CN111423532A - Molecular chain self-rotating fluorine-containing UV resin and preparation method thereof - Google Patents
Molecular chain self-rotating fluorine-containing UV resin and preparation method thereof Download PDFInfo
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- CN111423532A CN111423532A CN202010391340.7A CN202010391340A CN111423532A CN 111423532 A CN111423532 A CN 111423532A CN 202010391340 A CN202010391340 A CN 202010391340A CN 111423532 A CN111423532 A CN 111423532A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 46
- 239000011737 fluorine Substances 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 239000002253 acid Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229920001002 functional polymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001723 curing Methods 0.000 description 11
- 238000003848 UV Light-Curing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- 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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses molecular chain self-rotating type fluorine-containing UV resin and a preparation method thereof, wherein the molecular chain self-rotating type fluorine-containing UV resin is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl alcohol, 400 parts of anhydride 200-. The molecular chain self-rotating type fluorine-containing UV resin prepared by the invention has the advantages of high fluorine content, high curing speed, strong adhesion property, good hydrophobicity and the like.
Description
Technical Field
The invention relates to the field of preparation of high polymer resin, in particular to molecular chain self-rotating type fluorine-containing UV resin and a preparation method thereof.
Background
The UV light curing technology has the advantages of environmental protection, no VOC emission, low energy consumption, rapid curing and the like, and becomes a new green coating material technology with great development potential in the future. With the upgrading of the social industrial level and the people consumption level, more performance requirements are put forward on the UV curing resin, and particularly, the UV curing resin is highly smooth, highly hydrophobic, resistant to high and low temperature, resistant to acid and alkali corrosion and the like.
The fluorine-containing UV resin has great application potential due to the excellent hydrophobicity and weather resistance of the fluorine unit. The current fluorine-containing UV curing resin has the following problems: firstly, the fluorine content is generally not high; secondly, the process is complex in the preparation process of the resin, and most products contain organic solvents; thirdly, the light curing speed of the product with high fluorine content is slow; fourthly, the adhesive force of the fluorine-containing UV curing resin and most of base materials is weak; fifthly, most of the resins have the problem of precipitation of fluorine-containing small molecules.
Therefore, how to prepare the fluorine-containing UV resin which has the advantages of high curing speed, no solvent, high fluorine content, excellent adhesion with most base materials and no precipitation becomes a common problem to be solved urgently in the industry.
Disclosure of Invention
In order to overcome at least one defect in the prior art, the first aspect of the invention provides a molecular chain self-rotating fluorine-containing UV resin with high curing speed, and the detailed technical scheme of the invention is as follows:
a molecular chain self-rotating fluorine-containing UV resin is prepared from the following raw materials in parts by weight:
further, the acid anhydride comprises one or more of maleic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride and tetrahydrophthalic anhydride.
Further, the ethylene-epoxy bifunctional monomer comprises one or more of glycidyl acrylate, glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
Further, the fluorine-containing alcohol comprises one or more of octafluoropentanol, hexafluorobutanol, tetrafluoropropanol and trifluoroethanol.
The second aspect of the present invention provides a method for preparing a molecular chain self-rotating fluorine-containing UV resin, comprising the steps of:
weighing polyvinyl alcohol, anhydride, an ethylene-epoxy bifunctional monomer and fluorine-containing alcohol according to parts by weight;
step two, preparing modified linear carboxyl functional polymer:
adding polyvinyl alcohol and anhydride into a reaction kettle, slowly heating to 50-60 ℃, and dissolving.
Heating to 80-90 deg.C, reacting for 3-5 h, measuring the acid value of the reaction system, and ending the reaction when the acid value reaches 280-300 KOH/(mg/g).
Introducing a reactive photocuring group into a side chain of the modified linear carboxyl functional polymer;
slowly adding the ethylene-epoxy bifunctional monomer into a reaction kettle.
Heating to 80-90 ℃, keeping the temperature for reaction for 3-5 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 200-230 KOH/(mg/g).
Introducing fluorine-containing groups into the side chains of the modified linear carboxyl functional polymer;
slowly adding the fluorine-containing alcohol into the reaction kettle.
Heating to 100 ℃ and 120 ℃, charging nitrogen, keeping the temperature for reaction for 3-5 hours, measuring the acid value of the reaction system, and finishing the reaction when the acid value is less than 3 KOH/(mg/g).
Further, in the third step, the feeding time of the ethylene-epoxy bifunctional monomer is 1-2 hours.
Further, in the fourth step, the feeding time of the fluorine-containing alcohol is 1-2 hours.
The molecular chain self-rotating type fluorine-containing UV resin provided by the invention has a long straight-chain alkyl group as a matrix structure, and a lateral group contains a large amount of reactive double-bond UV curing groups and fluorine groups after being modified.
In the using process, the reactive double-bond UV curing groups on the long straight-chain alkyl are turned downwards to contact with the base material, so that the adhesive force of the UV curing material and the base material is improved, the fluorine-containing chain segments are turned upwards to the surface of the material, and the hydrophobicity and the acid and alkali resistance of the surface of the material are improved.
The molecular chain self-rotating fluorine-containing UV resin has the advantages of simple preparation process, no solvent in the whole process, high fluorine content, and no precipitation risk because fluorine is completely grafted on a polymer side chain. The side chain introduces more double-bond UV curable units, thereby improving the curing speed of the UV resin.
Detailed Description
The technical solutions in the embodiments of the present invention will be 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.
Example 1
100g of polyvinyl alcohol, 200g of maleic anhydride, 25g of glycidyl acrylate and 400g of octafluoropentanol are weighed.
Adding polyvinyl alcohol and maleic anhydride into a reaction kettle, slowly heating to 50 ℃, and dissolving.
The temperature is raised to 80 ℃, the reaction is carried out for 5 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 280 KOH/(mg/g).
Slowly adding glycidyl acrylate into the reaction kettle for 1 hour.
And (3) heating to 80 ℃, keeping the temperature for reaction for 5 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 200 KOH/(mg/g).
And slowly adding the octafluoropentanol into the reaction kettle for 1 hour.
Raising the temperature to 100 ℃, filling nitrogen, keeping the temperature for 5 hours, measuring the acid value of the reaction system, and finishing the reaction when the acid value is 0.4 KOH/(mg/g).
Example 2
100g of polyvinyl alcohol, 400g of methylhexahydrophthalic anhydride, 70g of glycidyl methacrylate and 500g of hexafluorobutanol were weighed.
Putting polyvinyl alcohol and methyl hexahydrophthalic anhydride into a reaction kettle, slowly heating to 60 ℃, and dissolving.
The temperature is raised to 90 ℃, the reaction is carried out for 3 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 300 KOH/(mg/g).
Slowly adding glycidyl methacrylate into the reaction kettle for 2 hours.
And (3) heating to 90 ℃, keeping the temperature for reaction for 3 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 230 KOH/(mg/g).
And slowly adding the hexafluorobutanol into the reaction kettle for 2 hours.
Raising the temperature to 120 ℃, filling nitrogen, keeping the temperature for reaction for 3 hours, and finishing the reaction when the acid value of the reaction system is measured and the acid value is 2.8 KOH/(mg/g).
Example 3
100g of polyvinyl alcohol, 400g of methyl tetrahydrophthalic anhydride, 35g of glycidyl methacrylate and 450g of hexafluorobutanol are weighed.
Putting polyvinyl alcohol and methyl tetrahydrophthalic anhydride into a reaction kettle, slowly heating to 60 ℃, and dissolving.
The temperature is raised to 90 ℃, the reaction is carried out for 3 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 290 KOH/(mg/g).
Slowly adding glycidyl methacrylate into the reaction kettle for 2 hours.
And (3) heating to 90 ℃, keeping the temperature for reaction for 3 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 220 KOH/(mg/g).
And slowly adding the hexafluorobutanol into the reaction kettle for 2 hours.
Raising the temperature to 120 ℃, filling nitrogen, keeping the temperature for reaction for 3 hours, and finishing the reaction when the acid value of the reaction system is measured and the acid value is 1.4 KOH/(mg/g).
Example 4
100g of polyvinyl alcohol, 300g of tetrahydrophthalic anhydride, 45g of glycidyl acrylate and 450g of tetrafluoropropanol are weighed.
Adding polyvinyl alcohol and tetrahydrophthalic anhydride into a reaction kettle, slowly heating to 50 ℃, and dissolving.
The temperature is raised to 85 ℃, the reaction is carried out for 4 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 285 KOH/(mg/g).
Slowly adding the glycidyl acrylate into the reaction kettle for 1 hour.
And raising the temperature to 85 ℃, keeping the temperature for reaction for 4 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 210 KOH/(mg/g).
Slowly adding the tetrafluoropropanol into the reaction kettle for 1 hour.
Raising the temperature to 110 ℃, filling nitrogen, keeping the temperature for reaction for 4 hours, and finishing the reaction when the acid value of the reaction system is measured and the acid value is 2.1 KOH/(mg/g).
Example 5
100g of polyvinyl alcohol, 240g of phthalic anhydride, 55g of glycidyl methacrylate and 480g of octafluoropentanol are weighed.
Adding polyvinyl alcohol and phthalic anhydride into a reaction kettle, slowly heating to 50 ℃, and dissolving.
The temperature is raised to 85 ℃, the reaction is carried out for 4 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 295 KOH/(mg/g).
Slowly adding glycidyl methacrylate into the reaction kettle for 1 hour.
And (3) heating to 85 ℃, keeping the temperature for reaction for 4 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 215 KOH/(mg/g).
And slowly adding the octafluoropentanol into the reaction kettle for 1 hour.
Raising the temperature to 115 ℃, charging nitrogen, keeping the temperature for reaction for 4 hours, and measuring the acid value of the reaction system, wherein the reaction is finished when the acid value is 1.6 KOH/(mg/g).
Example 6
100g of polyvinyl alcohol, 220g of methylhexahydrophthalic anhydride, 60g of glycidyl methacrylate and 495g of hexafluorobutanol were weighed.
Putting polyvinyl alcohol and methyl hexahydrophthalic anhydride into a reaction kettle, slowly heating to 55 ℃, and dissolving.
The temperature is raised to 85 ℃, the reaction is carried out for 4 hours, the acid value of the reaction system is measured, and the reaction is finished when the acid value reaches 290 KOH/(mg/g).
Slowly adding glycidyl methacrylate into the reaction kettle for 1 hour.
And raising the temperature to 85 ℃, keeping the temperature for reaction for 4 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 210 KOH/(mg/g).
And slowly adding hexafluorobutanol into the reaction kettle for 1 hour.
Raising the temperature to 115 ℃, charging nitrogen, keeping the temperature for reaction for 4 hours, measuring the acid value of the reaction system, and finishing the reaction when the acid value is 0.6 KOH/(mg/g).
In order to determine the properties of the molecular-chain self-rotating fluorine-containing UV resin prepared in each of the above examples after curing. Weighing 100 parts by mass of the molecular chain self-rotating fluorine-containing UV resin prepared in each example and 4 parts by mass of the photoinitiator (1173), uniformly stirring, respectively coating on a PET film and pouring in a special mold, and carrying out photocuring on a UV curing instrument. The curing instrument is a mercury lamp with the wavelength of 365nm and the curing energy of 80mj/cm2。
The UV resins prepared in the examples were tested for fluorine content, cure time and water contact angle and the results are shown in the following table:
table 1; post cure Properties of self-rotating UV-FLUORINE-CONTAINING resins prepared in different examples
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Content of fluorine/%) | 55.2 | 46.7 | 50.8 | 50.3 | 61.9 | 56.6 |
| Curing time/S | 1.2 | 1 | 1 | 1 | 1.5 | 1.2 |
| Water contact angle/° c | 106 | 102 | 105 | 105 | 110 | 108 |
As can be seen from the data analysis in Table 1, the curing time of the self-rotating type UV-containing resin prepared by the embodiments of the invention is within 1.5 seconds, and the curing speed is high. The fluorine content can reach more than 60 percent, the water contact angle can reach 110 degrees, and the water contact angle is gradually increased along with the increase of the fluorine content.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. The molecular chain self-rotating fluorine-containing UV resin is characterized by being prepared from the following raw materials in parts by weight:
2. molecular chain self-rotating type fluorine-containing UV resin according to claim 1, wherein said acid anhydride comprises one or more of maleic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride and tetrahydrophthalic anhydride.
3. Molecular chain self-rotating type fluorine-containing UV resin according to claim 1, wherein said ethylene-epoxy difunctional monomer comprises one or more of glycidyl acrylate, glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
4. Molecular chain self-rotating type fluorine-containing UV resin according to claim 1, wherein said fluorine-containing alcohol comprises one or more of octafluoropentanol, hexafluorobutanol, tetrafluoropropanol, and trifluoroethanol.
5. A method for producing a molecular chain self-rotating type fluorine-containing UV resin according to claim 1, comprising the steps of:
weighing polyvinyl alcohol, anhydride, an ethylene-epoxy bifunctional monomer and fluorine-containing alcohol according to parts by weight;
step two, preparing modified linear carboxyl functional polymer:
adding polyvinyl alcohol and anhydride into a reaction kettle, slowly heating to 50-60 ℃, and dissolving.
Heating to 80-90 deg.C, reacting for 3-5 h, measuring the acid value of the reaction system, and ending the reaction when the acid value reaches 280-300 KOH/(mg/g).
Introducing a reactive photocuring group into a side chain of the modified linear carboxyl functional polymer;
slowly adding the ethylene-epoxy bifunctional monomer into a reaction kettle.
Heating to 80-90 ℃, keeping the temperature for reaction for 3-5 hours, measuring the acid value of the system, and finishing the reaction when the acid value reaches 200-230 KOH/(mg/g).
Introducing fluorine-containing groups into the side chains of the modified linear carboxyl functional polymer;
slowly adding the fluorine-containing alcohol into the reaction kettle.
Heating to 100 ℃ and 120 ℃, charging nitrogen, keeping the temperature for reaction for 3-5 hours, measuring the acid value of the reaction system, and finishing the reaction when the acid value is less than 3 KOH/(mg/g).
6. The method for preparing molecular chain self-rotating type fluorine-containing UV resin according to claim 5, wherein the feeding time of the ethylene-epoxy bifunctional monomer in the third step is 1 to 2 hours.
7. The method for producing molecular chain self-rotating type fluorine-containing UV resin according to claim 5, wherein in the fourth step, the time period for charging the fluorine-containing alcohol is 1 to 2 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200464A (en) * | 1989-12-22 | 1993-04-06 | Nitto Chemical Industry Co. Ltd. | Water-soluble radical-curing polyvinyl alcohol derivative |
| WO1999014380A1 (en) * | 1997-09-18 | 1999-03-25 | Minnesota Mining And Manufacturing Company | Amphiphilic perfluoroalkyl modified polydienes and their use in the treatment of leather |
| JP2000239317A (en) * | 1999-02-19 | 2000-09-05 | Kyoeisha Chem Co Ltd | Partial esterification of polyvinyl alcohol |
| CN108048064A (en) * | 2017-12-19 | 2018-05-18 | 常州市阿曼特化工有限公司 | A kind of preparation method of long-acting water-based wax-proofing agent |
-
2020
- 2020-05-11 CN CN202010391340.7A patent/CN111423532A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200464A (en) * | 1989-12-22 | 1993-04-06 | Nitto Chemical Industry Co. Ltd. | Water-soluble radical-curing polyvinyl alcohol derivative |
| WO1999014380A1 (en) * | 1997-09-18 | 1999-03-25 | Minnesota Mining And Manufacturing Company | Amphiphilic perfluoroalkyl modified polydienes and their use in the treatment of leather |
| JP2000239317A (en) * | 1999-02-19 | 2000-09-05 | Kyoeisha Chem Co Ltd | Partial esterification of polyvinyl alcohol |
| CN108048064A (en) * | 2017-12-19 | 2018-05-18 | 常州市阿曼特化工有限公司 | A kind of preparation method of long-acting water-based wax-proofing agent |
Non-Patent Citations (1)
| Title |
|---|
| 宋震: "聚乙烯醇的氟化疏水改性及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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Application publication date: 20200717 |