CN108329342B - Organic silicon coupling agent and preparation method and application thereof - Google Patents
Organic silicon coupling agent and preparation method and application thereof Download PDFInfo
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- CN108329342B CN108329342B CN201810174075.XA CN201810174075A CN108329342B CN 108329342 B CN108329342 B CN 108329342B CN 201810174075 A CN201810174075 A CN 201810174075A CN 108329342 B CN108329342 B CN 108329342B
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- C—CHEMISTRY; METALLURGY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to an organic silicon coupling agent, and a preparation method and application thereof. The organosilicon coupling agent has a structure shown in formula (I), wherein gamma-glycidyl ether oxypropyl trimethoxysilane and acrylic acid are used for carrying out an epoxy ring-opening reaction to synthesize the organosilicon coupling agent which simultaneously contains hydroxyl, siloxane and carbon-carbon double bond multiple functional groups on a molecular structure, and when the organosilicon coupling agent is used as a capping agent for polyurethane reaction, the stability of the synthesized waterborne polyurethane can be improved, and meanwhile, a paint film formed by photocuring the synthesized waterborne polyurethane has more excellent performance. The experimental results show that: the waterborne polyurethane prepared by using the organosilicon coupling agent provided by the invention as an end-capping agent has good mechanical stability, the appearance of the waterborne polyurethane is transparent or semitransparent, and a paint film obtained by photocuring the waterborne polyurethane has good hardness, adhesive force, glossiness and water resistance.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to an organic silicon coupling agent, and a preparation method and application thereof.
Background
Currently, with the establishment of environmental regulations and the enhancement of environmental protection meanings in various developed countries, the trend of replacing traditional photocuring polyurethane coatings with waterborne photocuring (UV) polyurethane coatings is more and more obvious. The water-based UV polyurethane is an energy-saving material, and is prepared by firstly synthesizing a prepolymer from polyisocyanate and a hydroxyl-containing compound through step-by-step polyaddition reaction, and then introducing a hydrophilic group or adding an emulsifier through a chain extender to dissolve or disperse the hydrophilic group or the emulsifier in water. The waterborne polyurethane material takes water as a medium, has low content of Volatile Organic Compounds (VOC), does not contain free diisocyanate monomers, has low toxicity, is environment-friendly, has wide application prospect, is widely applied to automobile repair coatings, industrial coatings, furniture coatings and plastic coatings, and is also applied to the aspects of fabric, feather, paper and rubber softening finishing agents and the like. However, the traditional water-based UV polyurethane has the problems of poor adhesion, poor water resistance and weather resistance of a coating film, long surface drying and drying time and the like, and is a difficult point which troubles the application of the traditional water-based UV polyurethane for a long time.
The organic silicon compound has the characteristics of both organic compounds and inorganic compounds, and researches show that the organic silicon compound is adopted to modify the water-based UV polyurethane, so that various problems existing in the use of the organic silicon compound can be well improved. At present, hydroxyl silicone oil is generally introduced into a chain segment of waterborne polyurethane in organosilicon modified waterborne UV polyurethane, but the product obtained by the method has poor stability and often generates phase separation, and the obtained cured film is turbid and opaque when being observed apparently; silane coupling agents (KH550, KH570) may be involved directly in the synthesis reaction with the aqueous polyurethane, but silane epoxy reacts with carboxylic acid to hydrolyze, and thus the stability of the synthesized modified polyurethane is also affected.
Disclosure of Invention
In view of the above, the present invention aims to provide an organosilicon coupling agent, and a preparation method and an application thereof, wherein the organosilicon coupling agent modified aqueous UV polyurethane prepared by using the organosilicon coupling agent provided by the present invention as a capping agent has good stability, and a paint film formed by photocuring the polyurethane has good hardness, adhesion, glossiness and water resistance.
The invention provides an organic silicon coupling agent, which has a structure shown in a formula (I):
the invention provides a preparation method of the organic silicon coupling agent in the technical scheme, which comprises the following steps:
reacting gamma-glycidoxypropyltrimethoxysilane with acrylic acid in the presence of a polymerization inhibitor and a catalyst to obtain the organosilicon coupling agent with the structure of the formula (I).
Preferably, the polymerization inhibitor comprises p-hydroxyanisole and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide;
the catalyst comprises N, N-dimethylbenzylamine and/or dibutyltin dilaurate.
Preferably, the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the acrylic acid to the polymerization inhibitor to the catalyst is (70-80): (20-25): (0.2-0.4): (0.1-0.3).
Preferably, the reaction temperature is 70-80 ℃; the reaction time is 4-5 h.
The invention provides application of the organosilicon coupling agent in the technical scheme in preparation of organosilicon coupling agent modified waterborne UV polyurethane.
The invention provides a preparation method of organosilicon coupling agent modified waterborne UV polyurethane, which comprises the following steps:
a) reacting difunctional isocyanate and dihydric alcohol in the presence of a catalyst to obtain a first intermediate product;
b) reacting the first intermediate product with a hydrophilic agent to obtain a second intermediate product;
c) reacting said second intermediate product with said organosilicon coupling agent of claim 1 in the presence of a polymerization inhibitor to provide a third intermediate product;
d) reacting the third intermediate product with a salt forming agent to obtain a fourth intermediate product;
e) and mixing and stirring the fourth intermediate product and water to obtain the organosilicon coupling agent modified waterborne UV polyurethane.
Preferably, the difunctional isocyanate includes one or more of isophorone diisocyanate, toluene-2, 4-diisocyanate, and 4,4' -methylenebis (phenyl isocyanate);
the dihydric alcohol comprises one or more of poly 1, 4-butylene adipate glycol, polyethylene glycol and polycarbonate propylene glycol;
the catalyst comprises N, N-dimethylbenzylamine and/or dibutyltin dilaurate;
the hydrophilic agent comprises 2, 2-dimethylolpropionic acid and/or 2, 2-dimethylolbutyric acid;
the polymerization inhibitor comprises p-hydroxyanisole and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide;
the salt forming agent comprises triethylamine and/or triethanolamine.
Preferably, the mass ratio of the difunctional isocyanate, the dihydric alcohol, the catalyst, the hydrophilic agent, the polymerization inhibitor, the organosilicon coupling agent and the salt forming agent is (20-40): (50-80): (0.1-0.3): (2-5): (0.1-0.3): (2-8): (2-8).
The invention provides a cured paint film which is formed by mixing organosilicon coupling agent modified waterborne UV polyurethane prepared by the method of the technical scheme and a photoinitiator and then carrying out photocuring.
Compared with the prior art, the invention provides an organic silicon coupling agent and a preparation method and application thereof. The organosilicon coupling agent has a structure shown in a formula (I), wherein gamma-glycidoxypropyltrimethoxysilane (KH560) and Acrylic Acid (AA) are used for carrying out an epoxy ring-opening reaction to synthesize the organosilicon coupling agent (KH560-AA) which simultaneously contains hydroxyl, siloxane and carbon-carbon double bond (C ═ C) multiple functional groups on a molecular structure, and when the organosilicon coupling agent is used as an end-capping agent for polyurethane reaction, the stability of the synthesized waterborne polyurethane can be improved, and meanwhile, a paint film formed by photocuring the synthesized waterborne polyurethane has more excellent performance. The experimental results show that: the waterborne polyurethane prepared by using the organosilicon coupling agent provided by the invention as an end-capping agent has good mechanical stability, the appearance of the waterborne polyurethane is transparent or semitransparent, the hardness of a paint film obtained by photocuring the waterborne polyurethane is more than or equal to 2H, the adhesive force grade is 0-2 grade, the glossiness (60 ℃) is more than or equal to 81 degrees, and the water resistance is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared detection spectrum provided in example 1 of the present invention;
FIG. 2 is an infrared detection spectrum provided in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an organic silicon coupling agent, which has a structure shown in a formula (I):
the invention also provides a preparation method of the organic silicon coupling agent, which comprises the following steps:
reacting gamma-glycidoxypropyltrimethoxysilane with acrylic acid in the presence of a polymerization inhibitor and a catalyst to obtain the organosilicon coupling agent with the structure of the formula (I).
In the preparation method of the organosilicon coupling agent provided by the invention, gamma-glycidoxypropyltrimethoxysilane and acrylic acid react in the presence of a polymerization inhibitor and a catalyst to obtain the organosilicon coupling agent with the structure of the formula (I). Wherein the polymerization inhibitor includes, but is not limited to, p-hydroxyanisole (MEHQ) and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO); such catalysts include, but are not limited to, N-Dimethylbenzylamine (DMBA) and/or dibutyltin dilaurate (DBTDL); the mass ratio of the gamma-glycidyl ether oxypropyltrimethoxysilane to the acrylic acid to the polymerization inhibitor to the catalyst is (70-80): (20-25): (0.2-0.4): (0.1-0.3), specifically 76.6:23.1:0.2: 0.1; the reaction is preferably carried out under a nitrogen atmosphere; the reaction temperature is preferably 70-80 ℃; the preferable time of the reaction is 4-5 h. In the present invention, the γ -glycidoxypropyltrimethoxysilane and acrylic acid are preferably reacted in the following manner: firstly, gamma-glycidoxypropyltrimethoxysilane dissolved with a polymerization inhibitor and acrylic acid dissolved with a catalyst are prepared respectively, then the gamma-glycidoxypropyltrimethoxysilane dissolved with the polymerization inhibitor is heated to the reaction temperature under the nitrogen atmosphere, then the acrylic acid dissolved with the catalyst is dripped into the gamma-glycidoxypropyltrimethoxysilane dissolved with the polymerization inhibitor, the dripping speed is preferably 2-3 s/droplet, and the reaction is carried out for a period of time after the dripping is finished, so that a reaction product is obtained.
According to the invention, gamma-glycidoxypropyltrimethoxysilane (KH560) and Acrylic Acid (AA) are subjected to an epoxy ring-opening reaction to synthesize an organosilicon coupling agent (KH560-AA) which simultaneously contains hydroxyl, siloxane and carbon-carbon double bond (C ═ C) multiple functional groups on a molecular structure, and when the organosilicon coupling agent is used as a capping agent for polyurethane reaction, the stability of the synthesized waterborne polyurethane can be improved, and meanwhile, the paint film formed by photocuring the synthesized waterborne polyurethane has more excellent performance. The experimental results show that: the waterborne polyurethane prepared by using the organosilicon coupling agent provided by the invention as an end-capping agent has good mechanical stability, the appearance of the waterborne polyurethane is transparent or semitransparent, the hardness of a paint film obtained by photocuring the waterborne polyurethane is more than or equal to 2H, the adhesive force grade is 0-2 grade, the glossiness (60 ℃) is more than or equal to 81 degrees, and the water resistance is good.
The invention also provides application of the organic silicon coupling agent in preparation of the organic silicon coupling agent modified waterborne UV polyurethane. In the application provided by the invention, the organosilicon coupling agent is used as a blocking agent for preparing organosilicon coupling agent modified waterborne UV polyurethane, so that the prepared organosilicon coupling agent modified waterborne UV polyurethane has good stability, and a paint film formed by photocuring the prepared polyurethane has good hardness, adhesive force, glossiness and water resistance.
The invention also provides a preparation method of the organosilicon coupling agent modified waterborne UV polyurethane, which comprises the following steps:
a) reacting difunctional isocyanate and dihydric alcohol in the presence of a catalyst to obtain a first intermediate product;
b) reacting the first intermediate product with a hydrophilic agent to obtain a second intermediate product;
c) reacting said second intermediate product with said organosilicon coupling agent of claim 1 in the presence of a polymerization inhibitor to provide a third intermediate product;
d) reacting the third intermediate product with a salt forming agent to obtain a fourth intermediate product;
e) and mixing and stirring the fourth intermediate product and water to obtain the organosilicon coupling agent modified waterborne UV polyurethane.
In the preparation method of the organosilicon coupling agent modified waterborne UV polyurethane provided by the invention, firstly, difunctional isocyanate, dihydric alcohol and a catalyst are reacted. Wherein the difunctional isocyanates include, but are not limited to, one or more of isophorone diisocyanate (IPDI), toluene-2, 4-diisocyanate (TDI), and 4,4' -methylenebis (phenyl isocyanate) (MDI); the dihydric alcohol is a long-chain dihydric alcohol, including but not limited to one or more of poly 1, 4-butylene glycol adipate glycol (PBA), polyethylene glycol (PEG) and polycarbonate propylene glycol (PPC); the number average molecular weight of the dihydric alcohol is preferably 600-2000; catalysts include, but are not limited to, N-Dimethylbenzylamine (DMBA) and/or dibutyltin dilaurate (DBTDL); the mass ratio of the difunctional isocyanate to the dihydric alcohol is preferably (20-40): (50-80), more preferably (23-37): (54-68), specifically 27.2:65.3, 27.5:63, 23.3:67.2 or 36.2: 54.3; the mass ratio of the difunctional isocyanate to the catalyst is preferably (20-40): (0.1 to 0.3), more preferably (23 to 37): 0.3, specifically 27.2:0.3, 27.5:0.3, 23.3:0.3 or 36.2: 0.3; the reaction temperature is preferably 80-85 ℃; the reaction time is preferably 1-2 h. In the present invention, the reaction is preferably carried out as follows: firstly, mixing difunctional isocyanate and dihydric alcohol, then dripping a catalyst, and then heating to the reaction temperature for reaction for a period of time. After the reaction is finished, a first intermediate product is obtained.
And after a first intermediate product is obtained, mixing the first intermediate product and the hydrophilic agent for reaction. Wherein, the hydrophilic agent includes but is not limited to 2, 2-dimethylolpropionic acid (DMPA) and/or 2, 2-dimethylolbutyric acid (DMBA); the mass ratio of the hydrophilic agent to the difunctional isocyanate is preferably (2-5): (20-40), more preferably 3: (23-37), specifically 3:27.2, 3:27.5, 3:23.3 or 3: 36.2; the reaction temperature is preferably 70-80 ℃; the reaction time is preferably 2-3 h. In the present invention, the reaction is preferably carried out as follows: the first intermediate product is first cooled to below 55 deg.c, added with hydrophilic agent and then heated to reaction temperature for reaction for some time. And after the reaction is finished, obtaining a second intermediate product.
And after a second intermediate product is obtained, mixing the second intermediate product, the organosilicon coupling agent and the polymerization inhibitor for reaction. Wherein the organosilicon coupling agent is described above and is not described herein; the polymerization inhibitor includes, but is not limited to, p-hydroxyanisole (MEHQ) and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO); the mass ratio of the organosilicon coupling agent to the difunctional isocyanate is preferably (2-8): (20-40), more preferably (2-4): (23-37), specifically 2:27.2, 4:27.5, 4:23.3 or 4: 36.2; the mass ratio of the polymerization inhibitor to the difunctional isocyanate is preferably (0.1-0.3): (20 to 40), more preferably 0.2: (23-37), specifically 0.2:27.2, 0.2:27.5, 0.2:23.3 or 0.2: 36.2; the reaction temperature is preferably 45-55 ℃; the reaction time is preferably 1-2 h. In the present invention, the reaction is preferably carried out as follows: firstly, cooling the second intermediate product to the reaction temperature, then dropwise adding an organic silicon coupling agent dissolved with a polymerization inhibitor, and reacting for a period of time. And after the reaction is finished, obtaining a third intermediate product.
And after a third intermediate product is obtained, mixing the third intermediate product with a salt forming agent for reaction. Wherein the salt forming agent includes, but is not limited to, Triethylamine (TEA) and/or Triethanolamine (TEOA); the mass ratio of the salt forming agent to the difunctional isocyanate is preferably (2-8): (20-40), more preferably 2: (23-37,) specifically 2:27.2, 2:27.5, 2:23.3 or 2: 36.2; the reaction temperature is preferably 15-30 ℃, and particularly can be room temperature; the reaction time is preferably 0.5-2 h, and specifically can be 1 h. In the present invention, the reaction is preferably carried out as follows: the third intermediate product is first cooled to reaction temperature, and then added with salt forming agent for reaction for some time. And after the reaction is finished, obtaining a fourth intermediate product.
After a fourth intermediate product is obtained, the fourth intermediate product and water are mixed and stirred. Wherein the mass ratio of the fourth intermediate product to water is preferably 1: (2-3); the stirring speed is preferably 1000-1300 rpm; the stirring time is preferably 30-60 min. And after uniformly stirring, carrying out reduced pressure distillation to obtain the organosilicon coupling agent modified waterborne UV polyurethane with appropriate solid content.
According to the preparation method of the polyurethane, the specific organic silicon coupling agent is used as the end-capping agent, the waterborne polyurethane with good stability is prepared, and a paint film formed by photocuring the waterborne polyurethane has good hardness, adhesive force, glossiness and water resistance. The experimental results show that: the waterborne polyurethane prepared by the method has good mechanical stability, the appearance of the waterborne polyurethane is transparent or semitransparent, the hardness of a paint film obtained by photocuring the waterborne polyurethane is more than or equal to 2H, the adhesive force grade is 0-2 grade, the glossiness (60 degrees) is more than or equal to 81 degrees, and the water resistance is good.
The invention also provides a cured paint film which is formed by mixing the organosilicon coupling agent modified waterborne UV polyurethane prepared by the method of the technical scheme and a photoinitiator and then carrying out photocuring. Wherein the photoinitiator is available under the trade designation including but not limited to Darocur-1173; the mass ratio of the polyurethane to the photoinitiator is preferably 100: (1-10), more preferably 100: (3-5); the light intensity of the photocuring is preferably 30-40 mW/cm2(ii) a The time for photocuring is preferably 30-40 s.
The cured paint film provided by the invention is formed by photocuring waterborne polyurethane prepared by adopting a special end-capping reagent, and has good hardness, adhesive force, glossiness and water resistance. The experimental results show that: the hardness of the paint film provided by the invention is more than or equal to 2H, the adhesive force grade is 0-2 grade, the glossiness (60 ℃) is more than or equal to 81 degrees, and the water resistance is good.
For the sake of clarity, the following examples are given in detail.
Example 1:
synthesis of organosilicon coupling agent (KH560-AA)
In the synthesis process, the related raw materials comprise p-hydroxyanisole, gamma-glycidyl ether oxypropyl trimethoxysilane, N, N-dimethylbenzylamine and acrylic acid, wherein the content of hydroxyanisole in the total raw materials is 0.2 wt%, the content of gamma-glycidyl ether oxypropyl trimethoxysilane in the total raw materials is 76.6 wt%, the content of N, N-dimethylbenzylamine in the total raw materials is 0.1 wt%, and the content of acrylic acid in the total raw materials is 23.1 wt%.
The specific synthetic process comprises the following steps: adding gamma-glycidoxypropyltrimethoxysilane (KH560) dissolved with a polymerization inhibitor p-hydroxyanisole (MEHQ) into a four-neck flask provided with a thermometer, a gas-guide tube, a condenser tube and a stirring paddle, heating to 70-80 ℃ under the protection of nitrogen, slowly dropwise adding Acrylic Acid (AA) dissolved with a catalyst N, N-Dimethylbenzylamine (DMBA) at a dropwise adding rate of 2 s/drop, reacting for 4-5 h after dropwise adding is finished, and discharging to obtain the KH 560-AA.
KH560 and KH560-AA are subjected to infrared spectrum analysis, and the results are shown in FIG. 1, wherein FIG. 1 is the infrared detection spectrum provided in example 1 of the present invention. As can be seen from FIG. 1, the synthesized novel monomer KH560-AA is 3444cm in comparison with KH560-1A stretching vibration peak of-OH appears at 1727cm-1The peak appears in the ester bond, carbonyl C ═ O stretching vibration peak, 1632cm-1And 810cm-1A stretching vibration peak of C-C double bond C-C appears, and in addition, 910cm-1The absorption peak at the epoxy group has disappeared, which indicates that KH560 has undergone an epoxy ring-opening reaction with acrylic acid.
Example 2:
1) raw materials:
isophorone diisocyanate (IPDI): 27.2 wt%, poly 1, 4-butanediol adipate diol (PBA-600): 65.3 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, 3- (2, 3-glycidoxy) propyltrimethoxysilane-acrylic acid (KH 560-AA): 2 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt% and deionized water.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA), heating to 70-80 ℃ again, and reacting for 2-3 h; and cooling to 45-55 ℃ again, dropwise adding KH560-AA dissolved with a polymerization inhibitor (TEMPO) for reacting for 1-2 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine a reaction end point. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 34.9 wt%.
3) Structural characterization:
the infrared spectrum analysis of the final product is performed, and the result is shown in fig. 2, and fig. 2 is the infrared detection spectrum provided in example 2 of the present invention. As can be seen in FIG. 2, 2270cm-1The characteristic absorption peak of the-NCO had disappeared, which indicated that no residual-NCO had appeared in the system; at 3361cm-1The absorption peak is the stretching vibration peak of N-H on carbamate; 2957cm-1The absorption peak is C-H stretching vibration peak on methyl in methoxyl; 1730cm-1The absorption peak is the stretching vibration peak of carbonyl C ═ O in carbamate; 1542cm-1The absorption peak is a plane bending vibration peak of N-H; 809cm-1The absorption peak is the stretching vibration peak of C-C double bond; 1039cm-1The absorption peak is methoxy Si-OCH3The stretching vibration peak of (1). It can be seen that KH560-AA monomer has been successfully introduced into the polyurethane chain,
example 3:
1) raw materials:
isophorone diisocyanate (IPDI): 27.5 wt%, poly 1, 4-butanediol adipate diol (PBA-600): 63 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, 3- (2, 3-glycidoxy) propyltrimethoxysilane-acrylic acid (KH 560-AA): 4 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt% and deionized water.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA), heating to 70-80 ℃ again, and reacting for 2-3 h; and cooling to 45-55 ℃ again, dropwise adding KH560-AA dissolved with a polymerization inhibitor (TEMPO) for reacting for 1-2 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine a reaction end point. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 33.8 wt%.
Example 4:
1) raw materials:
toluene-2, 4-diisocyanate (TDI): 23.3 wt%, poly 1, 4-butanediol adipate diol (PBA-600): 67.2 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, 3- (2, 3-glycidoxy) propyltrimethoxysilane-acrylic acid (KH 560-AA): 4 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt% and deionized water.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA), heating to 70-80 ℃ again, and reacting for 2-3 h; and cooling to 45-55 ℃ again, dropwise adding KH560-AA dissolved with a polymerization inhibitor (TEMPO) for reacting for 1-2 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine a reaction end point. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 34.8 wt%.
Example 5:
1) raw materials:
isophorone diisocyanate (IPDI): 36.2 wt%, polyethylene glycol 600(PEG 600): 54.3 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, 3- (2, 3-glycidoxy) propyltrimethoxysilane-acrylic acid (KH 560-AA): 4 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt% and deionized water.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA), heating to 70-80 ℃ again, and reacting for 2-3 h; and cooling to 45-55 ℃ again, dropwise adding KH560-AA dissolved with a polymerization inhibitor (TEMPO) for reacting for 1-2 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine a reaction end point. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 34.4 wt%.
Comparative example 1:
1) raw materials:
isophorone diisocyanate (IPDI): 28 wt%, poly 1, 4-butanediol adipate diol (PBA-600): 67 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt%, deionized water, acetone: proper amount.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; and then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA), heating to 70-80 ℃ again, reacting for 2-3 h, and determining the reaction end point by titrating the-NCO content in the system by a toluene-di-n-butylamine method in the whole process. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 33.5 wt%.
Comparative example 2:
1) raw materials:
isophorone diisocyanate (IPDI): 27.5 wt%, poly 1, 4-butanediol adipate diol (PBA-600): 63 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, hydroxypropyl methacrylate (HEMA): 4 wt%, Triethylamine (TEA): 2 wt%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt%, deionized water, acetone: proper amount.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; and then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA) and hydroxypropyl methacrylate (HEMA), heating to 70-80 ℃ again, reacting for 2-3 h, and determining the reaction end point by titrating the-NCO content in the system by a toluene-di-n-butylamine method in the whole process. And finally, cooling to room temperature, adding Triethylamine (TEA) to react for 1 hour, adding 2-3 times of deionized water by mass, and stirring at a high speed (1000-1300 rpm) for 30-60 min to obtain a final product with the solid content of 33.7 wt%.
Comparative example 3:
1) raw materials:
isophorone diisocyanate (IPDI): 27.2% by weight, poly-1, 4-butanediol adipate diol (PBA-600, make-up polymer or number average molecular weight): 62.6 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, hydroxypropyl methacrylate (HEMA): 1.7 wt%, Triethylamine (TEA): 2 wt%, gamma-glycidoxypropyltrimethoxysilane (KH 650); 3%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt%, deionized water, acetone: proper amount.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; and then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA) and hydroxypropyl methacrylate (HEMA), heating to 70-80 ℃ again, reacting for 2-3 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine the reaction end point. Finally, cooling to room temperature, and adding Triethylamine (TEA) to react for 1 h; adding gamma-glycidoxypropyltrimethoxysilane (KH650) for reaction for 0.5h, adding 2-3 times of deionized water by mass, stirring at high speed (1000-1300 rpm) for 30-60 min, and obtaining a final product with the solid content of 33.7 wt%.
Comparative example 4:
1) raw materials:
isophorone diisocyanate (IPDI): 26.3 wt%, poly 1, 4-butanediol adipate glycol (PBA-600, make-up polymer or number average molecular weight): 61.7 wt%, 2, 2-dimethylolpropionic acid (DMPA): 3 wt%, hydroxypropyl methacrylate (HEMA): 1.5 wt%, Triethylamine (TEA): 2 wt%, gamma-glycidoxypropyltrimethoxysilane (KH 650); 5%, 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO): 0.2 wt%, dibutyltin dilaurate (DBTDL): 0.3 wt%, deionized water, acetone: proper amount.
2) The synthesis steps are as follows:
adding isophorone diisocyanate (IPDI) and poly adipic acid-1, 4-butanediol glycol (PBA) into a four-neck flask provided with a stirring paddle, a thermometer, an air duct and a condensing tube, dropwise adding a catalyst dibutyltin dilaurate (DBTDL), and heating to about 80-85 ℃ to react for 1-2 h; and then cooling to 45-55 ℃, adding a certain amount of dimethylolpropionic acid (DMPA) and hydroxypropyl methacrylate (HEMA), heating to 70-80 ℃ again, reacting for 2-3 h, and titrating the-NCO content in the system by using a toluene-di-n-butylamine method in the whole process to determine the reaction end point. Finally, cooling to room temperature, and adding Triethylamine (TEA) to react for 1 h; adding gamma-glycidoxypropyltrimethoxysilane (KH650) for reaction for 0.5h, adding 2-3 times of deionized water by mass, stirring at high speed (1000-1300 rpm) for 30-60 min, and obtaining a final product with the solid content of 33.7 wt%.
Performance testing
1) The performance test of the organosilicon coupling agent modified waterborne UV polyurethane is detailed in Table 1:
TABLE 1 Properties of organosilicon coupling agent modified waterborne UV polyurethane
2) The organosilicon coupling agent modified waterborne UV polyurethane prepared in the examples and the comparative examples is respectively mixed with a photoinitiator Darocur-1173 (the dosage of the photoinitiator is 3 percent of the mass of the polyurethane), then the mixture is coated on a glass substrate with the surface treatment, the coating thickness is controlled to be about 20mm, the glass substrate is irradiated and cured on a crawler-type photocuring machine of a 2 × 1000W medium-pressure mercury lamp for 30s, and the maximum light intensity of the central position of an irradiation platform is 37.5mW/cm2. And (3) carrying out performance test on the cured paint film, wherein the specific steps are as follows:
paint film hardness test
Reference GB/T6739-: and (3) coating a certain amount of sample on a tinplate or a glass sheet for curing, and testing the hardness of the paint film by using pencils with different hardness after the curing is completed.
Paint film adhesion test
Reference is made to GB/T9286-1998: and coating a certain amount of sample on a glass slide for curing, drawing a grid after the curing is completed, and measuring the adhesive force of the glass slide by using a 3M adhesive tape.
Gloss measurement of paint films
Reference GB/T9754-2007: coating a certain amount of sample on a black acrylic plate for curing, measuring different positions by a gloss meter after the curing is completed, and taking the average value of the positions, wherein the incident angle of light is 60 degrees.
Water resistance test of paint film
Reference is made to GB/T1733 + 1993: coating a certain amount of sample on a glass sheet, curing, placing in deionized water at normal temperature to immerse the film coating part 2/3 in water, and observing the change condition of the film coating after a period of time.
The results are detailed in table 2:
TABLE 2 test results for paint film properties
As can be seen from tables 1 and 2, the pure aqueous polyurethane emulsion has a small particle size, but has poor water resistance, low film hardness and poor adhesion to glass. The KH560-AA modified polyurethane emulsion has better performances in all aspects than the unmodified polyurethane emulsion. The KH560-AA monomer contains siloxane, and the surface-OH content of the monomer is increased due to certain hydrolysis in the emulsification process, so that the adhesive force between the monomer and glass is improved, and the adhesive force is improved; and the-OH is further dehydrated and condensed to form a three-dimensional network structure with compact performance, and water molecules are blocked to a certain extent after crosslinking and curing, so that the hardness and the water resistance are improved. The organosilicon modified emulsion is beneficial to improving the glossiness of the emulsion film, because organosilicon chain segments with larger flexibility in the organosilicon modified emulsion tend to be regularly arranged, a smoother film is formed, and the glossiness of the emulsion film is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of organosilicon coupling agent modified waterborne UV polyurethane comprises the following steps:
a) reacting difunctional isocyanate and dihydric alcohol in the presence of a catalyst to obtain a first intermediate product;
the difunctional isocyanate is one or more of isophorone diisocyanate, toluene-2, 4-diisocyanate and 4,4' -methylene bis (phenyl isocyanate);
the dihydric alcohol is one or more of poly adipic acid-1, 4-butanediol ester diol, polyethylene glycol and polycarbonate propylene glycol;
the catalyst is N, N-dimethylbenzylamine and/or dibutyltin dilaurate;
b) reacting the first intermediate product with a hydrophilic agent to obtain a second intermediate product;
the hydrophilic agent is 2, 2-dimethylolpropionic acid and/or 2, 2-dimethylolbutyric acid;
c) reacting the second intermediate product with an organosilicon coupling agent in the presence of a polymerization inhibitor to obtain a third intermediate product;
the organosilicon coupling agent has the structure of formula (I):
the polymerization inhibitor is p-hydroxyanisole and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide;
d) reacting the third intermediate product with a salt forming agent to obtain a fourth intermediate product;
the salt forming agent is triethylamine and/or triethanolamine;
e) and mixing and stirring the fourth intermediate product and water to obtain the organosilicon coupling agent modified waterborne UV polyurethane.
2. The method of claim 1, wherein the organosilicon coupling agent is prepared by the following steps:
I) reacting gamma-glycidoxypropyltrimethoxysilane with acrylic acid in the presence of a polymerization inhibitor and a catalyst to obtain the organosilicon coupling agent with the structure of the formula (I).
3. The production method according to claim 2, wherein in step I), the polymerization inhibitor is p-hydroxyanisole and/or 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide, and the catalyst is N, N-dimethylbenzylamine and/or dibutyltin dilaurate.
4. The preparation method according to claim 2, wherein in the step I), the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the acrylic acid to the polymerization inhibitor to the catalyst is (70-80): (20-25): (0.2-0.4): (0.1-0.3).
5. The preparation method according to claim 2, wherein in the step I), the reaction temperature is 70-80 ℃, and the reaction time is 4-5 h.
6. The method according to claim 1, wherein the mass ratio of the difunctional isocyanate, the diol, the catalyst, the hydrophilic agent, the polymerization inhibitor, the organosilicon coupling agent and the salt forming agent is (20-40): (50-80): (0.1-0.3): (2-5): (0.1-0.3): (2-8): (2-8).
7. A cured paint film formed by mixing the organosilicon coupling agent modified water-based UV polyurethane prepared by the method of any one of claims 1 to 6 and a photoinitiator and then carrying out photocuring.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158024A (en) * | 1992-11-26 | 1994-06-07 | Three Bond Co Ltd | Composition for gasket and sealing method |
| US6844376B1 (en) * | 2002-10-23 | 2005-01-18 | Henkel Corporation | Polyurethane compositions containing both radiation and moisture curable groups |
| CN1869139A (en) * | 2006-05-15 | 2006-11-29 | 汕头大学 | Ultraviolet light solidfication water polyurethane acrylate paint resin and its preparation method |
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
-
2018
- 2018-03-02 CN CN201810174075.XA patent/CN108329342B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158024A (en) * | 1992-11-26 | 1994-06-07 | Three Bond Co Ltd | Composition for gasket and sealing method |
| US6844376B1 (en) * | 2002-10-23 | 2005-01-18 | Henkel Corporation | Polyurethane compositions containing both radiation and moisture curable groups |
| CN1869139A (en) * | 2006-05-15 | 2006-11-29 | 汕头大学 | Ultraviolet light solidfication water polyurethane acrylate paint resin and its preparation method |
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| UV光固化水性聚氨酯丙烯酸酯的制备及其在包装卡纸涂料中的应用;马腾飞等;《2015 第十六届中国辐射固化年会暨中国感光学会 2015年学术年会论文报告集》;20150921;195-202页 * |
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