CN114621416B - Aqueous polyurethane dispersion, preparation method and application thereof in double-component spray adhesive - Google Patents

Aqueous polyurethane dispersion, preparation method and application thereof in double-component spray adhesive Download PDF

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CN114621416B
CN114621416B CN202011447387.7A CN202011447387A CN114621416B CN 114621416 B CN114621416 B CN 114621416B CN 202011447387 A CN202011447387 A CN 202011447387A CN 114621416 B CN114621416 B CN 114621416B
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aqueous polyurethane
polyurethane dispersion
component
acid
dispersion according
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CN114621416A (en
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王萃萃
纪学顺
晋云全
张斌
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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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
    • C08G18/70—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
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/28—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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • 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
    • 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

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

Abstract

The invention relates to a waterborne polyurethane dispersoid, a preparation method and application thereof in double-component glue spraying. The preparation of the aqueous polyurethane dispersion comprises the following steps of diluting and dissolving diisocyanate terminated prepolymer with acetone, carrying out shearing dispersion after amine chain extension reaction, and adding C-containing component into the dispersion 10 ‑C 25 And (3) performing post-chain extension reaction on the amine with the hydrophobic chain segment to obtain the aqueous polyurethane dispersoid. When the adhesive is used for preparing the bi-component spray adhesive, the adhesive can be immediately adhered by spraying on a substrate, and the prepared adhesive has the characteristics of no toxicity, environment friendliness, adhesion at room temperature, high adhesion strength, good heat resistance, soft hand feeling, secondary adhesion and the like.

Description

Aqueous polyurethane dispersion, preparation method and application thereof in double-component spray adhesive
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a waterborne polyurethane dispersoid, a preparation method and application thereof in double-component glue spraying.
Background
The glue spraying is an adhesive commonly used for producing soft furniture and is widely applied to the fields of furniture, cloth art, decoration, light materials and the like. Neoprene adhesives have long been widely appreciated. In recent years, some large adhesive companies (such as Kesi) at home and abroad start to push out a two-component aqueous neoprene adhesive, namely, neoprene latex is taken as a main component, and auxiliaries such as tackifying emulsion, curing agent and the like are added for simultaneous use. When the curing agent is in direct contact with neoprene latex, demulsification is generated to form a glue film, so that bonding is generated.
CN103865439a discloses a two-component aqueous neoprene spray adhesive, wherein one component is a mixture of aqueous neoprene emulsion, aqueous polyurethane emulsion and aqueous acrylic emulsion, and the other component is an auxiliary agent such as tackifying resin, curing agent, ultraviolet absorbent and the like, and the two components are mixed when in use. The first component is a mixture of three emulsions, the mixing process is complex, and the construction efficiency is affected. Meanwhile, the pH of the aqueous neoprene latex can be slowly reduced along with the time, so that the stability of the latex is directly affected, latex demulsifies and coagulates, the shelf life of the latex of a common manufacturer is very short, and great risks are caused to the use of customers.
CN107857913a discloses a storage-stable aqueous neoprene, which achieves the purpose of maintaining the pH stability of the system by adding lithium salt and complex in the latex to inhibit the overflow of chloride ions from the neoprene and to rapidly absorb the decomposed chloride ions, thereby improving the storage stability of the system. However, aqueous neoprene has problems of yellowing and halogen residue in use.
CN104531036a discloses a two-component aqueous polyurethane spray adhesive, which uses aqueous polyurethane as main raw material, aqueous catalyst as second component, and introduces normal-temperature oxidatively crosslinkable unsaturated double bond into the molecular structure of aqueous polyurethane, at normal temperature, the aqueous catalyst can dissociate water in aqueous polyurethane, and generated ions instantly activate unsaturated double bond in aqueous polyurethane to open, and coordinate with oxygen in air to dry, oxidatively crosslink, so that the base material is bonded rapidly. However, the mode of polymerizing the drier by matching with oxygen in the air is very low in efficiency, the water-based drier contains heavy metal elements, and meanwhile, a carboxylate system is adopted in the preparation of the water-based polyurethane emulsion, and the water-based polyurethane emulsion is neutralized by dimethylethanolamine solution, so that the emulsion VOC is higher, the influence on the body of workers is caused, and the environment is polluted.
CN103946256a discloses a cold contact adhesive, the adhesive can be bonded without activation, and the polyhydric alcohol adopted in the process of synthesizing polyurethane is crystalline and amorphous, but the adhesive prepared by the method has hard hand feeling, short maintenance time, can not be bonded for the second time, and limits the application range.
Therefore, developing a resin with good stability, soft hand feeling and excellent adhesive property, and simultaneously taking account of environmental protection has become one of the problems to be solved in the field.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and providing an aqueous polyurethane dispersion and a preparation method thereof. The aqueous polyurethane dispersion and the curing agent are sprayed on the substrate, so that the adhesion can be realized immediately. The adhesive prepared by the method has the characteristics of no toxicity, environment friendliness, adhesion at room temperature, high adhesion strength, good heat resistance, soft hand feeling, capability of realizing secondary adhesion and the like.
The invention also aims to provide the application of the double-component spray adhesive, which is suitable for bonding soft substrates such as furniture such as sofas and mattresses, sponge, leather, cloth and the like.
In order to achieve the above object, the present invention has the following technical scheme:
The invention provides an aqueous polyurethane dispersion which is prepared by reacting raw materials comprising the following components:
a) At least one polyester polyol having a melting temperature in the range of 40 to 80 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min;
b) At least one low crystallinity or non-crystalline polyester polyol and/or polyether polyol, said low crystallinity or non-crystalline polyester polyol meaning a melting temperature of less than 30 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min;
c) At least one polyisocyanate;
d) At least one hydrophilic compound, the hydrophilic group of the hydrophilic compound comprises one or two of an ionic group and a potential ionic group, and the hydrophilic compound contains 2-3 NCO reactive functional groups;
preferably, the method comprises the steps of,the ionic group is selected from carboxylate (-COO) - ) And/or sulfonate (-SO) 3 - ) The method comprises the steps of carrying out a first treatment on the surface of the The potentially ionic group refers to a functional group having a covalent bond, preferably a carboxyl group (-COOH) and/or a sulfonic acid group (-SO) 3 H) The method comprises the steps of carrying out a first treatment on the surface of the The NCO-reactive functional group is an amino group;
e) At least one C-containing 10 ～C 25 An amine compound of a hydrophobic segment;
f) Optionally, a compound comprising 1 to 3 amino groups.
The aqueous polyurethane dispersion of the invention comprises the following components in percentage by mass based on 100% of the total mass of the solid components (namely the sum of the mass of the components a) to f):
component a) 50 to 74 wt.%, preferably 55 to 73 wt.%;
component b) 14 to 39 wt.%, preferably 16 to 32 wt.%;
component c) 8.5 to 12%, preferably 9.5 to 11%;
component d) 1.5 to 2.7 wt.%, preferably 1.7 to 2.5 wt.%;
component e) 1 to 2.5 wt.%, preferably 1.5 to 2.2 wt.%;
component f) is 0 to 2.5% by weight, preferably 0 to 2% by weight.
Further, the polyester polyol of the component a) of the present invention has a number average molecular weight of 500 to 10000; preferably one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with the number average molecular weight of 1000-5000; further, one or more of a polyester polyol of the polyadipic acid series, a polycarbonate polyol and a polycaprolactone polyol having a number average molecular weight of 2000 to 4000 and a functionality of 2 are preferable, and 1, 4-butanediol adipate diol is more preferable.
Further, the component b) of the present invention, the low crystallinity or non-crystalline polyester polyol and/or polyether polyol has a number average molecular weight of 500 to 10000, preferably a diol and/or triol having a number average molecular weight of 1000 to 4000, more preferably a diol and/or triol having a number average molecular weight of 1000 to 3000;
More preferably, the low crystallinity or non-crystalline polyester polyol is one or more of a polyadipic acid series polyester polyol, a polybenzic acid series polyester polyol, a polycarbonate polyol having a number average molecular weight of 1000 to 3000 and a melting temperature of less than 35 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min; the polyester polyol of the polyadipic acid series and the polyester polyol of the polystyrene acid series are particularly preferably one or more of the group consisting of hexanediol neopentyl glycol adipate glycol, neopentyl glycol adipate glycol and 1, 6-hexanediol phthalate;
further preferred, the low crystallinity or non-crystalline polyester polyol is a linear polyester diol or a micro-branched polyester diol, e.g., obtainable by dehydration condensation by known means from carboxylic acids and/or anhydrides such as aliphatic, cycloaliphatic, aromatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides, and the like, including but not limited to one or more of succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride; the polyols include, but are not limited to, one or more of ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol;
Further preferred, the low crystallinity or non-crystalline polycarbonate polyol is a diol selected from the group consisting of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and a carbonate selected from the group consisting of diaryl carbonates, preferably diphenyl carbonate, preferably dimethyl carbonate; more preferably a polycarbonate polyol prepared by reacting 1, 5-pentanediol with dimethyl carbonate;
more preferably, the polyether polyol is a polyaddition product of styrene oxide, or a polyaddition product of one or more of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, etc., as a monomer; or polyether polyols obtained by polycondensation of polyols or mixtures thereof; or polyether polyols obtained by alkoxylation of polyols, amines and amino alcohols, more preferably polyoxyethylene polyols, polyoxypropylene polyols, particularly preferably polyoxypropylene ether diols.
Optionally, the low crystallinity or non-crystalline polyester polyol may also incorporate polyols having higher functionality, such as trimethylol propane, glycerol, or pentaerythritol.
In addition, alicyclic, aromatic dihydroxy and/or polyhydroxy compounds may also be used as the polyol for preparing the low crystallinity or amorphous polyester polyol, preferably polyester polyol obtained by dehydration polycondensation of one or more of isophthalic acid, terephthalic acid, adipic acid and one or more of neopentyl glycol, ethylene glycol, diethylene glycol.
Further, the component c) according to the invention is a polyisocyanate selected from aromatic, aliphatic or cycloaliphatic polyisocyanates, preferably one or more of aromatic, aliphatic or cycloaliphatic isocyanates having two isocyanate groups, more preferably diisocyanate Y (NCO) 2 Wherein Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms;
preferably, the diisocyanate is selected from one or more of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexanediisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-benzenediisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, tetramethylxylyl diisocyanate, p-xylyl diisocyanate.
Further preferred, the diisocyanate is a mixture of aliphatic and cycloaliphatic diisocyanates, for example a mixture of hexamethylene diisocyanate with one or more of 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, more preferably a mixture of hexamethylene diisocyanate with isophorone diisocyanate.
In some embodiments of the present invention, in addition to the simple diisocyanates described above, polyisocyanates having a functionality of more than 2 isocyanate groups per molecule may be used, such as polyisocyanates prepared by modification of one or more of the simple aliphatic, cycloaliphatic, araliphatic, aromatic diisocyanates or synthesized from at least two diisocyanates (having one or more of the structures uretdione, isocyanurate, urethane, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione).
The polyisocyanates of the invention may also comprise less than or equal to 5% by weight, based on polyurethane solids, of higher-functional polyisocyanates or modified polyisocyanates containing, for example, one or more of carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, biuret groups.
Further, the hydrophilic compound of the present invention is a compound containing 2 to 3 NCO-reactive groups together with at least one ionic or potential ionic group, preferably di-or tri-hydroxycarboxylic acid, di-or tri-hydroxysulfonic acid, di-or tri-sulfamic acid, di-or tri-aminocarboxylic acid or salts thereof, more preferably dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -B-alanine and alkali metal salts or ammonium salts of the above compounds; most preferred is one or both of N- (2-aminoethyl) -2-aminoethane sulfonate and/or N- (2-aminoethyl) -B-alanine salt.
In some embodiments of the invention, if a potentially ionic compound is used as component d), a neutralizing agent may be added before, during or after the dispersion. The neutralizing agent is added in an amount such that the potential ionic groups are partially or fully ionic groups. Suitable neutralizing agents are, for example, one or more of alkali metal compounds, alkaline earth metal compounds, examples of suitable neutralizing agents include, but are not limited to, one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, or calcium hydroxide, among others. In general, sufficient neutralizing agent is added such that the degree of neutralization is at least 50%, preferably at least 75%, and not more than 150% based on the acid groups introduced. The neutralization degree is particularly preferably 80 to 95%. The person skilled in the art understands that in addition to the acid groups being neutralized to form ionic groups, free neutralizing agents are present in the system, wherein the degree of neutralization = amount of neutralizing agent added/total amount of acid groups introduced, in which formula the term "amount" refers to molar amount.
Further, component e) according to the invention, said C-containing 10 ～C 25 The structure of the amino compound of the hydrophobic chain segment is shown as a formula I:
wherein R is C 10 ～C 25 Alkyl of (a);
the C-containing 10 ～C 25 The amine compound of the hydrophobic chain segment is a product obtained by Michael addition reaction of diethylenetriamine and esters shown in a formula II, wherein the structure of the esters shown in the formula II is expressed as follows:
wherein R is as defined in formula I, i.e. C 10 -C 25 Y is H atom or-CH 3 ；
Preferably, the esters of formula II include, but are not limited to, one or more of acrylic acid esters, methacrylic acid esters, more preferably, such as dodecyl methacrylate and/or hexadecyl methacrylate.
In some embodiments of the invention, the C-containing 10 -C 25 The amino compound of the hydrophobic chain segment is prepared by mixing diethylenetriamine, esters shown in a formula II, alkali and a solvent, heating and carrying out Michael addition reaction;
wherein, preferably, the mol ratio of the diethylenetriamine to the ester shown in the formula II is 1:0.4 to 0.7, preferably 1:0.5 to 0.66;
the alkali is selected from triethylamine, sodium ethoxide, sodium hydride, sodium amide and the like, and the dosage of the alkali is preferably 1.5-2.5 times of the mass of the diethylenetriamine.
The solvent is selected from dioxane, tetrahydrofuran, methyl tertiary butyl ether and the like; preferably, the solvent is used in an amount of 50 to 100 times the mass of diethylenetriamine.
The Michael addition reaction temperature is 50-80 ℃, preferably 65-75 ℃ and the time is 2-4 hours, preferably 3-4 hours.
After the reaction is finished, the method also comprises a reduced pressure distillation post-treatment operation, wherein the reduced pressure distillation condition is that the vacuum degree is 0.005-0.01Mpa, and the temperature is 80-100 ℃.
Further, component f) of the present invention, said compound comprising from 1 to 3 amino groups, said amino groups being primary and/or secondary;
preferably, the compound comprising 1 to 3 amino groups is a diamine and/or a triamine, preferably for example one or more of 1, 2-ethylenediamine, hydroxyethylethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), N-aminoethylpiperazine, 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane and diethylenetriamine, adipic acid dihydrazide, hydrazine hydrate; more preferably one or more of isophorone diamine, hydroxyethyl ethylenediamine, N-aminoethylpiperazine.
The aqueous polyurethane dispersion of the invention comprises 30 to 70 weight percent, preferably 40 to 50 weight percent of solid content, and the rest is water; the average particle diameter is usually from 100 to 300nm, preferably from 150 to 250nm.
The pH of the aqueous polyurethane dispersion is from 4 to 11, preferably from 7 to 9.
The invention also provides a preparation method of the aqueous polyurethane dispersion, which comprises the following steps:
1) Mixing the components a), b), c) and a solvent, and reacting under the protection of inert gas until the reaction mixture reaches the theoretical isocyanate content to obtain an isocyanate-terminated prepolymer;
2) Adding a solvent into the isocyanate-terminated prepolymer for dilution, then adding components d) and f) for chain extension reaction, and adding water into the mixture to disperse after the chain extension reaction is completed, so as to obtain an aqueous polyurethane dispersion 1;
3) Adding a solvent-dissolved component e) into the aqueous polyurethane dispersion 1 for chain extension reaction, and then removing the solvent by reduced pressure distillation to obtain the aqueous polyurethane dispersion.
In the preparation method of the present invention, in the steps 1) to 3), the solvent is a solvent which can be partially or completely removed by distillation during or after the dispersion, and the solvent is one or more selected from acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, 1-methyl-2-pyrrolidone, preferably acetone and/or butanone, more preferably acetone; the solvents in step 1) and step 2) may be the same or different;
Preferably, the solvent is added in step 1) in an amount of 0.05 to 0.3 times, preferably 0.1 to 0.2 times the total mass of the solids added in step 1) (i.e., the sum of the masses of components a) to c); the addition amount of the solvent in the step 2) is 1 to 3 times, preferably 1.2 to 2.2 times of the total mass of the solid matters added in the step 1); in step 3), the acetone-soluble component e) is present in a concentration of 20 to 30% by weight.
In the preparation method, in the step 1), the reaction temperature is 70-90 ℃, preferably 75-85 ℃; the time is 1 to 3 hours, preferably 1.5 to 2.5 hours; the reaction is carried out under the protection of an inert gas, preferably nitrogen. The conversion is generally monitored by tracking the NCO content of the reaction mixture. For this purpose, spectroscopic measurements (e.g. infrared or near infrared spectra, refractive index determination) and chemopotentiometric titration (e.g. chemotitration of the sample taken) can be carried out, preferably chemopotentiometric titration.
The preparation process according to the invention, step 1), wherein the reaction is carried out under the action of a catalyst known to the person skilled in the art for accelerating the NCO and OH reaction, selected from triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, dibutyltin oxide, tin dioctanoate or dibutyltin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate, bismuth 2-ethylhexanoate, preferably bismuth neodecanoate, bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate;
Preferably, the catalyst is used in an amount of 0.003 to 0.03% by weight based on the total mass of components a), b) and c).
In the preparation method, in the step 2), the chain extension reaction is carried out at the temperature of 30-50 ℃, preferably 35-45 ℃; the time is 1 to 30min, preferably 10 to 15min.
In the preparation method, in the step 2), after the water is added and dispersed, the solid content of the aqueous polyurethane dispersion 1 is 40-50% (based on the mass of water and solid matters).
In the preparation method, in the step 3), the chain extension reaction is carried out at room temperature for 1-30 min, preferably 5-10 min.
In the preparation method, in the step 3), the vacuum degree is 0.07-0.1 MPa and the temperature is 35-55 ℃.
The invention also provides application of the aqueous polyurethane dispersion, and the aqueous polyurethane dispersion can be matched with a curing agent to be used in the fields of adhesives, sealants and the like. According to the application, the invention provides a bi-component spray adhesive, which comprises the following components in parts by weight:
component A): 100 parts of aqueous polyurethane dispersion;
component B): 4-10 parts of curing agent, preferably 6-8 parts.
In the spray glue, the aqueous polyurethane dispersion is the aqueous polyurethane dispersion disclosed by the invention or prepared by the method disclosed by the invention.
In the glue spraying process of the invention,the curing agent is selected from salt solution containing metal ions, preferably CaCl with concentration of 2-5 wt% 2 Aqueous solutions and/or ZnSO 4 An aqueous solution.
When the two-component spray glue is used, the component A containing the aqueous polyurethane dispersion is sprayed on a base material and then sprayed with the component B, or two A, B components are sprayed on the base material simultaneously by using a two-component spray gun.
The bi-component spray adhesive is suitable for soft materials such as sponge, leather, cloth art and the like in soft material industry, and can be used in furniture industry such as mattresses, sofas, swivel chairs, pillows and the like; and is also widely applied to the manufacturing industry of vehicles such as automobile interiors, aviation, high-speed rail seats and the like.
According to the aqueous polyurethane dispersion, a certain amount of amine compounds with long carbon chain flexible structures are introduced into polyurethane side chains, the amine compounds have three amino groups, the amine compounds can react with NCO at the tail end of a polyurethane chain segment to play a role of a chemical crosslinking point, the heat resistance of a sample is improved, meanwhile, the introduction of a long carbon chain structure also increases the flexibility of the polyurethane chain segment, plasticizes the chain segment, the Tg is reduced, the viscosity maintenance time is prolonged, secondary bonding can be realized, the hand feeling of bonded materials is softer, and the problems of accelerator migration, heat resistance reduction and the like caused by the addition of a plasticizer into the existing aqueous polyurethane are avoided. Meanwhile, the addition amount of the amine compound needs to be controlled within the range of the invention, and the addition amount is too little, so that the heat resistance, the maintenance viscosity and the hand feeling of the material after bonding are not obviously improved, otherwise, the addition amount is too much, and the crystallization type of the polyurethane chain segment is damaged due to the increase of the flexible chain segment, so that the heat resistance is obviously reduced.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the water dispersion can be immediately bonded after being sprayed on a substrate together with the water-based curing agent, and the bonding strength is high;
2. the aqueous dispersion is sprayed on a substrate together with the aqueous curing agent, has good viscosity, can be bonded for the second time, has soft hand feeling and good heat resistance, and is particularly suitable for soft substrates such as sponge, leather, cloth and the like;
3. when the aqueous polyurethane dispersion is used, a compound plasticizer is not needed, and the influence caused by plasticizer migration is avoided.
Detailed Description
The technical scheme of the invention is further described below by combining the embodiments.
The main raw materials of the embodiment of the invention are as follows, and unless specified, the main raw materials are common raw materials purchased from the market:
component a):
polyester polyol I: poly (1, 4-butanediol adipate) glycol, M n =2000 g/mol, a melting temperature of 40 to 50℃as measured by differential scanning calorimetry at a heating rate of 20K/min according to DIN65467Wanhua chemistry);
polyester polyol II: poly (1, 4-butanediol adipate) glycol, M n =3000 g/mol, a melting temperature of 50-60℃measured by differential scanning calorimetry at a heating rate of 20K/min according to DIN65467 Wanhua chemistry);
polyester polyol III: poly (1, 6-hexanediol carbonate) diol having Mn=2000 g/mol and a melting temperature of 40 to 50℃as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/minEastern japan;
polyester polyol IV: polycaprolactone diol, mn=2000 g/mol, a melting temperature of 40-50 ℃ (PCL 220, japanese cellophane) measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min;
component b):
polyester polyol v: poly (diethylene glycol adipate) glycol, M n Melting temperature measured by differential scanning calorimetry at a heating rate of 20K/min according to DIN 65467-50 to-40℃ =2000 g/molWanhua chemistry);
polyester polyol vi: hexadiol neopentyl glycol ester diol of polyadipic acid, M n Melting temperature measured by differential scanning calorimetry at a heating rate of 20K/min according to DIN65467 of 20-30 ℃ (CMA 654, huamain chemistry) =1500 g/mol;
polyester polyol vii: poly (neopentyl glycol adipate) glycol, M n Melting temperature measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min of-45 to-35 ℃, (PNA 2000, warrior chemistry);
polyester polyol VIII: 1, 6-hexanediol phthalate, M n =2000 g/mol, a melting temperature of-30 to-20 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min (PH-56, spandex Stepan, usa);
polyether polyol I: polyoxypropylene ether diol, M n An amorphous polyol having a melting temperature of-60 to-50 c measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min =2000 g/mol,wanhua chemistry);
component c):
polyisocyanate I: hexamethylene diisocyanateWanhua chemistry);
polyisocyanate II: isophorone diisocyanateWanhua chemistry);
component d):
n- (2-aminoethyl) -2-aminoethane sulfonate:EVONIK, USA);
n- (2-aminoethyl) -B-alanine monosodium salt: (Shanghai Source leaf Biotechnology Co., ltd.); component e):
amine compound a: the preparation method comprises the steps of adding 10.3g of diethylenetriamine and 15.4g of dodecanol methacrylate into a three-necked flask, adding 520g of 1, 4-dioxane as a solvent, adding 16g of triethylamine as alkali, heating to 80 ℃ for reaction for 4 hours, recovering to room temperature, and distilling under reduced pressure to evaporate required components to obtain an amino compound A, wherein the structural formula is as follows:
for amino compounds A 1 HNMR, various hydrogen bond chemical shifts δh (300 mhz, cdcl) 3 ) The attribution of (2) is expressed as follows: a (0.88 ppm, t, 3H), b (1.19 ppm, d, 3H), c (1.26 ppm, m, 6H), d (1.29 ppm, m, 8H), e (1.31 ppm, m, 2H), f (1.43 ppm, m, 2H), g (1.62 ppm, m, 2H), h (2.49 ppm, m, 1H), i (2.52 ppm, m, 2H), j (2.62 ppm, m, 2H), k (2.66 ppm, m, 4H), l (4.08 ppm, t, 1H);
amine compound B: the preparation method comprises the steps of adding 10.3g of diethylenetriamine and 18.7g of hexadecyl methacrylate into a three-neck flask, adding 520g of 1, 4-dioxane as a solvent, adding 16g of triethylamine as alkali, heating to 80 ℃ for reaction for 4 hours, recovering to room temperature, and distilling under reduced pressure to evaporate required components to obtain an amino compound B, wherein the structural formula is as follows:
for amino compounds B 1 HNMR, various hydrogen bond chemical shifts δh (300 mhz, cdcl) 3 ) The attribution of (2) is expressed as follows: a (0.88 ppm, t, 3H), b (1.19 ppm, d, 3H), c (1.26 ppm, m, 14H), d (1.29 ppm, m, 8H), e (1.31 ppm, m, 2H), f (1.43 ppm, m, 2H), g (1.62 ppm, m, 2H), h (2.49 ppm, m, 1H), i (2.52 ppm, m, 2H), j (2.62 ppm, m, 2H), k (2.66 ppm, m, 4H),l(2.77ppm，t，1H),m(3.02ppm，d，1H),n(4.08ppm，t，2H)。
amino compound C: the preparation method comprises the steps of adding 10.3g of diethylenetriamine and 14.7g of butyl methacrylate into a three-neck flask, adding 520g of 1, 4-dioxane as a solvent, adding 16g of triethylamine as alkali, heating to 80 ℃ for reaction for 4 hours, recovering to room temperature, and distilling under reduced pressure to evaporate required components to obtain an amino compound C, wherein the structural formula is as follows:
For amino compounds C 1 HNMR, various hydrogen bond chemical shifts δh (300 mhz, cdcl) 3 ) The attribution of (2) is expressed as follows: a (0.90 ppm, t, 3H), b (1.19 ppm, d, 3H), c (1.45 ppm, m, 2H), d (1.62 ppm, m, 2H), e (2.49 ppm, m, 1H), f (2.52 ppm, m, 2H), g (2.62 ppm, m, 2H), h (2.66 ppm, m, 4H), i (2.77 ppm, t, 2H), j (4.08 ppm, t, 2H).
Amino compounds A-C 1 HNMR test method: bruker AC-400FT nuclear magnetic resonance tester; under test conditions of 300MHz using CDCl 3 To test the solvent, 7.26ppm hydrogen spectrum was scaled 77.16ppm carbon spectrum.
Component f):
isophorone diamine: (IPDA, vancomic chemistry);
hydroxyethyl ethylenediamine: (AEEA, euphorbia hirta BASF);
n-aminoethylpiperazine: (AEP, shanghai Michael chemical Co., ltd.).
Example 1
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 200g of polyester polyol I, 80g of polyester polyol V, 38g of isocyanate I, 0.019g of bismuth neodecanoate and 38g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring to react, NCO% is measured every 1h by sampling, and after 3h until the NCO% reaches below 2.03% of theoretical content, the reaction is stopped, so that an isocyanate-terminated prepolymer is obtained.
2) IsocyanideThe temperature of the acid ester end-capped prepolymer is reduced to about 60 ℃, 471g of acetone is added, the mixture is stirred, mixed and dissolved for 5min, and then 3g of isophorone diamine, 2g of N-aminoethylpiperazine and 5.7g of isophorone diamine are addedCarrying out chain extension reaction on the mixed solution with 43g of deionized water for 15min at 45 ℃, pouring the mixed solution into a dispersing cup, and adding 407g of water under high-speed shearing at 1500rpm to obtain aqueous polyurethane dispersion 1;
3) 7.5g of the amine-based compound A was dissolved with 30g of acetone, added to the aqueous polyurethane dispersion 1 and stirred for 10 minutes, and the acetone therein was removed by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 182nm as measured by laser correlation in the dispersed phase and a pH of 7.3.
Example 2
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 240g of polyester polyol I, 80g of polyester polyol VII, 38g of isocyanate I, 0.021g of bismuth neodecanoate, 43g of acetone and 80 ℃ are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring for reaction, NCO% is measured every 1h by sampling, and after 3h until NCO% reaches below 1.39% of theoretical content, the reaction is stopped, so that an isocyanate-terminated prepolymer is obtained.
2) The isocyanate-terminated prepolymer was cooled to about 60℃and added with 530g of acetone and stirred, mixed and dissolved for 5min, followed by the addition of 2.5g of isophorone diamine, 0.2g of N-aminoethylpiperazine and 5.7g Reacting with 34g deionized water for 15min at 45 ℃, pouring into a dispersing cup, and adding 468g of water under high-speed shearing at 1500rpm to obtain aqueous polyurethane dispersion 1;
3) 6g of the amine-based compound A was dissolved with 24g of acetone, and the mixture was stirred for 10 minutes in aqueous polyurethane dispersion 1, and the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 195nm as measured by laser correlation in the dispersed phase and a pH of 7.7.
Example 3
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 288g of polyester polyol I, 72g of polyester polyol VI, 35g of isocyanate I, 10g of isocyanate II, 0.024g of bismuth neodecanoate and 65g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring, and the mixture is reacted at 75 ℃, and after sampling and measuring NCO% every 1 hour, the reaction is stopped until NCO% reaches below 1.10% of theoretical content, so as to obtain the isocyanate-terminated prepolymer.
2) The isocyanate end capped prepolymer is cooled to about 60 ℃, 624g of acetone is added, stirred, mixed and dissolved for 5min, then 0.2g of hydroxyethyl ethylenediamine and 6.8g of acetone are addedWith 28g of deionized mixture, reacted at 45℃for 15 minutes, poured into a dispersing cup, and 471g of water was added under high-speed shearing at 1500rpm to obtain aqueous polyurethane dispersion 1.
3) 8g of amino compound A is dissolved by 32g of acetone, added into aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 222nm as determined by laser correlation in the dispersed phase and a pH of 7.1.
Example 4
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 220g of polyester polyol II, 110g of polyester polyol VIII, 23g of isocyanate I, 12g of isocyanate II, 0.022g of bismuth neodecanoate and 62g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring for reaction, NCO% is measured every 1h by sampling, and after 3h until NCO% reaches below 1.23% of theoretical content, the reaction is stopped, so that isocyanate-terminated prepolymer is obtained.
2) Cooling the isocyanate-terminated prepolymer to about 60 ℃, adding 668g of acetone, stirring, mixing and dissolving for 5min, and then adding 1.6g of hydroxyethyl ethylenediamine and 6.6gWith 33g of the deionized mixture, reacted at 45℃for 15 minutes, poured into a dispersing cup, and 368g of water was added under high-speed shearing at 1500rpm to obtain an aqueous polyurethane dispersion 1.
3) 6.4g of amino compound B is dissolved by 25.6g of acetone, added into the aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 48% by weight and an average particle diameter of 217nm as determined by laser correlation in the dispersed phase and a pH of 7.4.
Example 5
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 200g of polyester polyol III, 110g of polyether polyol I, 27g of isocyanate I, 12g of isocyanate II, 0.021g of bismuth neodecanoate and 52g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring for reaction at 80 ℃, NCO% is measured by sampling every 1h, and after 3h until the NCO% reaches below 1.25% of theoretical content, the reaction is stopped to obtain isocyanate-terminated prepolymer
2) The isocyanate-terminated prepolymer is cooled to about 60 ℃, 646g of acetone is added for stirring, mixing and dissolving for 5min, then 0.5g of hydroxyethyl ethylenediamine and a mixed solution of 8.5g N- (2-amino ethyl) -B alanine monosodium salt and 36g of deionized water are added for reaction for 10min at 45 ℃, poured into a dispersing cup, and 396g of water is added under high-speed shearing at 1500rpm, thus obtaining the aqueous polyurethane dispersion 1.
3) 7g of amino compound B is dissolved by 28g of acetone, added into the aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 214nm as determined by laser correlation in the dispersed phase and a pH of 7.4.
Example 6
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 190g of polyester polyol II, 140g of polyether polyol I, 23g of isocyanate I, 12g of isocyanate II, 0.022g of bismuth neodecanoate and 55g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring for reaction, NCO% is sampled and measured every 1 hour until NCO% reaches below 1.15% of theoretical content, and the reaction is stopped to obtain isocyanate-terminated prepolymer.
2) The isocyanate-terminated prepolymer is cooled to about 60 ℃, 675g of acetone is added, stirred, mixed and dissolved for 5min, then 2.5g of isophorone diamine and 6.6g of isophorone diamine are addedReacting with 36g deionized water mixture at 45 ℃ for 15min; into a dispersion cup, 417g of water was added under high shear at 1500rpm to give aqueous polyurethane dispersion 1.
3) 6g of amino compound B is dissolved by 24g of acetone, added into the aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 235nm as determined by laser correlation in the dispersed phase and a pH of 7.8.
Example 7
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) Into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 300g of polyester polyol IV, 60g of polyether polyol I, 37g of isocyanate I, 4g of isocyanate II, 0.024g of bismuth neodecanoate and 60g of acetone are added for reaction, NCO is sampled and measured every 1h, until NCO% reaches below the theoretical content of 1.06%, and the reaction is stopped, so that an isocyanate-terminated prepolymer is obtained.
2) Cooling the isocyanate-terminated prepolymer to about 60 ℃, adding 742g of acetone, stirring, mixing and dissolving for 5min, then adding a mixed solution of 0.6g of N-aminoethylpiperazine and 9g N- (2-aminoethyl) -B alanine monosodium salt and 38g of deionized water, and reacting for 15min at 45 ℃; into a dispersion cup, 458g of water was added under high shear at 1500rpm to give aqueous polyurethane dispersion 1.
3) Dissolving 5g of an amino compound B with 20g of acetone, adding the solution into the aqueous polyurethane dispersion 1, and stirring for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 214nm as determined by laser correlation in the dispersed phase and a pH of 7.6.
Example 8
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 220g of polyester polyol II, 110g of polyester polyol VIII, 23g of isocyanate I, 15g of isocyanate II, 0.022g of bismuth neodecanoate and 63g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring to react at the temperature of 85 ℃, NCO% is sampled and measured every 1h, and after 3h until NCO% reaches below the theoretical content of 1.49%, the reaction is stopped, so that the isocyanate-terminated prepolymer is obtained.
2) The isocyanate end capped prepolymer is cooled to about 60 ℃, 673g of acetone is added, stirred, mixed and dissolved for 5min, and then 5.7g of acetone is addedWith 23g of the deionized mixture, reacted at 45℃for 15 minutes, poured into a dispersing cup, and 386g of water was added under high-speed shearing at 1500rpm to obtain an aqueous polyurethane dispersion 1.
3) 11g of amino compound A is dissolved by 44g of acetone, added into aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 234nm as determined by laser correlation in the dispersed phase and a pH of 7.3.
Example 9
The preparation method of the aqueous polyurethane dispersion comprises the following steps:
1) 220g of polyester polyol II, 110g of polyester polyol VIII, 23g of isocyanate I, 15g of isocyanate II, 0.022g of bismuth neodecanoate and 63g of acetone are added into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring to react at the temperature of 85 ℃, NCO% is sampled and measured every 1h, and after 3h until NCO% reaches below the theoretical content of 1.49%, the reaction is stopped, so that the isocyanate-terminated prepolymer is obtained.
2) Isocyanate-terminated prepolymersCooling to 60deg.C, adding 673g acetone, stirring, mixing and dissolving for 5min, adding 5g isophorone diamine, 1g N-aminoethylpiperidine, and 5.7gWith 47g of the deionized mixture, reacted at 45℃for 15 minutes, poured into a dispersing cup, and 404g of water was added under high-speed shearing at 1500rpm to obtain an aqueous polyurethane dispersion 1.
3) 2.5g of amino compound A is dissolved by 10g of acetone, added into aqueous polyurethane dispersion 1 and stirred for 10min; the acetone was removed therefrom by distillation under reduced pressure to give an aqueous polyurethane dispersion having a solids content of 45% by weight and an average particle diameter of 223nm as determined by laser correlation in the dispersed phase and a pH of 7.4.
Comparative example 1
The procedure for the preparation of an aqueous polyurethane dispersion, reference example 1, differs from example 1 only in that 200g of polyester polyol I and 80g of polyester polyol V were replaced by 280g of polyester polyol I in step 1) to give an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 193nm as determined by laser correlation in the disperse phase and a pH value of 7.2.
Comparative example 2
The procedure for the preparation of an aqueous polyurethane dispersion, reference example 2, differs from example 2 only in that 240g of polyester polyol I and 80g of polyester polyol VII were replaced by 320g of polyester polyol VII in step 1), giving an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 207nm as determined by laser correlation in the disperse phase and a pH value of 7.3.
Comparative example 3
Preparation of an aqueous polyurethane dispersion the procedure is as described in example 1, with reference to example 1, except that the aqueous polyurethane dispersion 1 obtained in step 2) is used, the acetone therein is removed by distillation under reduced pressure, an aqueous polyurethane dispersion is obtained having a solids content of 42% by weight and an average particle diameter of 203nm as determined by laser correlation in the dispersed phase, and the pH is 7.1
Comparative example 4
The procedure for the preparation of an aqueous polyurethane dispersion, reference example 1, differs from example 1 only in that in step 3) the amino compound A is replaced by cetyl methacrylate, giving an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 189nm in the dispersed phase, determined by laser correlation, and a pH value of 7.1.
Comparative example 5
The procedure for the preparation of an aqueous polyurethane dispersion, reference example 1, differs from example 1 only in that in step 3) the amino compound a is replaced by an amino compound C, giving an aqueous polyurethane dispersion having a solids content of 42% by weight and an average particle diameter of 174 as determined by laser correlation in the dispersed phase and a pH value of 7.0.
Adhesive application:
preparing an air compressor, adjusting the pressure to 3Bar, and adjusting the pressure to 1.5mm caliber spray gun, wherein the sponge size is 10 multiplied by 5cm; 200g of each of the emulsions prepared in examples 1 to 7 and comparative examples 1 to 5 was placed in a two-component spray gun emulsion tank as component A, and CaCl having a concentration of 2.5wt% was obtained 2 200g of aqueous solution is placed in a curing agent tank of a two-component spray gun to be used as a component B, the flow rate of two nozzles is regulated by a flowmeter, and the emulsion nozzle and CaCl are controlled 2 The mass ratio of the water solution spouts is 100:7.
Wet tack test:
glue was sprayed evenly onto the sponge surface (about 100g/m 2 ) Folding the sponge in half, examining the wet adhesion, wet tack is classified as A, A + from low to high a++, a+++, a+++ 5 levels, the viscosity of a is the worst and, A++++ tack preferably;
and (3) secondary adhesion test:
glue was sprayed evenly onto the sponge surface (about 100g/m 2 ) Folding the sponge, tearing the sponge, bonding again, standing for 10min, and inspecting the secondary bonding performance according to the bouncing distance of the folded sponge;
adhesive strength:
placing the prepared sponge sample for 30min, uniformly tearing, judging the bonding strength according to whether the sponge is damaged or not, wherein the "material breakage" represents the substrate damage during tearing; "tear" means that the substrate is capable of being torn intact without breakage;
hand feel test:
after the prepared sponge sample is placed for 30min at normal temperature, the hand feeling is tested, and the hand feeling is scored according to the softness degree by 1-5, and the larger the hand feeling number is, the softer the sponge adhesive layer is after being attached;
heat resistance test:
And (3) placing the prepared sponge sample at normal temperature for 30min, and then placing the sponge sample in an oven at 80 ℃ for 8h according to the specific judgment of the bouncing off of the sponge.
Table 1 test of performance of examples and comparative examples
Note that: "free" means that the glue layer is not capable of adhering the substrates together.
As shown in Table 1, the examples of the present invention were superior to comparative examples 1 to 5 in wet adhesion, secondary adhesion, adhesive strength, hand feeling, heat resistance, and had a large practical application value.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the guidance of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (58)

1. An aqueous polyurethane dispersion, characterized in that it is prepared by reacting raw materials comprising the following components:
a) At least one polyester polyol having a melting temperature in the range of 40 to 80 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min;
b) At least one low-crystallinity or non-crystalline polyester polyol and/or low-crystallinity or non-crystalline polyether polyol, said low-crystallinity or non-crystalline polyester polyol meaning a melting temperature of less than 30 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min;
c) At least one polyisocyanate;
d) At least one hydrophilic compound, the hydrophilic group of the hydrophilic compound comprises one or two of an ionic group and a potential ionic group, and the hydrophilic compound contains 2-3 NCO reactive functional groups;
e) At least one C-containing 10 ～C 25 An amine compound of a hydrophobic segment; the C-containing 10 ～C 25 The structure of the amino compound of the hydrophobic chain segment is shown as a formula I:
wherein R is C 10 ～C 25 Alkyl of (a);
the C-containing 10 ～C 25 The amine compound of the hydrophobic chain segment is a product obtained by Michael addition reaction of diethylenetriamine and esters shown in a formula II, wherein the structure of the esters shown in the formula II is expressed as follows:
wherein R is as defined for formula I, Y is H atom or-CH 3 ；
f) Optionally, a compound comprising 1 to 3 amino groups;
the aqueous polyurethane dispersion comprises the following components in percentage by mass based on 100% of the total mass of the solid matters:
50-74 wt% of component a);
component b) 14 to 39 wt.%;
component c) 8.5-12%;
component d) 1.5 to 2.7wt%;
component e) 1 to 2.5 wt.%;
component f) 0 to 2.5 wt.%.
2. The aqueous polyurethane dispersion according to claim 1, characterized in that component d) the ionic groups are selected from carboxylate and/or sulfonate groups; the potential ionic group refers to a functional group with a covalent bond; the NCO-reactive functional group is an amino group.
3. The aqueous polyurethane dispersion according to claim 2, characterized in that the potentially ionic groups are carboxyl and/or sulfonic groups.
4. The aqueous polyurethane dispersion according to claim 1, wherein the composition of the component content based on 100% of the total mass of the solid content contained therein comprises:
55-73 wt% of component a);
16-32 wt% of component b);
component c) 9.5-11%;
component d) 1.7 to 2.5wt%;
component e) 1.5 to 2.2wt%;
component f) 0 to 2wt%;
the total content of components a) to f) is 100% by weight.
5. The aqueous polyurethane dispersion according to claim 1, wherein component a) the polyester polyol has a number average molecular weight of 500 to 10000; and/or
Component b) the low crystallinity or non-crystalline polyester polyol and/or polyether polyol has a number average molecular weight of 500 to 10000.
6. The aqueous polyurethane dispersion according to claim 5, wherein component a) the polyester polyol is one or more of a diol, a triol, a tetraol having a number average molecular weight of 1000 to 5000.
7. The aqueous polyurethane dispersion according to claim 6, wherein the polyester polyol is one or more of a polyester polyol of the polyadipic acid series, a polycarbonate polyol, and a polycaprolactone polyol having a number average molecular weight of 2000 to 4000 and a functionality of 2.
8. The aqueous polyurethane dispersion according to claim 7, wherein the polyester polyol has a number average molecular weight of poly (1, 4-butylene adipate) glycol.
9. The aqueous polyurethane dispersion according to claim 5, wherein component b) the low-crystallinity or non-crystalline polyester polyol and/or polyether polyol has a number average molecular weight of from 1000 to 4000.
10. The aqueous polyurethane dispersion according to claim 9, wherein the low crystallinity or non-crystalline polyester polyol and/or polyether polyol is a diol and/or triol having a number average molecular weight of 1000 to 3000.
11. The aqueous polyurethane dispersion according to claim 10, characterized in that the low crystallinity or non-crystalline polyester polyol is one or more of a polyadipic acid series polyester polyol, a polybenzic acid series polyester polyol, a polycarbonate polyol having a number average molecular weight of 1000 to 3000 and a melting temperature of less than 30 ℃ as measured by differential scanning calorimetry according to DIN65467 at a heating rate of 20K/min.
12. The aqueous polyurethane dispersion according to claim 11, wherein said low crystallinity or non-crystalline polyester polyol is one or more of poly (hexanediol neopentyl glycol adipate) diol, poly (neopentyl glycol adipate) diol, 1, 6-hexanediol phthalate.
13. The aqueous polyurethane dispersion according to claim 11, wherein the low crystallinity or non-crystalline polyester polyol is a linear polyester diol or a slightly branched polyester diol, obtained by dehydration condensation of a carboxylic acid and/or anhydride selected from one or more of succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride; the polyalcohol is selected from one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol and 1, 12-dodecanediol.
14. The aqueous polyurethane dispersion according to claim 11, wherein said low crystallinity or non-crystalline polycarbonate polyol is prepared by reacting a diol selected from the group consisting of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and a carbonate selected from the group consisting of diaryl carbonates, dialkyl carbonates.
15. The aqueous polyurethane dispersion according to claim 14, wherein the diaryl carbonate is diphenyl carbonate.
16. The aqueous polyurethane dispersion according to claim 14, wherein the dialkyl carbonate is dimethyl carbonate.
17. The aqueous polyurethane dispersion according to claim 14, wherein the low crystallinity or amorphous polycarbonate polyol is a polycarbonate polyol prepared by reacting 1, 5-pentanediol with dimethyl carbonate.
18. The aqueous polyurethane dispersion according to claim 10, wherein the polyether polyol is a polyaddition product of styrene oxide or a polyaddition product of one or more of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin as monomers; or polyether polyols obtained by polycondensation of polyols or mixtures thereof; or polyether polyols obtained by alkoxylation of polyols, amines and amino alcohols.
19. The aqueous polyurethane dispersion according to claim 18, wherein the polyether polyol is a polyoxyethylene polyol or a polyoxypropylene polyol.
20. The aqueous polyurethane dispersion according to claim 19, wherein the polyether polyol is polyoxypropylene ether glycol.
21. The aqueous polyurethane dispersion according to claim 1, characterized in that component c) the polyisocyanate is selected from aromatic, aliphatic or cycloaliphatic polyisocyanates; and/or
The hydrophilic compound of the component d) is a compound simultaneously containing 2-3 NCO reactive groups and at least one ionic or potential ionic group; and/or
Component f) the compound containing 1 to 3 amino groups, wherein the amino groups are primary amino groups and/or secondary amino groups.
22. The aqueous polyurethane dispersion according to claim 21, wherein component c) the polyisocyanate is selected from one or more of aromatic, aliphatic, cycloaliphatic isocyanates having two isocyanate groups.
23. The aqueous polyurethane dispersion according to claim 22, wherein the polyisocyanate is diisocyanate Y (NCO) 2 Wherein Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic group having 6 to 15 carbon atomsHydrocarbyl or divalent araliphatic hydrocarbon radicals containing 7 to 15 carbon atoms.
24. The aqueous polyurethane dispersion according to claim 23, characterised in that the diisocyanate is selected from one or more of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexanediisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-benzenediisocyanate, 2, 4-toluylene diisocyanate, 2, 6-toluylene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, para-xylylene diisocyanate.
25. The aqueous polyurethane dispersion according to claim 23, wherein the diisocyanate is a mixture of aliphatic and cycloaliphatic diisocyanates.
26. The aqueous polyurethane dispersion according to claim 25, characterised in that said diisocyanate is a mixture of hexamethylene diisocyanate with one or more of 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate.
27. The aqueous polyurethane dispersion according to claim 21, wherein component d) the hydrophilic compound is di-or tri-sulfamic acid, di-or tri-aminocarboxylic acid or a salt thereof.
28. The aqueous polyurethane dispersion according to claim 27, wherein the hydrophilic compound is N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -B-alanine, or an alkali metal or ammonium salt of the above compound.
29. The aqueous polyurethane dispersion according to claim 21, wherein when component d) is a potentially ionic compound, a neutralizing agent is added, said neutralizing agent being selected from one or more of alkali metal compounds, alkaline earth metal compounds.
30. The aqueous polyurethane dispersion according to claim 29, wherein the neutralizing agent is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide or calcium hydroxide.
31. The aqueous polyurethane dispersion according to claim 21, characterized in that component f) the compound containing 1 to 3 amino groups is a diamine and/or a triamine.
32. The aqueous polyurethane dispersion according to claim 31, characterised in that the compound comprising 1 to 3 amino groups is one or more of 1, 2-ethylenediamine, hydroxyethyl ethylenediamine, 1, 6-hexamethylenediamine, isophoronediamine, N-aminoethylpiperazine, 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane and diethylenetriamine, adipic acid dihydrazide, hydrazine hydrate.
33. The aqueous polyurethane dispersion according to claim 1, wherein the esters of formula ii comprise one or more of acrylic acid esters and methacrylic acid esters.
34. The aqueous polyurethane dispersion according to claim 33, wherein the esters of formula II are dodecyl methacrylate and/or hexadecyl methacrylate.
35. The aqueous polyurethane dispersion according to claim 1, wherein component e) the C-containing component 10 -C 25 The preparation process of amino compound with hydrophobic chain segment includes the steps ofMixing ethylene triamine, esters shown in a formula II, alkali and a solvent, heating and carrying out Michael addition reaction.
36. The aqueous polyurethane dispersion according to claim 35, wherein the molar ratio of diethylenetriamine to esters of formula ii is 1:0.4 to 0.7.
37. The aqueous polyurethane dispersion according to claim 36, wherein the molar ratio of diethylenetriamine to esters of formula ii is 1:0.5 to 0.66.
38. The aqueous polyurethane dispersion according to claim 35, wherein the base is selected from triethylamine, sodium ethoxide, sodium hydride, sodium amide, and the amount of the base is 1.5 to 2.5 times the mass of diethylenetriamine.
39. The aqueous polyurethane dispersion according to claim 35, wherein the solvent is selected from dioxane, tetrahydrofuran, methyl tertiary butyl ether; the solvent dosage is 50-100 times of the mass of the diethylenetriamine.
40. The aqueous polyurethane dispersion according to claim 35, wherein the michael addition reaction temperature is 50-80 ℃ for a period of 2-4 hours.
41. The aqueous polyurethane dispersion of claim 40, wherein the Michael addition reaction temperature is 65 to 75℃for a period of 3 to 4 hours.
42. The aqueous polyurethane dispersion according to claim 1, characterized in that it comprises a solids content of 30 to 70% by weight, the remainder being water; the average grain diameter is 100-300 nm;
the pH value of the aqueous polyurethane dispersion is 4-11.
43. The aqueous polyurethane dispersion according to claim 42, wherein the aqueous polyurethane dispersion contains 40 to 50% by weight of solids and the remainder is water.
44. The aqueous polyurethane dispersion of claim 42, wherein the average particle size is 150 to 250nm.
45. The aqueous polyurethane dispersion of claim 42, wherein the pH of the aqueous polyurethane dispersion is from 7 to 9.
46. A process for preparing an aqueous polyurethane dispersion according to any one of claims 1 to 45, comprising the steps of:
1) Mixing the components a), b), c) and a solvent, and reacting under the protection of inert gas until the reaction mixture reaches the theoretical isocyanate content to obtain an isocyanate-terminated prepolymer;
2) Adding a solvent into the isocyanate-terminated prepolymer for dilution, then adding components d) and f) for chain extension reaction, and adding water into the mixture to disperse after the chain extension reaction is completed, so as to obtain an aqueous polyurethane dispersion 1;
3) Adding a solvent-dissolved component e) into the aqueous polyurethane dispersion 1 for chain extension reaction, and then removing the solvent by reduced pressure distillation to obtain the aqueous polyurethane dispersion.
47. The process according to claim 46, wherein in steps 1) to 3), the solvent is a solvent which can be partially or completely removed by distillation during or after the dispersion, and the solvent is one or more selected from the group consisting of acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, 1-methyl-2-pyrrolidone; the solvents in step 1) and step 2) may be the same or different; and/or
In the step 1), the reaction temperature is 70-90 ℃ and the reaction time is 1-3 h; the reaction is carried out under the protection of inert gas or under the protection of nitrogen;
the reaction is carried out under the action of a catalyst, wherein the catalyst is selected from triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, dibutyl tin oxide, tin dioctanoate or dibutyl tin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate and bismuth 2-ethylhexanoate; and/or
In the step 2), the chain extension reaction is carried out at the temperature of 30-50 ℃ for 1-30 min; and/or
In the step 3), the chain extension reaction is carried out at room temperature for 1-30 min;
the vacuum degree is 0.07-0.1 MPa, and the temperature is 35-55 ℃.
48. The process according to claim 47, wherein the solvent is added in the amount of 0.05 to 0.3 times the total mass of the solid matters added in the step 1); the addition amount of the solvent in the step 2) is 1 to 3 times of the total mass of the solid matters added in the step 1); in step 3), the concentration of the solvent-dissolved component e) is 20 to 30wt%.
49. The process according to claim 48, wherein the solvent is added in the amount of 0.1 to 0.2 times the total mass of the solid matters added in the step 1).
50. The process according to claim 48, wherein the solvent is added in the amount of 1.2 to 2.2 times the total mass of the solid matters added in the step 1) in the step 2).
51. The process of claim 47, wherein in step 1), the reaction temperature is 75 to 85℃and the time is 1.5 to 2.5 hours.
52. The process of claim 47 wherein the catalyst is used in an amount of 0.003 to 0.03% of the total mass of components a), b) and c).
53. The process of claim 47, wherein in step 2), the chain extension is carried out at a temperature of 35 to 45℃for a period of 10 to 15 minutes.
54. The process of claim 47, wherein in step 3), the chain extension reaction is carried out for a period of time ranging from 5 to 10 minutes.
55. The bi-component spray adhesive is characterized by comprising the following components in parts by weight:
component A): 100 parts of aqueous polyurethane dispersion;
component B): 4-10 parts of curing agent;
the aqueous polyurethane dispersion is the aqueous polyurethane dispersion of any one of claims 1 to 45 or the aqueous polyurethane dispersion prepared by the method of claims 46 to 54.
56. The two-component spray adhesive of claim 55, wherein the composition comprises, in parts by weight:
component A): 100 parts of aqueous polyurethane dispersion;
component B): 6-8 parts of curing agent.
57. The two-part spray adhesive of claim 55 wherein the curing agent is selected from the group consisting of metal ion containing salt solutions.
58. The two-component spray adhesive of claim 57 wherein the curing agent is 2 to 5 weight percent CaCl 2 Aqueous solutions and/or ZnSO 4 An aqueous solution.
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