CN104650785B - A kind of boron modified phenolic resin sizing agent - Google Patents
A kind of boron modified phenolic resin sizing agent Download PDFInfo
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- CN104650785B CN104650785B CN201510022692.4A CN201510022692A CN104650785B CN 104650785 B CN104650785 B CN 104650785B CN 201510022692 A CN201510022692 A CN 201510022692A CN 104650785 B CN104650785 B CN 104650785B
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Abstract
The present invention relates to a kind of boron modified phenolic resin sizing agent, it is characterized in that comprising 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: 201310377365.1, the divisional application of the application for a patent for invention that name is called " a kind of boron modified phenolic resin sizing agent ".The invention belongs to chemical field, particularly relate to a kind of sizing agent utilizing polyborosiloxane and modified phenolic resins to synthesize.
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 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, is characterized in that comprising 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.
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 boron modified phenolic resin sizing agent, is characterized in that: obtained by 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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| Application Number | Priority Date | Filing Date | Title |
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| CN201310377365.1A CN103525346B (en) | 2013-08-27 | 2013-08-27 | Boron-modified phenolic resin adhesive |
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| CN201310377365.1A Division CN103525346B (en) | 2013-08-27 | 2013-08-27 | Boron-modified phenolic resin adhesive |
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| CN104650785B true CN104650785B (en) | 2015-09-23 |
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| CN201310377365.1A Active CN103525346B (en) | 2013-08-27 | 2013-08-27 | Boron-modified phenolic resin adhesive |
| CN201510022691.XA Active CN104650784B (en) | 2013-08-27 | 2013-08-27 | A kind of boron modified phenolic resin sizing agent |
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| CN104448176B (en) * | 2014-12-22 | 2016-08-17 | 沙县宏盛塑料有限公司 | The preparation method of a kind of phenol-formaldehyde resin modified and the phenol-formaldehyde resin modified prepared by the method |
| 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 |
| CN109734920A (en) * | 2018-12-17 | 2019-05-10 | 烟台德邦科技有限公司 | Preparation method of boron-containing adhesive |
| CN111793455A (en) * | 2020-07-28 | 2020-10-20 | 安徽大松树脂有限公司 | Preparation method of heat-resistant, oil-resistant and flexibility-resistant wood adhesive |
| CN114163593A (en) * | 2022-02-15 | 2022-03-11 | 北京玻钢院复合材料有限公司 | Polyether modified phenolic resin for heavy-load grinding wheel and preparation method thereof |
| CN114835903B (en) * | 2022-04-28 | 2023-03-14 | 北京理工大学 | Boron-containing silsesquioxane and preparation method thereof, modified phenolic resin and preparation method and application thereof |
| CN115322699A (en) * | 2022-07-26 | 2022-11-11 | 成都航天明江科技实业有限公司 | Pressure-sensitive adhesive tape with instant high temperature resistance of 550 DEG C |
Citations (3)
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2254934A1 (en) * | 2008-03-04 | 2010-12-01 | Dow Corning Corporation | Borosiloxane composition, borosiloxane adhesive, coated and laminated substrates |
| CN102627927B (en) * | 2012-03-26 | 2013-12-04 | 黑龙江省科学院石油化学研究院 | Medium temperature curing high temperature resistant phenolic adhesive |
| 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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Patent Citations (3)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 聚硼硅氧烷改性酚醛树脂耐高温胶粘剂的制备及性能;张斌;《高分子材料科学与工程》;20080630;第26卷(第4期);第152-155页 * |
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| CN104650784B (en) | 2015-09-23 |
| CN104650784A (en) | 2015-05-27 |
| CN103525346A (en) | 2014-01-22 |
| CN103525346B (en) | 2014-12-10 |
| CN104650785A (en) | 2015-05-27 |
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Effective date of registration: 20170509 Address after: 511500 Guangdong city of Qingyuan province Fogang County Shek Kok town industrial zone south of Kingboard Industrial Park Patentee after: JIANTAO (FOGANG) LAMINATION BOARD CO.,LTD. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20170509 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION 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 |