CN108752535B - Preparation method of terpene modified photocuring waterborne polyurethane - Google Patents
Preparation method of terpene modified photocuring waterborne polyurethane Download PDFInfo
- Publication number
- CN108752535B CN108752535B CN201810504471.4A CN201810504471A CN108752535B CN 108752535 B CN108752535 B CN 108752535B CN 201810504471 A CN201810504471 A CN 201810504471A CN 108752535 B CN108752535 B CN 108752535B
- Authority
- CN
- China
- Prior art keywords
- waterborne polyurethane
- preparation
- modified photocuring
- terpene
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 26
- 150000003505 terpenes Chemical class 0.000 title claims abstract description 24
- 235000007586 terpenes Nutrition 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920006264 polyurethane film Polymers 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 4
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 4
- 125000001443 terpenyl group Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000002904 solvent Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NAUBYZNGDGDCHH-UHFFFAOYSA-N N=C=O.N=C=O.CCCC(C)C Chemical compound N=C=O.N=C=O.CCCC(C)C NAUBYZNGDGDCHH-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920006313 waterborne resin Polymers 0.000 description 1
- 239000013035 waterborne resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of terpene modified photocuring waterborne polyurethane, which comprises the following steps of sequentially connecting: (1) mixing terpene, cross-linking agent, acrylic acid and water-based polyurethane; (2) and (2) adding an initiator into the material obtained in the step (1) to react for 2-4h, and then paving a film and irradiating by ultraviolet light to obtain the terpene modified photocuring waterborne polyurethane. The preparation method of the terpene modified photocuring waterborne polyurethane has the advantages of few steps and easy operation, and the prepared terpene modified photocuring waterborne polyurethane has good heat resistance, water resistance, mechanical property, hardness and solvent resistance, the mirror surface gloss reaches 100, the adhesive force is grade 1, the flexibility is 1mm, the surface drying time is less than 4 seconds, the film forming time is 2 minutes, the tensile strength is more than 20.0Mpa, the Tg is more than 17 ℃, the water resistance is excellent, and the solvent resistance is qualified.
Description
Technical Field
The invention relates to a preparation method of terpene modified photocuring waterborne polyurethane, belonging to a preparation method of photocuring waterborne polyurethane.
Background
Waterborne Polyurethane (WPU) is an environment-friendly polymer, which has the characteristics of traditional solvent-borne polyurethanes: the polyurethane has the advantages of good flexibility, low temperature resistance, fatigue resistance and the like, is environment-friendly, energy-saving, safe and reliable, is convenient to use and the like, but most of the polyurethane still has the defects of low water resistance, poor solvent resistance, difficulty in drying and the like, and has certain limitation in use. In order to improve various properties of the aqueous polyurethane material and expand the application range thereof, the research on modifying the aqueous polyurethane material has been greatly developed in recent years, and particularly, the research on modifying the aqueous polyurethane material is a hot spot.
Chinese patent document CN108034349A discloses a two-component aqueous polyurethane emulsion, which is prepared by synthesizing polycarbonate diol 2000, 2-methylpentane diisocyanate and lysine diisocyanate into a prepolymer, adding dimethylolpropionic acid, trimethylpentane diol and glycerol into the prepolymer, adding ammonia water for neutralization reaction, then adding octanitrosilsesquioxane, fully stirring, finally adding deionized water for high-speed shearing emulsification, removing an organic solvent by rotary evaporation to obtain a single-component aqueous polyurethane emulsion, adding a defoaming agent and a leveling agent into the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersoid, and mixing with a polyisocyanate curing agent to obtain the octanitrosilsesquioxane modified two-component aqueous polyurethane emulsion. Has better water resistance and heat resistance, but the film forming speed and the mechanical property of the film are required to be improved. Chinese patent document CN101568564A discloses an aqueous polyurethane resin composition prepared by reacting polyisocyanate, diol containing polyoxyethylene side chain, and (meth) acrylate containing at least 1 hydroxyl group, wherein the mechanical properties and heat resistance are still insufficient although the preparation cost of the product is low.
Disclosure of Invention
In order to overcome the defects of small hardness, poor heat resistance and water resistance, slow film forming and poor mechanical property of the waterborne polyurethane in the prior art, the invention provides the preparation method of the terpene modified photocuring waterborne polyurethane, and the prepared waterborne polyurethane has the characteristics of high tensile strength, fast film forming, good heat resistance and water resistance, good chemical reagent resistance and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of terpene modified photocuring waterborne polyurethane comprises the following steps of sequentially connecting:
(1) mixing terpene, cross-linking agent, acrylic acid and water-based polyurethane;
(2) and (2) adding an initiator into the material obtained in the step (1), reacting for 2-4h, then paving a film, and irradiating by ultraviolet light to obtain the terpene modified photocuring waterborne polyurethane.
The waterborne polyurethane can be waterborne polyurethane produced by Anhui chemical industry in Anhui province.
The surface drying time of the terpene modified photocuring waterborne polyurethane obtained by the method is less than 4 seconds, and the surface instant drying effect can be achieved.
The applicant finds that a single WPU emulsion has the defects of low solid content, poor water resistance, hardness and glossiness of an adhesive film and the like, and needs to be modified in order to expand the application range of the WPU emulsion.
In order to further ensure the performance of the obtained product, the preparation method of the terpene modified photocuring waterborne polyurethane preferably comprises the following steps in sequence:
(1) dripping the mixed liquid of terpene, cross-linking agent and acrylic acid into aqueous polyurethane for 25-35 minutes, and stirring uniformly after dripping;
(2) adding an initiator into the material obtained in the step (1), reacting for 2-3.5 hours under the stirring condition, then paving a film, and irradiating by ultraviolet light to obtain the terpene modified photocuring waterborne polyurethane, wherein the mass consumption of the initiator is 1-5% of the mass sum of acrylic acid and terpene.
In order to further ensure the mechanical property, the adhesive force and the water resistance of the obtained product, in the step (1), the mass usage of the terpene is 0.02-0.07% of the mass of the waterborne polyurethane, the mass usage of the acrylic acid is 15 +/-1% of the mass of the waterborne polyurethane, the cross-linking agent is pentaerythritol triacrylate, and the mass usage of the cross-linking agent is 0.003% of the mass of the waterborne polyurethane.
Pentaerythritol triacrylate is provided herein by Annage.
In order to further ensure the mechanical property of the obtained product, in the step (1), the water-based polyurethane is produced by Anhui chemical industry Co., Ltd, and the solid content is 20-30%. The solid content is mass content.
In order to further ensure the mechanical property, the adhesive force, the heat resistance and the water resistance of the obtained product, in the step (1), the terpene is any one or a mixture of two of isobornyl acrylate or isobornyl methacrylate in any ratio.
The applicant finds that isobornyl acrylate and isobornyl methacrylate can be organically combined with waterborne polyurethane to obtain novel photocuring waterborne polyurethane, the film forming time is shortened, the heat resistance, the water resistance and the mechanical property of the waterborne polyurethane are improved, and the waterborne resin with excellent performance is obtained.
In order to improve the reaction efficiency and the product quality, in the step (2), the initiator is a photoinitiator. Further preferably, in the step (2), the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173 photoinitiator), 1-hydroxycyclohexyl phenyl ketone (184 photoinitiator), or azobisisobutyronitrile.
In order to further improve the mechanical property, water resistance and solvent resistance of the product, in the step (2), the power of ultraviolet irradiation is 100-300w, and the time is 30 seconds to 3 minutes; the stirring speed in the step (1) and the step (2) is 650-750 r/min.
In the step (2), the solid content before film spreading is 20-40 wt%.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Has the advantages that: compared with the prior art, the preparation method of the terpene modified photocuring waterborne polyurethane has fewer steps and is easy to operate, the prepared terpene modified photocuring waterborne polyurethane has good heat resistance, water resistance, solvent resistance, weather resistance, mechanical property, hardness and solvent resistance, the mirror surface gloss reaches 100, the adhesive force is 1 grade, the flexibility is 1mm, the tensile strength is more than 20.0Mpa, the Tg is more than 17 ℃, the surface drying time is less than 4 seconds, and no VOC is released.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the product performance detection method was: the specular gloss is measured by GB/T1743-1979; the adhesion is determined by GB/T1720-1979; tensile strength and elongation at break were determined using GB/T528-1992; the water resistance is determined by GB/T1733-1993; the flexibility is measured by GB/T1731-1979; the thermal analysis is measured by a DSC differential scanning calorimeter, and the glass transition temperature Tg is used for representing the heat resistance of the waterborne polyurethane; the resistance to chemical agents is determined by GB 1763-1979.
The water-based polyurethane used in each example is produced by Anhui chemical industry Co., Ltd, the model is PU-106, and the solid content is 20-30%; the stirring speed in each case was 700 r/min.
Example 1
30.0g of waterborne polyurethane is slowly dripped into a mixed solution (dripping is completed in half an hour) of 5.0g of acrylic acid, 0.08g of pentaerythritol triacrylate and 1.5g of isobornyl acrylate under the stirring condition, after uniform stirring, 0.02g of photoinitiator azobisisobutyronitrile is slowly added (the photoinitiator is added in 5 minutes), stirring and reacting for 3 hours, then the product is paved on a polytetrafluoroethylene plate and irradiated by a 100w ultraviolet lamp for 3 minutes to prepare a terpenyl modified photocuring waterborne polyurethane film layer, and the surface drying time of the film layer is less than 4 seconds.
The product has mirror surface gloss of 130, adhesion of 1 grade, tensile strength of 20.32MPa, flexibility of 1.0mm, Tg of 17.7 ℃, water resistance: pure water for 9 days; 10% NAOH, 4 days, qualified solvent resistance (solvent is N-methyl pyrrolidone, ethanol and acetone) (no whitening), VOC release amount: 0, 3 minutes of film forming time, no yellowing and no cracking phenomena after a weather resistance experiment (irradiating for 24 hours at 60 ℃ in an ultraviolet light aging test box), and the tensile strength of the film is changed to 19.96 MPa.
Comparative example 1
30.0g of waterborne polyurethane is added into a 250mL three-neck flask which is provided with a stirrer and a constant pressure titration funnel, then the rotating speed is adjusted to 700r/min, the mixture is fully stirred for 2 hours, then the waterborne polyurethane is paved into a polytetrafluoroethylene plate to be kept stand and aired to form a film, and the surface drying time of the film layer is more than 10 minutes.
The product has mirror gloss of 106, adhesion of 1 grade, flexibility of 1mm, tensile strength of 1.05MPa, Tg of 3.5 ℃, water resistance: pure water for 2 days; 10 percent of NAOH, 0.5 day, unqualified solvent resistance (solvent is N-methyl pyrrolidone, ethanol and acetone) (whitening), one day of film forming time, yellowing and cracking phenomena occur through weather resistance experiments (irradiating for 24 hours at 60 ℃ in an ultraviolet light aging test box), and the tensile strength is reduced to 0.7 MPa.
Comparative example 2
30.0g of waterborne polyurethane is slowly dripped into a mixed solution of 5.0g of acrylic acid and 0.08g of pentaerythritol triacrylate under the stirring condition (dripping is finished for half an hour), 0.02g of photoinitiator azobisisobutyronitrile is dripped into the mixed solution for five minutes after the mixed solution is uniformly stirred, the mixed solution reacts for 3 hours, then the product is irradiated by an ultraviolet lamp for 3 minutes in a polytetrafluoroethylene plate to prepare an acrylate modified photocuring waterborne polyurethane film layer, and the surface drying time of the film layer is more than 10 minutes.
The product has mirror surface gloss of 125, adhesive force of 1 grade, tensile strength of 7.17MPa, flexibility of 1.5mm, Tg of 13.2 ℃, water resistance: pure water for 4 days; 10 percent of NAOH, 1 day, qualified solvent resistance (solvent is N-methyl pyrrolidone, ethanol and acetone) (no whitening), 3 minutes of film forming time, slight yellowing and slight cracking phenomena after weather resistance experiments (irradiation for 24 hours at 60 ℃ in an ultraviolet light aging test box), and the tensile strength is reduced to 5.93 MPa.
Comparing the performances of the products of the example 1 and the comparative examples 1 to 2, it can be seen that the terpene-based modified photocuring waterborne polyurethane prepared in the example 1 has higher mechanical property, better thermal property and solvent resistance than the single waterborne polyurethane and the photocuring waterborne polyurethane modified by only acrylic acid.
Example 2
30.0g of waterborne polyurethane is slowly dripped into a mixed solution (dripping is completed in half an hour) of 5.0g of acrylic acid, 0.08g of pentaerythritol triacrylate and 1.5g of isobornyl methacrylate under the stirring condition, after the uniform stirring, 0.02g of 1173 photoinitiator is dripped in five minutes, the reaction is completed in 3 hours, then the product is paved on a polytetrafluoroethylene plate and is irradiated by a 100w ultraviolet lamp for 3 minutes to prepare a terpenyl modified photocuring waterborne polyurethane film layer, and the surface drying time of the product is less than 4 seconds.
The product has mirror gloss 118, adhesion 1 grade, tensile strength of 21.33MPa, flexibility of 1.0mm, Tg of 16.5 ℃, water resistance: pure water for 9 days; 10% of NAOH, 4 days, qualified solvent resistance (solvent is N-methyl pyrrolidone, ethanol and acetone) (no whitening), VOC release amount: 0, 2 minutes of film forming time, no yellowing and no cracking phenomena after weather resistance experiments (in an ultraviolet light aging test box, at 60 ℃, for 24 hours of irradiation), and the tensile strength of the film is changed to 20.87 MPa.
Claims (2)
1. A preparation method of terpene modified photocuring waterborne polyurethane is characterized by comprising the following steps: 30.0g of waterborne polyurethane is slowly dripped into a mixed solution of 5.0g of acrylic acid, 0.08g of pentaerythritol triacrylate and 1.5g of isobornyl acrylate under the stirring condition, after dripping is completed for half an hour and stirring is uniform, 0.02g of photoinitiator azobisisobutyronitrile is added for five minutes, stirring reaction is performed for 3 hours, then the product is paved on a polytetrafluoroethylene plate and is irradiated by a 100w ultraviolet lamp for 3 minutes, a terpenyl modified photocuring waterborne polyurethane film layer is prepared, and the surface drying time of the film layer is less than 4 seconds.
2. A preparation method of terpene modified photocuring waterborne polyurethane is characterized by comprising the following steps: 30.0g of waterborne polyurethane, slowly dripping a mixed solution of 5.0g of acrylic acid, 0.08g of pentaerythritol triacrylate and 1.5g of isobornyl methacrylate under the stirring condition, dripping for half an hour, uniformly stirring, dripping 1173 g of photoinitiator in five minutes, stirring for reacting for 3 hours, then paving the product on a polytetrafluoroethylene plate, irradiating for 3 minutes by a 100w ultraviolet lamp, and preparing a terpenyl modified photocuring waterborne polyurethane film layer, wherein the surface drying time of the film layer is less than 4 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810504471.4A CN108752535B (en) | 2018-05-24 | 2018-05-24 | Preparation method of terpene modified photocuring waterborne polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810504471.4A CN108752535B (en) | 2018-05-24 | 2018-05-24 | Preparation method of terpene modified photocuring waterborne polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108752535A CN108752535A (en) | 2018-11-06 |
| CN108752535B true CN108752535B (en) | 2020-09-25 |
Family
ID=64005113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810504471.4A Expired - Fee Related CN108752535B (en) | 2018-05-24 | 2018-05-24 | Preparation method of terpene modified photocuring waterborne polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108752535B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028629B (en) * | 2019-04-28 | 2021-07-23 | 南京林业大学 | Preparation method of longifolene-based acrylate modified waterborne polyurethane |
| CN111040169B (en) * | 2019-12-30 | 2021-09-24 | 南京林业大学 | Terpenoid polysiloxane, preparation method thereof and modified two-component waterborne polyurethane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3055197B2 (en) * | 1991-01-14 | 2000-06-26 | 日本ポリウレタン工業株式会社 | Polyurethane adhesive composition |
| CN102911633B (en) * | 2012-10-18 | 2013-09-18 | 四川大学 | Branched-structure polyurethane-silicious polyacrylate hot melt adhesive and preparation method thereof |
| CN102977758B (en) * | 2012-12-24 | 2015-02-11 | 上海应用技术学院 | UV (ultraviolet) photocured water-based fluorine-containing polyurethane latex film and preparation method thereof |
-
2018
- 2018-05-24 CN CN201810504471.4A patent/CN108752535B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN108752535A (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Newly UV-curable polyurethane coatings prepared by multifunctional thiol-and ene-terminated polyurethane aqueous dispersions mixtures: Preparation and characterization | |
| CN107254251A (en) | A kind of aqueous UV urethane acrylate dispersoids with self-initiating function and preparation method thereof | |
| CN111116862B (en) | Hyperbranched castor oil-based aqueous UV curing prepolymer and preparation method and application thereof | |
| CN105419624A (en) | UV cured aqueous plastic coating and preparation method thereof | |
| CN108912296B (en) | Crosslinking type waterborne polyurethane and preparation method thereof | |
| CN101294046B (en) | Ultraviolet light solidified polyurethane water-based paint and preparation method thereof | |
| CN108752535B (en) | Preparation method of terpene modified photocuring waterborne polyurethane | |
| CN103242787A (en) | Acrylic acid modified water-based polyurethane adhesive and preparation method thereof | |
| CN110373016B (en) | Liquid crystal polyacrylate-liquid crystal polyurethane interpenetrating network liquid crystal elastomer | |
| CN102675831A (en) | High-weather-resistance and high-strength SMC (Super Multi-Coating) material as well as preparation method and application thereof | |
| CN110606931A (en) | Preparation method of waterborne light-cured self-repairing polyurethane resin | |
| Zhang et al. | The preparation and characterization of a novel self-healing based on the dynamic translocation of disulfide bonds | |
| CN105131806A (en) | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing | |
| CN108003802A (en) | One kind sticks agent based on progressively mechanism of polymerization thermic self-healing ultraviolet cured adhesive | |
| CN104211902A (en) | Preparation method of waterborne polyurethane emulsion and waterborne polyurethane emulsion prepared by preparation method | |
| CN114085517A (en) | Lignin-modified waterborne polyurethane film and preparation method thereof | |
| CN102212309B (en) | Method for preparing unsaturated polyester polyurethane block copolymer solventless coating | |
| CN101050334B (en) | Water paint solidified by ultraviolet light, preparation method and application | |
| CN110028629B (en) | Preparation method of longifolene-based acrylate modified waterborne polyurethane | |
| CN107722308B (en) | Rapid water response type shape memory polymer material and preparation method thereof | |
| CN112126395B (en) | Thixotropic ultraviolet curing adhesive | |
| CN104861769B (en) | Environment-friendly type UV light-curable inks and preparation method thereof | |
| CN103666034B (en) | UV cured printing ink of the little good luster of a kind of viscosity and preparation method thereof | |
| CN113831883A (en) | Yellowing-resistant waterborne polyurethane adhesive as well as preparation method and application thereof | |
| CN108660804B (en) | Ultraviolet curing ink for textiles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200925 |