CN111303365A - Preparation method of polythiourethane polymer resin - Google Patents
Preparation method of polythiourethane polymer resin Download PDFInfo
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- CN111303365A CN111303365A CN202010130203.8A CN202010130203A CN111303365A CN 111303365 A CN111303365 A CN 111303365A CN 202010130203 A CN202010130203 A CN 202010130203A CN 111303365 A CN111303365 A CN 111303365A
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- mercaptopropionate
- mercaptoacetate
- isocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1866—Catalysts containing secondary or tertiary amines or salts thereof having carbon-to-carbon unsaturated bonds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of polythiourethane polymer resin, which uses α -aminoketone to catalyze the addition reaction of a thiol component and an isocyanate component under the irradiation of ultraviolet light to obtain the polythiourethane polymer resin.
Description
Technical Field
The invention belongs to the field of light-cured materials, and particularly relates to a preparation method of polythiourethane polymer resin.
Background
Polyurethane is one of the most widely used polymer materials at present, has the advantages of good toughness, high hardness and the like, and is widely applied to the fields of adhesives, coatings, leather and the like. Compared with polyurethane, sulfur atoms in the polythiourethane replace oxygen atoms in the same main group, and the polythiourethane has the advantages of good toughness, high hardness, high tensile strength and the like similar to those of polyurethane, has the characteristics of high refractive index and low light dispersion, and can be applied to the fields of surface protection coatings, optical materials and the like. Polythiourethanes are generally prepared by the addition reaction of a thiol with a polyisocyanate.
Chinese patent application No. 201480025997.4 proposes a process for preparing polythiourethanes by mixing a thiol component with an isocyanate component, adding a metallic tin or nitrogen heterocycle as a catalyst, vacuum degassing in a casting mold, curing at 120 ℃ for 20 hours to obtain a material having a refractive index nDNot less than 1.60 and not less than 38 Abbe number. The material is prepared by a casting mold method, and has the disadvantages of complex construction operation, high curing temperature, long curing time, high production energy consumption, low efficiency and low product performance.
Chinese patent application No. 201780047593.9 proposes an improved method for preparing polythiourethane by adding metallic tin or azacyclo as a catalyst to a mixture of a polythiol component and an isocyanate component and adding an acid component to adjust the reactivity of the system to prevent local refractive index unevenness due to rapid curing. The system improves part of defects of a casting method, but still cannot solve the defects of high production energy consumption, low efficiency and the like.
The photo-curing material has attracted attention in the past fifty years due to the advantages of less energy consumption, excellent performance, low VOC emission and the like, and is applied to a plurality of fields including organic protective coatings, photo-curing printing ink, photo-curing adhesives, tooth repairing materials and the like.
Disclosure of Invention
The invention aims to provide a preparation method of polythiourethane polymer resin, which overcomes the defects of the prior art.
The invention relates to a preparation method of polythiourethane polymer resin, which is used for preparing polythiourethane polymer resin by the addition reaction of mercaptan and isocyanate under the irradiation of ultraviolet rays. The method specifically comprises the following steps:
mixing a mercaptan component and an isocyanate component in proportion, adding α -aminoketone in a certain mass proportion, stirring and mixing uniformly, and irradiating for 0.1-10 minutes under ultraviolet light to obtain the polymer material.
The α -aminoketone is selected from one or a combination of more of 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholine) and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, and the adding mass of α -aminoketone is 0.1-20% of the total mass of the materials, preferably 2-10%.
The thiol component is selected from ethanedithiol, 1, 4-butanedithiol, 1, 6-hexanedithiol, ethylene glycol di (3-mercaptopropionate), ethylene glycol di (2-mercaptoacetate), 1, 4-butanediol di (3-mercaptopropionate), 1, 4-butanediol di (2-mercaptoacetate), 1, 6-hexanediol di (3-mercaptopropionate), 1, 6-hexanediol di (2-mercaptoacetate), polyethylene glycol di (3-mercaptopropionate), polyethylene glycol di (2-mercaptoacetate), polypropylene glycol di (3-mercaptopropionate), polypropylene glycol di (2-mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), One or a combination of more of dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetra (2-mercaptoacetate), trimethylolpropane tri (2-mercaptoacetate), dipentaerythritol hexa (2-mercaptoacetate), pentaerythritol tetrathiol, 1, 4-phenyl dithiol, tetrakis (2-mercaptoethyl) silane, 1,3, 5-tris (3-mercaptopropyl) -1,3, 5-triazine-2, 4, 6-trione.
The isocyanate component is selected from isophorone diisocyanate, isophorone diisocyanate trimer, toluene diisocyanate trimer, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 2-bis (isocyano oxymethyl) cyclohexane, 1, 4-bis (isocyano oxymethyl) cyclohexane, trimethylbenzene triisocyanate, biphenyl diisocyanate, isophorone diisocyanate trimer, toluene diisocyanate trimer, hexamethylene diisocyanate, m-xylylene isocyanate, and hexamethylene diisocyanate trimer, or a combination thereof.
The sulfur alcohol component and the isocyanate component are mixed according to a certain proportion, so that the molar ratio of the mercapto functional group to the isocyanate functional group is 0.2: 1-5: 1, preferably 0.8: 1-1.3: 1;
the ultraviolet light is selected from light having a wavelength of 40 nm to 400 nm, preferably 200 nm to 370 nm.
α -aminoketone can generate α -cracking under ultraviolet irradiation to generate free radical and tertiary amine, as shown in the following figure, before ultraviolet irradiation, nitrogen atom is almost not alkaline because of electron-withdrawing effect and volume steric hindrance effect of carbon-oxygen double bond on carbonyl, after ultraviolet irradiation, the generated tertiary amine has no carbonyl on structure and is not affected by electron-withdrawing effect, and volume steric hindrance effect is released to show stronger alkalinity.
The tertiary amine catalyzed addition reaction of a thiol to an isocyanate comprises the steps of: the tertiary amine abstracts hydrogen atoms of the mercaptan to generate sulfur anions, the sulfur anions are added to carbon atoms of the isocyanate to obtain thiocarbamate anions, and the thiocarbamate anions abstracts the hydrogen atoms of the mercaptan to generate the sulfur anions and thiocarbamate; the sulfur anion re-adds … … to the carbon atom of the isocyanate and so on. When the tertiary amine is used for catalyzing the addition reaction of mercaptan and isocyanate, severe heat release is caused due to high reaction activity and too fast reaction in the early stage, the gel is easy to generate, high-temperature long-time baking is needed for improving the conversion rate in the later stage, and the defects of high production energy consumption, difficulty in operation, low efficiency and the like exist in practical application.
The invention uses α -amidoketone as photocatalyst, and uses tertiary amine generated after ultraviolet irradiation to catalyze the addition reaction of mercaptan and isocyanate, before ultraviolet irradiation, α -amidoketone has almost no alkalinity, mercaptan and isocyanate do not react and can be kept in a stable state for a long time, after ultraviolet irradiation, the generated tertiary amine has stronger alkalinity and can immediately catalyze the addition reaction of mercaptan and isocyanate, ultraviolet light can conveniently start the reaction like a switch, when in application construction, α -amidoketone is firstly dissolved in the mixture of mercaptan and isocyanate, proper construction modes such as spraying, roller coating, silk-screen printing, casting and the like are selected according to requirements to prefabricate into a required shape, and finally the required shape is irradiated under ultraviolet light, and the reaction is immediately carried out, and the reaction degree can be adjusted by adjusting parameters such as the intensity, time, temperature and the like of ultraviolet irradiation, thereby effectively avoiding the occurrence of gel, and having the advantages of convenient operation, high production efficiency, low production energy consumption and the like.
Compared with the prior art, the invention skillfully converts the thermal curing reaction process into the light curing reaction process, so that the reaction process becomes controllable, the occurrence of gel in the reaction process is avoided, the construction operation is simplified, and the production efficiency is improved; the method does not need high-temperature long-time baking, effectively reduces the production energy consumption, and is a technology with wide application prospect.
Drawings
FIG. 1 is a dynamic thermodynamic curve of polythiourethane polymer resin.
Detailed Description
Example 1:
mixing pentaerythritol tetra (3-mercaptopropionate) 12.2g, hexamethylene diisocyanate 8.4g and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone 1.1g, and placing in a high-pressure mercury lamp (light intensity of 50 mW/cm)2) Followed by irradiation for 2 minutes to obtain a transparent cured film.
The refractive index of the cured film was measured to be 1.562 and the wavelength of the test light was 633nm using a prism coupled waveguide tester Metricon 2010.
Glass transition temperature T of the cured film was tested using a dynamic thermomechanical analyzer DMA Q800 from TA, USAg67 ℃, the dynamic thermodynamic curve is shown in fig. 1, with a test frequency of 1Hz and a ramp rate of 3 ℃/min.
Example 2:
6.8g of tetrakis (2-mercaptoethyl) silane, 8.4g of hexamethylene diisocyanate and 0.3g of 2-methyl-4' - (methylthio) -2-morpholine benzophenone were mixed with stirring thoroughly and placed in a high-pressure mercury lamp (intensity of 50 mW/cm)2) Followed by irradiation for 2 minutes to obtain a transparent cured film.
The cured film was found to have a refractive index of 1.601 and a test light wavelength of 633nm using a prism coupled waveguide tester Metricon 2010.
Glass transition temperature T of the cured film was tested using a dynamic thermomechanical analyzer DMA Q800 from TA, USAgThe test frequency was 1Hz at 90 ℃, and the ramp rate was 3 ℃/min.
Example 3:
6.8g of tetrakis (2-mercaptoethyl) silane, 19.3g of hexamethylene diisocyanate trimer, 1.2g of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone were thoroughly stirred and mixed, and placed in a high-pressure mercury lamp (intensity of 50 mW/cm)2) Followed by irradiation for 2 minutes to obtain a transparent cured film.
The refractive index of the cured film was measured to be 1.571 using a prism coupled waveguide tester Metricon 2010, with a test light wavelength of 633 nm.
Glass transition temperature T of the cured film was tested using a dynamic thermomechanical analyzer DMA Q800 from TA, USAgAt 96 deg.C, the test frequency was 1Hz and the ramp rate was 3 deg.C/min.
Example 4:
11.7g of 1,3, 5-tris (3-mercaptopropyl) -1,3, 5-triazine-2, 4, 6-trione, 19.3g of hexamethylene diisocyanate trimer, 2.0g of 2-methyl-4' - (methylthio) -2-morpholine benzophenone were thoroughly mixed by stirring and placed in a high-pressure mercury lamp (light intensity: 50 mW/cm)2) Followed by irradiation for 2 minutes to obtain a transparent cured film.
The refractive index of the cured film was measured to be 1.564 using a prism coupled waveguide tester Metricon 2010, and the test light wavelength was 633 nm.
Glass transition temperature T of the cured film was tested using a dynamic thermomechanical analyzer DMA Q800 from TA, USAg101 ℃, test frequency 1Hz, and ramp rate 3 ℃/min.
Claims (10)
1. A preparation method of polythiourethane polymer resin is characterized in that:
the polythiourethane polymer resin is prepared by the addition reaction of mercaptan and isocyanate under the irradiation of ultraviolet rays.
2. The method of claim 1, wherein:
α -aminoketone is used as a catalyst to catalyze the addition reaction of mercaptan and isocyanate.
3. The method of claim 2, comprising the steps of:
mixing a mercaptan component and an isocyanate component in proportion, adding α -aminoketone in a certain mass proportion, stirring and mixing uniformly, and irradiating for 0.1-10 minutes under ultraviolet light to obtain the polymer material.
4. The production method according to claim 3, characterized in that:
the α -aminoketone is selected from one or a combination of more of 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholine) and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, and the addition mass of α -aminoketone is 0.1-20% of the total mass of the materials.
5. The method of claim 4, wherein:
α -aminoketone accounts for 2-10% of the total mass of the materials.
6. The production method according to claim 3, characterized in that:
the thiol component is selected from ethanedithiol, 1, 4-butanedithiol, 1, 6-hexanedithiol, ethylene glycol di (3-mercaptopropionate), ethylene glycol di (2-mercaptoacetate), 1, 4-butanediol di (3-mercaptopropionate), 1, 4-butanediol di (2-mercaptoacetate), 1, 6-hexanediol di (3-mercaptopropionate), 1, 6-hexanediol di (2-mercaptoacetate), polyethylene glycol di (3-mercaptopropionate), polyethylene glycol di (2-mercaptoacetate), polypropylene glycol di (3-mercaptopropionate), polypropylene glycol di (2-mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), One or a combination of more of dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetra (2-mercaptoacetate), trimethylolpropane tri (2-mercaptoacetate), dipentaerythritol hexa (2-mercaptoacetate), pentaerythritol tetrathiol, 1, 4-phenyl dithiol, tetrakis (2-mercaptoethyl) silane, 1,3, 5-tris (3-mercaptopropyl) -1,3, 5-triazine-2, 4, 6-trione.
7. The production method according to claim 3, characterized in that:
the isocyanate component is selected from isophorone diisocyanate, isophorone diisocyanate trimer, toluene diisocyanate trimer, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 2-bis (isocyano oxymethyl) cyclohexane, 1, 4-bis (isocyano oxymethyl) cyclohexane, trimethylbenzene triisocyanate, biphenyl diisocyanate, isophorone diisocyanate trimer, toluene diisocyanate trimer, hexamethylene diisocyanate, m-xylylene isocyanate, and hexamethylene diisocyanate trimer, or a combination thereof.
8. The production method according to claim 3,6 or 7, characterized in that:
the sulfur alcohol component and the isocyanate component are mixed according to a certain proportion, so that the molar ratio of the mercapto functional group to the isocyanate functional group is 0.2: 1-5: 1.
9. The method of claim 8, wherein:
the sulfur alcohol component and the isocyanate component are mixed according to a certain proportion, so that the molar ratio of the mercapto functional group to the isocyanate functional group is 0.8: 1-1.3: 1.
10. The production method according to claim 3, characterized in that:
the ultraviolet light has a wavelength of 40 nm to 400 nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967343A (en) * | 2010-10-22 | 2011-02-09 | 广州市博兴化工科技有限公司 | Light-curing colored paint |
| CN104471001A (en) * | 2012-04-12 | 2015-03-25 | 凯密特尔有限责任公司 | Matrices and sealants which are based on sulfur-containing polymers and which comprise a photoinitiator, curing and coating methods, and use of said matrices and sealants |
| CN105229046A (en) * | 2013-05-07 | 2016-01-06 | 布鲁诺博克化学有限责任公司及股份有限公司 | There is high limit tensile stress and low-gravity cast resin based on poly-thiocarbamate |
| US20170267804A1 (en) * | 2016-03-15 | 2017-09-21 | Board Of Regents, The University Of Texas System | Thiourethane polymers, method of synthesis thereof and use in additive manufacturing technologies |
| CN107454912A (en) * | 2015-02-13 | 2017-12-08 | 凯密特尔有限责任公司 | Coat method, accordingly device for the method, spacecraft through processing and application thereof of sulfur-bearing sealant |
-
2020
- 2020-02-28 CN CN202010130203.8A patent/CN111303365A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967343A (en) * | 2010-10-22 | 2011-02-09 | 广州市博兴化工科技有限公司 | Light-curing colored paint |
| CN104471001A (en) * | 2012-04-12 | 2015-03-25 | 凯密特尔有限责任公司 | Matrices and sealants which are based on sulfur-containing polymers and which comprise a photoinitiator, curing and coating methods, and use of said matrices and sealants |
| CN105229046A (en) * | 2013-05-07 | 2016-01-06 | 布鲁诺博克化学有限责任公司及股份有限公司 | There is high limit tensile stress and low-gravity cast resin based on poly-thiocarbamate |
| CN107454912A (en) * | 2015-02-13 | 2017-12-08 | 凯密特尔有限责任公司 | Coat method, accordingly device for the method, spacecraft through processing and application thereof of sulfur-bearing sealant |
| US20170267804A1 (en) * | 2016-03-15 | 2017-09-21 | Board Of Regents, The University Of Texas System | Thiourethane polymers, method of synthesis thereof and use in additive manufacturing technologies |
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