CN105968314A - Preparation method of super-hydrophilic polyurethane used as long-acting antifogging agent - Google Patents
Preparation method of super-hydrophilic polyurethane used as long-acting antifogging agent Download PDFInfo
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- CN105968314A CN105968314A CN201610512064.9A CN201610512064A CN105968314A CN 105968314 A CN105968314 A CN 105968314A CN 201610512064 A CN201610512064 A CN 201610512064A CN 105968314 A CN105968314 A CN 105968314A
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/631—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyesters and/or 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of super-hydrophilic polyurethane used as a long-acting antifogging agent, comprising the following steps: adding acrylic acid grafted modified polyester polyol into a reaction kettle; dehydrating at 100 DEG C to 150 DEG C in vacuum for 1h to 4h; after cooling to a room temperature, adding hexamethylene diisocyanate and adding acetone for dissolving; raising the temperature to 80 DEG C to 90 DEG C and dropwise adding a catalyst; reacting for 1.5h to 3h to obtain a pre-polymer; adding 2-hydroxy-3-(2-allyloxy)-1-sodium propylsulfonate salt into the pre-polymer and continually reacting for 0.5h; then adding silicon-containing diol and dihydromethyl propionic acid; raising the temperature to 60 DEG C to 75 DEG C and carrying out a chain extension reaction for 1h to 1.5h; after cooling to the room temperature, adding triethylamine under high-speed stirring and stirring for 5min to 10min; adding water for emulsifying to obtain the super-hydrophilic polyurethane. When being used as the antifogging agent, the super-hydrophilic polyurethane prepared by the invention has the advantages of good film forming property, high adhesive force, water washing resistance, long-acting antifogging effect and the like.
Description
Technical field
The invention belongs to antifoggant technical field, the preparation method of a kind of super hydrophilic polyurethane as long-acting antifoggant.
Background technology
Antifoggant is the dispersant of a kind of low-molecular-weight containing hydrophilic group, it is coated on transparent substance surface and can form coating, hydrophilic group in coating can adsorb the hydrone in air, at transparent substance moistened surface, diffuse to form moisture film (rather than globule), make the light through object will not produce scattering, it is to avoid the generation of fogging phenomenon.The main component of antifoggant is surfactant, such as the ester of xylitol, sorbitol palmitate, lauric acid or animi resin monoglyceride etc..Currently used antifoggant is a kind of instant antifog preparation, and the antifog persistent period is shorter, poor adhesive force, general only several days or tens days, by wiping or be flush with water rear defence fog effect and disappear at once, so can not use as long-acting antifoggant.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of super hydrophilic polyurethane as long-acting antifoggant, polyurethane prepared by the method successfully solve when as long-acting antifoggant the tradition antifoggant antifog time short, can not wiping, the problem such as can not wash.
For achieving the above object, the invention provides the preparation method of a kind of super hydrophilic polyurethane as long-acting antifoggant, comprise the following steps:
(1) the 5～10 acrylic graft-modified PEPAs of molar part are joined in reactor, vacuum dehydration 1～4 h at 100～150 DEG C, 15～30 molar part hexamethylene diisocyanates are added after being down to room temperature, add 20～40 molar part acetone solutions, it is warming up to 80～90 DEG C, dropping 0.2～0.25 molar part catalyst, after reaction 1.5～3h, obtains performed polymer；
(2) 2～5 molar part 2-hydroxyl-3-(2-propenyloxy group)-1-propyl sulfonic acid sodium salts are added continuation reaction 0.5h in performed polymer；
(3) it is subsequently adding 2 the～5 siliceous dihydroxylic alcohols of molar part and 3～6 molar part dihydromethyl propionic acids, is warming up to 60～75 DEG C, chain extending reaction 1～1.5 h；
(4), after being down to room temperature, add 3～6 molar part triethylamines under high velocity agitation, stir 5～10 min, add water emulsification and obtain super hydrophilic polyurethane.
Described catalyst is triethylenediamine；Described siliceous dihydroxylic alcohols is the one in 1,1,3,3-tetramethyl-1,3-disiloxane glycol, 3-(trimethyl silyl)-1,2-propylene glycol or diethyl silanediol.
Super hydrophilic polyurethane prepared by the present invention, when as antifoggant, has good film-forming property, the adhesive force advantage such as antifog high, water-fastness, long-acting.
Detailed description of the invention
Invention is further illustrated below in conjunction with embodiment.
Embodiment 1
As the preparation method of the super hydrophilic polyurethane of long-acting antifoggant, comprise the following steps:
(1) the 5 acrylic graft-modified PEPAs of mol are joined in reactor, vacuum dehydration 3 h at 110 DEG C, 20 mol hexamethylene diisocyanates are added after being down to room temperature, add 20 mol acetone solutions, it is warming up to 85 DEG C, drip 0.2 mol triethylenediamine, after reaction 1.5h, obtain performed polymer；
(2) 2 mol 2-hydroxyl-3-(2-propenyloxy group)-1-propyl sulfonic acid sodium salts are added continuation reaction 0.5h in performed polymer；
(3) it is subsequently adding the 2 siliceous dihydroxylic alcohols of mol and 3 mol dihydromethyl propionic acids, is warming up to 65 DEG C, chain extending reaction 1 h；
(4) after being down to room temperature, add 3 mol triethylamines under high velocity agitation, stir 5～10 min, add water emulsification and obtain super hydrophilic polyurethane.
Super hydrophilic polyurethane prepared by the present embodiment is as the performance test of glass coating:
| Test event | Method of testing | Test result |
| Appearance of coat | Range estimation | Slightly " rainbow " phenomenon |
| Anti-fog properties | Mist has been seen whether after steaming 2 minutes with the hot steam of about 60 DEG C on antifogging coating | Coating does not hazes |
| Wearability | 1kg heavy burden friction testing | 1kg bears a heavy burden, and after horizontal wet friction 3000 times, does not hazes |
Embodiment 2
As the preparation method of the super hydrophilic polyurethane of long-acting antifoggant, comprise the following steps:
(1) the 7.5 acrylic graft-modified PEPAs of mol are joined in reactor, vacuum dehydration 1h at 150 DEG C, 30 mol hexamethylene diisocyanates are added after being down to room temperature, add 40 mol acetone solutions, it is warming up to 90 DEG C, drip 0.25 mol triethylenediamine, after reaction 3h, obtain performed polymer；
(2) 5 mol 2-hydroxyl-3-(2-propenyloxy group)-1-propyl sulfonic acid sodium salts are added continuation reaction 0.5h in performed polymer；
(3) it is subsequently adding the 3 siliceous dihydroxylic alcohols of mol and 5 mol dihydromethyl propionic acids, is warming up to 65 DEG C, chain extending reaction 1 h；
(4) after being down to room temperature, add 5 mol triethylamines under high velocity agitation, stir 5～10 min, add water emulsification and obtain super hydrophilic polyurethane.
Super hydrophilic polyurethane prepared by the present embodiment is as the performance test of glass coating:
| Test event | Method of testing | Test result |
| Appearance of coat | Range estimation | Coating uniform, without " rainbow " phenomenon |
| Anti-fog properties | Mist has been seen whether after steaming 2 minutes with the hot steam of about 60 DEG C on antifogging coating | Coating does not hazes |
| Wearability | 1kg heavy burden friction testing | 1kg bears a heavy burden, and after horizontal wet friction 5000 times, does not hazes |
Embodiment 3
As the preparation method of the super hydrophilic polyurethane of long-acting antifoggant, comprise the following steps:
(1) the 10 acrylic graft-modified PEPAs of mol are joined in reactor, vacuum dehydration 2h at 120 DEG C, 30 mol hexamethylene diisocyanates are added after being down to room temperature, add 40 mol acetone solutions, it is warming up to 87 DEG C, drip 0.25 mol triethylenediamine, after reaction 3h, obtain performed polymer；
(2) 4 mol 2-hydroxyl-3-(2-propenyloxy group)-1-propyl sulfonic acid sodium salts are added continuation reaction 0.5h in performed polymer；
(3) it is subsequently adding the 5 siliceous dihydroxylic alcohols of mol and 3 mol dihydromethyl propionic acids, is warming up to 70 DEG C, chain extending reaction 1 h；
(4) after being down to room temperature, add 3 mol triethylamines under high velocity agitation, stir 5～10 min, add water emulsification and obtain super hydrophilic polyurethane.
Super hydrophilic polyurethane prepared by the present embodiment is as the performance test of glass coating:
| Test event | Method of testing | Test result |
| Appearance of coat | Range estimation | Coating uniform, without " rainbow " phenomenon |
| Anti-fog properties | Mist has been seen whether after steaming 2 minutes with the hot steam of about 60 DEG C on antifogging coating | Coating does not hazes |
| Wearability | 1kg heavy burden friction testing | After horizontal wet friction 10000 times, do not haze |
From above-mentioned the performance test results, the super hydrophilic polyurethane prepared by the method for the present invention has good antifogging effect, the advantage such as coating adhesion is strong, scrubbing resistance, anti-fog duration length, effectively solves the shortcoming that current antifoggant exists.
Claims (2)
1. the preparation method of the super hydrophilic polyurethane being used as long-acting antifoggant, it is characterised in that comprise the following steps:
(1) the 5～10 acrylic graft-modified PEPAs of molar part are joined in reactor, vacuum dehydration 1～4 h at 100～150 DEG C, 15～30 molar part hexamethylene diisocyanates are added after being down to room temperature, add 20～40 molar part acetone solutions, it is warming up to 80～90 DEG C, dropping 0.2～0.25 molar part catalyst, after reaction 1.5～3h, obtains performed polymer；
(2) 2～5 molar part 2-hydroxyl-3-(2-propenyloxy group)-1-propyl sulfonic acid sodium salts are added continuation reaction 0.5h in performed polymer；
(3) it is subsequently adding 2 the～5 siliceous dihydroxylic alcohols of molar part and 3～6 molar part dihydromethyl propionic acids, is warming up to 60～75 DEG C, chain extending reaction 1～1.5 h；
(4), after being down to room temperature, add 3～6 molar part triethylamines under high velocity agitation, stir 5～10 min, add water emulsification and obtain super hydrophilic polyurethane.
The preparation method of the super hydrophilic polyurethane as long-acting antifoggant the most according to claim 1, it is characterised in that: described catalyst is triethylenediamine；Described siliceous dihydroxylic alcohols is the one in 1,1,3,3-tetramethyl-1,3-disiloxane glycol, 3-(trimethyl silyl)-1,2-propylene glycol or diethyl silanediol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610512064.9A CN105968314A (en) | 2016-07-02 | 2016-07-02 | Preparation method of super-hydrophilic polyurethane used as long-acting antifogging agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610512064.9A CN105968314A (en) | 2016-07-02 | 2016-07-02 | Preparation method of super-hydrophilic polyurethane used as long-acting antifogging agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265195A (en) * | 2021-05-21 | 2021-08-17 | 海南赛诺实业有限公司 | PET heat-sealing film coating antifogging agent, PET antifogging easy-to-uncover film and preparation method and application thereof |
| CN113372800A (en) * | 2021-06-21 | 2021-09-10 | 山西新华防化装备研究院有限公司 | Long-acting antifogging hydrophilic coating liquid and preparation method thereof |
| CN113416338A (en) * | 2021-07-05 | 2021-09-21 | 海南赛诺实业有限公司 | Antifogging easy-to-tear coating film and preparation method thereof |
| CN116284679A (en) * | 2023-05-18 | 2023-06-23 | 山东一诺威聚氨酯股份有限公司 | Super-hydrophilic anti-fog thermoplastic polyurethane elastomer material and preparation method and application thereof |
-
2016
- 2016-07-02 CN CN201610512064.9A patent/CN105968314A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265195A (en) * | 2021-05-21 | 2021-08-17 | 海南赛诺实业有限公司 | PET heat-sealing film coating antifogging agent, PET antifogging easy-to-uncover film and preparation method and application thereof |
| WO2022241901A1 (en) * | 2021-05-21 | 2022-11-24 | 海南赛诺实业有限公司 | Pet heat-sealing film coating anti-fogging agent, pet anti-fogging easy-release film, preparation method therefor and application thereof |
| CN113372800A (en) * | 2021-06-21 | 2021-09-10 | 山西新华防化装备研究院有限公司 | Long-acting antifogging hydrophilic coating liquid and preparation method thereof |
| CN113372800B (en) * | 2021-06-21 | 2022-06-28 | 山西新华防化装备研究院有限公司 | Long-acting antifogging hydrophilic coating liquid and preparation method thereof |
| CN113416338A (en) * | 2021-07-05 | 2021-09-21 | 海南赛诺实业有限公司 | Antifogging easy-to-tear coating film and preparation method thereof |
| CN113416338B (en) * | 2021-07-05 | 2022-07-26 | 海南赛诺实业有限公司 | Anti-fog easy-uncovering coating film and preparation method thereof |
| WO2023279473A1 (en) * | 2021-07-05 | 2023-01-12 | 海南赛诺实业有限公司 | Anti-fog easily-removed coating film and preparation method therefor |
| CN116284679A (en) * | 2023-05-18 | 2023-06-23 | 山东一诺威聚氨酯股份有限公司 | Super-hydrophilic anti-fog thermoplastic polyurethane elastomer material and preparation method and application thereof |
| CN116284679B (en) * | 2023-05-18 | 2023-09-01 | 山东一诺威聚氨酯股份有限公司 | Super-hydrophilic anti-fog thermoplastic polyurethane elastomer material and preparation method and application thereof |
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Application publication date: 20160928 |