CN110330935A - A kind of water-based polyurethane adhesive and preparation method thereof - Google Patents

A kind of water-based polyurethane adhesive and preparation method thereof Download PDF

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CN110330935A
CN110330935A CN201910713372.1A CN201910713372A CN110330935A CN 110330935 A CN110330935 A CN 110330935A CN 201910713372 A CN201910713372 A CN 201910713372A CN 110330935 A CN110330935 A CN 110330935A
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water
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weight
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邱元进
饶长贵
陈国栋
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Fujian Huaxialan New Material Technology Co Ltd
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Fujian Huaxialan New Material Technology 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of water-based polyurethane adhesives and preparation method thereof.The water-based polyurethane adhesive adds a certain amount of auxiliary agent by a kind of self-crosslinking aqueous polyurethane dispersions and forms.The self-crosslinking aqueous polyurethane dispersions contain anions and canons functional group simultaneously.The water-based polyurethane adhesive is at fitting initial stage, anions and canons group in different polyurethane molecular chains mutually forms the very high ionic bond of bond energy, very strong self-crosslinking is provided, it acts synergistically simultaneously with the crystallization of flexible polyurethane segment molecule chain, polyurethane adhesive initial bond strength is improved rapidly, and later period adhesive strength is good, and storage stability is good, is conducive to industrialized production.

Description

A kind of water-based polyurethane adhesive and preparation method thereof
Technical field
The present invention relates to a kind of water-based polyurethane adhesives and preparation method thereof.
Background technique
With the development of science and technology, water-based polyurethane adhesive achieves significant progress, in multiple fields instead of molten Dosage form polyurethane adhesive.Water-based polyurethane adhesive solvent content is extremely low, environmentally protective, easy to use, later period adhesive strength Height, more and more people begin to focus on and use water-based polyurethane adhesive.
Currently, water-based polyurethane adhesive is compared with solvent borne polyurethane adhesive, it is maximum the disadvantage is that, aqueous poly- ammonia Ester gum stick crystallization rate is slow, and it is lower to be embodied directly in initial bond strength.This characteristic makes water-based polyurethane adhesive Using being not so good as, solvent borne polyurethane adhesive is extensive, especially in shoes water-based polyurethane adhesive field, due to part shoes Material is harder, or due to the operating reasons such as in place of not polishing, so that shoes portion tension in forming process is larger, it is existing Water-based polyurethane adhesive easily flicks after fitting since initial bond strength is lower, thus this certain customers still use it is molten The use wish of dosage form polyurethane adhesive, water-based polyurethane adhesive is lower.
Those skilled in the art have conducted extensive research work also based on this.CN108084945A proposes that one kind has containing nanometer The polyaminoester emulsion adhesive of machine montmorillonite, CN105647450A disclose a kind of environment-friendly water-based adhesive for shoes, comprising: modified Casein, polyacrylate, caprolactam, water dispersible polyisocyanates, sodium carboxymethylcellulose, amino resins, functional tree Rouge, dodecyl trimethyl ammonium chloride, aerosol-OT salt, dodecyl benzene sulfonic acid and curing agent.
There is problem in above technical scheme: the compatibility of CN108084945A technical solution, inorganic matter and organic matter compared with Difference, although above-mentioned technical proposal is matched using specified raw material and inorganic matter, batch wise differences even temperature, humidity of raw material etc. Condition of storage variation and transport etc. may cause phenomena such as flocculation, precipitating, may cause serious consequence in actual production.
CN105647450A the invention compounds component up to ten kinds or more, and slight formula changes or material supplier's variation is equal It may cause the variation of product stability, meanwhile, various ingredients, may be to the color inhibition of adhesive products due to the presence of aromatic ring Performance products negative effect, does not meet the adhesive requirement of footwear production.
Summary of the invention
The present invention provides a kind of water-based polyurethane adhesive of high initial bond strength, the technical solution that the present invention takes It is that the water-based polyurethane adhesive of high initial bond strength adds a certain amount of auxiliary agent by a kind of self-crosslinking aqueous polyurethane dispersions It forms.The self-crosslinkable polyurethane dispersions, general structure are as follows:
；
In formula, R1For、、、WithOne or more of；
R2General structure are as follows:, wherein R4ForStructure Block copolymer, a and b are the integer of 0-50, and 30≤a+b≤60, a > b；
R5Structure is；
R3For, wherein M is Na, K or NH4One of.
The high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) A mol is contained into R4The dihydroxyl compound and E mol 1 of structure, 2,7,8- bicyclic oxygroup octanes are added in reaction kettle, It is warming up to 90-130 DEG C of reaction 1-5 hours.It is cooled to 30-50 DEG C, E mol trimethylamine is added, is reacted 4-12 hours；
(2) product for obtaining step (1) is added in reaction kettle, is warming up to 110-150 DEG C, vacuumizes moisture removal, until moisture Weight ratio less than 0.1%；It is cooled to 40-50 DEG C, B mol is contained into R1System is added in the diisocyanate cpd of group, and It is warming up to 60-100 DEG C, reaction was cooled to 40-50 DEG C after 0.5-8 hours, obtained Isocyanate prepolymers body；
(3) butanone that 30-40 times of dihydroxyl compound of molfraction is added in Isocyanate prepolymers body reduces system viscosity, C mol N- (2- amino-ethyl) -2- aminoethane sulphonic acid salt is added, is warming up to 70-100 DEG C, reaction is cooled to after 2-16 hours 30-40℃；It adds D mol and contains R4The compound of structure is warming up to 60-95 DEG C, and reaction was cooled to 30-40 after 2-16 hours ℃；
(4) after 1-3 kg water is slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=6-8, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 45-55%, stirs evenly to get high initial stage Adhesive strength aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 980-997 parts by weight is taken, 1-5 parts by weight defoaming agent is sequentially added CoaddTMDF-825,1-5 parts by weight wetting agent CoaddTMW110 and 1-4 parts by weight of thickening agent CoaddTMU920,0-6 weight Part thickener CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive；
According to the molar ratio, A:C=5-20:1, B=A+C+0.5D, 0.1≤E/A≤0.7.
The water-based polyurethane adhesive of high initial bond strength of the present invention is dispersed by a kind of self-crosslinking aqueous polyurethane Body adds a certain amount of auxiliary agent and forms, and the self-crosslinking aqueous polyurethane dispersions contain anions and canons functional group, the height simultaneously At fitting initial stage, the anions and canons group in different polyurethane molecular chains is the water-based polyurethane adhesive of initial bond strength Mutually form the very high ionic bond of bond energy, very strong self-crosslinking be provided, at the same with the crystallization of flexible polyurethane segment molecule chain into Row synergistic effect, improves rapidly the initial bond strength of polyurethane adhesive, and later period adhesive strength is good, storage stability It is good, be conducive to industrialized production.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained with reference to embodiments.
Embodiment 1
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) 1 mol is contained into PEG-60 and 0.7 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, are warming up to 120 DEG C Reaction 1-5 hours；45 DEG C are cooled to, 0.7 mol trimethylamine is added, is reacted 10 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is 0.08%；Drop 2.7 mol are contained hexamethylene diisocyanate and system are added by temperature to 50 DEG C, and are warming up to 100 DEG C, after reaction 0.5 hour 40 DEG C are cooled to, Isocyanate prepolymers body is obtained；
(3) 2.5 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, and 0.2 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid ammonium, 70 DEG C are warming up to, reaction was cooled to 30 DEG C after 16 hours；1 mol PEG-60 is added, is risen For temperature to 95 DEG C, reaction was cooled to 40 DEG C after 2 hours；
(4) it after 1 kg water is slowly added dropwise, stirs and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=6, and it is 55% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 997 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110 and 1 parts by weight of thickening agent CoaddTMU920 stirred evenly up to high initial stage Adhesive strength water-based polyurethane adhesive F1.
Embodiment 2
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) 1mol is contained into PEG-42-co-PPG-15 and 0.1 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 90 DEG C react 5 hours.30 DEG C are cooled to, 0.1 mol trimethylamine is added, is reacted 12 hours；
(2) product that step (1) obtains is warming up to 110-150 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is 0.05%；40 DEG C are cooled to, system is added in 1.4 mol diisocyanate containing toluene, and be warming up to 60 DEG C, after reaction 8 hours 40 DEG C are cooled to, Isocyanate prepolymers body is obtained；
(3) 2.8 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, and 0.05 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid sodium, 70 DEG C are warming up to, reaction was cooled to 35 DEG C after 16 hours；Add 0.5 mol PEG-42- Co-PPG-15 is warming up to 60 DEG C, and reaction was cooled to 40 DEG C after 16 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=8, and it is 45% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 980 parts by weight is taken, 5 parts by weight defoaming agent Coadd are sequentially addedTM DF-825,5 parts by weight wetting agent CoaddTMW110,4 parts by weight of thickening agent CoaddTMU920 and 6 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F2.
Embodiment 3
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) by 1.5 mol PEG-22-co-PPG-8 and 0.3 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 120 DEG C react 3 hours.40 DEG C are cooled to, 0.3 mol trimethylamine is added, is reacted 6 hours；
(2) product that step (1) obtains is warming up to 130 DEG C, vacuumizes moisture removal, until the weight of moisture is 0.09%；Cooling To 40 DEG C, system is added in 2.2mol methyl diphenylene diisocyanate, and be warming up to 80 DEG C, reaction was cooled to 40 after 5 hours DEG C, obtain Isocyanate prepolymers body；
(3) 2kg butanone is added in Isocyanate prepolymers body reduces system viscosity, is added 0.3 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid potassium is warming up to 80 DEG C, and reaction was cooled to 40 DEG C after 9 hours；Add 0.8 mol PEG-22-co- PPG-8 is warming up to 85 DEG C, and reaction was cooled to 40 DEG C after 16 hours；
(4) after 1.5 kg water are slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=7, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 55%, stirs evenly to get high initial bond Intensity aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 990 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,2 parts by weight wetting agent CoaddTMW110,4 parts by weight of thickening agent CoaddTMU920 and 3 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F3.
Embodiment 4
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) by 2 mol PEG-35-co-PPG-5 and 0.8 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, heating It is reacted 2 hours to 130 DEG C.38 DEG C are cooled to, 0.8 mol trimethylamine is added, is reacted 8 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.1%； 50 DEG C are cooled to, system is added in 2.7 mol isophorone diisocyanate, and be warming up to 70 DEG C, reaction is cooled to after 7 hours 40 DEG C, obtain Isocyanate prepolymers body；
(3) 3 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, is added 0.2 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid ammonium is warming up to 90 DEG C, and reaction was cooled to 40 DEG C after 6 hours；Add 1 mol PEG-35-co-PPG- 5,85 DEG C are warming up to, reaction was cooled to 40 DEG C after 5 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=7, and it is 50% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 996 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110,1 parts by weight of thickening agent CoaddTMU920 and 1 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F4.
Embodiment 5
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) by 1 mol PEG-40-co-PPG-12 and 0.5 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 100 DEG C react 3 hours.35 DEG C are cooled to, 0.5 mol trimethylamine is added, is reacted 7 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.05%； 40 DEG C are cooled to, system is added in 1mol hexamethylene diisocyanate and 0.4mol isophorone diisocyanate, and heat up To 75 DEG C, reaction was cooled to 40 DEG C after 6 hours, obtained Isocyanate prepolymers body；
(3) 2.3kg butanone is added in Isocyanate prepolymers body reduces system viscosity, and 0.08 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid sodium, 85 DEG C are warming up to, reaction was cooled to 40 DEG C after 9 hours；Add 0.64 mol PEG-40- Co-PPG-12 is warming up to 75 DEG C, and reaction was cooled to 40 DEG C after 10 hours；
(4) after 1.8kg water is slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=8, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 55%, stirs evenly to get high initial bond Intensity aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 988 parts by weight is taken, 2 parts by weight defoaming agent Coadd are sequentially addedTM DF-825,3 parts by weight wetting agent CoaddTMW110 and 2 parts by weight of thickening agent CoaddTMU920,5 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F5.
Embodiment 6
A kind of high initial bond strength water-based polyurethane adhesive the preparation method comprises the following steps:
(1) by 1 mol PEG-30-co-PEG-5 and 0.15 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 110 DEG C react 2 hours.40 DEG C are cooled to, 0.15 mol trimethylamine is added, is reacted 12 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.09%； 50 DEG C are cooled to, system is added in 1 mol isophorone diisocyanate and 0.35 mol toluene di-isocyanate(TDI), and be warming up to 100 DEG C, reaction was cooled to 40 DEG C after 1 hour, obtained Isocyanate prepolymers body；
(3) 2kg butanone is added in Isocyanate prepolymers body reduces system viscosity, is added 0.12 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid potassium is warming up to 100 DEG C, and reaction was cooled to 30 DEG C after 2 hours；It adds 0.46 mol and contains R4Structure Compound is warming up to 95 DEG C, and reaction was cooled to 40 DEG C after 4 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=6, and it is 45% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 994 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110 and 1 parts by weight of thickening agent CoaddTMU920,3 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F6.
By water-based polyurethane adhesive F1 ~ F6 of high initial bond strength made from above-described embodiment and commercially available aqueous poly- ammonia Ester gum stick product F 7, F8, commercial solvents type polyurethane adhesive product F 9, F10 press " GB/T 19340-2014 shoes and case Packet adhesive " in regulation carry out initial bond strength and later period adhesive strength and test, the results are shown in Table 1.
1. polyurethane adhesive F1 ~ F10 initial bond strength of table and later period adhesive strength test result
Sample ID Initial bond strength, N/mm Later period adhesive strength, N/mm
Adhesive F1 16.64 24.12
Adhesive F2 17.12 25.34
Adhesive F3 16.74 23.36
Adhesive F4 16.94 24.92
Adhesive F5 18.40 26.88
Adhesive F6 17.46 25.68
Adhesive F7 11.96 24.32
Adhesive F8 13.14 25.76
Adhesive F9 18.18 25.2
Adhesive F10 17.78 24.9
As it can be seen from table 1 the initial bond strength of adhesive D1 ~ D6 is generally in 16N/mm or more, about later period adhesive strength 60% ~ 70%, it is suitable with solvent based product E1 and E2, and the initial bond strength of commercial product E1 and E2 are only that later period bonding is strong 50% or so of degree.And compare from later period adhesive strength, 10 adhesive products results are close.This absolutely prove adhesive D1 ~ D6 initial bond strength is good, can improve early strength rapidly in use, and on later period adhesive strength without influence.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalents made by bright, are included in protection scope of the present invention.

Claims (8)

1. a kind of water-based polyurethane adhesive, it is characterised in that: the water-based polyurethane adhesive is by a kind of self-crosslinking aqueous Dispersions of polyurethanes addition auxiliary agent forms, the self-crosslinkable polyurethane dispersions, general structure are as follows:
；
In formula, R1For、、、WithOne or more of；
R2General structure are as follows:, wherein R4ForStructure Block copolymer, a and b are the integer of 0-50, and 30≤a+b≤60, a > b；
R5Structure is；
R3For, wherein M is Na, K or NH4One of.
2. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) A mol is contained into R4The dihydroxyl compound and E mol 1 of structure, 2,7,8- bicyclic oxygroup octanes are added in reaction kettle, It is warming up to 90-130 DEG C of reaction 1-5 hours;It is cooled to 30-50 DEG C, E mol trimethylamine is added, is reacted 4-12 hours；
(2) product for obtaining step (1) is added in reaction kettle, is warming up to 110-150 DEG C, vacuumizes moisture removal, until moisture Weight ratio less than 0.1%；It is cooled to 40-50 DEG C, B mol is contained into R1System is added in the diisocyanate cpd of group, and It is warming up to 60-100 DEG C, reaction was cooled to 40-50 DEG C after 0.5-8 hours, obtained Isocyanate prepolymers body；
(3) butanone that 30-40 times of dihydroxyl compound of molfraction is added in Isocyanate prepolymers body reduces system viscosity, C mol N- (2- amino-ethyl) -2- aminoethane sulphonic acid salt is added, is warming up to 70-100 DEG C, reaction is cooled to after 2-16 hours 30-40℃；It adds D mol and contains R4The compound of structure is warming up to 60-95 DEG C, and reaction was cooled to 30-40 after 2-16 hours ℃；
(4) after 1-3 kg water is slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=6-8, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 45-55%, stirs evenly to get high initial stage Adhesive strength aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 980-997 parts by weight is taken, 1-5 parts by weight defoaming agent is sequentially added CoaddTMDF-825,1-5 parts by weight wetting agent CoaddTMW110 and 1-4 parts by weight of thickening agent CoaddTMU920,0-6 weight Part thickener CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive；
According to the molar ratio, A:C=5-20:1, B=A+C+0.5D, 0.1≤E/A≤0.7.
3. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) 1 mol is contained into PEG-60 and 0.7 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, are warming up to 120 DEG C Reaction 1-5 hours；45 DEG C are cooled to, 0.7 mol trimethylamine is added, is reacted 10 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is 0.08%；Drop 2.7 mol are contained hexamethylene diisocyanate and system are added by temperature to 50 DEG C, and are warming up to 100 DEG C, after reaction 0.5 hour 40 DEG C are cooled to, Isocyanate prepolymers body is obtained；
(3) 2.5 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, and 0.2 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid ammonium, 70 DEG C are warming up to, reaction was cooled to 30 DEG C after 16 hours；1 mol PEG-60 is added, is risen For temperature to 95 DEG C, reaction was cooled to 40 DEG C after 2 hours；
(4) it after 1 kg water is slowly added dropwise, stirs and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=6, and it is 55% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 997 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110 and 1 parts by weight of thickening agent CoaddTMU920 stirred evenly up to high initial stage Adhesive strength water-based polyurethane adhesive F1.
4. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) 1mol is contained into PEG-42-co-PPG-15 and 0.1 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 90 DEG C react 5 hours;30 DEG C are cooled to, 0.1 mol trimethylamine is added, is reacted 12 hours；
(2) product that step (1) obtains is warming up to 110-150 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is 0.05%；40 DEG C are cooled to, system is added in 1.4 mol diisocyanate containing toluene, and be warming up to 60 DEG C, after reaction 8 hours 40 DEG C are cooled to, Isocyanate prepolymers body is obtained；
(3) 2.8 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, and 0.05 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid sodium, 70 DEG C are warming up to, reaction was cooled to 35 DEG C after 16 hours；Add 0.5 mol PEG-42- Co-PPG-15 is warming up to 60 DEG C, and reaction was cooled to 40 DEG C after 16 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=8, and it is 45% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 980 parts by weight is taken, 5 parts by weight defoaming agent Coadd are sequentially addedTM DF-825,5 parts by weight wetting agent CoaddTMW110,4 parts by weight of thickening agent CoaddTMU920 and 6 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F2.
5. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) by 1.5 mol PEG-22-co-PPG-8 and 0.3 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 120 DEG C react 3 hours;40 DEG C are cooled to, 0.3 mol trimethylamine is added, is reacted 6 hours；
(2) product that step (1) obtains is warming up to 130 DEG C, vacuumizes moisture removal, until the weight of moisture is 0.09%；Cooling To 40 DEG C, system is added in 2.2mol methyl diphenylene diisocyanate, and be warming up to 80 DEG C, reaction was cooled to 40 after 5 hours DEG C, obtain Isocyanate prepolymers body；
(3) 2kg butanone is added in Isocyanate prepolymers body reduces system viscosity, is added 0.3 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid potassium is warming up to 80 DEG C, and reaction was cooled to 40 DEG C after 9 hours；Add 0.8 mol PEG-22-co- PPG-8 is warming up to 85 DEG C, and reaction was cooled to 40 DEG C after 16 hours；
(4) after 1.5 kg water are slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=7, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 55%, stirs evenly to get high initial bond Intensity aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 990 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,2 parts by weight wetting agent CoaddTMW110,4 parts by weight of thickening agent CoaddTMU920 and 3 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F3.
6. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) by 2 mol PEG-35-co-PPG-5 and 0.8 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, heating It is reacted 2 hours to 130 DEG C;38 DEG C are cooled to, 0.8 mol trimethylamine is added, is reacted 8 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.1%； 50 DEG C are cooled to, system is added in 2.7 mol isophorone diisocyanate, and be warming up to 70 DEG C, reaction is cooled to after 7 hours 40 DEG C, obtain Isocyanate prepolymers body；
(3) 3 kg butanone are added in Isocyanate prepolymers body reduces system viscosity, is added 0.2 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid ammonium is warming up to 90 DEG C, and reaction was cooled to 40 DEG C after 6 hours；Add 1 mol PEG-35-co-PPG- 5,85 DEG C are warming up to, reaction was cooled to 40 DEG C after 5 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=7, and it is 50% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 996 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110,1 parts by weight of thickening agent CoaddTMU920 and 1 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F4.
7. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) by 1 mol PEG-40-co-PPG-12 and 0.5 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 100 DEG C react 3 hours;35 DEG C are cooled to, 0.5 mol trimethylamine is added, is reacted 7 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.05%； 40 DEG C are cooled to, system is added in 1mol hexamethylene diisocyanate and 0.4mol isophorone diisocyanate, and heat up To 75 DEG C, reaction was cooled to 40 DEG C after 6 hours, obtained Isocyanate prepolymers body；
(3) 2.3kg butanone is added in Isocyanate prepolymers body reduces system viscosity, and 0.08 mol N- (2- amino second is added Base) -2- aminoethane sulphonic acid sodium, 85 DEG C are warming up to, reaction was cooled to 40 DEG C after 9 hours；Add 0.64 mol PEG-40- Co-PPG-12 is warming up to 75 DEG C, and reaction was cooled to 40 DEG C after 10 hours；
(4) after 1.8kg water is slowly added dropwise, stirring and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not Higher than 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise It to pH=8, and mends that be filled with water to aqueous polyurethane dispersion effective content in system be 55%, stirs evenly to get high initial bond Intensity aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 988 parts by weight is taken, 2 parts by weight defoaming agent Coadd are sequentially addedTM DF-825,3 parts by weight wetting agent CoaddTMW110 and 2 parts by weight of thickening agent CoaddTMU920,5 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F5.
8. water-based polyurethane adhesive according to claim 1, which is characterized in that the system of the water-based polyurethane adhesive Preparation Method are as follows:
(1) by 1 mol PEG-30-co-PEG-5 and 0.15 mol 1,2,7,8- bicyclic oxygroup octanes are added in reaction kettle, rise Temperature to 110 DEG C react 2 hours;40 DEG C are cooled to, 0.15 mol trimethylamine is added, is reacted 12 hours；
(2) product that step (1) obtains is warming up to 110 DEG C, vacuumizes moisture removal, until the weight ratio of moisture is less than 0.09%； 50 DEG C are cooled to, system is added in 1 mol isophorone diisocyanate and 0.35 mol toluene di-isocyanate(TDI), and be warming up to 100 DEG C, reaction was cooled to 40 DEG C after 1 hour, obtained Isocyanate prepolymers body；
(3) 2kg butanone is added in Isocyanate prepolymers body reduces system viscosity, is added 0.12 mol N- (2- amino-ethyl)- 2- aminoethane sulphonic acid potassium is warming up to 100 DEG C, and reaction was cooled to 30 DEG C after 2 hours；It adds 0.46 mol and contains R4Structure Compound is warming up to 95 DEG C, and reaction was cooled to 40 DEG C after 4 hours；
(4) it after 3 kg water are slowly added dropwise, stir and the butanone by way of vacuum distillation in recovery system, vapo(u)rizing temperature is not high In 74 DEG C, while suitable quantity of water is slowly added dropwise；When butanone content is down to 0.1% or less, stops distillation, dilute hydrochloric acid is slowly added dropwise extremely PH=6, and it is 45% that benefit, which is filled with water to aqueous polyurethane dispersion effective content in system, is stirred evenly strong to get high initial bond Spend aqueous polyurethane dispersion；
(5) the high initial bond strength aqueous polyurethane dispersion of 994 parts by weight is taken, 1 parts by weight defoaming agent Coadd is sequentially addedTM DF-825,1 parts by weight wetting agent CoaddTMW110 and 1 parts by weight of thickening agent CoaddTMU920,3 parts by weight of thickening agent CoaddTMU501 stirs evenly up to high initial bond strength water-based polyurethane adhesive F6.
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