CN101564662A - Method for synthesizing alkylphenol-polyethenoxy ether terpolymer surfactant - Google Patents
Method for synthesizing alkylphenol-polyethenoxy ether terpolymer surfactant Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an alkylphenol-polyethenoxy ether terpolymer surfactant, relating to ether surfactants used as a solubilizing agent, a wetting agent, an emulsifier and a foaming agent; the surfactant prepared with the method has a structural formula as follows, wherein EO is ethyleneoxide group (-CH2CH2O-), the addition mole number m thereof can be 4, 7, 10, 15, 20 or 30, and n can be 8, 9, 10 or 14; the synthesizing method comprises the following steps: firstly, 2-(3-(5-alkyl salicyl)-5-alkyl salicyl)-4-alkyl phenol is synthesized and an ionic liquid catalyst is added into the reaction of 4-alkyl phenol and paraformaldehyde; and secondly, the product of alkylphenol-polyethenoxy ether terpolymer surfactant is synthesized. The method has simple technique, adopts the recyclable ionic liquid catalyst, effectively reduces the environmental pollution and has short reaction time and higher yield of product.
Description
Technical field
Technical scheme of the present invention relates to the ether material surfactant as solubilizer, wetting agent, emulsifying agent and foaming agent, specifically a kind of synthetic method of alkylphenol-polyethenoxy ether terpolymer surfactant.
Background technology
With three identical or different surfactant monomer molecules, by chemical bond its molecule is linked together with linking group at its terminal hydrophyllic group or near near the terminal hydrophyllic group, the terpolymer surfactant (trimericsurfactant) of being known as, it is a kind of oligo surfactant of new development on Gemini surface active agent or Gemini surfactant basis.Domestic and foreign literature has had similar research report.
US3919429 proposes to make catalyst with hydrochloric acid, sulfuric acid, phosphoric acid and oxalic acid, alkyl phenol and formaldehyde condensation reaction, and rely on the distillation dehydration deacidification to obtain alkyl phenolic poly intermediate, and use the oxirane addition subsequently again, can prepare the degree of polymerization and be 1～9 poly surfactant.CN200510126038.4 proposes to make catalyst with potassium hydroxide, can obtain nonyl phenolic aldehyde tripolymer with the nonyl phenol and the formaldehyde condensation of fixed proportion amount, uses NaHCO respectively again
3Solution and saturated common salt water washing with the quarternary ammonium salt compound reaction, are prepared a kind of cationic tripolymer sufactant subsequently.These are that the preparation method of the terpolymer surfactant of catalyst exists equipment corrosion, wastewater treatment and catalyst circulation to some extent and uses shortcomings such as difficulty with Bronsted acid or alkali.CN200810152433.3 proposes with the nonyl phenol of fixed proportion amount and formaldehyde underwent hydroxymethylation and the trimerical method of dehydration condensation acquisition nonyl phenolic aldehyde, but because the preparation of this method purpose product is divided into three steps, and the preparation of the catalyst solid super acids that adopts needs high-temperature calcination, the needed reaction time of the preparation of its intermediate is 3～36 hours, the yield of intermediate is 69.8%, thereby there is the production process complexity in this technology, equipment investment is big, reaction time is long, the defective that yield has much room for improvement.
Ionic liquid as a kind of eco-friendly new catalyst in many chemosynthesis reactions such as Friedel-Craft reaction, Diels-Alder reaction, epoxidation reaction, hydrogenation reduction, be applied (Li Ruxiong. " green solvent-ion liquid synthetic with use ". Beijing: Chemical Industry Press, 2004 .).According to the literature, some complicated synthetic reactions adopt ionic-liquid catalyst all to obtain good effect, disclosed the method that adopts imidazoles or the ionic liquid-catalyzed synthesizing diphenyl methane of pyridines as CN200510010070.6, conversion ratio and productive rate all reach 100%; CN03116222.3 discloses and has adopted pyridine or glyoxaline ion liquid to make the technology of the synthetic diphenyl ether compound of reaction medium; CN03105027.1 has reported the ionic liquid-catalyzed long chain alkylating agent of adopting alkyl imidazole, alkylammonium salt and metal halide composition and the method that the diphenyl ether prepared in reaction goes out the straight chained alkyl diphenyl ether.These achievement in research explanations, ionic liquid replaces traditional catalyst and organic solvent medium, can improve chemical reaction process, improves reaction efficiency.
Summary of the invention
Technical problem to be solved by this invention is: the synthetic method that a kind of alkylphenol-polyethenoxy ether terpolymer surfactant is provided, this method is made catalyst with ionic liquid, has overcome the prior art complex technical process, and equipment investment is big, reaction time is long, the defective that yield is lower.
The present invention solves this technical problem the technical scheme that is adopted:
A kind of synthetic method of alkylphenol-polyethenoxy ether terpolymer surfactant, this alkylphenol-polyethenoxy ether terpolymer surfactant has following structural formula:
EO is the (CH of oxyethylene group group in the formula
2CH
2O-), its addition molal quantity m is 4,7,10,15,20 or 30, and n is 8,9,10 or 14,
It is characterized in that: adopted ionic-liquid catalyst in the preparation of intermediate, concrete preparation process is as follows:
The first step, intermediate 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-4-alkylphenol synthetic
Raw material 4-alkylphenol and paraformaldehyde are the 4-alkylphenol in molar ratio: the proportioning of paraformaldehyde=3: 2 adds and is equipped with in the reactor of nitrogen protection device; open and stir; add ionic-liquid catalyst then; the addition of ionic-liquid catalyst is the mass percent 0.9～2.0% of 4-alkylphenol and paraformaldehyde quality sum; heating and maintenance temperature are 105 ℃; react after 1 hour; the mixture that reaction is generated extracts with benzinum; the petroleum ether extract that will extract the upper strata that obtains thus distills then; steam benzinum; make terpolymer surfactant intermediate: 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-the 4-alkylphenol, its structural formula is as follows:
Above-mentioned raw materials 4-alkylphenol and above in the structural formula, alkyl on the phenyl ring is the straight chain aliphatic hydrocarbon, the atomicity n of its C and H is 8,9,10 or 14, the benzinum extract remainder that extracts the lower floor that obtains is thus added water to be stirred, standing separation, obtain the ionic-liquid catalyst layer, this ionic-liquid catalyst layer can be recycled after 80 ℃ of vacuum drying treatment;
Second step, product alkylphenol-polyethenoxy ether terpolymer surfactant synthetic
Intermediate 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base that the first step is made]-4-alkylphenol and be that 1% solid potassium hydroxide adds in the autoclave with this intermediate calculated mass percentage, be evacuated to 0.01MPa, after feeding nitrogen is replaced 3 times repeatedly, according to the selected (CH of oxyethylene group group
2CH
2O-) addition molal quantity m feeds the oxirane of 3m molal quantity, under agitation be warming up to 120 ℃, keep-up pressure then and be 1Mpa, reacted 2 hours, stop reaction, be cooled to room temperature, from autoclave, take out product, be alkylphenol-polyethenoxy ether terpolymer surfactant product with said structure formula;
Among the preparation method of abovementioned alkyl phenol polyethenoxy ether terpolymer surfactant, used ionic-liquid catalyst is i.e. [Emim] BF of 1-ethyl-3-methyl imidazolium tetrafluoroborate
4, 1-butyl-3-methyl imidazolium tetrafluoroborate is Bmim] BF
4Or 1-butyl-3-methylimidazole hexafluorophosphate is [Bmim] PF
6
Above-mentioned ionic-liquid catalyst [Emim] [BF
4], be to prepare by document (Jian-Ying Wang, Feng-Yun Zhao, Journalof Molecular Catalysis A:Chemical, 2008:279,153).
Above-mentioned ionic-liquid catalyst [Bmim] [BF
4] and [Bmim] [PF
6] be that (Feng Qi, Haijun Wang.J.Chem.Thermodynamics.2009 41:265) prepare by document.
The invention has the beneficial effects as follows:
(1) because the inventive method adopts ionic-liquid catalyst to replace traditional acid or base catalyst in the technical process of preparation alkylphenol-polyethenoxy ether terpolymer surfactant, described ionic-liquid catalyst is meant the organic liquid material of being made up of ion fully under room temperature and adjacent temperature, ionic liquid is compared with traditional organic solvent, water or supercritical fluid and had many good performances: a lot of chemical substances are comprised that organic matter and inorganic matter all have the fine solubility energy; Has higher ionic conductivity; Higher heat endurance; Higher polarity and solvation performance; Volatilization, not oxidation and not burning hardly; Viscosity is low; Thermal capacitance is big; All stable to water and air, so the ionic-liquid catalyst that the inventive method adopts easily reclaims, and can be recycled, easy to manufacture, reduced pollution effectively, to operator also safety to environment.
(2) technology of the inventive method is simple, processing ease.The preparation of the object of the invention product is divided into two steps, catalyst amount is few, the reactivity height, the reaction condition gentleness, and the preparation of the disclosed purpose product of CN200810152433.3 is divided into three steps, and because the catalyst that adopts is a solid super-strong acid, the preparation of solid super-strong acid needs high-temperature calcination.
(3) time of the inventive method synthetic reaction weak point was generally 1 hour, and efficient is higher, and the yield of intermediate is 95%, and the needed reaction time of preparation of CN 200810152433.3 disclosed intermediates is 3～36 hours, and the yield of intermediate is 69.8%.
(4) used ionic-liquid catalyst of the inventive method and product are easily separated, and the product post processing is simple, and recycling 5 times still has good catalytic effect.
(5) the inventive method is raw materials used cheap and easy to get, and the product yield height can effectively reduce production cost.The detailed data of beneficial effect is stated embodiment as follows.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is intermediate 2-[3-(5-decyl salicyl)-5-decyl salicyl that the inventive method embodiment 1 makes]-hydrogen nuclear magnetic resonance of 4-decyl phenol (n=10) (
1H NMR) spectrogram.
Fig. 2 is intermediate 2-[3-(5-decyl salicyl)-5-decyl salicyl that the inventive method embodiment 1 makes]-the nuclear magnetic resonance carbon of 4-decyl phenol (n=10) (
13C NMR) spectrogram.
Fig. 3 is product decyl phenol polyethenoxy ether terpolymer surfactant TDP-4 (n=10, infrared (FTIR) spectrogram m=4) that the inventive method embodiment 1 makes.
The specific embodiment
Embodiment 1
Decyl phenol polyethenoxy ether terpolymer surfactant TDP-4 synthetic (n=10, m=4)
First step intermediate 2-[3-(5-decyl salicyl)-5-decyl salicyl]-4-decyl phenol synthetic
4-decyl phenol and paraformaldehyde are 4-decyl phenol in molar ratio: the proportioning of paraformaldehyde=3: 2 adds and is equipped with in the reactor of nitrogen protection device, opens and stirs, and adds ionic-liquid catalyst [Bmim] [BF then
4], [Bmim] [BF
4] addition be 0.9% of 4-decyl phenol and paraformaldehyde quality sum, heating and maintenance temperature of charge are 105 ℃, react after 1 hour, reactant mixture is extracted with benzinum, the extract that will extract the upper strata that obtains thus distills then, steam benzinum and obtain terpolymer surfactant intermediate: 2-[3-(5-decyl salicyl)-5-decyl salicyl]-4-decyl phenol, productive rate is 95%; The benzinum extract remainder that extracts the lower floor that obtains is thus added water stir, standing separation obtains ionic-liquid catalyst [Bmim] [BF
4] layer, should [Bmim] [BF
4] layer after 80 ℃ of vacuum drying treatment, can be recycled.
In the operation, above the molal weight of used paraformaldehyde in single formaldehyde (as follows).
The 2-[3-that Fig. 1 makes for present embodiment (5-decyl salicyl)-5-decyl salicyl]-the hydrogen nuclear magnetic resonance spectrogram of 4-decyl phenol, therefrom as seen:
1H NMR (CDCl
3, 400MHz): 7.09 (2H, ArH), 6.98 (2H, ArH), 6.70 (2H, ArH), 6.69 (2H, ArH), 3.86 (2H, CH
2), 3.83 (2H, CH
2), 2.52 (2H, CH
2), 1.56 (2H, CH
2), 1.33～1.26 (10H, 5CH
2), 0.90 (t, 3H, CH
3).
The 2-[3-that Fig. 2 makes for present embodiment (5-decyl salicyl)-5-decyl salicyl]-the carbon-13 nmr spectra figure of 4-decyl phenol, therefrom as seen:
13C NMR (CDCl
3, 400MHz): 150.29,147.29,136.17,131.53,129.06,126.29,115.80,35.19,31.12,31.00,30.16,29.66,22.77,14.10.
Second step, product decyl phenol polyethenoxy ether terpolymer surfactant synthetic
Intermediate 2-[3-(5-decyl salicyl)-5-decyl salicyl that the 1mol first step is made]-4-decyl phenol and be that 1% solid potassium hydroxide adds in the autoclave with this intermediate calculated mass percentage, be evacuated to 0.01MPa, after feeding nitrogen is replaced 3 times repeatedly, according to (the CH of oxyethylene group group
2CH
2O-) addition molal quantity m=4 feeds the oxirane of 12mol, under agitation be warming up to 120 ℃, keep-up pressure then and be 1MPa, reacted 2 hours, stop reaction, be cooled to room temperature, from autoclave, take out product, promptly obtain product decyl phenol polyethenoxy ether terpolymer surfactant TDP-4, productive rate is 98%.
The infrared spectrum of the decyl phenol polyethenoxy ether terpolymer surfactant TDP-4 that Fig. 3 makes for present embodiment.Therefrom as seen, FTIR (KBr pressed disc method): 3 296 (υ OH), 1 115 (υ as C-O-C), 951,831 (ρ CH
2), 1 609 (υ C=C), 3 038 (υ C-H), 1 250 (υ as C-O-C).
Embodiment 2～23
In embodiment 2～23, listed purpose product (containing its used reactant feed in interior), ionic-liquid catalyst and addition, oxirane addition molal quantity (mol) and the product productive rate (%), synthetic reaction step and other process conditions are all with embodiment 1 in following table 1.
Adopt different ionic liquid catalyst and dosage thereof among table 1 embodiment 2～23
| Embodiment number | The purpose product | The addition of ionic-liquid catalyst accounts for the percentage (%) of 4-alkylphenol and paraformaldehyde quality sum | Ionic-liquid catalyst | Oxirane addition molal quantity (mol) | Product productive rate (%) |
| 1 | OPEO terpolymer surfactant top-4 (n=8, m=4) | 0.9 | [Bmim][BF 4] | 12 | 95 |
| 2 | top-7(n＝8，m＝7) | 1.5 | [Bmim][PF 6] | 21 | 95 |
| 3 | top-10(n＝8，m＝10) | 1.2 | [Emim][BF 4] | 30 | 94 |
| 4 | top-15(n＝8，m＝15) | 1.0 | [Bmim][BF 4] | 45 | 95 |
| 5 | top-20(n＝8，m＝20) | 1.4 | [Bmim][PF 6] | 60 | 95 |
| 6 | top-30(n＝8，m＝30) | 1.3 | [Bmim][BF 4] | 90 | 94 |
| 7 | NPE terpolymer surfactant (TNP)-4 (n=9, m=4) | 1.7 | [Emim][BF 4] | 12 | 95 |
| 8 | TNP-7(n＝9，m＝7) | 1.1 | [Bmim][PF 6] | 21 | 95 |
| 9 | TNP-10(n＝9，m＝10) | 0.9 | [Bmim][PF 6] | 30 | 97 |
| 10 | TNP-15(n＝9，m＝15) | 1.6 | [Bmim][BF 4] | 45 | 96 |
| 11 | TNP-20(n＝9，m＝20) | 1.9 | [Bmim][PF 6] | 60 | 98 |
| 12 | TNP-30(n＝9，m＝30) | 1.5 | [Bmim][PF 6] | 90 | 98 |
| 13 | Decyl phenol polyethenoxy ether terpolymer surfactant TDP-7 (n=10, m=7) | 1.4 | [Emim][BF 4] | 21 | 98 |
| 14 | TDP-10(n＝10，m＝10) | 2.0 | [Bmim][BF 4] | 30 | 98 |
| 15 | TDP-15(n＝10，m＝15) | 1.6 | [Bmim][PF 6] | 45 | 97 |
| 16 | TDP-20(n＝10，m＝20) | 1.2 | [Bmim][BF 4] | 60 | 98 |
| 17 | TDP-30(n＝10，m＝30) | 1.6 | [Bmim][BF 4] | 90 | 96 |
| 18 | Tetradecylphenol polyethenoxy ether terpolymer surfactant TMP-4 (n=14, m=4) | 1.8 | [Bmim][BF 4] | 12 | 98 |
| 19 | TMP-7(n＝14，m＝7) | 1.0 | [Bmim][PF 6] | 21 | 98 |
| 20 | TMP-10(n＝14，m＝10) | 1.1 | [Emim][BF 4] | 30 | 98 |
| 21 | TMP-15(n＝14，m＝15) | 1.7 | [Bmim][PF 6] | 45 | 98 |
| 22 | TMP-20(n＝14，m＝20) | 1.9 | [Emim][BF 4] | 60 | 98 |
| 23 | TMP-30(n＝14，m＝30) | 2.0 | [Bmim][BF 4] | 90 | 98 |
Embodiment 24
Adopt the critical micelle concentration of tensammetric determination surfactant solution, table 2 is critical micelle concentration (CMC) the value contrast of NPE terpolymer surfactant (TNP) and NPE unimolecule surfactant (NP).
The CMC value (25 ℃) of table 2TNP and NP
| The unimolecule surfactant | CMC/mmol·L -1 | Terpolymer surfactant | CMC/mmol·L -1 |
| NP-7 | 0.0682 | TNP-7 | 0.0009 |
| NP-10 | 0.0775 | TNP-10 | 0.0090 |
| NP-15 | 0.1033 | TNP-15 | 0.0098 |
| NP-20 | 0.1250 | TNP-20 | 0.0103 |
| NP-30 | 0.2034 | TNP-30 | 0.0160 |
As seen from the above table, the CMC value of TNP is than low 1～2 order of magnitude of NP, and surface-active is significantly increased.
Embodiment 25
With extracted residual ionic liquid layer among the embodiment 1～23, add water and stir, standing separation, ionic liquid layer were 80 ℃ of vacuum drying 4.5 hours, and the ionic liquid after the recycling can be directly used in reaction next time.Table 3 recycles the result for embodiment 1～23 intermediate ion liquid, and ionic-liquid catalyst recycles 5 times as can be seen still good catalytic effect.
Three kinds of ionic liquids of table 3 recycle the result
| [Bmim][BF 4] cycle-index | 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-productive rate (%) of 4-alkylphenol | [Bmim][PF 6]] cycle-index | 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-productive rate (%) of 4-alkylphenol | [Emim][BF 4] cycle-index | 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-productive rate (%) of 4-alkylphenol |
| 1 | 95 | 1 | 95 | 1 | 95 |
| 2 | 94 | 2 | 94 | 2 | 95 |
| 3 | 94 | 3 | 94 | 3 | 94 |
| 4 | 93 | 4 | 93 | 4 | 93 |
| 5 | 93 | 5 | 92 | 5 | 92 |
Infrared (FTIR) spectrogram of the product of embodiment 2～23 is with infrared (FTIR) spectrogram of implementing sharp 1.
Related % among above-mentioned all embodiment all is mass percents.
Claims (1)
1. the synthetic method of an alkylphenol-polyethenoxy ether terpolymer surfactant, this alkylphenol-polyethenoxy ether terpolymer surfactant has following structural formula:
EO is the (CH of oxyethylene group group in the formula
2CH
2O-), its addition molal quantity m is 4,7,10,15,20 or 30, and n is 8,9,10 or 14,
It is characterized in that: adopted ionic-liquid catalyst in the preparation of intermediate, concrete preparation process is as follows:
The first step, intermediate 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-4-alkylphenol synthetic
Raw material 4-alkylphenol and paraformaldehyde are the 4-alkylphenol in molar ratio: the proportioning of paraformaldehyde=3: 2 adds and is equipped with in the reactor of nitrogen protection device; open and stir; add ionic-liquid catalyst then; the addition of ionic-liquid catalyst is the mass percent 0.9～2.0% of 4-alkylphenol and paraformaldehyde quality sum; heating and maintenance temperature are 105 ℃; react after 1 hour; the mixture that reaction is generated extracts with benzinum; the petroleum ether extract that will extract the upper strata that obtains thus distills then; steam benzinum; make terpolymer surfactant intermediate: 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base]-the 4-alkylphenol, its structural formula is as follows:
Above-mentioned raw materials 4-alkylphenol and above in the structural formula, alkyl on the phenyl ring is the straight chain aliphatic hydrocarbon, the atomicity n of its C and H is 8,9,10 or 14, the benzinum extract remainder that extracts the lower floor that obtains is thus added water to be stirred, standing separation, obtain the ionic-liquid catalyst layer, this ionic-liquid catalyst layer can be recycled after 80 ℃ of vacuum drying treatment;
Second step, product alkylphenol-polyethenoxy ether terpolymer surfactant synthetic
Intermediate 2-[3-(5-alkylated salicylamide base)-5-alkylated salicylamide base that the first step is made]-4-alkylphenol and be that 1% solid potassium hydroxide adds in the autoclave with this intermediate calculated mass percentage, be evacuated to 0.01MPa, after feeding nitrogen is replaced 3 times repeatedly, according to the selected (CH of oxyethylene group group
2CH
2O-) addition molal quantity m feeds the oxirane of 3m molal quantity, under agitation be warming up to 120 ℃, keep-up pressure then and be 1Mpa, reacted 2 hours, stop reaction, be cooled to room temperature, from autoclave, take out product, be alkylphenol-polyethenoxy ether terpolymer surfactant product with said structure formula;
Among the preparation method of abovementioned alkyl phenol polyethenoxy ether terpolymer surfactant, used ionic-liquid catalyst is i.e. [Emim] BF of 1-ethyl-3-methyl imidazolium tetrafluoroborate
4, 1-butyl-3-methyl imidazolium tetrafluoroborate is Bmim] BF
4Or 1-butyl-3-methylimidazole hexafluorophosphate is [Bmim] PF
6
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584541A (en) * | 2012-01-18 | 2012-07-18 | 湘潭大学 | Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid |
| CN102936324A (en) * | 2012-12-07 | 2013-02-20 | 苏州井上高分子新材料有限公司 | Modified phenolic resin and preparation method thereof |
| CN104725629A (en) * | 2013-12-20 | 2015-06-24 | 上海是大高分子材料有限公司 | Preparation of alkylphenol polyoxyethylene ether phosphate formaldehyde condensation polymer surfactant |
| CN106582437A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Composite foaming agent and application thereof |
| CN106590600A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Carbon dioxide foam profile controlling method |
| WO2023116663A1 (en) * | 2021-12-21 | 2023-06-29 | 沈阳兴齐眼药股份有限公司 | Method for synthesizing tyloxapol |
Family Cites Families (1)
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| CN100531883C (en) * | 2005-11-30 | 2009-08-26 | 北京航空航天大学 | Tripolymer sufactant and preparing method |
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2009
- 2009-03-18 CN CN2009100681505A patent/CN101564662B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584541A (en) * | 2012-01-18 | 2012-07-18 | 湘潭大学 | Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid |
| CN102584541B (en) * | 2012-01-18 | 2015-11-25 | 湘潭大学 | A kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F |
| CN102936324A (en) * | 2012-12-07 | 2013-02-20 | 苏州井上高分子新材料有限公司 | Modified phenolic resin and preparation method thereof |
| CN102936324B (en) * | 2012-12-07 | 2014-05-07 | 苏州井上高分子新材料有限公司 | Modified phenolic resin and preparation method thereof |
| CN104725629A (en) * | 2013-12-20 | 2015-06-24 | 上海是大高分子材料有限公司 | Preparation of alkylphenol polyoxyethylene ether phosphate formaldehyde condensation polymer surfactant |
| CN104725629B (en) * | 2013-12-20 | 2017-04-12 | 上海是大高分子材料有限公司 | Preparation of alkylphenol polyoxyethylene ether phosphate formaldehyde condensation polymer surfactant |
| CN106582437A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Composite foaming agent and application thereof |
| CN106590600A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Carbon dioxide foam profile controlling method |
| CN106582437B (en) * | 2015-10-14 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of composite foamable agent and its application |
| CN106590600B (en) * | 2015-10-14 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of carbon dioxide foaming transfer drive method |
| WO2023116663A1 (en) * | 2021-12-21 | 2023-06-29 | 沈阳兴齐眼药股份有限公司 | Method for synthesizing tyloxapol |
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