CN105837773A - Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil - Google Patents
Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil Download PDFInfo
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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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- 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
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- 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
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Abstract
The invention belongs to the technical field of fine chemistry, and specifically, discloses a preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil. A cationic hyperbranched waterborne emulsion is made from raw materials of polyethylene glycol 600, rosin amine polyoxyethylene ether, hydroxypropyl silicone oil, castor oil, isophorone diisocyanate, trimethylol propane, N-methyldiethanolamine, and 3-aminopropyltriethoxysilane as a coupling agent. To overcome the defect of water resistance of the emulsion, silicone is further introduced to prepare the waterborne emulsion and provides the waterborne emulsion with excellent water resistance. The obtained emulsion can be applied to the fields, such as a water-based coating, a water-based adhesive, and a water-based ink, and provides the coating with excellent stability, water resistance, and high hardness without solvent. The obtained emulsion has excellent sterilization and mildew removal performance, can be applied to underwater oil pipes where microorganisms gather, and has an excellent inhibition and removal effect on waterborne microorganisms.
Description
Technical field
The present invention relates to technical field of fine, be specifically related to that a kind of organosilicon is dual with renewable vegetable oil changes
The preparation method of property hyperbranched aqueous polyurethane emulsion.
Background technology
Domestic start late with water paint due to water-base resin, compare external for, water-base resin and aqueous painting
Material is at the aspect poor-performing such as water-fast, oil resistant, resistance toization, hardness, wearability；The most single-component water-based polyurethane,
Far it is inferior to the application of double-component waterborne polyurethane coating, but double-component waterborne polyurethane has the isocyanic acid of residual
Ester, more or less has certain side effect to human body, and construction technology and condition are the most complex simultaneously；But single group
Part is only volatilized by water, then carries out crosslinking curing, and its combination property does not often have double-component good.Modified one-component
Aqueous polyurethane, can make aqueous one-component meet demand as far as possible.The achievement in research of this respect is reported not at present
Many.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, and a kind of novel combination property proposed
The preparation method of excellent aqueous polyurethane emulsion.
The composition of raw materials of the present invention compensate for the inferior position that prior art exists, and utilizes renewable resource castor oil, pine
Fragrant derivative modified water paint；With organosilicon further modified water-soluble super branched polyurethane emulsion, then configure
Coating；To improve the resistance to water of water paint, soil resistance；Hyperbranched aqueous polyurethane emulsion is as water-base resin
It is the focus of Recent study, but for emulsion, its water paint performance tends not to play and maximizes,
Or poor-performing is in double-component water paint；Water paint obtained by the present invention possess excellent stability and
High dispersive performance, by the water repellency that organosilicon is remarkable, can collect organosilicon, castor oil, polyurethane double excellent
Gesture is.
It is cation water-based that present patent application uses organosilicon, castor oil, rosin derivative, polyethylene glycol etc. to prepare
Base polyurethane prepolymer for use as, after combine trimethylolpropane, N methyldiethanol amine cross-links, and organo-silicon coupling agent blocks,
Glacial acetic acid neutralizes, and prepares the dual modified aqueous hyperbranched polyurethane of cationic silicones-renewable vegetable oil high
Dispersion emulsion.This cationic silicones-renewable vegetable oil dual modified aqueous hyperbranched polyurethane high dispersive breast
Liquid can use in some specific occasion by being configured to cation water-based coating；As oil pipe etc. is micro-under water
Biogenic accumulation is local, has good suppression to aqueous microorganism, the effect such as removes.
For realizing object above, a kind of organosilicon of the present invention is dual modified with renewable vegetable oil hyperbranched aqueous
The preparation method of polyaminoester emulsion, its step is as follows:
(1) in reaction vessel add Macrogol 600, Rosin Amine Polyoxyethylene Ether ether, hydroxypropyl silicone oil,
Castor oil, acetone and IPDI, be subsequently adding catalyst dibutyltin dilaurylate,
Back flow reaction 1.5h at 80 DEG C～95 DEG C, obtains performed polymer；
Described Macrogol 600 and IPDI mass ratio are 1.2:1～1.6:1, are preferably
1.25:1～1.5:1；
Described Rosin Amine Polyoxyethylene Ether ether consumption is the 60%～120% of IPDI quality, preferably
It is 78%～110%；
Described hydroxypropyl silicon oil dosage is the 9%-40% of IPDI quality, is preferably
22%-32%；
Described castor oil consumption is the 4%～14% of IPDI quality；
Preferably, described catalyst dibutyltin dilaurylate consumption is IPDI quality
0.3-0.5%；
Preferably, described acetone with IPDI magnitude relation is: 20～40mL:22.3g；
(2) after performed polymer is cooled to 55-60 DEG C, in performed polymer, trimethylolpropane and N-methyl are added
Diethanol amine, carries out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
Described trimethylolpropane consumption is in step (1) the 2%～9% of IPDI quality,
It is preferably 2.2%～4.5%；
Described N methyldiethanol amine consumption is IPDI quality in step (1)
5%～23%, preferably 8%～14%；
(3) it is cooled to 0 DEG C, adds coupling agent 3-aminopropyl triethoxysilane, chain extending reaction 30min；
Described coupling agent 3-aminopropyl triethoxysilane consumption is IPDI in step (1)
The 6%～14% of quality；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) adding deionized water, dispersion and emulsion 30min, last rotary evaporation removes acetone solvent, to obtain final product
Organosilicon and renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, solid content is 30-40%；
Described deionized water temperature below 25 DEG C, preferably ice deionized water.
Described preparation method can lead to nitrogen protection in course of reaction, preferably in step (1), (2) and (4)
Course of reaction in logical nitrogen.
Preferably, in step (5), described addition deionized water, the concrete operations of dispersion and emulsion 30min
Journey is as follows:
Being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up to 1200 from 600r/min
R/min, when emulsion from transparent through milky white become Day-Glo blue time, be adjusted to be not less than by mixing speed rapidly
2000r/min, and add rapidly ice deionized water dispersion and emulsion.
Compared with prior art, advantages of the present invention and having the beneficial effect that:
By organosilicon and castor oil, rosin derivative modified aqueous polyurethane, prepare hyperbranched aqueous polyurethane
High dispersive emulsion, the crosslinking of last coupling agent and end-blocking；Use organosilicon and improve its mechanical performance and water repellency, water
Property polyurethane improve its dispersiveness and stability, collection organosilicon and polyurethane advantage and one so that water paint
There is superior water repellency, wearability, brightness.
Detailed description of the invention
In following embodiment, embodiment 3 and 5 has logical nitrogen to protect in course of reaction, and remaining embodiment is not led to
Nitrogen is protected.
In following example, hydroxypropyl silicone oil is Noah's ark (Fugang) chemical material Co., Ltd product, model side
Boat AC-80, molecular weight is 1000-2000；
Rosin Amine Polyoxyethylene Ether ether is Linyi City Lanshan District Yong Ju industrial chemicals Co., Ltd, model lyyj-8.
Embodiment 1
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 32g polyethylene glycol (PEG) 600,18g Rosin Amine Polyoxyethylene Ether ether, 5.0g hydroxypropyl silicon
Oil, 2g castor oil, 25mL acetone and 22.3g IPDI join equipped with reflux condensation mode
In the there-necked flask of pipe and mechanical agitation rod, stir mixture, drip two (about 0.09g) catalyst dibutyltin
Dilaurylate, is warming up to 80 DEG C, and back flow reaction 1.5h obtains performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 0.5g tri-hydroxyl is added
Methylpropane and 2g N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 2g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
2000r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter is 143 ± 10nm), its solid content is 35%.
Embodiment 2
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 30g polyethylene glycol (PEG) 600,20g Rosin Amine Polyoxyethylene Ether ether, 6.0g hydroxypropyl silicon
Oil, 3g castor oil, 35mL acetone and 22.3g IPDI join equipped with reflux condensation mode
In the there-necked flask of pipe and mechanical agitation rod, stir mixture, drip two catalyst dibutyltin dilaurylate,
It is warming up to 80 DEG C, back flow reaction 1.5h, obtain performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 0.5g tri-hydroxyl is added
Methylpropane and 2g N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 2g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
2300r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter 177 ± 10nm), its solid content is 30%.
Embodiment 3
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 28g polyethylene glycol (PEG) 600,21g Rosin Amine Polyoxyethylene Ether ether, 7.0g hydroxypropyl silicon
Oil, 3g castor oil, 30mL acetone and 22.3g IPDI join equipped with reflux condensation mode
In the four-hole boiling flask of pipe, mechanical agitation rod and nitrogen inlet, stir mixture, drip two catalyst dibutyltin osmanthus
Acid dibutyl tin, is warming up to 80 DEG C, and back flow reaction 1.5h obtains performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 0.7g tri-hydroxyl is added
Methylpropane and 3g N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 2g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
2000r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter 196 ± 10nm), its solid content is 35%.
Step (1), (2) and (4) logical nitrogen in course of reaction in the present embodiment.
Embodiment 4
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 28g polyethylene glycol (PEG) 600,23g Rosin Amine Polyoxyethylene Ether ether, 6.0g hydroxypropyl silicon
Oil, 2g castor oil, 30mL acetone and 22.3g IPDI join equipped with reflux condensation mode
In the there-necked flask of pipe and mechanical agitation rod, stir mixture, drip two catalyst dibutyltin dilaurylate,
It is warming up to 95 DEG C, back flow reaction 1.5h, obtain performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 0.6g tri-hydroxyl is added
Methylpropane and 2g N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 1.5g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
3000r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter 162 ± 10nm), its solid content is 30%.
Embodiment 5
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 32g polyethylene glycol (PEG) 600,18g Rosin Amine Polyoxyethylene Ether ether, 6.0g hydroxypropyl silicon
Oil, 1.0g castor oil, 30mL acetone and 22.3g IPDI join equipped with returned cold
In the four-hole boiling flask of solidifying pipe, mechanical agitation rod and nitrogen inlet, stir mixture, drip two catalyst dibutyltin
Dilaurylate, is warming up to 90 DEG C, and back flow reaction 1.5h obtains performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 1.0g tri-hydroxyl is added
Methylpropane and 3g N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 2g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
2000r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter 233 ± 10nm), its solid content is 35%.
Step (1), (2) and (4) logical nitrogen in course of reaction in the present embodiment.
Embodiment 6
A kind of organosilicon and the preparation method of renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its
Step is as follows:
(1) by 32g polyethylene glycol (PEG) 600,20g Rosin Amine Polyoxyethylene Ether ether, 6.0g hydroxypropyl silicon
Oil, 1g castor oil, 40mL acetone and 22.3g IPDI join equipped with reflux condensation mode
In the there-necked flask of pipe and mechanical agitation rod, stir mixture, drip two catalyst dibutyltin dilaurylate,
It is warming up to 90 DEG C, back flow reaction 1.5h, obtain performed polymer；
(2) after step (1) gained performed polymer is cooled to 55-60 DEG C, in performed polymer, 0.5g tri-hydroxyl is added
Methylpropane and 2g N methyldiethanol amine 2g, carry out cross-linking reaction at 55-60 DEG C, and the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, drips 3g coupling agent 3-aminopropyl triethoxysilane, react 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) being added slowly with stirring ice deionized water, meanwhile, mixing speed is stepped up from 600r/min
To 1200r/min, when emulsion from transparent through milky white become Day-Glo blue time, rapidly mixing speed is adjusted to
2500r/min, and add rapidly ice deionized water dispersion and emulsion；
Step (5) total reaction time is 30min；
(6) rotary evaporation removes acetone solvent, obtains organosilicon dual modified with renewable vegetable oil hyperbranched
Aqueous polyurethane emulsion (particle diameter 202 ± 10nm), its solid content is 40%.
Organosilicon prepared by above example 1-6 and the dual modified hyperbranched aqueous poly-ammonia of renewable vegetable oil
The test result of ester product emulsion is shown in Table 1.
Table 1 each embodiment product test result
In table 1, the testing standard of each test event is as follows:
(resistance to water) GB/T 1,733 1993 paint film resistance to water determination method；
(hardness) GB/T 6,739 2006 paint and varnish pencil method measures hardness of paint film；
The mensuration of (resistance to green tea) GB 9274-1988 paint and varnish resistant to liquid medium；
(adhesive force test) GB/T 6739-2006 " paint and varnish pencil method measures hardness of paint film "；
(ageing-resistant time) GB/T 1865-2009 paint and varnish artificial weathering aging and man-made radiation expose to the open air；
(fracture elongation) GB/T19250 2013 polyurethane water-proof paint；
The mensuration salt solution of (salt water resistance test) GB/T 10834-2008 marine paint resistance to salt water and hot salt brine leaching；
(resistance to mould) GB/T 1,741 2007 paint film resistance to mould determination method.
Claims (10)
1. organosilicon and a preparation method for renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, its step is as follows:
(1) in reaction vessel, Macrogol 600, Rosin Amine Polyoxyethylene Ether ether, hydroxypropyl silicone oil, castor oil, acetone and IPDI are added, it is subsequently adding catalyst dibutyltin dilaurylate, back flow reaction 1.5h at 80 DEG C ~ 95 DEG C, obtains performed polymer；
(2) after performed polymer is cooled to 55-60 DEG C, adding trimethylolpropane and N methyldiethanol amine, carry out cross-linking reaction at 55-60 DEG C in performed polymer, the reaction time is 1.0h；
(3) it is cooled to 0 DEG C, adds coupling agent 3-aminopropyl triethoxysilane, chain extending reaction 30min；
(4) adding glacial acetic acid and be neutralized reaction, the reaction time is 30min, terminal pH=6-7；
(5) adding deionized water, dispersion and emulsion 30min, last rotary evaporation removes acetone solvent, obtains organosilicon and renewable vegetable oil dual modified hyperbranched aqueous polyurethane emulsion, and solid content is 30-40%.
Preparation method the most according to claim 1, it is characterised in that: described Macrogol 600 and IPDI mass ratio are 1.2:1 ~ 1.6:1.
Preparation method the most according to claim 1, it is characterised in that: described Rosin Amine Polyoxyethylene Ether ether consumption is the 60% ~ 120% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that: described hydroxypropyl silicon oil dosage is the 9%-40% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that: described castor oil consumption is the 4% ~ 14% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that: described trimethylolpropane consumption is the 2% ~ 9% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that: described N methyldiethanol amine consumption is the 5% ~ 23% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that: described coupling agent 3-aminopropyl triethoxysilane consumption is the 6% ~ 14% of IPDI quality.
Preparation method the most according to claim 1, it is characterised in that in step (5), described addition deionized water, the specific operation process of dispersion and emulsion 30min is as follows:
Under agitation adding ice deionized water, meanwhile, mixing speed is stepped up to 1200 r/min from 600 r/min, when emulsion from transparent through milky white become Day-Glo blue time, mixing speed is adjusted to be not less than 2000r/min, and adds ice deionized water dispersion and emulsion.
10. according to described preparation method arbitrary in claim 1-9, it is characterised in that: logical nitrogen in the course of reaction of step (1), (2) and (4).
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| CN109021550A (en) * | 2018-06-22 | 2018-12-18 | 同济大学 | A kind of hyperbranched aqueous polyurethane nano-zinc oxide composite material and preparation method thereof |
| CN110627995A (en) * | 2019-10-10 | 2019-12-31 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN111995730A (en) * | 2020-09-03 | 2020-11-27 | 东来涂料技术（上海）股份有限公司 | Waterborne polyurethane, waterborne polyurethane coating and preparation method thereof |
| WO2021029763A1 (en) * | 2019-08-09 | 2021-02-18 | Synthomer Sdn. Bhd. | Polymer latex composition for the preparation of an elastomeric film having self-healing properties |
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| CN108276551A (en) * | 2017-12-26 | 2018-07-13 | 合肥科天水性科技有限责任公司 | A kind of multiple cross-linked modified aqueous polyurethane resin of biology base and its preparation method and application |
| CN109021550A (en) * | 2018-06-22 | 2018-12-18 | 同济大学 | A kind of hyperbranched aqueous polyurethane nano-zinc oxide composite material and preparation method thereof |
| WO2021029763A1 (en) * | 2019-08-09 | 2021-02-18 | Synthomer Sdn. Bhd. | Polymer latex composition for the preparation of an elastomeric film having self-healing properties |
| CN114206950A (en) * | 2019-08-09 | 2022-03-18 | 昕特玛私人有限公司 | Polymer latex composition for preparing elastomer film with self-repairing property |
| CN110627995A (en) * | 2019-10-10 | 2019-12-31 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN110627995B (en) * | 2019-10-10 | 2021-06-25 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN111995730A (en) * | 2020-09-03 | 2020-11-27 | 东来涂料技术（上海）股份有限公司 | Waterborne polyurethane, waterborne polyurethane coating and preparation method thereof |
| CN113956434A (en) * | 2021-10-29 | 2022-01-21 | 山东圳谷新材料科技有限公司 | Hyperbranched organic amino silicon post-chain-extension modified waterborne polyurethane and preparation method thereof |
| WO2023103480A1 (en) * | 2021-12-07 | 2023-06-15 | 襄阳三沃航天薄膜材料有限公司 | High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof |
| CN115322706A (en) * | 2022-08-31 | 2022-11-11 | 福建华峰新材料有限公司 | Elastic and smooth adhesive and preparation method thereof |
| CN115322706B (en) * | 2022-08-31 | 2023-08-15 | 福建华峰新材料有限公司 | Elastic sliding adhesive and preparation method thereof |
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