CN103420810A - Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins - Google Patents
Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins Download PDFInfo
- Publication number
- CN103420810A CN103420810A CN201210160457XA CN201210160457A CN103420810A CN 103420810 A CN103420810 A CN 103420810A CN 201210160457X A CN201210160457X A CN 201210160457XA CN 201210160457 A CN201210160457 A CN 201210160457A CN 103420810 A CN103420810 A CN 103420810A
- Authority
- CN
- China
- Prior art keywords
- reaction
- cresol
- butyl
- tert
- hindered phenol
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins. The preparation method comprises steps: with strong acid resins as catalysts, and benzene or cyclohexane as a solvent, 2-tert-Butyl-p-cresol and dicyclopentadiene are subjected to a polymerization reaction to form phenol-type petroleum resins; the phenol-type petroleum resins and saturated alcohols with one to three carbons are subjected to an alkylation reaction to form polymerization-type asymmetric hindered phenol anti-oxidant resins in presence of phosphoric acid and nickel-containing catalysts; the alkylation reaction products are subjected to reduced pressure distillation to remove the unreacted raw materials and solvent to obtain polymerization-type asymmetric hindered phenol antioxidant resin products. The preparation method has obvious positive effects, the polymerization reaction and the alkylation reaction have high selectivity and conversion rate, and the yield is about 80%. What is more important is that compared to traditional hindered phenol antioxidants, the synthesized polymerization-type asymmetric hindered phenol antioxidant resins are advantaged by high antioxidant activity, high heat stability, extracting resistance, compatibility, non-toxic and environmentally friendly characteristics.
Description
Technical field
The present invention relates to prepare the method for aggretion type non-symmetrical hindered phenol kind antioxidant resin, be particularly related to by dicyclopentadiene, o-tert-butyl p-cresol and C1～C3 saturated alcohol, prepare the method for aggretion type non-symmetrical hindered phenol kind antioxidant resin through polymerization and alkylated reaction.
Background technology
Oxidation inhibitor is the polymer builder that a class can effectively reduce plastics or rubber item automatic oxidation reaction speed, delaying retrogradation degraded, and its application almost relates to all polymer products.Because most polymer need to just can be processed into goods through 220～350 ℃ of heating, and traditional oxidation inhibitor is easy to volatilization under high-temperature, thereby affects the performance of goods and cause the deterioration of environment.At present, oxidation inhibitor relatively is typically amine and phenols, and wherein amine antioxidants is mainly used in greatly rubber because of toxicity, and easy to change in use procedure, bad with hydro carbons oil product conformability.The main direction of research is the compound anti-aging agent of phenols and aggretion type phenolic antioxidant at present.By improving the oxidation inhibitor molecular weight, can apply to high temperature process.In existing synthesis technique, phenolic antioxidant ortho position group mostly is the tertiary butyl, when ortho position group volume is excessive, can suppress rotating freely of hydroxyl because of spatial obstacle, make free radical be difficult for approaching with-OH, thereby be difficult for Mulberry Extract, the antioxygenic activity of phenols is reduced greatly.And different ortho position groups has different antioxygen speed, adopt the oxidation inhibitor of different ortho positions group can regulate antioxygen speed.Develop in recent years high thermal stability, anti-extractable, consistency and nontoxic aggretion type oxidation inhibitor, improving molecular weight and asymmetric substituting group is the key that improves quality of item.Improving the oxidation inhibitor molecular weight can increase the consistency of oxidation inhibitor and polymkeric substance, improves oxidation inhibitor efficiency.But molecular mass also can not be too high, too high molecular weight also can affect the consistency of the intramolecular migration of oxidation inhibitor and oxidation inhibitor and basic material.By to thermostability, the considering of resistant to extraction and efficiency, relative molecular mass is the most suitable about 500～3000 oligopolymer.Usually the synthetic method of aggretion type oxidation inhibitor is to make by polymerization, by graft copolymerization, makes in addition.The phenolic antioxidant optimum weight is 500～1500, and polymerization type hindered phenol oxidation inhibitor relative molecular weight is more than 800.Current disclosed phenolic antioxidant document, as: CN 100424122C discloses a kind of p-cresol-dicyclopentadiene vinylbenzene oxidation inhibitor, and this kind of oxidation inhibitor, at phenolic hydroxyl group ortho position and styrene polymerization, only has a kind of larger ortho position group, and antioxygen efficiency is low.CN101402721A discloses the synthetic method of a kind of p-cresol-dicyclopentadiene isobutyl alkylene antioxidant resin, use concentrated sulfuric acid catalyst in this explained hereafter, strong corrosion is arranged, use atlapulgite Removal of catalyst and decolouring can produce a large amount of solid wastes, increase contaminate environment.CN101967223A discloses the synthetic method of a kind of methylphenol-dicyclopentadiene isobutyl-resin antioxidant, this technique be take composite sulfoacid as the butylation catalyzer, p-methyl phenol, dicyclopentadiene and iso-butylene are raw material synthesizing methyl phenol-dicyclopentadiene isobutyl-resin antioxidant, because only there is the tertiary butyl at ortho position on its oxidation inhibitor space structure, antioxidant effect is low; Raw material adopts iso-butylene, should not store and exist potential safety hazard.
Summary of the invention
The invention provides a kind of synthetic method of novel antioxidant, o-tert-butyl p-cresol, dicyclopentadiene and the C1～C3 saturated alcohol of take is raw material, under catalyst action, through polymerization and alkylated reaction synthesized polymer type non-symmetrical hindered phenol antioxidant resin.
The sterically hindered of ortho-substituent is an important factor that affects anti-oxidant activity.Larger ortho-substituent has larger sterically hindered, can provide protection to phenolic hydroxyl group, and less ortho-substituent makes phenolic hydroxyl group antioxygen speed of reaction faster, has increased its antioxygenic activity.Therefore asymmetric phenolic antioxidant has its unique advantage, and sterically hindered being enough to of the tertiary butyl provides protection to phenolic hydroxyl group on the one hand, and on ortho position, the antioxygen speed of reaction of less alkyl group is faster on the other hand, has therefore increased its antioxygenic activity.Below technical scheme of the present invention:
A kind of aggretion type non-symmetrical hindered phenol kind antioxidant resin has following structure:
Wherein n is 1～4.
Outward appearance is brown resin; Molecular-weight average 500～1000;
80～110 ℃ of softening temperatures, be dissolved in acetone and aromatic solvent, water insoluble and fats solvent.Its synthesis technique mainly comprises the following steps:
1) o-tert-butyl p-cresol and dicyclopentadiene are under catalyst action, generate phenol type petroleum resin through polyreaction, o-tert-butyl p-cresol and the catalyzer mass ratio that feeds intake is 1: 0.01～0.5, o-tert-butyl p-cresol and the solvent mass ratio that feeds intake is 1: 2～10, o-tert-butyl p-cresol and the dicyclopentadiene mass ratio that feeds intake is 1: 1～5, dicyclopentadiene drips charging, dropping temperature is 80～100 ℃, time for adding is 60～120min, temperature of reaction is 100～150 ℃, and the reaction times is 120～300min;
2) by step 1) gained phenol type petroleum resin, phosphoric acid and containing under the alumina catalyzation effect of active component nickel with C1～C3 saturated alcohol generation alkylated reaction, remove oligopolymer through underpressure distillation again, solvent and unreacting material make aggretion type non-symmetrical hindered phenol antioxidant resin; O-tert-butyl p-cresol and catalyst for alkylation reaction feed ratio are 1: 0.01～0.2, o-tert-butyl p-cresol and C1～C3 saturated alcohol mass ratio that feeds intake is 1: 0.05～0.5, time for adding 30～100min, temperature of reaction is 60～90 ℃, the reaction times is 60～180min.
Above-mentioned steps 1) described polymerisation catalysts is any one in highly acidic resin, solid super-strong acid, carried heteropoly acid, acid molecular sieve catalyst, phosphoric acid and sulfuric acid.
Above-mentioned steps 1) described o-tert-butyl p-cresol and solvent feed intake mass ratio be preferably 1: 3～6, o-tert-butyl p-cresol and the catalyzer mass ratio that feeds intake is preferably 0.1～0.3, o-tert-butyl p-cresol and dicyclopentadiene feed intake mass ratio be preferably 1: 1.2～2.5, dropping temperature is preferably 80～95 ℃, time for adding is preferably 60～100min, reaction times, temperature of reaction was for being preferably 100～120 ℃ in order to be preferably 210～270min.
Above-mentioned steps 2) described p-methyl phenol and catalyst for alkylation reaction mass ratio be preferably 1: 0.05～0.2, o-tert-butyl p-cresol and C1～C3 saturated alcohol feed intake mass ratio be preferably 1: 0.1～0.4, time for adding is preferably 30～60min, temperature of reaction is for being preferably 75～85 ℃, and the reaction times is for being preferably 90～150min.
Above-mentioned steps 1), step 2) described reaction solvent is any one in toluene or hexanaphthene.
Essence of the present invention is to improve the phenolic antioxidant molecular weight, and on the ortho position of phenolic antioxidant addition one alkyl, thereby make oxidation inhibitor there is better antioxidant effect.Compared with prior art, the invention has the advantages that: traditional oxidation inhibitor is at high temperature volatile, thereby affects the performance of goods, this product has higher molecular weight, existing high thermal stability, its applicable molecular weight also has good anti-extractable, consistency, nontoxic and environment friendly; The sterically hindered of ortho-substituent is an important factor that affects anti-oxidant activity.When ortho position group volume is excessive, can be because spatial obstacle has suppressed rotating freely of hydroxyl, make free radical be difficult for approaching with-OH, thereby be difficult for Mulberry Extract, the antioxygenic activity of phenols is reduced greatly.The phenolic antioxidant ortho position group that tradition is used mostly is the tertiary butyl.The phenolic hydroxyl group ortho position has that one less and a non-symmetrical hindered phenol structure antioxidant effect tertiary butyl is better.Sterically hindered being enough to of the tertiary butyl provides protection to phenolic hydroxyl group on the one hand, and on ortho position, less alkyl group makes the antioxygen speed of reaction of phenolic hydroxyl group faster on the other hand, therefore increased its antioxygenic activity; Alkylation catalyst catalyzed polymerization type antioxidant resin and the C1～C3 saturated alcohol alkylation reaction technique of exploitation, the danger of avoiding using iso-butylene etc. to bring, technique is simple and safe.
Embodiment
[embodiment 1]
Agitator is being housed, reflux exchanger, in the 500ml reactor of feeding device and nitrogen protection device, add 400g toluene, 100g o-tert-butyl p-cresol, 10g highly acidic resin catalyzer, with after nitrogen replacement, be heated to 83 ℃, drip dicyclopentadiene 120g with pump, time for adding 30min, after dropwising, be warming up to 113 ℃, after reaction 3.5h, add phosphatase 11 .5g, alkylation catalyst 9g, 85 ℃ of temperature of reaction, drip methyl alcohol 30g, time for adding 60min, drip and finish rear reaction 120min, reaction removes by filter resin catalyst after finishing, alkali cleaning and be washed to neutrality, the water vapour air lift is removed oligopolymer, underpressure distillation after solvent and unreacting material, be distilled to 206 ℃, cooling rear acquisition product 136g, calculating product yield is 79.2%.Product is brown resin, and GPC measures its molecular weight 600～660,86.2 ℃ of softening temperatures.
[embodiment 2]
Agitator is being housed, reflux exchanger, in the 500ml reactor of feeding device and nitrogen protection device, add 400g toluene, 100g o-tert-butyl p-cresol, 20g highly acidic resin catalyzer, with after nitrogen replacement, be heated to 90 ℃, drip dicyclopentadiene 160g with pump, time for adding 80min, after dropwising, be warming up to 120 ℃, after reaction 4h, add phosphoric acid 2g, alkylation catalyst 13.5g, 78 ℃ of temperature of reaction, drip methyl alcohol 35g, time for adding 45min, drip and finish rear reaction 100min, reaction removes by filter resin catalyst after finishing, alkali cleaning and be washed to neutrality, the water vapour air lift is removed oligopolymer, underpressure distillation after solvent and unreacting material, be distilled to 239 ℃, cooling rear acquisition product 152g, calculating product yield is 82.4%.Product is brown resin, and GPC measures its molecular weight 730～830,93.5 ℃ of softening temperatures.
[embodiment 3]
Agitator is being housed, reflux exchanger, in the 500ml reactor of feeding device and nitrogen protection device, add 600g toluene, 100g o-tert-butyl p-cresol, 12g highly acidic resin catalyzer, with after nitrogen replacement, be heated to 95 ℃, drip dicyclopentadiene 150g with pump, time for adding 90min, after dropwising, be warming up to 115 ℃, after reaction 4.5h, add phosphatase 11 .6g, alkylation catalyst 12g, 80 ℃ of temperature of reaction, drip methyl alcohol and 1: 1 raw material 40g of ethanol mol ratio, time for adding 40min, drip and finish rear reaction 120min, reaction removes by filter resin catalyst after finishing, alkali cleaning and be washed to neutrality, the water vapour air lift is removed oligopolymer, underpressure distillation after solvent and unreacting material, be distilled to 237 ℃, cooling rear acquisition product 156g, calculating product yield is 83.5%.Product is brown resin, and GPC measures its molecular weight 680～770,91.4 ℃ of softening temperatures.
Claims (5)
1. an aggretion type non-symmetrical hindered phenol kind antioxidant resin has following structure:
Wherein n is 1～4.
Outward appearance is brown resin; Molecular-weight average 600～1000;
80～115 ℃ of softening temperatures, be dissolved in acetone and aromatic solvent, water insoluble and fats solvent.Its synthesis technique mainly comprises the following steps:
1) o-tert-butyl p-cresol and dicyclopentadiene are under catalyst action, generate phenol type petroleum resin through polyreaction, o-tert-butyl p-cresol and the catalyzer mass ratio that feeds intake is 1: 0.01～0.5, o-tert-butyl p-cresol and the solvent mass ratio that feeds intake is 1: 2～10, o-tert-butyl p-cresol and the dicyclopentadiene mass ratio that feeds intake is 1: 1～5, dicyclopentadiene drips charging, dropping temperature is 80～100 ℃, time for adding is 60～120min, temperature of reaction is 100～150 ℃, and the reaction times is 120～300min;
2) by step 1) gained phenol type petroleum resin, phosphoric acid and containing under the alumina catalyzation effect of active component nickel with C1～C3 saturated alcohol generation alkylated reaction, remove oligopolymer through underpressure distillation again, solvent and unreacting material make aggretion type non-symmetrical hindered phenol antioxidant resin; O-tert-butyl p-cresol and catalyst for alkylation reaction feed ratio are 1: 0.01～0.2, o-tert-butyl p-cresol and C1～C3 saturated alcohol mass ratio that feeds intake is 1: 0.05～0.5, time for adding 30～100min, temperature of reaction is 60～90 ℃, the reaction times is 60～180min.
2. a kind of aggretion type non-symmetrical hindered phenol kind antioxidant resin according to claim 1, is characterized in that step 1) described polymerisation catalysts is any one in highly acidic resin, solid super-strong acid, carried heteropoly acid, acid molecular sieve catalyst, phosphoric acid and sulfuric acid.
3. a kind of aggretion type non-symmetrical hindered phenol kind antioxidant resin according to claim 1, it is characterized in that step 1) described o-tert-butyl p-cresol and solvent feed intake mass ratio be preferably 1: 3～6, o-tert-butyl p-cresol and the catalyzer mass ratio that feeds intake is preferably 0.1～0.3, o-tert-butyl p-cresol and dicyclopentadiene feed intake mass ratio be preferably 1: 1.2～2.5, dropping temperature is preferably 80～95 ℃, time for adding is preferably 60～100min, reaction times, temperature of reaction was for being preferably 100～120 ℃ in order to be preferably 210～270min.
4. a kind of aggretion type non-symmetrical hindered phenol kind antioxidant resin according to claim 1, it is characterized in that step 2) described p-methyl phenol and catalyst for alkylation reaction mass ratio be preferably 1: 0.05～and 0.2, o-tert-butyl p-cresol and C1～C3 saturated alcohol feed intake mass ratio be preferably 1: 0.1～0.4, time for adding is preferably 30～60min, temperature of reaction is for being preferably 75～85 ℃, and the reaction times is for being preferably 90～150min.
5. a kind of aggretion type non-symmetrical hindered phenol kind antioxidant resin according to claim 1, is characterized in that step 1), step 2) described reaction solvent is any one in toluene or hexanaphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210160457XA CN103420810A (en) | 2012-05-22 | 2012-05-22 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210160457XA CN103420810A (en) | 2012-05-22 | 2012-05-22 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103420810A true CN103420810A (en) | 2013-12-04 |
Family
ID=49646244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210160457XA Pending CN103420810A (en) | 2012-05-22 | 2012-05-22 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103420810A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631707A (en) * | 2016-11-16 | 2017-05-10 | 广东希必达新材料科技有限公司 | Method for preparing p-cresol dicyclopentadiene butylation product |
| CN106916432A (en) * | 2016-09-01 | 2017-07-04 | 艾特国际有限公司 | For stablizing polyoxygenated alkene PPG, the method for preventing its oxidative degradation |
| CN108863727A (en) * | 2018-06-09 | 2018-11-23 | 河北晟凯新材料科技有限公司 | A kind of method of synthesized polymer Hinered phenols antioxidant |
| CN109593198A (en) * | 2018-11-20 | 2019-04-09 | 吉林化工学院 | A kind of polymerized hindered phenolic antioxidant and preparation method thereof |
| CN111100242A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Dicyclopentadiene hydrogenated petroleum resin and preparation method thereof |
| CN115894391A (en) * | 2022-11-17 | 2023-04-04 | 万华化学集团股份有限公司 | Hindered phenol antioxidant and preparation method thereof, ABS emulsion type antioxidant composition and ABS resin prepared from ABS emulsion type antioxidant composition |
| CN115894391B (en) * | 2022-11-17 | 2024-11-12 | 万华化学集团股份有限公司 | Hindered phenol antioxidant, preparation method thereof, ABS emulsion type antioxidant composition and ABS resin prepared from ABS emulsion type antioxidant composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011031031A1 (en) * | 2009-09-10 | 2011-03-17 | Korea Kumho Petrochemical Co., Ltd. | Novel thio compounds and preparing method of the same |
| CN102224227A (en) * | 2008-11-24 | 2011-10-19 | 科聚亚公司 | Antioxidant compositions |
-
2012
- 2012-05-22 CN CN201210160457XA patent/CN103420810A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102224227A (en) * | 2008-11-24 | 2011-10-19 | 科聚亚公司 | Antioxidant compositions |
| WO2011031031A1 (en) * | 2009-09-10 | 2011-03-17 | Korea Kumho Petrochemical Co., Ltd. | Novel thio compounds and preparing method of the same |
Non-Patent Citations (2)
| Title |
|---|
| 张丽平等: "双环戊二烯酚型抗氧剂的高效液相色谱分析及其在聚丙烯中的应用研究", 《中国塑料》, vol. 23, no. 6, 30 June 2009 (2009-06-30), pages 81 - 85 * |
| 李铮: "聚合多酚抗氧剂BPCD的合成", 《精细石油化工》, vol. 25, no. 4, 31 July 2008 (2008-07-31) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916432A (en) * | 2016-09-01 | 2017-07-04 | 艾特国际有限公司 | For stablizing polyoxygenated alkene PPG, the method for preventing its oxidative degradation |
| CN106631707A (en) * | 2016-11-16 | 2017-05-10 | 广东希必达新材料科技有限公司 | Method for preparing p-cresol dicyclopentadiene butylation product |
| CN108863727A (en) * | 2018-06-09 | 2018-11-23 | 河北晟凯新材料科技有限公司 | A kind of method of synthesized polymer Hinered phenols antioxidant |
| CN111100242A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Dicyclopentadiene hydrogenated petroleum resin and preparation method thereof |
| CN109593198A (en) * | 2018-11-20 | 2019-04-09 | 吉林化工学院 | A kind of polymerized hindered phenolic antioxidant and preparation method thereof |
| CN109593198B (en) * | 2018-11-20 | 2021-05-11 | 吉林化工学院 | Polymerization type hindered phenol antioxidant and preparation method thereof |
| CN115894391A (en) * | 2022-11-17 | 2023-04-04 | 万华化学集团股份有限公司 | Hindered phenol antioxidant and preparation method thereof, ABS emulsion type antioxidant composition and ABS resin prepared from ABS emulsion type antioxidant composition |
| CN115894391B (en) * | 2022-11-17 | 2024-11-12 | 万华化学集团股份有限公司 | Hindered phenol antioxidant, preparation method thereof, ABS emulsion type antioxidant composition and ABS resin prepared from ABS emulsion type antioxidant composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103420810A (en) | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins | |
| CN103420807A (en) | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins | |
| CN109096099B (en) | Production method of 3, 5-di-tert-butyl-4-hydroxybenzoic acid | |
| CN103420808A (en) | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins | |
| WO2014038989A1 (en) | CATALYTIC REDUCTIVE CLEAVAGE OF A β-Ο-4 BOND OF ETHERS OR POLYETHERS SUCH AS LIGNIN | |
| CN103450131B (en) | The preparation method of a kind of dehydroacetic acid (DHA) and sodium salt thereof | |
| CN103420809A (en) | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins | |
| CN104447333B (en) | A kind of production method of liquid hindered phenol antioxidants 1135 | |
| CN104387417A (en) | Preparation method of environment-friendly antioxidant triphosphite | |
| CN102718634A (en) | Alkylene bialkylphenol compound and preparation method thereof | |
| CN109796303B (en) | Preparation method of isoprene glycol | |
| CN101337865A (en) | Method for preparing hydroxyl-containing calix[4]arene derivates | |
| CN102850413A (en) | Method for preparing sucrose fatty acid ester | |
| CN102603491B (en) | A kind of clean preparation method preparing bis-phenolic antioxidants | |
| CN106631707B (en) | Method for preparing p-cresol dicyclopentadiene butylated product | |
| CN113979843A (en) | Method for preparing alkenyl ether by direct catalytic cracking | |
| CN107235930A (en) | A kind of synthetic method of dyclonine hydrochloride | |
| CN108059717B (en) | Refining method and application of low-odor polyether polyol | |
| CN102070419A (en) | Method for catalyzing n-butyl aldehyde condensation reaction by magnesia catalysts and preparation of magnesia catalyst | |
| CN103613785B (en) | A kind of take solid sulphuric acid as the polymeric preparation method of 2,2,4-trimethylammonium-1,2-dihyaroquinoline of catalyzer | |
| CN105294403A (en) | Preparation process of tert-butylhydroquinone | |
| CN111116852A (en) | Solvent-free preparation method of thermal reaction type p-tert-butylphenol resin | |
| CN104592108A (en) | One-step synthetic process of rubber antioxidant RD | |
| CN109996776B (en) | Process for preparing (poly) alkylated phenols | |
| CN109251288B (en) | Preparation method of bio-based phenolic resin for laminated friction brake material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131204 |