TW464664B - Polysiloxane surfactants and methods of its manufacture - Google Patents

Abstract

The present invention provides novel polysiloxane surfactants with the following structures and methods of their manufacture, where R1 is the hydrogen or phenyl or alkyl group with the number of carbons 1-10; R2 is the hydrogen or alkyl group with the number of carbons 1-10 or alkoxyl group with the number of carbons 1-10; R3 is the hydrogen or alkyl group with the number of carbons 1-10 or alkoxyl group with the number of carbons 2-100; R4 is the hydrogen or alkyl group with the number of carbons 1-10; A is the anionic group, e.g. halide or OH or CH3SO4; x is the structural repeating unit and equal to or bigger than zero rational; y is the structural repeating unit and bigger than zero rational. The abilities of emulsifying, dispersing, defoaming and some special fundamental characteristics could be derived from this new type of polysiloxane copolymers.

Description

V. Description of the invention (1) Surfactants are widely used in various industries, such as wood, etc., and the addition of boundary agents, pesticides, medicine, and soil "industrial monosodium glutamate". The use of the agent is powerful, so the agent can be called emulsification and demulsification, foaming and defoaming ': J wet, disperse and agglutinate, based on the basic characteristics of the agent: adsorption,' f and other basic functions' and These are power drops. Surfactants with various functions formed by the above basic operations, solubilization and surface tension. ’, The comprehensive application of characteristics can be derived

子 '：：： 3 ί: The active agent has a high score with hydrophobic and hydrophilic groups. Γ 丨 Dendrobium, 5 / Ancient traditional agents are different and have some functions. Wei = 1 This is widely used In industries such as dispersants, coagulants, 2 > encapsulants and demulsifiers, etc., it is the current development trend of surfactants. The polysilicon gas-fired copolymer has higher hydrophobicity than ordinary hydrocarbon polymers and can bring about lower interfacial tension. Therefore, the present invention introduces a lysine group into a polysiloxane copolymer, making it a still molecule Type surfactant.

In Japanese Patent Kokoku No. 49-1 1 760, an ionic sintered oxygen-type surfactant is mixed with a functional polymer having a side chain or a terminal group, and it is found that it does not have good surfactant properties. 0 Shixi Oxygen Burn Type Surfactants such as Makoto Ohno, Kunio. Esumi and Kenjiro Meguro, JAOCS, Vol. 69; No. 1 'Maki and Koraori, Kagaku Kogyo, Vol. 73, No. 6 and Hyomen,

Vo 1. 7, No_ 11 is a study on non-ionic boundary agents.

Page 7 on some oxypropyl groups :: interfacial tension is indeed better than ordinary hydrocarbon surfactants, but the hydrophilic group of this conjugate is polyethylene oxide or propylene oxide. Reactive groups that can react with ethylene oxide or propylene oxide, enol (allyl alcoho1) and polypalladium alkoxide containing active hydrogen in the side chain: the reaction conditions are strict, the yield is low 'and Ethylene oxide or propylene oxide used in polyethylene oxide or polycyclization is highly flammable and poisonous. Salmon: The present invention provides a non-toxic, simple and high-yield method for preparing non- Ionic polymer siloxane type surfactant. The present invention relates to the preparation of polysiloxane co-products with reactive groups on the side chain, and the use of the reactive groups for chemical modification and introduction of hydrophilic groups to obtain nonionic and cationic polymer-type interface activities. Agent:

/ 3 (II)

Ri CH2CHjR2〇CIiCH-CH2N-R4 A 1 \ OH R3 where R is hydrogen or phenyl or carbon number 10 alkyl group; R is hydrogen or carbon number 1-10 entertainment group or terminal number 1 to 1 〇 Entertainment

5. Explanation on page 8 (3) R is hydrogen or a group containing an alkyl group having a carbon number of 10 or an alkoxy group having a carbon number of 2 to 100; R is hydrogen or a plurality of A is an anionic group X Is a repeating unit y is an alkyl group of repeating unit ~ 1 0; such as halogen or 0 Η or CH 3S 0 4; a rational number of 0 or greater; a rational number of greater than 0. The polylithic oxygen surfactant in the present invention has a good ability to reduce the interfacial tension in an aqueous solution, and can also be used as a dispersant, an aggregating agent, an antifoaming agent, an emulsifier, and the like. The above-mentioned polysiloxane surfactant of the present invention can be reacted with other silicon-containing compounds under the catalysis of an acid to obtain a polysiloxane copolymer with active hydrogen at the terminal. The compound is then substituted with a compound containing an epoxy group and an unsaturated double bond, such as allyl glycidyl ether, under a medium to obtain a polysiloxane copolymer having an epoxy group at the terminal. Poly-oxygenated copolymers with structures such as (I) or (〗 丨) can be obtained by reacting secondary, secondary or tertiary amines. The poly (%) oxygen copolymer having a structure such as (I) can further react with r 4A to form a poly dream oxygen cationic surfactant having a structure such as (II), and the definitions of R and A are the same as those of the chemical formula (I I). I. One St-O- The above silicon-containing compound that reacts with ii is a cyclic siloxane compound such as HeXamethy 1 cyc 1 〇trisi 1 ο Xane or Hexaphenylcyclo-page 9 46466 4 5. Description of the invention (4) trisiloxane or Octamethy1 Eye 1otetrasi1oxane, Octa-phenylcyclotetrasi loxane, or one or more of them alone or in combination. The above primary amine is a mono-substituted amine group, such as methylamine, ethylamine, Propylamine, tert-Buty 1 amine, 2-Aminoethanol or n-pentylamine. The above secondary amine is a disubstituted amine group, such as dimethylamine, diethylamine, diethanolamine, Di-n-butylamine, Ethylmethylamine, or sec-Butylmethylamine. 0 The above tertiary amine is a trisubstituted amine group, such as Trimethylamine, triethylamine, triethanolamine, n-Butylethylmethylamine or Dimethyl-ethy 1 am i ne ^ ° The following examples are given to make the features and advantages of the present invention clearer, but the following examples It is not intended to limit the scope of the invention. The scope of the invention should be based on the scope of the attached patent application. Example 1 In a four-neck reactor, 120 grams of Poly (methyl hydrogen siloxane) '70 grams of Octamethy1 eye 1otetrasiloxane and 10 Gram

Page 10 A 6 466 4 ——1 — " —- ____ V. Description of the Invention (5)

Hexamethyldisiloxane ’uses concentrated sulfuric acid as a catalyst, and a mechanical stirring device is installed. After passing nitrogen for about 10 minutes, the bottle mouth is sealed and the temperature is raised to 45. (: The reaction is stopped after 48 hours of reaction, and sodium bicarbonate is slowly added to neutralize concentrated sulfuric acid until the universal acid test paper shows that the pH value is greater than 5, and filtered to obtain polysiloxane with active hydrogen on the side chain. The product SH. Example 2 In a 500 ml reactor, 40 grams of sulfonium and about 50.5 grams of allyl glycidyl ether (excess) were dissolved in about 250 grams of anhydrous toluene, nitrogen was passed through, and Pt (platinum di viny ltetramethy 1 disilo -xane complex) catalyst at 75 ° C, followed by FT-IR. When the absorption peak of Si-H (21 6 5 cm-1) disappears completely, it means that the reaction is complete. Then use a rotary evaporator. (Rotavapor) extract most of the toluene and unreacted allyl glycidyl ether, put it in a 4 (Tc vacuum supply box, and dry it for 4 8 hours' to obtain a sintered copolymer with ethylene oxide group sg. Example 3 In a 500ml reactor, dissolve 50g of SG and 26.2 5g of diethanolamine in 350ml of ethanol, stir the reaction at 70eC for 10 hours, and then remove most of the solvent on a rotary evaporator. After being driven away, add about 2 50 m I of chloroform to dissolve, and steam with 10 m 1 The unreacted diethanolamine was extracted with water and repeated several times. Most of the

Page IIπ ^ 4 ^ β-4 ___________ V. Description of the invention (6) Solvent, then dissolve in ethanol and add a little magnesium sulphate and let stand overnight, filter, and then use a rotary evaporator to remove most of the ethanol. (The product was dried in a TC vacuum oven for 48 hours, as shown in the structure (I), where R is CH 3, R is CH 20, and R is CH 2 CH 20 H. Example 4 In a 250 ml reactor, 25 g of SG and 9. 15 grams of diethylamine (di-ethyl amine) was dissolved in 180 cu of 1 ethanol, and the reaction was stirred at a temperature of 7 (TC for 10 hours), and then most of the solvent was removed by using a rotary evaporator. It was re-precipitated several times to obtain a dark brown viscous substance. The upper layer of ether was discarded and dried in a vacuum oven at 60 ° C for 24 hours to obtain SDEA. In a 250 ml reactor, 30 g of SDEA was dissolved in 150 ml of alcohol. 20.8 g of dimethyl sulfate was dissolved in 50 ml of methanol and placed in a feeding tube, and slowly dropped at room temperature. After the drop was completed, stirring was continued for 8 hours to complete the reaction. After rotary evaporation Remove most of the methanol from the ether and reprecipitate in ether to obtain a brown sticky substance. Dry in a 60 ° C vacuum oven for 48 hours to obtain the product SQDEA, as shown in the structure (11), where R is CH3 ′, R is CH20, R is CH2CH3, R is CH3, and A is CH3S04. Example 5 In a 250ml reactor, take 20.7 grams of SHE in 120ml of methanol,

Page 12 464664_ V. Description of the invention (7) Take 14.2 3 g of dimethyl sulfuric acid in 30 ml of methanol and put it into the feeding tube, slowly drop in at room temperature, and continue stirring for 8 hours to make the reaction After the completion, the majority of the methanol was removed from the ether and re-precipitated several times in diethyl ether through a rotary evaporator. The upper diethyl ether was discarded and placed in a vacuum oven at 60 ° C for 4 8 hours to obtain the product SQHE, such as the structure (II ), Where R is CH3, R is CH20, R is CH2CH2OH, R is CH3, and A is CH3S04. Example 6 Weigh 20 grams of SG and 11.2 grams of triethylamine, place them in a 250 ml round bottom flask, add 150 ml of ethanol as a solvent, and react at 60 ° C for 8 hours. Dry the unreacted ethanol and triethylamine with a rotary evaporator and vacuum oven to obtain the product SQE, as shown in structure (II), where R is CH3, R is CH2 0, R and R are CH2CH3, and A is OH. Example 7 A polymer solution having a concentration of 1.0 g / L (Examples 3 and 5) was prepared by using a buffer solution of saturated pyrene molecules, and then diluted to different concentrations, and tested using a surface tensiometer (Lauda, TE 1C) at different concentrations. The results of the change in surface tension at the concentration are shown in Fig. 1. The structural formulas of CHE and CQHE in the figure are shown below.

~ 4 ~ 6 4 6 6 4 V. Description of the invention (8) CHE:

ftCH2. ° ch3 ch3 -c— c = o

OCH2CH—CH2N \ OH, ch2ch2oh ch2ch2oh — (ch2 ~

ch2ch2oh h2 《ch3 CH3S〇T ch2ch2oh CQHE: It can be clearly seen from Figure 1 that the polysiloxane surfactant of the present invention has a better ability to reduce surface tension than the common carbon-nitrogen-based hydrophobic agent. . Example 8 Using the product in Example 3 as a silica sand (siii ca) dispersant 'The evaluation of its dispersing ability was performed in the following manner: Dispersants of different proportions were taken and dissolved in 85 grams of distilled water, and potassium hydroxide was used. The aqueous solution was adjusted to a pH value of 10. 5 ± 0.1, and slowly added 15 grams of silica sand under mechanical stirring at 400 rpm. After being uniform, add about 50 grams of file beads (di a. 2 melon), change Grind at 800 rpm for one hour. Take about 80 ml of the mud and place it in the adapter of the Brookfield viscometer (Brookfield).

Page 14 -A6 456 4_____ V. Description of the invention (9) The stable viscosity value induced at a fixed shear rate. The result is shown in Figure 2. It can be seen from FIG. 2 that compared with the blank control group, the viscosity of Shi Xisha significantly reduced the viscosity of the dispersion system when the dispersant concentration was greater than 1% by weight. This result shows that the product in Example 3 has the dispersibility of silica sand. Example 9 In Example 1, the weight percentage composition was changed to 30% by weight, 40% by weight, or 50% by weight of Poli (methyl hydrogen siloxane), 65% by weight, 55% by weight, or 45% by weight Octamethylcyclotetrasiloxane and 5% by weight

Hexamethyldisiloxane synthesizes SH30, SH4 0, or SH50, and synthesizes SHE30, SHE40, and SHE50 as defoamers according to the methods of Examples 2 and 3. The defoaming test conditions for self-emulsification and silicone oil emulsification are as follows: (1) Self-emulsification The system takes 1.5 grams of SHE4 0 and SHE50, dissolves in 10 ml of distilled German water, and uses a homogenizer to emulsify and homogenize for three minutes at 10,000 revolutions per minute to form a stable self-emulsion. The defoaming effect was measured at a foaming agent sodium dodecyl benzoate (SDS) concentration of 0-25%, an air flow rate of 1 000 cc / min, a temperature of 40 ° C, and a defoamer concentration of 1 0.00 ppm. The results are shown in Figure 3 (2) Shixi Oil Emulsification System

Page 15 ^ U6-A £ 6-4 ----- 5. Description of the Invention (ίο) Take 1.5 grams of SHE40, dissolve in 10 ml of distilled water and 10 ml of silicone oil, and use a homogenizer at 10,000 per minute Turn to emulsify and homogenize for three minutes to form a stable silicone oil emulsion. Measure the foaming agent sodium dodecyl benzoate (SDS) at 0.25%, air flow rate of 1,000 cc / min, temperature of 40 ° C, and defoamer concentration of 1,000, 2500, and 5000 ppm. Defoaming effect. The results are shown in Figure 4. As can be seen from Fig. 3'4, all of them have the effect of defoaming. In Example 9, 1.5 grams of SHE30 and SHE40 were respectively dissolved in 10 ml of hot water and 10 m of stone oil, and homogenized by a homogenizer at 10,000 revolutions per minute for three minutes to form Stable silicone oil emulsion. The oil-moisture separation time and height are shown in the table below. It can be seen that the polysiloxane type surfactant used can stably form a silicone oil emulsion. Closing time_Separation high_ SHE30 Separation started after 10 daysΊ = 10 days, H = 0.15 (19ml) 30 days after complete separation T = 30 days' upper H = 5 (19 ml) lower H = 6 (19 ml)

Page 16 4 A66 4_ V. Description of the invention (11) H = 0.1 (19 ml upper H = 6 (19 ml) lower Η = 7.5 · 19 (19 ml SHE40 Separation started after 10 days T = 10 days 30 days later Complete separation T = 30 days Although the present invention has been disclosed as above with preferred embodiments, although it is not intended to limit the present invention, anyone skilled in the art can make changes without departing from the spirit and scope of the present invention. And retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application.

Brief description of the figure: Figure 1 shows the relationship between the concentration of different polysiloxane-based surfactants SHE, SQHE and the high-molecular-weight hydrocarbon-based intermediary agents CHE and CQHE and the interfacial tension of the aqueous solution. Figure 2 shows the viscosity relationship of silica sand with different dispersant SHE concentrations at pH = 10.5 ± 0.1. Figure 3 shows the relationship between the defoaming effect in the self-emulsifying system (SDS = 0.25%, defoamer = 1000 ppm). Figure 4 shows the relationship between the defoaming effect and the estimation in the silicone oil emulsification system (SDS = 0.25%) and different SHE40 concentrations.

Claims (1)

.4. A chemical compound with a structure of formula (I) or (π) R, R ^ Si-oHsi-ojyR! / Rs (I) Ri ch2ch2r2ch2ch-ch2n, R3 OH Rr (Bu Miao 丨 -〇 知 I ~; yRl / 3 Ri CH2CH2R2CH2CH-ch2n-r4 a (II) OH r3 h is hydrogen or a phenyl group or an alkyl group having a carbon number of 10; Rz is hydrogen or an alkyl group having a carbon number of 1-10 or an alkoxy group having a carbon number of 10; R3 is hydrogen or an alkyl group having a carbon number of 1 to 10 Or an alkoxy group having 2 to 100 carbon atoms; R4 is hydrogen or an alkyl group having 10 carbon atoms; A is an anionic group such as halogen or 0H or CH3S04; X is a repeating unit and is a rational number of 0 or greater than 0 Y is a repeated unit and is a rational number greater than 0. 2. A method for synthesizing chemical compounds as described in item 1 of the scope of patent application, including: Page 18 * «46466 4 VI. Scope of Patent Application (a) Substitute the active hydrogen in the compound with the following structure with allyl glycidyl ether. R TX RV ο 1 j R ^: H ο R-siIR Alkyl ethyl takes oxygen tricyclic ring and its substitution amount is taken as 21, each order is taken as a single, and should be reversed with the three amine production grades. Levels should be reversed one by one. Otoamine 7 amines 01 grade 0. 3 and and grade-substitute 3 and and grade It is the second generation of the amine grade to obtain the second method of the second method. The second amine is the second method of the second method. The second is the second method of the second method of the second method. Special amines Page 19