CN100427528C - Process for preparing modified benzoxazine - Google Patents
Process for preparing modified benzoxazine Download PDFInfo
- Publication number
- CN100427528C CN100427528C CNB2006101508810A CN200610150881A CN100427528C CN 100427528 C CN100427528 C CN 100427528C CN B2006101508810 A CNB2006101508810 A CN B2006101508810A CN 200610150881 A CN200610150881 A CN 200610150881A CN 100427528 C CN100427528 C CN 100427528C
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- modified benzoxazine
- polysulfide rubber
- solution
- preparation
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to preparation process of benzoxazine, and is especially process of preparing modified benzoxazine. The process of preparing modified benzoxazine includes the following steps: 1. mixing water solution of formaldehyde and phenol in the molar ratio of 2 to 1; 2. dissolving polysulfide rubber liquid in the solution through stirring; 3. mixing aniline and phenol in the molar ratio of 1 to 1 into the solution; 4. heating to react ; and 5. vacuum distilling the obtained yellow liquid the reaction produces to prepare modified benzoxazine. Compared with benzoxazine, the modified benzoxazine has greatly raised toughness and strength as well as slightly raised heat performance.
Description
Technical field
The present invention relates to the preparation method of benzoxazine.
Background technology
Benzoxazine is the hexa-member heterocycle system by O atom and N atomic building.This compounds can be under the heating or the effect of catalyzer ring-opening polymerization form the polymkeric substance of similar resol structure.Polyphenyl and oxazines possess outside the advantage of traditional resol, and open loop solidifies and need not catalyzer, do not have low molecule and emit, and the goods voidage is low, shrink little or do not have contraction.Existing benzoxazine toughness is relatively poor, though and traditional method for toughening has improved its toughness, the system thermotolerance obviously descends, and has influenced the performance of material.The simple thermofixation of tradition resol meeting discharges a large amount of small molecules fugitive constituents, then can have a strong impact on shortcomings such as its thermotolerance, intensity when making catalyzer with strong acid.
Summary of the invention
The present invention is relatively poor in order to solve existing benzoxazine toughness, though and traditional method for toughening has improved its toughness, the system thermotolerance obviously descends, and has influenced the performance of material; The simple thermofixation of tradition resol meeting discharges a large amount of small molecules fugitive constituents, then can have a strong impact on the problem of its thermotolerance, intensity when making catalyzer with strong acid, a kind of preparation method of modified benzoxazine is provided, and the concrete technical scheme that addresses the above problem is as follows:
The preparation method's of modified benzoxazine of the present invention step is as follows:
Step 2, get liquid polysulfide rubber 5%～15% by weight percentage and be dissolved in the described solution of step 1, stirring and dissolving is to homogeneous phase;
Step 3, aniline and phenol are got mol ratio 1: 1 mix with step 2 solution;
Step 4, the mixed solution of step 3 is put into heating installation internal heating to 100～110 ℃, isothermal reaction 4.5～5.5h;
Step 5, with the gained liquid underpressure distillation of step 4 reaction back, make modified benzoxazine of the present invention.
Under the situation about slightly improving of the thermal characteristics of the modified benzoxazine of the present invention preparation before than modification, toughness and intensity have but obtained significantly improving.Existing benzoxazine and epoxy blend, the tensile strength of solidifying the back material is: 38.71MPa, resistance to impact shock: 5.94KJm
-2And the tensile strength of material is behind the benzoxazine resin solidification after the modification: 55.22MPa, resistance to impact shock: 17.06KJm
-2
Description of drawings
Fig. 1 is the FTIR spectrogram of modified benzoxazine of the present invention, and Fig. 2 is the TGA spectrogram that solidifies Embedding Material, and a is the TGA spectrogram of unmodified system among the figure, and b is the TGA spectrogram of system after the modification.
Embodiment
Embodiment one: the step of present embodiment is as follows:
Step 2, get liquid polysulfide rubber 5%～15% by weight percentage and be dissolved in the described solution of step 1, stirring and dissolving is to homogeneous phase;
Step 3, aniline and phenol are got mol ratio 1: 1 mix with step 2 solution;
Step 4, the mixed solution of step 3 is put into heating installation internal heating to 100～110 ℃, isothermal reaction 4.5～5.5h;
Step 5, with the gained liquid underpressure distillation of step 4 reaction back, make modified benzoxazine of the present invention.
Embodiment two: present embodiment is got liquid polysulfide rubber 5% by weight percentage with the different step 2 that are of embodiment one; The Heating temperature of step 4 is 100 ℃, isothermal reaction 5.5h.Other step is identical with embodiment one.
Embodiment three: present embodiment is got liquid polysulfide rubber 10% by weight percentage with the different step 2 that are of embodiment one; The Heating temperature of step 4 is 105 ℃, isothermal reaction 5h.Other step is identical with embodiment one.
Embodiment four: present embodiment is got liquid polysulfide rubber 15% by weight percentage with the different step 2 that are of embodiment one; The Heating temperature of step 4 is 110 ℃, isothermal reaction 4.5h.Other step is identical with embodiment one.
With adopt aforesaid method make benzoxazine after the modification and epoxy blend, solidifying agent respectively proportionally 80～120 parts, 80～120 parts, 30～40 parts mix, at 45～55 ℃, insulation 1.5～2.5h, be warming up to 120～140 ℃ again, insulation 4.5～5.5h, the material after obtaining solidifying.The mechanical property of the material after it solidifies sees Table 1.Solidify back material glass temperature and see Table 2.
As can be seen under the situation that the system thermotolerance slightly improves, system toughness and intensity all are greatly improved from table 1 and table 2.
Table 1:
Table 2:
Claims (4)
1, the preparation method of modified benzoxazine is characterized in that the step for preparing is as follows:
Step 1, be that 37% formalin and phenol mix according to mol ratio at 2: 1 with concentration;
Step 2, get liquid polysulfide rubber 5%～15% by weight percentage and be dissolved in the described solution of step 1, stirring and dissolving is to homogeneous phase;
Step 3, aniline and phenol are got mol ratio 1: 1 mix with step 2 solution;
Step 4, the mixed solution of step 3 is put into heating installation internal heating to 100～110 ℃, isothermal reaction 4.5～5.5h;
Step 5, with the gained liquid underpressure distillation of step 4 reaction back, make modified benzoxazine of the present invention.
2, the preparation method of modified benzoxazine according to claim 1 is characterized in that step 2 gets liquid polysulfide rubber 5% by weight percentage; The Heating temperature of step 4 is 100 ℃, isothermal reaction 5.5h.
3, the preparation method of modified benzoxazine according to claim 1 is characterized in that step 2 gets liquid polysulfide rubber 10% by weight percentage; The Heating temperature of step 4 is 105 ℃, isothermal reaction 5h.
4, the preparation method of modified benzoxazine according to claim 1 is characterized in that step 2 gets liquid polysulfide rubber 15% by weight percentage; The Heating temperature of step 4 is 110 ℃, isothermal reaction 4.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101508810A CN100427528C (en) | 2006-10-12 | 2006-10-12 | Process for preparing modified benzoxazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101508810A CN100427528C (en) | 2006-10-12 | 2006-10-12 | Process for preparing modified benzoxazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1944491A CN1944491A (en) | 2007-04-11 |
| CN100427528C true CN100427528C (en) | 2008-10-22 |
Family
ID=38044160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101508810A Expired - Fee Related CN100427528C (en) | 2006-10-12 | 2006-10-12 | Process for preparing modified benzoxazine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100427528C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759615A (en) * | 2017-10-26 | 2018-03-06 | 华东理工大学 | A kind of full bio-based benzoxazine colophony and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000273135A (en) * | 1999-03-23 | 2000-10-03 | Hitachi Chem Co Ltd | Manufacture of phenol-based resin |
| CN1496378A (en) * | 2001-03-12 | 2004-05-12 | �������ɹ�ҵ��ʽ���� | Method for producing benzoxazine resin |
| JP2004156045A (en) * | 2003-12-22 | 2004-06-03 | Hitachi Chem Co Ltd | Friction material |
| CN1803887A (en) * | 2005-12-31 | 2006-07-19 | 四川东材企业集团有限公司 | Benzoxazine resin containing aralkyl structure, its preparation method and use |
-
2006
- 2006-10-12 CN CNB2006101508810A patent/CN100427528C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000273135A (en) * | 1999-03-23 | 2000-10-03 | Hitachi Chem Co Ltd | Manufacture of phenol-based resin |
| CN1496378A (en) * | 2001-03-12 | 2004-05-12 | �������ɹ�ҵ��ʽ���� | Method for producing benzoxazine resin |
| JP2004156045A (en) * | 2003-12-22 | 2004-06-03 | Hitachi Chem Co Ltd | Friction material |
| CN1803887A (en) * | 2005-12-31 | 2006-07-19 | 四川东材企业集团有限公司 | Benzoxazine resin containing aralkyl structure, its preparation method and use |
Non-Patent Citations (4)
| Title |
|---|
| 苯并噁嗪化合物的合成及固化. 张所信等.吉林化工学院学报，第20卷第3期. 2003 |
| 苯并噁嗪化合物的合成及固化. 张所信等.吉林化工学院学报，第20卷第3期. 2003 * |
| 苯并噁嗪树脂的研究进展. 谢倩等.热带农业科学，第24卷第4期. 2004 |
| 苯并噁嗪树脂的研究进展. 谢倩等.热带农业科学，第24卷第4期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1944491A (en) | 2007-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103980463B (en) | A kind of epoxy resin solvent-free low-temperature solidified agent and preparation method thereof and application | |
| CN110128982A (en) | A kind of fast fixing structure glue of room temperature and preparation method thereof | |
| CN103497311B (en) | A kind of epoxy resin polyamine curing agent and a kind of aqueous latex of epoxy hardener | |
| CN108997560A (en) | A kind of epoxy resin composite material and its preparation method and application | |
| KR960037597A (en) | Mixtures of phenolic novolacs for use with refractory aggregates and methods for preparing the mixtures | |
| CN102432786B (en) | Phenolic resin and preparation method thereof as well as proppant and preparation method thereof | |
| CN104588569A (en) | Fast-curing type high-temperature resistant binder and pre-coated sand thereof | |
| CN104312508B (en) | A kind of epoxy resin adhesive and preparation method thereof | |
| CN109321223A (en) | A kind of sand control agent, preparation method and the purposes for sand control | |
| CN104693391B (en) | A kind of epoxy phenolics and synthetic method thereof | |
| CN116162216B (en) | Preparation method of epoxy resin modified phenolic resin for petroleum fracturing sand | |
| CN100427528C (en) | Process for preparing modified benzoxazine | |
| CN103232605B (en) | A kind of hydrogenation phenolate cracking lignin and preparation method thereof | |
| CN102827351A (en) | Curing agent of epoxy resin and synthesis method thereof | |
| CN106496476A (en) | A kind of Effect of Organosilicon-modified Phenol-formaldehyde Resin and its application | |
| CN109535359A (en) | A method of alkali resistance phenolic resin is synthesized based on control solution ph | |
| CN108753229A (en) | A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive | |
| CN101914195A (en) | Heat-resistant epoxy resin compound for forming RTM, epoxy base resin and preparation method thereof | |
| RU2585638C1 (en) | Epoxy binder, prepreg based thereon and article made therefrom | |
| CN109265633A (en) | Lignin type benzoxazine and preparation method thereof | |
| CN108530591A (en) | The preparation method of 3D sand molds printing alkali phenolic resin | |
| CN104356858A (en) | Epoxy resin coating and preparation method thereof | |
| CN105859991B (en) | A kind of phenol-formaldehyde resin modified | |
| CN107721281A (en) | A kind of concrete | |
| CN107245191A (en) | A kind of rare earth modified plastics and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081022 Termination date: 20091112 |