CN107814907A - Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate - Google Patents
Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate Download PDFInfo
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- CN107814907A CN107814907A CN201711141207.0A CN201711141207A CN107814907A CN 107814907 A CN107814907 A CN 107814907A CN 201711141207 A CN201711141207 A CN 201711141207A CN 107814907 A CN107814907 A CN 107814907A
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a kind of preparation method of Diamond Search without amine type aqueous polyurethane polyacrylate, comprises the following steps：（1）By makrolon hexylene glycol vacuum dehydration, temperature is then reduced to 60 90 DEG C, IPDI, methyl methacrylate, dibutyl tin laurate is added, stirring reaction, naturally cools to room temperature；（2）Ultrasonic disperse, chain extender and crosslinking agent are then added, 2 3h are reacted at 60 90 DEG C；（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, 1 2h is reacted at 30 50 DEG C, obtains aqueous polyurethane emulsion；（4）70 90 DEG C are warming up to, the pH value of regulation system is 78, stands reaction, is cooled to room temperature.Method provided by the invention has synthesized the aqueous polyurethane polyacrylate with core shell structure（WPUA）, product is free of triethylamine, and emulsion property is stable, and heat resistance, water resistance, mechanical performance are excellent.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of Diamond Search is without amine type aqueous polyurethane polyacrylic acid
The preparation method of ester.
Background technology
Aqueous polyurethane (WPU) is the new polyurethane system using water as decentralized medium, not only with burning-point it is low, it is nontoxic,
The advantages that pollution-free, saving energy and easy processing, also with excellent Optical instrument, mechanical flight of steps leading to a palace hall energy, wear-resistant and resistance to ag(e)ing
It can wait, therefore be increasingly subject to the attention of people, and start to be used for the industries such as shoemaking, building, automobile, packaging for foodstuff.State in recent years
" low-carbon " cry more and more higher on border, it is domestic that health, environment and the degree of concern of sustainable development are also further lifted, to water
The cognition degree of property coating also greatly improves.WPU materials have more or less used volatile organic solvent in production or using process
(VOC) (such as acetone, ethyl acetate or methyl pyrrolidone), therefore the WPU of Diamond Search is in the industry such as packaging for foodstuff and cosmetics
More paid attention to by people.
The anionic WPU produced both at home and abroad at present is mostly carboxylic acid type, but result of study shows that high-performance WPU is mostly sulphur
Hydrochlorate type has sulfonic acid type and carboxylic acid type concurrently.Compared with carboxylic acid type WPU, sulfonic acid type WPU stability is good, and solid content is high.Due to
The presence of hydrophilic radical, water resistance, solvent resistance and the weatherability of WPU products etc. is poor, therefore it must be modified.Research
The methods of blending of personnel's generally use physics, block copolymerization, core-shell copolymerized and graft copolymerization, improves the performance of WPU products.Will be poly-
Urethane and polyacrylate organically combine and the aqueous polyurethane~polyacrylate (WPUA) for having both advantages concurrently of preparation is
" third generation aqueous polyurethane ".But WPUA heat resistance is poor, the application in some fields is limited to a certain extent, such as
Cigarette case Flexible-Packaging Industry requires material non-toxic, non-stimulated smell, does not burn, solvent complies fully with and is less than tobacco package most
New nation's standard, without doubtful benzene peak value, hardness is high, high temperature resistance diaphragm not loss of gloss, do not turn yellow, be non-discolouring etc..
How while WPUA heat resistances are improved, ensure that its combination property does not decline or do not changed, be WPUA performances
One difficult point of research.
The content of the invention
The defects of for prior art, the present invention provide a kind of system of the Diamond Search without amine type aqueous polyurethane polyacrylate
Preparation Method.
Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate, comprises the following steps：
（1）By makrolon hexylene glycol at 120 DEG C vacuum dehydration 1h, then reduce temperature to 60-90 DEG C, then be separately added into different
Isophorone diisocyanate, methyl methacrylate, dibutyl tin laurate, stirring reaction 60-90min, are naturally cooled to
Room temperature；
（2）By step（1）Obtained product ultrasonic disperse 30-50min, chain extender and crosslinking agent are then added, at 60-90 DEG C
React 2-3h；
（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, obtains the performed polymer of acrylic monomers end-blocking, it is anti-at 30-50 DEG C
1-2h is answered, obtains aqueous polyurethane emulsion；
（4）70-90 DEG C is warming up to, it is 7-8 that sodium hydroxide solution to the pH value of system that mass concentration is 20%, which is added dropwise, is stood anti-
40-70min is answered, is cooled to room temperature, that is, obtains Diamond Search without amine type aqueous polyurethane polyacrylate.
Preferably, step（1）Middle makrolon hexylene glycol, IPDI, methyl methacrylate, February
The mass ratio of dilaurylate addition is 3:6:7:3.
Preferably, step（2）The condition of middle ultrasonic disperse is：Ultrasonic power 200-500W, supersonic frequency 30-50Hz.
Preferably, step（2）Described in chain extender be the equal 1,4- butanediols and dimethylolpropionic acid of quality mixing
Thing.
Preferably, step（2）Described in crosslinking agent be trimethylolpropane.
Preferably, the IPDI, chain extender, crosslinking agent, the mass ratio of hydroxy-ethyl acrylate are 4:
0.4:0.5:1。
Advantages of the present invention：
Method provided by the invention has synthesized the aqueous polyurethane polyacrylate with core shell structure（WPUA）, product is without three
Ethamine, emulsion property is stable, and average grain diameter 50-55nm, heat resistance, water resistance, mechanical performance are excellent, are a kind of new nothings
VOC aqueous, environmental protective materials.
Embodiment
Embodiment 1
Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate, comprises the following steps：
（1）By makrolon hexylene glycol at 120 DEG C vacuum dehydration 1h, then reduce temperature to 60 DEG C, then be separately added into different Buddhist
That ketone diisocyanate, methyl methacrylate, dibutyl tin laurate, stirring reaction 60min, naturally cool to room temperature；
Wherein, makrolon hexylene glycol, IPDI, methyl methacrylate, dibutyl tin laurate add
Mass ratio is 3:6:7:3；
（2）By step（1）Obtained product is under conditions of ultrasonic power 200W, supersonic frequency 30Hz, ultrasonic disperse 30min,
Then chain extender and crosslinking agent are added, reacts 2h at 60 DEG C；The chain extender is the equal 1,4- butanediol and dihydroxy of quality
The mixture of methylbutanoic acid；The crosslinking agent is trimethylolpropane；
（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, the performed polymer of acrylic monomers end-blocking is obtained, is reacted at 30 DEG C
1h, obtain aqueous polyurethane emulsion；Wherein, the matter of IPDI, chain extender, crosslinking agent, hydroxy-ethyl acrylate
Amount is than being 4:0.4:0.5:1；
（4）70 DEG C are warming up to, it is 7 that sodium hydroxide solution to the pH value of system that mass concentration is 20%, which is added dropwise, stands reaction
40min, is cooled to room temperature, that is, obtains Diamond Search without amine type aqueous polyurethane polyacrylate.
Embodiment 2
Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate, comprises the following steps：
（1）By makrolon hexylene glycol at 120 DEG C vacuum dehydration 1h, then reduce temperature to 90 DEG C, then be separately added into different Buddhist
That ketone diisocyanate, methyl methacrylate, dibutyl tin laurate, stirring reaction 90min, naturally cool to room temperature；
Wherein, makrolon hexylene glycol, IPDI, methyl methacrylate, dibutyl tin laurate add
Mass ratio is 3:6:7:3；
（2）By step（1）Obtained product is under conditions of ultrasonic power 500W, supersonic frequency 50Hz, ultrasonic disperse 50min,
Then chain extender and crosslinking agent are added, reacts 3h at 90 DEG C；The chain extender is the equal 1,4- butanediol and dihydroxy of quality
The mixture of methylbutanoic acid；The crosslinking agent is trimethylolpropane；
（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, the performed polymer of acrylic monomers end-blocking is obtained, is reacted at 50 DEG C
2h, obtain aqueous polyurethane emulsion；Wherein, the matter of IPDI, chain extender, crosslinking agent, hydroxy-ethyl acrylate
Amount is than being 4:0.4:0.5:1；
（4）90 DEG C are warming up to, it is 8 that sodium hydroxide solution to the pH value of system that mass concentration is 20%, which is added dropwise, stands reaction
70min, is cooled to room temperature, that is, obtains Diamond Search without amine type aqueous polyurethane polyacrylate.
Embodiment 3
Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate, comprises the following steps：
（1）By makrolon hexylene glycol at 120 DEG C vacuum dehydration 1h, then reduce temperature to 80 DEG C, then be separately added into different Buddhist
That ketone diisocyanate, methyl methacrylate, dibutyl tin laurate, stirring reaction 80min, naturally cool to room temperature；
Wherein, makrolon hexylene glycol, IPDI, methyl methacrylate, dibutyl tin laurate add
Mass ratio is 3:6:7:3；
（2）By step（1）Obtained product is under conditions of ultrasonic power 400W, supersonic frequency 40Hz, ultrasonic disperse 40min,
Then chain extender and crosslinking agent are added, reacts 2.5h at 70 DEG C；The chain extender is the equal 1,4- butanediols and two of quality
The mixture of hydroxymethylbutyrate；The crosslinking agent is trimethylolpropane；
（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, the performed polymer of acrylic monomers end-blocking is obtained, is reacted at 40 DEG C
1.5h, obtain aqueous polyurethane emulsion；Wherein, IPDI, chain extender, crosslinking agent, hydroxy-ethyl acrylate
Mass ratio is 4:0.4:0.5:1；
（4）80 DEG C are warming up to, it is 7.5 that sodium hydroxide solution to the pH value of system that mass concentration is 20%, which is added dropwise, stands reaction
60min, is cooled to room temperature, that is, obtains Diamond Search without amine type aqueous polyurethane polyacrylate.
Claims (6)
1. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate, it is characterised in that：Comprise the following steps：
（1）By makrolon hexylene glycol at 120 DEG C vacuum dehydration 1h, then reduce temperature to 60-90 DEG C, then be separately added into different
Isophorone diisocyanate, methyl methacrylate, dibutyl tin laurate, stirring reaction 60-90min, are naturally cooled to
Room temperature；
（2）By step（1）Obtained product ultrasonic disperse 30-50min, chain extender and crosslinking agent are then added, at 60-90 DEG C
React 2-3h；
（3）End-capping reagent hydroxy-ethyl acrylate reaction 1h is added, obtains the performed polymer of acrylic monomers end-blocking, it is anti-at 30-50 DEG C
1-2h is answered, obtains aqueous polyurethane emulsion；
（4）70-90 DEG C is warming up to, it is 7-8 that sodium hydroxide solution to the pH value of system that mass concentration is 20%, which is added dropwise, is stood anti-
40-70min is answered, is cooled to room temperature, that is, obtains Diamond Search without amine type aqueous polyurethane polyacrylate.
2. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate according to claim 1, it is characterised in that：
Step（1）Middle makrolon hexylene glycol, IPDI, methyl methacrylate, dibutyl tin laurate add
The mass ratio added is 3:6:7:3.
3. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate according to claim 1, it is characterised in that：
Step（2）The condition of middle ultrasonic disperse is：Ultrasonic power 200-500W, supersonic frequency 30-50Hz.
4. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate according to claim 1, it is characterised in that：
Step（2）Described in chain extender be the equal 1,4- butanediols of quality and dimethylolpropionic acid mixture.
5. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate according to claim 1, it is characterised in that：
Step（2）Described in crosslinking agent be trimethylolpropane.
6. preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate according to claim 1, it is characterised in that：
The IPDI, chain extender, crosslinking agent, the mass ratio of hydroxy-ethyl acrylate are 4:0.4:0.5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711141207.0A CN107814907A (en) | 2017-11-17 | 2017-11-17 | Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711141207.0A CN107814907A (en) | 2017-11-17 | 2017-11-17 | Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate |
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| CN107814907A true CN107814907A (en) | 2018-03-20 |
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| CN201711141207.0A Withdrawn CN107814907A (en) | 2017-11-17 | 2017-11-17 | Preparation method of the Diamond Search without amine type aqueous polyurethane polyacrylate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535910A (en) * | 2018-10-31 | 2019-03-29 | 韶关市合众化工有限公司 | A kind of polyurethane-modified acrylic acid water-base resin and preparation method thereof with anti-corrosion function |
| CN110713771A (en) * | 2019-10-17 | 2020-01-21 | 刘杰 | Waterproof emulsion and preparation method thereof |
| WO2020111944A1 (en) | 2018-11-30 | 2020-06-04 | Stahl International B.V. | Process to prepare aqueous polyurethane dispersions that are substantially free of volatile organic compounds and that have a high solids content |
| CN115521490A (en) * | 2022-10-24 | 2022-12-27 | 山东奔腾漆业股份有限公司 | Preparation method of waterborne polyurethane |
| US12163277B2 (en) | 2018-11-30 | 2024-12-10 | Stahl International B.V. | Composite structure with polyurethane layers, which is substantially free of volatile organic compounds |
-
2017
- 2017-11-17 CN CN201711141207.0A patent/CN107814907A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535910A (en) * | 2018-10-31 | 2019-03-29 | 韶关市合众化工有限公司 | A kind of polyurethane-modified acrylic acid water-base resin and preparation method thereof with anti-corrosion function |
| WO2020111944A1 (en) | 2018-11-30 | 2020-06-04 | Stahl International B.V. | Process to prepare aqueous polyurethane dispersions that are substantially free of volatile organic compounds and that have a high solids content |
| NL2022104B1 (en) | 2018-11-30 | 2020-06-26 | Stahl Int B V | Process to prepare aqueous polyurethane dispersions that are substantially free of volatile organic compounds and that have a high solids content |
| US12163277B2 (en) | 2018-11-30 | 2024-12-10 | Stahl International B.V. | Composite structure with polyurethane layers, which is substantially free of volatile organic compounds |
| CN110713771A (en) * | 2019-10-17 | 2020-01-21 | 刘杰 | Waterproof emulsion and preparation method thereof |
| CN115521490A (en) * | 2022-10-24 | 2022-12-27 | 山东奔腾漆业股份有限公司 | Preparation method of waterborne polyurethane |
| CN115521490B (en) * | 2022-10-24 | 2023-11-17 | 山东奔腾漆业股份有限公司 | Preparation method of waterborne polyurethane |
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Application publication date: 20180320 |