WO2022013600A1

WO2022013600A1 - Modified carboxilate/vinyl ester copolymers for concrete admixtures

Info

Publication number: WO2022013600A1
Application number: PCT/IB2020/056651
Authority: WO
Inventors: Taghi SALEMNOUSH; Sahar Bayat; Alborz MAJZOOB HOSSEINI
Original assignee: Abadgaran Construction Chemicals
Priority date: 2020-07-15
Filing date: 2020-07-15
Publication date: 2022-01-20

Abstract

An exemplary copolymer may include a first constitutional unit that may include a transesterified vinyl acetate ester monomer. An exemplary transesterified vinyl acetate monomer may be transesterified with glycol units of 25 to 50 carbon atoms. An exemplary copolymer may further include a second constitutional unit that may include an esterified acid- containing monomer. An exemplary esterified acid-containing monomer may be esterified with glycol units of 25 to 50 carbon atoms and amine groups of 18 to 25 carbon atoms. An exemplary second constitutional unit may be copolymerized with an exemplary first constitutional unit to form the exemplary copolymer.

Description

MODIFIED CARBOXILATE/VINYL ESTER COPOLYMERS FOR CONCRETE

ADMIXTURES

TECHNICAL FIELD

[0001] The present disclosure relates to copolymers for cement or concrete admixtures and particularly to copolymers utilized as cement plasticizers and water reducing agents. More particularly, the present disclosure relates to a modified carboxylate/vinyl ester copolymer and methods for synthesizing the same.

BACKGROUND

[0002] Extensive research on new polycarboxylate-based polymeric products has led to development of a new category of additives for increasing the capabilities of cement compositions in terms of workability and compressive strength. Each of these newly developed additives and admixtures has been able to address various needs of the market.

[0003] Cement admixtures are generally added to cement composition in order to improve the durability and strength of concrete structures. Polycarboxylic acid cement dispersant among other types of dispersants have exhibited a higher water reducibility. Reduction of the unit water content in a cement composition may lead to an improvement of strength and durability of that cement composition. It should be understood that the water content of a cement composition may be limited due to the fact that although an increase in the amount of water used may improve the on-site workability, it may decrease compressive strength and may even lead to crack formation after hardening.

[0004] US 6,919,388 discloses carboxylate polymers exhibiting relatively higher water reducibility that are capable of improving the durability and strength of concrete by improving the air entraining properties of concrete. In their disclosure, the strength, durability, and behavior of concrete is controlled by controlling air entraining properties of concrete.

[0005] US 7,125,944 discloses a cement admixture that may include a combination of a specific (poly) alky lene glycol alkenyl ether compound obtained by using an unsaturated monocarboxylic acid monomer as an essential comonomer constituent in lieu of maleic acid that has so far been used, and a (poly)oxyalkylene group- and carboxyl group-containing compound. Such cement admixture shows excellent initial dispersing ability and dispersion retaining ability even in a high water reducing ratio range.

[0006] US 6,727,315 discloses a copolymer and a method for synthesizing and using the same, where the synthesized copolymer exhibits a higher water reduction ratio in cement compositions. In their disclosure, polyether glycol compositions along with an acidic comonomer are utilized for enhancing water reduction properties and on-site workability of the cement compositions. Here, controlling the fluidity of the cement composition may be possible by controlling air entraining properties of the cement composition.

[0007] Plank et al. in their patent application numbers US 2015/0065615 and US 2016/0083493 have disclosed cement admixtures, in which copolymers are utilized for reducing the unit water content of cement compositions and improving the on-site workability of such cement compositions.

[0008] EP 2336094 discloses a superplasticizer for concrete and other cement mixtures that is a low-foaming plasticizer that may promote the early mechanical strength development and retains the workability of fresh concrete for longer periods of time. In their disclosure, the superplasticizer may be obtained by reacting Polycarboxylic polymers with monofunctional polyethers and difunctional polyethers in the absence of strong acidic catalysts. Such superplasticizers may enhance the fluidity of a cement mixture; however, they may be associated with issues such as poor water reducibility and poor mechanical strength.

[0009] Polyether-based polycarboxylate compositions and polyester-based polycarboxylate compositions are among the leading cement dispersant compositions. However, due to the limitations associated with chemical basis of the monomers utilized in synthesizing such cement dispersants, they exhibit lower polymerization yield. This, along with other issues associated with the design and development of polyether-based polycarboxylate compositions and polyester-based polycarboxylate compositions has led to relatively poor water reduction properties.

[0010] There is, therefore, a need in the art for the development of superplasticizers that are capable of attaining higher water reduction ratios and better air entraining properties. There is, further a need for development of a dispersing agent that may allow for achieving higher water reduction ratios while preserving the workability and stability of cement compositions. SUMMARY

[0011] This summary is intended to provide an overview of the subject matter of the present disclosure and is not intended to identify essential elements or key elements of the subject matter, nor is it intended to be used to determine the scope of the claimed implementations. The proper scope of the present disclosure may be ascertained from the claims set forth below in view of the detailed description and the drawings.

[0012] According to one or more exemplary embodiments, the present disclosure is directed to a copolymer for cement admixtures. An exemplary copolymer may include a first constitutional unit that may include a transesterified vinyl acetate ester monomer. An exemplary transesterified vinyl acetate monomer may be transesterified with glycol units of 25 to 50 carbon atoms. An exemplary copolymer may further include a second constitutional unit that may include an esterified acid-containing monomer. An exemplary esterified acid-containing monomer may be esterified with glycol units of 25 to 50 carbon atoms and amine groups of 18 to 25 carbon atoms. An exemplary second constitutional unit may be copolymerized with an exemplary first constitutional unit to form the exemplary copolymer.

[0013] In an exemplary embodiment, an exemplary acid-containing monomer may include at least one of an unsaturated monocarboxylic acid monomer and an unsaturated dicarboxylic acid monomer. In an exemplary embodiment, an exemplary unsaturated monocarboxylic acid monomer may include at least one of acrylic acid, acrylic substituted alcohols, methacrylic acid, methyl methacrylic acid, and esters thereof, and mixtures thereof. In an exemplary embodiment, an exemplary unsaturated monocarboxylic acid monomer may include at least one of 2-hydoxyethyl methacrylate and 2-hydroxyethyl acrylate. In an exemplary embodiment, an exemplary unsaturated dicarboxylic acid monomer may include at least one of maleic anhydride, maleic acid, fumaric acid, and mixtures thereof.

[0014] In an exemplary embodiment, an exemplary first constitutional unit may include 150 to 300 units of an exemplary transesterified vinyl acetate ester monomer. In an exemplary embodiment, an exemplary second constitutional unit may include 300 to 500 units of the esterified acid-containing monomer.

[0015] In an exemplary embodiment, an exemplary copolymer for cement admixtures may further include a third constitutional unit. An exemplary third constitutional unit may include a monoethylenically unsaturated monomer containing sulfuric acid groups. In an exemplary embodiment, an exemplary monoethylenically unsaturated monomer containing sulfuric acid groups may include one of sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acids, vinyl sulfonic acid, and 2-(meth)acrylamido-2- methyl propane sulfonic acid, and salts thereof.

[0016] In an exemplary embodiment, an exemplary copolymer for cement admixtures may include 1 to 90 wt. % of the first constitutional unit, 1 to 90 wt. % of the second constitutional unit, and 1 to 60 wt. % of the third constitutional unit.

[0017] In an exemplary embodiment, an exemplary copolymer for cement admixtures may include50 to 90 wt. % of the first constitutional unit, 1 to 50 wt.% of the second constitutional unit, and 20 to 60 wt.% of the third constitutional unit.

[0018] In an exemplary embodiment, an exemplary transesterified vinyl acetate ester monomer may be selected from a transesterified styrene monomer and a transesterified homologs of styrene. [0019] According to one or more exemplary embodiments, the present disclosure is directed to a copolymer for cement admixtures, where the copolymer may include the following monomer unit:

[0020] In an exemplary embodiment, Ri and R2 may be one of hydrogen and Cl to C4 alkyl and R3 may include one of C3 to C18 alkyl group, a phenyl group, and a naphthyl group. In an exemplary embodiment, Ri and R2 may preferably include the same groups. In an exemplary embodiment, R3 may include at least one of linear C3 to C18 alkyl group, a linear phenyl group, and a linear naphthyl group. In an exemplary embodiment, R3 may further include at least one of branched C3 to C18 alkyl group, a branched phenyl group, and a branched naphthyl group. [0021] According to one or more exemplary embodiments, the present disclosure is directed to a method for synthesizing a copolymer. An exemplary method may include esterifying an acid-containing monomer and a vinyl acetate monomer, synthesizing a backbone of the copolymer by copolymerizing a mixture. An exemplary mixture may be prepared by dissolving the transesterified vinyl acetate monomer and the esterified acid-containing monomer comprising one of an esterified unsaturated monocarboxylic acid monomer and an esterified unsaturated dicarboxylic acid monomer in a protic or aprotic solvent. An exemplary method may further include adding thiol groups to the mixture as transfer agent, and adding peroxide groups to initiate polymerization. Esterifying the backbone of the copolymer include a further synthesis step prior to polymerization by adding glycol and glycol amine derived compounds from ethylene oxide to the mixture.

[0022] In an exemplary embodiment, adding thiol groups to the mixture may include adding thioglycolic acid, three mercaptanoic acid, mercaptoethanol and mixture of thereof to the mixture. In an exemplary embodiment, adding peroxide groups to initiate polymerization may include adding at least one of methyl ethyl ketone peroxide or tert- butyl hydroperoxide to the mixture.

[0023] In an exemplary embodiment, esterifying the backbone of the copolymer may include adding at least one diethylene glycol, diethylene glycol, polyethylene glycol derieved from ethylene oxide and their amine substituted to the mixture.

[0024] In an exemplary embodiment, copolymerizing the mixture may include copolymerizing the mixture at a temperature between 75 to 80 °C. In an exemplary embodiment, synthesizing the backbone of the copolymer may include dissolving 200 units of the vinyl acetate and 400 units of the acid-containing monomer in 400 units of protic or aprotic solvent.

[0025] In an exemplary embodiment, synthesizing the backbone of the copolymer may include copolymerizing the mixture, the mixture further comprising a monoethylenically unsaturated monomer containing sulfuric acid groups.

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The novel features which are believed to be characteristic of the present disclosure, as to its structure, organization, use and method of operation, together with further objectives and advantages thereof, will be better understood from the following drawings in which a presently preferred embodiment of the present disclosure will now be illustrated by way of example. It is expressly understood, however, that the drawings are for the purpose of illustration and description only and are not intended as a definition of the limits of the present disclosure. Embodiments of the present disclosure will now be described by way of example in association with the accompanying drawings in which:

[0027] FIG. 1 illustrates a monomer unit of a copolymer for cement admixtures, consistent with one or more exemplary embodiments of the present disclosure; and [0028] FIG. 2 illustrates a flow chart of a method for synthesizing a copolymer for cement admixtures, consistent with one or more exemplary embodiments of the present disclosure.

DETAILED DESCRIPTION

[0029] The novel features which are believed to be characteristic of the present disclosure, as to its structure, organization, use and method of operation, together with further objectives and advantages thereof, will be better understood from the following discussion.

[0030] The present disclosure relates to exemplary embodiments of a modified carboxylate/vinyl ester copolymer and a method for synthesizing a modified carboxylate/vinyl ester copolymer. An exemplary modified carboxylate/vinyl ester copolymer may be utilized as a cement admixture that may improve the durability and strength of concrete structures by reducing the amount of unit water used. An exemplary monomer for cement admixtures may include constitutional units made of transesterified vinyl acetate ester monomers and esterified acid-containing monomers. Such modified exemplary monomer may be utilized as a superplasticizer in cement mixtures and may reduce the water to cement ratio and may improve the overall characteristics of concrete or other cement mixtures. Exemplary characteristics that may be improved by an exemplary admixture may include shrinkage, durability and strength. [0031] An exemplary method for synthesizing the exemplary monomer for cement admixtures may include esterifying an acid-containing monomer and a vinyl acetate monomer, synthesizing a backbone of the copolymer by copolymerizing an exemplary monomer mixture. An exemplary monomer mixture may be prepared by dissolving the esterified vinyl acetate monomer and the esterified acid-containing monomer in a protic or aprotic solvent. An exemplary method for synthesizing the exemplary monomer for cement admixtures may further include adding thiol groups to the mixture as chain transfer agent, and adding peroxide groups to initiate polymerization.

[0032] FIG. 1 illustrates a monomer unit 100 of a copolymer for cement admixtures, consistent with one or more exemplary embodiments of the present disclosure. In an exemplary embodiment, Ri and R2 within monomer unit 100 may be one of hydrogen and C 1 to C4 alkyl groups. In an exemplary embodiment, Ri and R2 may be similar. For example, Ri and R2 may both include hydrogen groups or alternatively, Ri and R2 may both include one of Cl to C4 alkyl groups. In an exemplary embodiment, R3 within monomer unit 100 may be one of C3 to C18 alkyl group, a phenyl group, and a naphthyl group. In an exemplary embodiment, each of the aforementioned groups may either be linear or branched. For example, R3 may include at least one of linear C3 to C18 alkyl group, a linear phenyl group, and a linear naphthyl group. Alternatively, R3 may further include at least one of branched C3 to C18 alkyl group, a branched phenyl group, and a branched naphthyl group.

[0033] In an exemplary embodiment, a copolymer for cement admixtures may include a monomer unit, such as monomer unit 100 that may be formed by copolymerization of a plurality of constitutional units. In an exemplary embodiment, the plurality of constitutional units may include a first constitutional unit. An exemplary first constitutional unit may include a transesterified vinyl acetate ester monomer. An exemplary vinyl acetate monomer may be one of styrene and homologs of styrene such as vinyl toluene. In an exemplary embodiment, an exemplary transesterified vinyl acetate monomer may be transesterified with glycol units of 25 to 50 carbon atoms. This gives rise to transesterified vinyl alcohol products which may immediately undergo keto-enol tautomerization.

[0034] In an exemplary embodiment, the plurality of constitutional units may further include a second constitutional unit. An exemplary second constitutional unit may include an esterified acid-containing monomer. An exemplary acid-containing monomer may be one of an unsaturated monocarboxylic acid monomer and an unsaturated dicarboxylic acid monomer. An exemplary unsaturated monocarboxylic acid monomer may be one of acrylic acid, acrylic and methacrylic acid substituted alcohols such as 2-hydoxyethyl methacrylate, 2-hydroxyethyl acrylate, methoxy polyethylene glycol methacrylate, methacrylic acid, methyl methacrylic acid, esters of acrylic acid, such as ethyl acrylate and butyl acrylate, esters of methacrylic acid such as methyl methacrylate, and mixtures thereof. An exemplary unsaturated dicarboxylic acid monomer may be one of maleic anhydride, maleic acid, fumaric acid, and mixtures thereof. In an exemplary embodiment, esterified acid-containing monomer may be esterified with glycol units of 25 to 50 carbon atoms and amine groups of 18 to 25 carbon atoms, and may include one of 2-hydoxyethyl methacrylate, and 2-hydroxyethyl acrylate. The second constitutional unit copolymerized with the first constitutional unit. [0035] In an exemplary embodiment, a copolymer for cement admixtures may include a monomer unit, such as monomer unit 100 that may be formed by copolymerization of the first constitutional unit and the second constitutional unit. For example, an exemplary copolymer for cement admixtures may be formed by copolymerization of 150 to 300 units of transesterified vinyl acetate ester monomer and 300 to 500 units of the esterified acid- containing monomer.

[0036] In an exemplary embodiment, the plurality of constitutional units may include a third constitutional unit. An exemplary third constitutional unit may include a monoethylenically unsaturated monomer containing sulfuric acid groups. In an exemplary embodiment, the monoethylenically unsaturated monomer containing sulfuric acid groups may be one of sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acids, vinyl sulfonic acid, and 2-(meth) acrylamido-2-methyl propane sulfonic acid, and salts thereof.

[0037] In an exemplary embodiment, a copolymer for cement admixtures may include a monomer unit, such as monomer unit 100 that may be formed by copolymerization of the first constitutional unit, the second constitutional unit, and the third constitutional unit.

[0038] In an exemplary embodiment, a copolymer for cement admixtures may include 1 to 90 wt. % of the first constitutional unit, 1 to 90 wt. % of the second constitutional unit, and 1 to 60 wt. % of the third constitutional unit. In an exemplary embodiment, a copolymer for cement admixtures may include 50 to 90 wt. % of the first constitutional unit, 1 to 50 wt.% of the second constitutional unit, and 20 to 60 wt.% of the third constitutional unit.

[0039] FIG. 2 illustrates a flow chart of a method 200 for synthesizing a copolymer for cement admixtures, consistent with one or more exemplary embodiments of the present disclosure. In an exemplary embodiment, method 200 may be utilized for synthesizing a copolymer for cement admixtures may include a monomer unit, such as monomer unit 100. In an exemplary embodiment, method 200 may include a step 202 of esterifying an acid-containing monomer and a vinyl acetate monomer, a step 204 of synthesizing a backbone of the copolymer by copolymerizing a monomer mixture, a step 206 of adding thiol groups to the mixture, and a step 208 of adding peroxide groups to the mixture. In an exemplary embodiment, method 200 may further include a step 210 of preparing an aqueous solution of the copolymer.

[0040] In an exemplary embodiment, step 202 of esterifying an acid-containing monomer and a vinyl acetate monomer may include esterifying the acid-containing monomer and transesterifying the vinyl acetate monomer with at least one of diethylene glycol, diethylene glycol, polyethylene glycol derived from ethylene oxide and their amine substituted.

[0041] In an exemplary embodiment, step 204 of synthesizing a backbone of the copolymer by copolymerizing a monomer mixture may include copolymerizing a monomer mixture that may be prepared by dissolving the transesterified vinyl acetate monomer and the esterified acid- containing monomer in a protic or aprotic solvent. An exemplary vinyl acetate monomer may include at least one of styrene and homologs of styrene such as vinyl toluene. An exemplary acid-containing monomer may include at least one of an unsaturated monocarboxylic acid monomer and an unsaturated dicarboxylic acid monomer. An exemplary unsaturated monocarboxylic acid monomer may be one of acrylic acid, acrylic substituted alcohols, methacrylic acid, esters thereof, and mixtures thereof. An exemplary unsaturated dicarboxylic acid monomer may include one of maleic anhydride, maleic acid, fumaric acid, and mixtures thereof. As used herein, acrylic substituted alcohols may be at least one of 2-hydoxyethyl methacrylate and 2-hydroxyethyl acrylate.

[0042] In an exemplary embodiment, step 204 of synthesizing the backbone of the copolymer by copolymerizing the monomer mixture at a temperature between 75 to 80 °C. In an exemplary embodiment, step 204 of synthesizing the backbone of the copolymer may include dissolving 200 units of the transesterified vinyl acetate and 400 units of the esterified acid-containing monomer in 400 units of the protic or aprotic solvent. In an exemplary embodiment, the acid- containing monomer may include maleic anhydride.

[0043] In an exemplary embodiment, step 204 of synthesizing the backbone of the copolymer by copolymerizing the monomer mixture, where the monomer mixture may further include a monoethylenically unsaturated monomer containing sulfuric acid groups. In an exemplary embodiment, the monoethylenically unsaturated monomer containing sulfuric acid groups may be one of sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acids, vinyl sulfonic acid, and 2-(meth) acrylamido-2-methyl propane sulfonic acid, and salts thereof. [0044] In an exemplary embodiment, step 206 of adding thiol groups to the mixture may include adding thioglycolic acid, three mercaptanoic acid, mercaptoethanol and mixture of thereof to the mixture.

[0045] In an exemplary embodiment, step 208 of adding peroxide groups to initiate polymerization may include adding at least one of methyl ethyl ketone peroxide or tert -butyl hydroperoxide to the mixture.

[0046] In an exemplary embodiment, step 210 of preparing an aqueous solution of the copolymer may include changing the protic or aprotic solvent. In an exemplary embodiment, an aqueous solution of the copolymer with a concentration between 40 wt.% and 55 wt.% may be obtained by adding solvent to the mixture in the last step of polymerization, in parallel with cooling the polymer mixture.

[0047] In an exemplary embodiment, method 200 may include two distinct synthesis procedure where in the first step and prior to polymerization an esterified unsaturated mono or dicarboxylic acid is formed during the esterification process and in a second step the polymerization is carried out.

EXAMPLE

[0048] First step: Esterification

[0049] Methoxy polyethylene glycol methyl methacrylate was prepared in a 500 ml round bottomed flask equipped with a Dean and Stark apparatus, attached to a reflux condenser was used and charged with methyl methacrylic acid (0.05 mol), poly ethylene glycol (0.016 mol), catalyst (0.0.000065 mol). The reaction mixture was refluxed for 6 hours at fixed temperature of 110°C. The yields of ester formed was determined using GPC and GC. After completion of reaction, the catalyst was separated by decantation and reaction mixture was distilled to obtain the product. The catalyst was regenerated by refluxing in ethanol followed by drying and acid treating.

[0050] Second step: Polymerization

[0051] Placed inside a flask with 4 openings and provided with a thermometer, a dropping funnel, and a stirrer were 20 parts by weight of vinyl acetate, 50 parts of methoxy polyethylene glycol methacrylate (molar number of ethylene oxide addition n = 25) and 10 parts of thioglycolic acid and water (400 parts) was further added to form a uniform solution, the system temperature was maintained at 75°C by means of a warm oil bath and polymerization was initiated by adding 20 parts of a 70% aqueous solution of tert-butyl hydroperoxide over 4 hours by means of dropping funnel. Polymerization was completed after a continuous reaction for 4 hours.

[0052] While various implementations have been described, the description is intended to be exemplary, rather than limiting and it will be apparent to those of ordinary skill in the art that many more implementations and implementations are possible that are within the scope of the implementations. Although many possible combinations of features are shown in the accompanying figures and discussed in this detailed description, many other combinations of the disclosed features are possible. Any feature of any implementation may be used in combination with or substituted for any other feature or element in any other implementation unless specifically restricted. Therefore, it will be understood that any of the features shown and/or discussed in the present disclosure may be implemented together in any suitable combination. Accordingly, the implementations are not to be restricted except in light of the attached claims and their equivalents. Also, various modifications and changes may be made within the scope of the attached claims.

[0053] The embodiments have been described above with the aid of functional building blocks illustrating the implementation of specified functions and relationships thereof. The boundaries of these functional building blocks have been arbitrarily defined herein for the convenience of the description. Alternate boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed.

[0054] The foregoing description of the specific embodiments will so fully reveal the general nature of the disclosure that others can, by applying knowledge within the skill of the art, readily modify and/or adapt for various applications such specific embodiments, without undue experimentation, without departing from the general concept of the present disclosure. Therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guidance. [0055] The breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments but should be defined only in accordance with the following claims and their equivalents.

[0056] Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not to the exclusion of any other integer or step or group of integers or steps.

[0057] Moreover, the word "substantially" when used with an adjective or adverb is intended to enhance the scope of the particular characteristic; e.g., substantially planar is intended to mean planar, nearly planar and/or exhibiting characteristics associated with a planar element. Further use of relative terms such as “vertical”, “horizontal”, “up”, “down”, and “side-to-side” are used in a relative sense to the normal orientation of the apparatus.

Claims

WHAT IS CLAIMED IS:

1. A copolymer for cement admixtures, the copolymer comprising: a first constitutional unit comprising a transesterified vinyl acetate ester monomer, the transesterified vinyl acetate monomer transesterified with glycol units of 25 to 50 carbon atoms; and a second constitutional unit comprising an esterified acid-containing monomer, the esterified acid-containing monomer esterified with glycol units of 25 to 50 carbon atoms and amine groups of 18 to 25 carbon atoms, the second constitutional unit copolymerized with the first constitutional unit.

2. The copolymer of claim 1, wherein the acid-containing monomer comprises at least one of an unsaturated monocarboxylic acid monomer and an unsaturated dicarboxylic acid monomer.

3. The copolymer of claim 2, wherein the unsaturated monocarboxylic acid monomer comprises at least one of acrylic acid, methacrylic acid, methyl methacrylate, acrylic and methacrylic acid substituted alcohols, and mixtures thereof.

4. The copolymer of claim 3, wherein the unsaturated monocarboxylic acid monomer comprises at least one of 2-hydoxyethyl methacrylate, 2-hydroxyethyl acrylate, and methoxy polyethylene glycol methyl methacrylate.

5. The copolymer of claim 3, wherein the unsaturated dicarboxylic acid monomer comprises at least one of maleic anhydride, maleic acid, fumaric acid, and mixtures thereof.

6. The copolymer of claim 2, wherein the first constitutional unit comprises 150 to 300 units of transesterified vinyl acetate ester monomer.

7. The copolymer of claim 6, wherein the second constitutional unit comprises 300 to 500 units of the esterified acid-containing monomer.

8. The copolymer of claim 1, further comprising a third constitutional unit, the third constitutional unit comprising a monoethylenically unsaturated monomer containing sulfuric acid groups.

9. The copolymer of claim 8, wherein the third constitutional unit is selected from the group consisting of sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acids, vinyl sulfonic acid, and 2-(meth)acrylamido-2-methyl propanesulfonic acid, and salts of thereof.

10. The copolymer of claim 8, wherein the copolymer comprises 1 to 90 wt. % of the first constitutional unit, 1 to 90 wt. % of the second constitutional unit, and 1 to 60 wt. % of the third constitutional unit.

11. The copolymer of claim 8, wherein the copolymer comprises 50 to 90 wt. % of the first constitutional unit, 1 to 50 wt.% of the second constitutional unit, and 20 to 60 wt.% of the third constitutional unit.

12. The copolymer of claim 1, wherein the transesterified vinyl acetate ester monomer is selected from the group consisting of a transesterified styrene monomer and transesterified homologs of styrene.

13. The copolymer of claim 12, wherein the esterified acid-containing monomer is selected from the group consisting of acrylic acid, acrylic and methacrylic acid substituted alcohols, methacrylic acid, methyl methacrylate, methoxy polyethylene glycol methyl methacrylate and mixture of thereof.

14. A copolymer for cement admixtures, the copolymer comprising the following monomer unit:

wherein, Ri and R2 are selected from the group consisting of hydrogen and Cl to C4 alkyl. R3 comprises C3 to C 18 alkyl group and alkyl group is preferably a linear or branched alkyl group.

15. The copolymer of claim 14, wherein Ri and R2 are preferably the same.

16. The copolymer of claim 14, wherein R3 comprises at least one of linear C3 to C18 alkyl group, a linear phenyl group, and a linear naphthyl group.

17. The copolymer of claim 14, wherein R3 further comprises at least one of branched C3 to

C18 alkyl group, a branched phenyl group, and a branched naphthyl group.

18. A method for synthesizing a copolymer, the method comprising: esterifying an acid-containing monomer and a vinyl acetate monomer; synthesizing a backbone of the copolymer by copolymerizing a mixture, the mixture prepared by dissolving the esterified vinyl acetate monomer and the esterified acid- containing monomer comprising one of an esterified unsaturated monocarboxylic acid monomer and an esterified unsaturated dicarboxylic acid monomer in either protic or aprotic solvents; adding thiol groups to the backbone, as transfer agents; and adding peroxide groups to initiate polymerization.

19. The method of claim 17, wherein adding thiol groups to the backbone comprises adding thioglycolic acid, three mercapanoic acid, mercaptoethanol and mixture of thereof to the mixture.

20. The method of claim 13, wherein adding peroxide groups to the mixture to initiate polymerization comprises adding at least one of methyl ethyl ketone peroxide or tert-butyl hydroperoxide to the mixture.

21. The method of claim 13, wherein esterifying the acid-containing monomer comprises adding at least one of diethylene glycol, diethylene glycol, polyethylene glycol derived from ethylene oxide and their amine substituted to unsaturated mono or dicarboxylic acid at a temperature between 100 to 120 °C.

22. The method of claim 13, wherein adding glycol derived groups are preferably diethylene glycol, triethylene glycol, polyethylene glycol and their amine substituted to the mixture.

23. The method of claim 13, wherein copolymerizing the mixture comprises copolymerizing the mixture at a temperature between 75 to 80 °C.

24. The method of claim 17, wherein synthesizing the backbone of the copolymer comprises dissolving 200 units of the vinyl acetate and 400 units of the acid-containing monomer in 400 units of protic or aprotic solvent, the acid-containing monomer comprising maleic acid.

25. The method of claim 13, wherein synthesizing the backbone of the copolymer comprises copolymerizing the mixture, the mixture further comprising a monoethylenically unsaturated monomer containing sulfuric acid groups.