TWI235170B - Polyacrylic surfactants and methods of their manufacture - Google Patents

Abstract

The present invention provides novel polyacrylic surfactants with the following structures and methods of their manufacture, where R1 is the hydrogen or alkyl group with the number of carbons 2-10; R2 is the hydrogen or alkyl group with the number of carbons 1-50; R3 is the hydrogen or alkyl group with the number of carbons 1-10; A is the ionic, cationic and nonionic group, e.g. -N(R4)2 or -NC(R4)3<+>X<-> or -SO3<->M<+>; R4 is the hydrogen or alkyl group with the number of carbons 1-10 or alkoxyl group with the number of carbons 2-100; X is the halide or OH- or CH3SO4-; M is the metallic cationic group, e.g. Na+ or K+; x is the structural repeating unit, and equals to 0 < x < 10000 rational; y is the structural repeating unit, and equals to 0 < y < 10000 rational. The abilities of emulsifying, dispersing, flocculating and some special fundamental characteristics could be derived from this new type of polyacrylic copolymers.

Description

V. Description of the invention (1) Surfactants are widely used in various industries such as the beginning of life, t. Addition # 2 ::, agricultural fun, medicine, soil "industrial monosodium glutamate". The use of the boundary agent is strong. Therefore, the boundary agent can be called J-chemical and demulsification, foaming and defoaming, etc. :: work: disperse and agglutinate, based on the basic characteristics of the boundary agent: the basic function of Mingweiqiao And these are power drops. From the above basic action disk; i: J ί 丄 :: surface active agent with various functions. / 、 The application of Temple 4 can be derived from the South molecular-type surfactant is a tape. Its properties are the same as those of traditional traditional circles. The high-class boundary agent has no @, so it is broad, and lacks: it has some The function is to pass defoamers and demulsifiers, etc., for the current industry, the current development trend of dispersants, aggregating agents, / Xunma surfactants. Copolymers of Λκ ^ series are widely used industrially as surfactants. For example, 〇4! ^ 011 US patent 4 〇43 965 is acrylic acid and 1 dihydroperfluor〇ctyl methacrylate copolymer as the soil release finish in the rinse cycle of ahome laundry process; Portnoy U.S. Patent No. 4,680,128 is a low molecular weight acrylic acid and vinylsulfonic acid salt copolymer that can be used as a dispersant and a deagglomerating agent ((16 {1〇 (: (： 1118111;); Japanese Patent 6 1/1 452 54 is disclosed on dispersing organic or inorganic pigments. The addition of polyxyalkylene methacrylate and alky 1 methacrylate significantly improves the dispersion effect; it is found to be hydrophobic in Offenlegungsschrift 3,636,429 () ^ (11'〇011〇1) 丨 (:) and hydrophilic (117 (11'〇01111 丨 (:)) polymer formed by the polymerization of acrylic monomers, which will have mesophases in a specific concentration range of aqueous solution This copolymer has the properties of a surfactant, and can be described in the invention. (2) The effect of pH on 'increasing the viscosity of the water phase. The present invention provides a simple, readily available, inexpensive and high polymer A method for dressing with a small amount of interference, preparing a polyacrylic co-f 'with reactive groups on the side chain, and using its reactive base ring to chemically modify and guide human hydrophilic groups to obtain nonionic, anionic Or cationic polymer-type surfactant, the second

0H wherein hydrogen or alkyl having 2 to 10 carbon atoms; h is hydrogen or alkyl having 50 to carbon atom; &amp; hydrogen or carbon having 1 to 1 alkyl group; [〇 alkyl group; A is anionic, cationic and nonionic Radicals, such as ·· —N ^) 2 or -N (R / 3Xe or -SO / W; h is hydrogen or a carbon-containing number] ~; [0's alkyl group or carbon number 2 ~ 100 Oxygen; x is a halogen or 0H- or CH3S04-; a rational number of 1 000; a rational number of 1 000. M is a metal cation such as Na + or κ +; χ is a repeating unit, and is 0 &lt; X &lt; y is a repeating unit, and is &lt; y &lt; The polyacrylic surfactant in the present invention has a boundary of 1235170 in an aqueous solution. 5. Description of the invention (3) 'The ability to reduce the surface tension can also be applied As dispersant, coagulant, defoamer, emulsifier, etc. The above-mentioned polyacrylic surfactants of the present invention can be used with various types of acrylic compounds containing unsaturated double bonds and epoxy-containing compounds. Unsaturated double bond compounds, such as methacryl acid glycidyl ether, are copolymerized to obtain polyacrylic copolymers with epoxy groups on the side chains, which are then mixed with NH3, primary, secondary, and tertiary amines. Or react with NaHS03 to obtain a polyacrylic copolymer of structure (I) (non-ionic, cationic and anionic), wherein the non-ionic polyacrylic copolymer can further react with R2X to form a polyacrylic Cationic surfactant, and R2 and its definition are the same as above. Various types of acrylic compounds of unsaturated double bonds such as he X y 1 acrylate, hexyl methacrylate, 2-ethyl hexyl acrylate, iso-octyl acrylate, etc. 3,5,5-trimethyl hexyl aery 1 ate, etc. The above primary amines are mono-substituted amine groups, such as methylamine, ethylamine, propylamine, tert-butylamine, 2-aminoethanol or n-pentylamine, etc. The amine is a disubstituted amine group, such as dimethylamine, diethylamine, diethanolamine-di-n-butyl amine, ethylmethylamine, or sec-butylmethy lamine, etc. The above tertiary amine is a trisubstituted amine group, such as tri Fluorenylamine, triethylamine, triethanolamine, n-butylethy lmethy lamine or dimethylethylamine, etc.

1235170 V. Description of the invention (4) The following examples are given to make the features and advantages of the present invention clearer, but the following examples are not intended to limit the scope of the invention. The scope of the invention should be based on the attached application. The scope of patents shall prevail. Example 1 23.7 g of MMA (0.237 mole), 42.6 g of MAGE (0.3 mole), 6.63 g of 1-butanethiol and about 200 ml of 1,4-dioxane at room temperature It was placed in a nitrogen-filled reactor, preheated to 70 ° C, and then slowly added 1.326 g of AIBN (2 wt%) / 50ml dioxane solution. After the drop was completed, the reaction was continued for 4 hours. Stop the reaction. After the temperature is cooled, use a rotary evaporator to remove most of the di ο X ane. Place it in a large amount of methanol, dissolve it in dichloromethane, and re-precipitate in methanol several times. Place it in a vacuum oven at 60 ° C to dry it. In 24 hours, the product PMGMMA was obtained. π NMR ((5 ppm): 2.53 to 3.32 (protons of the epoxide group), 3.47 to 3.62 (-〇CS3 on MMA), 3.68 to 4.47 (-0C) J2- on MAGE) Epoxy equivalent (EEW): 254 eq./g. Molecular weight: 1800 g / inol; polydispersity index: 1.32. Example 2 20 g of PMGMMA / 100 ml of dichloroethane and 8 g of diethylamine / 100 ml of ethanol were placed in a 500 ml reaction container. Within 10 hours, the reaction was stirred at a temperature of ° C, and then most of the solvent was removed on a rotary evaporator.

Page 10 1235170_ V. Description of the invention (5) 'Re-precipitation several times, put it in a 60 t vacuum oven for 24 hours to obtain the product CDEANMR (5 ppm): 〇 · 58 ~ 2.42 (-CU2-C (CH3 )-), 1.08- 1.32 (-CH2N (CH2CH3) 2), 2.48-3.17 (-CH2 N (CH2 CH3) 2), 3.38 ~ 3 · 79 (-OCH3), 3.79 ~ 3.96 ( -CS (OH)-), 3.96 to 4.34 (-0CH2_). In a 251111 reactor, 10 g (1; 8) was dissolved in 1001111 methanol, 6.87 g of dimethyl sulfuric acid was dissolved in 50 ml of methanol and placed in a feeding tube, and slowly dropped at room temperature. 'After dripping, continue to stir for 8 hours to complete the reaction. Remove most of the methanol from the rotary evaporator and reprecipitate several times in ether. Put it in a 60 ° C vacuum oven and dry for 24 hours to obtain the product CQDEA. Structure (I), where R !, R2 * R3 is CH3, R4a (CH2CH3) 2CH3 in A, and X is CH3S04 "Η NMR (5 ppm): 0.35- 2.36 (-CH2 ~ C (CH3)-), 1.08-1.36 (~ CH2N + (CH2CH3) 2), 2.8 6-3.0 6 (-N + -CH3), 3.06-3.42 (-CH2N + -CH2CH3), 3.58- 3.69 (-0CH3), 3.69-3.95 (-CH (OH (OH) )-), 3.95 ^ 4.12 (-0CH2_CH (0H)-), 4.12 ^ 4.3 (Cg3S04-). 'Example 3 Put 34.6 grams of PMGMMA / 150ml dichloroethane and 19.82 grams of diethanolfe / 150ml ethanol in In a 500ml reactor, the reaction was carried out at a temperature of 70 ° C for 10 hours, and then most of the solvent was removed by a rotary evaporator, and then it was precipitated in 1,4-dioxane, and then dissolved in methanol and then precipitated in 1,4-dioxane several times, put in 60 ° C vacuum oven 48 hours, to obtain

1235170__ V. Description of the invention (6) • The product CHE, as shown in the structure (I), its center, R2 and private are CH3, and R4 in A is CH2CH2OH. 4 NMR (6 ppm): 2.68 to 3.04 (-CH2N (Cg2CH20H) 2), 3.62 to 3.82 (-CH2N (CH2C | J2〇H) 2), 3.84 to 3.96 (- CS (OH)-), 3.96 to 4.24 (-C00CH2-). Example 4 In a 250 ml reactor, take 7.5 g of CHE and dissolve it in 90 ml of methanol, take 5.15 g of dimethyl sulfuric acid and dissolve it in 30 ml of methanol and put it in a feeding tube. Slowly drop in at room temperature. After stirring for 8 hours to complete the reaction, the majority of the methanol was driven off by a rotary evaporator to be reprecipitated several times in ether, and dried in a vacuum oven at 60 ° C for 24 hours to obtain the product CQHE, such as the structure (I ), Where h and R ^ R3 are CH3, R4 in A is (CH2CH20H) 2CH3, and X is CH3S04NMR (ά ppm): 0.38 to 2.45 (-CS2-C (Cg3)-), 3.08- 3.24 (-N + -CH3), 3.24- 3.58 (-CH2N + CH2CH2OH)? 3.58-3.69 (-0CH3), 3.74-3.92 (-N + -CH2CH2OH), 3.92-4. 01 (-CH (OH)-), 4.01 ^ 4.18 (-〇CH2-CH (OH)-), 4.22 ~ 3.41 (CH3S04_). 'Example 5 20 grams of PMGMMA / 80 grams of 1,4-dioxane and 34.4 grams of sodium bisulfite / 120 grams of water were placed in a 500 ml reactor, and the reaction was stirred at 70 for 72 hours. Remove most of the solvent with a rotary evaporator and place it in a dialysis membrane

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(MW cut of f = 1 00) to remove the unreacted sodium bisulfite. The red-to-red evaporator removes most of the solvent, reprecipitates in methanol, and filters it into a 40 ° C vacuum oven. After drying for 48 hours, the product CHS is obtained, as shown in the age structure (I), where &amp; Minghe 1 is called, A is 3_Na +. 1} 1 position, °, (ppm): 3.12 (-CH2S03), 3.99 (-C | i (〇H)-), 4.33 to 4.43 (-〇CH2_). 'Example 6 A polymer solution (Examples 2, 3, 4 and 5) with a concentration of 10 g / L was prepared using a buffer solution of saturated pyrene molecules, and then diluted to different concentrations, and a surface tensiometer (Lauda, TE1C) test the change of surface tension at different concentrations. The results are shown in Figure 1. It is clearly observed in the figure that the polyacrylic surfactant of the present invention has the ability to reduce the interfacial tension in an aqueous solution. 1 Example 7 The products in Examples 3, 4, and 5 were used as silica sand (fumed si 1 ica, Dugussa, Aerosi 190 G) dispersant, and the evaluation of its dispersibility was performed in the following manner: Take Dispersants in different proportions are dissolved in 85 grams of distilled water, the pH value is adjusted to 10.5 with potassium hydroxide aqueous solution, and 15 grams of silica sand are slowly added under 400 rpm mechanical stirring. After homogenization, add about 50 grams Zirconium beads (di a. 2mm),

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5. Description of the invention (8) Change to 800 rPm for one hour. Take about 80 mi of siurry and put in viscosity. Ten (jrookheid) adapter, measured the stable viscosity value under a fixed rate with an appropriate spindle. The result is shown in Figure 2. Figure 3 shows the thickness of the dispersant corresponding to Figure 2. The obtained slurry was coated on a copper sheet with a thickness of 2 · 5 # m and placed in a 5 ° C oven for 6 hours. A small slice was pasted on ten pieces. A gold atom thin film is deposited on a coin and a vacuum, and the state of the particles is scanned with an electron microscope at a magnification of 1,000,000, and the observation is taken. ^ Figure 2: Knowing that the particles of silica sand itself are in Qiu When it is 105, the surface is filled with negatively charged particles, and the mutual repulsion makes the viscosity in the absence of dispersant 田 = when the polyacrylic dispersant of the present invention is added, the viscosity of the dispersion system is reunited ..., too large According to the results of the microscope in FIG. 3, it can be seen that when the surfactant of the present invention is added to the dispersion system, the silica sand particle distribution is more uniform and detailed, and the results show that the products of Examples 3, 4, and 5 of the present invention Example 8 with silica sand The product in Example 5 was used as the surfactant in the chemical mechanical polishing liquid of the dielectric layer, and the polishing liquid was prepared in the following manner: 0. 0015 wt% CHS dissolved in about 85 g of distilled water In a potassium hydroxide aqueous solution, the pH was adjusted to 1 0.5. And add citric acid as a buffer solution, and slowly add 15 grams of Shixisha under mechanical stirring at 4000 rpm, then add 500 grams of zirconium beads (dia · 2 mm), and grind at 1000 rpm instead! Hours. Resulting slurry

1235170 V. Description of the invention (9) ~~~ ^^ —---- Diluted with distilled water so that its solid content is equal to 12.5 wt%, and only the parameters shown in the table of γ main _ The dielectric layer was evaluated for polishing effects. Film Material Si〇2 Down Force (psi) 7 Back Pressure (psi) 3 Platen Speed (rpm) 20 Carrier Speed (rpm) 25 Slurry Flow Rate (ml / min) 150 Pre-wet Durat i on (sec) 10 Pre- wet Flow Rate (ml / min) 300 Temperature (° C) 37 Pad Condition Duration (sec) 30 Polishing Time (min) 1 After the chemical mechanical polishing, the wafer is sent to the CMP cleaning machine for cleaning. The steps are: 8 ^ 1 U · Water + Ultrasonic Oscillator 2, NH4〇H + Brush 3, D · I · Water + Ultrasonic Oscillator

4.D · I · Water + BSR 5.Sp i n Dry The removal rate of this abrasive for chemical mechanical polishing of the silicon dioxide dielectric layer is

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Claims (1)

1235170_ VI. Application patent scope 1. A polymer as an acrylic surfactant, which has the following structure: 'or2 och ^ jh—ch2a OH where Ri is hydrogen or an alkyl group having 2 to 10 carbon atoms; R2 Is hydrogen or an alkyl group having a carbon number of 50; R3 is a hydrogen or an alkyl group having a carbon number of 1 to 10; A is an anionic, cationic and nonionic group, for example: -N〇R4) 2 or -N (R4); X0 or -SO / W; R4 is hydrogen or a group containing an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 2 to 100 carbon atoms; X is halogen or 0H * &quot; or CH3S04_; M is Metal cations such as Na + or K +; X is a repeating unit and is a rational number of 0 &lt; X &lt;10000; y is a repeating unit and is a rational number of 0 &lt; y &lt; 10000. 2. The compound in item 1 of the scope of patent application is used as a dispersant. 3. The compound in item 1 of the scope of patent application is used as an emulsifier. 4. The compound in item 1 of the scope of patent application is used as agglutinating agent. 1235170 VI. Scope of Patent Application Page 18