CN105131877A - Silane modified phenolic resin adhesive - Google Patents
Silane modified phenolic resin adhesive Download PDFInfo
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- CN105131877A CN105131877A CN201510517988.3A CN201510517988A CN105131877A CN 105131877 A CN105131877 A CN 105131877A CN 201510517988 A CN201510517988 A CN 201510517988A CN 105131877 A CN105131877 A CN 105131877A
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- silane
- phenolic resin
- chavicol
- modified phenolic
- resin adhesive
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Abstract
A silane modified phenolic resin adhesive has a preparation method comprising the steps: firstly, adding silane and allylphenol in an organic solvent, stirring evenly, then slowly heating up in a nitrogen atmosphere, during the period of the temperature of 30-50 DEG C, adding a prepared chloroplatinic acid isopropanol solution in batches, continuing reaction for 2-4 hours at the temperature of 70 DEG C, when a sample is taken for measurement to obtain the allyl double bond content being 0, finishing the reaction, carrying out reduced pressure removal of the solvent, then adding an alkali catalyst, heating and stirring, slowly dropwise adding aldehyde under the condition of the temperature of 40-50 DEG C, controlling the dropwise adding time to be within 30 minutes-45 minutes, continuing to heat up to 60-80 DEG C, carrying out heat preservation for 25-40 minutes, continuing to heat to 80-100 DEG C, keeping reflux for 1-3 hours, after completion of reflux, starting to cool, when the temperature drops to 50-60 DEG C, adding an ethanol solvent, stirring for 30-40 minutes, forming a transparent solution, cooling, and then discharging and molding. The prepared silane modified phenolic resin is uniform and stable and has no poor compatibility and other problems; and the prepared adhesive after curing has excellent water resistance, toughness, aging resistance and oxidation resistance.
Description
Technical field
The present invention relates to a kind of silane-modified phenolic resin adhesive, belong to phenolic resin adhesive technical field.
Background technology
Resol is the class organic synthetic resin be made up through condensation reaction of phenol or its homologue and aldehydes.It is as one of three large resins (epoxy resin, resol, unsaturated polyester resin), because having good electrical insulation capability, mechanical property, ablation resistance, corrosion resistance nature and higher thermotolerance and good water tolerance, be widely used in the aspects such as electric, automobile making and mechanical industry.The character of phenolic resin self limits its application in a lot of field, and the rigidity aromatic ring that the methylene radical as closely piled up in its structure connects, makes resol show very large fragility; And there is phenolic hydroxyl group and the methylene radical of easily oxidation, reduce thermotolerance and the scale resistance of resol.In order to meet more and more higher performance requirement, the modification of resol becomes the large focus studied now.
Mainly concentrating on silicone resin or silicoorganic compound and resol physical blending about Effect of Organosilicon-modified Phenol-formaldehyde Resin realizes modification object at present, resin prepared by these method of modifying also exists poor compatibility, unstable product quality, and structure and molecular weight are all uncertain, drastically influence the mechanical property of goods.
Publication number CN102675572B discloses the application of a kind of organosilicon modifier in modified phenolic resins, improves the thermotolerance of matrix material, mechanicalness and insulating property; Publication number CN101724226B discloses a kind of hyper-branched silicone resin of silicone active functional group, has carried out modification to thermosetting resin, improves toughness and thermostability.But in above-mentioned operational path, there is severe reaction conditions, higher to the technical requirements of equipment and personnel.Have no the report of silane-modified resol for the preparation of sizing agent at present.
Summary of the invention
The object of the invention is, according to existing sizing agent Problems existing, the present invention discloses a kind of preparation method of silane-modified phenolic resin adhesive, prepared silane-modified phenolic resin adhesive structure-controllable, product is stablized, and after resin solidification, thermotolerance, scale resistance, flame retardant properties, water tolerance, toughness are greatly improved.
Realizing technical scheme of the present invention is:
A kind of silane-modified phenolic resin adhesive of the present invention, its preparation method is as follows: first join in organic solvent by silane and chavicol, after stirring, slowly heat up under nitrogen atmosphere, add the chloroplatinic acid-catalysis agent solution prepared 30 to 50 DEG C of periods in batches, reaction 2-4 hour is continued at 70 DEG C, it is to be sampled when to record allyl double bonds content be 0, reaction terminates, removal of solvent under reduced pressure, then alkaline catalysts is added, heated and stirred, aldehyde is dripped at leisure under the condition of 40-50 DEG C, time for adding controls in 30 minutes-45 minutes, and continue to be warmed up to 60-80 DEG C, insulation 25-40 minute, continue to be heated to 80-100 DEG C, keep backflow 1-3 hour, cooling is started after backflow, when temperature is down to 50-60 DEG C, add alcohol solvent, stir 30-40 minute, form clear solution, after cooling, discharging is shaping.
This reaction principle chemical equation is expressed as follows:
Described silane is the one in Trimethoxy silane, triethoxyl silane, dimethoxymethylsilane or diethoxymethylsilane; Described chavicol is the one in o-allyl phenol, a chavicol or p-allylphenol; The mol ratio of described silane and chavicol is 1.0-1.5:1.0.
Described organic solvent is the one in toluene, dimethylbenzene or acetone, and its quality is 1.2-3 times of silane and chavicol quality sum.
Platinic chloride consumption in described isopropyl alcohol solution of chloroplatinic acid is the 0.01%-0.05% of chavicol quality, and the quality of Virahol is 1000-5000 times of Platinic chloride weight.
Described alkaline catalysts is the one in potassium hydroxide, sodium hydroxide, hydrated barta or oxyammonia, and its quality is the 10-25% of chavicol quality.
Described aldehyde is the one in formaldehyde, acetaldehyde or paraformaldehyde, and the mass ratio of its aldehyde and chavicol is 1.0-5.4:1.0.
Compared with prior art, beneficial effect is embodied in technical solution of the present invention: organoalkoxysilane is introduced phenols by Si―H addition reaction by the present invention, and then and formaldehyde reaction, there is not the problems such as poor compatibility in prepared silane-modified resol stable homogeneous; And be a controlled process in resin structure synthesis.Sizing agent prepared by the present invention solidifies rear water tolerance, toughness, ageing-resistant, oxidation resistent susceptibility is excellent.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
The silane-modified resol of the present embodiment obtains according to following steps:
By 0.15mol(24.6g) triethoxyl silane and 0.10mol(13.42g) o-allyl phenol join in 46g toluene, after stirring, slowly heat up under nitrogen atmosphere, add Platinic chloride and the 1.35g aqueous isopropanol of the 0.00135g prepared 30 to 50 DEG C of periods in batches, reaction is continued 2 hours at 70 DEG C, it is to be sampled when to record allyl double bonds content be 0, reaction terminates, removal of solvent under reduced pressure, then 1.35g sodium hydroxide catalyst is added, heated and stirred, 13.42g formaldehyde is dripped at leisure under the condition of 40 DEG C, time for adding controls in 30 minutes-45 minutes, and continue to be warmed up to 60 DEG C, be incubated 25 minutes, continue to be heated to 80 DEG C, keep backflow 1 hour, cooling is started after backflow, when temperature is down to 50 DEG C, add ethanol, stir 30-40 minute, form clear solution, after cooling, discharging is shaping.
Embodiment 2
The silane-modified resol of the present embodiment obtains according to following steps:
By 0.1mol(12.26) Trimethoxy silane and 0.1mol(13.42g) between chavicol join in 40g dimethylbenzene, after stirring, slowly heat up under nitrogen atmosphere, add the 0.0067g Platinic chloride and 14g aqueous isopropanol that prepare 30 to 50 DEG C of periods in batches, reaction is continued 4 hours at 70 DEG C, it is to be sampled when to record allyl double bonds content be 0, reaction terminates, removal of solvent under reduced pressure, then 2.68g potassium hydroxide catalyst is added, heated and stirred, 26.87g acetaldehyde is dripped at leisure under the condition of 50 DEG C, time for adding controls in 30 minutes-45 minutes, and continue to be warmed up to 80 DEG C, be incubated 40 minutes, continue to be heated to 100 DEG C, keep backflow 3 hours, cooling is started after backflow, when temperature is down to 60 DEG C, add ethanol, stir 40 minutes, form clear solution, after cooling, discharging is shaping.
Embodiment 3
The silane-modified resol of the present embodiment obtains according to following steps:
By 0.14mol(14.84g) dimethoxymethylsilane and 0.10mol(13.42g) p-allylphenol joins in 84g acetone, after stirring, slowly heat up under nitrogen atmosphere, add the 0.0065g Platinic chloride and 33g aqueous isopropanol that prepare 30 to 50 DEG C of periods in batches, reaction is continued 3 hours at 70 DEG C, it is to be sampled when to record allyl double bonds content be 0, reaction terminates, removal of solvent under reduced pressure, then 3.3g ammonium hydroxide catalyzer is added, heated and stirred, 72.46g paraformaldehyde is dripped at leisure under the condition of 45 DEG C, time for adding controls in 30 minutes-45 minutes, and continue to be warmed up to 70 DEG C, be incubated 30 minutes, continue to be heated to 90 DEG C, keep backflow 2 hours, cooling is started after backflow, when temperature is down to 60 DEG C, add ethanol, stir 40 minutes, form clear solution, after cooling, discharging is shaping.
Claims (6)
1. a silane-modified phenolic resin adhesive, it is characterized in that: described sizing agent is obtained by following steps: first join in organic solvent by silane and chavicol, after stirring, slowly heat up under nitrogen atmosphere, add the isopropyl alcohol solution of chloroplatinic acid prepared 30 to 50 DEG C of periods in batches, reaction 2-4 hour is continued at 70 DEG C, it is to be sampled when to record allyl double bonds content be 0, reaction terminates, removal of solvent under reduced pressure, then alkaline catalysts is added, heated and stirred, aldehyde is dripped at leisure under the condition of 40-50 DEG C, time for adding controls in 30 minutes-45 minutes, and continue to be warmed up to 60-80 DEG C, insulation 25-40 minute, continue to be heated to 80-100 DEG C, keep backflow 1-3 hour, cooling is started after backflow, when temperature is down to 50-60 DEG C, add alcohol solvent, stir 30-40 minute, form clear solution, after cooling, discharging is shaping.
2. the silane-modified phenolic resin adhesive of one according to claim 1, is characterized in that: described silane is the one in Trimethoxy silane, triethoxyl silane, dimethoxymethylsilane or diethoxymethylsilane; Described chavicol is the one in o-allyl phenol, a chavicol or p-allylphenol; The mol ratio of silane and chavicol is 1.0-1.5:1.0.
3. the silane-modified phenolic resin adhesive of one according to claim 1, is characterized in that: described organic solvent is the one in toluene, dimethylbenzene or acetone, and its quality is 1.2-3 times of silane and chavicol quality sum.
4. the silane-modified phenolic resin adhesive of one according to claim 1, it is characterized in that: the Platinic chloride consumption in described isopropyl alcohol solution of chloroplatinic acid is the 0.01%-0.05% of chavicol quality, the quality of Virahol is 1000-5000 times of Platinic chloride weight.
5. the silane-modified phenolic resin adhesive of one according to claim 1, is characterized in that: described alkaline catalysts is the one in potassium hydroxide, sodium hydroxide, hydrated barta or oxyammonia, and its quality is the 10-25% of chavicol quality.
6. the silane-modified phenolic resin adhesive of one according to claim 1, is characterized in that: described aldehyde is the one in formaldehyde, acetaldehyde or paraformaldehyde, and the mass ratio of its aldehyde and chavicol is 1.0-5.4:1.0.
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| CN201510517988.3A CN105131877B (en) | 2015-08-24 | 2015-08-24 | A kind of silane-modified phenolic resin adhesive |
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| CN201510517988.3A CN105131877B (en) | 2015-08-24 | 2015-08-24 | A kind of silane-modified phenolic resin adhesive |
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| CN105131877B CN105131877B (en) | 2017-10-10 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754062A (en) * | 2016-03-15 | 2016-07-13 | 东北林业大学 | Low-hydroscopicity phenolic resin insulating gel and preparation method thereof |
| WO2018098923A1 (en) * | 2016-12-02 | 2018-06-07 | 广东生益科技股份有限公司 | Styryl siloxy phenolic resin, preparation method therefor and application thereof |
| CN110102704A (en) * | 2019-05-28 | 2019-08-09 | 沙县宏盛塑料有限公司 | A kind of modification phenolic resin-based precoated sand and preparation method thereof |
| CN110591029A (en) * | 2019-09-30 | 2019-12-20 | 河南工业大学 | Preparation method for synthesizing organic silicon modified phenolic resin by ester exchange method |
| CN113264728A (en) * | 2021-05-12 | 2021-08-17 | 烟台蒙特混凝土有限公司 | High-strength high-toughness concrete and preparation method thereof |
| CN113666956A (en) * | 2021-08-25 | 2021-11-19 | 上海橡实化学有限公司 | Salicylaldimine silane coupling agent, and preparation method and application thereof |
| CN114196024A (en) * | 2022-01-10 | 2022-03-18 | 万华化学集团股份有限公司 | Organic silicon modified phenolic resin and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012025699A1 (en) * | 2010-08-27 | 2012-03-01 | Saint-Gobain Isover | Phenolic resin, method for preparing same, sizing composition for mineral fibers and resulting product |
| CN102675572A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Application of organic silicon modifier in modified thermosetting phenolic resin |
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2015
- 2015-08-24 CN CN201510517988.3A patent/CN105131877B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012025699A1 (en) * | 2010-08-27 | 2012-03-01 | Saint-Gobain Isover | Phenolic resin, method for preparing same, sizing composition for mineral fibers and resulting product |
| CN102675572A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Application of organic silicon modifier in modified thermosetting phenolic resin |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754062A (en) * | 2016-03-15 | 2016-07-13 | 东北林业大学 | Low-hydroscopicity phenolic resin insulating gel and preparation method thereof |
| CN105754062B (en) * | 2016-03-15 | 2018-01-23 | 东北林业大学 | A kind of low water absorbable phenolic resin insulating cement |
| WO2018098923A1 (en) * | 2016-12-02 | 2018-06-07 | 广东生益科技股份有限公司 | Styryl siloxy phenolic resin, preparation method therefor and application thereof |
| CN108148162A (en) * | 2016-12-02 | 2018-06-12 | 广东生益科技股份有限公司 | A kind of styryl siloxy phenolic resin and its preparation method and application |
| CN108148162B (en) * | 2016-12-02 | 2019-09-13 | 广东生益科技股份有限公司 | A kind of styryl siloxy phenolic resin and its preparation method and application |
| CN110102704A (en) * | 2019-05-28 | 2019-08-09 | 沙县宏盛塑料有限公司 | A kind of modification phenolic resin-based precoated sand and preparation method thereof |
| CN110102704B (en) * | 2019-05-28 | 2020-12-18 | 沙县宏盛塑料有限公司 | Modified phenolic resin-based precoated sand and preparation method thereof |
| CN110591029A (en) * | 2019-09-30 | 2019-12-20 | 河南工业大学 | Preparation method for synthesizing organic silicon modified phenolic resin by ester exchange method |
| CN110591029B (en) * | 2019-09-30 | 2021-10-26 | 河南工业大学 | Preparation method for synthesizing organic silicon modified phenolic resin by ester exchange method |
| CN113264728A (en) * | 2021-05-12 | 2021-08-17 | 烟台蒙特混凝土有限公司 | High-strength high-toughness concrete and preparation method thereof |
| CN113666956A (en) * | 2021-08-25 | 2021-11-19 | 上海橡实化学有限公司 | Salicylaldimine silane coupling agent, and preparation method and application thereof |
| CN114196024A (en) * | 2022-01-10 | 2022-03-18 | 万华化学集团股份有限公司 | Organic silicon modified phenolic resin and preparation method and application thereof |
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