CN116120564A - Modified phenolic resin special for glass protection oil and preparation method thereof - Google Patents
Modified phenolic resin special for glass protection oil and preparation method thereof Download PDFInfo
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- CN116120564A CN116120564A CN202310124640.2A CN202310124640A CN116120564A CN 116120564 A CN116120564 A CN 116120564A CN 202310124640 A CN202310124640 A CN 202310124640A CN 116120564 A CN116120564 A CN 116120564A
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- phenolic resin
- tannin
- modified phenolic
- parts
- depolymerized
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000011521 glass Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 235000018553 tannin Nutrition 0.000 claims abstract description 105
- 229920001864 tannin Polymers 0.000 claims abstract description 105
- 239000001648 tannin Substances 0.000 claims abstract description 105
- 239000000243 solution Substances 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 241000278701 Acacia mangium Species 0.000 claims 1
- 235000017631 Acacia mangium Nutrition 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 44
- 230000001681 protective effect Effects 0.000 description 16
- 238000005299 abrasion Methods 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 241000220479 Acacia Species 0.000 description 3
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 244000215068 Acacia senegal Species 0.000 description 2
- 235000006491 Acacia senegal Nutrition 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N flavone Chemical group O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the technical field of resins, and particularly discloses a modified phenolic resin special for glass protection oil and a preparation method thereof. The modified phenolic resin special for the glass protection oil comprises the following raw materials in parts by weight: 70-90 parts of phenol, 30-60 parts of depolymerized tannin, 60-70 parts of formaldehyde aqueous solution with the mass concentration of 35-37%, 10-15 parts of sodium hydroxide aqueous solution with the mass concentration of 35-40% and 8-10 parts of polyethyleneimine; based on the depolymerized tannin, the depolymerized tannin is prepared from the following raw materials in parts by weight: 3-5 parts of tannin, 75-85 parts of absolute ethanol solution of 2-methyl furan and 0.5-1.5 parts of hydrochloric acid with the mass concentration of 15-20%. The method has the advantage of improving the film stripping speed of the glass protection oil while improving the adhesion of the glass protection oil on the glass surface.
Description
Technical Field
The invention relates to the technical field of resin, in particular to a modified phenolic resin special for glass protection oil and a preparation method thereof.
Background
In conventional glass processing processes, the glass to be processed is typically left unprotected. In the subsequent cutting or edging process of the glass in the unprotected state, the surface of the glass is easy to cause slight or severe scratch, the glass can be polished flat after long-time polishing, a large amount of polishing powder is consumed, and the glass cannot be polished flat and is directly scrapped.
In order to solve the technical problem, various glass protection oils are developed in the market, wherein the glass protection oils are mainly printed on the surface of glass through silk screen printing, and a layer of protection film is formed on the surface of the glass after Ultraviolet (UV) curing so as to resist scratches, clamping injuries caused by smelting tools, external forces and the like; and removing the protective film in dilute alkali liquor after the glass processing is finished.
However, the performance of the UV curing glass protective oil on the market is not mature, and the abrasion resistance and the adhesive force of the glass protective oil are in contradictory relation with the stripping performance of alkali liquor, namely the glass protective oil with good abrasion resistance and adhesive force is not easy to strip, and the cleaning is difficult; and in the demolding process, the glass protection oil can fall off in a piece, so that the condition that the water pipe is blocked during hanging frames and mass production occurs, thereby greatly consuming production time and increasing the cost of manpower and material resources.
Disclosure of Invention
In order to improve the film stripping speed of the glass protection oil while improving the adhesion of the glass protection oil on the glass surface, the application provides a modified phenolic resin special for the glass protection oil and a preparation method thereof.
In a first aspect, the present application provides a modified phenolic resin dedicated to glass protection oil, which adopts the following technical scheme:
the modified phenolic resin special for the glass protection oil comprises the following raw materials in parts by weight: 70-90 parts of phenol, 30-60 parts of depolymerized tannin, 60-70 parts of formaldehyde aqueous solution with the mass concentration of 35-37%, 10-15 parts of sodium hydroxide aqueous solution with the mass concentration of 35-40% and 8-10 parts of polyethyleneimine;
based on the depolymerized tannin, the depolymerized tannin is prepared from the following raw materials in parts by weight: 3-5 parts of tannin, 75-85 parts of absolute ethanol solution of 2-methyl furan and 0.5-1.5 parts of hydrochloric acid with the mass concentration of 15-20%.
By adopting the technical scheme, as the depolymerized tannin and the polyethyleneimine are adopted for preparing the modified phenolic resin, firstly, the hydroxyl content in the modified phenolic resin is increased by introducing the depolymerized tannin, so that the adhesive property of the modified phenolic resin is increased, and when the modified phenolic resin is applied to glass protection oil, the adhesive force, the hardness and the wear resistance between the glass protection oil and the glass surface are increased, and meanwhile, the reactivity of the depolymerized tannin is high, so that the reactivity of the modified phenolic resin in a film removal solution can be promoted, and the film removal speed of the glass protection oil containing the modified phenolic resin is further improved; secondly, after the polyethyleneimine is added, amino in the polyethyleneimine can react with normal quinone in a tannin skeleton to form C=N and/or C-N groups, and the amino can also react with methyl in the phenolic resin to form C-N groups, so that the adhesion, hardness and wear resistance of glass protection oil using the modified phenolic resin on the glass surface are further improved; thirdly, the molecular mass of the depolymerized tannin is reduced relative to that of the tannin, the content of active functional groups is increased, the methylation and polymerization reaction of the depolymerized tannin and formaldehyde are promoted by the increase of reaction sites, a network structure with high crosslinking density is formed, and at the same time, the Michael addition and/or Schiff base generation reaction of amino groups in the polyethyleneimine and the normal quinone in the tannin can increase the crosslinking density, so that the physical and chemical crosslinking between the tannin phenolic resin and the adhered surface is enhanced; finally, catechol structures in a crosslinked network are uniformly distributed on the network structure through the interaction of hydrogen bonds and cations, so that the solubility of the modified phenolic resin in a sodium hydroxide solution is remarkably improved, and the film stripping speed of glass protection oil using the modified phenolic resin is remarkably improved.
Optionally, the tannin is acacia equiseti bark tannin.
Optionally, the mass ratio of the 2-methylfuran to the absolute ethyl alcohol in the absolute ethyl alcohol solution of the 2-methylfuran is 1: (2-3.2).
By adopting the technical scheme, the 2-methyl furan reacts with the flavone units of the tannin, so that the depolymerized tannin with high chemical activity is obtained, and further the depolymerized tannin can fully react with other raw materials in the modified phenolic resin system, and further the adhesion strength, hardness, wear resistance and film stripping speed of glass protection oil containing the modified phenolic resin are improved.
Optionally, the depolymerized tannin is prepared by a method comprising the steps of: mixing tannin, anhydrous ethanol solution of 2-methylfuran and hydrochloric acid, heating, stirring to obtain reaction solution, ice-bath cooling the reaction solution, adjusting the reaction solution to be slightly acidic, evaporating, and drying to obtain depolymerized tannin.
Optionally, an aqueous solution of sodium carbonate with a mass concentration of 10-15% is used for adjusting the pH value of the reaction solution, and the pH value of the reaction solution is 6.3-6.7 when the reaction solution is slightly acidic.
Optionally, the heating temperature is 45-55 ℃, the stirring speed is 300-500rpm, the stirring time is 30-40min, and the reaction solution is cooled to 0-2 ℃ in an ice bath.
By adopting the technical scheme, the raw materials are fully reacted to prepare the depolymerized tannin with high reactivity.
Optionally, the weight ratio of the polyethyleneimine to the depolymerized tannin is 1: (4-4.8).
By adopting the technical scheme, the film stripping speed of the glass protection oil is improved while the adhesion, hardness and wear resistance of the modified phenolic resin to the glass protection oil are improved by adjusting the weight ratio of the polyethyleneimine to the depolymerized tannin.
In a second aspect, the present application provides a preparation method of a modified phenolic resin dedicated to glass protection oil, which adopts the following technical scheme:
the preparation method of the modified phenolic resin special for the glass protection oil comprises the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde aqueous solution and sodium hydroxide solution, and heating to obtain tannin-based phenolic resin;
s2: and mixing and stirring the polyethyleneimine and the tannin-based phenolic resin to obtain the modified phenolic resin.
By adopting the technical scheme, the raw materials are mixed in batches and fully mixed, so that the raw materials are fully matched for use and play a role to prepare the modified phenolic resin.
Optionally, the heating temperature in the step S1 is 85-95 ℃ and the heating time is 30-40min; the stirring temperature in the step S2 is 25-35 ℃, and the stirring time is 30-40min.
By adopting the technical scheme, the raw materials are fully reacted, and the modified phenolic resin which can obviously improve the adhesive force, the hardness, the wear resistance and the film stripping speed of the glass protective oil when the modified phenolic resin is applied to the glass protective oil is prepared.
In summary, the present application has the following beneficial effects:
because the application adopts the depolymerized tannin and the polyethyleneimine, on one hand, the introduction of the depolymerized tannin increases the hydroxyl content in the modified phenolic resin, and the addition of the polyethyleneimine enables the amino contained in the polyethyleneimine to react with the normal quinone in the tannin skeleton to form C=N and/or C-N groups, thereby obviously improving the adhesive force, the hardness and the wear resistance of the glass protection oil containing the modified phenolic resin; meanwhile, due to the fact that the content of the active functional groups in the depolymerized tannin is increased, methylation and polymerization reaction of the depolymerized tannin and formaldehyde are promoted, a network structure with high crosslinking density is formed, and amino groups in the polyethyleneimine react with normal quinone in the tannin to further increase the crosslinking density of the modified phenolic resin, so that physical and chemical crosslinking between the tannin-based phenolic resin and the adhered surface is enhanced. On the other hand, the depolymerization tannin has high reactivity, can promote the reactivity of the modified phenolic resin in the film removing solution, and meanwhile, the catechol structure in the crosslinked network is uniformly distributed on the network structure through the interaction of hydrogen bond and cation, so that the solubility of the modified phenolic resin in the sodium hydroxide solution is obviously improved, and the film removing speed of the glass protection oil using the modified phenolic resin is obviously improved. Detailed Description
The present application is described in further detail below with reference to examples.
Preparation example of depolymerized tannin
The evaporating temperature is 25-35 deg.C, the freeze-drying temperature is-10-20 deg.C, and the time is 40-50h.
Preparation example 1
A depolymerized tannin, comprising the following raw materials by weight:
an absolute ethanol solution of 3g of acacia senegal tannin and 75g of 2-methyl furan, wherein: the mass ratio of the 2-methylfuran to the absolute ethyl alcohol is 1:2. 1.5g of hydrochloric acid with the mass concentration of 15 percent.
A depolymerized tannin is prepared by the following steps:
mixing tannin, anhydrous ethanol solution of 2-methylfuran and hydrochloric acid, heating at 45 ℃ at 300rpm, stirring for 40min to obtain a reaction solution, cooling the reaction solution to 0 ℃ in an ice bath, then, when the pH value of the reaction solution is adjusted to 6.3 by using 10% sodium carbonate aqueous solution by mass concentration, evaporating at 25 ℃, and freeze-drying at-10 ℃ for 50h to obtain depolymerized tannin.
Preparation example 2
A depolymerized tannin, comprising the following raw materials by weight:
5g of acacia maritima bark tannin and 85g of absolute ethanol solution of 2-methyl furan, wherein: the mass ratio of the 2-methylfuran to the absolute ethyl alcohol is 1:3.2, hydrochloric acid with the mass concentration of 120 percent is 0.5.
A depolymerized tannin is prepared by the following steps:
mixing tannin, anhydrous ethanol solution of 2-methylfuran and hydrochloric acid, heating at 55 ℃ at 500rpm, stirring for 30min to obtain a reaction solution, cooling the reaction solution to 2 ℃ in an ice bath, then, when the pH value of the reaction solution is adjusted to 6.7 by using 15% sodium carbonate aqueous solution by mass concentration, evaporating at 35 ℃, and freeze-drying at-20 ℃ for 40h to obtain depolymerized tannin.
Preparation example 3
A depolymerized tannin, comprising the following raw materials by weight:
an absolute ethanol solution of 4g of acacia senegal tannin and 80g of 2-methyl furan, wherein: the mass ratio of the 2-methylfuran to the absolute ethyl alcohol is 1:2.6 g of hydrochloric acid with the mass concentration of 17 percent.
A depolymerized tannin is prepared by the following steps:
mixing tannin, anhydrous ethanol solution of 2-methylfuran and hydrochloric acid, heating at a rotation speed of 400rpm at 50 ℃ and stirring for 35min to obtain a reaction solution, cooling the reaction solution to 1 ℃ in an ice bath, then, when the pH value of the reaction solution is adjusted to 6.5 by using a sodium carbonate aqueous solution with a mass concentration of 12%, evaporating at 30 ℃ and freeze-drying at-15 ℃ for 45h to obtain depolymerized tannin.
Preparation example 4
A depolymerized tannin, comprising the following raw materials by weight:
4g of acacia maritima bark tannin and 85g of absolute ethanol solution of 2-methyl furan, wherein: the mass ratio of the 2-methylfuran to the absolute ethyl alcohol is 1:3. 1g of hydrochloric acid with the mass concentration of 16 percent.
A depolymerized tannin is prepared by the following steps:
mixing tannin, anhydrous ethanol solution of 2-methyl furan and hydrochloric acid, heating at a rotating speed of 450rpm for 32min at 50 ℃ to obtain a reaction solution, cooling the reaction solution to 0 ℃ in an ice bath, and then evaporating at 25 ℃ and freeze-drying at-20 ℃ for 45h when the pH value of the reaction solution is adjusted to 6.5 by using a sodium carbonate aqueous solution with a mass concentration of 10% to obtain depolymerized tannin.
Preparation example 5
Depolymerization tannin is different from preparation example 3 in that an anhydrous ethanol solution of equal weight and equal mass concentration of dodecyl mercaptan is used instead of an anhydrous ethanol solution of 2-methyl furan.
Examples
Example 1
The modified phenolic resin comprises the following raw materials in parts by weight:
70g of phenol, 30g of depolymerized tannin, 70g of formaldehyde aqueous solution with the mass concentration of 35%, 15g of sodium hydroxide aqueous solution with the mass concentration of 35% and 8g of polyethyleneimine.
A modified phenolic resin is prepared by the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde water solution and sodium hydroxide solution, and heating at 85deg.C for 40min to obtain tannin-based phenolic resin;
s2: and stirring the polyethyleneimine and the tannin-based phenolic resin for 40min at 25 ℃ to obtain the modified phenolic resin.
Example 2
The modified phenolic resin comprises the following raw materials in parts by weight:
90g of phenol, 60g of depolymerized tannin, 60g of formaldehyde aqueous solution with the mass concentration of 37%, 10g of sodium hydroxide aqueous solution with the mass concentration of 40% and 10g of polyethyleneimine.
A modified phenolic resin is prepared by the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde water solution and sodium hydroxide solution, and heating at 95deg.C for 30min to obtain tannin-based phenolic resin;
s2: and stirring the polyethyleneimine and the tannin-based phenolic resin for 30min at 35 ℃ to obtain the modified phenolic resin.
Example 3
The modified phenolic resin comprises the following raw materials in parts by weight:
80g of phenol, 45g of depolymerized tannin, 65g of formaldehyde aqueous solution with the mass concentration of 36%, 13g of sodium hydroxide aqueous solution with the mass concentration of 37% and 9g of polyethyleneimine.
A modified phenolic resin is prepared by the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde water solution and sodium hydroxide solution, and heating at 90deg.C for 35min to obtain tannin-based phenolic resin;
s2: and stirring the polyethyleneimine and the tannin-based phenolic resin for 35min at the temperature of 30 ℃ to obtain the modified phenolic resin.
Example 4
The modified phenolic resin comprises the following raw materials in parts by weight:
80g of phenol, 45g of depolymerized tannin, 60g of formaldehyde aqueous solution with the mass concentration of 35%, 12g of sodium hydroxide aqueous solution with the mass concentration of 40% and 9g of polyethyleneimine.
A modified phenolic resin is prepared by the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde water solution and sodium hydroxide solution, and heating at 88 ℃ for 36min to obtain tannin-based phenolic resin;
s2: and stirring the polyethyleneimine and the tannin-based phenolic resin for 36min at the temperature of 32 ℃ to obtain the modified phenolic resin.
Example 5
A modified phenolic resin was different from example 3 in that the depolymerized tannin used was the one prepared from preparation example 5.
Example 6
A modified phenolic resin differing from example 3 in that the weight of polyethyleneimine is unchanged and the weight ratio of polyethyleneimine to depolymerized tannins is 1:4.
example 7
A modified phenolic resin differing from example 3 in that the weight of polyethyleneimine is unchanged and the weight ratio of polyethyleneimine to depolymerized tannins is 1:4.8.
example 8
A modified phenolic resin differing from example 3 in that the weight of polyethyleneimine is unchanged and the weight ratio of polyethyleneimine to depolymerized tannins is 1:4.4.
example 9
A modified phenolic resin differing from example 3 in that the weight of polyethyleneimine is unchanged and the weight ratio of polyethyleneimine to depolymerized tannins is 1:3.3.
example 10
A modified phenolic resin differing from example 3 in that the weight of polyethyleneimine is unchanged and the weight ratio of polyethyleneimine to depolymerized tannins is 1:6.8.
comparative example
Comparative example 1
A modified phenolic resin differs from example 3 in that an equivalent weight of tannin is used in place of the depolymerized tannin during the preparation.
Comparative example 2
A modified phenolic resin differs from example 3 in that polyethyleneimine is not used in the preparation.
Detection method
1. Demolding Performance test
The glass protection oils prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to release property test as follows: and (3) printing the glass protective oil on the surface of the glass, immersing the glass with the glass protective oil protective coating in a sodium hydroxide aqueous solution with the mass concentration of 5% at 80 ℃ after light curing, and observing the demolding time and state of the glass protective oil protective coating from the glass. The shorter the stripping treatment time is, the faster the cured and crosslinked glass protection oil swells in alkali solution and the better the stripping property is; the number of replicates for each set of samples was five and the average demold time for each set of samples was calculated and recorded in table 1.
2. Adhesion test
The glass protection oils prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to adhesion testing according to GB/T1720-1979 paint film adhesion assay; the measured adhesive force is divided into seven grades from one grade to seven grades, wherein the one grade is the optimal adhesive force, and the seven grades are the worst adhesive force; the adhesion of each set of samples is recorded in table 1.
3. Paint film hardness test
The glass protective oils prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to hardness test, the test method being according to GB/T6739-2006 method for measuring paint film hardness by the colored paint and varnish pencil method; wherein the hardness measured by the glass protective oil is divided into 18 grades according to the hardness of the pencil, namely 9B, 8B, 7B, 6B, 5B, 4B, 3B, 2B, B, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H and 9H, wherein the grade 9B is the softest and the grade 9H is the hardest; the hardness of each set of samples is recorded in table 1.
4. Abrasion resistance test
The glass protective oils prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to abrasion resistance test, the abrasion resistance was characterized by the weight loss of the paint film according to GB1768-1979 method for abrasion resistance of coating film, the smaller the weight loss of the paint film, the better the abrasion resistance; the wear resistance in each set of samples is recorded in table 1.
TABLE 1
Combining examples 1-5 and table 1, it can be seen that the combined action of depolymerized tannins and polyethyleneimine can significantly improve the adhesion, hardness and wear resistance of the glass protection oil comprising the modified phenolic resin and improve the film stripping speed of the glass protection oil on the glass surface; this is because the introduction of depolymerized tannins and polyethyleneimines enables the introduction of hydroxyl, c=n and C-N groups into the modified resin and forms a crosslinked three-dimensional network structure, most notably enhancing the adhesion, hardness and wear resistance of the glass protection oil comprising the modified phenolic resin; meanwhile, catechol structures in a cross-linked network are uniformly distributed on a three-dimensional network structure through interaction of hydrogen bonds and cations under the high reactivity of depolymerized tannin, so that the film stripping speed of glass protection oil using the modified phenolic resin is improved.
In combination with examples 3, 6-10 and Table 1, it can be seen that when the weight ratio of depolymerized tannins to polyethyleneimine is 1: (4-4.8) the glass protective oil containing the modified phenolic resin has the strongest adhesion, hardness and wear resistance, and the highest film removal speed. When the weight of depolymerized tannin is too high or too low relative to that of polyethyleneimine, the adhesion, hardness and abrasion resistance of the glass protective oil are lowered, and the film stripping speed is slowed down, probably because when the weight ratio of depolymerized tannin and polyethyleneimine is not coordinated, the synergistic effect between the two cannot be fully exerted, a three-dimensional network structure with a sufficient number of groups or high crosslinking degree is generated, so that the distribution of catechol on the network structure is affected, and the adhesion, hardness, abrasion resistance and film stripping speed of the glass protective oil containing the modified phenolic resin are negatively affected.
In combination with example 3, comparative examples 1-2 and Table 1, it can be seen that depolymerized tannins and polyethyleneimines are indispensable in preparing the modified phenolic resin, and that the absence of either component negatively affects the adhesion, hardness, abrasion resistance and film stripping speed of the glass protective oil comprising the modified phenolic resin.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. A modified phenolic resin special for glass protection oil is characterized in that: the material comprises the following raw materials in parts by weight: 70-90 parts of phenol, 30-60 parts of depolymerized tannin, 60-70 parts of formaldehyde aqueous solution with the mass concentration of 35-37%, 10-15 parts of sodium hydroxide aqueous solution with the mass concentration of 35-40% and 8-10 parts of polyethyleneimine;
based on the depolymerized tannin, the depolymerized tannin is prepared from the following raw materials in parts by weight: 3-5 parts of tannin, 75-85 parts of absolute ethanol solution of 2-methyl furan and 0.5-1.5 parts of hydrochloric acid with the mass concentration of 15-20%.
2. The modified phenolic resin special for glass protection oil according to claim 1, wherein the modified phenolic resin is characterized in that: the tannin is Acacia mangium bark tannin.
3. The modified phenolic resin special for glass protection oil according to claim 1, wherein the modified phenolic resin is characterized in that: the mass ratio of the 2-methyl furan to the absolute ethyl alcohol in the absolute ethyl alcohol solution of the 2-methyl furan is 1: (2-3.2).
4. The method for preparing the modified phenolic resin special for the glass protection oil, which is disclosed in claim 1, is characterized in that: the depolymerized tannin is prepared by a method comprising the following steps: mixing tannin, anhydrous ethanol solution of 2-methylfuran and hydrochloric acid, heating, stirring to obtain reaction solution, ice-bath cooling the reaction solution, adjusting the reaction solution to be slightly acidic, evaporating, and drying to obtain depolymerized tannin.
5. The modified phenolic resin special for glass protection oil according to claim 4, wherein the modified phenolic resin is characterized in that: the pH value of the reaction solution is regulated by using 10-15% sodium carbonate aqueous solution by mass concentration, and the pH value of the reaction solution is 6.3-6.7 when the reaction solution is slightly acidic.
6. The modified phenolic resin special for glass protection oil according to claim 4, wherein the modified phenolic resin is characterized in that: the heating temperature is 45-55 ℃, the stirring speed is 300-500rpm, the stirring time is 30-40min, and the reaction solution is cooled to 0-2 ℃ in an ice bath.
7. The modified phenolic resin special for glass protection oil according to claim 1, wherein the modified phenolic resin is characterized in that: the weight ratio of the polyethyleneimine to the depolymerized tannin is 1: (4-4.8).
8. The method for preparing the modified phenolic resin special for glass protection oil according to any one of claims 1 to 7, wherein the method comprises the following steps: the modified phenolic resin is prepared by a method comprising the following steps:
s1: mixing depolymerized tannin with phenol, formaldehyde aqueous solution and sodium hydroxide solution, and heating to obtain tannin-based phenolic resin;
s2: and mixing and stirring the polyethyleneimine and the tannin-based phenolic resin to obtain the modified phenolic resin.
9. The method for preparing the modified phenolic resin special for the glass protection oil, which is disclosed in claim 8, is characterized in that: the heating temperature is 85-95 ℃ and the heating time is 30-40min in the step S1; the stirring temperature in the step S2 is 25-35 ℃, and the stirring time is 30-40min.
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