CN104559867A - Preparation method of phenolic resin adhesive - Google Patents
Preparation method of phenolic resin adhesive Download PDFInfo
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- CN104559867A CN104559867A CN201410801412.5A CN201410801412A CN104559867A CN 104559867 A CN104559867 A CN 104559867A CN 201410801412 A CN201410801412 A CN 201410801412A CN 104559867 A CN104559867 A CN 104559867A
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- rosin
- phenolic resin
- polyborosiloxane
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract
The invention discloses a preparation method of a phenolic resin adhesive. The preparation method is characterized by comprising the following steps of firstly, synthesizing polyborodiphenysiloxane; secondly, synthesizing rosin-modified phenolic resin; and thirdly, preparing an adhesive. The preparation method for polyborodiphenysiloxane in the phenolic resin adhesive is relatively mild in condition, simple in operation, free of generating harmful gases and environment-friendly; the prepared polyborodiphenysiloxane is excellent in high-temperature resistance; and meanwhile, the rosin-modified phenolic resin is combined with polyborodiphenysiloxane, so that the adhesive with better adhesion performance is provided, and the adhesive has a favorable application prospect.
Description
Technical field
The present patent application is on 08 27th, 2013 applying date, and application number is: 201310377803.4, the divisional application of the application for a patent for invention that name is called " a kind of preparation method of phenolic resin adhesive ".The invention belongs to chemical field, particularly relate to a kind of preparation method of phenolic resin adhesive.
Background technology
Polyborosiloxane has excellent resistance toheat.There are research and utilization boric acid and organosilicon preformed polymer to prepare polyborosiloxane, and use it for the modification of resol, modified resin Residual carbon significantly improves, but the cohesive force of modified phenolic resin adhesive does not significantly improve (Zhang Bin etc., polymer material science and engineering, 2008,152).There is research in polyborosiloxane, introduce Resorcinol structure, obtain polyborosiloxane, the following technological line preparation of main employing at present: application melt-polycondensation, with Resorcinol, modification is carried out to polyborosiloxane, obtain high temperature resistant polyborosiloxane (Zhan Hongwei, Cao Jin, Journal of Functional Polymers .1995,8,439).In above-mentioned route, there is following problem: its severe reaction conditions, need 300 DEG C of high temperature, very high to vacuum level requirements, also very high to the technical requirements of equipment and personnel.
Resol price is very low, raw material has easily been bought, production technique and production unit simple, has become one of indispensable material of industrial sector, and application widely.Pure phenolic aldehyde resin thermal stability and high thermal resistance not high enough, modified, the impelling strength, cementability, physical strength, thermotolerance, flame retardant resistance, dimensional stability, curing speed, moulded manufacturability etc. of resol, be improved respectively.
Summary of the invention
The present invention devises a kind of preparation method of phenolic resin adhesive, its object is to the resol after Abietyl modified to be combined with polyborosiloxane provide a kind of bond properties better sizing agent, meanwhile, the preparation method of polyborosiloxane is improved, overcomes the problems of the prior art.
To achieve these goals, present invention employs following scheme:
A preparation method for phenolic resin adhesive, is characterized in that comprising following steps:
Step one: synthesis polyborosiloxane;
Step 2: synthesis rosin modified phenolic resin;
Step 3: prepare sizing agent.
Described step one joins in organic solvent by organo-siloxane and boric acid, under catalyzer existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add polyphenol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane;
Described step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin;
Described step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.1-1:2, obtains synvaren.
Organo-siloxane described in step one: boric acid: the mol ratio of polyphenol is 1:1 ~ 2:0.25 ~ 1, and catalyst levels is 1 ‰ of monomer total mass.
Organo-siloxane described in step one is vinyltrimethoxy silane.
Solvent described in step one is diethylene glycol dimethyl ether or dioxane.
Catalyzer described in step one is any one in tin protochloride, titanium tetrachloride, Indian red.
Polyphenol described in step one is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
Formaldehyde in rosin condensation Intermediate Preparation described in step 2: 4-dodecylphenol: rosin mol ratio is 5:2:7.
Oxalic acid described in step 2 and toluenesulphonic acids mass ratio are 1:1, and described oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
The mass ratio of polyborosiloxane described in step 3 and rosin modified phenolic resin is 0.3-1:2.
The preparation method of this phenolic resin adhesive has following beneficial effect:
1, the inventive method can complete the preparation of rosin modified phenolic resin and series product at a reactor, decreases facility investment.
2, the present invention is by organo-siloxane and boric acid, polyphenol polycondensation, and synthesis is containing a large amount of terminal hydroxy group and have the polyborosiloxane of excellent heat resistance; After mixing with resol, its thermotolerance and bonding strength can be improved.
3, the present invention prepares polyborosiloxane method mild condition, simple to operate, without harmful gas generation, environmental protection, and gained polyborosiloxane resistance to elevated temperatures is excellent, and overall craft route of the present invention is simple, greatly reduces energy consumption.
4, the present invention does not have by product and waste water and gas to discharge in reaction process, is a kind of production process of environmental protection.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
The preparation method of phenolic resin adhesive of the present invention:
Step one joins in diethylene glycol dimethyl ether by vinyltrimethoxy silane and boric acid, under tin protochloride existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, and tin protochloride consumption is 1 ‰ of monomer total mass.
Step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in rosin condensation Intermediate Preparation: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
Step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.3:2, obtains synvaren.
Embodiment 2
Step one joins in diethylene glycol dimethyl ether by vinyltrimethoxy silane and boric acid, under titanium tetrachloride existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, and titanium tetrachloride consumption is 1 ‰ of monomer total mass.
Step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in rosin condensation Intermediate Preparation: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
Step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.5:2, obtains synvaren.
Embodiment 3
Step one joins in diethylene glycol dimethyl ether by vinyltrimethoxy silane and boric acid, under Indian red existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, and Indian red consumption is 1 ‰ of monomer total mass.
Step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in rosin condensation Intermediate Preparation: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
Step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.6:2, obtains synvaren.
Embodiment 4
Step one joins in dioxane by vinyltrimethoxy silane and boric acid, under titanium tetrachloride existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, and titanium tetrachloride consumption is 1 ‰ of monomer total mass.
Step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in rosin condensation Intermediate Preparation: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
Step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.8:2, obtains synvaren.
Embodiment 5
Step one joins in dioxane by vinyltrimethoxy silane and boric acid, under Indian red existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, and Indian red consumption is 1 ‰ of monomer total mass.
Step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in rosin condensation Intermediate Preparation: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
Step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 1:2, obtains synvaren.
Polyphenol in above-described embodiment 1-5 has all selected pyrocatechol, when all the other conditions are substantially identical, only change the reaction ratio of polyborosiloxane and rosin modified phenolic resin, then to the product obtained in embodiment through gluing, solidification, measure its cohesive strength.Experimental result shows, the cohesive strength of the sizing agent obtained when polyborosiloxane and rosin modified phenolic resin mix by the mass ratio of 0.8:2 is maximum.
Above in conjunction with specific embodiments to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (3)
1. a preparation method for phenolic resin adhesive, comprises following steps: step one: synthesis polyborosiloxane; Step 2: synthesis rosin modified phenolic resin; Step 3: prepare sizing agent; Described step one joins in organic solvent by organo-siloxane and boric acid, under catalyzer existent condition, is progressively warmed up to 140 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, continues reaction 4h; Then add polyphenol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Organo-siloxane described in step one: boric acid: the mol ratio of polyphenol is 1:1 ~ 2:0.25 ~ 1, and catalyst levels is 1 ‰ of monomer total mass; Organo-siloxane described in step one is vinyltrimethoxy silane; Solvent described in step one is diethylene glycol dimethyl ether or dioxane; Catalyzer described in step one is any one in tin protochloride, titanium tetrachloride, Indian red; Described step 2 adds in reactor by rosin, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added reactor; heat to 150 DEG C; pressure brings up to 0.7Mpa, reacts 2 hours, namely obtain rosin condensation intermediate under constant temperature and pressure; Then tetramethylolmethane, triethylamine and dimethyl silicone oil are added the reactor of rosin condensation intermediate, be warmed up to 200 DEG C, controlled by pressure at 0.1Mpa, start agitator and stir, constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Described step 3 to get in step one rosin modified phenolic resin that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 0.1-1:2, obtains synvaren; Oxalic acid described in step 2 and toluenesulphonic acids mass ratio are 1:1, and described oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality; The mass ratio of polyborosiloxane described in step 3 and rosin modified phenolic resin is 0.3-1:2.
2. phenolic resin adhesive according to claim 1, is characterized in that: the polyphenol described in step one is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
3. phenolic resin adhesive according to claim 1, is characterized in that: formaldehyde in the rosin condensation Intermediate Preparation described in step 2: 4-dodecylphenol: rosin mol ratio is 5:2:7.
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| CN105348459A (en) * | 2015-12-11 | 2016-02-24 | 彤程化学（中国）有限公司 | Rosin-modified resorcinol formaldehyde resin and preparation method and application thereof |
| CN115741923A (en) * | 2022-11-24 | 2023-03-07 | 寿光市鲁丽木业股份有限公司 | Anti-corrosion and anti-bacterial bamboo oriented shaving board and preparation method thereof |
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| CN104262559B (en) * | 2014-09-10 | 2016-02-24 | 北京林业大学 | A kind of environment-friendly type rosin modified phenolic resin and preparation method thereof |
| CN107793973A (en) * | 2017-11-29 | 2018-03-13 | 广西众昌树脂有限公司 | Modified phenolic resin adhesive and preparation method thereof |
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| CN101942070A (en) * | 2010-09-03 | 2011-01-12 | 华南理工大学 | Phenolic resin for color offset printing ink and preparation method thereof |
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| CN101805584B (en) * | 2010-03-19 | 2013-05-08 | 东华大学 | Single-component wet cured polyurethane adhesive with high temperature resistance and long opening time and preparation thereof |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
| CN102718940B (en) * | 2012-06-28 | 2013-11-27 | 广州高金技术产业集团有限公司 | High-bonding-strength and high-temperature-resisting phenolic resin modified polyurethane adhesive and preparation method thereof |
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| CN101942070A (en) * | 2010-09-03 | 2011-01-12 | 华南理工大学 | Phenolic resin for color offset printing ink and preparation method thereof |
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| CN105348459A (en) * | 2015-12-11 | 2016-02-24 | 彤程化学（中国）有限公司 | Rosin-modified resorcinol formaldehyde resin and preparation method and application thereof |
| CN115741923A (en) * | 2022-11-24 | 2023-03-07 | 寿光市鲁丽木业股份有限公司 | Anti-corrosion and anti-bacterial bamboo oriented shaving board and preparation method thereof |
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| CN104559868B (en) | 2016-06-22 |
| CN103602298B (en) | 2014-11-26 |
| CN104559866A (en) | 2015-04-29 |
| CN103602298A (en) | 2014-02-26 |
| CN104559868A (en) | 2015-04-29 |
| CN104559867B (en) | 2016-06-22 |
| CN104559866B (en) | 2016-06-22 |
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Effective date of registration: 20191106 Address after: 314100 room 427, No.16 Fuxing Avenue, Xitang Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Xitang Industry Co., Ltd Address before: 322000, building 2, building 1, 2 District, Zhu Cun, Jiangdong village, Jiangdong Street, Zhejiang, Yiwu, China. A Patentee before: Yu Guohong |