CN103468183B - Phenolic resin adhesive - Google Patents
Phenolic resin adhesive Download PDFInfo
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- CN103468183B CN103468183B CN201310377814.2A CN201310377814A CN103468183B CN 103468183 B CN103468183 B CN 103468183B CN 201310377814 A CN201310377814 A CN 201310377814A CN 103468183 B CN103468183 B CN 103468183B
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- phenolic resin
- rosin
- polyborosiloxane
- resin adhesive
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Abstract
The invention relates to a phenolic resin adhesive which is characterized in that a preparation method of the phenolic resin adhesive comprises the following steps that 1, polyborosiloxane is synthesized; 2, rosin modified phenolic resin is synthesized; and 3, the adhesive is prepared. In the phenolic resin adhesive, a preparation method of polyborosiloxane is relatively mild in condition, simple to operate, green and environment-friendly, and does not generate harmful gas; prepared polyborosiloxane is outstanding in high temperature resistance; and the rosin modified phenolic resin is combined with polyborosiloxane, so that the adhesive is better in bonding property, and has a good application prospect.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind 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 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;
Rapid three: 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.
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
Phenolic resin adhesive of the present invention obtains according to following steps:
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 (5)
1. a phenolic resin adhesive, is characterized in that: obtained by 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.
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.
4. phenolic resin adhesive according to claim 1, it is characterized in that: oxalic acid described in step 2 and toluenesulphonic acids mass ratio are 1:1, described oxalic acid and the overall add-on of toluenesulphonic acids are 0.15% of rosin quality.
5. phenolic resin adhesive according to claim 1, is characterized in that: the mass ratio of polyborosiloxane described in step 3 and rosin modified phenolic resin is 0.3-1:2.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310377814.2A CN103468183B (en) | 2013-08-27 | 2013-08-27 | Phenolic resin adhesive |
| CN201510087760.5A CN104694062B (en) | 2013-08-27 | 2013-08-27 | A kind of phenolic resin adhesive |
| CN201510087757.3A CN104694061B (en) | 2013-08-27 | 2013-08-27 | A kind of phenolic resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310377814.2A CN103468183B (en) | 2013-08-27 | 2013-08-27 | Phenolic resin adhesive |
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| CN201510087757.3A Division CN104694061B (en) | 2013-08-27 | 2013-08-27 | A kind of phenolic resin adhesive |
| CN201510087760.5A Division CN104694062B (en) | 2013-08-27 | 2013-08-27 | A kind of phenolic resin adhesive |
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| CN103468183B true CN103468183B (en) | 2015-03-18 |
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Citations (3)
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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 |
| CN102718940A (en) * | 2012-06-28 | 2012-10-10 | 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 |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
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2013
- 2013-08-27 CN CN201310377814.2A patent/CN103468183B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
| CN102718940A (en) * | 2012-06-28 | 2012-10-10 | 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 |
Non-Patent Citations (3)
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| "对苯二酚改性聚二苯基硼硅氧烷的研究";展红卫 等;《功能高分子学报》;19951231;第8卷(第4期);第439-444页 * |
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Effective date of registration: 20160930 Address after: 225510, Ma 986 Road, Jiangyan District, Jiangsu, Taizhou Patentee after: 5ELEM HI-TECH CORPORATION Address before: 322023 Zhejiang, Yiwu Jiangdong Street under the village of Zhu A District, building 2, unit two, building 1 Patentee before: Yu Guohong |