CN106750162A - The preparation method of modified WPU coated films - Google Patents
The preparation method of modified WPU coated films Download PDFInfo
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- CN106750162A CN106750162A CN201611115680.7A CN201611115680A CN106750162A CN 106750162 A CN106750162 A CN 106750162A CN 201611115680 A CN201611115680 A CN 201611115680A CN 106750162 A CN106750162 A CN 106750162A
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- wpu
- modified
- hydroxyl alkyl
- added
- polysiloxanes
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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
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C09D175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to synthetic resin and plastics arts, and in particular to a kind of preparation method of modified WPU coated films.The preparation method of modified WPU coated films, comprises the following steps：（1）Synthesis end-capping reagent tetramethyl disiloxane；（2）Synthesis hydroxyl alkyl polysiloxanes；（3）The polysiloxane-modified WPU of synthesis hydroxyl alkyl.The modified WPU coated films excellent in stability that the present invention is made, the adhesive force of film is good on polycarbonate plate, and the span of hardness range is quite big.
Description
Technical field
The present invention relates to synthetic resin and plastics arts, and in particular to a kind of preparation side of modified WPU coated films
Method.
Background technology
, with water as decentralized medium, non-ignitable, nontoxic, environmental pollution is small, resource-saving, in coating, glue for aqueous polyurethane (WPU)
The fields such as glutinous agent and ink are used widely, and are progressively replacing solvent borne polyurethane.WPU includes aqueous polyurethane, water
Three kinds of dispersion liquid and aqueous emulsion, according to the charge property of hydrophilic radical, WPU can be divided into anionic, cationic and non-again
Ionic.Due to containing hydrophilic radical in WPU strands, so water resistance is unsatisfactory.With traditional solvent borne polyurethane phase
Than the mechanical property and surface property of film all have much room for improvement.Polysiloxanes has special surface property, chemical-resistant resistance rotten
The advantages of corrosion, hydrophobicity, electrical insulating property.The functional group introduced in the side base or end group of polysiloxanes generally can be divided into two classes：
One class is that functional group connects on the silicon atoms, referred to as functionalized silicon base, and this polysiloxanes is easily prepared, and activity is big, but the copolymerization for generating
Thing hydrolytic stability is poor；Another kind of is that functional group is connected on the organic group being connected with silicon atom, referred to as carbon functional group, this poly-
Siloxanes silicon-carbon is connected, good stability, with more actual application value.Hydroxyl alkyl is introduced in polysiloxanes segment to make
Reactive polysiloxanes are re-used as the soft section of polyurethane, are by effective means of the advantage of polysiloxanes with people WPU.
The content of the invention
The present invention is directed to propose a kind of preparation method of modified WPU coated films.
Technical program of the present invention lies in：
The preparation method of modified WPU coated films, comprises the following steps：
（1）Synthesis end-capping reagent tetramethyl disiloxane：
Nitrogen is protected, and 8.14 g magnesium powders, 50 mL dimethyl dichlorosilane (DMCS)s and 140 mL tetrahydrochysenes are sequentially added in flask with three necks,round bottom
Furans, liquid is grey black in bottle；0.54mL iodoethane and iodine are added, slow heating is started simultaneously at and is warming up to 65 DEG C, tetrahydrochysene
Furans starts backflow, a large amount of foams occurs, and after lasting about 2 h, liquid is changed into yellow in bottle, and foam is reduced；Reheat backflow 1h
After lower the temperature, filter, wash filter residue with benzene, refilter, filtrate is in yellow green；Distillation filtrate, removes solvent benzol and unreacted two
Dimethyl dichlorosilane (DMCS)；Hydrochloric acid catalysis hydrolysis is instilled in vinasse, 48 h are kept stirring for；It is 5% sodium carbonate with mass fraction
Solution is washed, point liquid, upper strata vacuum distillation after natrium carbonicum calcinatum drying, collects 58 DEG C of cuts, and what is obtained is purpose product
Tetramethyl disiloxane；
（2）Synthesis hydroxyl alkyl polysiloxanes：
Tetramethyl disiloxane and octamethylcy-clotetrasiloxane are added in flask with three necks,round bottom, adds catalyst to keep system
Alkaline state；Stirred after nitrogen displacement, slow intensification is heated to 80 DEG C, and tetramethyl disiloxane starts ring-opening polymerisation；About 1 h
Solution viscosity gradually increases afterwards；Temperature is reduced to 65 DEG C, is kept stirring for, after about 20 h of reaction, obtain hydroxy-end capped hydroxyl alkyl
Polysiloxanes, stops heating；With distilled water washing reaction product, point liquid, until washing out liquid shows neutral；Collect supernatant liquid,
50 DEG C of 7 h of vacuum drying；
（3）The polysiloxane-modified WPU of synthesis hydroxyl alkyl：
Hydroxyl alkyl polysiloxanes and MDI are added in flask with three necks,round bottom, and adds acetone solvent；Nitrogen is protected, heat temperature raising
To acetone reflux, certain hour is reacted, the hydroxyl of hydroxyl alkyl polysiloxanes changes with the isocyanate group reaction generation polysiloxanes of MDI
The base polyurethane prepolymer for use as of property；Polyethers 210, DMPA, BD chain extensions to reaction terminating, the modified WPU of generation purpose product are added afterwards；Drop
After warming to room temperature, TEA is added and the dispersion at a high speed that adds water, acetone is extracted in decompression out, obtain the polysiloxane-modified WPU dispersions of hydroxyl alkyl
Body；Polycarbonate plate is cut into 7cm × 7cm, is dried after cleaning, then to coat hydroxyl alkyl respectively polysiloxane-modified on side thereon
WPU emulsions, the h of natural drying 24, repeatedly film twice, per the h of minor tick 24, after film terminates, dries 48 h again thereafter, obtains final product
To modified WPU coated films.
The technical effects of the invention are that：
The modified WPU coated films excellent in stability that the present invention is made, the adhesive force of film is good on polycarbonate plate, and hard
The span for spending scope is quite big.
Specific embodiment
The preparation method of modified WPU coated films, comprises the following steps：
（1）Synthesis end-capping reagent tetramethyl disiloxane：
Nitrogen is protected, and 8.14 g magnesium powders, 50 mL dimethyl dichlorosilane (DMCS)s and 140 mL tetrahydrochysenes are sequentially added in flask with three necks,round bottom
Furans, liquid is grey black in bottle；0.54mL iodoethane and iodine are added, slow heating is started simultaneously at and is warming up to 65 DEG C, tetrahydrochysene
Furans starts backflow, a large amount of foams occurs, and after lasting about 2 h, liquid is changed into yellow in bottle, and foam is reduced；Reheat backflow 1h
After lower the temperature, filter, wash filter residue with benzene, refilter, filtrate is in yellow green；Distillation filtrate, removes solvent benzol and unreacted two
Dimethyl dichlorosilane (DMCS)；Hydrochloric acid catalysis hydrolysis is instilled in vinasse, 48 h are kept stirring for；It is 5% sodium carbonate with mass fraction
Solution is washed, point liquid, upper strata vacuum distillation after natrium carbonicum calcinatum drying, collects 58 DEG C of cuts, and what is obtained is purpose product
Tetramethyl disiloxane；
（2）Synthesis hydroxyl alkyl polysiloxanes：
Tetramethyl disiloxane and octamethylcy-clotetrasiloxane are added in flask with three necks,round bottom, adds catalyst to keep system
Alkaline state；Stirred after nitrogen displacement, slow intensification is heated to 80 DEG C, and tetramethyl disiloxane starts ring-opening polymerisation；About 1 h
Solution viscosity gradually increases afterwards；Temperature is reduced to 65 DEG C, is kept stirring for, after about 20 h of reaction, obtain hydroxy-end capped hydroxyl alkyl
Polysiloxanes, stops heating；With distilled water washing reaction product, point liquid, until washing out liquid shows neutral；Collect supernatant liquid,
50 DEG C of 7 h of vacuum drying；
（3）The polysiloxane-modified WPU of synthesis hydroxyl alkyl：
Hydroxyl alkyl polysiloxanes and MDI are added in flask with three necks,round bottom, and adds acetone solvent；Nitrogen is protected, heat temperature raising
To acetone reflux, certain hour is reacted, the hydroxyl of hydroxyl alkyl polysiloxanes changes with the isocyanate group reaction generation polysiloxanes of MDI
The base polyurethane prepolymer for use as of property；Polyethers 210, DMPA, BD chain extensions to reaction terminating, the modified WPU of generation purpose product are added afterwards；Drop
After warming to room temperature, TEA is added and the dispersion at a high speed that adds water, acetone is extracted in decompression out, obtain the polysiloxane-modified WPU dispersions of hydroxyl alkyl
Body；Polycarbonate plate is cut into 7cm × 7cm, is dried after cleaning, then to coat hydroxyl alkyl respectively polysiloxane-modified on side thereon
WPU emulsions, the h of natural drying 24, repeatedly film twice, per the h of minor tick 24, after film terminates, dries 48 h again thereafter, obtains final product
To modified WPU coated films.
Wherein, MDI is '-diphenylmethane diisocyanate, and DMPA is dihydromethyl propionic acid, and BD is Isosorbide-5-Nitrae butanediol, and TEA is three
Ethamine.
Claims (1)
1. be modified the preparation method of WPU coated films, it is characterised in that：Comprise the following steps：
（1）Synthesis end-capping reagent tetramethyl disiloxane：
Nitrogen is protected, and 8.14 g magnesium powders, 50 mL dimethyl dichlorosilane (DMCS)s and 140 mL tetrahydrochysenes are sequentially added in flask with three necks,round bottom
Furans, liquid is grey black in bottle；0.54mL iodoethane and iodine are added, slow heating is started simultaneously at and is warming up to 65 DEG C, tetrahydrochysene
Furans starts backflow, a large amount of foams occurs, and after lasting about 2 h, liquid is changed into yellow in bottle, and foam is reduced；Reheat backflow 1h
After lower the temperature, filter, wash filter residue with benzene, refilter, filtrate is in yellow green；Distillation filtrate, removes solvent benzol and unreacted two
Dimethyl dichlorosilane (DMCS)；Hydrochloric acid catalysis hydrolysis is instilled in vinasse, 48 h are kept stirring for；It is 5% sodium carbonate with mass fraction
Solution is washed, point liquid, upper strata vacuum distillation after natrium carbonicum calcinatum drying, collects 58 DEG C of cuts, and what is obtained is purpose product
Tetramethyl disiloxane；
（2）Synthesis hydroxyl alkyl polysiloxanes：
Tetramethyl disiloxane and octamethylcy-clotetrasiloxane are added in flask with three necks,round bottom, adds catalyst to keep system
Alkaline state；Stirred after nitrogen displacement, slow intensification is heated to 80 DEG C, and tetramethyl disiloxane starts ring-opening polymerisation；About 1 h
Solution viscosity gradually increases afterwards；Temperature is reduced to 65 DEG C, is kept stirring for, after about 20 h of reaction, obtain hydroxy-end capped hydroxyl alkyl
Polysiloxanes, stops heating；With distilled water washing reaction product, point liquid, until washing out liquid shows neutral；Collect supernatant liquid,
50 DEG C of 7 h of vacuum drying；
（3）The polysiloxane-modified WPU of synthesis hydroxyl alkyl：
Hydroxyl alkyl polysiloxanes and MDI are added in flask with three necks,round bottom, and adds acetone solvent；Nitrogen is protected, heat temperature raising
To acetone reflux, certain hour is reacted, the hydroxyl of hydroxyl alkyl polysiloxanes changes with the isocyanate group reaction generation polysiloxanes of MDI
The base polyurethane prepolymer for use as of property；Polyethers 210, DMPA, BD chain extensions to reaction terminating, the modified WPU of generation purpose product are added afterwards；Drop
After warming to room temperature, TEA is added and the dispersion at a high speed that adds water, acetone is extracted in decompression out, obtain the polysiloxane-modified WPU dispersions of hydroxyl alkyl
Body；Polycarbonate plate is cut into 7cm × 7cm, is dried after cleaning, then to coat hydroxyl alkyl respectively polysiloxane-modified on side thereon
WPU emulsions, the h of natural drying 24, repeatedly film twice, per the h of minor tick 24, after film terminates, dries 48 h again thereafter, obtains final product
To modified WPU coated films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611115680.7A CN106750162A (en) | 2016-12-07 | 2016-12-07 | The preparation method of modified WPU coated films |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611115680.7A CN106750162A (en) | 2016-12-07 | 2016-12-07 | The preparation method of modified WPU coated films |
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| CN106750162A true CN106750162A (en) | 2017-05-31 |
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| CN201611115680.7A Pending CN106750162A (en) | 2016-12-07 | 2016-12-07 | The preparation method of modified WPU coated films |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840987A (en) * | 2018-06-28 | 2018-11-20 | 优美特（北京）环境材料科技股份公司 | The polyalcohol modified aqueous polyurethane emulsion of organosilicon and preparation method |
-
2016
- 2016-12-07 CN CN201611115680.7A patent/CN106750162A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840987A (en) * | 2018-06-28 | 2018-11-20 | 优美特（北京）环境材料科技股份公司 | The polyalcohol modified aqueous polyurethane emulsion of organosilicon and preparation method |
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Application publication date: 20170531 |