EP-4739638-A2 - MIKTOARM STAR POLYMER AS CEMENT FLUID ADDITIVES

EP4739638A2EP 4739638 A2EP4739638 A2EP 4739638A2EP-4739638-A2

Abstract

Miktoarm star polymers are provided either as an aqueous solution or as thin micro-flakes and the process of making the star polymers thereof. These polymers bear short polyacrylic segment(s) and long buoyant sulfonated polymer segment(s), which found to be effective additives both as cement slurry water retention and plasticizer.

Inventors

LIU, LEO ZHAOQING
LU, YANRONG

Assignees

Solenis Technologies Cayman, L.P.

Dates

Publication Date: 20260513
Application Date: 20240705

Claims (20)

1. A miktoarm star polymer comprising: one or more distinct polymer chain(s) bearing one or more of a functional monomeric unit chosen from carboxylic acid, phosphate acid ester, and phosphonate; one or more hydrophilic polymer chain(s) bearing one or more of a functional monomeric unit chosen from sulfonate and sulfate, and combinations thereof.
2. The miktoarm star polymer according to claim 1 , wherein the one or more distinct polymer chain(s) and one or more hydrophilic polymer chain(s) form a star polymer diverging from a moiety bearing polyfunctional radical transfer function chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
3. The miktoarm star polymer according to claim 1, further comprising additional monomeric units different from the monomers of the distinct polymer chain(s) and the hydrophilic polymer chain(s).
4. The miktoarm star polymer according to claim 1, wherein the one or more distinct polymer chain(s) and the one or more hydrophilic polymer chain(s) are derived from polythiols bearing three or more thiol or mercaptan functional groups.
5. The miktoarm star according to claim 2, wherein the polyfunctional radical transfer function is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer(s) act as chain transfer agents to grow the hydrophilic polymer chain(s), thus forming the miktoarm star copolymer.
6. The miktoarm star polymer according to any of claims 1-5, wherein one or more of the distinct polymer chain(s) comprises poly acrylic acid arm(s) having a weight average molecular weight of from about 1000 to about 50000 Daltons and the one or more hydrophilic polymer chain(s) comprises sulfonated or sulfated arm(s) having a weight average molecular weight of from about 10000 to about 1.000,000 Daltons.
7. The miktoarm star polymer according to any of claims 1 to 5, wherein one or more of the hydrophilic polymer chain(s)s comprises one sulfonic acid-containing monomer or its salt alone or with one or more other monomer.
8. The miktoarm star polymer according to claim 7, wherein the sulfonic acidcontaining monomer is chosen from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallyl sulfonic acid, allylhydroxypropanesulfoinic acid, or the salts thereof; styrene sulfonate; or allyl polyoxyethylene sulfate ester salt.
9. The miktoarm star polymer according to claim 3, wherein the additional monomeric unit is derived from acrylamide, methyacrylamide, N,N- dimethyl(meth)acrylamide. N-N-diethyl(meth)acrylamide, or isopropyl(meth)acrylamide; N-tert-butylacrylamide, or amides of a, P-ethylenically unsaturated mono- or dicarboxylic acids with diamines having one or more primary or secondary amine group; N,N-diallylamines, or N,N-diallyl-N-alkylamines; esters of a, p-ethylenically unsaturated mono- or dicarboxylic acids with C2-30 alkanediols or their alkoxylates; tetrahydrofurfuryl acrylate; N-vinylcaprolactam, N-vinylpyrolidone, N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpiperidone, N-vinyl-5-methyl-2- pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6- ethyl-2-piperidone. N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam. vinylpyridine, a, -ethylenically unsaturated ethers of C2-30 alkanediols or their alkoxylates, or combinations thereof.
10. A process of producing a miktoarm star polymer comprising: a) preparing a thiol-bearing telechelic polymer chain by polymerizing a composition comprising monomers bearing carboxylic acids, phosphate acid esters, phosphonates, and combinations thereof; a polythiol or mercaptan-bearing moiety and a radical initiator; b) preparing a monomer solution comprising one or more monomer(s) bearing sulfonate or sulfate functional groups to form one or more hydrophilic polymer chain(s) or segment(s); c) combining the thiol-bearing telechelic polymer chain from step a) with the monomer solution containing one or more functional monomers bearing sulfonate or sulfate of step b) and initiating polymerization with radical initiator(s); d) continuing the polymerization reaction until the thiol concentration is non- detectable by using Ellman assay techniques thereby producing a miktoarm star polymer diverging from a moiety bearing polyfunctional radical transfer function chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
11. The process according to claim 10. further comprising additional monomeric units different from those in the thiol-bearing telechelic polymer chain(s) and the hydrophilic polymer chain(s), wherein the additional monomer units bears functions other than those in the thiol-bearing telechelic polymer chain(s) and the hydrophilic polymer chain(s).
12. The process according to claim 10, wherein the polyfunctional radical transfer function is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer chain(s) act as chain transfer agents to grow the hydrophilic polymer chain(s), thus forming the miktoarm star copolymer.
13. The process according to claim 12, wherein one or more but not all of the thiol or mercaptan functional groups is attached to the one or more distinct polymer chain(s) and the remaining thiol functional groups on the one or more distinct polymer chain(s) act as chain transfer agents to grow the hydrophilic polymer chain(s).
14. The process according to any one of claims 10 to 13, wherein the one or more distinct polymer chain(s) comprises a polyacrylic acid arm having a molecular weight of from about 1000 to about 50000 and the one or more hydrophilic polymer chain(s) comprise sulfonated arms having a molecular weight of from about 10000 to about 1,000,000.
15. The process according to any one of claims 10 to 13, wherein the hydrophilic polymer chain(s) is chosen from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallyl sulfonic acid, allylhydroxypropanesulfoinic acid, or its salts and allyl polyoxyethylene sulfate ester salt alone or with acrylamide, methacrylamide, N,N-dimethyl(meth)acrylamide. N-N-diethyl(meth)acrylamide. isopropyl(meth)acrylamide; N-tert-butylacrylamide, amides of a, P-ethylenically unsaturated mono- or dicarboxylic acids with diamines having one or more primary or secondary amine group; N.N-diallylamines, and N,N-diallyl-N-alkylamines; esters of a. P-ethylenically unsaturated mono- or dicarboxylic acids with C2-30 alkanediols or their alkoxylates; and tetrahydrofurfuryl acrylate; N-vinylcaprolactam, N-vinylpyrolidone, N- vinylacetamide, N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpiperidone. N- vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone. N-vinyl-6-methyl-2- piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, and N-vinyl- 7-ethyl-2-caprolactam, vinylpyridine, and a, p-ethylenically unsaturated ethers of C2-30 alkanediols or their alkoxylates.
16. The process according to any one of claims 10-13, wherein the polymerization reaction is continued until the thiol concentration is non-detectable based on Ellman assay techniques.
17. A method for reducing fluid loss in mortar or concrete processes comprising: providing a mortar ground or concrete slu -; adding to the mortar ground or concrete slurry a miktoarm star polymer comprising one or more one or more distinct polymer chain bearing one or more of functional monomeric unit chosen from carboxylic acid, phosphate acid ester, and phosphonate; one or more hydrophilic polymer chain(s) bearing one or more functional monomeric units chosen from sulfonate and sulfate, and combinations thereof.
18. The method according to claim 17. wherein the one or more distinct polymer chain(s) and one or more hydrophilic polymer chain(s) form a star polymer diverging from a moiety bearing polyfunctional radical transfer function chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
19. The method according to claim 17, wherein the polyfunctional radical transfer function is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer chain(s) act as chain transfer agents to grow the one or more hydrophilic polymer chain(s), thus forming the miktoarm star polymer.
20. The method according to any one of claims 17 to 19, wherein the miktoarm star polymer acts as a dispersant or superplasticizer in mortar or concrete processes.

Description

MIKTOARM STAR POLYMER AS CEMENT FLUID ADDITIVES TECHNICAL FIELD [0001] The present disclosure generally relates to a miktoarm star (p-star) polymer, the process of making the star poly mer and use of the star polymer in mortar or concrete applications and processes. BACKGROUND [0002] Water retention in cement grouts or mortar systems are critical for the settled material strength and permeability. Water could be lost from mortar system as a result of negative capillary forces. In the exploration of oil and gas, cement slurry is used to seal oil and gas well. However, water could be filtered out from cement slurry under the high hydrostatic pressure of the cementing column and the hot temperature surrounding the formation. [0003] Various additives are used in mortar grouts or cement slurry such as defoamers, dispersants, plasticizers, retardants as well as water retention or fluid loss control agents. However, these additives can interact with mortar or cement as well as with each other in undesirable ways. For example, dispersants or retardants can adversely affect the fluid loss control agents, making the latter less effective. On the other hand, some of the fluid loss control agents rely on the thickening effect caused by interstitial water of the slurry or mortar from added polymeric materials such as polysaccharides and other synthetic polymers. The use of such polymeric fluid loss control agents may be limited by high solid volume fraction of cement slurry, which is often higher than 50% for high demand applications. Therefore, there is still a demand and need for a fluid loss control agent with little or no negative affect as mentioned above. It is desirable that single additives have multiple functions. For example, a water retention or fluid loss control agent for cement could also serve as a dispersant or superplasticizer, thus limiting the cost of use and environment impacts. [0004] To enhance the interaction of water retention or fluid loss control agent with the substrate without negative impact from other additives in the compositions or without thickening the substrate have been tried, such as using a divinyl ether cross-linked microgel with limited success. Such fluid loss control agents still thickens mortar systems and cement slurries. Di-block polymers as fluid loss control has been tried using a first shorter chain polymer block bonding to the substrate particles and a second longer chain polymer block that extends out into the fluid surrounding the particles, thus creating hairy cement particles. [0005] Such products were shown to have efficacy as fluid loss control agent for a particular type of well cementing. However, the production of the di-block polymer utilized large amounts of organic solvent for its first short chain block, and it takes more than a day to produce the product. Therefore, there is still a need to have a more economic fluid loss control product but with higher efficacy or dual or even multiple functions. [0006] Polymers with precisely controlled structure and function are in high demand across a diverse array of applications. One prototypical example is a class of branched block copolymers known as miktoarm stars u- stars) polymers. Miktoarm star (p-star) polymers are those comprising two or more arm compositions, arm topologies, arm molecular weights (MWs), and/or arm chain end functionalities connected at a common junction. They have been obtained through various methods (M. Liu et al Chem. Mater. 2022, 34, 6188-6290; H. latrou et al Polymer Chemistry Series No 25, Miktoarm Star Polymers: from Basics of Branched Architecture to Synthesis, Self-assembly and Applications). However, such polymers have limited industrial applications due to the expensive organic solvent processes which are not environmentally friendly. [0007] Miktoarm star (p-star) polymers are usually formed by using either multifunctional initiators, multifunctional chain transfer agents, or multifunctional coupling agents. In comparison with linear polymers, the star-branched polymers have unique properties including narrow molecular weight distributions; low viscosities at low- molecular weights either in liquid form or in solution due to their compact structures; high viscosities at high molecular weights due to extensive entanglements. BRIEF SUMMARY [0008] Provided is a w ater-borne miktoarm star polymer composition that includes one or more distinct polymer chain(s) or segment(s) bearing one or more of functional monomeric unit chosen from carboxylic acid, phosphate acid ester, and phosphonate; hydrophilic polymer chain(s) or segment(s) bearing one or more of the functional monomeric unit chosen from sulfonate and sulfate, and combinations thereof. The one or more distinct polymer chain(s) or segment(s) and the one or more hydrophilic polymer chain(s) or segment(s) form the arms of the star polymer diverging from a moiety bearing polyfunctional radical transfer function chosen from thiol o