CN104592916B - A kind of making method of boron modified phenolic resin sizing agent - Google Patents
A kind of making method of boron modified phenolic resin sizing agent Download PDFInfo
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- CN104592916B CN104592916B CN201510000866.7A CN201510000866A CN104592916B CN 104592916 B CN104592916 B CN 104592916B CN 201510000866 A CN201510000866 A CN 201510000866A CN 104592916 B CN104592916 B CN 104592916B
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- polyborosiloxane
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Abstract
The present invention relates to a kind of making method of boron modified phenolic resin sizing agent, comprise following steps: step one: synthesis polyborosiloxane (PBSH); Step 2: synthesis modification resol; Step 3: prepare boron modified phenolic resin sizing agent.Polyborosiloxane method condition is prepared comparatively gentle in boron modified phenolic resin sizing agent of the present invention, simple to operate, without harmful gas generation, environmental protection, gained polyborosiloxane resistance to elevated temperatures is excellent, containing a large amount of terminal hydroxy group, as properties-correcting agent, high thermal resistance and the cohesive strength of resol being improved simultaneously, providing a kind of feasible method for preparing thermostable phenolic resin sizing agent.
Description
Technical field
The present patent application is on 08 27th, 2013 applying date, and application number is: 201310377320.4, the divisional application of the application for a patent for invention that name is called " a kind of making method of boron modified phenolic resin sizing agent ".The invention belongs to chemical field, particularly relate to a kind of making method utilizing polyborosiloxane and modified phenolic resins synthetic adhesive.
Background technology
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, people have carried out large quantity research to its modification, to improve its thermotolerance and cohesive strength.
Polyborosiloxane (PBS) 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 PBSH, the following technological line of main employing prepares PBSH at present: in nitrogen atmosphere, first carry out bulk reaction by two halosilanes and boric acid, add quinol solution afterwards and continue reaction, obtain PBSH(expense ease big, coatings industry .1991,3,8).In above-mentioned route, there is following problem: wherein adopt halosilanes and acid reaction, generate the HCl gas having pungent odour, there is very high corrodibility.
Summary of the invention
The present invention devises a kind of making method of boron modified phenolic resin sizing agent, its object is to provide high temperature resistant altogether, the sizing agent of high bond strength, improves, customer service the problems of the prior art to the preparation method of polyborosiloxane (PBSH) meanwhile.
To achieve these goals, present invention employs following scheme:
A kind of boron modified phenolic resin sizing agent, comprises following steps:
Step one: synthesis polyborosiloxane (PBSH);
Step 2: synthesis modification resol;
Step 3: prepare boron modified phenolic resin sizing agent.
Described step one joins in organic solvent by organo-siloxane and boric acid, under catalyzer existent condition, is progressively warmed up to 200 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, reaction 1-5h; Then add polyphenol, reaction 4-10h, after water pump Depressor response 1.5 ~ 3h, obtains polyborosiloxane (PBSH);
Described step 2 gets an acidic catalyst of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 1-4h is reacted under the condition of 125 DEG C, after cooling down, add the basic catalyst of 1.5 weight parts, the organic solvent of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins;
Described step 3 to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 1-6:10, obtains boron modified phenolic resin tackiness agent.
Organo-siloxane described in step one: boric acid: the mol ratio of polyphenol is 1:1 ~ 2:0.25 ~ 1, catalyst levels is 1 ~ 2 ‰ of monomer total mass.
Organo-siloxane described in step one is the mixture that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2.
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.
An acidic catalyst described in step 2 is the tosic acid of 25wt%, and described basic catalyst is the ammoniacal liquor of 20wt%, and described organic solvent is vinylbenzene.
The mass ratio of polyborosiloxane described in step 3 and modified phenolic resins is 2-5:10.
The making method of this boron modified phenolic resin sizing agent has following beneficial effect:
1, 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.
2, 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.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
Step one: mixture phenyltrimethoxysila,e and methyltrimethoxy silane made according to weight fraction 1:2 and boric acid join in diethylene glycol dimethyl ether, under tin protochloride existent condition, progressively be warmed up to 200 DEG C from 90 DEG C in nitrogen atmosphere in lower 3 hours, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, and catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 2h is reacted under the condition of 125 DEG C, after cooling down, add the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins;
Step 3: to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain and mix by the mass ratio of 2:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 2
Step one: mixture phenyltrimethoxysila,e and methyltrimethoxy silane made according to weight fraction 1:2 and boric acid join in dioxane, under tin protochloride existent condition, progressively be warmed up to 200 DEG C from 90 DEG C in nitrogen atmosphere in lower 3 hours, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, and catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 2h is reacted under the condition of 125 DEG C, after cooling down, add the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins;
Step 3: to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain and mix by the mass ratio of 3:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 3
Step one: mixture phenyltrimethoxysila,e and methyltrimethoxy silane made according to weight fraction 1:2 and boric acid join in dioxane, under titanium tetrachloride existent condition, progressively be warmed up to 200 DEG C from 90 DEG C in nitrogen atmosphere in lower 3 hours, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, and catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 2h is reacted under the condition of 125 DEG C, after cooling down, add the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins;
Step 3: to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain and mix by the mass ratio of 4:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 4
Step one: mixture phenyltrimethoxysila,e and methyltrimethoxy silane made according to weight fraction 1:2 and boric acid join in diethylene glycol dimethyl ether, under Indian red existent condition, progressively be warmed up to 200 DEG C from 90 DEG C in nitrogen atmosphere in lower 3 hours, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, and catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 2h is reacted under the condition of 125 DEG C, after cooling down, add the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins;
Step 3: to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain and mix by the mass ratio of 5:10, obtain boron modified phenolic resin tackiness agent.
Polyphenol in above-described embodiment 1-4 has all selected Resorcinol, when all the other conditions are substantially identical, only change the reaction ratio of polyborosiloxane and modified phenolic resins, 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 modified phenolic resins mix by the mass ratio of 4:10 is maximum.
Above in conjunction with the 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 (1)
1. a making method for boron modified phenolic resin sizing agent, comprises the following steps:
Step one: synthesis polyborosiloxane; Step 2: synthesis modification resol; Step 3: prepare boron modified phenolic resin sizing agent; Described step one joins in organic solvent by organo-siloxane and boric acid, under catalyzer existent condition, is progressively warmed up to 200 DEG C in nitrogen atmosphere in lower 3 hours from 90 DEG C, reaction 1-5h; Then add polyphenol, reaction 4-10h, after water pump Depressor response 1.5 ~ 3h, obtains polyborosiloxane; Organo-siloxane described in step one: boric acid: the mol ratio of polyphenol is 1:1 ~ 2:0.25 ~ 1, catalyst levels is 1 ~ 2 ‰ of monomer total mass; Organo-siloxane described in step one is the mixture that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2; Solvent described in step one is dioxane; Catalyzer described in step one is any one in tin protochloride, titanium tetrachloride, Indian red; Described step 2 gets an acidic catalyst of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, 1-4h is reacted under the condition of 125 DEG C, after cooling down, add the basic catalyst of 1.5 weight parts, the organic solvent of 12 weight parts and the formaldehyde of 18 weight parts, react at the dehydrated under vacuum of 0.6KPa, after transparent, obtain modified phenolic resins; Described step 3 to get in step one modified phenolic resins that obtained polyborosiloxane and step 2 obtain to mix by the mass ratio of 1-6:10, obtains boron modified phenolic resin tackiness agent; An acidic catalyst described in step 2 is the tosic acid of 25wt%, and described basic catalyst is the ammoniacal liquor of 20wt%, and described organic solvent is vinylbenzene; The mass ratio of polyborosiloxane described in step 3 and modified phenolic resins is 2-5:10.
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| CN201510000866.7A CN104592916B (en) | 2013-08-27 | 2013-08-27 | A kind of making method of boron modified phenolic resin sizing agent |
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| CN201310377320.4A CN103468182B (en) | 2013-08-27 | 2013-08-27 | Preparation method of boron modified phenolic resin adhesive |
| CN201510000866.7A CN104592916B (en) | 2013-08-27 | 2013-08-27 | A kind of making method of boron modified phenolic resin sizing agent |
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| CN201510000880.7A Active CN104592918B (en) | 2013-08-27 | 2013-08-27 | A kind of making method of boron modified phenolic resin sizing agent |
| CN201310377320.4A Active CN103468182B (en) | 2013-08-27 | 2013-08-27 | Preparation method of boron modified phenolic resin adhesive |
| CN201510000868.6A Active CN104592917B (en) | 2013-08-27 | 2013-08-27 | A kind of making method of boron modified phenolic resin sizing agent |
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| CN104630935B (en) * | 2015-03-16 | 2016-06-29 | 山东莱芜润达新材料有限公司 | A kind of preparation method of high-strength composite resin fiber |
| CN104892009B (en) * | 2015-05-13 | 2016-09-28 | 武汉科技大学 | A kind of high volume stability does not burn modified resin of slide plate and preparation method thereof |
| CN105837770B (en) * | 2016-05-09 | 2018-01-02 | 盐城仁创砂业科技有限公司 | A kind of Modification Phenol-formaldehyde Resin for Casting and preparation method thereof |
| CN106543390B (en) * | 2016-10-21 | 2018-10-26 | 沈阳化工大学 | A kind of tetrahydroxy polyhedral silsesquioxane heat-resistant phenolic resins preparation method |
| CN109867965A (en) * | 2019-03-26 | 2019-06-11 | 华东理工大学 | A kind of high-temperature-resisting silicon rubber material and the preparation method and application thereof |
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| CN1844179A (en) * | 2006-03-14 | 2006-10-11 | 同济大学 | Process for in-situ preparation of nano silicon dioxide and boron modified phenol-formaldehyde resin nano composites |
| CN101693821A (en) * | 2009-10-16 | 2010-04-14 | 江苏苏嘉集团新材料有限公司 | Boron modified phenolic resin binder for refractory materials |
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
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| KR20100137440A (en) * | 2008-03-04 | 2010-12-30 | 다우 코닝 코포레이션 | Borosiloxane composition, borosiloxane adhesive, coated and laminated substrates |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844179A (en) * | 2006-03-14 | 2006-10-11 | 同济大学 | Process for in-situ preparation of nano silicon dioxide and boron modified phenol-formaldehyde resin nano composites |
| CN101693821A (en) * | 2009-10-16 | 2010-04-14 | 江苏苏嘉集团新材料有限公司 | Boron modified phenolic resin binder for refractory materials |
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
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| CN103468182B (en) | 2014-11-26 |
| CN104592918B (en) | 2016-02-03 |
| CN104592917A (en) | 2015-05-06 |
| CN104592917B (en) | 2016-02-03 |
| CN104592918A (en) | 2015-05-06 |
| CN103468182A (en) | 2013-12-25 |
| CN104592916A (en) | 2015-05-06 |
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Effective date of registration: 20170426 Address after: 523443 Guangdong province Dongguan City Dongkeng Town Road No. 26 on the two corners of a building society Patentee after: Dongguan Derun adhesive tape Co., Ltd. Address before: Jiangdong District 315040 Zhejiang city of Ningbo Province Ning Chuan Lu gold homes 4 Building No. 18 Room 606 Patentee before: Li Kegong |