO 18.5wt%), prepare two-component system.
By finding out in table 1, based on side chain provided by the invention and the main chain dispersions of polyurethanes containing siloxanes Mono-/bis-component adhesive and only of the early strength of single-component adhesive relative to the dispersions of polyurethanes for the siloxanes not contained Side chain contains the one-package adhesive (comparative example 14 of the dispersions of polyurethanes of siloxanes(1)、14(2), 15) for, initial stage is strong Degree and later strength are declined slightly, but the amplitude very little declined, are met performance requirement, are had substantially no effect on normal use.
Test the heat resistance of composite material
Initial stage is heat-resisting: by ready-made test specimen, hanging the counterweight of 500 grams of weight, is placed in 80 DEG C of baking ovens, tests it at 30 points In clock, length that test specimen pulls open.
Later period is heat-resisting: ready-made test specimen being placed at room temperature for 3 days, the counterweight of 1 kilogram of weight is being hung, is placed on 70 DEG C of baking ovens In, it is tested in 24 hours, the length that test specimen pulls open.
Wet-heat resisting: being placed at room temperature for 3 days for ready-made test specimen, hanging the counterweight of 500 grams of weight, be placed on 70 DEG C of temperature/ In the baking oven of 95% humidity, test test specimen all pulls open the required time.
Test result is shown in Table 2.
The heat resistance of adhesive on 2 different substrate materials of table
Note: (1) the one-component formula for being added without curing agent is indicated；
(2) it indicates when configuring adhesive, another be added is equivalent to lotion 5wt%'s161 (Yantai Wanhuas Chemistry, NCO 18.5wt%), prepare two-component system.
List as can be seen from Table 2 based on side chain provided by the invention and the main chain dispersions of polyurethanes containing siloxanes (comparison is real for the single-component adhesive of dispersions of polyurethanes of the early strength of component adhesive relative to side chain without containing siloxanes Apply example 14(1)) for, initial stage is heat-resisting, the later period is heat-resisting, wet-heat resisting is all significantly improved, and especially wet-hot aging performance is substantially Degree is promoted, or even than two component adhesive (comparative example 14 (2)) and only side chain contains the dispersions of polyurethanes of siloxanes The wet-hot aging performance of one-package adhesive (comparative example 15) will be got well.This is mainly due to the siloxanes phases on side chain and main chain Hydrolysis, crosslinking occur between mutually, film crosslink density increases considerably, and the heat resistance and wet-hot aging performance of film obviously mention It is high.
By the aqueous dispersion of this patent preparation in 75 DEG C of placement 72h, after observing high temperature storage, adhesive is on rubber to viscous Close the influence of intensity.The results are shown in Table 3
After 3 high temperature storage of table, the intensity of the adhesive on rubber substrate
Note: (1) the one-component formula for being added without curing agent is indicated；
(2) it indicates when configuring adhesive, another be added is equivalent to lotion 5wt%'s161 (Yantai Wanhuas Chemistry, NCO 18.5wt%), prepare two-component system.
Can significantly it find out from table 3, the dispersions of polyurethanes of side chain and main chain containing siloxanes segment, high gentle Storage 3 days, adhesion strength will not occur significantly to change.And in comparative example, no siloxanes segment and only side chain contains siloxanes Dispersions of polyurethanes there is the reduction of apparent adhesion strength.This illustrates side chain and main chain containing siloxanes segment Dispersions of polyurethanes has excellent storage stability.

Claims (13)

1. the aqueous dispersion of polyurethane or polyurethane-urea, which is characterized in that included in the polyurethane or the water of polyurethane-urea Polyurethane or polyurethane-polyurea in dispersion are the reaction products reacted by following components:
A) at least one silicone components, the silicone components contain at least two NCO reactive functional groups, and former with silicon Sub-key even at least two groups be methoxyl group and/or ethyoxyl,
B) at least one silicone components, the silicone components contain a NCO reactive functional groups, and with silicon atom key Even at least two groups be methoxyl group and/or ethyoxyl,
C) polyol component that at least one degree of functionality is 2~4,
D) at least one polyisocyanate component,
E) at least one hydrophilic compounds component, the hydrophilic radical of the hydrophilic compounds include ionic group, ionogenic group, One of non-ionic group is a variety of, and the hydrophilic compounds contain 2~3 NCO reactive functional groups,
F) at least one NCO is reactive, non-ionic hydrophilic compound of single functionality,
G) optional small molecule amine chain extender, and
H) optional other isocyanate-reactive compounds.
2. the aqueous dispersion of polyurethane according to claim 1 or polyurethane-urea, which is characterized in that at least two NCO are anti- Answering property functional group is at least two amino or at least two hydroxyls or at least one amino and a hydroxyl.
3. the aqueous dispersion of polyurethane according to claim 1 or 2 or polyurethane-urea, which is characterized in that component a) is institute State the 0.02-5 weight % of solid part of polyurethane or polyurethane-urea aqueous dispersion, preferably 0.1-3 weight %, more preferable 0.2~ 2.5 weight %；Component b) is 0.1-4 the weight %, preferably 0.3- of solid part of the polyurethane or polyurethane-urea aqueous dispersion 2 weight %, more preferable 0.4~1.5 weight %；Component c) is solid part of the polyurethane or polyurethane-urea aqueous dispersion 5-94 weight %, preferably 8-90 weight %, more preferable 70~90 weight %；Component d) is the polyurethane or polyurethane-urea water The 5-40 weight % of solid part of dispersion, preferably 8-30 weight %, more preferable 8~20 weight %；Component e) is the poly- ammonia 0.2~50 weight % of solid part of ester or polyurethane-urea aqueous dispersion, preferably 0.5~40 weight %, more preferable 1~5 weight Measure %；Component f) is 0.01~20 weight %, preferably 0.05- of solid part of the polyurethane or polyurethane-urea aqueous dispersion 10 weight %, more preferable 0.5~3 weight %；Component g) is the 0- of solid part of the polyurethane or polyurethane-urea aqueous dispersion 10 weight %, preferably 0.5~5 weight %, more preferable 0.5~3 weight %；Component h) is the polyurethane or polyurethane-urea The 0-15 weight % of solid part of aqueous dispersion, preferably 0-8 weight % or 1~8 weight %.
4. the aqueous dispersion of polyurethane according to any one of claim 1-3 or polyurethane-urea, which is characterized in that group Dividing a) is the siloxanes at least two amino, such as selected from N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, 1,3- Two (aminopropyl) tetramethyl disiloxanes, more preferable N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(ammonia second Base)-gamma-aminopropyl-triethoxy-silane, one of N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane or more Kind.
5. the aqueous dispersion of polyurethane described in any one of -4 or polyurethane-urea according to claim 1, which is characterized in that group Dividing b) is bis- (3- triethoxysilylpropyltetrasulfide) amine, bis- (3- trimethoxy-silylpropyl) amine, bis- (3- triethoxies Silyl ether) amine, one of bis- (3- trimethoxysilylethylgroup group) amine or a variety of, preferably bis- (3- triethoxies Silylpropyl) amine and/or bis- (3- trimethoxy-silylpropyl) amine.
6. the aqueous dispersion of polyurethane according to any one of claims 1-5 or polyurethane-urea, which is characterized in that group Point c) be the glycol and/or polyalcohol that molal weight is 20-15000, preferably molal weight for 80-5000 glycol or three Alcohol；More preferable molal weight is in the polyester containing 2-3 hydroxyl, polycarbonate, polylactone and the small molecular alcohol of 80-5000 It is one or more.
7. the aqueous dispersion of polyurethane according to claim 1 to 6 or polyurethane-urea, which is characterized in that group Divide e) for N- (2- aminoethyl) -2- aminoethane sulphonic acid salt and/or dihydromethyl propionic acid salt and/or Ymer120.
8. the aqueous dispersion of polyurethane described in any one of -7 or polyurethane-urea according to claim 1, which is characterized in that group Divide the component containing polyethoxy segment f) for single functionality, molal weight 200-8000, each molecule ethylene oxide Number is 4-200, preferably molal weight 500-3000, and each molecule ethylene oxide number is 12-75；And/or
Component g) is aliphatic and/or alicyclic uncle and/or secondary monoamine or diamines or triamine or amino alcohol；
More preferably isophorone diamine, N- (2- ethoxy) ethylene diamine, 1,6- hexamethylene diamine and theirs is mixed Close object；
Component g) further preferably molar ratio is 0.5~10:1, the preferably isophorone diamine of 1~5:1 and N- (2- hydroxyl second Base) ethylene diamine mixture；And/or
Component h) is selected from one or more among following: sealer such as diacetylmonoxime, dimethyl pyrazole, caprolactam, the third two Acid esters, triazole, triazol-dimethyl, tert-butyl benzyl amine, cyclopentanone carboxyl ethyl ester；Unsaturationization containing polymerization activity group Close object, such as hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hy-droxybutyl, methacrylate, acrylic acid hydroxyl Propyl ester, hydroxy propyl methacrylate, pentaerythritol triacrylate, monoepoxide, di-epoxide and/or polyepoxide With the hydroxyl-functional reaction product of acrylic or methacrylic acid.
9. the aqueous dispersion of polyurethane according to claim 1 to 8 or polyurethane-urea, which is characterized in that group Divide d) is the organic compound at least two isocyanate groups, preferably diisocyanate Y (NCO)2, wherein Y is represented and is contained The divalent aliphatic alkyl of 4-12 carbon atom, the alicyclic divalent hydrocarbon radical containing 6-15 carbon atom, two containing 6-15 carbon atom Valence aromatic hydrocarbyl or divalent araliphatic alkyl containing 7-15 carbon atom, more preferable tetramethylene diisocyanate, pentamethylene Diisocyanate, hexamethylene diisocyanate, ten dimethylene diisocyanates, 1,4- hexamethylene diisocyanate, different Fo Er Ketone diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate, 4,4'- dicyclohexyl propane diisocyanate, two isocyanide of 1,4- benzene Acid, 2,4- toluene diisocynate, 2,6- toluene diisocynate, 4,4'- diphenylmethane diisocyanate, 2,2'- and 2,4'- hexichol One of methylmethane diisocyanate, tetramethyl xylene phenyl diisocyanate, terephthaldehyde's group diisocyanate are a variety of, into The mixture of one step preferred hexamethylene diisocyanate and isophorone diisocyanate, or use two isocyanide of hexa-methylene The mixture of acid esters and 4,4'- dicyclohexyl methyl hydride diisocyanate.
10. the aqueous dispersion of polyurethane according to claim 1 to 9 or polyurethane-urea, which is characterized in that poly- The aqueous dispersion of urethane or polyurethane-urea has 15~70wt%, the preferably solid content of 30~60wt%；And/or
The pH value of the dispersion is 4~11, preferably 5~10；And/or
The average grain diameter of polyurethane or polyurethane-urea is 20~750nm, preferably 50~450nm.
11. the preparation method of the aqueous dispersion of polyurethane according to claim 1 to 10 or polyurethane-urea, Be characterized in that, (A) makes component c), d with one or more steps reaction), f) and optional h) react isocyanate terminated pre- to be formed Polymers, (B) make the prepolymer and component a), b with one or two-stage reaction), e) and optional g) react, (C) is by step (B) Reaction product it is water-dispersible or dissolution, wherein in step (A) and/or (B) optionally using one kind can during dispersion or Pass through distillation fraction or the solvent completely removed later.
12. the aqueous dispersion of polyurethane described in any one of -11 or polyurethane-urea is used to prepare coating according to claim 1 Agent, adhesive or sealant purposes.
13. a kind of coating agent, adhesive or sealant comprising as claim 1-11 described in any item aqueous dispersions and Optional emulsifier, light stabilizer, antioxidant, filler, antisettling agent, defoaming agent, wetting agent, flowing regulator, reactivity One of diluent, plasticizer, neutralizer, catalyst, secondary solvent, thickener, pigment, dyestuff, delustering agent, tackifier or It is a variety of.
CN201810865635.6A 2018-08-01 2018-08-01 The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application Pending CN109081897A (en)

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CN110387030A (en) * 2019-06-04 2019-10-29 中海油常州涂料化工研究院有限公司 A kind of ionic waterborne curing agent and preparation method thereof based on biology base pentamethylene diisocyanate
CN110903458A (en) * 2019-12-23 2020-03-24 万华化学集团股份有限公司 Preparation method of closed waterborne polyurethane used as aramid fiber surface treatment agent, prepared closed waterborne polyurethane and application
CN111187564A (en) * 2020-03-05 2020-05-22 清远粤绿新材料技术有限公司 Heat-conducting coating capable of heating polyurethane automobile decoration film and manufacturing method thereof
CN111465631A (en) * 2017-12-21 2020-07-28 科思创德国股份有限公司 Adhesives with adjustable adhesion based on special polyurethaneureas, their production and use
CN111690360A (en) * 2020-06-22 2020-09-22 万华化学（北京）有限公司 Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof
CN111958746A (en) * 2020-08-17 2020-11-20 万华化学集团股份有限公司 Polyurethane urea dispersoid, adhesive composite material and application of polyurethane urea dispersoid and adhesive composite material in preparation of aldehyde-free added ultrathin high-density fiberboard
CN112778487A (en) * 2019-11-05 2021-05-11 万华化学集团股份有限公司 Aqueous dispersion of polyurethane or polyurethane-urea, preparation method and application thereof
CN112979900A (en) * 2019-12-18 2021-06-18 万华化学集团股份有限公司 Aqueous polyurethane or polyurethane-urea dispersions, method for the production thereof and use thereof
CN113136020A (en) * 2020-01-20 2021-07-20 万华化学集团股份有限公司 Water-based polyurethane polymer and preparation method thereof, single-component water-based polyurethane waterproof coating and preparation method and application thereof
CN113631616A (en) * 2019-03-05 2021-11-09 陶氏环球技术有限责任公司 Aqueous polyurethane dispersion and process for producing the same
CN113698567A (en) * 2020-05-21 2021-11-26 万华化学集团股份有限公司 Hydrophilic siloxane modified polyurethane or polyurethane-urea aqueous dispersion, preparation method and application
CN114409864A (en) * 2020-10-28 2022-04-29 万华化学集团股份有限公司 Aqueous polyurethane or polyurethane-urea dispersions, method for the production thereof and use thereof
CN114479626A (en) * 2022-01-26 2022-05-13 陈培坤 Coating composition
CN114621670A (en) * 2020-12-14 2022-06-14 万华化学集团股份有限公司 Aqueous polyurethane-urea dispersions, method for the production thereof and use thereof
CN114854004A (en) * 2022-04-25 2022-08-05 山西省建筑科学研究院有限公司 Nonionic diamino hydrophilic chain extender, preparation method thereof and preparation method of nonionic aqueous polyurea
CN115011230A (en) * 2022-07-06 2022-09-06 杭州之江有机硅化工有限公司 Polyurethane three-proofing paint and preparation method thereof

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CN111465631B (en) * 2017-12-21 2022-07-12 科思创德国股份有限公司 Adhesives with adjustable adhesion based on special polyurethaneureas, their production and use
CN111465631A (en) * 2017-12-21 2020-07-28 科思创德国股份有限公司 Adhesives with adjustable adhesion based on special polyurethaneureas, their production and use
CN113631616B (en) * 2019-03-05 2023-06-16 陶氏环球技术有限责任公司 Aqueous polyurethane dispersion and method for producing same
CN113631616A (en) * 2019-03-05 2021-11-09 陶氏环球技术有限责任公司 Aqueous polyurethane dispersion and process for producing the same
CN110387030A (en) * 2019-06-04 2019-10-29 中海油常州涂料化工研究院有限公司 A kind of ionic waterborne curing agent and preparation method thereof based on biology base pentamethylene diisocyanate
CN112778487A (en) * 2019-11-05 2021-05-11 万华化学集团股份有限公司 Aqueous dispersion of polyurethane or polyurethane-urea, preparation method and application thereof
CN112979900A (en) * 2019-12-18 2021-06-18 万华化学集团股份有限公司 Aqueous polyurethane or polyurethane-urea dispersions, method for the production thereof and use thereof
CN110903458A (en) * 2019-12-23 2020-03-24 万华化学集团股份有限公司 Preparation method of closed waterborne polyurethane used as aramid fiber surface treatment agent, prepared closed waterborne polyurethane and application
CN113136020A (en) * 2020-01-20 2021-07-20 万华化学集团股份有限公司 Water-based polyurethane polymer and preparation method thereof, single-component water-based polyurethane waterproof coating and preparation method and application thereof
CN113136020B (en) * 2020-01-20 2022-08-05 万华化学集团股份有限公司 Water-based polyurethane polymer and preparation method thereof, single-component water-based polyurethane waterproof coating and preparation method and application thereof
CN111187564A (en) * 2020-03-05 2020-05-22 清远粤绿新材料技术有限公司 Heat-conducting coating capable of heating polyurethane automobile decoration film and manufacturing method thereof
CN113698567B (en) * 2020-05-21 2023-01-13 万华化学集团股份有限公司 Hydrophilic siloxane modified polyurethane or polyurethane-urea aqueous dispersion, preparation method and application
CN113698567A (en) * 2020-05-21 2021-11-26 万华化学集团股份有限公司 Hydrophilic siloxane modified polyurethane or polyurethane-urea aqueous dispersion, preparation method and application
CN111690360B (en) * 2020-06-22 2023-03-03 万华化学（北京）有限公司 Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof
CN111690360A (en) * 2020-06-22 2020-09-22 万华化学（北京）有限公司 Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof
CN111958746A (en) * 2020-08-17 2020-11-20 万华化学集团股份有限公司 Polyurethane urea dispersoid, adhesive composite material and application of polyurethane urea dispersoid and adhesive composite material in preparation of aldehyde-free added ultrathin high-density fiberboard
CN114409864A (en) * 2020-10-28 2022-04-29 万华化学集团股份有限公司 Aqueous polyurethane or polyurethane-urea dispersions, method for the production thereof and use thereof
CN114409864B (en) * 2020-10-28 2023-12-19 万华化学集团股份有限公司 Aqueous polyurethane or polyurethane-urea dispersion, method for the production and use thereof
CN114621670A (en) * 2020-12-14 2022-06-14 万华化学集团股份有限公司 Aqueous polyurethane-urea dispersions, method for the production thereof and use thereof
CN114621670B (en) * 2020-12-14 2023-05-30 万华化学集团股份有限公司 Aqueous polyurethane-urea dispersions, method for the production and use thereof
CN114479626A (en) * 2022-01-26 2022-05-13 陈培坤 Coating composition
CN114854004A (en) * 2022-04-25 2022-08-05 山西省建筑科学研究院有限公司 Nonionic diamino hydrophilic chain extender, preparation method thereof and preparation method of nonionic aqueous polyurea
CN114854004B (en) * 2022-04-25 2024-01-23 山西省建筑科学研究院集团有限公司 Nonionic type double-amino hydrophilic chain extender, preparation method thereof and preparation method of nonionic type aqueous polyurea
CN115011230A (en) * 2022-07-06 2022-09-06 杭州之江有机硅化工有限公司 Polyurethane three-proofing paint and preparation method thereof

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