WO2020048040A1 - 一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用 - Google Patents

一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用 Download PDF

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WO2020048040A1
WO2020048040A1 PCT/CN2018/121302 CN2018121302W WO2020048040A1 WO 2020048040 A1 WO2020048040 A1 WO 2020048040A1 CN 2018121302 W CN2018121302 W CN 2018121302W WO 2020048040 A1 WO2020048040 A1 WO 2020048040A1
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component
parts
diisocyanate
reaction
polyvinyl acetate
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PCT/CN2018/121302
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English (en)
French (fr)
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王萃萃
刘姗
周天文
周操
张洁
王海梅
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万华化学集团股份有限公司
万华化学（宁波）有限公司
上海万华科聚化工科技发展有限公司
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Publication of WO2020048040A1 publication Critical patent/WO2020048040A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the technical field of vinyl acetate modified aqueous polyurethane resin, and particularly relates to an aqueous polyurethane-polyvinyl acetate resin, and a preparation method and application thereof.
  • Polyvinyl acetate emulsion uses water as the dispersed phase. It has the advantages of low raw material cost, polymerization can be carried out under normal pressure, non-toxic and harmless, and high bonding strength. It is widely used in the field of adhesives.
  • the domestic production of polyvinyl acetate emulsion is second only to urea-formaldehyde resin glue, and it is second in the production and application of adhesives.
  • there are some inherent disadvantages of polyvinyl acetate emulsions such as poor water resistance, cold resistance, and mechanical stability; under wet and hot conditions, its bonding strength will be greatly reduced; poor creep resistance, and long-term load or The adhesive layer is liable to slip under high temperature.
  • those skilled in the art have been working to modify polyvinyl acetate to improve its overall performance, so modified polyvinyl acetate has appeared on the market.
  • Water-based polyurethane adhesive is an adhesive that uses water instead of organic solvents as a dispersion medium. It is safe to use, non-toxic and harmless, and does not pollute the environment.
  • waterborne polyurethane adhesives such as low solid content leading to slow drying speed and high solid content leading to high construction viscosity; these defects severely limit the application of waterborne polyurethane adhesives. Therefore, by modifying it to improve the comprehensive performance of water-based polyurethane adhesives, improve its application effect, and expand its application range, it has become a hot spot in the research of polyurethane industry today.
  • modified polyvinyl acetate is mainly divided into two types: physical modification and chemical modification.
  • the physical modification is to use a mechanical mixing method to uniformly mix the polyurethane aqueous dispersion or the polyvinyl acetate emulsion, but this simple physical blending can easily cause delamination due to the incompatibility of the two phases, leading to co-existence.
  • the mixed emulsion has a short storage period; at the same time, due to the low pH value of polyvinyl acetate, the two tend to produce slag when mixed.
  • Chemical modification is the introduction of polyurethane molecular chains on the polyvinyl acetate molecular chain or the formation of an interpenetrating network structure, so that the modified product not only has the excellent low temperature resistance of polyurethane, but also the excellent adhesion of polyvinyl acetate. ⁇ guests ⁇ Strength.
  • Chinese patent CN106478890A discloses a method for preparing an aqueous polyurethane-polyvinyl acetate hybrid emulsion.
  • a double-bond polyurethane prepolymer monomer is prepared, and then polymerized by a seed emulsion polymerization method.
  • the polymer and vinyl acetate form a mixed reaction system.
  • the polyurethane prepolymer exists as a monomer in the reaction system, and copolymerizes with vinyl acetate, so that the polyurethane monomer can be grafted to the macromolecular chain of polyvinyl acetate. Therefore, the flexibility of the polyvinyl acetate molecular chain is greatly improved.
  • due to the introduction of comonomers into the molecular chain the adhesion performance of this method is reduced; at the same time, the operation of this process is extremely complicated, which brings inconvenience to subsequent production and industrialization.
  • Chinese patent CN 103249751 A discloses a method for preparing a heat-sealable coating. First, an aqueous polyurethane dispersion is prepared, and then the aqueous ethylene vinyl acetate copolymer dispersion is blended in the subsequent coating formulation process.
  • the mixing system can be as low as Films were formed at room temperature. However, since the two dispersions need to be mixed before use, in addition to the cumbersome process, the compatibility or stability of the system may also have problems, and the initial strength is not easy to establish.
  • the blending components used It is an ethylene vinyl acetate emulsion.
  • Chinese patent CN105199455B discloses a method for preparing a general-purpose inkjet coating machine for weak solvent ink printing, which is a method for preparing polyurethane prepolymer and polyether polyol, vinyl acetate monomer, polyurethane catalyst, vinyl acetate initiator, and defoaming. Mixing agent, ultraviolet absorber, and fixing agent, coated on inkjet consumables, and made after curing at high temperature. During the heating process, the polyurethane prepolymer and the polyether polyol react with each other, and the vinyl acetate monomer polymerizes. They form an interpenetrating network structure with each other.
  • the prepared coating has good low-temperature properties and anti-aging properties. However, there is no water dispersion process in this process, which is very different from the preparation process of water-based polyurethane-polyvinyl acetate, and the subsequent construction process is also different.
  • An object of the present invention is to provide an aqueous polyurethane-polyvinyl acetate resin, a method for preparing the same, and applications based on the problems of existing aqueous emulsions of adhesives, and the overall performance of the aqueous polyurethane-polyvinyl acetate resin is excellent. (High solid content, good construction performance); the prepared adhesive has good heat resistance, excellent mechanical properties, good storage stability, and the preparation process is easy to implement.
  • the present invention provides an aqueous polyurethane-polyvinyl acetate resin, which is prepared by reacting raw materials including the following components:
  • chain extender includes an amine chain extender and a sulfonic acid type hydrophilic chain extender containing active hydrogen, wherein the amine chain extender includes a small molecule diamine containing active hydrogen Chain extender
  • the capping agent is a monoamine-based small molecule capping agent
  • the amount of each component is:
  • the diisocyanate-terminated prepolymer of component A) is prepared by using a raw material reaction including the following components:
  • Diisocyanate preferably one or more selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, more preferably One or both of self isophorone diisocyanate and hexamethylene diisocyanate;
  • Polyether diol and / or polyester diol having an average molecular weight of 500-3000 g / mol, preferably 1500-2000 g / mol; preferably selected from polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol , Polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate glycol, polyadipate 1,4-butanediol diol, Among the poly (pentane adipate) neopentyl glycol diols, the poly (1,6-hexanediol adipate) diols, and the poly (pentanediol adipate) 1,6-hexanediol ester diols One or more, more preferably one or two selected from the group consisting of 1,4-butanediol poly adipate and 1,6-hexane
  • the polymerization unit of the olefin ether is propylene oxide and / or ethylene oxide, and more preferably ethylene oxide; among them, the number of ethylene oxide units in each molecule of the polyoxyalkylene ether is preferably 4 to 200, more preferably 12 to 75;
  • component S3 is preferably from Tego Chemie One or more of D-3403, YmerTM N120 from Perstrop, and MPEG1200 from Lotte Korea, more preferably MPEG1200 from Lotte Korea;
  • Catalyst preferably selected from triethylamine, 1,4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, bis- ( One or more of 2-ethylhexanoate) tin, bismuth neodecanoate, and bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate.
  • the sulfonic acid type hydrophilic chain extender (S6) containing active hydrogen is selected from 2- (2-aminoethyl) ) Sodium aminoethanesulfonate, Sodium 2- (2-aminoethyl) aminopropanesulfonate, Sodium 1,4-butanediol-2-sulfonate and Sodium 1,2-dihydroxy-3-propanesulfonate
  • 2- (2-aminoethyl) Sodium aminoethanesulfonate
  • Sodium 2- (2-aminoethyl) aminopropanesulfonate Sodium 1,4-butanediol-2-sulfonate
  • Sodium 1,2-dihydroxy-3-propanesulfonate One or more of these are more preferably sodium 2- (2-aminoethyl) aminoethanesulfonate.
  • the molecular weight of the small molecule diamine chain extender containing active hydrogen is 59-200 g / mol, preferably selected from ethylenediamine, hexamethylene One or more of methyldiamine, pentamethylenediamine, hydroxyethylethylenediamine, isophoronediamine, 4,4-diphenylmethanediamine, and diethanolamine, more preferably From one or both of hydroxyethyl ethylenediamine and isophorone diamine.
  • the amine-based chain extender (S7) further includes a bisamino polyetheramine having a number average molecular weight of 200-600; a specific structure of the bisamino polyetheramine is as follows:
  • the bisamino polyetheramine may be selected from Huntsman's ED Series products are selected from HK-511 and / or ED-600, for example.
  • the monoamine-based small molecule capping agent (S8) of component C) includes a monoamine containing no mercapto group and / or a monoamine containing a mercapto group.
  • the monoamine without mercapto has a molecular weight of 59-200 g / mol, and is more preferably selected from ethylamine, diethylamine, isopropylamine, butylamine, cyclohexylamine, ethanolamine, N-methylethanolamine, One or more of diethanolamine, diisopropanolamine, and 2-propanolamine, and more preferably diethanolamine.
  • the thiol-containing monoamine is cysteamine, and its molecular structure is as follows:
  • the water-based polyurethane-polyvinyl acetate resin provided according to the present invention is preferably based on 100 parts by weight of components A) -C),
  • the amount of S1 is 10.5-16 parts, more preferably 11-13 parts;
  • the amount of S2 is 74-83 parts, more preferably 78-82 parts;
  • the amount of S3 used is 1.7-4 parts, more preferably 2.0-4 parts, even more preferably 2.7-4 parts, even more preferably 3-4 parts;
  • the amount of S4 is 0.002-0.03 parts, more preferably 0.003-0.01 parts;
  • the amount of the sulfonic acid type hydrophilic chain extender (S6) containing active hydrogen is 2.5-5 parts, more preferably 3-4 parts;
  • the amount of the small molecule diamine chain extender containing active hydrogen is 0.1-2 parts, more preferably 0.5-1.6 parts;
  • the amount of the bisamino polyetheramine is 0-2 parts, more preferably 0.3-0.5 parts;
  • the amount of the thiol-free monoamine is 0.05-0.3 parts, more preferably 0.1-0.2 parts;
  • the amount of the mercapto-containing monoamine is 0-0.1 parts, and more preferably 0.02-0.04 parts.
  • the molar ratio of the component S1 to the component S2 is (1.5-2.4): 1, and more preferably (1.5-2): 1.
  • the amount of the vinyl acetate (S9) in component D) is 50-100 parts by weight.
  • the amount of the protective colloid (S10) in component E) is 0.5-1.5% by weight of vinyl acetate.
  • the protective colloid is selected from one or more of polyvinyl alcohol, ethoxyalkylphenol, and urethane-crosslinked 1,2-ethylene glycol, and more preferably polyvinyl alcohol .
  • the amount of the radical initiator (S11) in the component F) is 0.15-0.5% by weight of vinyl acetate.
  • the free radical initiator is composed of an oxidizing agent and a reducing agent
  • the oxidizing agent is preferably selected from the group consisting of ammonia persulfate, sodium persulfate, potassium persulfate, dibenzoyl peroxide, and t-butyl hydrogen peroxide.
  • the reducing agent is preferably one or more selected from the group consisting of insurance powder, white block, sodium bisulfite, and erythorbic acid; more preferably, the radical initiator of component F) is tert-butyl
  • a combination of hydrogen peroxide and powder for example, the mass ratio of the two can be 1: (1-2).
  • the raw material for preparing the water-based polyurethane-polyvinyl acetate resin further includes component G): an organic solvent (S5), and the added amount is component A ) -C) 1-2 times the sum of parts by weight; the organic solvent as component G) is used to dissolve each reaction component when preparing the diisocyanate-terminated prepolymer;
  • the organic solvent is selected from acetone and / or methyl ethyl ketone, and still more preferably acetone.
  • Another object of the present invention is to provide a method for preparing an aqueous polyurethane-polyvinyl acetate resin as described above, including the following steps:
  • step (1) dissolving and diluting the diisocyanate-terminated prepolymer obtained in step (1) to obtain the diisocyanate-terminated prepolymer after dilution;
  • step (3) The product obtained in step (3) is mixed with component E), and then component F) is added to initiate a polymerization reaction to obtain an aqueous polyurethane-vinyl acetate crude emulsion.
  • AMP-95 that is, 2-amino-2-methyl-1-propanol
  • the reaction process conditions for preparing the diisocyanate-terminated prepolymer include: a reaction temperature of 75-85 ° C; and the NCO of the reaction system reaches a theoretical value Stop the reaction at some time.
  • NCO is defined as the mass fraction of isocyanate groups in the sample, expressed in%, and the calculation formula is:
  • M NCO and M OH are respectively the molar amounts of isocyanate and hydroxyl groups in all raw materials of the sample, mol;
  • M is the mass of the sample, g;
  • the component D) is used to dissolve and dilute the diisocyanate-terminated prepolymer;
  • the conditions for the solution and dilution include: a temperature of 50-60 ° C and a time of 5-10min;
  • the component G ) Is an organic solvent, selected from acetone and / or methyl ethyl ketone, preferably acetone; the organic solvent is added in an amount of 1-2 times the sum of parts A) -C) by weight.
  • the chain extension reaction process conditions include: a reaction temperature of 45-50 ° C. and a reaction time of 15-25 min; more preferably, the amount of water in the aqueous solution of the component B) is the component B) 3-5 times the quality;
  • the process conditions for the capping reaction include: a reaction temperature of 45-50 ° C. and a reaction time of 5-10 min; more preferably, the amount of water in the aqueous solution of the component C) is the component C) 3-5 times the quality;
  • the adding condition of the component D) is directly adding after the end-capping reaction, and the adding method is: adding all the components D) at a time or adding a part of the component D) first, and shearing and dispersing to obtain an aqueous polyurethane- After the vinyl acetate mixed emulsion is added, the remaining component D) is added thereto; the aqueous polyurethane-vinyl acetate mixed emulsion swells in component D), and the swelling temperature is 35-45 ° C.
  • component D) when component D) is added in batches, one-half mass of component D) is first added for shear dispersion, and then the remaining one-half mass of component D) is The vinyl acetate mixed emulsion was mixed for swelling. By adding component D) in batches, the stability of the system can be better guaranteed.
  • the protective colloid of the component E) is added for stirring and mixing, and the mixing time is 0.5-1 h; the initiation temperature of the free radical initiator added to the component F) is 35-45 °C, polymerization temperature is 40-45 ° C, polymerization time is 2-3h.
  • the way of removing the solvent is distillation under reduced pressure; for example, the pH of the coarse emulsion can be adjusted by adding the AMP-95 dropwise.
  • the invention also provides the application of the water-based polyurethane-polyvinyl acetate resin as described above or the water-based polyurethane-polyvinyl acetate resin prepared by the preparation method described above as an adhesive.
  • the water-based polyurethane-polyvinyl acetate resin is used in the field of shoe rubber, plastic suction, laminating rubber, and automotive interior rubber.
  • the hydrophilicity of the water-based polyurethane-polyvinyl acetate resin provided by the present invention is mainly achieved by a sulfonic acid-type hydrophilic chain extender (for example, sodium sulfamate) containing active hydrogen, without the need for neutralization and avoiding The odor and VOC from low boiling point neutralizers such as triethylamine have good environmental performance.
  • the sulfonic acid-type hydrophilic chain extender containing active hydrogen uses sodium sulfamate, which is a strong acid and alkali salt, which is not easily hydrolyzed, so that the product has better water resistance.
  • an aqueous polyurethane-polyvinyl acetate interpenetrating network structure is formed, which combines the advantages of water-based polyurethane and polyvinyl acetate, reducing the hydrolyzability of polyvinyl acetate and improving
  • the film-forming property is increased, the compatibility between the two phases is increased, the stability of the emulsion and the initial peel strength of the adhesive are improved.
  • the water-based polyurethane-polyvinyl acetate resin provided by the present invention has high solid content and excellent comprehensive performance by adjusting each component as a reaction raw material;
  • a diamino polyetheramine with a different molecular weight and a different structure than a small molecule diamine chain extender is used as a co-chain extender. Because the molecule contains a hydrophilic group, the The hydrophilic effect is increased, and the slag content in vinyl acetate emulsion polymerization is effectively improved;
  • the use of a monoamine containing a mercapto group as a synergistic end-capping agent not only effectively controls the molecular weight of the PU portion, but also the mercapto group can act as a chain transfer agent during the polymerization of vinyl acetate and also effectively function as a chain transfer agent.
  • a suitable molecular weight has a very positive effect on the performance of the resin applied to the adhesive; for example, the storage stability of the adhesive prepared from the aqueous polyurethane-polyvinyl acetate resin obtained by the present invention Good, excellent mechanical properties (such as peel strength), good heat resistance;
  • an aqueous polyurethane-polyvinyl acetate resin is provided, which is prepared by reacting raw materials including the following components:
  • chain extender includes an amine chain extender and a sulfonic acid type hydrophilic chain extender containing active hydrogen, wherein the amine chain extender includes a small molecule diamine containing active hydrogen Chain extender
  • the capping agent is a monoamine-based small molecule capping agent
  • the amount of each component is:
  • Component D 30-120 parts by weight
  • Component E) component D) 0.4-3% by weight, component D),
  • Component F Component D) 0.1-1.1% by weight, component D),
  • the diisocyanate-terminated prepolymer is prepared by reacting raw materials including the following components:
  • Polyether diol and / or polyester diol having an average molecular weight of 500-3000 g / mol, preferably 1500-2000 g / mol; selected from polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, Polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate glycol, polyadipate 1,4-butanediol diol, polymer One of neopentyl glycol adipate, poly (6-hexanediol adipate), and neopentyl glycol adipate 1,6-hexanediol ester diol One or more, preferably one or two selected from the group consisting of a poly 1,4-butanediol adipate and a 1,6-hexanediol adipate;
  • the polymerization unit of the olefin ether is propylene oxide and / or ethylene oxide, preferably ethylene oxide; wherein the number of ethylene oxide units in each molecule of the polyoxyalkylene ether is 4 to 200, It is preferably 12 to 75;
  • component S3 is preferably a Tego Chemie company One or more of D-3403, YmerTM N120 from Perstrop, and MPEG1200 from Lotte Korea, more preferably MPEG1200 from Lotte Korea;
  • Catalyst selected from triethylamine, 1,4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, bis- (2 -Ethylhexanoate) tin, bismuth neodecanoate, and bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate.
  • the active hydrogen-containing sulfonic acid type hydrophilic chain extender (S6) is selected from sodium 2- (2-aminoethyl) aminoethanesulfonate, 2- ( One or more of 2-aminoethyl) sodium aminopropanesulfonate, sodium 1,4-butanediol-2-sulfonate and sodium 1,2-dihydroxy-3-propanesulfonate, preferably 2 -Sodium (2-aminoethyl) aminoethanesulfonate.
  • the molecular weight of the small molecule diamine chain extender containing active hydrogen is 59-200 g / mol, and is selected from ethylenediamine and hexamethylenediamine. Or one or more of pentamethylenediamine, hydroxyethylethylenediamine, isophoronediamine, 4,4-diphenylmethanediamine, and diethanolamine, preferably selected from hydroxyethylethyl One or two of diamine and isophorone diamine.
  • the amine-based chain extender (S7) further includes a bisamino polyetheramine having a number average molecular weight of 200-600; a specific structure of the bisamino polyetheramine is as follows:
  • the bisamino polyetheramine may be selected from Huntsman's ED Series products are, for example, selected from HK-511 and / or ED-600.
  • a diamine small molecule chain extender containing active hydrogen is mixed with a diamino polyetheramine as an amine chain extender, which can play a synergistic role. Because the molecule contains a hydrophilic group, The hydrophilic effect of the polyurethane segment is increased, and the slag content of the vinyl acetate emulsion polymerization is effectively improved.
  • the monoamine-based small molecule capping agent (S8) of component C) includes a thiol-free monoamine and / or a thiol-containing monoamine.
  • the thiol-free monoamine has a molecular weight of 59-200 g / mol and is selected from the group consisting of ethylamine, diethylamine, isopropylamine, butylamine, cyclohexylamine, ethanolamine, N-methylethanolamine, diethanolamine, and diisocyanate.
  • ethylamine diethylamine
  • isopropylamine butylamine
  • cyclohexylamine ethanolamine
  • ethanolamine N-methylethanolamine
  • diethanolamine diisocyanate.
  • propanolamine and 2-propanolamine more preferably diethanolamine.
  • the thiol-containing monoamine is cysteamine, and its molecular structural formula is as follows:
  • the amount of S1 is 10.5-16 parts, for example, 12 parts, 14 parts, 15 parts, preferably 11-13 parts;
  • the amount of S2 is 74-83 parts, for example, 75 parts, 77 parts, 80 parts, preferably 78-82 parts;
  • the amount of S3 is 1.7-4 parts, for example, 2.0 parts, 2.7 parts, 3.1 parts, 3.5 parts, 3.8 parts, preferably 3-4 parts;
  • the amount of S4 is 0.002-0.03 parts, for example, 0.005 parts, 0.008 parts, 0.012 parts, 0.015 parts, 0.02 parts, 0.025 parts, preferably 0.003-0.01 parts;
  • the weight part of the obtained diisocyanate-terminated prepolymer is equal to the sum of the amounts of the used amounts of the reaction raw materials S1-S4.
  • the amount of the sulfonic acid-type hydrophilic chain extender (S6) containing active hydrogen is 2.5-5 parts, for example, 2.8 parts, 3.1 parts, 3.5 parts, 3.8 parts, 4.3 parts, 4.5 parts Number, preferably 3-4 copies;
  • the amount of the small molecule diamine chain extender containing active hydrogen is 0.1-2 parts, for example, 0.3 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 Number of parts, preferably 0.5-1.6 parts;
  • the amount of the bisamino polyetheramine is 0-2 parts, for example, 0.1 parts, 0.2 parts, 0.6 parts, 0.8 parts, 1 part, 1.5 parts, preferably 0.3-0.5 parts;
  • the amount of the mercapto-free monoamine is 0.05-0.3 parts, for example, 0.06 parts, 0.08 parts, 0.12 parts, 0.15 parts, 0.18 parts, and preferably 0.1-0.2 parts;
  • the amount of the mercapto-containing monoamine is 0-0.1 parts, for example, 0.01 parts, 0.03 parts, 0.05 parts, 0.07 parts, 0.09 parts, and preferably 0.02-0.04 parts.
  • the molar ratio of the component S1 to the component S2 is (1.5-2.4): 1, and more preferably (1.5-2): 1.
  • Such a group distribution ratio is easier to make the prepared adhesive have better Initial strength and initial heat resistance.
  • a thiol-free monoamine is used in combination with a thiol-containing monoamine, and the thiol-containing monoamine acts as a synergistic capping agent, which not only effectively controls the molecular weight of the PU portion, but also the thiol group can be
  • vinyl acetate acts as a chain transfer agent and also effectively controls the molecular weight of polyvinyl acetate.
  • a suitable molecular weight has a positive effect on the application performance of the resin.
  • the amount of the vinyl acetate (S9) in component D) is 50-100 parts by weight.
  • the amount of the protective colloid (S10) in component E) is 0.5-1.5% by weight of vinyl acetate.
  • the protective colloid is selected from one or more of polyvinyl alcohol, ethoxyalkylphenol, and urethane-crosslinked 1,2-ethylene glycol, and is preferably polyvinyl alcohol.
  • the amount of the free radical initiator in component F) is 0.15-0.5% by weight of vinyl acetate; preferably, the free radical initiator is composed of an oxidizing agent and a reducing agent, and the oxidizing agent is preferably selected from ammonia persulfate Or more of sodium persulfate, potassium persulfate, dibenzoyl peroxide, and tert-butyl hydroperoxide; the reducing agent is preferably selected from the group consisting of insurance powder, white block, sodium bisulfite, and isocyanate One or more of ascorbic acid; more preferably, the free radical initiator of component F) is a combination of tert-butyl hydroperoxide and insurance powder; preferably such a combination has a high initiation efficiency as an initiator, which is favorable for polymerization Improved efficiency and elimination of residuals.
  • the raw material for preparing the aqueous polyurethane-polyvinyl acetate resin further includes component G): an organic solvent, the amount of which is 1-2 times the sum of the components A) -C) by weight;
  • the organic solvent is selected from acetone and / or methyl ethyl ketone, and more preferably acetone.
  • Another object of the present invention is to provide a method for preparing an aqueous polyurethane-polyvinyl acetate resin as described above, including the following steps:
  • step (1) dissolving and diluting the diisocyanate-terminated prepolymer obtained in step (1) to obtain the diisocyanate-terminated prepolymer after dilution;
  • step (3) Mix the product obtained in step (3) with component E), and then add component F) to initiate the polymerization reaction to obtain an aqueous polyurethane-vinyl acetate crude emulsion.
  • the reaction process conditions for preparing the diisocyanate-terminated prepolymer include: a reaction temperature of 75-85 ° C .; and stopping the reaction when the NCO of the reaction system reaches a theoretical value.
  • NCO is defined as the mass fraction of isocyanate groups in the sample, expressed in%, and the calculation formula is:
  • M NCO and M OH are respectively the molar amounts of isocyanate and hydroxyl groups in all raw materials of the sample, mol;
  • M is the mass of the sample, g;
  • step (2) component G) is used to dissolve and dilute the diisocyanate-terminated prepolymer.
  • the conditions for the solution and dilution include: temperature is 50-60 ° C, time is 5-10min; component G) is organic
  • the solvent is selected from acetone and / or methyl ethyl ketone, preferably acetone; the organic solvent is added in an amount of 1-2 times the sum of parts by weight of components A) -C).
  • the process conditions of the chain extension reaction include: a reaction temperature of 45-50 ° C. and a reaction time of 15-25 min; the amount of water in the aqueous solution of the component B) is 3% of the mass of the component B) -5 times; the aqueous solution of component B) described herein may refer to first mixing an amine chain extender and a sulfonic acid type hydrophilic chain extender (S6) containing active hydrogen to obtain a mixture, and then using it Dilute with deionized water to obtain an aqueous solution containing a mixture of component S7 and component S6;
  • S6 sulfonic acid type hydrophilic chain extender
  • step (3) the process conditions for the end-capping reaction include: a reaction temperature of 45-50 ° C. and a reaction time of 5-10 min; in an aqueous solution of the component C), the amount of water used is the mass of the component C) 3-5 times;
  • the adding condition of the component D) is directly adding after the end-capping reaction, and the adding method is: adding all of the component D) at a time or (partly adding) adding a part of the component D) first, and cutting After cutting and dispersing to obtain an aqueous polyurethane-vinyl acetate mixed emulsion, the remaining component D) is added thereto; the aqueous polyurethane-vinyl acetate mixed emulsion swells in component D); the swelling temperature is 35-45 ° C .
  • the component D) is added in batches.
  • the resulting polyurethane-vinyl acetate mixed emulsion is fully swelled.
  • the prepared emulsion can have good storage stability.
  • step (4) the protective colloid of the component E) is added and mixed, and the mixing time is 0.5-1h; the initiation temperature of the free radical initiator added to the component F) is 35-45 ° C, and the polymerization is performed.
  • the reaction temperature is 40-45 ° C, and the polymerization reaction time is 2-3h.
  • the method of removing the solvent in step (5) is distillation under reduced pressure.
  • the solvent to be removed here mainly refers to the diisocyanate-terminated prepolymer obtained by dissolving and diluting step (1) in step (2).
  • the organic solvent used; the manner of adjusting the pH of the macroemulsion can be, for example, adding AMP-95 and adding dropwise.
  • the solid content of the aqueous polyurethane-polyvinyl acetate resin according to the present invention is 45-57%, preferably 50-55%.
  • the average particle size of the water-based polyurethane-polyvinyl acetate resin is 150 to 250 nm, and preferably 170 to 220 nm.
  • the invention also provides the application of the water-based polyurethane-polyvinyl acetate resin as described above or the water-based polyurethane-polyvinyl acetate resin prepared by the preparation method described above as an adhesive.
  • the water-based polyurethane-polyvinyl acetate resin is used in the field of shoe rubber, plastic suction, laminating rubber, and automotive interior rubber.
  • CMA-654 polypentyl adipate, pentanediol, hexanediol ester glycol, hydroxyl value is 74.8 mgKOH / g, number average molecular weight ⁇ 1500, functionality is 2, Yantai Huada Chemical);
  • A95 sodium 2- (2-aminoethyl) aminoethanesulfonate, solid content is 51 ⁇ 2% aqueous solution, amine value is 260 ⁇ 20mgKOH / g, German EVONIK company)
  • IPDA isophorone diamine, Wanhua Chemical Group Co., Ltd.
  • Hk-511 polyetheramine, Huntsman
  • MMA methyl methacrylate, Jilin Petrochemical
  • Polyvinyl alcohol 2488 low viscosity type polyvinyl alcohol, 88% alcoholysis rate, Aladdin
  • Polyvinyl alcohol 1788 low viscosity type polyvinyl alcohol, 88% alcoholysis rate, Aladdin
  • the crude emulsion is distilled under reduced pressure to remove the solvent acetone, and the pH is adjusted to 7.0-9.0 by using AMP-95 to obtain a milky blue-blue water-based polyurethane-polyvinyl acetate emulsion with a solid content of 47% by weight and a particle size. 160nm.
  • the crude emulsion is distilled under reduced pressure to remove the solvent acetone, and the pH is adjusted to 7.0-9.0 by using AMP-95 to obtain a milky blue and clear water-based polyurethane-polyvinyl acetate emulsion; the solid content is 45% by weight and the particle size is 153nm.
  • the crude emulsion is distilled under reduced pressure to remove the solvent acetone, and the pH is adjusted to 7.0-9.0 by using AMP-95 to obtain a milky blue and clear blue water-based polyurethane-polyvinyl acetate emulsion; the solid content is 50% by weight and the particle size is 172nm.
  • the crude emulsion is distilled under reduced pressure to remove the solvent acetone, and the pH is adjusted to 7.0-9.0 by using AMP-95 to obtain a milky blue and clear blue water-based polyurethane-polyvinyl acetate emulsion; the solid content is 50% by weight and the particle size is 197nm.
  • the preparation of the sample is as follows:
  • the specific process is: firstly treat the substrate 1 (rubber) and substrate 2 (rubber) with ethanol, and then dry them for use; first, apply each of the above-mentioned adhesive dispersions thinly to a width of 2.5 cm using a brush and 15 cm long strips of the above-mentioned substrate 1 and substrate 2 were dried in an oven at 65 ° C. for 5 minutes, and then taken out and pressed at 30 kg / cm 2 for 10 seconds to obtain a composite material A.
  • Composite material B and composite material C were prepared by the same method.
  • the peeling strength was measured with a GOTECH tensile machine at a peeling rate of 200 mm / min.
  • 2-Later heat resistance Place the prepared test piece at room temperature for 3 days, hang a weight of 1 kg, and place it in an oven at 70 ° C to test the length of the test piece in 24 hours.
  • 3-Damp and heat resistance Place the prepared test piece at room temperature for 3 days, hang a weight of 500 grams, and place it in an oven at 70 ° C temperature / 95% humidity. Test the test piece within 24 hours, and pull it open length.
  • the water-based polyurethane-vinyl acetate resin prepared by using CMA-654, and the composite material prepared based on the water-based polyurethane-vinyl acetate resin provided by the present invention is heat-resistant at the initial stage. And the resistance to humidity and heat has been significantly improved.
  • the composite material made based on the water-based polyurethane-vinyl acetate resin provided by the present invention has a significant improvement in heat resistance in the later period.
  • cysteamine and bisaminopolyetheramine were added to the reaction system, and the initial heat resistance of the resins obtained was higher than that of the resins obtained in Examples 4-5. Hot sex is better.
  • the aqueous polyurethane-vinyl acetate resin emulsion prepared in the present application was left at 70 ° C. for 72 hours. After the resin emulsion is stored at high temperature, the effect of the adhesive prepared on the rubber substrate on the peel strength is observed. The results are shown in Table 3.
  • Example 6 By comparing Example 6 with other examples, adding polyetheramine as a diamine chain extender and cysteamine as a small molecule end-capping agent, the sample has significantly better heat resistance, moisture resistance, adhesive strength, and performance after high temperature storage. In other embodiments, this is because the addition of the two substances can well coordinate the molecular weight of the emulsion and the storage temperature performance.

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Abstract

一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用，该树脂采用包括以下各组分的原料制备得到：A)二异氰酸酯封端预聚物；B)扩链剂；包括胺类扩链剂和含有活泼氢的磺酸型亲水扩链剂，其中，胺类扩链剂包括含有活泼氢的二元胺扩链剂；C)封端剂；其为单胺基封端剂；D)醋酸乙烯酯；E)保护胶体；F)自由基引发剂。所得树脂具有优异的综合性能(如，固含量高、施工性能好，所制得的胶黏剂耐热性能优异、粘接强度高)，且制备过程易于实现。

Description

一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用 技术领域
本发明属于醋酸乙烯酯改性水性聚氨酯树脂的技术领域，尤其涉及一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用。
背景技术
聚醋酸乙烯酯乳液以水为分散相，其具有原料成本低廉、聚合可在常压下进行、无毒无害且粘接强度高等优点而广泛应用于胶黏剂领域。国内聚醋酸乙烯酯乳液产量仅次于脲醛树脂胶，在胶黏剂生产和应用中处于第二位。然而，聚醋酸乙烯酯乳液存在一些固有的缺点，如，耐水性、耐寒性以及机械稳定性均较差；湿热条件下，其粘接强度会大幅下降；抗蠕变性差，在长期载荷作用或高温作用下胶层易发生滑动。为了克服上述缺点，拓宽其应用范围，本领域的技术人员一直致力于对聚醋酸乙烯酯进行改性，以改善其综合性能，因而，市场上出现了改性聚醋酸乙烯酯。
水性聚氨酯胶黏剂是以水替代有机溶剂作为分散介质的胶黏剂，其使用安全，无毒无害，不污染环境。但是，目前水性聚氨酯胶黏剂还存在一些缺陷，如，固含量低导致干燥速度慢，固含量高导致施工粘度大；这些缺陷严重限制了水性聚氨酯胶黏剂的推广应用。因此，通过对其进行改性以改善水性聚氨酯胶黏剂的综合性能，提高其应用效果，扩大其应用范围，成为当今聚氨酯产业研究的热点。
目前，改性聚醋酸乙烯酯主要分物理改性和化学改性两种。物理改性是利用机械混合方法使聚氨酯水分散体或者聚醋酸乙烯酯乳液均匀混合，但这种简单的物理共混会因存在两相不相容问题而很容易出现分层现象，从而导致共混乳液储存期较短；同时，由于聚醋酸乙烯酯的pH值较低，两者在混合时容易出渣。化学改性是在聚醋酸乙烯酯分子链上引入聚氨酯分子链或是两者形成互穿网络结构，使改性后的产品既具有聚氨酯优良的耐低温性能，又具有聚醋酸乙烯酯优异的粘接强度。
中国专利CN 106478890 A公开了一种水性聚氨酯-聚醋酸乙烯酯杂化乳液的制备方法，先制备一种双键聚氨酯预聚物单体，然后利用种子乳液聚合方法进行聚合，聚氨酯预聚物单体和醋酸乙烯酯形成混合反应体系，聚氨酯预聚物以单体的形式存在于反应体系中，并与醋酸乙烯酯发生共聚反应，使聚氨酯单体能接枝到聚醋酸乙烯酯的大分子链上，从而大幅提高聚醋酸乙烯酯分子链的柔顺性能。然而，该方法由于分子链中引入了共聚单体，其粘接性能下降；同时这种工艺操作极其复杂，给以后生产和产业化带来不便。
中国专利CN 103249751 A公开了一种热封性涂料的制备方法，先制备一种水性聚氨酯分散体，再在后期涂料配制过程中共混水性乙烯乙酸乙烯酯共聚分散体，该混合体系可以在低至室温的温度下成膜。但是，由于在使用前需要先将两种分散体混合，该方法除了工艺繁琐外，体系的相容性或稳定性也可能存在问题，初期强度也不容易建立，同时其选用的共混组分是乙烯乙酸乙烯酯乳液。
中国专利CN 105199455 B公开了一种弱溶剂墨水打印用通用型喷绘涂料机器制备方法，是将聚氨酯预聚体与聚醚多元醇、醋酸乙烯酯单体、聚氨酯催化剂、醋酸乙烯引发剂、消泡剂、紫外线吸收剂、固色剂混合，涂布在喷绘耗材上，高温固化后制成。在加热过程中聚氨酯预聚体、聚醚多元醇相互反应，以及醋酸乙烯酯单体发生聚合，它们相互之间形成互穿网络结构，所制备的涂料具有较好的低温性能、抗老化性能。但是，该工艺没有水分散过程，与水性聚氨酯-聚醋酸乙烯酯的制备工艺存在很大差别，后续的施工过程也不同。
因此，如何开发一种综合性能优异，生产工艺简单的水性聚氨酯-聚醋酸乙烯酯乳液，是目前胶黏剂行业需要攻克的一道重大难题。
发明内容
本发明的目的在于，针对现有胶黏剂用水性乳液存在的问题，提供一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用，该水性聚氨酯-聚醋酸乙烯酯树脂的综合性能优异(固含量高、施工性能好)；所制得的胶黏剂耐热性能好、力学性能优异、存储稳定性佳，制备过 程易于实现。
为了实现上述目的，本发明提供一种水性聚氨酯-聚醋酸乙烯酯树脂，采用包括如下组分的原料反应制得：
A)二异氰酸酯封端预聚物；
B)扩链剂；所述扩链剂包括胺类扩链剂和含有活泼氢的磺酸型亲水扩链剂，其中，所述胺类扩链剂包括含有活泼氢的小分子二元胺扩链剂；
C)封端剂；所述封端剂为单胺基小分子封端剂；
D)醋酸乙烯酯；
E)保护胶体；
F)自由基引发剂；
各组分的用量为：
Figure PCTCN2018121302-appb-000001
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，组分A)所述二异氰酸酯封端预聚物采用包括如下组分的原料反应制得：
S1、二异氰酸酯，优选选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或多种，更优选选自异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或两种；
S2、聚醚二元醇和/或聚酯二元醇，其平均分子量为500-3000g/mol，优选为1500-2000g/mol；优选选自聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或多种，更优选选自聚己二酸1,4-丁二醇酯二元醇和聚己二酸1,6-己二醇酯二元醇中的一种或两种；
S3、对异氰酸酯呈反应活性的、单官能度的含有聚乙氧基链段的组分，其分子量为500-3000g/mol；优选为包含至少一个羟基的聚氧化烯醚，且所述聚氧化烯醚的聚合单元为环氧丙烷和/或环氧乙烷，更优选为环氧乙烷；其中，优选所述聚氧化烯醚的每个分子中环氧乙烷单元的个数为4～200，更优选为12～75；组分S3优选为Tego Chemie公司的
Figure PCTCN2018121302-appb-000002
D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG1200中的一种或多种，更优选为韩国乐天公司的MPEG1200；
S4、催化剂，优选选自三乙胺、1,4-二氮杂双环-[2,2,2]-辛烷、氧化二丁锡、二辛酸锡、二月桂酸二丁锡、双-(2-乙基己酸)锡、新癸酸铋和2-乙基己酸铋中的一种或多种，更优选为新癸酸铋。
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，组分B)中，所述含有活泼氢的磺酸型亲水扩链剂(S6)选自2-(2-氨基乙基)氨基乙磺酸钠、2-(2-氨基乙基)氨基丙磺酸钠、1,4-丁二醇-2-磺酸钠和1,2-二羟基-3-丙磺酸钠中的一种或多种，更优选为2-(2-氨基乙基)氨基乙磺酸钠。
优选地，组分B)的胺类扩链剂(S7)中，所述含有活泼氢的小分子二元胺扩链剂的分子量为59-200g/mol，优选选自乙二胺、六亚甲基二胺、五亚甲基二胺、羟乙基乙二胺、异佛尔酮二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或多种，更优选选自羟乙基乙二胺和异佛尔酮二胺中的一种或两种。
优选地，所述胺类扩链剂(S7)还包括双氨基聚醚胺，其数均分子量为200-600；所述双氨基聚醚胺的具体结构如下：
Figure PCTCN2018121302-appb-000003
其中，y：(x+z)＝(3～1.5)：1；且x+z的取值范围为1-3.6，y的取值范围为2-9。所述双氨基聚醚胺可选自亨斯曼的
Figure PCTCN2018121302-appb-000004
ED Series系列产品，例如选自HK-511和/或ED-600。
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，组分C)的单胺基小分子封端剂(S8)包括不含巯基的单胺和/或含有巯基的单胺。
优选地，所述不含巯基的单胺，其分子量为59-200g/mol，更优选选自乙胺、二乙胺、异丙胺、丁胺、环己胺、乙醇胺、N-甲基乙醇胺、二乙醇胺、二异丙醇胺和2-丙醇胺中的一种或多种，进一步优选为二乙醇胺。
优选地，所述含有巯基的单胺为半胱胺，其分子结构式如下：
Figure PCTCN2018121302-appb-000005
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，以组分A)-C)的总重量为100份数计，
S1的用量为10.5-16份数，更优选为11-13份数；
S2的用量为74-83份数，更优选为78-82份数；
S3的用量为1.7-4份数，更优选为2.0-4份数，进一步优选为2.7-4份数，更进一步优选为3-4份数；
S4的用量为0.002-0.03份数，更优选为0.003-0.01份数；
所述含有活泼氢的磺酸型亲水扩链剂(S6)的用量为2.5-5份数，更优选为3-4份数；
所述含有活泼氢的小分子二元胺扩链剂的用量为0.1-2份数，更优选为0.5-1.6份数；
所述双氨基聚醚胺的用量为0-2份数，更优选为0.3-0.5份数；
所述不含巯基的单胺的用量为0.05-0.3份数，更优选为0.1-0.2份数；
所述含有巯基的单胺的用量为0-0.1份数，更优选为0.02-0.04份数。
优选地，所述组分S1与组分S2的摩尔比为(1.5-2.4)：1，更优选为(1.5-2)：1。
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，组分D)中所述醋酸乙烯酯(S9)的用量为50-100重量份。
优选地，组分E)中所述保护胶体(S10)的用量为醋酸乙烯酯重量份的0.5-1.5％。优选地，所述保护胶体选自聚乙烯醇、乙氧基烷基苯酚、氨基甲酸乙酯交联的1,2-亚乙基二醇中的一种或多种，更优选为聚乙烯醇。
优选地，组分F)中所述自由基引发剂(S11)的用量为醋酸乙烯酯重量份的0.15-0.5％。
优选地，所述自由基引发剂为氧化剂与还原剂组成，所述氧化剂优选选自过硫酸氨、过硫酸钠、过硫酸钾、过氧化二苯甲酰和叔丁基过氧化氢中的一种或多种；所述还原剂优选选自保险粉、吊白块、亚硫酸氢钠和异抗坏血酸中的一种或多种；更优选地，组分F)的自由基引发剂为叔丁基过氧化氢和保险粉的组合；例如，其两者的质量比可以为1：(1-2)。
根据本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，优选地，制备所述水性聚氨酯-聚醋酸乙烯酯树脂的原料还包括组分G)：有机溶剂(S5)，其加入量为组分A)-C)的重量份之和的1-2倍；作为组分G)的有机溶剂用于在制备二异氰酸酯封端的预聚物时溶解各反应组分；
更优选地，所述有机溶剂选自丙酮和/或丁酮，进一步优选为丙酮。
本发明的另一个目的在于，提供一种如上所述水性聚氨酯-聚醋酸乙烯酯树脂的制备方法，包括如下步骤：
(1)制备二异氰酸酯封端的预聚物；
(2)将步骤(1)所得二异氰酸酯封端的预聚物进行溶解稀释，得到稀释后的二异氰酸酯封端的预聚物；
(3)用水分别稀释组分B)、组分C)，制得组分B)的水溶液和组分C)的水溶液；将步骤(2)所得产物与组分B)的水溶液接触进行扩链反应；扩链反应结束后加入组分C)的水溶液进行封端反应，再至封端反应结束后一次性或者分批次加入组分D)醋酸乙烯酯，剪切分散得到水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将步骤(3)得到的产物与组分E)混合，再加入组分F)引 发聚合反应，得到水性聚氨酯-醋酸乙烯酯粗乳液。
根据本发明提供的制备方法，优选地，所述制备方法还包括步骤(5)，即对步骤(4)得到的水性聚氨酯-醋酸乙烯酯粗乳液进行脱溶剂并调节其pH值，使其pH值＝7.0-9.0，得到所述水性聚氨酯-聚醋酸乙烯酯树脂。
步骤(5)中，对得到的水性聚氨酯-醋酸乙烯酯粗乳液脱溶剂并用例如AMP-95(即2-氨基-2-甲基-1-丙醇)调节其pH＝7.0-9.0，得到所述水性聚氨酯-聚醋酸乙烯酯树脂。
根据本发明提供的制备方法，优选地，步骤(1)中，制备所述二异氰酸酯封端的预聚物的反应工艺条件包括：反应温度为75-85℃反应；至反应体系的NCO到达理论值时停止反应。这里，NCO定义为样品中异氰酸酯基团的质量分数，以％表示，计算式为：
Figure PCTCN2018121302-appb-000006
其中，M NCO、M OH分别为样品所有原料中异氰酸酯和羟基的摩尔量，mol；
M为样品质量，g；
42为NCO的摩尔质量，g/mol。
优选地，步骤(2)中，采用组分G)对二异氰酸酯封端的预聚物进行溶解稀释；其溶解稀释条件包括：温度为50-60℃，时间为5-10min；所述组分G)为有机溶剂，选自丙酮和/或丁酮，优选为丙酮；有机溶剂的加入量为组分A)-C)的重量份之和的1-2倍。
优选地，步骤(3)中，其扩链反应工艺条件包括：反应温度为45-50℃，反应时间15-25min；更优选所述组分B)的水溶液中，其水的用量为组分B)质量的3-5倍；
步骤(3)中，其封端反应工艺条件包括：反应温度为45-50℃，反应时间为5-10min；更优选所述组分C)的水溶液中，其水的用量为组分C)质量的3-5倍；
所述组分D)的加入条件为封端反应结束直接加入，其加入方式为：将全部的所述组分D)一次性加入或者先加入一部分组分D)，剪 切分散得到水性聚氨酯-醋酸乙烯酯混合乳液后再在其中加入剩余的组分D)；水性聚氨酯-醋酸乙烯酯混合乳液在组分D)中发生溶胀，所述溶胀的温度为35-45℃。一些实施方式中，组分D)在进行分批加入时，先加入二分之一质量的组分D)进行剪切分散，再将剩余二分之一质量的组分D)与水性聚氨酯-醋酸乙烯酯混合乳液混合进行溶胀。通过将组分D)进行分批加入，可更好的保证体系的稳定性。
优选地，步骤(4)中，加入所述组分E)的保护胶体进行搅拌混合，混合的时间为0.5-1h；加入所述组分F)的自由基引发剂的引发温度为35-45℃，聚合反应温度为40-45℃，聚合反应时间为2-3h。
优选地，步骤(5)中，所述脱溶剂的方式为减压蒸馏；调节粗乳液pH值例如，可通过滴加加入所述AMP-95的方式。
本发明还提供一种如上所述的水性聚氨酯-聚醋酸乙烯酯树脂或如上所述的制备方法制得的水性聚氨酯-聚醋酸乙烯酯树脂作为胶黏剂的应用。
根据本发明提供的应用，优选地，所述水性聚氨酯-聚醋酸乙烯酯树脂应用于鞋胶领域、吸塑胶领域、复膜胶领域以及汽车内饰胶领域。
本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，其亲水性主要通过含有活泼氢的磺酸型亲水扩链剂(例如，氨基磺酸钠盐等)实现，且无需中和，避免了三乙胺等低沸点中和剂带来的气味及VOC，环保性能好。在一些优选实施方案中，含有活泼氢的磺酸型亲水扩链剂使用氨基磺酸钠盐，其属于强酸强碱盐，不易水解，使得产品有更好的耐水性。在聚氨酯合成阶段加入醋酸乙烯酯，引发聚合后形成了水性聚氨酯-聚醋酸乙烯酯互穿网络结构，结合了水性聚氨酯和聚醋酸乙烯酯各自的优点，降低了聚醋酸乙烯酯的水解性，提高了其成膜性，增加了两相间相容性，提高了乳液稳定性和胶黏剂的初期剥离强度。
相对于现有技术，本发明技术方案的有益效果在于：
(1)本发明提供的水性聚氨酯-聚醋酸乙烯酯树脂，通过调整作为反应原料的各组分，其固含量高、综合性能优异；
(2)在优选实施方式中，使用与小分子二元胺扩链剂不同分子量、 不同结构的双氨基聚醚胺作为协同扩链剂，由于分子中含有亲水基团，使聚氨酯链段的亲水效果增加，对醋酸乙烯酯乳液聚合中的渣含起到有效的改善作用；
(3)在优选实施方式中，搭配使用含有巯基的单胺作为协同封端剂，不仅有效控制PU部分的分子量，同时巯基可以在醋酸乙烯酯聚合时起到链转移剂的作用，也有效起到控制聚醋酸乙烯酯的分子量，合适的分子量对树脂应用于胶黏剂的性能起到很好的积极作用；例如，本发明所得水性聚氨酯-聚醋酸乙烯酯树脂制备的胶黏剂存储稳定性好、力学性能优异(如剥离强度)、耐热性良好；
(4)本发明生产工艺简单，便于操作，安全无毒。
具体实施方式
为了能够详细地理解本发明的技术特征和内容，下面将更详细地描述本发明的优选实施方式。虽然实施例中描述了本发明的优选实施方式，然而应该理解，可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。
在本发明的一种示例中，提供一种水性聚氨酯-聚醋酸乙烯酯树脂，采用包括如下组分的原料反应制得：
A)二异氰酸酯封端预聚物；
B)扩链剂；所述扩链剂包括胺类扩链剂和含有活泼氢的磺酸型亲水扩链剂，其中，所述胺类扩链剂包括含有活泼氢的小分子二元胺扩链剂；
C)封端剂；所述封端剂为单胺基小分子封端剂；
D)醋酸乙烯酯；
E)保护胶体；
F)自由基引发剂；
各组分的用量为：
组分A)、B)和C)的总和       100重量份；
组分D)                     30-120重量份，
例如，40重量份、50重量份、60重量份、80重量份、100重量 份、110重量份；
组分E)                         组分D)重量份的0.4-3％，
例如，0.5％、0.7％、1％、1.5％、2％、2.5％；
组分F)                         组分D)重量份的0.1-1.1％，
例如，0.2％、0.4％、0.5％、0.7％、0.9％、1％。
在一些优选实施方式中，所述二异氰酸酯封端预聚物采用包括如下组分的原料反应制得：
S1、二异氰酸酯，选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或多种，优选选自异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或两种；
S2、聚醚二元醇和/或聚酯二元醇，其平均分子量为500-3000g/mol，优选为1500-2000g/mol；选自聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或多种，优选选自聚己二酸1,4-丁二醇酯二元醇和聚己二酸1,6-己二醇酯二元醇中的一种或两种；
S3、对异氰酸酯呈反应活性的、单官能度的含有聚乙氧基链段的组分，其分子量为500-3000g/mol；其为包含至少一个羟基的聚氧化烯醚，且所述聚氧化烯醚的聚合单元为环氧丙烷和/或环氧乙烷，优选为环氧乙烷；其中，所述聚氧化烯醚的每个分子中环氧乙烷单元的个数为4～200，优选为12～75；组分S3优选为Tego Chemie公司的
Figure PCTCN2018121302-appb-000007
D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG1200中的一种或多种，更优选为韩国乐天公司的MPEG1200；
S4、催化剂，选自三乙胺、1,4-二氮杂双环-[2,2,2]-辛烷、氧化二丁锡、二辛酸锡、二月桂酸二丁锡、双-(2-乙基己酸)锡、新癸酸铋和2-乙基己酸铋中的一种或多种，更优选为新癸酸铋。
在一些优选实施方式中，组分B)中，所述含有活泼氢的磺酸型亲水扩链剂(S6)选自2-(2-氨基乙基)氨基乙磺酸钠、2-(2-氨基乙基) 氨基丙磺酸钠、1,4-丁二醇-2-磺酸钠和1,2-二羟基-3-丙磺酸钠中的一种或多种，优选为2-(2-氨基乙基)氨基乙磺酸钠。
组分B)的胺类扩链剂(S7)中，所述含有活泼氢的小分子二元胺扩链剂的分子量为59-200g/mol，选自乙二胺、六亚甲基二胺、五亚甲基二胺、羟乙基乙二胺、异佛尔酮二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或多种，优选选自羟乙基乙二胺和异佛尔酮二胺中的一种或两种。
优选地，所述胺类扩链剂(S7)还包括双氨基聚醚胺，其数均分子量为200-600；所述双氨基聚醚胺的具体结构如下：
Figure PCTCN2018121302-appb-000008
其中，y：(x+z)＝(3～1.5)：1；且x+z的取值范围为1-3.6，y的取值范围为2-9。在一些示例中，所述双氨基聚醚胺可选自亨斯曼的
Figure PCTCN2018121302-appb-000009
ED Series系列产品，例如，选自HK-511和/或ED-600。
在优选实施方式中，通过含有活泼氢的二元胺小分子扩链剂与双氨基聚醚胺混合后作为胺类扩链剂，能够起到协同的作用，由于分子中含有亲水基团，使聚氨酯链段的亲水效果增加，对醋酸乙烯酯乳液聚合的渣含起到有效的改善作用。
在一些优选实施方式中，组分C)的单胺基小分子封端剂(S8)包括不含巯基的单胺和/或含有巯基的单胺。
所述不含巯基的单胺，其分子量为59-200g/mol，选自乙胺、二乙胺、异丙胺、丁胺、环己胺、乙醇胺、N-甲基乙醇胺、二乙醇胺、二异丙醇胺和2-丙醇胺中的一种或多种，更优选为二乙醇胺。
所述含有巯基的单胺为半胱胺，其分子结构式如下：
Figure PCTCN2018121302-appb-000010
在一些示例中，以组分A)-C)的总重量为100份数计，
S1的用量为10.5-16份数，例如，12份数、14份数、15份数，优选为11-13份数；
S2的用量为74-83份数，例如，75份数、77份数、80份数，优选为78-82份数；
S3的用量为1.7-4份数，例如，2.0份数、2.7份数、3.1份数、3.5份数、3.8份数，优选为3-4份数；
S4的用量为0.002-0.03份数，例如，0.005份数、0.008份数、0.012份数、0.015份数、0.02份数、0.025份数，优选为0.003-0.01份数；
本发明中，所得二异氰酸酯封端预聚物的重量份与反应原料S1-S4的用量份数之和相等。
所述含有活泼氢的磺酸型亲水扩链剂(S6)的用量为2.5-5份数，例如，2.8份数、3.1份数、3.5份数、3.8份数、4.3份数、4.5份数，优选为3-4份数；
所述含有活泼氢的小分子二元胺扩链剂的用量为0.1-2份数，例如，0.3份数、0.4份数、0.6份数、0.8份数、1份数、1.2份数、1.5份数，优选为0.5-1.6份数；
所述双氨基聚醚胺的用量为0-2份数，例如，0.1份数、0.2份数、0.6份数、0.8份数、1份数、1.5份数，优选为0.3-0.5份数；
所述不含巯基的单胺的用量为0.05-0.3份数，例如，0.06份数、0.08份数、0.12份数、0.15份数、0.18份数，优选为0.1-0.2份数；
所述含有巯基的单胺的用量为0-0.1份数，例如，0.01份数、0.03份数、0.05份数、0.07份数、0.09份数，优选为0.02-0.04份数。
优选地，所述组分S1与组分S2的摩尔比为(1.5-2.4)：1，更优选为(1.5-2)：1，此种组分配比更易使制备的胶黏剂具有更好的初期强度和初期耐热性能。
在优选实施方式中，组分C)中通过不含巯基的单胺与含有巯基 的单胺搭配使用，含有巯基的单胺作为协同封端剂，不仅有效控制PU部分的分子量，同时巯基可以在醋酸乙烯酯聚合时起到链转移剂的作用，也有效起到控制聚醋酸乙烯酯的分子量，合适的分子量对树脂的应用性能起到很好的积极作用。
在一些优选实施方式中，组分D)中所述醋酸乙烯酯(S9)的用量为50-100重量份。
组分E)中所述保护胶体(S10)的用量为醋酸乙烯酯重量份的0.5-1.5％。所述保护胶体选自聚乙烯醇、乙氧基烷基苯酚、氨基甲酸乙酯交联的1,2-亚乙基二醇中的一种或多种，优选为聚乙烯醇。
组分F)中所述自由基引发剂的用量为醋酸乙烯酯重量份的0.15-0.5％；优选地，所述自由基引发剂为氧化剂与还原剂组成，所述氧化剂优选选自过硫酸氨、过硫酸钠、过硫酸钾、过氧化二苯甲酰和叔丁基过氧化氢中的一种或多种；所述还原剂优选选自保险粉、吊白块、亚硫酸氢钠和异抗坏血酸中的一种或多种；更优选地，组分F)的自由基引发剂为叔丁基过氧化氢和保险粉的组合；优选此种组合作为引发剂的引发效率高，有利于聚合效率的提高和残单的消除。
在一些示例中，制备所述水性聚氨酯-聚醋酸乙烯酯树脂的原料还包括组分G)：有机溶剂，其加入量为组分A)-C)重量份之和的1-2倍；
优选地，所述有机溶剂选自丙酮和/或丁酮，进一步优选为丙酮。
本发明的另一个目的在于，提供一种如上所述水性聚氨酯-聚醋酸乙烯酯树脂的制备方法，包括如下步骤：
(1)制备二异氰酸酯封端的预聚物；
(2)将步骤(1)所得二异氰酸酯封端的预聚物进行溶解稀释，得到稀释后的二异氰酸酯封端的预聚物；
(3)用水分别稀释组分B)、组分C)，制得组分B)的水溶液和组分C)的水溶液；将步骤(2)所得产物与组分B)的水溶液接触进行扩链反应；扩链反应结束后加入组分C)的水溶液进行封端反应，再至封端反应结束后一次性或者分批次加入组分D)醋酸乙烯酯，剪切分散得到水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将步骤(3)得到的产物与组分E)混合，再加入组分F)引发聚合反应，得到水性聚氨酯-醋酸乙烯酯粗乳液。
在一些优选实施方式中，所述制备方法还包括步骤(5)，即对步骤(4)得到的水性聚氨酯-醋酸乙烯酯粗乳液脱溶剂并用例如AMP-95(即2-氨基-2-甲基-1-丙醇)调节其pH＝7.0-9.0，使此时的粗乳液到达正常乳液的pH值，得到所述水性聚氨酯-聚醋酸乙烯酯树脂。
在一些示例中，步骤(1)中，制备所述二异氰酸酯封端的预聚物的反应工艺条件包括：反应温度为75-85℃反应；至反应体系的NCO到达理论值时停止反应。这里，NCO定义为样品中异氰酸酯基团的质量分数，以％表示，计算式为：
Figure PCTCN2018121302-appb-000011
其中，M NCO、M OH分别为样品所有原料中异氰酸酯和羟基的摩尔量，mol；
M为样品质量，g；
42为NCO的摩尔质量，g/mol。
步骤(2)中，采用组分G)对二异氰酸酯封端的预聚物进行溶解稀释；其溶解稀释条件包括：温度为50-60℃，时间为5-10min；所述组分G)为有机溶剂，选自丙酮和/或丁酮，优选为丙酮；有机溶剂的加入量为组分A)-C)的重量份之和的1-2倍。
步骤(3)中，其扩链反应工艺条件包括：反应温度为45-50℃，反应时间15-25min；所述组分B)的水溶液中，其水的用量为组分B)质量的3-5倍；这里所述组分B)的水溶液可以指的是，先将胺类扩链剂和含有活泼氢的磺酸型亲水扩链剂(S6)混合后得到混合物，再将其用去离子水进行稀释，得到含有组分S7和组分S6混合物的水溶液；
步骤(3)中，其封端反应工艺条件包括：反应温度为45-50℃，反应时间为5-10min；所述组分C)的水溶液中，其水的用量为组分C)质量的3-5倍；
所述组分D)的加入条件为封端反应结束直接加入，其加入方式为：将全部的所述组分D)一次性加入或者(分批次加入)先加入一部分组分D)，剪切分散得到水性聚氨酯-醋酸乙烯酯混合乳液后再在其中加入剩余的组分D)；水性聚氨酯-醋酸乙烯酯混合乳液在组分D)中发生溶胀；所述溶胀的温度为35-45℃。将组分D)采用分批次加入的方式，通过先加入一部分组分D)，剪切分散后再在其中加入剩余的组分D)使得到的水性聚氨酯-醋酸乙烯酯混合乳液充分溶胀，可以使所制得的乳液储存稳定性好。
步骤(4)中，加入所述组分E)的保护胶体进行搅拌混合，混合的时间为0.5-1h；加入所述组分F)的自由基引发剂的引发温度为35-45℃，聚合反应温度为40-45℃，聚合反应时间为2-3h。
在一些示例中，步骤(5)中，所述脱溶剂的方式为减压蒸馏，这里需要脱除的溶剂主要是指步骤(2)中溶解稀释步骤(1)所得二异氰酸酯封端的预聚物所用的有机溶剂；调节粗乳液pH值的方式例如可以为加入AMP-95且滴加加入。
本发明所述的水性聚氨酯-聚醋酸乙烯酯树脂的固含量为45-57％，优选为50-55％。水性聚氨酯-聚醋酸乙烯酯树脂的平均粒子尺寸为150-250nm，优选为170-220nm。
本发明还提供一种如上所述的水性聚氨酯-聚醋酸乙烯酯树脂或如上所述的制备方法制得的水性聚氨酯-聚醋酸乙烯酯树脂作为胶黏剂的应用。
根据本发明提供的应用，优选地，所述水性聚氨酯-聚醋酸乙烯酯树脂应用于鞋胶领域、吸塑胶领域、复膜胶领域以及汽车内饰胶领域。
原料来源：
1、
Figure PCTCN2018121302-appb-000012
(异佛尔酮二异氰酸酯，NCO含量约为37.8％，万华化学集团股份有限公司)；
Figure PCTCN2018121302-appb-000013
(1,6-己二异氰酸酯，NCO含量约为50％，万华化学集团股份有限公司)；
2、PBA-2000(聚己二酸1,4-丁二醇酯二醇，羟值为56mgKOH/g， 数均分子量＝2000，官能度为2，烟台华大化学)；
PHA-2000(聚己二酸1,6-己二醇酯二醇，羟值为56mgKOH/g，数均分子量＝2000，官能度为2，烟台华大化学)；
CMA-654(聚己二酸新戊二醇己二醇酯二醇，羟值为74.8mgKOH/g，数均分子量≈1500，官能度为2，烟台华大化学)；
3、MPEG1200(聚乙二醇单甲醚，羟值为46.75mgKOH/g，数均分子量＝1200，官能度为1，韩国乐天)；
4、有机铋催化剂(新癸酸铋，美国领先化学公司)；
5、有机溶剂(丙酮，宁波万华)；
6、
Figure PCTCN2018121302-appb-000014
A95(2-(2-氨基乙基)氨基乙磺酸钠，固含量为51±2％水溶液，胺值为260±20mgKOH/g，德国EVONIK公司)；
7、IPDA(异佛尔酮二胺，万华化学集团股份有限公司)；
羟乙基乙二胺(扬子石化-巴斯夫有限责任公司)；
Hk-511(聚醚胺，亨斯曼)；
ED-600(聚醚胺，亨斯曼)；
8、DEOA(二乙醇胺，扬子石化-巴斯夫有限责任公司)；
巯基乙胺(半胱胺，西格玛)；
9、VAc(醋酸乙烯酯，成都艾科试剂有限公司)；
MMA(甲基丙烯酸甲基，吉林石化)；
BA(丙烯酸丁酯，上海华谊)；
10、聚乙烯醇2488低粘度型(聚乙烯醇，醇解率为88％，阿拉丁)；
聚乙烯醇1788低粘度型(聚乙烯醇，醇解率为88％，阿拉丁)；
11、叔丁基过氧化氢(兰州石化)和保险粉(连二亚硫酸钠，西陇化工)。
12、AMP-95(2-氨基-2-甲基-1-丙醇，美国陶氏化学)；
实施例1：(加入聚醚胺且不加入半胱胺)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入10g
Figure PCTCN2018121302-appb-000015
30g
Figure PCTCN2018121302-appb-000016
194g PHA-2000、7g  MPEG1200、100ppm有机铋催化剂、21g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的3.97％时，降温至60℃左右加入341g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将5g羟乙基乙二胺、4g Hk-511和10.2g
Figure PCTCN2018121302-appb-000017
用80g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应20min；将0.64g二乙醇胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入60g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入333g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的60g醋酸乙烯酯并搅拌溶胀30min后，加入1.2g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.12g叔丁基过氧化氢和0.12g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去溶剂丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显的水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为47wt％，粒径大小为160nm。
实施例2：(加入聚醚胺且不加入半胱胺)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入30g
Figure PCTCN2018121302-appb-000018
230g PBA-2000、9.7g MPEG1200、100ppm有机铋催化剂、23g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的1.71％，降温至60℃左右加入381g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1.3g羟乙基乙二胺、0.5g ED-600和10.2g
Figure PCTCN2018121302-appb-000019
用46g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应20min；将0.23g二乙醇胺用1g去离子水稀释后，加入反应体系 并进行封端反应5min；最后加入67.4g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入451g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的67.4g醋酸乙烯酯并搅拌溶胀30min后，加入2.02g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.18g叔丁基过氧化氢和0.18g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去溶剂丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为45wt％，粒径大小为153nm。
实施例3：(不加入聚醚胺且加入半胱胺)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000020
24g
Figure PCTCN2018121302-appb-000021
210g PBA-2000、8g MPEG1200、100ppm有机铋催化剂、22g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的2.18％时，降温至60℃左右加入353g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1.5g羟乙基乙二胺、1.6g IPDA和10.2g
Figure PCTCN2018121302-appb-000022
用53g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应20min；将0.21g二乙醇胺和0.15g半胱胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入82g醋酸乙烯酯并搅拌5min，在剪切分散条件下加入335g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入0.82g聚乙烯醇1788低粘度型并搅拌0.5h，再加入0.11g叔丁基过氧化氢和0.11g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去溶剂丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为50wt％，粒径大小为172nm。
实施例4：(聚醚胺和半胱胺均没加入)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000023
24g
Figure PCTCN2018121302-appb-000024
230g PBA-2000、5.5g MPEG1200、100ppm有机铋催化剂、23g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的1.78％时，降温至60℃左右加入378g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1.5g羟乙基乙二胺和10.2g
Figure PCTCN2018121302-appb-000025
用47g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应搅拌20min；将0.43g二乙醇胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入81g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入427g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的80g醋酸乙烯酯并搅拌溶胀30min后，加入1.61g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.2g叔丁基过氧化氢和0.2g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为47wt％，粒径大小为208nm。
实施例5：(聚醚胺和半胱胺均没加入)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000026
24g
Figure PCTCN2018121302-appb-000027
230g PBA-2000、9g  MPEG1200、100ppm有机铋催化剂、24g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的1.72％，降温至60℃左右加入383g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1g羟乙基乙二胺、0.8g乙二胺和7g
Figure PCTCN2018121302-appb-000028
用35g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应搅拌20min；将0.39g二乙醇胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入163g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入363g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的163g醋酸乙烯酯并搅拌溶胀30min后，加入3.26g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.27g叔丁基过氧化氢和0.27g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去溶剂丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为50wt％，粒径大小为197nm。
实施例6：(同时加入协同扩链剂和协同封端剂)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000029
24g
Figure PCTCN2018121302-appb-000030
230g PBA-2000、8.5g MPEG1200、100ppm有机铋催化剂、24g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的1.72％，降温至60℃左右加入383g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1.2g羟乙基乙二胺、1g ED-600和9.7g
Figure PCTCN2018121302-appb-000031
用45g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链 反应搅拌20min；将0.36g二乙醇胺和0.06g半胱胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入135g醋酸乙烯酯搅拌2-3min，在剪切分散条件下加入353g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的135g醋酸乙烯酯并搅拌溶胀30min后，加入2.7g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.27g叔丁基过氧化氢和0.27g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为50wt％，粒径大小为182nm。
实施例7：(同时加入协同扩链剂和协同封端剂)
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000032
24g
Figure PCTCN2018121302-appb-000033
205g PHA-2000、10g MPEG1200、100ppm有机铋催化剂、21g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的2.26％，降温至60℃左右加入349g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1g羟乙基乙二胺、3g IPDA、1g HK-511和7.8g
Figure PCTCN2018121302-appb-000034
用49g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应搅拌20min；将0.5g二乙醇胺和0.1g半胱胺用2.5g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入148g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入337g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的148g醋酸乙烯酯并搅拌溶胀30min后，加入3.5g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.3g叔丁基过氧化氢和0.3g保险粉(连二亚硫酸钠)引发聚合，每30min 再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到水性聚氨酯-醋酸乙烯酯粗乳液；
(5)将该粗乳液减压蒸馏除去丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液；其固含量为50wt％，粒径大小为185nm。
对比例1：
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入8g
Figure PCTCN2018121302-appb-000035
24g
Figure PCTCN2018121302-appb-000036
205g PHA-2000、10g MPEG1200、100ppm有机铋催化剂、21g丙酮，80℃下进行反应，生成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测NCO，直至NCO到达理论值的2.26％，降温至60℃左右加入349g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将1.2g羟乙基乙二胺、1g HK-511、3g IPDA和7.8g
Figure PCTCN2018121302-appb-000037
用49g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应搅拌20min；将0.41g二乙醇胺用2g去离子水稀释后，加入反应体系并进行封端反应5min；最后加入98g甲基丙烯酸甲酯、148g丙烯酸丁酯搅拌2-3min，在剪切分散条件下加入216g水，得水性聚氨酯-丙烯酸酯混合乳液；
(4)将体系升温至45℃，加入0.246g叔丁基过氧化氢和0.246g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，制得粗乳液；
(5)将该粗乳液减压蒸馏除去丙酮，制得乳白色蓝光明显水性聚氨酯-丙烯酸酯乳液；其固含量为52wt％，粒径大小为230nm。
对比例2：
(1)向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入11g
Figure PCTCN2018121302-appb-000038
33g
Figure PCTCN2018121302-appb-000039
230g CMA-654、9g MPEG1200、100ppm有机铋催化剂、25g丙酮，80℃下进行反应，生 成二异氰酸酯封端的预聚物；
(2)反应过程中取样监测体系的NCO，直至NCO到达理论值的2.43％，降温至60℃左右加入400g丙酮搅拌5min，得到稀释后的二异氰酸酯封端的预聚物；
(3)将3.5g羟乙基乙二胺和10.2g
Figure PCTCN2018121302-appb-000040
用55g去离子水稀释后，在45℃条件下加入反应体系并搅拌进行扩链反应20min；将0.6g二乙醇胺用2g去离子水稀释后，加入反应体系反应5min；在加入142g醋酸乙烯酯并搅拌2-3min，在剪切分散条件下加入360g水，剪切分散后得水性聚氨酯-醋酸乙烯酯混合乳液；
(4)将体系升温至45℃，加入剩余的142g醋酸乙烯酯搅拌溶胀30min，加入3.0g聚乙烯醇1788低粘度型搅拌0.5h，再加入0.28g叔丁基过氧化氢和0.28g保险粉(连二亚硫酸钠)引发聚合，每30min再次加入相同量的引发剂，共引发4次，引发完毕保温30min，得到粗乳液；
(5)将该粗乳液减压蒸馏除去丙酮，用AMP-95调节pH到7.0-9.0，制得乳白色蓝光明显水性聚氨酯-聚醋酸乙烯酯乳液，其固含量为50wt％，粒径大小为177nm。
粘合剂的制备：
将100g各实施例和对比例制得的水性分散体、0.05g BYK024(毕克化学)混合，在500rpm条件下搅拌5min，再加入0.2g Tego245(迪高)，再搅拌5min，再加入0.15g Vesmody U604(万华化学)，然后在600rpm搅拌10min，得到粘合剂。
试样的制备如下：
用以下材料作为基材与粘合剂进行复合制备复合材料试样：
复合材料 基材1 基材2
A 橡胶 橡胶
B 帆布 帆布
C PVC PVC
具体过程为：首先对基材1(橡胶)、基材2(橡胶)用乙醇进行处理，之后晾干待用；使用刷子首先将上述各粘合剂分散体细薄地施涂到2.5cm宽且15cm长的上述基材1和基材2条形物上并在65℃烘箱中干燥5分钟，后取出在30kg/cm 2压合10秒，制得复合材料A。
使用同样的方法制备复合材料B、复合材料C。
测试复合材料的剥离强度：
用GOTECH拉力机在200mm/min的剥离速率下测定剥离强度。
1-初期强度：压合完后直接到拉力机测试其剥离强度。
2-后期强度：将试件在室温放置24小时后，测试其剥离强度。
测试结果见表1。
表1各复合材料的剥离强度
Figure PCTCN2018121302-appb-000041
由表1中可以看出，相对于水性聚氨酯-丙烯酸酯树脂和CMA-654制备的水性聚氨酯-醋酸乙烯酯树脂来说，基于本发明提供的水性聚氨酯-醋酸乙烯酯树脂制得的复合材料的初期强度有明显提高。
测试复合材料的耐热性：
1-初期耐热：将做好的试件，挂一个重500克的砝码，放在80℃烘箱中，测试其在30分钟内，试件拉开的长度。
2-后期耐热：将做好的试件在室温放置3天，挂一个重1千克的 砝码，放在70℃烘箱中，测试其在24小时内，试件拉开的长度。
3-耐湿热：将做好的试件在室温放置3天，挂一个重500克的砝码，放在70℃温度/95％湿度的烘箱中，测试其在24小时内，试件拉开的长度。
测试结果见表2。
表2各复合材料的耐热性和耐湿性
Figure PCTCN2018121302-appb-000042
由表2可以看出，(1)相对于对比例2采用CMA-654制备的水性聚氨酯-醋酸乙烯酯树脂，基于本发明提供的水性聚氨酯-醋酸乙烯酯树脂制得的复合材料在初期耐热和耐湿热方面有明显提升。相对于对比例1制得的水性聚氨酯-丙烯酸酯树脂来说，基于本发明提供的水性聚氨酯-醋酸乙烯酯树脂制得的复合材料在后期耐热上有明显提升。(2)实施例1-3、实施例6-7中，因反应体系加入了半胱胺和双氨基聚醚胺，其所得树脂的初期耐热性均比实施例4-5所得树脂的耐热性要好。
高温处理后的粘合性测试：
将本申请制备的水性聚氨酯-醋酸乙烯酯树脂乳液在70℃条件下放置72h。观察树脂乳液高温存储后，用其制得的粘合剂在橡胶基材上对剥离强度影响。结果如表3所示。
表3高温存储后，橡胶基材上的粘合剂的剥离强度
Figure PCTCN2018121302-appb-000043
从表3可以明显的看出，基于本申请提供的水性聚氨酯-醋酸乙烯酯树脂，在高温存储3天，剥离强度不会发生明显的改变，这说明本申请的水性聚氨酯-醋酸乙烯酯树脂具有优异的存储稳定性。
通过实施例6和其它实施例相比，加入聚醚胺作为二胺扩链剂、半胱胺作为小分子封端剂，样品的耐热、耐湿、粘结强度、高温储存后的性能明显优于其它实施例，这是因为两种物质的加入，可以很好的协调乳液的分子量大小，以及储存温度性能。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。

Claims (10)

  1. 一种水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，采用包括如下组分的原料反应制得：
    A)二异氰酸酯封端预聚物；
    B)扩链剂；所述扩链剂包括胺类扩链剂和含有活泼氢的磺酸型亲水扩链剂，其中，所述胺类扩链剂包括含有活泼氢的小分子二元胺扩链剂；
    C)封端剂；所述封端剂为单胺基小分子封端剂；
    D)醋酸乙烯酯；
    E)保护胶体；
    F)自由基引发剂；
    各组分的用量为：
    Figure PCTCN2018121302-appb-100001
  2. 根据权利要求1所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，组分B)中，所述含有活泼氢的磺酸型亲水扩链剂选自2-(2-氨基乙基)氨基乙磺酸钠、2-(2-氨基乙基)氨基丙磺酸钠、1,4-丁二醇-2-磺酸钠和1,2-二羟基-3-丙磺酸钠中的一种或多种，优选为2-(2-氨基乙基)氨基乙磺酸钠；
    组分B)的胺类扩链剂中，所述含有活泼氢的小分子二元胺扩链剂的分子量为59-200g/mol，优选选自乙二胺、六亚甲基二胺、五亚甲基二胺、羟乙基乙二胺、异佛尔酮二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或多种，更优选选自羟乙基乙二胺和异佛尔酮二胺中的一种或两种；
    优选地，所述胺类扩链剂还包括双氨基聚醚胺，其数均分子量为200-600；所述双氨基聚醚胺的具体结构如下：
    Figure PCTCN2018121302-appb-100002
    其中，y：(x+z)＝(3～1.5)：1；且x+z的取值范围为1-3.6，y的取值范围为2-9。
  3. 根据权利要求2所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，组分C)的单胺基小分子封端剂包括不含巯基的单胺和/或含有巯基的单胺；
    所述不含巯基的单胺，其分子量为59-200g/mol，优选选自乙胺、二乙胺、异丙胺、丁胺、环己胺、乙醇胺、N-甲基乙醇胺、二乙醇胺、二异丙醇胺和2-丙醇胺中的一种或多种，更优选为二乙醇胺；
    优选地，所述含有巯基的单胺为半胱胺，其分子结构式如下：
    Figure PCTCN2018121302-appb-100003
  4. 根据权利要求3所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，所述二异氰酸酯封端预聚物采用包括如下组分的原料反应制得：
    S1、二异氰酸酯，优选选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或多种，更优选选自异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或两种；
    S2、聚醚二元醇和/或聚酯二元醇，其平均分子量为500-3000g/mol，优选为1500-2000g/mol；优选选自聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或多种，更优选选自聚己二酸1,4-丁二醇 酯二元醇和聚己二酸1,6-己二醇酯二元醇中的一种或两种；
    S3、对异氰酸酯呈反应活性的、单官能度的含有聚乙氧基链段的组分，其分子量为500-3000g/mol；优选为包含至少一个羟基的聚氧化烯醚，且所述聚氧化烯醚的聚合单元为环氧丙烷和/或环氧乙烷，更优选为环氧乙烷；其中，优选所述聚氧化烯醚的每个分子中环氧乙烷单元的个数为4～200，更优选为12～75；组分S3优选为Tego Chemie公司的
    Figure PCTCN2018121302-appb-100004
    D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG1200中的一种或多种，更优选为韩国乐天公司的MPEG1200；
    S4、催化剂，优选选自三乙胺、1,4-二氮杂双环-[2,2,2]-辛烷、氧化二丁锡、二辛酸锡、二月桂酸二丁锡、双-(2-乙基己酸)锡、新癸酸铋和2-乙基己酸铋中的一种或多种，更优选为新癸酸铋。
  5. 根据权利要求4所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，以组分A)-C)的总重量为100份数计，
    S1的用量为10.5-16份数，优选为11-13份数；
    S2的用量为74-83份数，优选为78-82份数；
    S3的用量为1.7-4份数，优选为2.0-4份，更优选为2.7-4份，进一步优选为3-4份数；
    S4的用量为0.002-0.03份数，优选为0.003-0.01份数；
    所述含有活泼氢的磺酸型亲水扩链剂的用量为2.5-5份数，优选为3-4份数；
    所述含有活泼氢的小分子二元胺扩链剂的用量为0.1-2份数，优选为0.5-1.6份数；
    所述双氨基聚醚胺的用量为0-2份数，优选为0.3-0.5份数；
    所述不含巯基的单胺的用量为0.05-0.3份数，优选为0.1-0.2份数；
    所述含有巯基的单胺的用量为0-0.1份数，优选为0.02-0.04份数；
    优选地，所述组分S1与组分S2的摩尔比为(1.5-2.4)：1，更优选为(1.5-2)：1。
  6. 根据权利要求1-5中任一项所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，
    组分D)中所述醋酸乙烯酯的用量为50-100重量份；
    组分E)中所述保护胶体的用量为醋酸乙烯酯重量份的0.5-1.5％；优选地，所述保护胶体选自聚乙烯醇、乙氧基烷基苯酚、氨基甲酸乙酯交联的1,2-亚乙基二醇中的一种或多种，更优选为聚乙烯醇；
    组分F)中所述自由基引发剂的用量为醋酸乙烯酯重量份的0.15-0.5％；优选地，所述自由基引发剂为氧化剂与还原剂组成，所述氧化剂优选选自过硫酸氨、过硫酸钠、过硫酸钾、过氧化二苯甲酰和叔丁基过氧化氢中的一种或多种；所述还原剂优选选自保险粉、吊白块、亚硫酸氢钠和异抗坏血酸中的一种或多种；更优选地，组分F)的自由基引发剂为叔丁基过氧化氢和保险粉的组合。
  7. 根据权利要求1-6中任一项所述的水性聚氨酯-聚醋酸乙烯酯树脂，其特征在于，制备所述水性聚氨酯-聚醋酸乙烯酯树脂的原料还包括组分G)：有机溶剂，其加入量为组分A)-C)的重量份之和的1-2倍；
    优选地，所述有机溶剂选自丙酮和/或丁酮，更优选为丙酮。
  8. 一种如权利要求1-7中任一项所述水性聚氨酯-聚醋酸乙烯酯树脂的制备方法，其特征在于，包括如下步骤：
    (1)制备二异氰酸酯封端的预聚物；
    (2)将步骤(1)所得二异氰酸酯封端的预聚物进行溶解稀释，得到稀释后的二异氰酸酯封端的预聚物；
    (3)用水分别稀释组分B)、组分C)，制得组分B)的水溶液和组分C)的水溶液；将步骤(2)所得产物与组分B)的水溶液接触进行扩链反应；扩链反应结束后加入组分C)的水溶液进行封端反应，再至封端反应结束后一次性或者分批次加入组分D)醋酸乙烯酯，剪切分散得到水性聚氨酯-醋酸乙烯酯混合乳液；
    (4)将步骤(3)得到的产物与组分E)混合，再加入组分F)引 发聚合反应，得到水性聚氨酯-醋酸乙烯酯粗乳液；
    优选地，所述制备方法还包括步骤(5)，即对步骤(4)得到的水性聚氨酯-醋酸乙烯酯粗乳液进行脱溶剂并调节其pH值，使其pH值＝7.0-9.0，得到所述水性聚氨酯-聚醋酸乙烯酯树脂。
  9. 根据权利要求8所述的制备方法，其特征在于，
    步骤(1)中，制备所述二异氰酸酯封端的预聚物的反应工艺条件包括：反应温度为75-85℃反应；至反应体系的NCO到达理论值时停止反应；
    步骤(2)中，采用组分G)对二异氰酸酯封端的预聚物进行溶解稀释；其溶解稀释条件包括：温度为50-60℃，时间为5-10min；所述组分G)为有机溶剂，选自丙酮和/或丁酮，优选为丙酮；有机溶剂的加入量为组分A)-C)的重量份之和的1-2倍；
    步骤(3)中，其扩链反应工艺条件包括：反应温度为45-50℃，反应时间15-25min；优选所述组分B)的水溶液中，其水的用量为组分B)质量的3-5倍；
    步骤(3)中，其封端反应工艺条件包括：反应温度为45-50℃，反应时间为5-10min；优选所述组分C)的水溶液中，其水的用量为组分C)质量的3-5倍；
    所述组分D)的加入条件为封端反应结束直接加入，其加入方式为：将全部的所述组分D)一次性加入或者先加入一部分组分D)，剪切分散得到水性聚氨酯-醋酸乙烯酯混合乳液后再在其中加入剩余的组分D)；水性聚氨酯-醋酸乙烯酯混合乳液在组分D)中发生溶胀，所述溶胀的温度为35-45℃；
    步骤(4)中，加入所述组分E)的保护胶体进行搅拌混合，混合的时间为0.5-1h；加入所述组分F)的自由基引发剂的引发温度为35-45℃，聚合反应温度为40-45℃，聚合反应时间为2-3h；
    步骤(5)中，所述脱溶剂的方式为减压蒸馏。
  10. 权利要求1-7中任一项所述的水性聚氨酯-聚醋酸乙烯酯树脂 或权利要求8-9中任一项所述的制备方法制得的水性聚氨酯-聚醋酸乙烯酯树脂作为胶黏剂的应用；
    优选地，所述水性聚氨酯-聚醋酸乙烯酯树脂应用于鞋胶领域、吸塑胶领域、复膜胶领域以及汽车内饰胶领域。
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