CN103145935A - Method for preparing phenolic resin for energy storage electric carbon - Google Patents
Method for preparing phenolic resin for energy storage electric carbon Download PDFInfo
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- CN103145935A CN103145935A CN2013100315717A CN201310031571A CN103145935A CN 103145935 A CN103145935 A CN 103145935A CN 2013100315717 A CN2013100315717 A CN 2013100315717A CN 201310031571 A CN201310031571 A CN 201310031571A CN 103145935 A CN103145935 A CN 103145935A
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Abstract
The invention discloses a method for preparing phenolic resin for energy storage electric carbon. The preparation method includes a first step of adding phenol and methanal into an enamel reaction kettle in proportion, starting to stir, adding flexibilizer, titrating and adding a part of composite acid catalysts into the enamel reaction kettle, a second step of heating the enamel reaction kettle, a third step of cooling the enamel reaction kettle, and titrating and adding a part of composite acid catalysts into the enamel reaction kettle, a fourth step of cooling the enamel reaction kettle, continuing titrating and adding remaining composite acid catalysts into the enamel reaction kettle, keeping boiling for a while, a fifth step of adding plasticizer and hydrophilic and oleophylic agents into the enamel reaction kettle and carrying out stirring and reaction, a sixth step of adding alkaline matters to enable potential of hydrogen (PH) to be adjusted to be alkalescence and then carrying out stirring, reaction, heating and dewatering, and a seventh step of carrying out heating and pressurizing after dewatering is completed, and then discharging under the protection of inert gases to obtain the phenolic resin for the energy storage electric carbon. Reaction through adoption of the method is smooth in process, not prone to implosion and kettle explosion, safe and reliable. Products prepared through the method are low in melting point and large in electric energy storage amount, and holes are convenient to form, and hole structures in carbon materials can be conveniently formed.
Description
Technical field
The present invention relates to the high molecular polymer technical field, a kind of fusing point is low specifically, the electric energy reserves are large, drilling is convenient and react mild, safe and reliable energy storage electrical carbon with the preparation method of resol.
Background technology
Resol is the general designation of phenols and the aldehydes resin that reaction forms under the condition that catalyzer exists.Adopt the resol of traditional preparation method of phenolic resin preparation, can't satisfy the ingredient requirement of energy storage electrical carbon.
Summary of the invention
The objective of the invention is the defective for prior art, provide that a kind of fusing point is low, the electric energy reserves are large, drilling is convenient and reacts mild, safe and reliable energy storage electrical carbon with the preparation method of resol.
The objective of the invention is to solve by the following technical programs:
A kind of energy storage electrical carbon preparation method of resol is characterized in that described preparation method carries out in the steps below:
(1) phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.8-0.9, start and stir and add toughner, then titration adds part combination of acidic catalyzer, and the mixture ph value of enamel reaction still is adjusted to 2.1-2.4;
(2) progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 80-85 ℃, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, and boiling is rear the maintenance 0.5-1.5 hour steadily, then was cooled to 75-80 ℃;
(3) titration adds part combination of acidic catalyzer again, and the temperature automatic heating in enamel reaction still was kept approximately 0.5-1 hour to boiling, then was cooled to 75-80 ℃;
(4) continue titration and add remaining combination of acidic catalyzer, the temperature automatic heating in enamel reaction still was kept approximately 1.5-2.5 hour to boiling;
(5) add softening agent and hydrophilic and oleophilic agent and stirring reaction 0.5-1 hour in enamel reaction still;
(6) add alkaline matter that pH value is adjusted into weakly alkaline in enamel reaction still, then make the interior temperature of enamel reaction still be elevated to 100-110 ℃ after stirring reaction 0.5-1 hour and dewatered 0.5-1.5 hour;
(7) pressurization after being warmed up to 150-160 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.
Toughner in described step (1) is one or both in cashew nut oil, tung oil, polycaprolactam, paracril.
The weight of the toughner in described step (1) is the 10-25% of phenol weight.
Combination of acidic catalyzer in described step (1) is the nitration mixture that boric acid, hydrochloric acid and phosphoric acid form.
The weight ratio of the combination of acidic catalyzer in described step (1), (3) and (4) is 30-35%:40-50%:15-30%.
Softening agent in described step (5) is that the weight of a kind of and softening agent in butter, butter is the 5-15% of phenol weight, and the weight of hydrophilic and oleophilic agent is the 1-2% of phenol weight.
Add one or both in KOH, NaOH, NaHCO3, NH4H2PO4, KH2PO4 that pH value is adjusted into 7.0-8.0 in described step (6) in enamel reaction still.
The weight of the alkaline matter in described step (6) is the 1-2% of phenol weight.
Discharging pressure in described step (7) in enamel reaction still is 0.1-0.2MPa.
Finished product energy storage electrical carbon in described step (7) is not more than 3.0% with the water content of resol.
The present invention has the following advantages compared to existing technology:
The present invention is difficult for implode, quick-fried still by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, safe and reliable, simultaneously the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of combination of acidic catalyzer.
The present invention is by adding the butter that is beneficial to granulating and forming, butter etc. as softening agent in reaction process, and the hydrophilic and oleophilic agent that adds in addition makes the consistency of softening agent and resol better, is conducive to extrude with drilling even; The energy storage electrical carbon that makes has with resol and is low to moderate the fusing point of 70-80 ℃, can reduce the speed of curing reaction during extruding pelletization, is beneficial to the extruding pelletization moulding, is difficult for stopping up in forcing machine, is conducive to the moulding of carbon material pore structure.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.8, start that to stir and to add weight be that the cashew nut oil of phenol weight 10% is as toughner, then titration adds the combination of acidic catalyzer of 30% weight, and the mixture ph value of enamel reaction still is adjusted to 2.3-2.4; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 85 ℃, owing to being thermopositive reaction, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 0.5 hour after boiling steadily, then be cooled to 80 ℃; Titration adds the combination of acidic catalyzer of 47% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 0.8 hour to boiling, then was cooled to 75 ℃; Continue the combination of acidic catalyzer that titration adds remaining 23% weight, the temperature automatic heating in enamel reaction still was kept approximately 2.5 hours to boiling; Then adding weight in enamel reaction still is that 9% butter of phenol weight are the hydrophilic and oleophilic agent of phenol weight 1% and stirring reaction 1 hour as softening agent and weight; Adding weight in enamel reaction still is that the KOH of phenol weight 1.2% is adjusted into 7.2-7.4 with pH value, then stirring reaction makes temperature in enamel reaction still be elevated to 110 ℃ to dewater 0.5-1 hour after 0.5 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.15MPa after being warmed up to 150 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Embodiment 2
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.85, start that to stir and to add weight be that the tung oil of phenol weight 12% and polycaprolactam are as toughner, then titration adds the combination of acidic catalyzer of 33% weight, and the mixture ph value of enamel reaction still is adjusted to 2.2-2.3; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 80 ℃, owing to being thermopositive reaction, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 0.8 hour after boiling steadily, then be cooled to 75 ℃; Titration adds the combination of acidic catalyzer of 45% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 0.9 hour to boiling, then was cooled to 75 ℃; Continue the combination of acidic catalyzer that titration adds remaining 22% weight, the temperature automatic heating in enamel reaction still was kept approximately 2 hours to boiling; Then adding weight in enamel reaction still is that 5% butter of phenol weight is the hydrophilic and oleophilic agent of phenol weight 1% and stirring reaction 1 hour as softening agent and weight; Adding weight in enamel reaction still is NaOH and the NaHCO of phenol weight 1.5%
3Mixed solution pH value is adjusted into 7.7-7.8, then stirring reaction makes temperature in enamel reaction still be elevated to 100 to dewater 0.5-1.5 hour after 0.8 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.13MPa after being warmed up to 160 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Embodiment 3
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.9, start that to stir and to add weight be that the cashew nut oil of phenol weight 20% and paracril are as toughner, then titration adds the combination of acidic catalyzer of 35% weight, and the mixture ph value of enamel reaction still is adjusted to 2.1-2.2; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 83 ℃, owing to being thermopositive reaction, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 1.2 hours after boiling steadily, then be cooled to 78 ℃; Titration adds the combination of acidic catalyzer of 45% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 0.8 hour to boiling, then was cooled to 78 ℃; Continue the combination of acidic catalyzer that titration adds remaining 20% weight, the temperature automatic heating in enamel reaction still was kept approximately 1.5 hours to boiling; Then adding weight in enamel reaction still is that 15% butter of phenol weight are the hydrophilic and oleophilic agent of phenol weight 2% and stirring reaction 1 hour as softening agent and weight; Adding weight in enamel reaction still is the NH of phenol weight 2%
4H
2PO
4And KH
2PO
4Mixed solution pH value is adjusted into 7.9-8.0, then stirring reaction makes temperature in enamel reaction still be elevated to 110 ℃ to dewater about 1.5 hours after 0.5 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.2MPa after being warmed up to 155 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Embodiment 4
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.83, start that to stir and to add weight be that the paracril of phenol weight 20% and tung oil are as toughner, then titration adds the combination of acidic catalyzer of 32% weight, and the mixture ph value of enamel reaction still is adjusted to 2.3-2.4; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 85 ℃, owing to being thermopositive reaction, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 1.5 hours after boiling steadily, then be cooled to 80 ℃; Titration adds the combination of acidic catalyzer of 50% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 1 hour to boiling, then was cooled to 80 ℃; Continue the combination of acidic catalyzer that titration adds remaining 18% weight, the temperature automatic heating in enamel reaction still was kept approximately 1.5 hours to boiling; Then adding weight in enamel reaction still is that 8% butter of phenol weight is the hydrophilic and oleophilic agent of phenol weight 1.4% and stirring reaction 0.6 hour as softening agent and weight; Adding weight in enamel reaction still is the NaHCO of phenol weight 1.7%
3And KH
2PO
4Mixed solution pH value is adjusted into 7.7-7.8, then stirring reaction makes temperature in enamel reaction still be elevated to 105 ℃ to dewater 1-1.5 hour after 0.9 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.13MPa after being warmed up to 158 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Embodiment 5
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.88, start that to stir and to add weight be that the cashew nut oil of phenol weight 25% and tung oil are as toughner, then titration adds the combination of acidic catalyzer of 35% weight, and the mixture ph value of enamel reaction still is adjusted to 2.1-2.2; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 85 ℃, owing to being thermopositive reaction, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 1.5 hours after boiling steadily, then be cooled to 75 ℃; Titration adds the combination of acidic catalyzer of 50% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 1 hour to boiling, then was cooled to 80 ℃; Continue the combination of acidic catalyzer that titration adds remaining 15% weight, the temperature automatic heating in enamel reaction still was kept approximately 1.5 hours to boiling; Then adding weight in enamel reaction still is that 14% butter of phenol weight is the hydrophilic and oleophilic agent of phenol weight 1.9% and stirring reaction 1 hour as softening agent and weight; Adding weight in enamel reaction still is that the KOH of phenol weight 2% and the mixture of NaOH are adjusted into 7.0-7.2 with pH value, then stirring reaction makes temperature in enamel reaction still be elevated to 110 ℃ to dewater about 1 hour after 0.8 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.2MPa after being warmed up to 160 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Embodiment 6
Phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.82, start that to stir and to add weight be that the paracril of phenol weight 22% is as toughner, then titration adds the combination of acidic catalyzer of 30% weight, and the mixture ph value of enamel reaction still is adjusted to 2.3-2.4; Then progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 85 ℃, owing to being thermopositive reaction, the temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, kept 1 hour after boiling steadily, then be cooled to 75 ℃; Titration adds the combination of acidic catalyzer of 40% weight again, and the temperature automatic heating in enamel reaction still was kept approximately 1 hour to boiling, then was cooled to 80 ℃; Continue the combination of acidic catalyzer that titration adds remaining 30% weight, the temperature automatic heating in enamel reaction still was kept approximately 2.5 hours to boiling; Then adding weight in enamel reaction still is that 12% butter of phenol weight are the hydrophilic and oleophilic agent of phenol weight 1.6% and stirring reaction 0.7 hour as softening agent and weight; Adding weight in enamel reaction still is the NaHCO of phenol weight 1.5%
3PH value is adjusted into 7.6-7.8, and then stirring reaction makes temperature in enamel reaction still be elevated to 100 ℃ to dewater 0.5-1 hour after 0.6 hour, and is tack-free as index in room temperature cold water take resin; Be forced into 0.17MPa after being warmed up to 150 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.The finished product energy storage electrical carbon that obtains with the water content of resol be not more than 3.0% and fusing point be 70-80 ℃, by adding stage by stage the combination of acidic catalyzer to make reaction mild in reaction process, be difficult for implode, quick-fried still, safe and reliable, the over-all properties that adds energy storage electrical carbon such as can improving electric energy reserves, drilling efficient of while combination of acidic catalyzer; Adding of hydrophilic and oleophilic agent makes the consistency of softening agent and resol better, be conducive to extrude with drilling even, can reduce the speed of curing reaction during extruding pelletization, be beneficial to the extruding pelletization moulding, be difficult for stopping up in forcing machine, be conducive to the moulding of carbon material pore structure.
Above embodiment only for explanation technological thought of the present invention, can not limit protection scope of the present invention with this, every technological thought that proposes according to the present invention, and any change of doing on the technical scheme basis is within all falling into protection domain of the present invention; The technology that the present invention does not relate to all can be realized by prior art.
Claims (10)
1. an energy storage electrical carbon with the preparation method of resol, is characterized in that described preparation method carries out in the steps below:
(1) phenol and formaldehyde are added enamel reaction still according to the ratio of mol ratio 1:0.8-0.9, start and stir and add toughner, then titration adds part combination of acidic catalyzer, and the mixture ph value of enamel reaction still is adjusted to 2.1-2.4;
(2) progressively pass into steam heating in the chuck of enamel reaction still, stopped heating when the temperature in enamel reaction still is elevated to 80-85 ℃, temperature meeting automatic-ascending in enamel reaction still is to boiling state at this moment, and boiling is rear the maintenance 0.5-1.5 hour steadily, then was cooled to 75-80 ℃;
(3) titration adds part combination of acidic catalyzer again, and the temperature automatic heating in enamel reaction still was kept approximately 0.5-1 hour to boiling, then was cooled to 75-80 ℃;
(4) continue titration and add remaining combination of acidic catalyzer, the temperature automatic heating in enamel reaction still was kept approximately 1.5-2.5 hour to boiling;
(5) add softening agent and hydrophilic and oleophilic agent and stirring reaction 0.5-1 hour in enamel reaction still;
(6) add alkaline matter that pH value is adjusted into weakly alkaline in enamel reaction still, then make the interior temperature of enamel reaction still be elevated to 100-110 ℃ after stirring reaction 0.5-1 hour and dewatered 0.5-1.5 hour;
(7) pressurization after being warmed up to 150-160 ℃ after dehydration is completed, the protection bottom discharge at rare gas element at last obtains energy storage electrical carbon resol.
2. energy storage electrical carbon according to claim 1 is with the preparation method of resol, it is characterized in that toughner in described step (1) is one or both in cashew nut oil, tung oil, polycaprolactam, paracril.
3. energy storage electrical carbon according to claim 1 and 2 is with the preparation method of resol, and the weight that it is characterized in that the toughner in described step (1) is the 10-25% of phenol weight.
4. energy storage electrical carbon according to claim 1 with the preparation method of resol, is characterized in that the combination of acidic catalyzer in described step (1) is the nitration mixture that boric acid, hydrochloric acid and phosphoric acid form.
5. according to claim 1 or 4 described energy storage electrical carbon with the preparation method of resol, is characterized in that the weight ratio of the combination of acidic catalyzer in described step (1), (3) and (4) is 30-35%:40-50%:15-30%.
6. energy storage electrical carbon according to claim 1 is with the preparation method of resol, it is characterized in that softening agent in described step (5) is that the weight of a kind of and softening agent in butter, butter is the 5-15% of phenol weight, the weight of hydrophilic and oleophilic agent is the 1-2% of phenol weight.
7. energy storage electrical carbon according to claim 1 with the preparation method of resol, is characterized in that adding KOH, NaOH, NaHCO in described step (6) in enamel reaction still
3, NH
4H
2PO
4, KH
2PO
4In one or both pH value is adjusted into 7.0-8.0.
8. energy storage electrical carbon according to claim 1 is with the preparation method of resol, and the weight that it is characterized in that the alkaline matter in described step (6) is the 1-2% of phenol weight.
9. energy storage electrical carbon according to claim 1 with the preparation method of resol, is characterized in that in described step (7), the discharging pressure in enamel reaction still is 0.1-0.2MPa.
10. energy storage electrical carbon according to claim 1 is with the preparation method of resol, it is characterized in that the finished product energy storage electrical carbon in described step (7) is not more than 3.0% with the water content of resol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082859A (en) * | 2017-05-12 | 2017-08-22 | 浙江杭摩合成材料股份有限公司 | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing |
| CN108192052A (en) * | 2017-12-26 | 2018-06-22 | 宜兴市天宇世纪高新科技有限公司 | A kind of preparation method of phenolic aldehyde base carbon fibre phenolic resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161740A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Preparation method phenolic resin |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
-
2013
- 2013-01-28 CN CN2013100315717A patent/CN103145935A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161740A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Preparation method phenolic resin |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082859A (en) * | 2017-05-12 | 2017-08-22 | 浙江杭摩合成材料股份有限公司 | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing |
| CN108192052A (en) * | 2017-12-26 | 2018-06-22 | 宜兴市天宇世纪高新科技有限公司 | A kind of preparation method of phenolic aldehyde base carbon fibre phenolic resin |
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Effective date of registration: 20141118 Address after: 100020, Beijing, Chaoyang District, 16 Wai Street, China Life Building, 5 floor, South District Applicant after: BEIJING ZHONGSHIHONG INSTALLATION ENGINEERING CO., LTD. Address before: Xinjiezhen Zhenxin West Road Yixing Jiangsu province 214204 city of Wuxi City, No. 6-8 Applicant before: Jiangsu Guozheng New Material Technology Co., Ltd. |
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| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20151216 |
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| C20 | Patent right or utility model deemed to be abandoned or is abandoned |