CN103626941B - Bisphenol a modified phenolic resin and preparation method thereof - Google Patents
Bisphenol a modified phenolic resin and preparation method thereof Download PDFInfo
- Publication number
- CN103626941B CN103626941B CN201310530178.2A CN201310530178A CN103626941B CN 103626941 B CN103626941 B CN 103626941B CN 201310530178 A CN201310530178 A CN 201310530178A CN 103626941 B CN103626941 B CN 103626941B
- Authority
- CN
- China
- Prior art keywords
- phenol
- bisphenol
- phenolic resin
- modified phenolic
- dihydroxyphenyl propane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of bisphenol A modified phenolic resin, the polycondensation of advanced line type phenol novolacs, then add dihydroxyphenyl propane and carry out copolyreaction, finally dewater, refiningly to obtain product; Or first obtained line style phenol novolac crude resin, linear bisphenol A phenolic aldehyde crude resin respectively, then the two is mixed, refiningly to obtain product.The present invention effectively can improve intensity and the insulating property of phenolic resin curing thing, excellent product performance.
Description
Technical field
The present invention relates to a kind of bisphenol A modified phenolic resin and preparation method thereof.
Background technology
Line style phenol novolacs, for cast material, insulating material etc., high comprehensive performance, and also price is low, stable performance, therefore applies very extensive.
Improving intensity and the insulating property of cured article, is the basic demand that resol is applied to cast material, insulating material etc.Determine at solidifying agent, strongthener, when construction technology is optimized, from matrix resin, modification is carried out to line style phenol novolacs, to improve its condensate performance, become very necessary.
Summary of the invention
The object of the present invention is to provide a kind of effective intensity of raising phenolic resin curing thing and bisphenol A modified phenolic resin of insulating property and preparation method thereof.
Technical solution of the present invention is:
A kind of bisphenol A modified phenolic resin, is characterized in that: obtained by one of following method:
Method one: the polycondensation of advanced line type phenol novolacs, then add dihydroxyphenyl propane and carry out copolyreaction, finally dewaters, refiningly to obtain product;
Method two: obtained line style phenol novolac crude resin, linear bisphenol A phenolic aldehyde crude resin respectively, then the two is mixed, refiningly to obtain product.
A preparation method for bisphenol A modified phenolic resin, is characterized in that: comprise the following steps:
Step 1. dihydroxyphenyl propane dissolves
Dihydroxyphenyl propane is dropped into reactor one, then add solvent, the weight ratio of solvent and dihydroxyphenyl propane is 0.5 ~ 5:1, stirs lower dissolving, for subsequent use;
The building-up reactions of step 2. line style phenol novolacs
Phenol is dropped into reactor two with aldehyde after mixing, and the mol ratio of aldehyde and phenol is 0.1 ~ 1.0:1, and add acid catalyst, the amount of catalyzer is 0.01 ~ 3% of phenol weight, carries out the certain hour reaction of 60 ~ 180 minutes under stirring at 80 ~ 110 DEG C;
The building-up reactions of step 3. bisphenol A modified phenolic resin
After step 2 terminates, in reactor two, add step 1 product, the weight ratio that step 1 product and step 2 product amount to into solid resin is 0.2 ~ 2.0:1, carries out the reaction of 60 ~ 180 minutes under stirring at 90 ~ 100 DEG C;
Refining of step 4. bisphenol A modified phenolic resin
Step 3 adds NaOH and neutralizes, be neutralized to PH scope 6 ~ 8 after terminating, and heats up and removes the water of reaction generation, when reaching 100 ~ 110 DEG C, uses filter paper filtering, and the salt that removing neutralization generates obtains bisphenol A modified phenolic resin crude resin;
The purification of step 5. bisphenol A modified phenolic resin
Step 4 is warming up to 150 ~ 170 DEG C, desolvation and residual phenol after terminating, and keep 30 ~ 120 minutes under vacuum tightness is absolute pressure 2 ~ 20KPa, except after vacuum, blowing obtains sample.
A preparation method for bisphenol A modified phenolic resin, is characterized in that: comprise the following steps:
Step 1. dihydroxyphenyl propane dissolves
Dihydroxyphenyl propane is dropped into reactor one, then add solvent, the ratio of solvent and dihydroxyphenyl propane is 0.5 ~ 5:1, dissolves under stirring at 50 ~ 100 DEG C, for subsequent use;
The building-up reactions of step 2. linear bisphenol A phenolic resin
After step 1 terminates, add aldehyde toward reactor one, the weight ratio of aldehyde and phenol is 0.05 ~ 0.5:1, and add acid catalyst, the amount of catalyzer is 0.01 ~ 3% of phenol weight, carries out the reaction of 60 ~ 180 minutes under stirring at 90 ~ 100 DEG C;
Refining of step 3. linear bisphenol A phenolic resin
Step 2 adds NaOH and neutralizes, be neutralized to PH scope 6 ~ 8 after terminating, and heats up and removes the water of reaction generation, when reaching 100-110 DEG C, uses filter paper filtering, and the salt that removing neutralization generates obtains linear bisphenol A phenolic resin crude resin, for subsequent use;
The building-up reactions of step 4. line style phenol novolacs
Drop into reactor two after being mixed with aldehyde by phenol, the mol ratio of aldehyde and phenol is 0.1 ~ 1.0:1, and add acid catalyst, the amount of catalyzer is 0.01 ~ 3% of phenol weight, carries out the reaction of 60 ~ 180 minutes under stirring at 80 ~ 110 DEG C;
Refining of step 5. line style phenol novolacs
Step 4 adds NaOH and neutralizes, be neutralized to PH scope 6 ~ 8 after terminating, and heats up and removes the water of reaction generation, when reaching 100 ~ 110 DEG C, uses filter paper filtering, and the salt that removing neutralization generates obtains line style phenol novolacs crude resin, for subsequent use;
The mixing of step 6. bisphenol A modified phenolic resin and purification
After step 5 terminates, line style phenol novolacs crude resin is mixed with linear bisphenol A phenolic resin crude resin, be warming up to 150 ~ 170 DEG C of desolvations and residual phenol, keep 30 ~ 120 minutes under vacuum tightness is absolute pressure 2 ~ 20KPa, except after vacuum, blowing obtains sample.
Described dihydroxyphenyl propane is the one in the polymeric carbon grade of purity more than 99.8% and epoxy grade bis phenol A, dihydroxyphenyl propane mother liquor, dihydroxyphenyl propane cracking residue; Solvent is the one in toluene, dimethylbenzene, ethylene glycol, propyl carbinol; Phenol is the one in the alkylphenol of phenol, ortho position or para-orientation; Aldehyde is the one in formaldehyde, acetaldehyde, paraformaldehyde; Acid catalyst is the one in oxalic acid, hydrochloric acid, phosphoric acid.
Dihydroxyphenyl propane mother liquor is the intermediate product of industrial production dihydroxyphenyl propane, when referring to industrial production dihydroxyphenyl propane, and the mother liquor (coenocytism content 4.2%, these are only typical value for mononuclear structure content 9.3%, dual-core architecture content 86.5%) after fractional crystallization dihydroxyphenyl propane.
Dihydroxyphenyl propane cracking residue is the by product of industrial production dihydroxyphenyl propane, when referring to industrial production dihydroxyphenyl propane, catalytic pyrolysis is carried out to dihydroxyphenyl propane mother liquor, reclaim bottom product (the mononuclear structure content 3.6% after phenol and isopropenyl phenol, double-core part-structure 23.2%, coenocytism content 73.2%, these are only typical value).
Illustrate: mononuclear structure refers to that phenol, isopropenyl phenol, C-3 phenol etc. belong to mononuclear structure containing a benzene ring structure in molecule;
Dual-core architecture refers to containing two benzene ring structures in molecule, dihydroxyphenyl propane and 2,4 isomer and 2, and 2 isomer etc. belong to dual-core architecture;
Coenocytism refers to that triphenol, four phenol etc. belong to coenocytism containing multiple benzene ring structure in molecule.
The present invention effectively can improve intensity and the insulating property of phenolic resin curing thing, excellent product performance.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the gas phase gel chromatography figure of sample one.
Fig. 2 is the gas phase gel chromatography figure of sample two.
Fig. 3 is the gas phase gel chromatography figure of sample three.
Fig. 4 is the gas phase gel chromatography figure of sample four.
Embodiment
Embodiment 1
Take dihydroxyphenyl propane cracking residue 100 parts of weight, drop into reactor one, add toluene 100 parts of weight, stir, be heated to 80 DEG C of dissolvings, for subsequent use.Take phenol 100 parts of weight, drop into reactor two, add 37% formalin, 51 parts of weight, add oxalic acid 0.8 part of weight, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 120 minutes.Add the resin solution in reactor one toward reactor two, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 90 minutes.Slowly add the neutralization of the 10%NaOH aqueous solution, until reactor two resin solution PH reaches the scope of 6 ~ 8.Heat up dehydration to 105 DEG C, uses Büchner funnel suction filtration, the salt that removing neutralization generates.Heat up, vacuumize and remove toluene and phenol, at 160 ± 5 DEG C, keep 60 minutes under 10 ± 5KPa.Blowing, obtained sample 1.
Embodiment 2
Take dihydroxyphenyl propane mother liquor 100 parts of weight, drop into reactor one, add propyl carbinol 100 parts of weight, stir, be heated to 80 DEG C of dissolvings, for subsequent use.Take phenol 100 parts of weight, drop into reactor two, add 37% formalin, 72 parts of weight, add oxalic acid 0.8 part of weight, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 60 minutes.Add the resin solution in reactor one toward reactor two, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 120 minutes.Slowly add the neutralization of the 10%NaOH aqueous solution, until reactor two resin solution PH reaches the scope of 6 ~ 8.Heat up dehydration to 105 DEG C, uses Büchner funnel suction filtration, the salt that removing neutralization generates.Heat up, vacuumize and remove toluene and phenol, at 160 ± 5 DEG C, keep 60 minutes under 10 ± 5KPa.Blowing, obtained sample 2.
Embodiment 3
Take dihydroxyphenyl propane (polymeric carbon grade) 100 parts of weight, drop into reactor one, add propyl carbinol 100 parts of weight, stir, be heated to 80 DEG C of dissolvings, add 37% formalin, 21 parts of weight, add oxalic acid 0.8 part of weight, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 180 minutes.Slowly add the neutralization of the 10%NaOH aqueous solution, until reactor one resin solution PH reaches the scope of 6 ~ 8.Heat up dehydration to 105 DEG C, uses Büchner funnel suction filtration, the salt that removing neutralization generates, for subsequent use.Take phenol 100 parts of weight, drop into reactor two, add 37% formalin, 51 parts of weight, add oxalic acid 1.6 parts of weight, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 180 minutes.Slowly add the neutralization of the 10%NaOH aqueous solution, until reactor two resin solution PH reaches the scope of 6 ~ 8.Heat up dehydration to 105 DEG C, uses Büchner funnel suction filtration, the salt that removing neutralization generates.By the mixing of two kinds of resin solutions, heat up, vacuumize and remove propyl carbinol and phenol, at 160 ± 5 DEG C, keep 60 minutes under 10 ± 5KPa.Blowing, obtained sample 3.
Comparative example 1
Take phenol 100 parts of weight, drop into reactor, add 37% formalin, 57.5 parts of weight, add oxalic acid 0.8 part of weight, be warming up to 95 DEG C, at 95 ± 5 DEG C, react backflow 180 minutes.Slowly add the neutralization of the 10%NaOH aqueous solution, until resin solution PH reaches the scope of 6 ~ 8.Heat up dehydration to 105 DEG C, uses Büchner funnel suction filtration, the salt that removing neutralization generates.Heat up, vacuumize and remove phenol, at 160 ± 5 DEG C, keep 60 minutes under 10 ± 5KPa.Blowing, obtained sample 4.
Bisphenol A modified phenolic resin is analyzed
Embodiment and comparative example obtain resol sample, and analysis indexes is as follows:
Illustrate: softening temperature uses ring and ball method to measure; Gel time, measuring temperature is 150 DEG C; Free phenol refers to free-phenol, uses gas chromatography determination.
Bisphenol A modified phenolic resin applicating evaluating
Bisphenol A modified phenolic resin is mainly used in matrix material, particularly cast material and insulating material.The present invention, for insulating material (bakelite), makes applicating evaluating.
The making of bakelite
Resol sample 1 obtains bakelite sample 1, and resol sample 2 obtains bakelite sample 2, and resol sample 3 obtains bakelite sample 3, and resol sample 4 obtains bakelite sample 4.
Make formula:
Making step:
Resol and wood powder, urotropine, Zinic stearas, nigrosine are mixed by given formula, pulverizes through small-sized Kun press heat refining, naturally cooling, use micromill at 120 DEG C, sieve, obtained bakelite.
Bakelite sample is through press compression molding, and moulding compound performance testing index is as follows:
Condition of molding 180 DEG C/30MPa/2min.mm
-1
Conclusion
Bisphenol A modified phenolic resin, for bakelite, compares with phenol novolacs, has better mechanical strength and insulating property.
Claims (3)
1. a bisphenol A modified phenolic resin, is characterized in that: obtained by following method: the polycondensation of advanced line type phenol novolacs, then adds dihydroxyphenyl propane and carry out copolyreaction, finally dewaters, refiningly to obtain product.
2. a preparation method for bisphenol A modified phenolic resin according to claim 1, is characterized in that: comprise the following steps:
Step 1. dihydroxyphenyl propane dissolves
Dihydroxyphenyl propane is dropped into reactor one, then add solvent, the weight ratio of solvent and dihydroxyphenyl propane is 0.5 ~ 5:1, stirs lower dissolving, for subsequent use;
The building-up reactions of step 2. line style phenol novolacs
Phenol is dropped into reactor two with aldehyde after mixing, and the mol ratio of aldehyde and phenol is 0.1 ~ 1.0:1, and add acid catalyst, the amount of catalyzer is 0.01 ~ 3% of phenol weight, carries out the certain hour reaction of 60 ~ 180 minutes under stirring at 80 ~ 110 DEG C;
The building-up reactions of step 3. bisphenol A modified phenolic resin
Step 2 is added step 1 product, is carried out the reaction of 60 ~ 180 minutes under stirring at 90 ~ 100 DEG C after terminating in reactor two;
Refining of step 4. bisphenol A modified phenolic resin
Step 3 adds NaOH and neutralizes, be neutralized to pH scope 6 ~ 8 after terminating, and heats up and removes the water of reaction generation, when reaching 100 ~ 110 DEG C, uses filter paper filtering, and the salt that removing neutralization generates obtains bisphenol A modified phenolic resin crude resin;
The purification of step 5. bisphenol A modified phenolic resin
Step 4 is warming up to 150 ~ 170 DEG C, desolvation and residual phenol after terminating, and keep 30 ~ 120 minutes under vacuum tightness is absolute pressure 2 ~ 20KPa, except after vacuum, blowing obtains sample.
3. the preparation method of bisphenol A modified phenolic resin according to claim 2, is characterized in that: described dihydroxyphenyl propane is the one in the polymeric carbon grade of purity more than 99.8% and epoxy grade bis phenol A, dihydroxyphenyl propane mother liquor, dihydroxyphenyl propane cracking residue; Solvent is the one in toluene, dimethylbenzene, ethylene glycol, propyl carbinol; Phenol is the one in the alkylphenol of phenol, ortho position or para-orientation; Aldehyde is the one in formaldehyde, acetaldehyde, paraformaldehyde; Acid catalyst is the one in oxalic acid, hydrochloric acid, phosphoric acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510413618.5A CN105017714B (en) | 2013-11-01 | 2013-11-01 | The preparation method of bisphenol A modified phenolic resin |
| CN201310530178.2A CN103626941B (en) | 2013-11-01 | 2013-11-01 | Bisphenol a modified phenolic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310530178.2A CN103626941B (en) | 2013-11-01 | 2013-11-01 | Bisphenol a modified phenolic resin and preparation method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510413618.5A Division CN105017714B (en) | 2013-11-01 | 2013-11-01 | The preparation method of bisphenol A modified phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626941A CN103626941A (en) | 2014-03-12 |
| CN103626941B true CN103626941B (en) | 2016-01-20 |
Family
ID=50208413
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510413618.5A Active CN105017714B (en) | 2013-11-01 | 2013-11-01 | The preparation method of bisphenol A modified phenolic resin |
| CN201310530178.2A Active CN103626941B (en) | 2013-11-01 | 2013-11-01 | Bisphenol a modified phenolic resin and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510413618.5A Active CN105017714B (en) | 2013-11-01 | 2013-11-01 | The preparation method of bisphenol A modified phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN105017714B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343224A (en) * | 2019-07-16 | 2019-10-18 | 沙县宏盛塑料有限公司 | The preparation method of bisphenol A modified phenolic resin and modified alkyd resin moulding material |
| CN111909334A (en) * | 2020-07-22 | 2020-11-10 | 山东宇世巨化工有限公司 | Preparation method of low-expansion resin curing agent and low-expansion resin curing agent |
| CN116162216B (en) * | 2023-04-20 | 2023-07-07 | 山东宇世巨化工有限公司 | Preparation method of epoxy resin modified phenolic resin for petroleum fracturing sand |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415640A (en) * | 2002-08-28 | 2003-05-07 | 广州宏昌电子材料工业有限公司 | Method for preparing line-type bisphenol Aphenolic resin by using aqueous solution process |
| CN101096403A (en) * | 2006-06-29 | 2008-01-02 | 西北工业大学 | Linetype bisphenol F phenolic resin and preparation method thereof |
| CN101497683A (en) * | 2008-02-02 | 2009-08-05 | 中国石油化工集团公司 | Preparation of linear bisphenol A phenolic resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066855A (en) * | 1992-06-11 | 1992-12-09 | 沈阳化工学院 | The acetal legal system is equipped with the method for phenol aldehyde type epoxy resin |
| CN100562535C (en) * | 2006-04-20 | 2009-11-25 | 西北工业大学 | The production technique of lacquer resins |
-
2013
- 2013-11-01 CN CN201510413618.5A patent/CN105017714B/en active Active
- 2013-11-01 CN CN201310530178.2A patent/CN103626941B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415640A (en) * | 2002-08-28 | 2003-05-07 | 广州宏昌电子材料工业有限公司 | Method for preparing line-type bisphenol Aphenolic resin by using aqueous solution process |
| CN101096403A (en) * | 2006-06-29 | 2008-01-02 | 西北工业大学 | Linetype bisphenol F phenolic resin and preparation method thereof |
| CN101497683A (en) * | 2008-02-02 | 2009-08-05 | 中国石油化工集团公司 | Preparation of linear bisphenol A phenolic resin |
Non-Patent Citations (2)
| Title |
|---|
| 双酚A改性甲阶段酚醛树脂的合成和表征;赵春玲等;《粘结》;20021020;第23卷(第5期);第9-11页 * |
| 线型双酚A酚醛树脂结构的研究;陈立新等;《第十二次全国环氧树脂应用技术学术交流会论文集》;20071001;185-189 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105017714A (en) | 2015-11-04 |
| CN103626941A (en) | 2014-03-12 |
| CN105017714B (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103319314B (en) | The synthetic method of Bisphenol F under salt bath system | |
| CN105255109B (en) | Phthalonitrile modified benzoxazine and epoxy resin composite material and preparation and application | |
| CN103626941B (en) | Bisphenol a modified phenolic resin and preparation method thereof | |
| CN105315419A (en) | Preparing method for ablation-resisting boron-modified thermoplastic phenolic resin | |
| CN102584541A (en) | Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid | |
| CN103087280A (en) | Method for synthesizing phenolic resins by using paraformaldehyde | |
| CN102812060B (en) | Solid resol-type phenolic resin and method for producing same | |
| KR20110102409A (en) | Novolac resin and method for producing same | |
| CN102977298B (en) | Lignin and boronic acid modified phenolic resin and method for preparing same | |
| CN103319672A (en) | Tear resistant phenolic resin and preparation method thereof | |
| CN102875752B (en) | Lignin modified thermoplastic phenolic resin and preparation method thereof | |
| CN105566590A (en) | Method for preparing modified phenolic resin and application thereof | |
| CN103467683A (en) | Preparation method for thermosetting phenolic resin and thermosetting phenolic resin prepared with method | |
| CN103613729B (en) | A kind of preparation method of modified phenolic resins | |
| CN103588942B (en) | High Performance Phenolic Resins composition and method of making the same | |
| TWI466965B (en) | Method for producing novolak resin and novolak resin | |
| CN102181026A (en) | Production method for electronic-grade phenolic resin | |
| CN102633967B (en) | A kind of preparation technology of bamboo lignin modified phenolic resins | |
| WO2024011789A1 (en) | Preparation method for phenol phenolic resin and product obtained thereby | |
| CN102161740A (en) | Preparation method phenolic resin | |
| CN109535359A (en) | A method of alkali resistance phenolic resin is synthesized based on control solution ph | |
| CN100564417C (en) | Be used to make the preparation method of the resol of Resins, epoxy | |
| CN103483765B (en) | A kind of phenol resin composition and preparation method thereof | |
| KR101267734B1 (en) | Phenol-formaldehyde resin and method of manufacturing phenol-formaldehyde resin | |
| CN103450263A (en) | Preparation method of phosphorus-modified phenolic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |