TWI226318B - Concrete admixture additive - Google Patents

Abstract

The objective of the present invention is to provide a chemical additive that can be blended into concrete admixture to increase the flowability, reduce the slump and enhance the compression strength of the concrete admixture without needing additional water in the concrete admixture. A concrete admixture additive of the invention was derived from reacting a mixture of olefins/cyclic olefins-maleic anhydride copolymers and methoxy polyethylene glycol amines and/or polyethylene glycol monoalkyl ethers, or a mixture of styrene-maleic anhydride copolymers and methoxy polyethylene glycol amines and/or polyethylene glycol monoalkyl ethers, or a mixture of styrene-olefins/cyclic olefins-maleic anhydride terpolymers and methoxy polyethylene glycol amines and/or polyethylene glycol monoalkyl ethers. These reactions lead to the formation of a kind of carboxylic salt containing polymer, which can be used alone as additive in concrete admixture. Only a small amount of this substance is needed to provide excellent water reduction, high concrete flowability and high early strength. Due to these properties, the additive is very useful in providing more options of construction method.

Description

1226318 发明 Description of the invention: [Technical field to which the invention belongs] The chemical additive of the present invention relates to a kind of high performance water reducing agent for ready-mixed concrete, which is blended in concrete and only a small amount is excellent. Water reduction can improve the fluidity of concrete, improve the performance of slump, and various compressive strength. Therefore, chemical additives have a high water reduction rate. Even if the concrete ratio design of low cement dosage and low chemical dosage is used, high quality concrete can still be produced, which gives the construction project excellent workability and provides the best Construction method selection. [Previous technology] 10 In general construction concrete mixing process, a large amount of water can be added to increase fluidity. However, too much water will reduce the compressive strength and other properties of the concrete. Insufficient water will easily cause the deterioration of the concrete's collapse performance. , Which is not conducive to the choice of work methods. Therefore, various chemical agents have been proposed in order to improve the flowability of ready-mixed concrete without increasing the amount of water. 15 Traditional concrete water reducing agents are made by using lignin as the main component, followed by adding acidified sodium formate (Naphthalene). Although this type of medicine is relatively low cost, it cannot play concrete water reducing effect with low effective ingredients and low usage. If Type F water reducing agent with high water reduction rate is based on pure Naphthalene, the slump loss of concrete will be very high. fast. Recently, acrylic acid or maleic acid needles and copolymers of Alkenyl Ethers and their derivatives have been proposed to improve the flowability of ready-mixed concrete [Japanese Patent Publication (Kokai) Nos 285140/88 and 163108 / 90]. In addition, the copolymers of maleic anhydride and its salts, S derivatives and Hydroxy-Terminated Allylether 1226318, and copolymers of maleic anhydride and partially esterified styrene are also considered to enhance the flowability of ready-mixed concrete [US Patent No 4,471,100 and 5,158,996]. This type of chemical agent can be classified as a carboxylic acid series chemical agent, but the ready-mixed concrete added with the aforementioned agent cannot provide all the required properties. For example, the acrylic acid copolymer after the esterification reaction can provide Ready-mixed concrete has good fluidity, but also extends its hardening time. [Summary of the Invention] Therefore, the object of the present invention is to provide a chemical mixing of ready-mixed concrete with various properties such as mixing in concrete, which can improve the fluidity of the concrete, improve the slump performance, and the compressive strength of 10. Agent. In the present invention, the chemical admixture for ready-mixed concrete of the present invention is based on olefins / Cyclic Olefins-Maleic Anhydride copolymer (Olefins / Cyclic Olefins-Maleic Anhydride Copolymer) and a certain proportion. A mixture of Methoxy 15 Polyethylene Glycol Amine and / or ethylene glycol monolayer is used for the reaction, or a styrene-maleic anhydride copolymer (Styrene-Maleic Anhydride Copolymer) and a certain proportion of Methoxy Polyethylene Glycol Amine and / or a mixture of ethylene glycol monoalkyl ethers may be used for the reaction. A styrene-olefin / cycloolefin-malein 20 anhydride terpolymer (Styrene- Olefins / Cyclic Olefins-Maleic Anhydride

Terpolymer) is reacted with a mixture of Methoxy Polyethylene Glycol Amine and / or Polyethylene Glycol Mono Alkyl Ether. These reactions can form a carboxylate polymer. This type of polymer 1226318 can be used alone or in combination with some agents to make a high-performance ready-mixed concrete chemical additive, which is excellent with a small amount. The water reduction rate improves the fluidity of concrete and has a better early strength effect, which is helpful for the selection of construction methods. 5 [Embodiments] Regarding the technical means adopted by the present invention to achieve the above-mentioned objects and features and their effects, the following preferred embodiments are described below: The chemical admixture of the ready-mixed concrete of the present invention is olefins / Cyclic Olefins, Maleic Anhydride Copolymer 10 (Olefins / Cyclic Olefins-Maleic Anhydride Copolymer) alcohol amine-alcohol ether derivatives, or styrene-maleic acid gf copolymer (Styrene -Maleic Anhydride Copolymer) alcohol amine-alcohol ether derivatives, or Styrene-Olefins / Cyclic Olefins-Maleic Anhydride-terpolymer (Styrene- Olefins / Cyclic 15 Olefins-Maleic Anhydride Terpolymer) ο Use the above polymer and a certain proportion of Methoxy Polyethylene Glycol Amine, or a polyethylene glycol monomer Ethyl ether, or a mixture of the two, is reacted. After the reaction, it is acidified to produce a carboxylic acid polymer, which is then ionized with alkali metal cations, alkaline earth metal cations, or ammonium. Basic compounds convert carboxylic acid polymers into ionic polymers. The structure of these polymers can be represented by the following general formula:

7 1226318 wherein R may be the same or different and is selected from the group consisting of hydrogen or methyl;

X is selected from the group including p P

C 6_C10 aromatic group, C5_C6 cycloalkane group or M0 alkoxy group;

C2_c5 aliphatic group of the second-line selection and or residue,

Or ^^ in the group, wherein R5 and R6 10 15 are two: ,,, the same or different 'is selected from the group consisting of hydrogen, halo, Cl, alkyl. 6_1. : Aryl group, C6, fluoroaromatic group, Ci i0 alkoxy group, h. In the group consisting of dilute group, aralkyl group, C8-12 arylalkenyl group or C * 7 pinane aryl group; RR can be the same or different, and is selected from the group including NHR7, OR7, or OM, μ is a metal test cation, alkaline earth metal The cation or bond cation 'R is selected from the group consisting of 0xyalkylene or p〇ly〇xyalkylene, and its chemical formula is (ZQ) PR8, where z is selected from the group consisting of CrC5 aliphatic groups, p The value is a positive integer from $ to ι〇〇, R8 is selected from the group consisting of Ci_C5 aliphatic group or C6_C⑺ aromatic group; 1, m and n each represent the mole ratio in the polymer structure, where 1 has a value of 0 to 25, m has a value of 0 to 25, n has a value of 0 to 50, and at least two of 1, m and η ^ 丨; a preferred example is a value of 010 m The value is 0 to 10, the value of n is 0 to 25; the best example 1 is 0 to 5, the value of m is 0 to 5, and the value of n is 0 to 25. 20 1226318

The composition of the above-mentioned ready-mixed concrete chemical additives, among which R is preferably hydrogen. x is preferably γ is more than 隹 The composition of the above-mentioned pre-dropped concrete chemical additives, examples of which are Phenyl or Sulfonated phenyl. The composition of the aforementioned chemical admixture for ready-mixed concrete, an example of which is ch2—ch2-- 10 The composition of the chemical admixture of the aforementioned ready-mixed concrete, an example of which is --ch-ch2—or 0 CH. Ch9 • CH2—CH = CH—CH2-Y is better or the composition of the above-mentioned suspected soil chemical additives. The example of Y is ^^. The composition of the above-mentioned ready-mixed concrete chemical additives, of which Y is. Better than 15 20 About the method for preparing and synthesizing the composition of the above-mentioned ready-mixed concrete chemical additives, the following first to fourth reagents are sequentially added, and the temperature is 20 to 180 ° c. The reaction can be mixed to obtain the target product. The compounds used in the reaction are: (1) The first reagent is a high molecular polymer containing 1 to 75 weight percent, and its structure is as follows: R11 I R I 1 C—I-CH- X ·

CH-CH-

9 1226318 R and R may be the same or different and are selected from the group consisting of hydrogen or methyl; x 'is selected from the group consisting of C6_Cl () aromatic group, c5_c6 cycloalkane group or Cl-ίο alkoxy group In the ethnic group; y is remote from C2-C5 aliphatic groups including saturated or unsaturated,

In the group formed, R and R may be the same or different, and are selected from the group consisting of hydrogen, halogen, Cmo alkyl, c6_1 () aromatic group, c61 () fluoroaromatic group, Ci_i, alkoxy group, and 10 alkenyl group. , C7_u aralkyl, Q-arene, or c7 n alkaryl groups; r, s, and t each represent a mole ratio in the polymer structure, where r has a value of 0 to 25, s It has a value of 0 to 25, t has a value of 0 to 50, and at least two of ^ s and t-!. The best example is that the value of γ is 0, the value of s 15 is 0 to 10, and the value is 0 to 0; the best example 1 • is the value of 0 to 5, the value of s is 0 to 5, and the value of t is 〇 ~ 25. (2) The second reagent is 1 to 75 weight percent of 0xyalkylene or Polyoxyalkylene, and its representative chemical formula is h2N (z, 〇) 氺 u or H〇 (Z′〇) qR18, where P is selected from the group consisting of C2_C5 aliphatic In the group consisting of 20 groups, the value of q is a positive integer from 5 to 100, and r18 is selected from the group consisting of Ci C5 month aliphatic groups or C6-C1G aromatic groups. (3) The third reagent is inorganic acid H2S04, HC1, HNO3, BFs, SnCi2 or sulfonic acid organic acid containing weight percent

MeS03H, C2H5S03H, C4H9S03H, CF3S03H, CC13S03H 10 I2263l8, benzoic acid, p-benzenesulfonic acid, o-toluenesulfonic acid, etc. (4) The fourth reagent is a test reagent containing 1 to 10 weight percent, and its representative chemical formula is MOR19, where M is an alkali metal cation such as Na or K, an alkaline earth metal cation such as Mg or Ca, or an ammonium cation such as NH4 R19 is selected from the group consisting of chlorine, Cio alkyl, C6]] aromatic group, C110 alkoxy 'aryl group, c ^ 2 arylalkenyl group or Cm alkaryl group. The composition of the aforementioned chemical admixture for ready-mixed concrete, among which R11 is preferably hydrogen. Among the above-mentioned ready-mixed concrete chemical additives, two preferred examples are hydrogen. For the composition of the above-mentioned ready-mixed concrete chemical additives, a preferred example of X is Phenyl. The composition of the above-mentioned ready-mixed concrete chemical admixture, among which x is a preferable example, Sulfonated Phenyl. The composition of the aforementioned chemical admixtures for ready-mixed concrete, among which the preferred example of γ is -ch2- ch2-an example of -0 is -crCH2-the composition of the chemical admixture for the above-mentioned 2 mixed concrete, of which Y is preferred or a CH2 —CH: CH_CH2—or a mixture of the two

The composition of the above-mentioned ready-mixed concrete chemical additives, among which Y is preferred The composition of the above-mentioned ready-mixed concrete chemical additives, among which Y is preferably 11 1226318

The example is the preferred embodiment 1. 5 Put 5 units of norbornene, 25 units of maleic anhydride, and 0.5 units of AIBN into the reaction bottle, add 200 ml of benzene as a solvent, stir for 10 minutes, and then slowly After heating, and then reacting at 80 ° C for 2 hours, a white solid was obtained after filtration. The product was a norbornene-marine anhydride copolymer with an average molecular weight of 4,500. 10 Preferred Embodiment 2: Put 2.5 units of norbornene, 2.5 units of styrene, 25 units of maleic anhydride, and 0-5 units of AIBN into a reaction bottle, add 300 ml of benzene as a solvent, and stir for 10 minutes. It was then slowly heated, and then reacted at 80 15 ° C for 3 hours. After filtration, a white solid was obtained. This solid was a copolymer of norbornene-styrene-maleic anhydride with an average molecular weight of 5600. Preferred Embodiment III ······································································································································································································································································································. Add 21.2 units of EO: PO = 32: 10 and an average molecular weight of 2000 (Methoxy Polyalkoxy Amine, Huntsman Jeffamine® M-2070), heat the solution to 90 ° C, stir the reaction for 5 hours, and then add 1 M sulfuric acid The solution was allowed to react for 4 hours. After a maximum of 1226318, the solution was neutralized with a 1 N NaOH aqueous solution. The obtained product was a brown viscous liquid (Polymer E1). Using the steps of the preferred embodiment, a series of styrene with different molar ratios can be obtained. Derivatives obtained by reacting a maleic anhydride copolymer with poly 5 ethanolamine having an average molecular weight of 2000. These derivatives are viscous liquids. Preferred embodiment 4: 26.5 units of styrene-marine anhydride copolymer (3:10 mole ratio, average molecular weight 3800; Sartomer SMA® EF-30) are dissolved in 100 single 10-position isopropanol, and EO is added. : PO = 3: 2 and 21.2 units of polyethylene glycol monomethyl ether with an average molecular weight of 750. The solution was heated to 110 ° C, then stirred for 5 hours, and then added with 1 M sulfuric acid solution for 4 hours. N Ca (OH) 2 solution was neutralized, and the obtained product was a brown viscous liquid (Polymer E2). 015 By using the steps of the preferred embodiment, a series of styrene-marine anhydride copolymers with different molar ratios can be obtained. Derivatives obtained by reacting with polyethanolamine having an average molecular weight of 2000. These derivatives are all viscous liquids. Preferred Embodiment 5: 20 Dissolve 26 · 5 units of styrene · marine anhydride copolymer (3:10 mole ratio, average molecular weight 3800; Sartomer SMA® EF-30) in 100 units of isopropanol and add EO: PO = 32: 10 and Methoxy Polyalkoxy Amine (Huntsman Jeffamine® M-2070) with an average molecular weight of 10.5 units, and then add EO: PO = 3: 2 and an average of 13 1226318 with a molecular weight of 750 Alcohol monomethyl ether 10.7 units, first the solution is heated to 90 ° C, stirred for 5 hours, then heated to 110 ° C, reacted for 2 hours, and then added 1 M sulfuric acid solution for 4 hours, and finally in 1 N NaOH aqueous solution And, the obtained product is a brown viscous liquid 5 (Polymer E3). Using the steps of the preferred embodiment, a series of styrene-marine anhydride copolymers with different molar ratios and polyethanolamine with an average molecular weight of 2000 can be obtained. And derivatives of ethylene glycol monomethyl ether with an average molecular weight of 750. These derivatives are all viscous liquids. 10 Preferred Embodiment 6: 26.5 units of norbornene-marin anhydride copolymer (1: 5 mole ratio, average molecular weight 4500, prepared in Example 1) are dissolved in 100 units of isopropanol, and EO is added. : PO = 32: 10 and an average molecular weight of 2000 Methoxy Polyalkoxy Amine (Huntsman Jeffamine® M-2070) 21.2 units, the solution was heated to 90 ° C, then stirred for 5 hours, and then added 1 Μ The sulfuric acid solution was reacted for 4 hours, and finally neutralized with a 1 N Ca (OH) 2 aqueous solution. The obtained product was a brown viscous liquid (Polymer E4). 20 Using the steps of the preferred embodiment, a series of different mole ratios can be obtained. Derivatives obtained by reacting the norbornene-marin anhydride copolymer with polyethanolamine having an average molecular weight of 2000. These derivatives are viscous liquids. Preferred embodiment seven: 14 1226318 Dissolve 26.5 units of norbornene-marin anhydride copolymer (1: 5 mole ratio, average molecular weight 4500, * made in Example 1) in 100 units of isopropyl, and add EOiPOO and polyethylene glycol monomethyl ether 21.2 units with an average molecular weight of 75. The solution was heated to U (rc, then allowed to react for 5 hours, and then added to the sulfuric acid solution for 4 hours, and finally with! N

The product was neutralized with NaOH, and the obtained product was a brown viscous liquid (p kiss followed by £ 5). Using the steps of the preferred embodiment, a series of norbornene-maleic anhydride copolymers with different molar ratios and average Derivatives obtained by reacting poly 10 ethanolamine with a molecular weight of 75. These derivatives are all viscous liquids. Preferred embodiment eight: 26 · 5 units of norbornene-malein anhydride copolymer (1: 5 mole ratio, average molecular weight 4500, prepared in Example 1) are dissolved in 100 units of iso15 propanol In the process, polyethanolamine (Methoxy Polyalkoxy Amine 'Huntsman) with EO: PO = 32: 1 and an average molecular weight of 2000 was added.

Jeffamine® M-2070) 10.5 units, then add polyethylene glycol monomethyl ether 10.7 units with E〇: p〇 = 3: 2 and an average molecular weight of 50, and first heat the solution to 90 ° C. Stir the reaction for 5 hours, then raise the temperature to u00c, react for 2 hours, then add 1 M sulfuric acid solution to react for 4 hours, and finally neutralize with i N Ca (〇H) 2. The obtained product is a brown viscous liquid ( polymer E6). By using the steps of this example, we can obtain a series of different molecular ratios of norbornene-malein anhydride copolymers with polyethanolamine with average molecular weight and ethylene glycol monomethyl scale with average molecular weight of 75. The obtained 15 1226318 derivatives are all viscous liquids. Preferred Embodiment Nine: 26.5 units of a norbornene-styrene-marine anhydride terpolymer (1: 1: 10 5 mole ratio, average molecular weight 5600, prepared in Example 2) are dissolved in 100 units of isopropyl alcohol. To propanol, add EO: PO = 32: 10 and an average molecular weight of 2000 units of Methoxy Polyalkoxy Amine (Huntsman Jeffamine® M-2070) 21.2 units, heat the solution to 90 ° C, and then stir the reaction for 5 hours Then, add 1 M sulfuric acid solution to react for 4 hours, and then neutralize with 1 N NaOH after 10 hours. The obtained product is a brown viscous liquid (Polymer E7). Using the steps of the preferred embodiment, a series of different moles can be obtained. Derivatives obtained by reacting a ratio of a norbornene-styrene-marine anhydride copolymer with a polyethanolamine having an average molecular weight of 2000. These derivatives are all viscous 15 thick liquids. Preferred embodiment ten: Dissolve 26.5 units of norbornene-styrene-marine anhydride terpolymer (1: 1: 10 mole ratio, average molecular weight 5600, prepared by the preferred embodiment two) to 20 to 100 In the unit of isopropanol, add 21.2 units of polyethylene glycol monomethyl ether with EO: PO = 3: 2 and an average molecular weight of 750, heat the solution to 110 ° C, then stir the reaction for 5 hours, and then add 1 M sulfuric acid The solution was reacted for 4 hours, and finally neutralized with 1 N Ca (OH) 2. The obtained product was a brown viscous liquid (Polymer E8). 〇16 1226318 Using the steps of the preferred embodiment, a series of different molar ratios can be obtained. Derivatives obtained by reacting a norbornene-styrene-marine anhydride copolymer with polyethanolamine having an average molecular weight of 750. These derivatives are viscous liquids. 5 Preferred embodiment Η—: Dissolve 26.5 units of norbornene-styrene-marine anhydride terpolymer (1: 1: 10 mole ratio, average molecular weight 5600, prepared by the preferred embodiment 2) in In 100 units of isopropanol, add 10.5 units of Polyethanolamine (Methoxy Polyalkoxy Amine, Huntsman Jeffamine® M-2070) with an average molecular weight of 10 and EO: PO = 32:10, and then add E0: P0 = 3: 2 and average Polyethylene glycol monomethyl ether with a molecular weight of 750 is 10.7 units. The solution is first heated to 90 ° C, stirred for 5 hours, then heated to 110 ° C, reacted for 2 hours, and then added 1 M sulfuric acid solution for 4 hours. At 15 o'clock, it was finally neutralized with 1 N NaOH, and the obtained product was a brown sticky tung liquid (Polymer E9). Using the steps of this preferred embodiment, a series of different mole ratios of norbornene-styrene-marine anhydride copolymers and polyethanolamine with an average molecular weight of 2000 and ethylene glycol monofluorenyl ether with an average molecular weight of 750 can be obtained. 20 Derivatives obtained from the reaction. These derivatives are viscous liquids. Preferred embodiment twelve: 26.5 units of butadiene-maleic anhydride copolymer (Butadiene-Maleic Anhydride Copolymer, Total Acid = 12 to 14 wt%, 17 1226318 average molecular weight 3100; Sartomer Ricon® 130MA-13) are dissolved In 100 units of isopropanol, add 21.2 units of Methoxy Polyalkoxy Amine (Huntsman Jeffamine® M-2070) with EO: PO = 32: 10 and an average molecular weight of 2000. Heat the solution to 90 ° C, then 5 Stir the reaction for 5 hours, add 1 M sulfuric acid solution for 4 hours, and finally neutralize with 1 N Ca (OH) 2 aqueous solution. The resulting product is a brown viscous liquid (Polymer E10). By using the steps of the preferred embodiment, a series of derivatives obtained by reacting a series of butadiene-malein anhydride copolymers with an average molecular weight of 2,000 ethanolamine with different molar ratios can be obtained. These derivatives are all viscous liquids. Preferred Embodiment Thirteen: 26.5 units of Butadiene-Maleic Anhydride Copolymer (Total Acid = 12 ~ 14 wt%, 15 average molecular weight 3100; Sartomer Ricon® 130MA-13) are dissolved in To 100 units of isopropanol, add 21.2 units of polyethylene glycol monomethyl ether with EO: PO = 3: 2 and an average molecular weight of 750. Heat the solution to 110 ° C, then stir for 5 hours, then add 1 The sulphuric acid solution was reacted for 4 hours, and finally neutralized with a 1 N NaOH aqueous solution. The obtained product was a brown viscous liquid 20 (Polymer El 1). Using the steps of the preferred embodiment, a series of tins with different mole ratios can be obtained. Derivatives obtained by reacting a diene-marine anhydride copolymer with a polyethanolamine having an average molecular weight of 2000. These derivatives are all viscous liquids. 18 1226318 Preferred Embodiment Fourteen: 26.5 units of Butadiene-Maleic Anhydride Copolymer (Total Acid = 19 ~ 21 wt%, average molecular weight 7500; Sartomer Ricon® 131MA-20) In 100 5 units of isopropanol, add 10.5 units of Polyethanolamine (Methoxy Polyalkoxy Amine, Huntsman Jeffamine® M-2070) with an average molecular weight of 2000 and EO: · PO = 32:10, and then add EO: PO = 3: 2 And the average molecular weight is 750 units of polyethylene glycol monomethyl ether 10.7 units, the solution is first heated to 90 ° C, stirred for 5 hours, then heated to 110 ° C, reacted for 2 10 hours, and then added 1 M sulfuric acid solution to react After 4 hours, the product was neutralized with 1 N Ca (OH) 2 aqueous solution. The obtained product was a brown viscous liquid (Polymer E12). Using the steps of the preferred embodiment, a series of styrene with different mole ratios could be obtained. Derivatives obtained by reacting a maleic anhydride copolymer with poly 15 ethanolamine with an average molecular weight of 2000 and ethylene glycol monomethyl ether with an average molecular weight of 750. These derivatives are viscous liquids. Preferred embodiment fifteen: 26.5 units of butadiene-malein anhydride copolymer (Butadiene-20 Maleic Anhydride Copolymer, Total Acid = 19 ~ 21 wt%, average molecular weight 7500; Sartomer Ricon® 131MA-20) are dissolved in In 100 units of isopropanol, add EO: PO = 32: 10 and an average molecular weight of 2000 (Methoxy Polyalkoxy Amine, Huntsman Jeffamine⑧M-2070) 21.2 units, and heat the solution to 90 ° C, then 19 1226318. The reaction was stirred for 5 hours, then added 1 M sulfuric acid solution for 4 hours, and finally neutralized with 1 N NaOH aqueous solution. The obtained product was a brown viscous liquid (Polymer E13). Using the steps of this preferred embodiment, a Derivatives obtained by reacting a series of different mole 5 ratios of norbornene-marin anhydride copolymers with polyethanolamine with an average molecular weight of 2000. These derivatives are viscous liquids. Preferred embodiment sixteen: 26.5 units of styrene-marine anhydride copolymer (3:10 mole ratio 10, average molecular weight 3800; Sartomer SMA® EF-30) are dissolved in 100 units of isopropanol, and EO is added : PO = 32: 10 and an average molecular weight of 2000 Methoxy Polyalkoxy Amine (Huntsman Jeffamine® M-2070) 21 · 2 units, stir at room temperature for 5 hours, and then add 1 M sulfuric acid solution for 4 hours , And finally neutralized with 1 N NaOH water 15 solution, the obtained product is a yellow-brown viscous liquid (Polymer E14). 〇Using the steps of the preferred embodiment, a series of styrene-maleic anhydride with different molar ratios can be obtained. Derivatives obtained by reacting the copolymer with a polyethanolamine having an average molecular weight of 2000. These derivatives are all viscous liquids. 20 Preferred embodiment 17: 26.5 units of styrene-marine anhydride copolymer (3:10 mole ratio, average molecular weight 3800; Sartomer SMA® EF-30) are dissolved in 100 units of isopropanol, and EO is added : PO = 3: 2 and poly 20 1226318 ethylene glycol monofluorenyl ether with an average molecular weight of 750 21.2 units, the solution was heated to 50 ° C, then stirred for 5 hours, and then added 1 M sulfuric acid solution for 4 hours, and finally Neutralize with 1 N Ca (OH) 2 aqueous solution. The product obtained is a yellow-brown viscous liquid (Polymer E15). 〇 Using the steps of this preferred embodiment, a series of styrene · Marin with different molar ratios can be obtained. Derivatives obtained by reacting anhydride copolymers with polyethanolamine having an average molecular weight of 2000. These derivatives are viscous liquids. Preferred Embodiment 18: 10 Dissolve 26 · 5 units of styrene-marine anhydride copolymer (3:10 mole ratio, average molecular weight 3800; Sartomer SMA® EF-30) in 100 units of isopropanol. Add 10: 5 units of EO: PO = 32: 10 and an average molecular weight of 2000 (Methoxy Polyalkoxy Amine, Huntsman Jeffamine® M-2070), and then add EO: PO = 3: 2 and an average molecular weight of 750 to 750 Ethylene glycol monomethyl ether 10.7 units, stirred at room temperature for 5 hours, then added 1 M sulfuric acid solution for 4 hours, and finally neutralized with 1 N NaOH aqueous solution. The obtained product was a yellow viscous liquid (Polymer E16). By using the steps of this preferred embodiment, a series of Mohr 20 ratios of styrene-marine anhydride copolymers can be obtained by reacting polyethanolamine with an average molecular weight of 2000 and ethylene glycol monomethyl ether with an average molecular weight of 750. Derivatives, these derivatives are viscous liquids. Nineteenth preferred embodiment: 21 1226318 Dissolve 26 · 5 units of norbornene-styrene-marine anhydride terpolymer (1: 1: 10 mole ratio, average molecular weight 5600, prepared in Example 2) In 100 units of isopropanol, 21: 2 units of Methoxy Polyalkoxy Amine (Huntsman 5 Jeffamine® M-2070) were added with EO: PO = 32: 10 and an average molecular weight of 2000, and the solution was heated to 18 〇 ° C, and then react for 2 hours, then add 1 μ sulfuric acid solution for 2 hours, and finally neutralize with 1 N NaOH. The obtained product is a brown viscous liquid (Polymer E17). 〇Use the steps of the preferred embodiment A series of derivatives derived from the reaction of borneol-phenylene-maleic acid if copolymers with an average molecular weight of 2000 in different mole ratios of 10 are obtained. These derivatives are viscous liquids. Preferred embodiment twenty: 26.5 units of a norbornene-styrene-marine anhydride terpolymer (1: 1: 10 mole ratio, average molecular weight 5600, prepared by the preferred embodiment two) are dissolved in 1 To 〇OO units of isopropanol, EO: PO == 3: 2 and 212 units of polyethylene glycol monomethyl ether with an average molecular weight of 750 were added, and the solution was heated to i80c > c, followed by stirring for 2 hours. After adding M sulfuric acid solution for 2 hours, it was finally neutralized with 1 N Ca (OH) 2. The obtained product was a brown viscous liquid (Polymer E18). By using the steps of this preferred embodiment, a series of derivatives obtained by reacting a series of norbornene-styrene-maleic acid needle copolymers with an average molecular weight of 750 can be obtained. These derivatives are viscous 22 1226318 Liquid. Preferred embodiment twenty-one: 26.5 units of a norbornene-styrene-marine anhydride terpolymer (1: 1: 10 5 mole ratio, average molecular weight 5600, prepared by the second preferred embodiment) are dissolved. In 100 units of isopropanol, add EO: PO = 32 ·· 10 and an average molecular weight of 2000 (Methoxy Polyalkoxy Amine, Huntsman Jeffamine® M-2070) 10.5 units, and then add EO: PO = 3: 2 and Polyethylene glycol monomethyl ether with an average molecular weight of 750 is 10.7 10 units. The solution is first heated to 90 ° C, stirred for 2 hours, then heated to 180 ° C, reacted for 1 hour, and then added 1 M sulfuric acid solution to react 4 Hours, and finally neutralized with 1 N NaOH. The obtained product was a brown viscous liquid (Polymer E19). 〇 Using the steps of the preferred embodiment, a series of norbornene-styrene-marin with different ratios of 15 ears can be obtained Derivatives obtained by reacting an acid anhydride copolymer with polyethanolamine having an average molecular weight of 2000 and ethylene glycol monomethyl ether having an average molecular weight of 750. These derivatives are viscous liquids. List of water reduction comparison results: 20 The polymer E3 of the preferred embodiment 5 is formulated into a water reducing agent with a solid content of 15%. These solutions can be used to make cement with water and cement. In addition, a naphthalenesulfonic acid powder water reducer with a solid content of 92% was formulated into concrete with cement and water. Under the same mix design, the difference between the water reduction rate and slump loss of the agent was compared. 1226318 The water reduction rate test of the pharmaceutical is designed according to ASTM C494 with a dosage of 307 kg / m3 of cement and 210 kg / m3 of water as the control group. The mixer is rotated for 3 minutes and stopped for 3 minutes in the standard way specified in ASTM C192. , And then rotate and mix for 2 minutes. Comparison of the water reduction rate of tacit acid admixture and naphthalene transverse acid admixture Water reduction rate (%) 25% 20% 15% 10% 5% 0%

1.0% 0.3% 0.4% 0.5% 0.6% 0.7% Additive dosage (%) Cement (kg / m3) Water (kg / m3) Fine aggregate (kg / m3) Coarse aggregate (kg / m3) Water reducer (kg / m3) Carboxylic acid-based water reduction rate Plain 307 210 837 930 0 0 No.l 307 191 906 985 0.92 (0.3%) 10% No. 2 307 187 919 996 1.23 (0.4%) 12% No. 3 307 183 921 1000 1.56 (0.5%) 14% No. 4 307 179 924 1005 1.84 (0.6%) 16% No. 5 307 174 932 1014 2.14 (0.7%) 17% No. 6 307 168 935 1017 3.07 (1.0%) 20% low The solid component of the carboxylic acid water reducing agent has a higher water reduction rate than the traditional sulfonic acid water reducing agent 24 1226318, and if the dosage of the medicine exceeds 1%, the water reducing effect of the sulfonic acid admixture is not good, and it is easy to cause water bleeding and serious Retarded, and the sulfonic acid is 0 8 6 4 2 0 8 1X 1X 1X 1X (mo) dmnfs

Relation between Slump & Time

PolycarboxyKc naphthalene 0 min 30 min 60 min Time The field loss of water reducing agent is also more serious than that of Wei acid type water reducing agent. Type of slump (cm) Compression strength (psi) Omi η 30mi m 60mi n Ida y 7da y 14da y 28da y Polycarboxylic Acid 19 17 15 492 279 l 3997 5432 naphthalene 17 14 10 521 273 l 3966 5374 It can be known from the above results The chemical admixture of the ready-mixed concrete of the present invention is mixed in the concrete and has a good water reduction rate and can improve the fluidity of the concrete. Its slump performance, compressive strength and early hardening strength, etc. 25 1226318 Various performances are greatly improved β. In summary, Wei of the present invention achieves the expected effect, and Shen Wangyu has not been seen in publications or used publicly. It meets the requirements of new invention patents, innovations, and industrial applicability. , Apply for a patent according to law. The above description is only an embodiment of the present invention. Any easy modifications and equivalent changes made in accordance with the spirit of the present invention should be covered by the scope of patent application below.

26

Claims (1)

1226318 Scope of patent application: 1 · A pre-mixed soil-reducing chemical chemical additive, which is mixed with cement and hearth at a dosage of 0.05 to 0.5 weight percent. The structure of the chemical additive is: R1 R2 C ¥ t \-(y) where R1 and R2 may be the same or different and are selected from the group consisting of hydrogen or methyl; X is selected from the group consisting of cvCk aromatic group, q-C6 cycloalkane group or Ci 10 oxygen Y is selected from the group consisting of C2-C5 aliphatic groups including saturated or unsaturated, or In the group formed, "and R6 may be the same or different, and are selected from the group consisting of hydrogen, halogen, q alkyl, Cho aryl, Cq, fluoro aryl, cMG alkoxy, C21 () alkenyl, C7 -U aralkyl, C: 8 · 2 arene or CVn alkaryl; R3, R4 may be the same or different, and are selected from the group consisting of Nhr7, OR7 ′ OH or OM + M is an alkali metal cation, alkaline earth metal cation, or ammonium cation; R7 is selected from the group consisting of Oxyalkylene or Polyoxyalkylenem, and its chemical formula is (Z0) pR8, where z is selected from the group consisting of aliphatic groups In the formula, the value of p is a positive integer of 5 to 100, and R8 is selected from the group consisting of a CrC5 aliphatic group or a C6_Cio aromatic group; m and η each represent a mole in the polymer structure. Proportions, where ι 27 1226318 has a value of 0 to 25, m has a value of 0 to 25, n has a value of 0 to 50, and at least two of η are -1. 2. According to the first patent application scope For the ready-mixed concrete chemical additives, the value of 1 is 0 to 10, the value of m is 0 to 10, and the value of η is 0 to 25. There are at least two of pentium and η-1. 3. According to the chemical addition of ready-mixed concrete as described in item 1 of the scope of patent application, where: the value of 1 is 0 ~ 5 'and the value of m is 0 ~ 5, the value of η is 0 ~ 25,], at least two of im and η are -1. 4. The chemical filling and filling of the ready-mixed concrete according to item 1 of the scope of the patent application where:, d, where R1 is Hydrogen. 5. According to the chemical admixture of ready-mixed concrete described in item 1 of the scope of the patent application where:, 'The R2 is hydrogen. 6. According to the chemical admixture of ready-mixed concrete described in the scope of the patent application, item 1, Among them,, the X is Phenyl. 7. The chemical filling and filling of the ready-mixed concrete according to item 1 in the scope of the patent application where: θ The X is Sulfonated Phenyl. 8. According to the first item in the scope of Shen Qing patent The chemical admixtures for ready-mixed concrete include: 28 1226318 The Y is -CH2_CH2-. 9. According to the chemical admixtures for ready-mixed concrete described in item 1 of the patent application scope, wherein: Mix. The Y is ch ~ ch2 a or One ch2—ch = ch-ch2—one who H-one of ^ h2 10. According to the patent application Chemical additives of the ready-mixed filling of the concrete item Shu, wherein: the square 11. The ready-mix and Y is a chemical fill additives in item i of the scope of patent applications based on concrete, wherein: The Y is a 12 · —method for manufacturing chemical additives for ready-mixed concrete, which sequentially makes a first reagent, a second reagent, a third reagent, and a fourth reagent at a temperature of 50 to 18 (TC The chemical additive is obtained by mixing and reacting under the conditions, wherein: the-reagent is a high molecular polymer containing 1 to 75 weight percent, and its structure is · R11 R12 c-CH-X, ~ (Yk ~ ^ ch -ch- R and R2 may be the same or different; 'is selected from the group consisting of hydrogen or fluorenyl group; ^ is selected from the group consisting of cvc10 aromatic group, C5_C6 ring group group or Cl- group. Y system k includes C2_C5 aliphatic group which is saturated or unsaturated, 29 1226318 Or in the group consisting of, wherein R15 and R16 may be the same or different, and are selected from the group consisting of hydrogen, halogen, C In the group consisting of alkenyl, Qu aralkyl, Cs. 2 arene or C7U alkaryl; I *, s, and t each represent a mole ratio in the polymer structure, where r has 0 to 25 Value, s has a value of 0 to 25, t has a value of 0 to 50, at least two of r, 3, and -1; the second reagent is 75% by weight of Oxyalkylene or Poxylyalkylene, Its representative chemical formula is H2N (Z, 0) qR18 or H〇 (Z'0) qR18, where Z 'is selected from the group consisting of C2_c5 aliphatic groups, and the value of q is 5 to 100. Integer, rM is selected from the group consisting of Ci_C5 aliphatic group or C6-Cio aromatic group; the second reagent is a mineral acid containing 2 to 4 weight percent of inorganic acids h2so4, HC1, HN03, BF3, SnC12 Or sulfonic organic acids MeS0H, c2h5so3h, c4h9so3h, cf3so3h, CC13S03H, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, etc .; the fourth reagent is a cation, an alkaline earth metal cation such as Mg or Ca, or NH4, etc. Ammonium cations, Ri9 selects free hydrogen, Ci iQ alkyl, c6 · fluorene aromatic group, alkoxy group, C7_u aralkyl group, C8 i2 aromatic The group consisting of an aryl group or an alkyl group ^ ⑴. 13. The method for manufacturing ready-mixed concrete chemical filling 30 1226318 as described in item 12 of the scope of the patent application, wherein: the value of 1 is 0 to 10, the value of m is 0 to 10, and the value of η is 0. At least two of ~ 25,1, m and η are -1. 14. The method for manufacturing ready-mixed concrete chemical additives according to item 2 of the scope of the patent application, wherein: the value of 1 is 0 to 5, the value of m is 0 to 5, and the value of η is 0 to 25. There are at least two of i, m and η. 15. The method for manufacturing a ready-mixed concrete chemical filler according to item 12 of the scope of the patent application, wherein: R11 is hydrogen. 16. The method for manufacturing a ready-mixed concrete chemical filler according to item 12 of the scope of the patent application, wherein: R12 is hydrogen. Dosing method, where: X is Phenyl. Π. According to the method of manufacturing chemical additives for ready-mixed concrete described in Section 12 of the application, in which ... is. According to the n-item of the scope of the paper, the preparation of chemical compounds for ready-mixed money soil X is Sulfonated Phenyl. Chemical filling of pre-cast concrete as described in item 12. 19. Adding method according to the 12th scope of the patent application, where: Y is -ch2-ch2 Chemical filling of concrete as described in item 12 of 20. According to the scope of patent application The twelfth method of dosing, where: 31 1226318 The Y is ch-ch2 or CH2—ch: ch-ch2—or a ch2 mixture of the two. \ 21. The method for manufacturing a ready-mixed concrete chemical filler according to item 12 of the scope of the patent application, wherein: Y is ^ 〇22 · According to the method for manufacturing a pre-mixed concrete chemical filler described in the scope of the patent application for item 12 Agent method, where: The Y is 32