CN100480349C - Method for preparing modified aqueous adhesion agent of polyurethane - Google Patents
Method for preparing modified aqueous adhesion agent of polyurethane Download PDFInfo
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- CN100480349C CN100480349C CNB2007100262112A CN200710026211A CN100480349C CN 100480349 C CN100480349 C CN 100480349C CN B2007100262112 A CNB2007100262112 A CN B2007100262112A CN 200710026211 A CN200710026211 A CN 200710026211A CN 100480349 C CN100480349 C CN 100480349C
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Abstract
This invention discloses a method for preparing modified aqueous polyurethane adhesive. The method comprises: (1) modifying epoxy resin with modifier to obtain modified epoxy resin; (2) reacting polyisocyanate with polyester or polyol polyether, and adding chain extender to obtain polyurethane with prepolymer; (3) modifying polyurethane prepolymer with modified epoxy resin to obtain modified polyurethane prepolymer; (4) adding water, dispersing by a high-speed disperser, and adding neutralizer and crosslinking agent to obtain modified aqueous polyurethane adhesive. This invention introduces epoxy resin into the modification of aqueous polyurethane adhesive, thus combines high modulus, high strength and good chemical resistance of epoxy resin with the advantages of polyurethane resin. The modified aqueous polyurethane adhesive can meet the needs of automobile inner decoration materials. The method has such advantages as simple process, and low cost.
Description
Technical field
The present invention relates to can be used for the preparation method of a kind of modified water-soluble tackiness agent in fields such as automotive interior material, timber, packaging film, fiber, leather, specifically relate to adopt a kind of Resins, epoxy of modification to come modified polyurethane, obtain a kind of preparation method of modified aqueous adhesion agent of polyurethane.
Background technology
The cry of public opinion of preserving the ecological environment grows with each passing day, and some developed countries have formulated fire codes and solvent rules in succession, have limited the use of solvent-based adhesive, and this becomes inevitable trend with regard to the exploitation that makes aqueous adhesive.At present, in China's aqueous adhesive, still based on " three urea formaldehydes " glue, polyvinyl acetate glue and acrylate resin glue etc." three urea formaldehydes " glue in use can produce irritating smell and toxic formaldehyde, and environment is polluted; The water tolerance of vinyl acetate resin glue, thermotolerance and adhesiveproperties are all relatively poor; The lower temperature resistance of acrylic size and cementability are not good.Water-based polyurethane adhesive, be called for short water-based PU tackiness agent, overcome the shortcoming of above aqueous adhesive, it has, and resistance to low temperature is good, bonding strength is high, snappiness good, do not fire, nontoxic, free from environmental pollution, save advantage such as the energy, have vast potential for future development.
Yet the water-based polyurethane adhesive performance that China is studied can't satisfy the needs of multiple material, show that mainly cohesive strength is low, rate of drying is slow, high thermal resistance is relatively poor, theoretical still applied research all lags behind very much, and output is very little, kind is single, does not satisfy the domestic market far away to the growing demand of this high-quality environment protective type tackiness agent.Therefore how improving its bonding strength is the problem that current scholar's research polyurethane adhesive will solve.
This patent is introduced modified epoxy in the water-based polyurethane adhesive modification, obtain the water-based polyurethane adhesive of epoxy resin modification, improved the performance of aqueous polyurethane greatly, this tackiness agent with water as solvent, help environmental protection, its excellent performance has vast potential for future development in fields such as automotive interior material, timber, fiber, leathers.
Summary of the invention
The object of the invention is the shortcoming that exists at existing tackiness agent, provides that a kind of cohesive strength height, rate of drying are fast, water-tolerant, the preparation method is simple, cost is low modified polyurethane adhesive preparation method.
For achieving the above object, the present invention has taked following technical scheme:
A kind of preparation method of modified aqueous adhesion agent of polyurethane comprises the steps:
(1) modified epoxy is synthetic: Resins, epoxy is incorporated with in the conversion unit of agitator, thermometer and condenser, adds the properties-correcting agent reaction, under 120～150 ℃, react 2～3h, obtain the Resins, epoxy of modification; In mass, the properties-correcting agent addition is 1～10% of a Resins, epoxy total amount; Described properties-correcting agent is phosphoric acid or acetic acid;
(2) preparation of base polyurethane prepolymer for use as: in the conversion unit that agitator, thermometer and condenser are housed, add polyisocyanates and oligomer polyol, under 60～80 ℃, reaction 2～3h adds chainextender then, reaction 2～5h, the apparent viscosity size is added acetone, obtains base polyurethane prepolymer for use as; Described chainextender is 1,4-butyleneglycol, neopentyl glycol, ethylene glycol, glycol ether, glycerine, MALEIC ANHYDRIDE, TriMethylolPropane(TMP), quadrol, diethylenetriamine, triethylene tetramine or dimethylol propionic acid, is called for short DMPA;
(3) base polyurethane prepolymer for use as of modification is synthetic: use the modified epoxy modified polyurethane prepolymer down at 60～80 ℃, react 2～3h, obtain the base polyurethane prepolymer for use as of modification; The amount of modified epoxy is 5%～15% of an isocyanic ester total amount;
(4) modified aqueous adhesion agent of polyurethane is synthetic: the base polyurethane prepolymer for use as to modification adds water, disperses with high speed dispersor, adds neutralizing agent and linking agent, obtains modified aqueous adhesion agent of polyurethane; Described linking agent account for total solid content 0.1%～3%, degree of neutralization is 80～100%, 35～40 ℃ of emulsifying temperatures, emulsification times 5～20min, rate of dispersion 2000～3000rpm/min; Described linking agent is quadrol, butanediamine, carbodiimide, trimethylol melamine, dimethylolurea or aziridine.
Described Resins, epoxy resin is preferably E-06, E-12, E-13, E-16, E-20, E-44 or E-51.
Described polyisocyanates is preferably tolylene diisocyanate, be called for short TDI, hexamethylene diisocyanate, be called for short HDI, isophorone diisocyanate, be called for short IPDI, ditan-4,4 '-vulcabond, be called for short MDI, poly methylene poly phenyl poly isocyanate, be called for short PAPI, xylylene diisocyanate, be called for short XDI.
Described oligomer polyol is preferably polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, polycarbonate diol, polycaprolactone glycol, polybutadiene diol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
Described neutralizing agent is preferably hydrochloric acid, acetate, a methyl iodide, sodium hydroxide, ammoniacal liquor, triethylamine, methylamine or trolamine.
With respect to prior art, the present invention has following advantage:
(1) Resins, epoxy is introduced in the modification of polyurethane adhesive, the degree of crosslinking and the cohesive strength of water-based polyurethane adhesive have been improved, by the epoxy group(ing) of Resins, epoxy and the NCO radical reaction of hydroxyl and vulcabond, adopt chemical process Resins, epoxy to be incorporated in the molecular structure of urethane, formation has the aqueous polyurethane of crosslinking structure, high film amount with Resins, epoxy, the advantages of advantages such as high strength and chemical resistant properties are good and urethane resin is got up, reduced the cost of resin, made the polyurethane adhesive of synthetic modification have the performance of Resins, epoxy and urethane.Make that prepared tackiness agent rate of drying is fast, hardness is high, water-tolerant, cohesive strength height, can satisfy the demand of automobile and other multiple material adhesives;
(2) Resins, epoxy is introduced in the modification of aqueous polyurethane emulsion, the advantages of advantage and urethane resin such as high film amount, high strength and the chemical resistant properties of Resins, epoxy be good is got up, reduce the cost of resin, make the polyurethane adhesive of synthetic modification have the performance of Resins, epoxy and urethane, and rate of drying is fast, hardness is high, water-tolerant, cohesive strength height, can satisfy the demand of multiple automotive interior material;
(3) by latex particle design, synthetic polymer emulsion.Whole process using self-emulsification carries out letex polymerization need not add emulsifying agent in emulsion polymerization process, eliminated the influence of low molecule emulsifying agent to glued membrane;
(4) adopt before in and technology, reduce the content of VOC in the emulsion;
(5) the inventive method is easy to operate, technology is simple, with short production cycle, process cost is low, is easy to promotion and application;
(6) water-based polyurethane adhesive of the epoxy resin modification of the present invention's preparation, its performance is suitable with the performance of external similar water-based polyurethane adhesive, and cost is more much lower than external sample.
Embodiment
For better understanding the present invention, the present invention is done detailed description further below in conjunction with embodiment.The contriver has developed the examples of many successful of the different situations of a lot of adaptations through secular experimental exploring, provide several representative embodiment below, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
5g E-12 adding is had in the conversion unit of agitator, thermometer and condenser, add properties-correcting agent phosphoric acid 0.25g, make the Resins, epoxy of modification at 120 ℃ of reaction 2h; With 100g TDI, 140g molecular weight be 1000 polyoxypropyleneglycol at 60 ℃ of reaction 2h, add 6g ethylene glycol, 20g dimethylol propionic acid then, reaction 5h gets base polyurethane prepolymer for use as; The Resins, epoxy of above-mentioned modification is joined in this performed polymer, with prepolymer reaction 2h, get the base polyurethane prepolymer for use as of epoxy resin modification, be cooled to 40 ℃ then, add among the 18gTEA at last and emulsification 5min, add water-dispersion 5min under the 2000r/min rotating speed, the aqueous solution that adds 3g EDA again carries out chain extension, gets modified aqueous adhesion agent of polyurethane.These product performance relatively see Table 1 with external certain company's product performance.
As shown in table 1, the product of present embodiment preparation rotary viscosity, glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent and external product when thickening not is basic identical, but because the present invention introduces Resins, epoxy in the water-based polyurethane adhesive modification, a bit get up high film amount, high strength and the chemical resistant properties of Resins, epoxy is good etc. with the advantages of urethane resin, adopt domestic starting material simultaneously mostly, can satisfy the demand of the multiple interior material of automobile, and total cost is more much lower than external like product, preparation technology simple, be easy to promotion and application.
Table 1
| Quality index | External certain company's product | The product of present embodiment |
| Solid content, % | 38 | 37 |
| Rotary viscosity (not thickening) | 0.7 | 0.75 |
| The glued membrane tensile strength, MPa | 14.6 | 15.0 |
| 180 ° of stripping strengths (glued board-leatheroid): N.m -1 | 650 | 660 |
Embodiment 2
12.8g E-20 adding is had in the conversion unit of agitator, thermometer and condenser, add properties-correcting agent phosphatase 11 .28g,, make Resins, epoxy at 150 ℃ of reaction 3h; With the 280g molecular weight be 2000 polyethylene glycol adipate glycol, 85g HDI join be equipped with thermometer, agitator and and the dry reaction equipment of condenser in, react 3h down at 80 ℃, add the 10g neopentyl glycol then, 14g is along butyryl oxide, reaction 2h, reaction process apparent viscosity size is added acetone, obtains base polyurethane prepolymer for use as; The Resins, epoxy of above-mentioned modification is joined in this performed polymer, reaction 3h, get the base polyurethane prepolymer for use as of epoxy resin modification, be cooled to 45 ℃ then, add 10g ammoniacal liquor, in and 10min, add entry at the 3000r/min rotating speed, disperse 20min, the aqueous solution that adds the 8g ethylene glycol diglycidylether again carries out chain extension, gets the polyurethane adhesive of modification.These product performance are as shown in table 2 with external certain company's product performance comparable situation.
Table 2
| Quality index | External certain company's product | The product of present embodiment |
| Solid content, % | 38 | 39 |
| Rotary viscosity (not thickening) | 0.7 | 0.8 |
| The glued membrane tensile strength, MPa | 14.6 | 14.1 |
| 180 ° of stripping strengths (glued board-leatheroid): N.m -1 | 650 | 675 |
As shown in table 2, the product of present embodiment preparation is rotary viscosity when thickening not, the glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent are a little more than external product, but because the present invention introduces Resins, epoxy in the water-based polyurethane adhesive modification, high film amount with Resins, epoxy, high strength and the chemically-resistant advantages with urethane resin of acting charitably etc. a bit, simultaneously adopt domestic starting material to synthesize a kind of high-performance tackiness agent fully, can satisfy the demand of the multiple interior material of automobile, and present embodiment product preparation cost is more much lower than abroad, its technology is simple, be easy to promotion and application.
Embodiment 3
2g E-51 adding is had in the conversion unit of agitator, thermometer and condenser, add properties-correcting agent acetic acid 0.15g, make the Resins, epoxy of modification at 135 ℃ of reaction 2.5h; 20g IPDI and 100g polytetrahydrofuran diol add 20g ethylene glycol then at 70 ℃ of reaction 2.5h, the 21g dimethylol propionic acid, and reaction 4h gets base polyurethane prepolymer for use as; The Resins, epoxy of above-mentioned modification is joined in this performed polymer, with prepolymer reaction 2.5h, get the base polyurethane prepolymer for use as of epoxy resin modification, be cooled to 40 ℃ again, add among the 6g NaOH and 10min, add water-dispersion 3min at the 2500r/min rotating speed, the aqueous solution that adds 5g N-methyldiethanolamine again carries out chain extension, gets the modified waterborne polyurethane tackiness agent.These product performance are as shown in table 3 with external certain company's product performance comparable situation.
Table 3
| Quality index | External certain company's product | The product of present embodiment |
| Solid content, % | 38 | 38 |
| Rotary viscosity (not thickening) | 0.7 | 0.69 |
| The glued membrane tensile strength, MPa | 14.6 | 14.1 |
| 180 ° of stripping strengths (glued board-leatheroid): N.m -1 | 650 | 650 |
As shown in table 3, the product of present embodiment preparation is rotary viscosity when thickening not, the glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent and external product are basic identical, but because the present invention introduces Resins, epoxy in the water-based polyurethane adhesive modification, high film amount with Resins, epoxy, the advantages of advantages such as high strength and chemical resistant properties are good and urethane resin is got up, simultaneously adopt domestic starting material to synthesize a kind of high-performance tackiness agent fully, can satisfy the demand of the multiple interior material of automobile, and present embodiment product preparation cost is more much lower than abroad, its technology is simple, be easy to promotion and application;
Embodiment 4
The 10gE-06 adding is had in the conversion unit of agitator, thermometer and condenser, add properties-correcting agent acetic acid 0.1g,, make Resins, epoxy at 140 ℃ of reaction 2.5h; 200g polycarbonate diol and 125g MDI are joined in the exsiccant conversion unit that thermometer, agitator and condenser are housed, react 2h down at 80 ℃, add the 13.4g TriMethylolPropane(TMP) then, the 15g dimethylol propionic acid, reaction 4h, reaction process apparent viscosity size is added acetone, obtains base polyurethane prepolymer for use as; The Resins, epoxy of above-mentioned modification is joined in the performed polymer,, obtain the base polyurethane prepolymer for use as of epoxy resin modification with prepolymer reaction 2h, be cooled to 45 ℃ again, add the 15g trolamine, in and 12min, add entry at the 3000r/min rotating speed, disperse 15min to get the polyurethane adhesive of modification.These product performance are as shown in table 4 with external certain company's product performance comparable situation.
Table 4
| Quality index | External certain company's product | The product of present embodiment |
| Solid content, % | 38 | 38.5 |
| Rotary viscosity (not thickening) | 0.7 | 0.85 |
| The glued membrane tensile strength, MPa | 14.6 | 15.2 |
| 180 ° of stripping strengths (glued board-leatheroid): N.m -1 | 650 | 700 |
As shown in table 4, the product of present embodiment preparation is rotary viscosity when thickening not, the glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent are compared some performance and also are better than external product with external product, because the present invention introduces Resins, epoxy in the water-based polyurethane adhesive modification, high film amount with Resins, epoxy, the advantages of advantages such as high strength and chemical resistant properties are good and urethane resin is got up, simultaneously adopt domestic starting material to synthesize a kind of high-performance tackiness agent fully, can satisfy the demand of the multiple interior material of automobile, and present embodiment product preparation cost is more much lower than abroad, its technology is simple, be easy to promotion and application.
Claims (5)
1, a kind of preparation method of modified aqueous adhesion agent of polyurethane is characterized in that comprising the steps:
(1) modified epoxy is synthetic: Resins, epoxy is incorporated with in the conversion unit of agitator, thermometer and condenser, adds properties-correcting agent, under 120～150 ℃, react 2～3h, obtain the Resins, epoxy of modification; In mass, the properties-correcting agent addition is 1～10% of a Resins, epoxy total amount; Described properties-correcting agent is phosphoric acid or acetic acid;
(2) preparation of base polyurethane prepolymer for use as: in the conversion unit that agitator, thermometer, prolong are housed, add polyisocyanates and oligomer polyol, under 60～80 ℃, reaction 2～3h adds chainextender then, and reaction 2～5h obtains base polyurethane prepolymer for use as; Described chainextender is 1,4 one butyleneglycol, neopentyl glycol, ethylene glycol, glycol ether, glycerine, MALEIC ANHYDRIDE, TriMethylolPropane(TMP), quadrol, diethylenetriamine, triethylene tetramine or dimethylol propionic acid;
(3) base polyurethane prepolymer for use as of modification is synthetic: use the modified epoxy modified polyurethane prepolymer down at 60～80 ℃, react 2～3h, obtain the base polyurethane prepolymer for use as of modification; The amount of modified epoxy is 5%～15% of an isocyanic ester total amount;
(4) modified aqueous adhesion agent of polyurethane is synthetic: add water to modified polyurethane prepolymer, disperse with high speed dispersor, add neutralizing agent and linking agent, obtain modified aqueous adhesion agent of polyurethane; Described linking agent accounts for 0.1%～3% of total solid content, and degree of neutralization is 80～100%, 35 ℃～40 ℃ of emulsifying temperatures, emulsification times 5～20min, rate of dispersion 2000～3000rpm/min; Described linking agent is quadrol, butanediamine, carbodiimide, trimethylol melamine, dimethylolurea or aziridine.
2, the preparation method of modified aqueous adhesion agent of polyurethane according to claim 1 is characterized in that described Resins, epoxy is E-06, E-12, E-13, E-16, E-20, E-44 or E-51.
3, the preparation method of modified aqueous adhesion agent of polyurethane according to claim 1, it is characterized in that described polyisocyanates be tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditan-4,4 '-vulcabond, poly methylene poly phenyl poly isocyanate or xylylene diisocyanate.
4, the preparation method of modified aqueous adhesion agent of polyurethane according to claim 1, it is characterized in that described oligomer polyol is polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, polycarbonate diol, polycaprolactone glycol, polybutadiene diol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
5, the preparation method of modified aqueous adhesion agent of polyurethane according to claim 1 is characterized in that described neutralizing agent is hydrochloric acid, acetate, a methyl iodide, sodium hydroxide, ammoniacal liquor, triethylamine, methylamine or trolamine.
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| CN114854359A (en) * | 2022-06-15 | 2022-08-05 | 福建合润包装涂料有限公司 | Sealant for steel drum and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161049A (en) * | 1995-09-15 | 1997-10-01 | H·B·富勒许可及融资股份有限公司 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
| WO1999047072A1 (en) * | 1998-03-18 | 1999-09-23 | Tyndale Plains-Hunter, Ltd. | Hydrophilic polyether polyurethanes containing carboxylic acid |
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2007
- 2007-01-05 CN CNB2007100262112A patent/CN100480349C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161049A (en) * | 1995-09-15 | 1997-10-01 | H·B·富勒许可及融资股份有限公司 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
| WO1999047072A1 (en) * | 1998-03-18 | 1999-09-23 | Tyndale Plains-Hunter, Ltd. | Hydrophilic polyether polyurethanes containing carboxylic acid |
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