CN102492113B - Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) - Google Patents
Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) Download PDFInfo
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- CN102492113B CN102492113B CN 201110390204 CN201110390204A CN102492113B CN 102492113 B CN102492113 B CN 102492113B CN 201110390204 CN201110390204 CN 201110390204 CN 201110390204 A CN201110390204 A CN 201110390204A CN 102492113 B CN102492113 B CN 102492113B
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Abstract
The invention discloses a method for preparing a waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI). A diisocyanate system formed by combining polyester polyol, the TDI and the HDI is reacted to produce a prepolymer, hydrophilic chain extender and a polyatomic alcohol monomer are added for further reaction, chain extension is performed based on micromolecule dihydric alcohol, and finally the waterborne polyurethane adhesive based on the TDI and the HDI is prepared. The solid content of the prepared waterborne polyurethane adhesive can reach to40-50%, initial adhesion is large, and cohesive strength is high. When the waterborne polyurethane adhesive is used, heat-resisting temperature can reach above 160 DEG C without adding a curing agent, the viscosity is controlled in a range of 200-500cp, and polyvinyl chloride (PVC)/ PVC peel strength can reach 5-7N/mm2.
Description
Technical field
The invention belongs to the organic polymer material technical field, relate to a kind of preparation method of polyurethane adhesive, particularly relate to a kind of preparation method of water-based polyurethane adhesive.The water-based polyurethane adhesive of the present invention preparation can be used for exempting to coat with lacquer the bonding of materials such as timber, PVC, leather, fabric, paper in the industries such as decoration, automotive trim, fabrication, lamination, shoemaking.
Background technology
Along with developing rapidly of modernization industry, the environment-friendly type aqueous polyurethane tackiness agent replaces the solvent borne polyurethane tackiness agent has become inexorable trend.Compare with the solvent borne polyurethane tackiness agent, water-based polyurethane adhesive does not have the solvent stink, and is nontoxic, pollution-free, easy to operate, and storing safety, convenient more and more is subject to people's attention.
Isocyanic ester aliphatics product for the preparation of water-based polyurethane adhesive has isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) etc.
US Patent No. P 6147155 points out can prepare softness and the high aqueous polyurethane of intensity with HDI.But when using HDI separately, form very thick paste based on the prepolymer of HDI when the emulsification, be difficult for carrying out chain extending reaction, perhaps when carrying out chain extending reaction with amine, generates insoluble polyureas flocculated particle, limited the commodity application of product.In order to address the above problem, USP 4870129 has adopted the binary isocyanic ester system that is made of HDI and IPDI to make polyurethane binder.This patent has used a kind of special sulfonic acid diamines to introduce ionic group as chainextender, its preparation technology must produce prepolymer by first chain extension, and then be distributed in the water, increased the difficulty of disperseing, therefore used a large amount of acetone to reduce the viscosity of prepolymer, and because the IPDI price is higher, the cost of this polyurethane binder is increased.
CN1362436A has adopted the ternary or the multicomponent isocyanate compound system that are made of HDI, tetramethylene Xylene Diisocyanate (TMXDI) and other vulcabond to make polyurethane binder as initiator, this tackiness agent heat resisting temperature is lower, be up to 125 ℃, can not fully satisfy the demand of existing market.CN101173031B has adopted the binary isocyanic ester system that is made of HDI and methylenediphenyl diisocyanates (MDI) to make polyurethane binder, this tackiness agent preferred embodiment is applied to shoe-making field, and the problem that bonding dry film loses viscosity may occur when its tack temperature is higher than 65 ℃, so its product is not suitable for using in the high temperature bond field.
Above patent shows that HDI is a kind of vulcabond that is widely used in the preparation aqueous polyurethane, but uses HDI to be difficult for successfully preparing aqueous polyurethane separately; Prepare prepolymer with HDI and two kinds of vulcabond of IPDI, must use a large amount of solvents; With TMXDI with and prepare aqueous polyurethane with the mixture of other vulcabond, cohesiveness is good inadequately when using as tackiness agent; With the aqueous polyurethane of HDI and two kinds of vulcabond preparations of MDI, its product should not use in the high temperature bond field.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of the water-based polyurethane adhesive based on HDI-TDI, the mixture system that this tackiness agent is made up of HDI and two kinds of vulcabond of TDI is made as starting raw material.
The preparation method of the water-based polyurethane adhesive based on HDI-TDI of the present invention may further comprise the steps:
The performed polymer of a, usefulness polyester polyol and HDI reaction generation-OH end group adds the performed polymer that tolylene diisocyanate (TDI) reacts generation-NCO end group then;
B, interpolation hydrophilic chain extender and polyvalent alcohol monomer further react;
C, with small molecules dibasic alcohol chain extension;
D, with in the triethylamine and conditioned reaction liquid to pH value 6～7, add the acetone reduction material viscosity that accounts for polyester polyol weight 5%～20%, be dispersed into light blue translucent emulsion with deionized water;
E, vacuum removal solvent acetone obtain the water-based polyurethane adhesive based on HDI-TDI.
The concrete preparation method who the present invention is based on the water-based polyurethane adhesive of HDI-TDI is:
Add HDI in a, the polyester polyol after dehydration, 70～90 ℃ of reaction 1.5～2.5h, the performed polymer of generation-OH end group; Be cooled to 30～50 ℃, add TDI and continue reaction 3～5h, the performed polymer of generation-NCO end group;
The amount that adds vulcabond should satisfy: the mole ratio of isocyanate group and polyester polyols alcoholic extract hydroxyl group is 1.7～4: 1, and wherein the mole ratio of TDI and HDI is 3～6: 1;
B, interpolation hydrophilic chain extender and polyvalent alcohol monomer, in 50～70 ℃ of chain extending reaction 1～2h, wherein, the mole ratio of hydrophilic chain extender and polyester polyol is 0.3～2: 1, the mole ratio of polyvalent alcohol monomer and polyester polyol satisfies 0.01～1: 1;
C, be 0.02～0.5: 1 ratio according to the mole ratio of small molecules dibasic alcohol and polyester polyol, add the small molecules dibasic alcohol, in 50～70 ℃ of chain extending reaction 1～3h;
In d, the usefulness triethylamine and pH value to 6～7 of conditioned reaction liquid add the acetone that accounts for polyester polyol weight 5～20% and reduce the material viscosity, add deionized water and stirring 2～6h, are dispersed into the light blue translucent emulsion of solid content 40%～50%;
E, vacuum decompression remove solvent acetone, obtain the water-based polyurethane adhesive based on HDI-TDI.
Among the preparation method of the present invention, described polyester polyol refers to a kind of in poly-adipic acid glycol ester, poly-adipic acid butanediol ester, poly-adipic acid glycol ether ester, poly-adipic acid hexylene glycol ester, poly-adipic acid DOPCP or the poly-adipic acid dipropylene glycol ester, perhaps several arbitrary proportion mixture.
Among the preparation method of the present invention, the hydrophilic chain extender of use refers to dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl half ester, hydroxacetic acid, 2 hydroxy propanoic acid, resorcylic acid or dyhydrobutanedioic acid.
Employed polyvalent alcohol monomer is glycerine, tetramethylolmethane, TriMethylolPropane(TMP) or tricresyl phosphate glycol ester among the preparation method of the present invention.
Among the preparation method of the present invention, the small molecules dibasic alcohol of use refers to 1,4-butyleneglycol, ethylene glycol, propylene glycol, hexylene glycol, glycol ether or Triethylene glycol.
The water-based polyurethane adhesive solid content based on HDI-TDI that adopts the inventive method to prepare can reach 40-50%; The tackiness agent initial bonding strength is big, and the cohesive strength height can satisfy the needs that high strength bond requires; And the tackiness agent activation temperature is low, has only 60 ℃; The heat resisting temperature height of tackiness agent need not add solidifying agent during use.
Among the preparation method of the present invention, select for use the binary isocyanic ester system of TDI and HDI composition as starting raw material, both remedy HDI and prepared shortcoming on the performance that water-based polyurethane adhesive brings as starting raw material separately, guaranteed the economy of final adhesive products again, thereby can enough be extensive use of at industrial circle, and the introducing of TDI has not only reduced the cost of water-based polyurethane adhesive, has also effectively increased cohesive strength and the initial bonding strength of tackiness agent.In addition, add the resistance toheat that the polyvalent alcohol monomer can significantly improve water-based polyurethane adhesive, emulsion property is stable, and initial adhesive strength is big.The water-based polyurethane adhesive of preparation can not add solidifying agent in use, and its heat resisting temperature reaches more than 160 ℃, and viscosity can be controlled at 200～500cp, and the PVC/PVC stripping strength can reach 5～7 N/mm simultaneously
2
The water-based polyurethane adhesive that adopts preparation method of the present invention to produce can be used for automotive interior trim, wrapping material, timber, PVC and leather etc., all reaches the required product quality indicator of user in environmental protection, solid content, initial adhesive strength, water tolerance and aspect such as heat-resisting.Preparation method of the present invention also has advantages such as plant factor height, transportation cost and unit product energy expenditure are low.
Embodiment
Embodiment 1
In four-hole boiling flask, add the poly-adipic acid butanediol ester of 75g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 70 ℃, add 3g HDI reaction 2h, then add 13.5g TDI reaction 1h, add 3.5g dimethylol propionic acid and 0.75g tricresyl phosphate glycol ester reaction 0.5h again, add 0.2g 1 again, 4-butyleneglycol reaction 2.5h carries out neutralization reaction 30min with the 2.5g triethylamine, reduces the material viscosity with 5g acetone simultaneously, add the 95g deionized water, vacuumize and obtain water-based polyurethane adhesive after removing solvent acetone.This product is light blue emulsion, 180 ℃ of its heat resisting temperatures, solid content 50%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 2
In four-hole boiling flask, add the poly-adipic acid DOPCP of 81g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 75 ℃, add 4.9g HDI reaction 2.2h, then add 14.2g TDI reaction 1.5h, add 6g dimethylolpropionic acid and 0.8g TriMethylolPropane(TMP) reaction 1h again, add 0.15g glycol ether reaction 2h again, carry out neutralization reaction 30min with the 3.5g triethylamine, reduce the material viscosity with 15g acetone simultaneously, add the 150g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 190 ℃ of its heat resisting temperatures, solid content 40%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 3
In four-hole boiling flask, add the poly-adipic acid hexylene glycol ester of 79g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 76 ℃, add 4.2g HDI reaction 2.5h, then add 15.8g TDI reaction 1.2h, add 6.5g2-hydroxy-propionic acid and 0.85g glycerine reaction 1.5h again, add 1.5g Triethylene glycol reaction 2.5h again, carry out neutralization reaction 30min with the 3.6g triethylamine, reduce the material viscosity with 13g acetone simultaneously, add the 130g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 170 ℃ of its heat resisting temperatures, solid content 44%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 4
In four-hole boiling flask, add the poly-adipic acid butanediol ester of 50g and the poly-adipic acid DOPCP of 30g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 70 ℃, add 4.3g HDI reaction 2h, then add 16.1g TDI reaction 1.5h, add 7g dimethylol propionic acid and 1g tricresyl phosphate glycol ester reaction 1h again, add 1.4g hexylene glycol reaction 2.5h again, carry out neutralization reaction 30min with the 4g triethylamine, reduce the material viscosity with 15g acetone simultaneously, add the 140g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 175 ℃ of its heat resisting temperatures, solid content 42%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 5
In four-hole boiling flask, add the poly-adipic acid glycol ester of 85g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 72 ℃, add 3.6g HDI reaction 2h, then add 15.3g TDI reaction 1h, add 5.3g dimethylol propionic acid and 0.8g TriMethylolPropane(TMP) reaction 0.5h again, add 0.51g propylene glycol reaction 2.5h again, carry out neutralization reaction 30min with the 3.4g triethylamine, reduce the material viscosity with 12g acetone simultaneously, add the 97g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 180 ℃ of its heat resisting temperatures, solid content 50%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 6
In four-hole boiling flask, add the poly-adipic acid DOPCP of 77g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 69 ℃, add 3.3g HDI reaction 2h, then add 14g TDI reaction 1h, add 4.6g dihydroxypropionic acid and 0.72g tetramethylolmethane reaction 0.5h again, add 1g glycol ether reaction 2.5h again, carry out neutralization reaction 30min with the 3.1g triethylamine, reduce the material viscosity with 9g acetone simultaneously, add the 105g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 170 ℃ of its heat resisting temperatures, solid content 48%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 7
In four-hole boiling flask, add the poly-adipic acid DOPCP of 40g and the poly-adipic acid glycol ester of 40g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 71 ℃, add 3.4g HDI reaction 2h, then add 14.5g TDI reaction 1.5h, add 5.3g dimethylol propionic acid and 0.8g TriMethylolPropane(TMP) reaction 1.5h again, add 1.5g Triethylene glycol reaction 1.5h again, carry out neutralization reaction 30min with the 3.2g triethylamine, reduce the material viscosity with 8g acetone simultaneously, add the 100g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 165 ℃ of its heat resisting temperatures, solid content 49%, PVC/PVC stripping strength 5～7N/mm
2
Embodiment 8
In four-hole boiling flask, add the poly-adipic acid hexylene glycol ester of 82g, heating and melting, 120 ℃ vacuumize 1.5h, cool to 74 ℃, add 3.5g HDI reaction 2h, then add 14.9g TDI reaction 1h, add 5.1g dimethylol propionic acid and 0.8g tricresyl phosphate glycol ester reaction 0.5h again, add 2.8g Triethylene glycol reaction 2.5h again, carry out neutralization reaction 30min with the 3.3g triethylamine, reduce the material viscosity with 11g acetone simultaneously, add the 110g deionized water, vacuumize and remove solvent acetone and namely obtain water-based polyurethane adhesive.This product is light blue emulsion, 160 ℃ of its heat resisting temperatures, solid content 47%, PVC/PVC stripping strength 5～7N/mm
2
Claims (5)
1. preparation method based on the water-based polyurethane adhesive of HDI-TDI is characterized in that preparing according to following steps:
Add HDI in a, the polyester polyol after dehydration, 70～90 ℃ of reaction 1.5～2.5h, the performed polymer of generation-OH end group; Be cooled to 30～50 ℃, add TDI and continue reaction 3～5h, the performed polymer of generation-NCO end group;
The amount that adds vulcabond should satisfy: the mole ratio of isocyanate group and polyester polyols alcoholic extract hydroxyl group is 1.7～4: 1, and wherein the mole ratio of TDI and HDI is 3～6: 1;
B, interpolation hydrophilic chain extender and polyvalent alcohol monomer, in 50～70 ℃ of chain extending reaction 1～2h, wherein, the mole ratio of hydrophilic chain extender and polyester polyol is 0.3～2: 1, the mole ratio of polyvalent alcohol monomer and polyester polyol satisfies 0.01～1: 1;
C, be 0.02～0.5: 1 ratio according to the mole ratio of small molecules dibasic alcohol and polyester polyol, add the small molecules dibasic alcohol, in 50～70 ℃ of chain extending reaction 1～3h;
In d, the usefulness triethylamine and pH value to 6～7 of conditioned reaction liquid add the acetone that accounts for polyester polyol weight 5～20% and reduce the material viscosity, add deionized water and stirring 2～6h, are dispersed into the light blue translucent emulsion of solid content 40%～50%;
E, vacuum decompression remove solvent acetone, obtain the water-based polyurethane adhesive based on HDI-TDI.
2. according to the preparation method by the described water-based polyurethane adhesive based on HDI-TDI of claim 1, it is characterized in that described polyester polyol refers to a kind of in poly-adipic acid glycol ester, poly-adipic acid butanediol ester, poly-adipic acid glycol ether ester, poly-adipic acid hexylene glycol ester, poly-adipic acid DOPCP or the poly-adipic acid dipropylene glycol ester, perhaps several arbitrary proportion mixture.
3. according to the preparation method by the described water-based polyurethane adhesive based on HDI-TDI of claim 1, it is characterized in that described hydrophilic chain extender refers to dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl half ester, hydroxacetic acid, 2 hydroxy propanoic acid, resorcylic acid or dyhydrobutanedioic acid.
4. according to the preparation method by the described water-based polyurethane adhesive based on HDI-TDI of claim 1, it is characterized in that described polyvalent alcohol monomer is glycerine, tetramethylolmethane, TriMethylolPropane(TMP) or tricresyl phosphate glycol ester.
5. according to the preparation method by the described water-based polyurethane adhesive based on HDI-TDI of claim 1, it is characterized in that described small molecules dibasic alcohol refers to 1,4-butyleneglycol, ethylene glycol, propylene glycol, hexylene glycol, glycol ether or Triethylene glycol.
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| CN 201110390204 CN102492113B (en) | 2011-12-01 | 2011-12-01 | Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) |
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| CN 201110390204 CN102492113B (en) | 2011-12-01 | 2011-12-01 | Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) |
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| CN103242254B (en) * | 2013-04-23 | 2014-09-24 | 嘉宝莉化工集团股份有限公司 | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer |
| CN103694940A (en) * | 2013-12-15 | 2014-04-02 | 山西省应用化学研究所 | Method for preparing fast curing one-component water-based polyurethane adhesive |
| CN106519180A (en) * | 2016-10-26 | 2017-03-22 | 江苏乘鹰新材料股份有限公司 | High-temperature self-repairing polyurethane emulsion and preparation method thereof |
| CN108752552B (en) * | 2018-06-06 | 2020-12-01 | 上海华谊精细化工有限公司 | Preparation method of branched waterborne polyurethane nanocomposite |
| CN112079986B (en) * | 2020-09-21 | 2022-07-12 | 兰州科时西西里健康科技有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN115044020B (en) * | 2021-10-25 | 2023-11-03 | 上海联景高分子材料有限公司 | Application of polyester polyol in adhesive for food packaging |
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| DE69832063T2 (en) * | 1998-08-28 | 2006-07-13 | Council Of Scientific And Industrial Research | An improved process for the preparation of stable aqueous urethane dispersions |
| US6231985B1 (en) * | 1999-05-18 | 2001-05-15 | Ashland Inc. | Heat and radio frequency-curable two-pack soy protein-based polyurethane adhesive compositions |
| CN100497429C (en) * | 2002-01-18 | 2009-06-10 | 段友芦 | Aqueous polyurethane dispersing liquid and preparation thereof as tackiness agent and coating |
| CN101173031B (en) * | 2006-11-01 | 2010-11-03 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN101824299B (en) * | 2010-04-30 | 2012-10-03 | 山西省应用化学研究所 | Method for preparing single-component high-solid content water-based polyurethane adhesive |
| CN102153984B (en) * | 2011-01-26 | 2013-06-26 | 山西省应用化学研究所 | Method for preparing single-component high-heat-resistance aqueous polyurethane adhesive |
| CN102140327B (en) * | 2011-02-28 | 2013-11-27 | 中国科学院宁波材料技术与工程研究所 | Storable plant oil-based polyurethane wood adhesive and preparation method and application thereof |
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