CN100424122C - Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene - Google Patents
Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene Download PDFInfo
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- CN100424122C CN100424122C CNB2006100171265A CN200610017126A CN100424122C CN 100424122 C CN100424122 C CN 100424122C CN B2006100171265 A CNB2006100171265 A CN B2006100171265A CN 200610017126 A CN200610017126 A CN 200610017126A CN 100424122 C CN100424122 C CN 100424122C
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- dicyclopentadiene
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Abstract
This invention discloses an antioxidant of p-methylphenol-dicyclopentadiene-styrene resin. The resin is white or yellowish powder, with an average molecular weight of 650-850, a melting point of 100-115 deg.C, an ash content of 0.05%, and an average particle size of 10-30 mum. The resin is soluble in aromatic solvents such as styrene, acetone and alcohols, while insoluble in water and fatty solvents. The resin can be used as a high-efficiency antioxidant in rubber products and polymers such as SBR and carboxylated SBR latex, ABS, NBR, BR, SBS, SIS and their derivatives. The resin can also be used in stability protection in the manufacture of the above rubber products and polymers.
Description
Technical field
The invention discloses a kind of new antioxidant, a kind of Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin especially is provided, belong to chemosynthesis technical field.
Background technology
At present, the antioxidant that is used for plastics and rubber item technical field has a variety of, wherein, it is more that 1010 antioxidants use, the polyphenol antioxidant resin of import increases just gradually, but because one of main production raw material that this antioxidant resin adopts is an iso-butylene, use under must condition of high voltage in the production process and store, therefore, exist certain potential safety hazard, and not so good with the consistency of plastics and rubber, thermotolerance is relatively poor, affects the result of use of this series products under the stable condition.
Summary of the invention
The invention provides a kind of Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin, have intermiscibility and resistance toheat preferably with plastic cement.
Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin of the present invention has following structural formula:
Outward appearance is white or pale yellow powder.
Molecular-weight average is: 650～850
Fusing point: 100～115 ℃
Ash oontent: 0.05%
Median size: 10～30 μ m
Solubleness: be dissolved in aromatic solvent, as vinylbenzene, acetone and alcoholic solvent, water insoluble and fats solvent.
Synthesis technique of the present invention is as follows
P-methyl phenol added in the cyclohexane solvents by 1: 3.5～5 times weight stir, the solid super acid catalyst that adds 0.1～0.15 part, temperature rising reflux, in reflux course, splash into 0.75～0.8 part dipentadiene and cyclohexane solution (weight ratio is 1: 1), titration time is 30～60 minutes, reacted 3～5 hours, drip 0.3～0.4 part of vinylbenzene then, titration time is 2～3 hours, reacts filtering recovering catalyst 2 hours, reaction solution is handled by activated carbon decolorizing, remove by filter gac, enter to steam in the still kettle to slip to remove and desolvate, get product of the present invention after the cooling.
The present invention is used for rubber item, high molecular polymer as the anti-oxidant purposes of the derivative of SBR and carboxylated SBR latex, ABS, NBR, BR, SBS and SIS etc. as efficient antioxidants.
The present invention is used for comprising the purposes of stability protection of the production engineering of above compound.
Experimental example 1
Volatility test, because volatility of the present invention is extremely low, so antioxidant effect is more lasting, consumption is extremely low, unites use with DLTDP, has synergistic effect, anti-volatility is better.
Experimental example 2
The anti-aging test of macromolecular material such as be used for mattress, carpet, served as a contrast.
Experimental example 3
The anti-washing composition drop of natural rubber gloves in the time of 70 ℃ goes out test.
The antioxidant property simultaneous test table of the present invention and phenol antioxidant
| Single phenol | Bis-phenol | The present invention | |
| |
200～300 | 340～430 | 650～850 |
| Volatility | High | In | Extremely low |
| Discolouration | Flavescence | Redden | Nondiscoloration |
| Water-fast/washing composition drop goes out | In | High | Low |
| Resistance to deterioration | Difference | Generally | Good |
See Fig. 1, Fig. 2, Fig. 3 for details.
Above-mentioned experiment shows, the present invention's other phenol antioxidant relatively has high oxidation-resistance, and is water-fast or going out property of wash resistant agent drop is fabulous, nondiscoloration, the characteristics that ageing resistance is good.
Positively effect of the present invention is: synthesis technique is safe and reliable, the reaction conditions gentleness, and the catalyzer environmental protection, pollution-free phenomenon exists, and consumption economy can be widely used in food grade and medical grade product technique field.
Description of drawings
Fig. 1 is the volatility curve figure of the present invention and phenol antioxidant.
Fig. 2 goes out graphic representation for the anti-washing composition drop of the present invention and phenol antioxidant.
Fig. 3 is the anti-aging graphic representation of the present invention and phenol antioxidant.
Embodiment
By following examples the present invention is described for example further, and do not limit the present invention in any way, under the prerequisite that does not deviate from technical solution of the present invention, any change or change that those of ordinary skills that the present invention did are realized easily all will fall within the claim scope of the present invention.
Embodiment 1
The p-methyl phenol of 10kg is added in the cyclohexane solvent of 35kg and stir, the large porous strong acid resin catalyst that adds 1kg, temperature rising reflux, in reflux course, splash into dipentadiene and the cyclohexane mixing solutions (weight ratio is 1: 1) of 8kg, titration time is 30 minutes, reacted 5 hours, drip the vinylbenzene of 3kg then, titration time is 2 hours, reacts filtering recovering catalyst 2 hours, reaction solution is handled by activated carbon decolorizing, remove by filter gac, enter to steam in the still kettle to slip to remove and desolvate, get product of the present invention after the cooling.
This product outward appearance is white or pale yellow powder, and molecular-weight average is: 650～850, and fusing point: 100～115 ℃, ash oontent: 0.05%, median size: 10～30 μ m, solubleness: be dissolved in aromatic solvent, as vinylbenzene, acetone and alcoholic solvent, water insoluble and fats solvent.
Embodiment 2
The p-methyl phenol of 10kg and the cyclohexane solvent of 50kg are stirred, the zirconium sulfate catalyst that adds 1.5kg, temperature rising reflux, in reflux course, splash into dipentadiene and the cyclohexane solution (weight ratio is 1: 1) of 7.5kg, titration time is 50 minutes, reacted 4 hours, drip the vinylbenzene of 4kg then, titration time is 1.5 hours, reacts filtering recovering catalyst 2 hours, reaction solution is handled by activated carbon decolorizing, remove by filter gac, enter to steam in the still kettle to slip to remove and desolvate, get product of the present invention after the cooling.
This product outward appearance is white or pale yellow powder, and molecular-weight average is: 650～850, and fusing point: 100～115 ℃, ash oontent: 0.05%, median size: 10～30 μ m, solubleness: be dissolved in aromatic solvent, as vinylbenzene, acetone and alcoholic solvent, water insoluble and fats solvent.
Embodiment 3
The cyclohexane solvent that in the p-methyl phenol of 10kg, adds 45kg, stir, the solid super acid catalyst that adds 1kg, temperature rising reflux, in reflux course, splash into dipentadiene and the cyclohexane solution (weight ratio is 1: 1) of 8kg, titration time is 50 minutes, reacted 4 hours, and dripped the vinylbenzene of 3.5kg then, titration time is 2.5 hours, reacted 2 hours, filtering recovering catalyst is handled reaction solution by activated carbon decolorizing, remove by filter gac, enter to steam in the still kettle to slip to remove and desolvate, get product of the present invention after the cooling.
This product outward appearance is white or pale yellow powder, and molecular-weight average is: 650～850, and fusing point: 100～115 ℃, ash oontent: 0.05%, median size: 10～30 μ m, solubleness: be dissolved in aromatic solvent, as vinylbenzene, acetone and alcoholic solvent, water insoluble and fats solvent.
Claims (3)
1. Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin has following structural formula:
Outward appearance is white or pale yellow powder; Molecular-weight average is: 650～850;
Fusing point: 100～115 ℃; Ash oontent: 0.05%; Median size: 10～30 μ m;
Solubleness: be dissolved in aromatic solvent, acetone and alcoholic solvent, water insoluble and fats solvent.
2. the synthesis technique of the described Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin of claim 1, may further comprise the steps: p-methyl phenol is added in the cyclohexane solvents by 1: 3.5～5 times weight parts stir, the solid super acid catalyst that adds 0.1～0.15 weight part, temperature rising reflux, in reflux course, splash into the dipentadiene of 0.75～0.8 weight part and the mixing solutions of cyclohexane, its weight ratio is 1: 1, titration time is 30～60 minutes, reacted 3～5 hours, drip the vinylbenzene of 0.3～0.4 weight part then, titration time is 2～3 hours, reacts filtering recovering catalyst 2 hours, reaction solution is handled by activated carbon decolorizing, remove by filter gac, enter to steam in the still kettle to slip to remove and desolvate, get product after the cooling.
3. Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin according to claim 1 is in the anti-oxidant purposes of rubber item, high molecular polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100171265A CN100424122C (en) | 2006-08-23 | 2006-08-23 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100171265A CN100424122C (en) | 2006-08-23 | 2006-08-23 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
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| Publication Number | Publication Date |
|---|---|
| CN1916060A CN1916060A (en) | 2007-02-21 |
| CN100424122C true CN100424122C (en) | 2008-10-08 |
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| CNB2006100171265A Expired - Fee Related CN100424122C (en) | 2006-08-23 | 2006-08-23 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101967223A (en) * | 2010-09-28 | 2011-02-09 | 江苏飞亚化学工业有限责任公司 | Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant |
| CN115322278A (en) * | 2022-08-03 | 2022-11-11 | 杭摩科技新材料(阜阳)有限公司 | Sulfonated nitrostyrene resin and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0915130A1 (en) * | 1997-11-12 | 1999-05-12 | Raschig GmbH | Anti-ageing agent for copolymers and terpolymers of styrene |
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| CN1479755A (en) * | 2000-12-11 | 2004-03-03 | ��˹����ѧ��֬��˾ | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| CN1532214A (en) * | 2003-03-19 | 2004-09-29 | 韩国燃气公司 | Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom |
-
2006
- 2006-08-23 CN CNB2006100171265A patent/CN100424122C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0915130A1 (en) * | 1997-11-12 | 1999-05-12 | Raschig GmbH | Anti-ageing agent for copolymers and terpolymers of styrene |
| CN1479755A (en) * | 2000-12-11 | 2004-03-03 | ��˹����ѧ��֬��˾ | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| CN1532214A (en) * | 2003-03-19 | 2004-09-29 | 韩国燃气公司 | Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom |
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| CN1916060A (en) | 2007-02-21 |
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Assignee: Zhangjiagang Shunchang Chemical Co., Ltd. Assignor: Yang Yanwei Contract fulfillment period: 2008.10.8 to 2026.8.22 contract change Contract record no.: 2008320001053 Denomination of invention: Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene Granted publication date: 20081008 License type: Exclusive license Record date: 20081023 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.10.8 TO 2026.8.22; CHANGE OF CONTRACT Name of requester: ZHANGJIAGANG SHUNCHANG CHEMICAL CO., LTD. Effective date: 20081023 |
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Granted publication date: 20081008 Termination date: 20110823 |