CN112898621B - Emulsifier, preparation method thereof and application of emulsifier in latex foaming product - Google Patents
Emulsifier, preparation method thereof and application of emulsifier in latex foaming product Download PDFInfo
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- CN112898621B CN112898621B CN202110281007.5A CN202110281007A CN112898621B CN 112898621 B CN112898621 B CN 112898621B CN 202110281007 A CN202110281007 A CN 202110281007A CN 112898621 B CN112898621 B CN 112898621B
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 118
- 239000004816 latex Substances 0.000 title claims abstract description 56
- 229920000126 latex Polymers 0.000 title claims abstract description 56
- 238000005187 foaming Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- 239000002253 acid Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims abstract description 25
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 25
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000003784 tall oil Substances 0.000 claims abstract description 23
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005642 Oleic acid Substances 0.000 claims abstract description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000013311 vegetables Nutrition 0.000 claims abstract description 15
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 8
- 239000008158 vegetable oil Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 37
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 239000004480 active ingredient Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 235000021319 Palmitoleic acid Nutrition 0.000 claims description 13
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 235000019864 coconut oil Nutrition 0.000 claims description 4
- 239000003240 coconut oil Substances 0.000 claims description 4
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 abstract description 101
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 11
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 abstract description 8
- 230000001804 emulsifying effect Effects 0.000 abstract description 7
- 230000000087 stabilizing effect Effects 0.000 abstract description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 4
- 235000021313 oleic acid Nutrition 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 18
- VAKMIIPDYZXBEV-DPMBMXLASA-M potassium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [K+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O VAKMIIPDYZXBEV-DPMBMXLASA-M 0.000 description 18
- 229940096992 potassium oleate Drugs 0.000 description 17
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000010008 shearing Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- -1 and the pH value Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 229920001821 foam rubber Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002889 oleic acids Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of latex foaming, and provides an emulsifier, a preparation method thereof and application thereof in a latex foaming product. The emulsifier provided by the invention is prepared from tall oil acid, ricinoleic acid, vegetable oil acid, sodium hydroxide, a surfactant T-220 and water. The invention utilizes tall oil acid, ricinoleic acid, vegetable oleic acid and sodium hydroxide to react, and adds the surfactant T-220 to improve the performance of the emulsifier, finally the emulsifier which takes sodium oleate as the main component and has quick foaming, fine foam and good foam stabilizing performance is obtained. The emulsifier provided by the invention has good emulsifying effect, good dispersing and emulsifying effects in a natural latex system, the latex foaming product is prepared by using the emulsifier provided by the invention, the obtained product has rich and fine cells, and the emulsifier still has excellent foaming performance under the condition that aluminum hydroxide exists, and the foam shrinkage rate of the obtained product is low.
Description
Technical Field
The invention relates to the technical field of latex foaming, in particular to an emulsifier, a preparation method thereof and application thereof in a latex foaming product.
Background
The latex sponge is a latex foaming product with a large number of foam cell structures inside, and has the characteristics of high elasticity, shock absorption, compression fatigue resistance, good bearing performance, comfort, durability and the like.
The latex sponge is prepared by foaming natural latex, and at present, the traditional foaming systems adopted by latex product factories are potassium oleate and potassium ricinoleate systems. The traditional foaming system is quite original in production process, is generally prepared by adopting the reaction of vegetable oleic acid or ricinoleic acid and potassium hydroxide, and the purity, the consumption, the reaction temperature and the like of raw materials are lack of standardization, so that index errors and fluctuation of the obtained product are quite large, and quite a plurality of uncertain factors are brought to subsequent latex foaming.
In addition, when potassium oleate and potassium ricinoleate are used for foaming, only one of the potassium oleate and the potassium ricinoleate cannot be used, the two types of potassium ricinoleate are required to be matched according to a certain proportion, otherwise, the foaming effect is poor, the standard dosage is difficult to determine when the dosages of the potassium oleate and the potassium ricinoleate are adjusted due to large fluctuation of the product quality of the potassium oleate and the potassium ricinoleate, the whole adjustment process is very complicated, and great raw material waste is brought to factories through repeated dosage adjustment.
In addition, when the potassium oleate and the potassium ricinoleate are used for foaming, the phenomena of coarse cells and foam perforation are very easy to occur, so that a latex foaming product is provided with holes, the phenomenon of slag falling and the like of the product can occur, the foam stability of the potassium oleate and the potassium ricinoleate is poor, the foam shrinkage rate of the product is high, and the quality of the latex foaming product is reduced.
Disclosure of Invention
In view of the above, the invention provides an emulsifier, a preparation method thereof and application thereof in latex foaming products. The emulsifier provided by the invention has good emulsifying effect, excellent foaming and foam stabilizing performance, rich and fine foam and low foam shrinkage rate of products.
In order to achieve the above object, the present invention provides the following technical solutions:
the emulsifier is prepared from the following raw materials in percentage by mass: 6 to 12 percent of tall oil acid, 6 to 12 percent of ricinoleic acid, 3 to 9 percent of vegetable oleic acid, 2.5 to 3.0 percent of sodium hydroxide, 3 to 10 percent of surfactant T-2203 and the balance of water; the vegetable oil acid comprises one or more of palmitoleic acid, coconut oil acid, soybean oil acid and rapeseed oil acid.
Preferably, the acid value of the tall oil acid is 180 to 200mgKOH/g.
Preferably, the ricinoleic acid has an acid value of 170 to 190mgKOH/g.
Preferably, the acid value of the vegetable oil acid is 270-300 mgKOH/g.
Preferably, the content of the active ingredient of the surfactant T-220 is 24-26 wt%.
Preferably, the content of the effective components in the emulsifier is 17-23 wt%, and the pH value of the emulsifier is 9-11; the water solubility of the emulsifier is more than or equal to 10 percent, and the alcohol solubility is more than or equal to 10 percent.
The invention also provides a preparation method of the emulsifier, which comprises the following steps:
mixing water and sodium hydroxide solution to obtain sodium hydroxide solution;
mixing the sodium hydroxide solution, tall oil acid, ricinoleic acid and vegetable oleic acid for reaction to obtain a reaction solution;
and mixing the reaction solution with a surfactant T-220 to obtain the emulsifier.
Preferably, the temperature of the reaction is 60-100 ℃ and the time is 1-2 h.
The invention also provides an application of the emulsifier prepared by the scheme or the preparation method of the scheme in a latex foaming product.
Preferably, the amount of the emulsifier is 3-6% of the mass of the emulsion.
The invention provides an emulsifier which is prepared from the following raw materials in percentage by mass: 6 to 12 percent of tall oil acid, 6 to 12 percent of ricinoleic acid, 3 to 9 percent of vegetable oleic acid, 2.5 to 3.0 percent of sodium hydroxide, 3 to 10 percent of surfactant T-2203 and the balance of water; the vegetable oil acid comprises one or more of palmitoleic acid, coconut oil acid, soybean oil acid and rapeseed oil acid. The invention uses tall oleic acid, ricinoleic acid, vegetable oleic acid and sodium hydroxide to react to obtain the emulsifier taking sodium oleate as a main component, the traditional emulsifier is potassium oleate or potassium ricinoleate, the sodium oleate is slowly foamed and is not generally used as the emulsifier, and the invention combines the three oleic acids, and the emulsifier which takes sodium oleate as the main component, and has fast foaming, fine foam and good high-temperature foam stabilizing performance is obtained by controlling the proportion of the three oleic acids. In addition, the surfactant T-220 is added into the emulsifier, and the double bond is contained in the surfactant T-220 product, so that the emulsion participates in the reaction in the emulsion polymerization process, the water resistance of the emulsion is better, and the storage, transportation and freeze thawing stability of the emulsion can be improved; and the surfactant T-220 has excellent water resistance, dispersibility and stability, and can improve the dispersibility and particle size distribution of the emulsion and improve the emulsifying capacity of the emulsion after being added into the emulsion.
The invention also provides a preparation method of the emulsifier. The preparation method provided by the invention has simple steps, is easy to operate and is easy to carry out industrial production.
The invention also provides application of the emulsifier in the latex foaming product. The emulsifier provided by the invention has good emulsifying effect, good dispersing and emulsifying effects in a natural latex system, easy foaming, fine foam holes and good high-temperature foam stabilizing performance, the foam holes of the product prepared by using the emulsifier are rich and fine, and the emulsifier still has excellent foaming performance under the condition that aluminum hydroxide exists, so that the foam shrinkage of the product is low.
Drawings
FIG. 1 is a graph showing the foaming of the latex sponge prepared in application example 1 and comparative example 1.
Detailed Description
The invention provides an emulsifier which is prepared from the following raw materials in percentage by mass: 6 to 12 percent of tall oil acid, 6 to 12 percent of ricinoleic acid, 3 to 9 percent of vegetable oleic acid, 2.5 to 3.0 percent of sodium hydroxide, 3 to 10 percent of surfactant T-2203 and the balance of water.
The preparation raw materials used in the invention are all commercially available unless otherwise specified.
The raw materials for preparing the emulsifier provided by the invention comprise, by mass, 6-12% of tall oil acid, preferably 8-10%. In the present invention, the acid value of the tall oil acid is preferably 180 to 200mgKOH/g, more preferably 185 to 198mgKOH/g, and most preferably 196mgKOH/g.
The raw materials for preparing the emulsifier provided by the invention comprise 6-12% of ricinoleic acid, preferably 8-10% by mass. In the present invention, the acid value of the ricinoleic acid is preferably 170 to 190mgKOH/g, more preferably 175 to 185mgKOH/g, and most preferably 181mgKOH/g.
The emulsifier provided by the invention is prepared from 3-9% of vegetable oleic acid, preferably 5-8% by mass. In the invention, the vegetable oil acid preferably comprises one or more of palmitoleic acid, coconut oil acid, soybean oil acid and rapeseed oil acid, more preferably palmitoleic acid, and the palmitoleic acid has wide sources and low cost, and the use of palmitoleic acid as a raw material can further reduce the cost of the emulsifier.
The raw materials for preparing the emulsifier provided by the invention comprise 2.5-3.0% of sodium hydroxide, and more preferably 2.6-2.8% of sodium hydroxide by mass fraction. In the present invention, the purity of the sodium hydroxide is preferably 99% or more.
The raw materials for preparing the emulsifier provided by the invention comprise, by mass, 3-10% of a surfactant T-2203, preferably 5-8%. In the present invention, the active ingredient content of the surfactant T-220 is preferably 24 to 26wt%, more preferably 25wt%; in the present invention, the surfactant T-220 is in the form of an aqueous solution. In a specific embodiment of the invention, the surfactant T-220 is purchased from Qingdao Ruenox chemical Co., ltd, model number is in particular Raynol T-220.
The emulsifier provided by the invention comprises the following raw materials in percentage by mass. In the present invention, the water is preferably distilled water.
In the present invention, the content of the active ingredient in the emulsifier is preferably 17 to 23wt%, more preferably 18 to 22wt%, and the active ingredient in the emulsifier specifically refers to the total amount of the active ingredient in the surfactant T-220 and sodium oleate, and the mass of the sodium oleate is calculated on the total amount of sodium tall oleate, sodium ricinoleate and sodium vegetable oleate; the pH value of the emulsifier is preferably 9-11, more preferably 9.5-10.5; the water solubility of the emulsifier is preferably more than or equal to 10%, and the alcohol solubility is preferably more than or equal to 10%; the water solubility refers specifically to the solubility of the emulsifier in water, and the alcohol solubility refers specifically to the solubility of the emulsifier in absolute ethanol.
The invention also provides a preparation method of the emulsifier, which comprises the following steps:
mixing water and sodium hydroxide solution to obtain sodium hydroxide solution;
mixing the sodium hydroxide solution, tall oil acid, ricinoleic acid and vegetable oleic acid for reaction to obtain a reaction solution;
and mixing the reaction solution with a surfactant T-220 to obtain the emulsifier.
In the invention, water and sodium hydroxide are mixed to obtain sodium hydroxide solution, and in the specific embodiment of the invention, the water is preferably added into a reaction kettle, then stirring is started, sodium hydroxide is slowly added, and stirring is carried out until the sodium hydroxide is completely dissolved.
After the sodium hydroxide solution is obtained, the sodium hydroxide solution, tall oil acid, ricinoleic acid and vegetable oleic acid are mixed for reaction to obtain a reaction solution. In the present invention, the temperature of the reaction is preferably 60 to 100 ℃, more preferably 80 ℃, and the time of the reaction is preferably 1 to 2 hours, more preferably 1.5 hours. The method comprises the steps of mixing tall oil acid, ricinoleic acid and vegetable oleic acid to obtain mixed oleic acid, slowly heating sodium hydroxide solution in a reaction kettle, slowly adding the mixed oleic acid into the reaction kettle, and after the temperature in the reaction kettle is raised to 60-80 ℃, preserving heat for reaction, wherein the reaction time is counted from the reaction temperature to the required temperature; in the present invention, the heating rate to the reaction temperature is preferably 0.5 to 1.0 ℃/min; in the reaction process, tall oil acid, ricinoleic acid and vegetable oil acid react with sodium hydroxide to generate tall oil sodium oleate, ricinoleic acid sodium and vegetable oil sodium.
After the reaction liquid is obtained, the reaction liquid and the surfactant T-220 are mixed to obtain the emulsifier. The invention preferably adds the surfactant T-220 into the reaction kettle under the condition of keeping the reaction temperature after the reaction is finished, then lowers the temperature to 60 ℃, and then samples and detects or barrels.
After the emulsifier is obtained, the invention preferably samples and detects the obtained emulsifier, and the pH value, water solubility and alcohol solubility of the obtained emulsifier meet the requirements of the scheme, and can be considered to be qualified.
The invention also provides an application of the emulsifier in the scheme or the emulsifier prepared by the preparation method in the scheme in a latex foaming product; in the present invention, the amount of the emulsifier is preferably 3 to 6% by mass, more preferably 4 to 5% by mass, of the latex; the latex is preferably natural latex. The specific method of application of the emulsifier is not particularly limited, and methods well known to those skilled in the art can be adopted.
In a specific embodiment of the present invention, the method for preparing a latex foam article using the emulsifier of the present invention preferably comprises the steps of:
mixing rubber and an emulsifier, stirring, adding a vulcanized dispersion and an oxidative dispersion, stirring at a first high speed, adding a coagulant dispersion, and stirring at a second high speed and stirring at a slow speed in sequence to obtain a foam;
pouring the foam body into a mould and standing to obtain foam gel;
and (3) sequentially drying and steaming the foam gel, and demolding to obtain the latex foam product.
In the invention, the rotation speeds of the first high-speed stirring and the second high-speed stirring are independently preferably 240-360 r/min; the time of the first high-speed stirring is preferably 2-4 min, more preferably 3min, and the time of the first high-speed stirring is preferably 1-1.5 min, more preferably 1min; the rotating speed of the slow stirring is preferably 60-100 r/min, and the rotating speed of the slow stirring is preferably 1-1.5 min, and more preferably 1min; in particular embodiments of the present invention, the raw materials are preferably added to a jar of a commercial whisk for whisk, with high speed whisk high speed gear and low speed whisk low speed gear. The present invention is not particularly limited to the vulcanized dispersion, the oxidative dispersion and the coagulant dispersion, and the above-mentioned dispersions known to those skilled in the art can be used; in a specific embodiment of the invention, the vulcanizing dispersion is preferably a sulfur dispersion, the oxidizing dispersion is preferably a zinc oxide dispersion, and the coagulant dispersion is preferably a sodium fluorosilicate dispersion; in the present invention, the temperature of the drying is preferably 110 to 130 ℃, more preferably 120 ℃, and the time of the drying is preferably 4 to 6min, more preferably 5min; the steaming is preferably performed in a steam box, the temperature of the steaming is preferably 100 ℃, and the time is preferably 15-20 min. The invention has no special requirement on the mould, and the mould is selected according to the specific shape of the target latex foaming product.
After demolding, the invention preferably carries out water washing and drying on the emulsion foaming product after demolding in sequence. The specific conditions of the water washing and drying are not particularly required, and the method is well known to those skilled in the art.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
An emulsifier comprises the following components in percentage by mass: tall oil acid 8%, ricinoleic acid 8%, palmitoleic acid 5%, sodium hydroxide 2.5%, surfactant T-220 (active ingredient 25%, solvent water, purchased from Qingdao Rueno chemical Co., ltd., model Raynol T-220) 5%, and distilled water in balance; wherein, the acid value of tall oil acid is 196mgKOH/g, the acid value of ricinoleic acid is 181mgKOH/g, and the acid value of palmitoleic acid is 280mgKOH/g.
The preparation method of the emulsifier comprises the following steps: mixing tall oil acid, ricinoleic acid and palmitoleic acid to obtain an oleic acid mixture; distilled water is pumped into a reaction kettle, stirring is started, weighed sodium hydroxide is slowly added to be completely dissolved, steam is started to start heating, an oleic acid mixture is slowly put into the reaction kettle to react, when the temperature in the reaction kettle reaches 80 ℃, the reaction is kept for 1 hour, then a surfactant T-220 is added, and then the temperature is reduced to 60 ℃ and sampling is carried out for detection.
The detection result shows that the obtained emulsifier is light yellow transparent liquid, the PH is 9.5, the water solubility is more than or equal to 10%, and the alcohol solubility is more than or equal to 10%. The resulting emulsifier was designated PM-6303.
Example 2
An emulsifier comprises the following components in percentage by mass: 10% of tall oil acid, 10% of ricinoleic acid, 3% of palmitoleic acid, 3% of sodium hydroxide, 4% of surfactant T-220 (the active ingredient is 25%, the solvent is water, purchased from Qingdao Rueno chemical Co., ltd., model Raynol T-220) and the balance of distilled water; wherein, the acid value of tall oil acid is 196mgKOH/g, the acid value of ricinoleic acid is 181mgKOH/g, and the acid value of palmitoleic acid is 280mgKOH/g.
The preparation method of the emulsifier comprises the following steps: mixing tall oil acid, ricinoleic acid and palmitoleic acid to obtain an oleic acid mixture; distilled water is pumped into a reaction kettle, stirring is started, weighed sodium hydroxide is slowly added to be completely dissolved, steam is started to start heating, an oleic acid mixture is slowly put into the reaction kettle to react, when the temperature in the reaction kettle reaches 80 ℃, the reaction is kept for 1 hour, then a surfactant T-220 is added, and then the temperature is reduced to 60 ℃ and sampling is carried out for detection.
The detection result shows that the obtained emulsifier is light yellow transparent liquid, the PH is 10.5, the water solubility is more than or equal to 10%, and the alcohol solubility is more than or equal to 10%.
Application example 1
The emulsion product was prepared using the emulsifier prepared in example 1, as follows:
200g of natural rubber is weighed and added into a material jar of a commercial eggbeater, then 8g of the emulsifier prepared in the example 1 is added, and stirring is started; sequentially adding 14g of sulfur dispersion and 14g of zinc oxide dispersion into the material jar, and then stirring at a high speed of 5 stages for 3min; 6g of sodium fluosilicate dispersoid is added into a material cylinder, then the mixture is stirred for 1min at a high speed, then the mixture is stirred for 1min at a slow speed at a 1 st gear, and the stirring is stopped, so that a foam body is obtained. Foam the foam is poured into a mold, the foam is smoothed, then weighed, and the weight of the foam is recorded, allowed to stand until a foam gel is formed, and the gel time (i.e., the period of time between completion of foaming and formation of the gel) is recorded.
After forming foam gel, putting the mold into an electric oven, keeping the temperature of the electric oven at 120 ℃, and standing for 5min; taking the die out of the electric oven, then putting the die into a steam box, keeping the temperature of the steam box at 100 ℃, and steaming for 15min; taking the mould out of the steam box, taking the formed latex sponge out of the mould, washing the latex sponge body with water, and then putting the latex sponge body into an electric oven to dry the water.
And measuring the height of the dried latex sponge body, and shearing off the foam to observe the fineness of the foam inside.
Comparative example 1
The method comprises the steps of adopting potassium oleate with 20% of active ingredients and potassium ricinoleate with 35% of active ingredients as emulsifying agents, wherein the adding amount of the potassium oleate is 6g, the adding amount of the potassium ricinoleate is 2g, other conditions are the same as those of application example 1, recording gel time in the operation process, filling the foam weight of a mould, testing the height of the latex sponge after the latex sponge is obtained, and shearing off the foam to observe the foam fineness inside.
The experimental data of application example 1 and comparative example 1 are shown in table 1.
TABLE 1 application example 1 and comparative example 1 raw material usage and product test data for preparing latex sponge
As can be seen from the data in table 1, the emulsion sponge is prepared by using the emulsifier of example 1, the gel time is similar to that of the conventional foaming agent, in the field, different emulsifiers have different effects on the gel time of emulsion foaming, the gel time is too fast, foam is easy to generate voids, the curing time of a foam product is too slow, the foam shrinkage is serious, if the gel time of the emulsifier is too different from that of the conventional emulsifying system, the vulcanization system for preparing the emulsion foaming product needs to be readjusted, the readjustment of the vulcanization system is very complicated, when the emulsifier of the invention is used, the gel time of the foam is basically the same as that of the conventional emulsifying agent, and in the practical application process, the adjustment of the vulcanization system is not needed, and the emulsifier of the invention is directly used for replacing the conventional emulsifying agent; in addition, when the emulsifier of the invention is used, the foam weight of the full mold is smaller, the foam height of the product is higher, which shows that the emulsifier of the embodiment 1 is used for foaming, the foam holes of the obtained foam body and the foaming product are more abundant, and the foam stability is better.
The internal foaming conditions of the latex sponges obtained in application example 1 and comparative example 1 are shown in fig. 1, and it can be seen from fig. 1 that the latex sponges prepared by using the emulsifier of example 1 have finer cells and substantially no large bubbles, while the latex sponges prepared by using the conventional emulsifier system have more large bubbles.
Application example 2
A latex product was prepared using the emulsifier prepared in example 2, the amount of sulfur dispersion was changed to 16g, the amount of zinc oxide dispersion was changed to 16g, the amount of sodium fluorosilicate dispersion was changed to 8g, and the other conditions were the same as in application example 1. And (3) recording gel time in the operation process, filling the foam weight of the die, testing the height of the latex sponge after the latex sponge is obtained, and shearing the foam to observe the fineness of the foam inside.
Comparative example 2
The method comprises the steps of adopting potassium oleate with 20% of active ingredients and potassium ricinoleate with 35% of active ingredients as emulsifying agents, wherein the adding amount of the potassium oleate is 6g, the adding amount of the potassium ricinoleate is 2g, other conditions are the same as those of application example 2, recording gel time in the operation process, filling the foam weight of a mould, testing the height of the latex sponge after the latex sponge is obtained, and shearing off the foam to observe the foam fineness inside.
The experimental data of application example 1 and comparative example 1 are shown in table 2.
TABLE 2 application example 2 and comparative example 2 raw material amounts and product test data for preparing latex sponge
As can be seen from the data in table 2, the emulsion sponge is prepared by using the emulsifier of example 2, the gel time is slightly shorter than that of the conventional foaming agent under the same time of the vulcanization system, and in the actual production process, the production efficiency can be improved and the fineness of the foam can be improved by using the emulsifier of the invention; and when the emulsifier of the invention is used, the foam weight of a full mold is smaller, the foam height of the product is higher, which shows that the foam is formed by using the emulsifier of the embodiment 2, and the foam holes of the obtained foam are more abundant and the foam stability is better.
In addition, the results obtained by observing the fineness of the internal foam of the obtained latex sponge are similar to those of fig. 1, and the cells of the latex sponge prepared by using the emulsifier of example 2 are finer and substantially free of large bubbles, while there are more large bubbles in the latex sponge prepared by using the conventional emulsifier system.
Application example 3
Aluminum hydroxide plays roles of filling, flame retarding and the like in a latex foam product, but the foaming property of an emulsifier is affected by the addition of the aluminum hydroxide, and the foaming effect of the emulsifier is tested under the condition of adding the aluminum hydroxide. The method comprises the following steps:
250g of natural rubber and 40g of aluminum hydroxide are weighed and added into a material jar of a commercial eggbeater, then 12g of the emulsifier prepared in the example 1 is added, and stirring is started; 21g of sulfur dispersion and 18g of zinc oxide dispersion are sequentially added into the material jar, and then 5-grade high-speed stirring is carried out for 3min; 9g of sodium fluosilicate dispersoid is added into a material cylinder, then the mixture is stirred for 1min at a high speed, then the mixture is stirred for 1min at a slow speed at a 1 st gear, and the stirring is stopped, so that a foam body is obtained. Foam the foam is poured into a mold, the foam is smoothed, then weighed, and the weight of the foam is recorded, allowed to stand until a foam gel is formed, and the gel time (i.e., the period of time between completion of foaming and formation of the gel) is recorded.
After forming foam gel, putting the mold into an electric oven, keeping the temperature of the electric oven at 120 ℃, and standing for 5min; taking the die out of the electric oven, then putting the die into a steam box, keeping the temperature of the steam box at 100 ℃, and steaming for 20min; taking the mould out of the steam box, taking the formed latex sponge out of the mould, washing the latex sponge body with water, and then putting the latex sponge body into an electric oven to dry the water.
And measuring the height of the dried latex sponge body, and shearing off the foam to observe the fineness of the foam inside.
Comparative example 3
The method comprises the steps of adopting potassium oleate with 20% of active ingredients and potassium ricinoleate with 35% of active ingredients as emulsifying agents, wherein the adding amount of the potassium oleate is 9g, the adding amount of the potassium ricinoleate is 3g, recording gel time in the operation process and the foam weight of a full mold under the same conditions as in application example 3, testing the height of the latex sponge after the latex sponge is obtained, and shearing off the foam to observe the foam fineness inside.
The experimental data of application example 1 and comparative example 1 are shown in table 3.
TABLE 3 raw material usage and product test data for the preparation of latex sponge using example 3 and comparative example 3
Wherein: the method for calculating the foam shrinkage comprises the following steps: when the latex sponge was just removed from the mold, the length and width of the foam were measured and recorded as D and E, respectively, and after 72 hours, the foam contracted with complete curing of the foam, at which time the length and width of the foam were again measured and recorded as D1 and E1, and then the shrinkage of the foam was calculated according to the following formula:
foam shrinkage= (length shrinkage s1+width shrinkage S2)/2;
foam length shrinkage s1= (foam size D-foam size D1)/foam size D100%;
foam width shrinkage s2= (foam size E-foam size E1)/foam size E100%;
foam shrinkage= (length shrinkage s1+width shrinkage S2)/2.
As can be seen from the data in table 3, after the addition of aluminum hydroxide, the foaming was performed using the emulsifier of example 1, the gel time of the foam and the foam height of the product were similar to those of the conventional emulsifier, but the foam shrinkage was low, indicating that the emulsifier of example 1 had a better foaming effect in the presence of aluminum hydroxide than the conventional emulsifier.
Application example 4
An emulsion product containing aluminum hydroxide was prepared using the emulsifier prepared in example 2, the amount of sulfur dispersion was changed to 16g, the amount of zinc oxide dispersion was changed to 16g, the amount of sodium fluorosilicate dispersion was changed to 8g, and the other conditions were the same as in application example 3. And (3) recording gel time in the operation process, filling the foam weight of the die, testing the height of the latex sponge after the latex sponge is obtained, and shearing the foam to observe the fineness of the foam inside.
Comparative example 4
The method comprises the steps of adopting potassium oleate with 20% of active ingredients and potassium ricinoleate with 35% of active ingredients as emulsifying agents, wherein the adding amount of the potassium oleate is 9g, the adding amount of the potassium ricinoleate is 3g, the other conditions are the same as those of application example 4, recording gel time in the operation process, filling the foam weight of a mould, testing the height of the latex sponge after the latex sponge is obtained, and shearing off the foam to observe the foam fineness inside.
The experimental data of application example 1 and comparative example 1 are shown in table 4.
TABLE 4 raw material usage and product test data for the preparation of latex sponge of application example 4 and comparative example 4
The method of calculating the shrinkage of the foam was the same as in Table 3.
As can be seen from the data in table 4, after the addition of aluminum hydroxide, the foaming was performed using the emulsifier of example 2, the gel time of the foam was shorter than that of the conventional emulsifier, and the foam height of the product was slightly higher than that of the conventional emulsifier, and the foam shrinkage of the foamed product prepared using the emulsifier of example 2 was low, indicating that the emulsifier of example 2 had a better foaming effect in the presence of aluminum hydroxide than the conventional emulsifier.
In-water foaming comparison experiment
100 g of water was weighed, 2% of the emulsifier prepared in example 1 was added, stirred with a stirrer at high speed (5 th gear) for 3min, then stirred at low speed (1 st gear) for 1min, 300 ml of foam was poured into a beaker, and the foam heights were measured at 5min, 10min, 15min, 20min, 25min and 30min, respectively, after standing and observation.
The foaming experiment is carried out in water by adopting a traditional emulsifier system (the active ingredients are mixed by potassium oleate with 20% and potassium ricinoleate with 35% according to the volume ratio of 3:1), the experimental conditions are the same as the above conditions, the experiment is carried out simultaneously, and the foam height under the same time is tested.
The results obtained are shown in Table 5.
TABLE 5 results of in-water foaming comparison experiments
| 1′ | 5′ | 10′ | 15′ | 20′ | 25′ | 30′ | |
| Traditional emulsifier (cm) | 7.7 | 7.5 | 7 | 5 | 4.4 | 3.8 | 3.3 |
| Example 1 (cm) | 7.5 | 7.3 | 7.2 | 7 | 6.9 | 6.8 | 6.6 |
As can be seen from the data in Table 4, when the conventional emulsifier is used for foaming, the foam height gradually decreases with the increase of time, while when the emulsifier of the invention is used for foaming, the foam height decreases slightly with the increase of time, which indicates that the foam stabilizing performance of the emulsifier of the invention is better.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The application of the emulsifier in the latex foaming product is characterized in that the emulsifier is prepared from the following raw materials in percentage by mass: 6 to 12 percent of tall oil acid, 6 to 12 percent of ricinoleic acid, 3 to 9 percent of vegetable oleic acid, 2.5 to 3.0 percent of sodium hydroxide, 3 to 10 percent of surfactant T-2203 and the balance of water; the vegetable oil acid comprises one or more of palmitoleic acid, coconut oil acid, soybean oil acid and rapeseed oil acid; the acid value of the tall oil acid is 180-200 mgKOH/g; the acid value of the ricinoleic acid is 170-190 mgKOH/g; the acid value of the vegetable oleic acid is 270-300 mgKOH/g; the content of the active ingredients of the surfactant T-220 is 24-26 wt%.
2. The use according to claim 1, wherein the content of active ingredient in the emulsifier is 17-23 wt%, and the pH of the emulsifier is 9-11; the water solubility of the emulsifier is more than or equal to 10 percent, and the alcohol solubility is more than or equal to 10 percent.
3. The use according to claim 1, wherein the method of preparing the emulsifier comprises the steps of:
mixing water and sodium hydroxide solution to obtain sodium hydroxide solution;
mixing the sodium hydroxide solution, tall oil acid, ricinoleic acid and vegetable oleic acid for reaction to obtain a reaction solution;
and mixing the reaction solution with a surfactant T-220 to obtain the emulsifier.
4. Use according to claim 3, characterized in that the temperature of the reaction is 60-100 ℃ for 1-2 hours.
5. The use according to claim 1, characterized in that the emulsifier is used in an amount of 3-6% of the mass of the latex.
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| EP1013704B1 (en) * | 1998-12-21 | 2003-03-19 | Goldschmidt AG | Use of ricinolic acid metal salts in the preparation of polyurethane foams |
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