CN112029087A - Cardanol polyoxyethylene ether and preparation method and application thereof - Google Patents
Cardanol polyoxyethylene ether and preparation method and application thereof Download PDFInfo
- Publication number
- CN112029087A CN112029087A CN202010904241.4A CN202010904241A CN112029087A CN 112029087 A CN112029087 A CN 112029087A CN 202010904241 A CN202010904241 A CN 202010904241A CN 112029087 A CN112029087 A CN 112029087A
- Authority
- CN
- China
- Prior art keywords
- polyoxyethylene ether
- cardanol
- cardanol polyoxyethylene
- preparation
- reaction
- 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
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 99
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 99
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 99
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 71
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- -1 ester compound Chemical class 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003599 detergent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 230000007423 decrease Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 10
- 238000005187 foaming Methods 0.000 abstract description 7
- 239000002932 luster Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 230000007794 irritation Effects 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 239000004744 fabric Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 244000226021 Anacardium occidentale Species 0.000 description 4
- 229920002494 Zein Polymers 0.000 description 4
- 235000020226 cashew nut Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000005019 zein Substances 0.000 description 4
- 229940093612 zein Drugs 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- 108091005658 Basic proteases Proteins 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000002566 Capsicum Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses cardanol polyoxyethylene ether, which has the following structure:
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to cardanol polyoxyethylene ether with light color, low smell and strong foaming capacity, and a preparation method and application thereof.
Background
Cashew Nut Shell Liquid (CNSL) is a byproduct of cashew nut processing, the content of the cashew nut shell liquid is about 25% -30%, and the annual output is about 50 ten thousand tons. The main component of CNSL is cardanol, and the content is as high as 90%. The meta position of the phenolic hydroxyl group of cardanol is an unsaturated alkyl substituent containing 15 carbons, and the unique structure of cardanol enables the cardanol to be used for synthesizing a surfactant.
The cardanol polyoxyethylene ether is a nonionic surfactant and has important application in the aspects of pesticides, coal refining, washing, medicaments, pigment surface treatment, metal corrosion inhibition and the like. In recent years, the synthesis and application of cardanol polyoxyethylene ether are reported in succession.
In 2011, cardanol is used as a starting material for the pepper to be synthesized with ethylene oxide to obtain cardanol polyoxyethylene ether with different polymerization degrees, the emulsifying performance of the cardanol polyoxyethylene ether is researched, and the cardanol polyoxyethylene ether can be used as a pesticide emulsifier instead of TX-10 through tests (Shenyang: northeast university, 2011). In 2015, Xuxiamin et al studied the compounding of cardanol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and obtained a compound with good cleaning effect on metals (J. journal of chemical industry, 2015, 6, 35-36). In 2016, Wang group reported the surface activity of cardanol polyoxyethylene ether with 10 ethylene oxide adducts and the effect of different additives on its surface activity (j. daily chemical industry, 2017, 47(09), 492-.
As described above, in recent years, studies on cardanol polyoxyethylene ether have been lacking in the development and application of products having a high degree of polymerization, and studies on foamability have been lacking, and untreated cardanol polyoxyethylene ether is generally dark in color and has an unpleasant odor. Therefore, the development of a cardanol polyoxyethylene ether foaming agent with light color and low odor is particularly important.
Disclosure of Invention
The first purpose of the invention is to provide a novel cardanol polyoxyethylene ether with light color, low odor and strong foaming capacity.
The second purpose of the invention is to provide a preparation method of the cardanol polyoxyethylene ether.
The third purpose of the invention is to provide the application of the cardanol polyoxyethylene ether as a foaming agent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides cardanol polyoxyethylene ether with low irritation and strong foaming capacity, which has the following structure:
m is the unsaturation degree of cardanol as a raw material and is 0-3, n is the average polymerization degree, wherein:
there is a well established theoretical achievement for the research on the cardanol component, and the carbon chain of the cardanol raw material provided by any one raw material supplier can meet the above m requirement and structural requirement, and the above requirement is illustrative and not restrictive. The theory about the information of the components of cashew nut shell oil and cardanol can refer to: ladmiral V, Jeannin R, Fernandes Lizarzu K, et al, aromatic biobased Polymer latex from cardanol [ J ]. European Polymer Journal,2017,93: 785-.
n is the average polymerization degree calculated from the average molecular weight, and the average molecular weight is calculated from the hydroxyl value, which is detailed in the calculation part of the molecular weight of cardanol polyoxyethylene ether.
The hydroxyl value range of the cardanol polyoxyethylene ether is 55-75.
The second aspect of the invention provides a preparation method of the cardanol polyoxyethylene ether, which comprises the following steps:
adding cardanol and an alkaline catalyst into a closed reaction kettle in a nitrogen atmosphere, and under the condition that the temperature is 100-110 ℃, introducing nitrogen to dehydrate for 5-60 min under the negative pressure of 0.08-0.1 MPa of vacuum degree, adding ethylene oxide at the temperature of 110-120 ℃ to start reaction, continuously increasing the temperature in the reaction kettle after adding the ethylene oxide, controlling the reaction temperature to be 150-170 ℃ through condensed water, controlling the pressure in the reaction kettle to be 0.1-0.2 MPa in the feeding process, continuing the reaction until the pressure in the reaction kettle does not decrease after the feeding is finished, degassing for 1-60 min under the negative pressure of 0.1MPa after the reaction is finished, adding 30% hydrogen peroxide at 50-80 deg.C, stirring at 60-75 deg.C for 5-20 min, adding glacial acetic acid for neutralization, and cooling to room temperature, adding the ester compound, and uniformly stirring to obtain the cardanol polyoxyethylene ether.
The mass ratio of the cardanol to the ethylene oxide is 1 (1.5-5), and preferably 1 (2.2-3.5).
The mass ratio of the alkaline catalyst to the cardanol is (0.005-0.02): 1, preferably (0.01-0.0125): 1.
The mass ratio of the ester compound to the cardanol is (0.01-0.03): 1, and preferably (0.015-0.02): 1.
The alkaline catalyst is potassium hydroxide or sodium hydroxide.
The adding amount of the hydrogen peroxide is 0.003-0.005 of the total mass of the cardanol polyoxyethylene ether obtained by the reaction.
The ester compound is phenoxyethyl ester.
The mass ratio of the glacial acetic acid to the cardanol is (0.005-0.02): 1, and preferably (0.009-0.02): 1.
The third aspect of the invention provides a use of the cardanol polyoxyethylene ether as a foaming agent.
The invention provides a laundry detergent containing the cardanol polyoxyethylene ether in a fourth aspect.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the cardanol polyoxyethylene ether provided by the invention can be used as a foaming agent, and compared with the traditional foaming agent, the cardanol polyoxyethylene ether foaming agent has the advantages of good foam stability, light color, low odor and simplicity in preparation. The cardanol polyoxyethylene ether provided by the invention is light in color and low in smell, and lays a foundation for popularization of cardanol polyoxyethylene ether surfactants.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The hydroxyl value is an important index for the qualification of various synthesized polyether products in industry, the molecular weight of the polyether products can be obtained by measuring the hydroxyl value, and the average polymerization degree n of the polyether is further calculated.
Theoretical hydroxyl number (56100 × starting functionality)/molecular weight of polyether
The basic parameters of cardanol used in the examples of the present invention are shown in table 1:
TABLE 1
Example 1
The preparation method of the cardanol polyoxyethylene ether comprises the following steps:
putting 234.64g cardanol into a closed reaction kettle, adding 2.94g potassium hydroxide catalyst, replacing air in the reaction kettle with nitrogen for 3 times, heating to 100-110 ℃, keeping the temperature, introducing nitrogen to dehydrate for 30min under the negative pressure of 0.08MPa of vacuum degree, starting adding ethylene oxide under the condition of 112.4 ℃, controlling the pressure in the reaction kettle to be 0.1-0.2 MPa in the feeding process, controlling the reaction temperature to be 150-170 ℃, finishing feeding after 765g ethylene oxide is added, continuing to react until the pressure in the reaction kettle does not decrease, degassing for 10min under the negative pressure of 0.1MPa, adding 3g hydrogen peroxide with the concentration of 30% (adding 30% hydrogen peroxide according to 0.003 of the theoretical yield of the obtained cardanol polyoxyethylene ether) when the temperature is reduced to 75 ℃, stirring for 15min under the condition of 60-75 ℃, adding 3g glacial acetic acid for neutralization, cooling to room temperature, adding 4.5g phenoxyethyl ester, and stirring uniformly, obtaining the cardanol polyoxyethylene ether.
The structure of the cardanol polyoxyethylene ether prepared in this example is as follows:
m is the unsaturation degree of the cardanol as the raw material, and is 0-3,
the starting functionality was 1.2 and the polyether molecular weight was 1143.32.
And (3) measuring the hydroxyl value of cardanol polyoxyethylene ether: 58.88, and the average degree of polymerization n calculated from the hydroxyl value was 19.12.
Example 2
The preparation method of the cardanol polyoxyethylene ether comprises the following steps:
197g of cardanol is put into a closed reaction kettle, 2.31g of potassium hydroxide catalyst is added, air in the reaction kettle is replaced by nitrogen for 3 times, the temperature is raised to 100-110 ℃, the temperature is kept, dehydration is carried out for 30min under the negative pressure of 0.1MPa of vacuum degree, ethylene oxide is started to be added under the condition of 120 ℃, the pressure in the reaction kettle is controlled to be 0.1-0.2 MPa in the feeding process, the reaction temperature is controlled to be 150-170 ℃, after 574g of ethylene oxide is added, the reaction is continued until the pressure in the reaction kettle is not reduced, degassing is carried out for 10min under the negative pressure of 0.1MPa, when the temperature is reduced to 65 ℃, 2g of hydrogen peroxide with the concentration of 30% (adding 30% of hydrogen peroxide according to 0.005 of the theoretical yield of cardanol polyoxyethylene ether of the product), stirring is carried out for 15min at the temperature of 60-75 ℃, 2g of glacial acetic acid is added for neutralization, 3.1g of phenoxyethyl ester is added after the temperature is reduced to the room temperature, obtaining the cardanol polyoxyethylene ether.
The structure of the cardanol polyoxyethylene ether prepared in this example is as follows:
m is the unsaturation degree of the cardanol as the raw material, and is 0-3,
the starting functionality was 1.2 and the polyether molecular weight was 946.57.
Obtaining the hydroxyl value of cardanol polyoxyethylene ether: 71.12, and the degree of polymerization was 14.65 calculated from the hydroxyl value.
Example 3
The preparation method of the cardanol polyoxyethylene ether comprises the following steps:
putting 213g cardanol into a closed reaction kettle, adding 2.12g sodium hydroxide catalyst, replacing air in the reaction kettle with nitrogen for three times, heating to 100-110 ℃, keeping the temperature, dehydrating for 30min under the negative pressure of 0.1MPa of vacuum degree, starting to add ethylene oxide under the condition of 120 ℃, controlling the pressure in the reaction kettle to be between 0.1 and 0.2MPa in the feeding process, controlling the reaction temperature to be between 150 and 170 ℃, finishing feeding after 527g of ethylene oxide is added, continuing to react until the pressure in the reaction kettle does not decrease, degassing for 10min under the negative pressure of 0.1MPa, adding 3.7g hydrogen peroxide with the concentration of 30% (adding 30% hydrogen peroxide according to 0.005 of the theoretical yield of cardanol polyoxyethylene ether) when the temperature decreases to 80 ℃, stirring for 15min at the temperature of 60-75 ℃, adding 2g glacial acetic acid for neutralization, adding 3.7g phenoxyethyl ester when the temperature decreases to room temperature, and uniformly stirring, obtaining the cardanol polyoxyethylene ether.
The structure of the cardanol polyoxyethylene ether prepared in this example is as follows:
m is the unsaturation degree of the cardanol as the raw material, and is 0-3,
the functionality of the starting material was 1.2 and the molecular weight of the polyether was 976.93
The obtained cardanol polyoxyethylene ether is measured to have a hydroxyl value as follows: 68.91, degree of polymerization calculated from hydroxyl number 15.34.
And (3) performance measurement: preparing 1% concentration water solution from cardanol polyoxyethylene ether prepared in examples 1-3, placing the water solution in a test tube with a plug in the same specification, uniformly and forcefully oscillating for 30 times, and measuring the height h of the foam after 30 seconds1After 5min, determining the foam height h again2The higher the h, the better the foamability, h2/h1The greater the foam stability the better. The results are shown in table 2:
TABLE 2
| Sample (I) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Height h of foam1/mm(t＝30s) | 115 | 121 | 95 | 92 | 82 |
The mass ratio of ethylene oxide to cardanol in comparative example 1 is 9:1, the mass ratio of ethylene oxide to cardanol in comparative example 2 is 10:1, the reaction temperature is 130-150 ℃, the pressure is 0-0.1 Mpa, and the rest is the same as that of example 1, and as can be seen from the foam height data in table 2, the foaming performance of the cardanol polyoxyethylene ether prepared in examples 1-3 is better than that of comparative examples 1 and 2.
Other sample 1 and other sample 2 are iso-tridecanol nonionic surfactants with better foaming property (other sample 1 is specially iso-tridecanol polyether 1396, other sample 2 is specially iso-tridecanol block polyether 1393), and other sample 3 is AES ionic surfactant (sodium lauryl tetradecanol polyoxyethylene ether sulfate). Foam height test method the results are shown in table 3, as measured according to the method described above:
TABLE 3
Irritation test: weighing 0.5g of zein, preparing 100ml of a sample solution to be detected with the concentration of 2%, placing the weighed zein in a prepared sample diluting solution, stirring for 2 hours, filtering out the sample solution, weighing the mass of the zein dissolved by the sample solution, calculating the mass difference of the zein before and after dissolution, wherein the larger the numerical value is, the stronger the irritation is. The results are shown in Table 4:
TABLE 4
| Sample (I) | Example 1 | Example 2 | Example 3 | Other samples 1 | Other samples 2 | Other samples 3 |
| Irritation per gram | 0.0705 | 0.0438 | 0.0533 | 0.0718 | 0.1094 | >0.5 |
The data in tables 3 and 4 show that: the foaming property of cardanol polyoxyethylene ether in examples 1, 2 and 3 is better than that of other samples 1 and 2 which are nonionic surfactants. As an ionic surfactant, the foamability of the other sample 3 is better than that of the cardanol polyoxyethylene ether in examples 1-3, and the foam stability is better than that of examples 1 and 3. However, it can be seen from the irritation test that the irritation of the other sample 3 is much higher than that of examples 1 to 3 and other samples 1 and 2, and the irritation comparison test of examples 1 to 3 with other samples 1 and 2 shows that the irritation of cardanol polyoxyethylene ether in examples 1 to 3 is lower than that of the other samples 1 and 2 which are both nonionic surfactants.
The experiments preliminarily prove that the cardanol polyoxyethylene ether with good foamability and foam stability and low irritation can be prepared by the method.
Example 4
The formula of a laundry detergent using cardanol polyoxyethylene ether prepared in example 1 as a foaming agent is shown in table 5:
TABLE 5
| Components | The amount of components added/%) |
| AES | 5～10 |
| Alkyl glycosides | 5～15 |
| Cardanol polyoxyethylene ether | 5～10 |
| Methylisothiazolinone | 0.1～0.5 |
| Chelating agent (glutamic acid diacetic acid tetrasodium) | 0.5～1 |
| Alkaline protease | 0.5～1 |
| H2O | To 100 of |
A preparation method of a laundry detergent taking cardanol polyoxyethylene ether prepared in example 1 as a foaming agent comprises the following steps:
mixing and dissolving surfactant raw materials AES, alkyl glycoside and cardanol polyoxyethylene ether in water according to the proportion at 25 ℃, stirring the mixed solution for 1h under the water bath heating condition of 40-50 ℃, adding a chelating agent, alkaline protease and methylisothiazolinone into the stirred solution respectively, and storing the obtained laundry detergent sample at room temperature.
The basic properties of the laundry detergent are as follows:
the detergency test is implemented according to the national standard method GB/T13174-2008:
preparing the prepared liquid laundry detergent into 1000ml of 2% solution by using 250mg/kg of hard water, placing the standard dirty cloth and the diluted liquid laundry detergent in a decontamination tester for washing for 20min at the temperature of 30 ℃, taking out the dirty cloth, rinsing, airing, calculating the whiteness difference of the dirty cloth before and after washing, and obtaining the whiteness difference value before and after washing shown in the table, wherein the preparation method of the standard liquid laundry detergent is detailed in GBT13174-2008.
TABLE 6
| Item | Example 4 | Standard laundry detergent |
| Poor whiteness before and after cleaning of carbon black stained cloth | 9.66 | 7.25 |
| Poor whiteness before and after cleaning of protein dirty cloth | 14.45 | 3.91 |
| Poor whiteness before and after cleaning of sebum stained cloth | 8.03 | 5.40 |
From the data, the laundry detergent prepared from the cardanol polyoxyethylene ether prepared by the method has better performance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The cardanol polyoxyethylene ether is characterized by having the following structure:
m is the unsaturation degree of cardanol as a raw material and is 0-3, n is the average polymerization degree, wherein:
2. the cardanol polyoxyethylene ether according to claim 1, wherein the hydroxyl value of the cardanol polyoxyethylene ether is in the range of 55-75.
3. The preparation method of cardanol polyoxyethylene ether according to claim 1 or 2, characterized by comprising the following steps:
adding cardanol and an alkaline catalyst into a closed reaction kettle in a nitrogen atmosphere, and under the condition that the temperature is 100-110 ℃, introducing nitrogen to dehydrate for 5-60 min under the negative pressure of 0.08-0.1 MPa of vacuum degree, adding ethylene oxide at the temperature of 110-120 ℃ to start reaction, continuously increasing the temperature in the reaction kettle after adding the ethylene oxide, controlling the reaction temperature to be 150-170 ℃ through condensed water, controlling the pressure in the reaction kettle to be 0.1-0.2 MPa in the feeding process, continuing the reaction until the pressure in the reaction kettle does not decrease after the feeding is finished, degassing for 1-60 min under the negative pressure of 0.1MPa after the reaction is finished, adding 30% hydrogen peroxide at 50-80 deg.C, stirring at 60-75 deg.C for 5-20 min, adding glacial acetic acid for neutralization, and cooling to room temperature, adding the ester compound, and uniformly stirring to obtain the cardanol polyoxyethylene ether.
4. The preparation method of cardanol polyoxyethylene ether according to claim 3, characterized in that the mass ratio of cardanol to ethylene oxide is 1 (1.5-5).
5. The preparation method of cardanol polyoxyethylene ether according to claim 3, wherein the mass ratio of the alkali catalyst to cardanol is (0.005-0.02): 1.
6. The preparation method of cardanol polyoxyethylene ether according to claim 3, characterized in that the mass ratio of the ester compound to cardanol is (0.01-0.03): 1.
7. The preparation method of cardanol polyoxyethylene ether according to claim 3, wherein said alkaline catalyst is potassium hydroxide or sodium hydroxide.
8. The preparation method of cardanol polyoxyethylene ether according to claim 3, wherein the amount of hydrogen peroxide added is 0.003-0.005 of the total mass of cardanol polyoxyethylene ether obtained by reaction;
the ester compound is phenoxyethyl ester;
the mass ratio of the glacial acetic acid to the cardanol is (0.005-0.02): 1.
9. Use of cardanol polyoxyethylene ether prepared by the method of any one of claims 3-8 as a foaming agent.
10. A laundry detergent characterized by containing the cardanol polyoxyethylene ether prepared by the method of any one of claims 3 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010904241.4A CN112029087A (en) | 2020-09-01 | 2020-09-01 | Cardanol polyoxyethylene ether and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010904241.4A CN112029087A (en) | 2020-09-01 | 2020-09-01 | Cardanol polyoxyethylene ether and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112029087A true CN112029087A (en) | 2020-12-04 |
Family
ID=73590811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010904241.4A Pending CN112029087A (en) | 2020-09-01 | 2020-09-01 | Cardanol polyoxyethylene ether and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112029087A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087894A (en) * | 2021-04-01 | 2021-07-09 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN114656627A (en) * | 2022-03-11 | 2022-06-24 | 华东理工大学 | Rosin amine polyoxyethylene ether and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941894A (en) * | 2009-07-09 | 2011-01-12 | 滨州美东树脂有限公司 | Cardanol polyoxyethylene ether and preparation method thereof |
| CN102351664A (en) * | 2009-08-10 | 2012-02-15 | 常熟耐素生物材料科技有限公司 | Preparation method of pentadecylphenol polyoxyethylene ether high-biodegradability surfactant |
| CN106117539A (en) * | 2016-06-16 | 2016-11-16 | 常熟耐素生物材料科技有限公司 | Cardanol polyoxyethylene ether mono sulfosuccinates and its preparation method and application |
-
2020
- 2020-09-01 CN CN202010904241.4A patent/CN112029087A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941894A (en) * | 2009-07-09 | 2011-01-12 | 滨州美东树脂有限公司 | Cardanol polyoxyethylene ether and preparation method thereof |
| CN102351664A (en) * | 2009-08-10 | 2012-02-15 | 常熟耐素生物材料科技有限公司 | Preparation method of pentadecylphenol polyoxyethylene ether high-biodegradability surfactant |
| CN106117539A (en) * | 2016-06-16 | 2016-11-16 | 常熟耐素生物材料科技有限公司 | Cardanol polyoxyethylene ether mono sulfosuccinates and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087894A (en) * | 2021-04-01 | 2021-07-09 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN113087894B (en) * | 2021-04-01 | 2022-10-21 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN114656627A (en) * | 2022-03-11 | 2022-06-24 | 华东理工大学 | Rosin amine polyoxyethylene ether and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112029087A (en) | Cardanol polyoxyethylene ether and preparation method and application thereof | |
| CN106318686B (en) | Efficient environment-friendly concentrated hard surface cleaning agent | |
| CN110777017A (en) | Environment-friendly laundry detergent and preparation method thereof | |
| CN111154558A (en) | Super-concentrated laundry detergent and preparation method thereof | |
| CN112142969A (en) | Preparation method of phenol polyoxyethylene ether and preparation method of high molecular weight phenol polyoxyethylene polyoxypropylene ether | |
| CN105154200B (en) | A kind of special low bubble long-life environment-friendly water-based synthetic cutting fluid of novel aluminum alloy mobile phone shell processing and preparation method thereof | |
| WO2001083879A1 (en) | Composition for pretreating fiber materials | |
| CN113372570B (en) | Lignin glyceryl ether phosphate and preparation method and application thereof | |
| CN103882161B (en) | A kind of mating type lanolin fatting agent and preparation method thereof | |
| CN110183324B (en) | Preparation process of stearate | |
| CN114806738B (en) | Animal fiber cleaning agent composition suitable for low-temperature use as well as preparation method and application thereof | |
| CN111286423A (en) | Multi-effect normal-temperature neutral liquid detergent and preparation method thereof | |
| CN113973816B (en) | Compound system and preparation method and application thereof | |
| CN106750247B (en) | A kind of preparation method of low free alcohol AEO | |
| CN108441351A (en) | A kind of weaving degreaser | |
| CN111117803A (en) | Low-foaming surfactant composition | |
| CN113604294A (en) | Commercial laundry detergent and preparation method thereof | |
| CN108865486B (en) | Collar cleaner and preparation method thereof | |
| CN107313258A (en) | A kind of silk fabric refining is with low bubble alkali-resistant penetrant | |
| EP3719104B1 (en) | Surfactant and detergent containing surfactant | |
| CN117661318A (en) | Multifunctional phosphorus-free environment-friendly scouring agent and preparation method and application thereof | |
| CN112458470A (en) | Novel neutral bright cleaning agent and preparation method and use method thereof | |
| CN112724050B (en) | Phosphorus-free alkali-resistant solubilizer and preparation and application thereof | |
| CN115387126B (en) | Preparation method of high-stability low-solvent softening agent for cotton | |
| CN111533898B (en) | Fatty alcohol polyoxybutylene ether polyglycerol ether and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201204 |