CN110964165A - Self-catalytic double-component waterborne polyurethane and preparation method thereof - Google Patents
Self-catalytic double-component waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN110964165A CN110964165A CN201911281253.XA CN201911281253A CN110964165A CN 110964165 A CN110964165 A CN 110964165A CN 201911281253 A CN201911281253 A CN 201911281253A CN 110964165 A CN110964165 A CN 110964165A
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- waterborne polyurethane
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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
- C08G18/28—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
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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Abstract
The invention discloses autocatalysis type bi-component waterborne polyurethane and a preparation method thereof. And (2) matching the epoxy resin base polyalcohol water dispersion containing the tertiary amine group with polyisocyanate to prepare the bi-component waterborne polyurethane with the self-catalyzed crosslinking reaction characteristic. The cross-linking polymerization speed of the bi-component waterborne polyurethane prepared by matching the common polyol aqueous dispersion and the polyisocyanate is low, 7 days are required for the cross-linking reaction under the room temperature condition, while 3-4 days are required for the cross-linking reaction under the room temperature condition of the bi-component waterborne polyurethane prepared by the invention, so that the cross-linking film forming speed of the bi-component waterborne polyurethane is obviously improved. According to the invention, the tertiary amine group contained in the molecular structure of the polyol is used for providing catalytic activity, and compared with the method of additionally adding a small molecular metal compound or a tertiary amine catalyst to accelerate the crosslinking reaction of the two-component waterborne polyurethane, no toxic small molecular compound is separated out, and the method is safe and environment-friendly.
Description
Technical Field
The invention relates to autocatalysis type bi-component waterborne polyurethane and a preparation method thereof, in particular to bi-component waterborne polyurethane of which a polyol component is epoxy resin-based polyol aqueous dispersion containing tertiary amine groups in a molecular structure.
Background
The double-component waterborne polyurethane coating has high glossiness, good mechanical property, chemical resistance, weather resistance and the like, and can be widely applied to the fields of automobile finish, automobile refinishing paint, wood coating, plastic coating and the like instead of a solvent-based double-component polyurethane coating. However, the double-component waterborne polyurethane has the same defects, the double-component waterborne polyurethane is formed by mixing and crosslinking the polyol aqueous dispersion and the polyisocyanate curing agent, the film forming process is complex, and the film forming process is a heterogeneous film forming among latex particles comprising a plurality of physical and chemical processes. As a result, the crosslinking and film forming speed of the bi-component waterborne polyurethane is low, the crosslinking reaction needs more than 7 days at room temperature, and the construction efficiency is low. Therefore, how to increase the crosslinking film-forming speed of the two-component waterborne polyurethane becomes an important breakthrough for accelerating the development of the two-component waterborne polyurethane.
The added micromolecular catalyst can improve the crosslinking reaction speed of the bi-component waterborne polyurethane. The most widely used polyurethane crosslinking catalysts at present are organometallic compounds and tertiary amine compounds. The common metal organic compound catalysts are organic tin, bismuth, zinc, zirconium and the like. The research shows that the organic bismuth/zinc composite catalyst follows a two-stage reaction kinetic rule to the reaction of isocyanate group and hydroxyl group, and the influence of the catalyst dosage on the crosslinking speed of the two-component waterborne polyurethane is obvious. However, with the increasing awareness of environmental protection and health safety, the use of metal organic compound catalysts in the fields of food packaging, toys for children, and the like has been limited. Currently, more small-molecular tertiary amine catalysts are triethylamine, triethanolamine, N-dimethylethanolamine and the like. However, the small molecule tertiary amine catalyst only plays a catalytic role in the polyurethane film forming process and does not participate in the crosslinking reaction, exists in the crosslinked polymer in a free state, is volatile, generates an unpleasant smell, and increases the emission of toxic volatile organic compounds. Recent studies have shown that the exposure of operators to air at a certain concentration of tertiary amine for 30 minutes to several hours can cause blurred vision, and long-term exposure can cause occupational diseases such as glaucoma. Therefore, how to improve the environmental friendliness of the catalyst is a key scientific problem in the research field of the two-component waterborne polyurethane.
Disclosure of Invention
The invention aims to provide autocatalysis type bi-component waterborne polyurethane and a preparation method thereof. Mixing the epoxy resin-based polyol aqueous dispersion containing the tertiary amine group with polyisocyanate according to a certain proportion, stirring and mixing uniformly, and crosslinking to form a film to prepare the autocatalysis type bi-component waterborne polyurethane. The tertiary amine group contained in the epoxy resin-based polyol structure is used for catalyzing the crosslinking reaction of polyol hydroxyl and isocyanate group, so that the crosslinking film-forming speed of the double-component waterborne polyurethane is improved.
The technical scheme of the invention is as follows: an autocatalytic two-component waterborne polyurethane, wherein a polyol component for forming the two-component waterborne polyurethane is an epoxy resin-based polyol aqueous dispersion containing a tertiary amine group in a molecular structure.
A method for preparing the autocatalytic two-component waterborne polyurethane of claim 1, wherein an epoxy resin-based polyol aqueous dispersion containing a tertiary amine group is mixed with polyisocyanate, stirred and mixed uniformly, and crosslinked to form a film to prepare the autocatalytic two-component waterborne polyurethane.
The epoxy resin-based polyol aqueous dispersion containing the tertiary amine group and the preparation method thereof are disclosed in Chinese patent application No. ZL201810797992.3, wherein the hydroxyl value is 90-200 mg/g, the Z average particle size of the aqueous dispersion is 30-500 nm, and the viscosity is 20-600 mPa & s (at 25 ℃, the solid content is 35-45%).
The polyisocyanate is a conventional commercially available hydrophilically modified dimer or trimer diisocyanate curing agent.
The mixing ratio of the epoxy resin base polyalcohol water dispersion containing the tertiary amine group and the polyisocyanate is 1: 1-2 of the ratio of hydroxyl groups to isocyanate groups according to the amount of the substance.
Advantageous effects
1. According to the invention, the tertiary amine group contained in the molecular structure of the polyol is used for providing catalytic activity, so that the crosslinking film-forming rate of the bi-component waterborne polyurethane is remarkably increased, and the use efficiency is improved.
2. The tertiary amine group with catalytic activity provided by the invention is contained in the molecular structure of the polyalcohol, and compared with the method of additionally adding a small molecular metal compound or a tertiary amine catalyst to accelerate the crosslinking reaction of the bi-component waterborne polyurethane, no toxic small molecular compound is separated out, and the method is safe and environment-friendly.
Drawings
FIG. 1 shows the IR trace of the crosslinking reaction of comparative two-component aqueous polyurethane, example 1 and example 2 at room temperature (25 ℃ C., 60% humidity). Comparative polyol aqueous dispersion containing no tertiary amine group, which reacted slowly with isocyanate, the isocyanate group did not disappear completely after 6 days at room temperature, and curing was incomplete. Example 1 is a diethanolamine modified epoxy resin based polyol aqueous dispersion containing tertiary amine groups which reacts rapidly with isocyanate and completely disappears after 3 days at room temperature indicating that the crosslinking reaction is complete. Example 2 is an aqueous dispersion of a benzylaminoethanol modified epoxy-based polyol containing tertiary amine groups that reacts moderately rapidly with isocyanate and substantially eliminates isocyanate groups after 4 days at room temperature. The result shows that the tertiary amine group in the polyol structure has obvious catalytic promotion effect on the crosslinking reaction of the bi-component waterborne polyurethane, and the promotion effect is more obvious when the steric hindrance of the group connected with the tertiary amine is smaller.
Detailed Description
A preparation method of autocatalysis type bi-component waterborne polyurethane is characterized in that epoxy resin base polyalcohol aqueous dispersion containing tertiary amine groups and polyisocyanate are mixed according to a certain proportion, stirred and mixed uniformly, and are crosslinked to form a film to prepare the autocatalysis type bi-component waterborne polyurethane. The preparation reaction process is shown as the following formula:
the epoxy resin-based polyol aqueous dispersion containing the tertiary amine group is self-emulsifying anionic epoxy resin-based polyol aqueous dispersion, epoxy resin reacts with amino alcohol (including any one of diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-tert-butyl ethanolamine and N-benzylethanolamine) to prepare epoxy resin-based polyol containing the tertiary amine group, diisocyanate and 2, 2-bis (hydroxymethyl) propionic acid or 2, 2-bis (hydroxymethyl) butyric acid are used for modifying, and then the epoxy resin-based polyol aqueous dispersion is directly dispersed in water after being neutralized by alkali to obtain the self-emulsifying anionic epoxy resin-based polyol aqueous dispersion. The hydroxyl value of the epoxy resin-based polyol is 90-200 mg/g, the Z-average particle diameter of the aqueous dispersion is 30-500 nm, and the viscosity of the aqueous dispersion is 20-600 mPa & s, and the preparation method refers to Chinese patent application No. ZL201810797992.3, namely the autocatalytic epoxy resin-based polyol aqueous dispersion and the preparation method thereof.
The used polyisocyanate is a common commercial hydrophilic modified diisocyanate dimer or trimer curing agent industrial product, the solid content is 70-100%, and the isocyanate group content is 8-22%. The manufacturers are named as Wuhanshi Quanxing New Material science and technology Limited company D100 and S100, Shanghai Si Sheng Polymer Material Limited company EC385, science wound
Polyisocyanates, bostto EasaquaTMPolyisocyanates, and the like.
The hydroxyl groups and the isocyanate groups are mixed according to a certain proportion, wherein the mass ratio of the hydroxyl groups to the isocyanate groups is 1: 1-2.
Comparative example
Two-component waterborne polyurethane prepared from an epoxy resin-based polyol aqueous dispersion not containing a tertiary amine group in the molecular structure was used as a comparison.
The epoxy resin-based polyol TME-NPG is prepared by reacting terpene-based epoxy resin TME with neopentyl glycol (NPG). Then, chain extension is carried out on Hexamethylene Diisocyanate (HDI), 2-bis (hydroxymethyl) propionic acid (DMPA) and TME-NPG, sodium hydroxide is used for neutralization, and water dispersion is carried out, so that epoxy resin based polyol (WTNP, the structural formula is shown in the specification) water dispersion with a similar molecular structure and without tertiary amine groups is obtained, the solid content is 35%, and the hydroxyl value is 158.7 mg/g.
And (3) mixing 10.0g of WTNP aqueous dispersion and 2.4g of polyisocyanate D100, uniformly stirring, coating, and drying at room temperature to form a film, thereby preparing the non-autocatalysis type bi-component waterborne polyurethane. The infrared analysis shows that the complete crosslinking time of the two-component waterborne polyurethane is 7 days, the hardness of a paint film is H, the flexibility is 0.5mm, the adhesive force is 1 grade, and the impact strength is more than or equal to 50kg cm.
Example 1
The terpene-based epoxy resin TME reacts with diethanol amine (DEA) to prepare epoxy resin-based polyol TME-DEA. Then, chain extension is carried out on Hexamethylene Diisocyanate (HDI), 2-bis (hydroxymethyl) propionic acid (DMPA) and TME-DEA, sodium hydroxide is used for neutralization, and water dispersion is carried out, so that the epoxy resin base polyol (WTDP, the structural formula is shown in the specification) water dispersion with the molecular structure containing the tertiary amine group is obtained, the solid content is 35%, and the hydroxyl value is 256.4 mg/g.
10.0g of WTDP aqueous dispersion is matched with 3.8g of polyisocyanate D100, the mixture is uniformly stirred, coated and dried at room temperature to form a film, and the autocatalytic bi-component waterborne polyurethane is prepared. The infrared analysis shows that the complete crosslinking time of the two-component waterborne polyurethane is 3 days, the hardness of a paint film is 2H, the flexibility is 0.5mm, the adhesive force is 1 grade, and the impact strength is more than or equal to 50kg cm.
Example 2
The preparation method comprises the steps of reacting terpenyl epoxy resin TME with N-Benzylethanolamine (BEA) to prepare epoxy resin-based polyol TME-BEA. Then, chain extension is carried out on Hexamethylene Diisocyanate (HDI), 2-bis (hydroxymethyl) propionic acid (DMPA) and TME-BEA, sodium hydroxide is used for neutralization, and water dispersion is carried out, so that the epoxy resin base polyol (WTBP, structural formula shown in the specification) water dispersion with the molecular structure containing the tertiary amine group is obtained, the solid content is 35%, and the hydroxyl value is 121.2 mg/g.
10.0g of WTBP aqueous dispersion is matched with 2.2g of polyisocyanate D100, the mixture is uniformly stirred, coated and dried at room temperature to form a film, and the autocatalytic bi-component waterborne polyurethane is prepared. The infrared analysis shows that the complete crosslinking time of the bi-component waterborne polyurethane is 4 days, the hardness of a paint film is 2H, the flexibility is 0.5mm, the adhesive force is 1 grade, and the impact strength is more than or equal to 50kg cm.
Example 3
Epoxy-based polyol E20-MEA was prepared by reacting bisphenol A epoxy E20 with N-Methylethanolamine (MEA). Then, chain extension is carried out on Hexamethylene Diisocyanate (HDI), 2-bis (hydroxymethyl) propionic acid (DMPA) and E20-MEA, sodium hydroxide is used for neutralization, and water dispersion is carried out, so that epoxy resin based polyol (WBMP, the structural formula is shown in the specification) water dispersion with a molecular structure containing tertiary amine groups is obtained, the solid content is 40%, and the hydroxyl value is 172.2 mg/g.
10.0g of WBMP water dispersion and 2.6g of polyisocyanate S100 are mixed, stirred uniformly, coated, dried at room temperature to form a film, and the autocatalytic bi-component waterborne polyurethane is prepared. The infrared analysis shows that the complete crosslinking time of the two-component waterborne polyurethane is 3 days, the hardness of a paint film is 2H, the flexibility is 0.5mm, the adhesive force is 1 grade, and the impact strength is more than or equal to 50kg cm.
Example 4
Epoxy resin-based polyol E20-BEA was prepared by reacting bisphenol A epoxy resin E20 with N-Benzylethanolamine (BEA). Then, chain extension is carried out on Hexamethylene Diisocyanate (HDI), 2-bis (hydroxymethyl) propionic acid (DMPA) and E20-BEA, sodium hydroxide is used for neutralization, and water dispersion is carried out, so that the epoxy resin based polyol (WBBP, structural formula shown in the specification) water dispersion with the molecular structure containing the tertiary amine group is obtained, the solid content is 40%, and the hydroxyl value is 161.6 mg/g.
10.0g of WBBP aqueous dispersion and 2.5g of polyisocyanate D100 are mixed, stirred uniformly, coated, dried at room temperature to form a film, and the autocatalytic bi-component waterborne polyurethane is prepared. The infrared analysis shows that the complete crosslinking time of the bi-component waterborne polyurethane is 4 days, the hardness of a paint film is 3H, the flexibility is 0.5mm, the adhesive force is 1 grade, and the impact strength is more than or equal to 50kg cm.
Claims (5)
1. An autocatalytic two-component waterborne polyurethane is characterized in that a polyol component for forming the two-component waterborne polyurethane is an epoxy resin-based polyol aqueous dispersion containing a tertiary amine group in a molecular structure.
2. A method for preparing the autocatalytic two-component waterborne polyurethane of claim 1, wherein an epoxy resin based polyol aqueous dispersion containing a tertiary amine group is mixed with polyisocyanate, stirred and mixed uniformly, and crosslinked to form a film to prepare the autocatalytic two-component waterborne polyurethane.
3. The method for preparing autocatalytic two-component waterborne polyurethane of claim 2, wherein the epoxy resin based polyol aqueous dispersion containing tertiary amine group and the method for preparing the same are as described in chinese patent application No. ZL201810797992.3, the hydroxyl value is 90-200 mg/g, the Z average particle diameter of the aqueous dispersion is 30-500 nm, and the viscosity is 20-600 mPa-s (25 ℃, 35% -45% solid content).
4. The process for preparing autocatalytic two-component waterborne polyurethane of claim 2 wherein the polyisocyanate is a conventional commercially available hydrophilically modified dimer or trimer diisocyanate curing agent.
5. The method for producing autocatalytic two-component waterborne polyurethane of claim 2, wherein the ratio of the epoxy resin based polyol aqueous dispersion containing tertiary amine groups to the polyisocyanate is 1: 1-2 of the ratio of hydroxyl groups to isocyanate groups.
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Citations (6)
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| EP1034203B1 (en) * | 1997-12-04 | 2003-04-23 | Henkel Kommanditgesellschaft auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
| CN102516561A (en) * | 2011-12-09 | 2012-06-27 | 中国林业科学研究院林产化学工业研究所 | Anionic terpenyl epoxy resin polyolamine aqueous dispersion, its preparation method and application |
| KR101609806B1 (en) * | 2014-09-22 | 2016-04-06 | 주식회사 헵스켐 | Preparation of waterborne polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and aterborne polyurethane resin |
| CN106221546A (en) * | 2016-08-18 | 2016-12-14 | 上海倍力新材料有限公司 | As the aqueous polyurethane dispersing liquid of the multiple self-crosslinking of coating, preparation method and its usage |
| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| CN109180897A (en) * | 2018-07-19 | 2019-01-11 | 中国林业科学研究院林产化学工业研究所 | Epoxy resin-based polyalcohol water dispersoid of self-catalysis type ring and preparation method thereof |
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2019
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| EP1034203B1 (en) * | 1997-12-04 | 2003-04-23 | Henkel Kommanditgesellschaft auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
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| KR101609806B1 (en) * | 2014-09-22 | 2016-04-06 | 주식회사 헵스켐 | Preparation of waterborne polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and aterborne polyurethane resin |
| CN106221546A (en) * | 2016-08-18 | 2016-12-14 | 上海倍力新材料有限公司 | As the aqueous polyurethane dispersing liquid of the multiple self-crosslinking of coating, preparation method and its usage |
| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| CN109180897A (en) * | 2018-07-19 | 2019-01-11 | 中国林业科学研究院林产化学工业研究所 | Epoxy resin-based polyalcohol water dispersoid of self-catalysis type ring and preparation method thereof |
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