CN110818866A - Silane modified resin and preparation method and application thereof - Google Patents
Silane modified resin and preparation method and application thereof Download PDFInfo
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- CN110818866A CN110818866A CN201911190946.8A CN201911190946A CN110818866A CN 110818866 A CN110818866 A CN 110818866A CN 201911190946 A CN201911190946 A CN 201911190946A CN 110818866 A CN110818866 A CN 110818866A
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
Abstract
The invention relates to silane modified resin and a preparation method and application thereof, belonging to the technical field of silane modified resin. The preparation method of the silane modified resin comprises the following steps: s1: taking a phenol raw material shown as a general formula I and an aldehyde raw material shown as a general formula II, and carrying out polymerization reaction to obtain a thermoplastic phenolic resin; s2: adding silane resin into the thermoplastic phenolic resin, and carrying out silane primary polymerization reaction to obtain silane modified phenolic resin; s3: adding an alkaline silane catalyst and an accelerant into the silane modified phenolic resin to carry out silane secondary polymerization reaction, thus obtaining the silane modified resin. In the preparation method, the chemical functional group of the thermoplastic phenolic resin is introduced into the chemical functional group of the silane resin for secondary polymerization reaction, so that the adhesive property and the mechanical property of the phenolic resin are improved, the product has excellent adhesive force and heat resistance, and the product has good protection effect on glass and the characteristic of easy cleaning when being applied to the processing procedure of mobile phone glass.
Description
Technical Field
The invention relates to the technical field of silane modified resin, in particular to silane modified resin and a preparation method and application thereof.
Background
When the existing mobile phone glass is processed, a large piece of glass is firstly manufactured, a mobile phone factory performs cutting and processing according to different mobile phone production requirements, and a protective film is not used in the cutting processing process, but the processing reject ratio is high. In order to improve the yield, some manufacturers use unmodified linear phenolic resin as a protective film, when the protective film is used, the linear thermoplastic phenolic resin is sprayed on mobile phone glass, and is dried to form a lens protective film, and the lens is subjected to processes of cutting, grinding, removing the protective film and the like. However, such films have the problems of incomplete curing, poor bonding effect with lenses, or excessive curing, and difficult removal of the protective film after processing, so that the lenses are prone to surface damage and damage in the processing and grinding process, the yield is reduced after processing, the defective proportion is still too high, and the cost of lens processing is relatively increased.
Disclosure of Invention
Therefore, it is necessary to provide a silane modified resin for solving the above problems, and a protective film made of the silane modified resin has good adhesion when applied to a mobile phone glass processing procedure, has a good protective effect on mobile phone glass, and has the characteristic of easy cleaning.
A preparation method of silane modified resin comprises the following steps:
s1: taking a phenol raw material shown as a general formula I and an aldehyde raw material shown as a general formula II, and carrying out polymerization reaction to obtain a thermoplastic phenolic resin;
wherein: r1, R2, R3 are independently optionally selected from: hydrogen, linear or branched C1-C18 alkyl, linear or branched C1-C18 alkylbenzene;
wherein: n is selected from: an integer of between 1 and 10, and,
(CH2) n represents a linear or branched alkyl group;
s2: adding silane resin into the thermoplastic phenolic resin, and carrying out silane primary polymerization reaction to obtain silane modified phenolic resin;
s3: adding an alkaline silane catalyst and an accelerant into the silane modified phenolic resin to carry out silane secondary polymerization reaction, thus obtaining the silane modified resin.
In the preparation method, the silane resin chemical functional group is introduced into the thermoplastic phenolic resin chemical functional group to carry out silane secondary polymerization reaction, and by utilizing the characteristic of a Si-O chemical structure in the silane resin, in the chemical reaction process, an O-Si-O oxygen silicon oxide chemical chain is formed with an oxygen element of the phenolic resin or a C-O-Si-O carbon oxygen silicon oxide chemical chain is formed with a carbon element, so that the adhesive property and the mechanical property of the phenolic resin are improved, the product has excellent adhesive force and heat resistance, and when the preparation method is applied to the processing procedure of mobile phone glass, the preparation method has the characteristics of good protection effect on the glass and easy cleaning.
In one embodiment, in step S1, the phenolic starting material is selected from: in step S1, the phenolic starting material is selected from: at least one of phenol, bisphenol a, bisphenol F and bisphenol S, the aldehyde raw material being selected from the group consisting of: at least one of formaldehyde, paraformaldehyde, trioxymethylene, and furfural.
In one embodiment, the silane resin is selected from: a methoxy-or ethoxy-containing silane compound; the basic silane catalyst is selected from: a silane compound containing an amino functional group.
In one embodiment, the molar ratio of the phenolic raw material to the aldehyde raw material is 1: 0.3-2; the molar ratio of the silane resin to the phenolic raw material is 1: 0.01-0.1; the molar ratio of the basic catalyst to the phenolic raw material is 1: 0.01-0.5.
In one embodiment, in the step of S3, a solvent is further added, and the molar ratio of the solvent to the aldehyde raw material is 1: 0.1-0.9. To remove unreacted starting materials and other impurities soluble in the solvent.
In one embodiment, the solvent is an alcohol or ketone solvent.
In one embodiment, the accelerator is selected from: leveling agents, antioxidants, epoxy resins and polyurethanes.
In one embodiment, in the step S1, the polymerization conditions are: the pressure is normal pressure or negative pressure, the temperature is 50-210 ℃, and the time is 0.5-10 hours;
in the step S2, adding silane resin after the temperature is reduced to 140-190 ℃, wherein the conditions of the silane primary polymerization reaction are as follows: the pressure is normal pressure or negative pressure, the temperature is 150-;
in the step S3, the conditions of the silane secondary polymerization reaction are as follows: the temperature is 60-90 ℃ and the time is 1-4 hours.
In one embodiment, in the step S1, the mixture is heated at 50-90 ℃ for 0.5-1.5 hours, heated to 90-110 ℃, refluxed and maintained at 3-5 hours, dehydrated at 120-140 ℃ for 2-4 hours under normal pressure, dehydrated under vacuum and heated to 190-200 ℃;
in the step S2, adding silane resin after the temperature is reduced to 140-150 ℃, heating to 160-180 ℃, reacting for 1-3 hours, and performing a silanization reaction;
in the step S3, after the temperature is reduced to room temperature to form silane modified phenolic resin, the modified resin is taken, added with solvent, added with alkaline silane catalyst and accelerant, heated to 60-80 ℃, reacted for 2-4 hours, and then secondary silane polymerization is carried out.
The invention also discloses the silane modified resin prepared by the preparation method.
The invention also discloses application of the silane modified resin in processing mobile phone glass.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a preparation method of silane modified resin, which is characterized in that a thermoplastic phenolic resin chemical functional group is introduced into a silane resin chemical functional group to carry out secondary polymerization reaction, and an O-Si-O oxygen silicon oxide chemical chain is formed with an oxygen element of phenolic resin or a C-O-Si-O carbon oxygen silicon oxide chemical chain is formed with a carbon element in the chemical reaction process by utilizing the characteristic of a Si-O chemical structure in the silane resin, so that the adhesive property and the mechanical property of the phenolic resin are improved, and the product has excellent adhesive force and heat resistance.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The preparation method of the silane modified resin comprises the following steps:
s1: taking a phenol raw material shown as a general formula I and an aldehyde raw material shown as a general formula II, and carrying out polymerization reaction to obtain a thermoplastic phenolic resin;
wherein: r1, R2, R3 are independently optionally selected from: hydrogen, linear or branched C1-C18 alkyl, linear or branched C1-C18 alkylbenzene;
wherein: n is selected from: an integer of between 1 and 10, and,
(CH2) n represents a linear or branched alkyl group;
s2: adding silane resin into the thermoplastic phenolic resin, and carrying out silane primary polymerization reaction to obtain silane modified phenolic resin;
s3: adding alkaline silane catalyst and promoter into the silane modified phenolic resin to carry out silane secondary polymerization reaction to obtain silane modified resin
The silane modified resin has the following chemical structure:
the silane modified resin has excellent adhesion to organic matters and inorganic matters, excellent water resistance and high temperature resistance, and can be used for processing protective films for mobile phone glass.
The silane resin is selected from: a methoxy-or ethoxy-containing silane compound; the basic silane catalyst is selected from: a silane compound containing an amino functional group.
Because the self-hardening organic silicon protective film has strong alkali groups and self-hardening property, the organic silicon protective film is sprayed on mobile phone glass and dried by slight heating (such as drying and heating temperature of 60-150 ℃) to form Semi-curing state so as to form a protective film. After the mobile phone glass is cut and ground, the mobile phone glass can be easily cleaned by using an alkaline solvent, so that the mobile phone glass can be used for processing a protective film, and the appearance of the mobile phone glass is not damaged.
The starting materials used in the following examples are all commercially available.
Wherein: phenol (available from Zhonghai oil, Guangdong, Huizhou), aqueous formaldehyde (44% formaldehyde, available from Guangdong Star chemical), silane resin (available from Xinyue chemical, Japan), oxalic acid (available from national chemical, Shandong), bisphenol A (available from south Asia chemical, Jiangsu), hexamethyltetramine (available from Lanzhou chemical).
Example 1
A silane modified resin is prepared by the following steps:
s1: according to the following phenol: oxalic acid: the molar ratio of formaldehyde is 1: 0.05-0.1: 0.5-1.2, phenol, oxalic acid and formaldehyde aqueous solution are sequentially put into a reactor, stirred and heated to 70 ℃ under the normal pressure state, the temperature is maintained for one hour, then the temperature is raised to 100 ℃ under the normal pressure, and the reflux reaction is carried out and the temperature is maintained for 4 hours. Dehydrating to 130 ℃ at normal pressure, and reacting for 3 hours at the temperature; vacuum dewatering and heating to 195 deg.c.
S2: cooling to 140 ℃, adding silane resin (the adding amount is 1-10% of the input amount of phenol), heating to 170 ℃, reacting for two hours, and performing silane one-time polymerization reaction to obtain the silane modified phenolic resin.
The reaction equation in the above reaction process is as follows:
s3: taking the silane modified phenolic resin, firstly using an ethanol solvent to dissolve the resin, adding an alkaline silane catalyst (the adding proportion is 0.5-20 percent of the resin amount) and an accelerant (the adding proportion is 1-10 percent of the resin amount), heating to 70 ℃, carrying out secondary silane polymerization reaction, and reacting for 3 hours to prepare the silane modified resin.
Example 2
A thermoplastic phenolic resin is prepared by the following method:
according to the following phenol: oxalic acid: the molar ratio of formaldehyde is 1: 0.05-0.1: 0.5-1.2, phenol, oxalic acid and formaldehyde aqueous solution are taken and put into a reactor in sequence, stirred under the normal pressure state and heated to 70 ℃, the temperature is maintained for 1 hour at 70 ℃, reflux reaction is carried out under the normal pressure state, the temperature is raised to 100 ℃, and the temperature is maintained for 4 hours at 100 ℃. Vacuum dewatering, raising the temperature to 170 ℃, and cooling to obtain the thermoplastic phenolic resin.
Example 3
A bisphenol A modified phenolic resin is prepared by the following method:
according to the following phenol: bisphenol A: oxalic acid: and (2) taking phenol, bisphenol A, oxalic acid and formaldehyde aqueous solution, sequentially putting the phenol, the bisphenol A, the oxalic acid and the formaldehyde aqueous solution into a reactor, stirring the mixture under normal pressure, heating the mixture to 70 ℃, maintaining the temperature for 1 hour at 70 ℃, ensuring that the bisphenol A is completely dissolved, heating the mixture to 100 ℃ under normal pressure to perform reflux reaction, maintaining the temperature at 100 ℃ for 4 hours, performing vacuum dehydration until the temperature is raised to 190 ℃, and cooling the mixture to obtain the bisphenol A modified phenolic resin.
Comparative example 1
The protective film resin for the mobile phone glass is prepared by the following method:
the protective film resin a was prepared by dissolving the phenol resin thermoplastic resin prepared in example 2 in an ethanol solution, adding an alkaline catalyst (hexamethyltetramine), heating to 70 ℃ and reacting for 3 hours.
Comparative example 2
The protective film resin for the mobile phone glass is prepared by the following method:
taking the silane-modified phenol resin prepared in step S2 in example 1, referring to step S3 in example 1, the resin was dissolved in an ethanol solvent, and an alkaline silane catalyst (alkaline silane resin) and an accelerator (epoxy resin and urethane resin) were added to the solution, and the mixture was heated to 70 ℃ to react for 3 hours, thereby preparing a protective film resin B.
Comparative example 3
The protective film resin for the mobile phone glass is prepared by the following method:
the bisphenol a-modified phenol resin obtained in example 3 was dissolved in an ethanol solvent, and an alkaline catalyst (alkaline silane resin) was added thereto, and the temperature was raised to 70 ℃ to react for 3 hours, thereby obtaining a protective film resin C.
Examples of the experiments
The protective film resin A, B, C prepared above was uniformly coated on a cell phone glass lens, and after drying, the adhesion and cleaning removal rate were compared, and the results are shown in the following table.
TABLE 1 adhesion and cleaning Rate results
Note: and 3B represents: a small portion of the sheet is separated along the edge portion of the square and the intersection of the squares. Squares with 5% -15% area are affected.
4B represents: there was little coating separation at the grid intersections and less than 5% of the area was affected.
5B represents: the edges of the cuts were smooth with no square separation.
The cleaning conditions of the alkaline cleaning are as follows: washing with 10% NaOH (sodium hydroxide) water solution at 30 deg.C and normal temperature
The above results show that the protective film resin B has the best adhesion and the alkaline cleaning rate is excellent, indicating that it can be completely removed under alkaline conditions.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the silane modified resin is characterized by comprising the following steps:
s1: taking a phenol raw material shown as a general formula I and an aldehyde raw material shown as a general formula II, and carrying out polymerization reaction to obtain a thermoplastic phenolic resin;
wherein: r1, R2, R3 are independently optionally selected from: hydrogen, linear or branched C1-C18 alkyl, linear or branched C1-C18 alkylbenzene;
H2Cn＝O
II
wherein: n is selected from: an integer of between 1 and 10, and,
(CH2) n represents a linear or branched alkyl group;
s2: adding silane resin into the thermoplastic phenolic resin, and carrying out silane primary polymerization reaction to obtain silane modified phenolic resin;
s3: adding an alkaline silane catalyst and an accelerant into the silane modified phenolic resin to carry out silane secondary polymerization reaction, thus obtaining the silane modified resin.
2. The method according to claim 1, wherein in the step of S1, the phenolic material is selected from the group consisting of: at least one of phenol, bisphenol a, bisphenol F and bisphenol S, the aldehyde raw material being selected from the group consisting of: at least one of formaldehyde, paraformaldehyde, trioxymethylene, and furfural.
3. The method for preparing a silane-denatured resin according to claim 1, characterized in that the silane resin is selected from: a methoxy-or ethoxy-containing silane compound; the basic silane catalyst is selected from: a silane compound containing an amino functional group.
4. The method for producing the silane-denatured resin according to claim 1, wherein the molar ratio of the phenolic raw material to the aldehyde raw material is 1: 0.3-2; the molar ratio of the silane resin to the phenolic raw material is 1: 0.01-0.1; the molar ratio of the basic silane catalyst to the phenolic raw material is 1: 0.01-0.5.
5. The method according to claim 1, wherein a solvent is further added in the step of S3, and the molar ratio of the solvent to the aldehyde raw material is 1: 0.1-0.9.
6. The method for preparing the silane-denatured resin according to claim 1, wherein the solvent is an alcohol or ketone solvent.
7. The method for producing the silane-denatured resin according to any one of claims 1 to 6, wherein the accelerator is selected from the group consisting of: leveling agents, antioxidants, epoxy resins and polyurethanes.
8. The method for producing the silane-denatured resin according to any one of claims 1 to 6, wherein in the step of S1, the polymerization reaction conditions are: the pressure is normal pressure or negative pressure, the temperature is 50-210 ℃, and the time is 0.5-10 hours;
in the step S2, adding silane resin after the temperature is reduced to 140-190 ℃, wherein the conditions of the silane primary polymerization reaction are as follows: the pressure is normal pressure or negative pressure, the temperature is 150-;
in the step S3, the conditions of the silane secondary polymerization reaction are as follows: the temperature is 60-90 ℃ and the time is 1-4 hours.
9. A silane-denatured resin produced by the production method described in any one of claims 1 to 8.
10. Use of the silane-denatured resin of claim 9 in the processing of glass for cellular phones.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1784462A (en) * | 2003-05-28 | 2006-06-07 | 茵迪斯佩克化学公司 | Silane-modified phenolic resins and applications thereof |
| CN104610521A (en) * | 2014-12-30 | 2015-05-13 | 广州市白云化工实业有限公司 | Silane modified phenolic resin and preparation method thereof |
| CN107955328A (en) * | 2017-12-27 | 2018-04-24 | 珠海邦瑞合成材料有限公司 | A kind of low-temperature fast-curing thermoplasticity powder phenolic resin for color resin grinding tool and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1784462A (en) * | 2003-05-28 | 2006-06-07 | 茵迪斯佩克化学公司 | Silane-modified phenolic resins and applications thereof |
| CN104610521A (en) * | 2014-12-30 | 2015-05-13 | 广州市白云化工实业有限公司 | Silane modified phenolic resin and preparation method thereof |
| CN107955328A (en) * | 2017-12-27 | 2018-04-24 | 珠海邦瑞合成材料有限公司 | A kind of low-temperature fast-curing thermoplasticity powder phenolic resin for color resin grinding tool and preparation method thereof |
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