CN104073144B - Oriental lacquer compounded double-component terpenyl waterborne polyurethane and preparation method thereof - Google Patents
Oriental lacquer compounded double-component terpenyl waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN104073144B CN104073144B CN201410330556.7A CN201410330556A CN104073144B CN 104073144 B CN104073144 B CN 104073144B CN 201410330556 A CN201410330556 A CN 201410330556A CN 104073144 B CN104073144 B CN 104073144B
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Abstract
The invention discloses oriental lacquer compounded double-component terpenyl waterborne polyurethane and a preparation method thereof. The preparation method comprises the following steps: stirring and uniformly mixing a terpenyl epoxy resin polyhydric alcohol emulsion with hydrophilically modified polyisocyanate and oriental lacquer; and adding water to disperse to obtain the oriental lacquer compounded double-component terpenyl waterborne polyurethane. The preparation method disclosed by the invention is simple and convenient, and the prepared oriental lacquer compounded double-component terpenyl waterborne polyurethane synergically forms a film through enzymatic reaction and chemical cross-linking reaction, so that the comprehensive performance of the waterborne polyurethane is improved.
Description
Technical field
The present invention relates to a kind of dual-component aqueous polyurethane and preparation method thereof, more particularly, to a kind of Resina Toxicodendri verniciflui composite bicomponent
Terpenes base water polyurethane and preparation method thereof.
Background technology
Aqueous polyurethane is the green material with water as disperse medium, the enhancing with people's environmental consciousness and to dress
The raising that decorations require, aqueous polyurethane coating replaces solvent based coating to become a kind of inevitable development trend.But due to aqueouss
Polyurethane generally there are that solid content is low, the low shortcoming of poor water resistance, original viscosity, and range of application is restricted.Therefore, it is necessary to it is logical
Cross the modified combination property improving aqueous polyurethane.
In recent years, the worsening shortages of Fossil fuel and environmental problem increasingly serious sustainable development is proposed higher will
Ask, development environment friendly material has become study hotspot.Natural macromolecular material because having that raw material is renewable, source is wide, can
Degraded, the low advantage of cost and there is application and development prospect.Natural polymer is composite modified with aqueous polyurethane, and preparation is suitable for
The high performance material of different demands, is that the integrated application of natural polymer and water-base polyurethane material provides new thinking.Mesh
Before, Chinese scholars existing more report, modified rosin, shallow lake in terms of the composite modified aqueous polyurethane of natural macromolecular material
The composite of the natural macromolecular material modified aqueous polyurethane such as powder, nano-cellulose preparation has preferable combination property.
Natural raw lacquer have the good reputation of " king of coating ", is a kind of renewable, eco-friendly natural ecological coating.Resina Toxicodendri verniciflui
In contain a large amount of active groups, can with aqueous polyurethane cross-linking reaction, improve composite the degree of cross linking.With other natural polymers
Son is compared, and the unique distinction of Resina Toxicodendri verniciflui also resides in, and under normal temperature condition, Resina Toxicodendri verniciflui is with enzymatic laccol radical polymerization and laccol-polysaccharide-egg
The supermolecular mechanism film forming of white matter, paint film has prominent durability, corrosion-resistant, antioxidation and the performance such as wear-resistant.
Content of the invention
It is an object of the invention to provide a kind of Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane and preparation method thereof.Should
Method, by Resina Toxicodendri verniciflui and dual-component aqueous polyurethane direct combination, using the good characteristic of Resina Toxicodendri verniciflui enzymatic film forming, is prepared high performance
Biomass-based composition polymer, also for Resina Toxicodendri verniciflui, the application in water paint field provides new approach.
The technical scheme is that
The polyisocyanate of terpenyl epoxy resin polyalcohol emulsion and hydrophilic modifying is pressed hydroxyl and isocyanate group material
Amount than 1:0.8～1.4 mix homogeneously.Add Resina Toxicodendri verniciflui, stir 5～10min, be combined with the Resina Toxicodendri verniciflui that water is separated into certain solid content
Bi-component terpenyl aqueous polyurethane emulsion.
The solid masses percentage composition of described terpenyl epoxy resin polyalcohol emulsion be 30～45%, hydroxyl value be 70～
150mg/g.
Described polyisocyanate is the hexamethylene diisocyanate trimer of hydrophilic modifying.
The bi-component water that the described polyisocyanate by terpenyl epoxy resin polyalcohol emulsion and hydrophilic modifying forms
Property polyurethane, solid masses percentage composition be more than 50%, ph be 5～8.
Described Resina Toxicodendri verniciflui can be the natural raw lacquer of filtering and impurity removing or refined Resina Toxicodendri verniciflui；Resina Toxicodendri verniciflui is in compound system
Solid masses percentage composition be 0～25%.
Described Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion can 20～40 DEG C of temperature, relative humidity 40～
Film forming under conditions of 80%.Paint film surface drying dries 1～5h in 130 DEG C of baking ovens, tests paint film property.
Beneficial effect
(1) the poly- ammonia of Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueouss is prepared in Resina Toxicodendri verniciflui and bi-component terpenes base water polyurethane blending
Ester emulsion, works in coordination with film forming by enzymatic reaction with chemical crosslink reaction, improves Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane
The combination property of film forming matter.
(2) containing the hydrophobic carbochain that a large amount of benzene ring structures and hydrophobicity are stronger in the molecular structure of Resina Toxicodendri verniciflui main component laccol,
By Resina Toxicodendri verniciflui composite modified bi-component terpenes base water polyurethane, improve mechanical mechanics property and the water resistance of aqueous polyurethane.
Brief description
Fig. 1 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of embodiment 1.
Fig. 2 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of embodiment 2.
Fig. 3 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of embodiment 3.
Fig. 4 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of embodiment 4.
Fig. 5 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of embodiment 5.
Fig. 6 is the Resina Toxicodendri verniciflui composite bicomponent terpenyl aqueous polyurethane emulsion granularmetric analyses of comparative example 1.
Specific embodiment
The polyisocyanate of terpenyl epoxy resin polyalcohol emulsion and hydrophilic modifying is pressed hydroxyl and isocyanate group material
Amount obtain bi-component terpenes base water polyurethane than 1:0.8～1.4 mix homogeneously.In bi-component terpenes base water polyurethane
Add weight/mass percentage composition to be 0～25% but be not equal to 0 natural raw lacquer or refined Resina Toxicodendri verniciflui emulsion, stir 5～10min, with water
It is separated into the complex emulsions of certain solid content.Complex emulsions become under conditions of 20～40 DEG C of temperature, relative humidity 40～80%
Film, paint film surface drying dries 1～5h in 130 DEG C of baking ovens, tests paint film property.
The terpenyl epoxy resin polyalcohol that the present invention uses is self-emulsified nonionic terpenyl epoxy resin polyalcohol, Gu
Weight percentage composition is 30～45%, hydroxyl value is 70～150mg/g.Preparation method with reference to national inventing patent " self emulsifying non-from
Embodiment 1 in subtype terpenyl epoxy resin polyalcohol emulsion and preparation method, purposes (patent No. zl201010259772.9) ".
Polyisocyanate used in the present invention is the hexamethylene diisocyanate trimer of hydrophilic modifying, such as bodyguard Quanxing, Wuhan dress
The decoration paint company limited trade mark is the polyisocyanate of d80.
Form double groups of polyisocyanate by terpenyl epoxy resin polyalcohol and hydrophilic modifying used in the present invention
Divide aqueous polyurethane system, it is 5～8 that solid masses percentage composition is more than 50%, ph.
Resina Toxicodendri verniciflui used in the present invention can be the natural raw lacquer of filtering and impurity removing or refined Resina Toxicodendri verniciflui, laccol quality
Percentage composition is more than 50%, and biodiversity percentage composition is less than 30%.
Embodiment 1: in compound system, add the Resina Toxicodendri verniciflui emulsion that weight/mass percentage composition is 5%.
By 15.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 35%) and 4.68g polyisocyanate
Ester mix homogeneously.Add 0.5g Resina Toxicodendri verniciflui, stir 5min, add 11.0g water by several times, being dispersed into solid masses percentage composition is 30%
Complex emulsions.The equal particle diameter of emulsion z is 0.253 μm, and particle diameter distribution concordance is 0.213, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, film forming under conditions of 20 DEG C of temperature, relative humidity 70%, paint
Film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 6.55mpa, elongation at break 44.78%,
Pliability 0.5mm, glossiness 89.7, water absorption rate 23.93%.
Embodiment 2: in compound system, add the Resina Toxicodendri verniciflui emulsion that weight/mass percentage composition is 10%.
By 15.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 35%) and 3.9g polyisocyanate
Mix homogeneously.Add 0.9g Resina Toxicodendri verniciflui, stir 5min, add 10.5g water by several times, being dispersed into solid masses percentage composition is 30%
Complex emulsions.The equal particle diameter of emulsion z is 0.241 μm, and particle diameter distribution concordance is 0.204, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, film forming under conditions of 20 DEG C of temperature, relative humidity 50%, paint
Film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 7.37mpa, elongation at break 56.37%,
Pliability 0.5mm, glossiness 87.3, water absorption rate 19.09%.
Embodiment 3: in compound system, add the Resina Toxicodendri verniciflui emulsion that weight/mass percentage composition is 15%.
By 10.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 35%) and 3.12g polyisocyanate
Ester mix homogeneously.Add 1.0g Resina Toxicodendri verniciflui, stir 5min, add 8.5g water by several times, being dispersed into solid masses percentage composition is 30%
Complex emulsions.The equal particle diameter of emulsion z is 0.258 μm, and particle diameter distribution concordance is 0.222, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, film forming under conditions of 25 DEG C of temperature, relative humidity 60%, paint
Film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 9.76mpa, elongation at break 63.65%,
Pliability 0.5mm, glossiness 91.4, water absorption rate 16.58%.
Embodiment 4: in compound system, add the Resina Toxicodendri verniciflui emulsion that weight/mass percentage composition is 20%.
By 10.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 35%) and 3.12g polyisocyanate
Ester mix homogeneously.Add 1.32g Resina Toxicodendri verniciflui, stir 5min, add 9.1g water by several times, being dispersed into solid masses percentage composition is 30%
Complex emulsions.The equal particle diameter of emulsion z is 0.303 μm, and particle diameter distribution concordance is 0.255, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, temperature be 20 DEG C, relative humidity be 50% under conditions of become
Film, paint film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 11.04mpa, elongation at break
68.73%, pliability 0.5mm, glossiness 90.9, water absorption rate 14.51%.
Embodiment 5: in compound system, add the Resina Toxicodendri verniciflui emulsion that weight/mass percentage composition is 25%.
By 10.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 30%) and 2.67g polyisocyanate
Ester mix homogeneously.Add 2.2g Resina Toxicodendri verniciflui, stir 5min, add 8.2g water by several times, being dispersed into solid masses percentage composition is 30%
Complex emulsions.The equal particle diameter of emulsion z is 1.07 μm, and particle diameter distribution concordance is 0.540, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, film forming under conditions of 20 DEG C of temperature, relative humidity 50%, paint
Film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 9.35mpa, elongation at break 51.39%,
Pliability 0.5mm, glossiness 89.8, water absorption rate 11.76%.
Comparative example 1: without Resina Toxicodendri verniciflui
By 10.0g terpenyl epoxy resin polyalcohol emulsion (solid masses percentage composition 30%) and 2.67g polyisocyanate
Ester mix homogeneously.Add 4.5g water, be dispersed into the complex emulsions that solid masses percentage composition is 30%.The equal particle diameter of emulsion z is
0.256 μm, particle diameter distribution concordance is 0.217, and emulsion particle diameter distribution is as shown in Figure 1.
By complex emulsions on polyfluortetraethylene plate film, film forming under conditions of 20 DEG C of temperature, relative humidity 40%, paint
Film surface drying dries 3h in 130 DEG C of baking ovens.The performance of test paint film is: tensile strength 7.67mpa, elongation at break 31.98%,
Pliability 0.5mm, glossiness 89.4, water absorption rate 21.27%.
Note: paint film water absorption rate assay method:
Paint film is made 25mm × 25mm size, is dried and weighs, be designated as w1；Then soak in distilled water at room temperature
24h, takes out diaphragm, blots surface moisture with filter paper, weighs, is designated as w2.It is calculated as follows paint film water absorption rate (q).
Claims (4)
1. a kind of preparation method of Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane it is characterised in that: by terpenyl asphalt mixtures modified by epoxy resin
Fat polyalcohol emulsion is mixed homogeneously than 1:0.8 ~ 1.4 with the amount of isocyanate group material by hydroxyl with the polyisocyanate of hydrophilic modifying
Obtain bi-component terpenes base water polyurethane, add Resina Toxicodendri verniciflui, stir, be separated into the Resina Toxicodendri verniciflui Composite Double of certain solid content with water
Component terpenyl aqueous polyurethane emulsion；The solid masses percentage composition of described bi-component terpenes base water polyurethane is more than 50
%, ph are 5 ~ 8.
2. the preparation method of Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane as claimed in claim 1 is it is characterised in that institute
The solid masses percentage composition of the terpenyl epoxy resin polyalcohol emulsion stated is 30 ~ 45 %, and hydroxyl value is 70 ~ 150 mg/g.
3. the preparation method of Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane as claimed in claim 1 is it is characterised in that institute
The polyisocyanate stated is the hexamethylene diisocyanate trimer of hydrophilic modifying.
4. the preparation method of Resina Toxicodendri verniciflui composite bicomponent terpenes base water polyurethane as claimed in claim 1 is it is characterised in that institute
The Resina Toxicodendri verniciflui stated includes the natural raw lacquer of filtering and impurity removing, refined Resina Toxicodendri verniciflui；Solid masses percentage composition in compound system for the Resina Toxicodendri verniciflui is 0
~ 25% but be not equal to 0.
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| CN201410330556.7A CN104073144B (en) | 2014-07-11 | 2014-07-11 | Oriental lacquer compounded double-component terpenyl waterborne polyurethane and preparation method thereof |
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| CN201410330556.7A CN104073144B (en) | 2014-07-11 | 2014-07-11 | Oriental lacquer compounded double-component terpenyl waterborne polyurethane and preparation method thereof |
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Families Citing this family (4)
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| CN108997935A (en) * | 2018-05-25 | 2018-12-14 | 繁昌县若木营造装饰工程有限公司 | A kind of modified raw lacquer composite coating and preparation method thereof |
| CN110204971A (en) * | 2019-06-04 | 2019-09-06 | 浙江天地化工有限公司 | Antiseptic and rustproof paint of a kind of water-based metal and preparation method thereof |
| CN110655861B (en) * | 2019-09-27 | 2021-04-06 | 中华全国供销合作总社西安生漆涂料研究所 | Epoxy tung oil-based waterborne polyurethane modified raw lacquer and preparation method thereof |
| CN116874716B (en) * | 2023-08-24 | 2024-05-28 | 山东高速集团有限公司创新研究院 | Preparation method of terpene type epoxy polyurethane prepolymer, obtained product and application of terpene type epoxy polyurethane prepolymer in asphalt modification |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757710A (en) * | 2012-06-01 | 2012-10-31 | 安徽省金盾涂料有限责任公司 | Water paint |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757710A (en) * | 2012-06-01 | 2012-10-31 | 安徽省金盾涂料有限责任公司 | Water paint |
Non-Patent Citations (4)
| Title |
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| Crosslinking Reaction and Properties of Two-Component Waterborne Polyurethane from Terpene-Maleic Ester Type Epoxy Resin;Guo-min Wu等;《Applied Polymer science》;20120625;第133页左栏实验部分第1-2段、第133页右栏表1 * |
| 生漆成膜的分子机理;张飞龙;《中国生漆》;20120331;第31卷(第1期);第13-20页 * |
| 生漆改性及其应用进展;孙祥玲等;《生物质化学工程》;20140331;第48卷(第2期);第43页第2段 * |
| 阳离子型萜烯基环氧树脂多元醇的合成及其分散稳定性研究;吴国民等;《林产化学与工业》;20091231;第29卷(第6期);第1-6页 * |
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