CN108752546A - A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof - Google Patents
A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof Download PDFInfo
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- CN108752546A CN108752546A CN201810473129.2A CN201810473129A CN108752546A CN 108752546 A CN108752546 A CN 108752546A CN 201810473129 A CN201810473129 A CN 201810473129A CN 108752546 A CN108752546 A CN 108752546A
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- Prior art keywords
- phenol
- formaldehyde resin
- plant polyenoid
- resin modified
- preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
In novolak resin field, the features such as phenolic resin is with its excellent high temperature resistant, high bond strength, it is used widely in friction material, adhesive field, the present invention provides a kind of preparation methods of plant polyenoid phenol phenol-formaldehyde resin modified, according to plant polyenoid phenol phenol-formaldehyde resin modified made from this method, not only there is cost of material advantage, and the problem that brittleness is big after aerodux cures can be improved since plant polyenoid phenol contains longer carbochain, substantially increase antistripping, the tensile resistance of phenolic resin.
Description
Technical field
The present invention relates to the production field of phenolic resin, more particularly to a kind of preparation of plant polyenoid phenol phenol-formaldehyde resin modified
Method.
Background technology
In novolak resin field, the features such as phenolic resin is with its excellent high temperature resistant, high bond strength, rubbing
Material, adhesive field are used widely, but when not doing toughening modifying, solidfied material is generally partially crisp, antistripping, cracking resistance,
Shock resistance is poor.Phenolic resin modified purpose mainly improves its brittleness or other physical properties, improves it and increases to fiber
The adhesive property of strong material.
Therefore in order to overcome phenolic resin brittleness big, peel strength is weak, and researcher has carried out largely phenolic resin
Research carrys out the toughness of phenol-formaldehyde resin modified, improves mechanical property, while improving its processing performance, reduces cost.
Invention content
The problem to be solved in the present invention is to provide a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified, according to this
Plant polyenoid phenol phenol-formaldehyde resin modified made from method, not only there is a cost of material advantage, and due to plant polyenoid phenol contain compared with
Long carbochain can improve the big problem of brittleness after aerodux solidification, substantially increase phenolic resin antistripping,
Tensile resistance.
A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof, includes the following steps：
（1）By plant polyenoid phenol, phenol, by n (plant polyenoid phenol)：N (phenol)=0.05 ~ 0.30:0.70 ~ 0.95, catalyst I
Flask is added by the 2 ~ 5% of phenol and plant polyenoid phenol gross mass, is warming up to 50 DEG C~90 DEG C, poly first is slowly added several times
Aldehyde reacts 0.5~1.5h at 70 DEG C~90 DEG C, is warming up to 80 DEG C~90 DEG C 0.5~1.5h of reaction；
（2）It is uniform that stirring solvent is added, reacts 0.5h at 75 DEG C~95 DEG C；
（3）60 DEG C~70 DEG C are cooled to, liquid epoxies is added and reacts 1~3h；
（4）Catalyst II, 0.5~1.5h of stirring is added；
（5）25 DEG C~40 DEG C are cooled to, discharging obtains plant polyenoid phenol phenol-formaldehyde resin modified.
Further, step（1）In, catalyst I is selected from sodium hydroxide, barium hydroxide, ammonium hydroxide, sodium carbonate, alkali metal, carbon
Sour hydrogen sodium, tertiary amines, oxalic acid, sulfuric acid, hydrochloric acid, to one or more kinds of mixtures in benzene methanesulfonic acid；.
Further, step（2）In, one kind in toluene, dimethylbenzene, ethyl alcohol, isopropanol, ethyl acetate of solvent or
More than one mixture.
Further, step（3）In, the one kind of liquid epoxies in E-44, E-51, E-208.
Further, step（4）In, catalyst II be selected from N, N- dimethyl cyclohexyl amines, bis- (2- dimethylaminoethyls) ethers,
N, N, N', N'- tetramethyl Alkylenediamine, triethylamine, N, one kind in N- dimethyl benzylamines, triethanolamine, DMEA.
The ingredient of following structural formula is included at least by the plant polyenoid phenol phenol-formaldehyde resin modified that above method is prepared：
R1=H or OH；
R2=C15H31, C15H29Or C15H27；
For a further understanding of the present invention, with reference to embodiment to a kind of plant polyenoid phenol modified phenolic resin provided by the invention
Fat and preparation method thereof is described, and protection scope of the present invention is not limited by the following examples.
Specific embodiment
Embodiment 1：
Flask is added in 150g plant polyenoid phenol, 900g phenol, 32g30% sodium hydroxides, 55 degree is warming up to, slowly adds several times
Enter 324g paraformaldehydes, reacted 1 hour under 70 degree, be warming up to 90 degree and react 40 minutes, 320 toluene are added, react 30 under 85 degree
Minute, ethyl alcohol is added and stirs evenly, cools to 75 degree, 80gE-51 liquid epoxies is added and reacts 2 hours, 1.6g 2 is added,
4,6- tri- (dimethylamino methyl) phenol stir 30 minutes, cool to 40 degree of dischargings.
Embodiment 2：
Flask is added in 135g plant polyenoid phenol, 200g phenol, 13.4g30% sodium hydroxides, is warming up to 55 degree, slowly several times
It is added 324g paraformaldehydes, 70 degree lower reactions 1 hour are warming up to 90 degree and react 40 minutes, 320 toluene are added, are reacted under 85 degree
30 minutes, ethyl alcohol is added and stirs evenly, cools to 75 degree, 120gE-51 liquid epoxies is added and reacts 2 hours, 2.4g is added
2,4,6- tri- (dimethylamino methyl) phenol stir 30 minutes, cool to 40 degree of dischargings.
Embodiment 3：
Flask is added in 180g plant polyenoid phenol, 225g phenol, 18g30% sodium hydroxides, 55 degree is warming up to, slowly adds several times
Enter 360g paraformaldehydes, reacted 1 hour under 70 degree, be warming up to 90 degree and react 40 minutes, 320 toluene are added, react 30 under 85 degree
Minute, ethyl alcohol is added and stirs evenly, cools to 75 degree, 80gE-51 liquid epoxies is added and reacts 2 hours, 1.6g 2 is added,
4,6- tri- (dimethylamino methyl) phenol stir 30 minutes, cool to 40 degree of dischargings.
Plant polyenoid phenol phenol-formaldehyde resin modified obtained by embodiment 1-3 is coated on the iron plate of 15cm*5cm sandblastings,
70 DEG C of baking ovens are placed in, are dried 30 minutes；The aluminum crossed with solvent wiping stretching weight is bonded at product, 0.35-1.0Mpa is used
Pressure goes to suppress, and holding condition of cure is 150 DEG C of 30min, and 165 DEG C of 15min, 200 DEG C of 5min are cooled to room temperature, utilizes
PosiTest AT-A test tensile strength, such as following table：
| Example 1 | Example 2 | Example 3 | A-64 | |
| Tensile strength Mpa | 0.8 | 0.67 | 0.72 | 0.68 |
By being compared with A-64 more famous in industry, the prepared anti-stripping of plant polyenoid phenol phenol-formaldehyde resin modified through the invention
It can meet market demands from, tensile resistance.
Claims (6)
1. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified, which is characterized in that include the following steps：
（1）By plant polyenoid phenol, phenol, by the amount n (plant polyenoid phenol) of substance：N (phenol)=0.05 ~ 0.30:0.70 ~ 0.95,
Flask is added by phenol and the 2 ~ 5% of plant polyenoid phenol gross mass in catalyst I, is warming up to 50 DEG C~90 DEG C, is slowly added several times
Paraformaldehyde reacts 0.5~1.5h at 70 DEG C~90 DEG C, is warming up to 80 DEG C~90 DEG C 0.5~1.5h of reaction；
（2）It is uniform that stirring solvent is added, reacts 0.5h at 75 DEG C~95 DEG C；
（3）60 DEG C~70 DEG C are cooled to, liquid epoxies is added and reacts 1~3h；
（4）Catalyst II, 0.5~1.5h of stirring is added；
（5）25 DEG C~40 DEG C are cooled to, discharging obtains plant polyenoid phenol phenol-formaldehyde resin modified.
2. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified according to claim 1, which is characterized in that step
（1）In, catalyst I is selected from sodium hydroxide, barium hydroxide, ammonium hydroxide, sodium carbonate, alkali metal, sodium bicarbonate, tertiary amines, oxalic acid, sulphur
Acid, hydrochloric acid, to one or more kinds of mixtures in benzene methanesulfonic acid.
3. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified according to claim 1, which is characterized in that step
（2）In, one or more kinds of mixtures of the solvent in toluene, dimethylbenzene, ethyl alcohol, isopropanol, ethyl acetate.
4. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified according to claim 1, which is characterized in that step
（3）In, the one kind of liquid epoxies in E-44, E-51, E-208.
5. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified according to claim 1, which is characterized in that step
（4）In, catalyst II is selected from N, N- dimethyl cyclohexyl amines, bis- (2- dimethylaminoethyls) ethers, N, N, N', N'- tetramethyl alkylenes
Base diamines, triethylamine, N, one kind in N- dimethyl benzylamines, triethanolamine, DMEA.
6. a kind of preparation method of plant polyenoid phenol phenol-formaldehyde resin modified according to claim 1-5, which is characterized in that system
Standby obtained phenolic resin includes at least the ingredient of following structural formula：
R1=H or OH；
R2=C15H31, C15H29Or C15H27；
。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810473129.2A CN108752546A (en) | 2018-05-17 | 2018-05-17 | A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810473129.2A CN108752546A (en) | 2018-05-17 | 2018-05-17 | A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072547A1 (en) * | 2007-12-20 | 2009-06-24 | Nanoresins AG | Modified phenolic resin |
| CN102363643A (en) * | 2011-06-28 | 2012-02-29 | 衡阳恒缘电工材料有限公司 | Preparation method of cardanol modified phenolic resin |
| CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
| CN103122054A (en) * | 2013-02-19 | 2013-05-29 | 中国西电集团公司 | Method for modifying phenolic resin by using cardanol |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
-
2018
- 2018-05-17 CN CN201810473129.2A patent/CN108752546A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072547A1 (en) * | 2007-12-20 | 2009-06-24 | Nanoresins AG | Modified phenolic resin |
| CN102363643A (en) * | 2011-06-28 | 2012-02-29 | 衡阳恒缘电工材料有限公司 | Preparation method of cardanol modified phenolic resin |
| CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
| CN103122054A (en) * | 2013-02-19 | 2013-05-29 | 中国西电集团公司 | Method for modifying phenolic resin by using cardanol |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
Non-Patent Citations (4)
| Title |
|---|
| 上海市化轻公司第二化工供应部编: "《化工产品应用手册 合成材料助剂 食品添加剂》", 31 May 1989, 上海科学技术出版社 * |
| 李红强: "《胶粘原理、技术及应用》", 31 January 2014, 华南理工大学出版社 * |
| 贺英等: "《涂料树脂化学》", 31 July 2007, 化学工业出版社 * |
| 黄发荣等: "《酚醛树脂及其应用》", 31 January 2003, 化学工业出版社 * |
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