CN100354313C - Controlled polymerization - Google Patents

Abstract

The present invention discloses an emulsion polymerization process that comprises: (1) preparing an aqueous polymerization medium which is comprised of (a) at least one monomer, (b) a polymerization control agent, and an emulsifier, wherein the emulsifier is prepared in-situ within the aqueous polymerization medium; and (2) initiating polymerization of said monomer within the aqueous polymerization medium. The subject invention more specifically reveals an emulsion polymerization process that comprises: (1) preparing a monomer solution which is comprised of (a) at least one monomer, (b) a conjugate acid of a surfactant with a pK<SUB>a </SUB>of less than 14, and (c) a controlled free radical polymerization agent; (2) preparing an aqueous medium which is comprised of (a) water, and (b) a conjugate base of a weak acid wherein the pK<SUB>b </SUB>of the base is less than 14; and (3) mixing the monomer solution with the aqueous medium under conditions that result in the in-situ formation of an emulsifier, and (4) initiating free radical polymerization.

Description

Controlled polymerization

The application requires the right of priority of the U.S. Provisional Application sequence number 60/437,542 of submission on December 31st, 2002.

Invention field

The present invention relates under multiple condition, use the method and composition of multiple monomer controlled polymerization in emulsion system.The present invention also relates to prepare the method for described emulsion system.In addition, the invention still further relates to the polymkeric substance and the multipolymer of available described emulsion system preparation.

Background of invention

Synthetic polymer is big nation's material, has range of application relatively widely.The basic structural unit of polymkeric substance is called monomer, has invented the multiple method for preparing polymkeric substance from monomer.The preparation polymkeric substance make great efforts the earliest concentrate on the molecular formula of controlling polymers and prepare on the useful material from ready-made chemical feedstocks.Along with the development of polymer arts, polymer molecular structure becomes obvious day by day in the importance of its many properties of decision, and the technology of controlling polymers molecular structure also begins to occur simultaneously.Over the past two decades, the quantity and the ability thereof of the technology of implementation structure control all are much improved on molecular level.Expect that this trend will continue, because bet focus in structure and the character of several nanometers to the range scale inner control material of hundreds of nanometer day by day in most fields of science and engineering.

For synthetic polymer, its molecular structure great majority are controlled in polymerization process, and described polymerization process generally includes from many less molecules (for example monomer) and forms polymer.The degree of control depends on many factors, and the term that is used to describe various forms of " controlled polymerization " is existed great dispute.But what day by day obtain admitting is, when describing the method for the polymkeric substance that obtains having predetermined molar mass and lower polymolecularity according to this, it is suitable using " controlled polymerization " this term.If side reaction appears in polymerization, but its degree is not significantly disturbed the control to the molecular structure of polymer chain, and then described polymerization also may be defined as " controlled polymerization ".The chain polymerization of the main type of great majority comprises anionoid polymerization, cationoid polymerisation, ring-opening metathesis polymerization (ROMP), polycoordination and radical polymerization, can carry out according to " control " polymerization process under suitable condition.

No matter how, reaching the key of the required condition of controlled polymerization, method is production stage in the simplified method to suppress unwanted side reaction simultaneously.This is by the moisture in the minimizing system of trying one's best in the past or removes moisture and partly realize from system.Along with the discovery of the catalyzer of anti-functional group that more is applicable to polycoordination, olefin metathesis and cationoid polymerisation, and the appearance that realizes the method for control radical polymerization, the existence of water no longer becomes unsurmountable obstacle.In fact, the unremitting pursue of eco-friendly more water base manufacture method and product has greatly been encouraged exploitation to water controlled polymerization method.The control letex polymerization is attractive especially to water-insoluble monomer and polymkeric substance, all exists the fierce international competition of developing practical emulsion polymerisation process in academia and industrial community.

Inspection to document shows that in general, conventional emulsion polymerization technology is not good to the effect of controlled polymerization.In many cases, main problem is to cause slowly, and " activity " agent simultaneously or its precursor are low by the transfer rate that water enters growing polymer particles.For avoiding these problems, many research groups have used novel more technology, to obtain better emulsion and to realize higher transfer rate.Modal technology is " miniemulsion " technology.Adopt this technology, the conventional emulsions of preformed monomer, tensio-active agent, hydrophobic materials and water is handled with clarifixator or ultrasonic horn under shear conditions, makes more tiny self stabilization drop.Described fine drop becomes polymerization site, thereby has avoided the requirement by the water transmission.Two main drawbacks of miniemulsion technology are: (1) needs special, expensive equipment, and (2) use hydrophobic materials (for example n-Hexadecane), and this is undesirable in many possible application.

Second kind of technology of preparation fine drop is " microemulsion " technology, and the initial monomers drop that described technology produces usually is in the scope of 5nm, and final polymer beads is in the scope of 30-40nm.This technology needs a large amount of tensio-active agents usually, because the amount of tensio-active agent often equals or exceeds existing monomeric amount, seldom is used for controlled polymerization.

The third technology that realizes the control letex polymerization has adopted inoculation method with initiated polymerization.Adopt this technology, a part of monomer at first mixes with initiator, control agent, water and tensio-active agent.This is made up material mixing and allows its reaction for some time, add other monomer then.The purpose of fs is to allow initiator form " activity " oligopolymer or " seed " under the condition of tensio-active agent-monomer more higher than relatively (being microemulsion).Though this technology is owing to some advantage that does not need hydrophobic materials or Special Equipment to have to be better than the miniemulsion technology, it does not solve and use the existing basic problem of controlled polymerization technology in emulsion, as compare the slow or long reaction time of its velocity of initiation with solution reaction.

As if in view of above situation, need possess following feature based on the practical emulsion process of controlled polymerization technology: (1) produces stable emulsion without hydrophobic materials or Special Equipment; (2) adopt conventional tensio-active agent and soap level; (3) realize causing fast and increasing; (4) reasonably realizing transforming fully in the time.

Summary of the invention

The invention provides the universal method that realizes monomeric controlled polymerization in the emulsion by all main chain polymerization mechanism, described chain polymerization mechanism comprises radical polymerization, carbocationic polymerization, anionoid polymerization, ring-opening metathesis polymerization and polycoordination.Therefore the present invention provides the approach that obtains multiple polymers, described polymkeric substance from homopolymer and random copolymers to segmented copolymer with complex construction (for example hyperbranched, brush shape, nuclear-shell, star).Therefore, target of the present invention provides the multiple monomer polymeric controlled polymerization method separately or together in emulsion that can allow.

The wide range of adoptable initiator of the inventive method and controlled polymerization reagent comprises the initiator and the control agent that seem very little to the water-based process action effect in other respects.This is to combine by the microemulsified new principle that ultimate principle and Russian investigator with controlled polymerization describe in the article of delivering in the recent period (Russ.Chem.Rev.2001,70,791) to realize.As far as our knowledge goes, this technical combinations was never reported in the past.The invention provides simple, general and high-efficiency method and be implemented in controlled polymerization in the emulsion, and need need not take the exhibiting high surface promoting agent in order to producing miniemulsion technology, the microemulsion technology of stable emulsion, or multistep inoculation method.

The invention discloses the emulsion polymerisation process that may further comprise the steps: the aqueous polymerization medium that (1) preparation is made up of at least a monomer, polymerization control agent and emulsifying agent, wherein said emulsifying agent is in the aqueous polymerization made acid-stable in situ; (2) in described aqueous polymerization medium, cause described monomeric polymerization.Described control agent can be the reagent by all dominant mechanism control radical polymerizations, and described mechanism comprises that (RAFT) shifted in reversible addition fracture, nitroxide (nitroxide) mediates polymerization (NMP), atom transfer radical polymerization (ATRP) and degradation and shifts (degenerativetransfer) (DT).Also can use the control free radical polymerisation process that is used to be correlated with, as toluylene (DPE) mediation polymerization with based on the control agent of the RAFT (MADIX) of xanthate.Described control agent also can be the polymerization that is used to follow non-free radical mechanism, as the reagent of cationoid polymerisation, anionoid polymerization, ring-opening metathesis polymerization (ROMP), acyclic dienes metathesis polymerization (ADMET) and polycoordination.Described control agent can directly add in the reaction mixture, and perhaps original position produces.

An importance of the present invention is by making latent (latent) tensio-active agent of organic soluble and water soluble surfactant active's activator reaction original position produce (Russ.Chem.Rev.2001 in the presence of at least a monomer in water-bearing media, 70,791) emulsifying agent, the solubleness of wherein said monomer in water is limited.Described emulsifying agent can be the combination of aniorfic surfactant, cationic surfactant, nonionic surface active agent or these tensio-active agents.The various chemical reactions of wide range comprise that acid/alkali neutralization reaction, hydrolysis reaction, nucleophilic addition(Adn) and replacement(metathesis)reaction all can be used to from multiple latent surfactant/surfactant activator combination produced in situ emulsifying agent.

The present invention has further disclosed and has comprised following a kind of emulsion polymerisation process, described method comprises: (1) preparation aqueous polymerization medium, described medium by (a) at least a monomer and (b) polymerization control agent and emulsifying agent form, wherein said emulsifying agent is in described aqueous polymerization medium made acid-stable in situ; (2) in described aqueous polymerization medium, cause described monomeric polymerization.

Those skilled in the art have readed over after specification sheets of the present invention, the drawings and Examples, and other aspects of the present invention will be conspicuous concerning them.

The invention also discloses a kind of emulsion polymerisation process, described method comprises: (1) preparation monomer solution, described solution is by (a) at least a monomer and (b) pK _aThe conjugate acid of tensio-active agent less than 14 and (c) control radical polymerization mixture form; (2) preparation water-bearing media, described medium by (a) water and (b) the faintly acid conjugate base form the pK of wherein said alkali _bLess than 14; (3) described monomer solution is mixed under the condition that can cause the emulsifying agent original position to form with described water-bearing media; (4) cause radical polymerization.

Detailed Description Of The Invention

The present invention relates to the controlled polymerization method in the emulsion system.Control realizes that by using " control agent " described control agent provides the reaction path and the corresponding dynamic behavior of " activity " type polymerization process.The term that the chemistry bound pair is used to describe alleged usually " activity " or " control " polyreaction exists great dispute.Szwarc introduced first in 1956 term " living polymerization " (Nature 1956,178,1168-9), in order to be described in the anionic chain polymerization that it carries out not occurring in the method irreversible chain rupture method (as chain transfer and termination).Such polymerization provides the strictness control to polymer terminal group, makes and can pass through two or more monomeric synthetic segmented copolymers of polymerization according to the order of sequence.Develop again subsequently in order to generate many other chain polymerization methods of segmented copolymer.Major part is all kept away unavoidable chain transfer or chain termination reaction in these methods.For these methods defined with Szwarc " activity " polymerization is distinguished mutually, for example " control " polymerization, " false active " polymerization, " accurate active " polymerization and such term of " control/activity " polymerization have been introduced.Term " control " is in this article in order to describe all polymerization processs that acquisition according to this has the polymkeric substance of predetermined molar mass and low polymolecularity.

What phrase used herein " shown in (certain) formula " do not have a mind to limit, and it " comprises " the common mode that is used by phrase and uses.It can be identical or different in order to expression for option in this article that term " independently is selected from ".For example in the situation of R group, term " independently is selected from " expression R group (R for example ¹, R ², R ³) can be identical (R for example ¹, R ²And R ³All can be substituted alkyl) or different (R for example ¹And R ²Can be substituted alkyl, and R ³Can be aryl).Unless otherwise, specified R group has the R group corresponding structure under art-recognized and this title.For purposes of illustration, this paper has defined representational R group.These definition are intended to replenish and explanation well known to a person skilled in the art definition, rather than to the eliminating of well-known definitions.

Term " alkyl " is in this article in order to refer to the saturated or unsaturated acyclic hydrocarbon base of side chain or non-side chain.Typical alkyl comprises for example methyl, ethyl, n-propyl, sec.-propyl, 2-propenyl (or allyl group), normal-butyl, isobutyl-, the tertiary butyl (or 2-methyl-propyl), amyl group, hexyl, vinyl (or alkenyl), alkynyl group etc.In specific embodiment, alkyl has 1-200 carbon atom or 1-50 carbon atom or 1-20 carbon atom.

Term " cycloalkyl " refers to saturated or unsaturated, as to have monocycle or the multiple condensed ring non-aromatic hydrocarbyl of ring-type.Suitable cycloalkyl comprises for example cyclopentyl, cyclohexyl, cyclooctene base, two suberyl etc.In specific embodiment, cycloalkyl has 3-200 carbon atom or 3-50 carbon atom or 3-20 carbon atom.

" substituted alkyl " refers to that wherein one or more hydrogen atoms that are connected with carbon on the alkyl are by another group such as halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl and aforesaid alkyl that combination replaced thereof.Suitable substituted alkyl comprises for example benzyl and trifluoromethyl.

" substituted cycloalkyl " refers to that wherein one or more hydrogen atoms that are connected with carbon on the cycloalkyl are by another group such as halogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, Heterocyclylalkyl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, boryl, phosphino-, amino, silyl, sulfenyl, seleno and aforementioned cycloalkyl that combination replaced thereof.Suitable substituted cycloalkyl comprises 4-methoxyl group cyclohexyl and 4,5-dibromo ring heptan-4-thiazolinyl.

Term " assorted alkyl " refers to that wherein one or more hydrogen atoms that are connected with carbon on the alkyl are selected from abovementioned alkyl that heteroatoms replaced or the substituted alkyl of N, O, P, B, S, Si, Se and Ge.Key between carbon atom and the heteroatoms can be saturated bond or unsaturated link(age).Therefore, the alkyl that is replaced by Heterocyclylalkyl, substituted heterocycle alkyl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, boryl, phosphino-, amino, imino-, silyl, sulfenyl or seleno is in the scope of the assorted alkyl of term.Suitable assorted alkyl comprises for example cyano group, benzyl acyl group, 2-pyridyl, 2-furyl, Me ₃SiO (CH ₂) ₃CH ₂, (c-C ₆H ₁₁) ₇Si ₈O ₁₂(CH ₂) ₂CH ₂

Term " Heterocyclylalkyl " refers to above-mentioned cycloalkyl, is replaced but one or more or all carbon atoms on wherein saturated or the unsaturated cyclic group are selected from the heteroatoms of N, O, P, B, S, Si, Se and Ge.Suitable Heterocyclylalkyl comprises for example piperazinyl, morpholinyl, THP trtrahydropyranyl, tetrahydrofuran base, piperidyl and pyrrolidyl.

Term " substituted heterocycle alkyl " refers to aforementioned Heterocyclylalkyl, but wherein the one or more hydrogen atoms on any atom of Heterocyclylalkyl are replaced by another group such as halogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, Heterocyclylalkyl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, boryl, phosphino-, amino, silyl, sulfenyl, seleno and combination thereof.Suitable substituted heterocycle alkyl comprises for example N methyl piperazine base, 3-dimethylamino morpholine.

Term " aryl " refers to can be the aromatic substituent of monocyclic aromatic rings or multiple aromatic ring, and described multiple aromatic ring can condense together, can be covalently bound or be connected to common group such as methylene radical or ethylidene part.Common linking group also can be carbonyl (as in benzophenone), or is heteroatoms, as oxygen in the phenyl ether or the nitrogen in the pentanoic.Aromatic ring can comprise phenyl, naphthyl, xenyl, phenyl ether, pentanoic and benzophenone etc.In specific embodiment, aryl has 1-200 carbon atom or 1-50 carbon atom or 1-20 carbon atom.

Term " substituted aryl " refers to that one or more hydrogen atoms of wherein being connected with any carbon atom are by aforementioned aryl that one or more following functional group replaced: alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, Heterocyclylalkyl, substituted heterocycle alkyl, halogen, haloalkyl are (as CF ₃), hydroxyl, amino, phosphino-, alkoxyl group, amino, sulfenyl and condense with aromatic ring, covalently bound or be connected to the saturated and unsaturated cyclic hydrocarbon of common group such as methylene radical or ethylidene part.Common linking group also can be carbonyl, as cyclohexyl-phenyl ketone.The object lesson of substituted aryl comprises perfluorophenyl, chloro-phenyl-, 3,5-3,5-dimethylphenyl, 2,6-diisopropyl phenyl etc.

The aromatic ring that one or more carbon atoms that term " heteroaryl " refers to aromatic ring are wherein replaced by heteroatoms such as nitrogen, oxygen, boron, selenium, phosphorus, silicon or sulphur.Heteroaryl can be such structure: monocyclic aromatic rings, multiple aromatic ring or with one or more aromatic rings of one or more non-aromatic ring couplings.In having the structure of multiple ring, described ring can condense together, can be covalently bound or be connected to common group such as methylene radical or ethylidene part.Common linking group also can be carbonyl, as in phenylpyridyl ketone.Ring used herein such as thiophene, pyridine, different  azoles, phthalimide, pyrazoles, indoles, furans etc., or the benzo-fused analogue of these rings are all defined by term " heteroaryl ".

Term " substituted heteroaryl " refers to that the one or more hydrogen atoms on any atom of the part of hetero-aromatic ring wherein are selected from for example aforementioned heteroaryl that another group replaced of following group: halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, boryl, phosphino-, amino, silyl, sulfenyl, seleno and combination thereof.Suitable substituted heteroaryl comprises for example 4-N, the N-Dimethylamino pyridine.

Term " alkoxyl group " refers to-OZ ' group that wherein Z ' is selected from alkyl as herein described, substituted alkyl, cycloalkyl, substituted cycloalkyl, Heterocyclylalkyl, substituted heterocycle alkyl, silyl and combination thereof.Suitable alkoxyl group comprises for example methoxyl group, oxyethyl group, benzyloxy, tert.-butoxy etc.Relational language is " aryloxy ", and wherein Z ' is selected from aryl, substituted aryl, heteroaryl, substituted heteroaryl and combination thereof.Suitable examples of aryloxy comprises phenoxy group, substituent phenoxy, 2-pyridyloxy, 8-quinoline oxy (quinalinoxy) etc.

Term " silyl " refers to-SiZ ¹Z ²Z ³Group, wherein Z ¹, Z ²And Z ³Independently be selected from hydrogen, halogen, alkyl, substituted alkyl, cycloalkyl, Heterocyclylalkyl, heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof separately.

Term " boryl " refers to-BZ ¹Z ²Group, wherein Z ¹And Z ²Independently be selected from hydrogen, halogen, alkyl, substituted alkyl, cycloalkyl, Heterocyclylalkyl, heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof separately.

Term " phosphino-" refers to PZ ¹Z ²Group, wherein Z ¹And Z ²Independently be selected from hydrogen, halogen, alkyl, substituted alkyl, cycloalkyl, Heterocyclylalkyl, heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof separately.

Term " amino " refers to-NZ ¹Z ²Group, wherein Z ¹And Z ²Independently be selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, Heterocyclylalkyl, substituted heterocycle alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof separately.

Term " sulfenyl " refers to SZ ' group, and wherein Z ' is selected from hydrogen, halogen, alkyl, substituted alkyl, cycloalkyl, Heterocyclylalkyl, heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof.

Term " seleno " refers to-SeZ ' group that wherein Z ' is selected from hydrogen, halogen, alkyl, substituted alkyl, cycloalkyl, Heterocyclylalkyl, heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl group, aryloxy, amino, silyl and combination thereof.

Term " saturated " refers to do not have two keys and triple bond between each atom of group such as ethyl, cyclohexyl, pyrrolidyl etc.

Term " unsaturated " refers to have one or more pairs of keys and triple bond between each atom of group such as vinyl, ethynyl,  azoles quinoline base, cyclohexenyl, ethanoyl etc.

When key concrete part of its terminal nothing or the atomic time that chemical formula indicated, mean the chemical name rule of the standard of following, described key is represented the methyl on the correct position or on the connection site.

For purposes of illustration, polyreaction is divided into following 10 classes by its reaction mechanism similarity: atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), reversible addition fracture are shifted (RAFT), degradation transfer (DT), anionoid polymerization, cationoid polymerisation, polycoordination, ring-opening metathesis polymerization (ROMP), acyclic dienes metathesis polymerization (ADMET) and are related to other polyreactions of stabilized radical (SFR).The corresponding description that these types reach polymerization mechanism is intended to illustrate specific embodiment, is not intended to get rid of any other polymerization mechanism that those skilled in the art generally acknowledge.

Atom transfer radical polymerization (ATRP)

ATRP is a kind of catalyzed reversible oxide-reduction method of realizing controlled polymerization by the easy transfer of unstable group (being X) between growing polymer chain (P) and control agent (being M-L).Usually, described unstable group is halogen atom (being X=I, Br or Cl), and control agent is to shift the stable metal/ligand combination (for example M-L and X-M-L) of maintenance in two kinds of relevant different oxidation state with the inner electron of X.Chain polymerization can take dual mode to cause.For " directly ATRP ", usually be by making control agent (being M-L) and the initiator for reaction that contains very unsettled X group (being Q-X) realize causing.For " anti-ATRP ", initiator is generally conventional free radical initiator (being Q-Q), and unstable group (X) and control agent (M-L) are introduced into the form of metal halide complex compound (being X-M-L) together.The dominant mechanism feature of two kinds of ATRP mechanism describes in diagram 1.Its state-of-art is regularly at large summarized (Adv.Polym Sci.2002,159,1 by Matyjaszewski; Prog.Polym.Chem.2001,26,337; Chem Rev.2001,101,2921).

Diagram 1

Nitroxide-mediated polymerization (NMP)

Use nitroxide-mediated (i.e. control) radical polymerization to be developed in a large number.Described many dissimilar nitroxides, also had many methods to generate nitroxide in order to original position.No matter what nitroxide, also no matter its production method how, the dominant mechanism feature of NMP is that nitroxide (is R ₂NO) to the reversible coupling of growing polymer chain free radical (P).

The early stage NMP method that Solomon etc. (United States Patent (USP) the 4th, 581, No. 429) describe has reported that the alkoxylamine with unstable O-X key (is R ₂NOX) purposes in control radical polymerization.Alkoxylamine is simultaneously brought into play its function as radical initiator and nitroxide control agent source.Georges etc. (United States Patent (USP) the 5th, 401, No. 804) have adopted free nitroxide control agent, control the free radical chain type polymerization that is caused by the conventional free radical initiator as TEMPO (promptly 2,2,6,6-tetramethyl piperidine-1-oxygen base).(PCT WO 0053640) such as Nesvada etc. (United States Patent (USP) the 6th, 262, No. 206) and Klaerner proved the nitroxide compound and the alkoxylamine that also can use derived from the reaction of nitrone and radical source afterwards.Vanhoorne etc. (U.S. Patent application 2002/0165331 A1) have described based on the NMP method derived from the nitroxide of the reaction of nitrogen oxide (being NO).The existing regularly detailed summary of the state-of-art of NMP (referring to Matyjaszewski, K.Controlled Radical Plymerization; ACS Symp.Series685:Washington D.C.1998).

(RAFT) shifted in reversible addition fracture

The RAFT controlled polymerization is to take place by the quick chain transfer between growing polymer free radical and slumber (dormant) polymer chain.After the initiation, control agent becomes the part of slumber polymer chain.The dominant mechanism feature of RAFT describes in diagram 2.

Diagram 2

(PCT WO 0160792) such as Rizzardo etc. (PCT WO 9801478) and Lai described trithiocarbonate (Z=SR) and dithioesters (Z=R) purposes as control agent.Charmot etc. (WO 9858974) have described that (MADIX: the similar approach of polymer design is carried out in exchange Z=OR) by the xanthan gum ester.Charmot etc. (U.S. Patent application 2002/0065380) have also described relevant dithio acylhydrazone (dithioacylhydrazone) (Z=NR (N=CR ₂)) by being the purposes that RAFT mechanism is carried out controlled polymerization.The existing detailed summary regularly of the state-of-art of RAFT.

In the RAFT polymerization, initiator produces free radical, and the latter reacts with polymerisable monomer subsequently.Thereby monomer free radical and other monomer reactions, growth form chain, and chain can react with control agent such as dithioesters again.Control agent can rupture, and perhaps forms R, and the latter will form new chain with another monomer reaction, maybe will continue to increase.In theory, growth can continue to monomer and no longer exists and stop step and occur.After polymerization for the first time finished, under specific situation, second kind of monomer can join in the system, formed segmented copolymer.Such technology also can be in order to synthetic multi-block polymer, graftomer, star polymer, gradient polymer and end group functional polymer.

Degradation shifts (DT)

In degradation shifted, controlled polymerization was (to be P by the macromolecular radical chain that increases ¹And P ²) between the direct exchange of atom or group take place.Used control agent is generally and has unstable C-X key (n-C for example ₆F ₁₃I, α-bromo-ester or alpha-iodine ester) organic radical (organyl) halogenide, essential atom of DT or group (being X) can be provided.

Matyjaszewski etc. (Macromolecules, 1995,28,2093 and Macromolecules, 1995,28,8051) have described alkyl iodide by the purposes of DT to controlled polymerization.Pouraiimady etc. (EP applies for No. 0947527) have described the purposes of activation organic radical iodide by controlled polymerization formation water-based segmented copolymer.Perfluoroalkyl iodides is used for DT, and the purposes that is included in the controlled polymerization in the miniemulsion is described by (Macromolecules 2002,35,6154) such as (Macromol.Rapid.Commun.2000,21,921) such as Farcet and Apostolo.

Other polyreactions that relate to stabilized radical (SFR)

The common trait of control radical polymerization is to use control agent to introduce reaction path, so that the reversible formation slumber of the macro-radical polymer chain from increasing.Under typical condition, the equilibrium theory of tide of reversible reaction is partial to the slumber polymer chain widely, this is reduced to such degree with regard to the concentration that makes macro-radical, and promptly to compare with rate of rise be negligible to the terminated speed that causes of dimolecular reaction (for example combined with radical).ATRP, RAFT, NMP and DT controlled polymerization have been carried out detailed research, and the detailed mechanism that has proposed for these systems.The reaction mechanism of other situations is not also set up fully, is clearly but any is arranged, i.e. the adding of particular agent can promote the reversible formation of stabilized radical, causes occurring controlling the behavioural characteristic of radical polymerization.

A kind of such reagent is 1,1-toluylene (DPE), and it is described as the additive that can control radical polymerization by (WO0144327, WO 0039169 and WO 0037507) such as Raether.The polymolecularity of polymkeric substance is measured and is shown, the control degree of DPE-controlled polymerization is lower than the being seen control degree of other control free radical methods.But the DPE method provides the practical advantages that is better than additive method for control radical polymerization.Raether etc. (Macromol.Symp.2002,177,25) have reported that DPE produces the purposes of segmented copolymer on technical scale, and it is next according to managing the control that explanation is carried out with DPE to have proposed three kinds of mechanism.

Anionoid polymerization

Active anionic polymerization is " control " polymerization, its dominant mechanism feature (shown in the diagram 3) many books (referring to Hsieh, H.L.; Quirk, R.P.Anionic Polymerization:Principles and Practical Applications (anionoid polymerization: principle and practical application); Marcel Dekker:New York, 1996) and survey article (referring to Hadjichristidis, N.; Pitsikalis, M.; Pispas, S.; Iatrou, H.; Chem.Rev.2001,101 (12), all discuss in 3747-3792).Initiator and monomer reaction produce the negatively charged ion intermediate, and the latter can produce the polymer chain of growth with other monomer reaction.Control agent is generally the cationic substance that original position produces.Though the structure of these materials is usually undistinct as yet, their existence need keep electric neutrality, and their composition has far-reaching influence to polymerisation run.

Diagram 3

Active anionic polymerization is the universal method of producing segmented copolymer, has implemented this method with multiple monomer, and described monomer comprises vinylbenzene, acrylate, epoxide, lactone, siloxanes, conjugated diolefine etc.Because as if water has serious negative impact to most of active anionic polymerizations, all can not carry out anionoid polymerization in water-bearing media for many years.But, to recent report (Macromolecules such as Rehor, 2002,35,8688 of the anionoid polymerization in the miniemulsion; Polymer such as Barrere, 2001,42,7239; Macromolecules, 2001,34,7276; Macromolecules such as Maitre, 2000,33,7730; Macromolecules such as Limouzin, 2003,36,667) but prove another pair of shoes, the control anionoid polymerization that existing expection is implemented in the emulsion is well-founded.

Cationoid polymerisation

The control cationoid polymerisation is compared its mechanism with ATRP control radical polymerization many similarities, because most polymer chain all is slumber at any given time.Initiation produces cationic intermediates, and the latter can produce the polymer chain of growth with other monomer reaction.With what increase competition mutually is the reversible addition of control agent (being Z-), and described control agent usually is the anionic species that original position produces.It is low-level that balance between reactive cationic polymers chain and the slumber chain remains on the concentration of reactive chain, thereby side reaction (for example termination reaction) is minimized.The dominant mechanism feature of control cationoid polymerisation describes in diagram 4.

Diagram 4

As if as the situation in anionoid polymerization, water has serious negative impact to most of positively charged ion chain polymerizations, all can not carry out the positively charged ion chain polymerization in water-bearing media for many years.But, to recent report (Macromolecules such as Satoh, 2001,34,396 of " activity " cationoid polymerisation in aqueous solution and the miniemulsion; Macromolecules, 2000,33,5836; Macromolecules, 2000,33,4660; Macromolecules, 2000,33,5830; Macromolecules, 2000,33,5405) but negated this saying.

Polycoordination

Olefinic polymerization is one of most important commercial catalyzed reaction, and it is usually by the incompatible realization of polycomplexation.Have a lot of methods to cause polycoordination, but all methods finally all produce the intermediate of the covalent linkage between the polymeric chain that alkene can be inserted into control agent and growth.The main chain growth step of the vinyl polymerization that is undertaken by metal catalytic Cossee mechanism describes in diagram 5.The classical mechanism of the polycoordination of this alkene and alkynes was discussed in many books (referring to Chien, Coordination Polymerization (polycoordination), Academic Press:NewYork, 1975), the development in this field is had regular summary.(referring to: Chem.Rev.2000 such as Ittel, 100,1169).

Diagram 5

Except that Cossee mechanism, other several mechanism of polycoordination have also been determined.For example, Rooney-Green mechanism relates to the formation of metal ring butane (metallacyclobutanes) (referring to Turner and Schrock, J.Am.Chem.Soc., 1982,104,2331), and the polycoordination of conjugated diolefine it is believed that by π-allyl complex and undertaken.

Polycoordination can be finished under multiple condition, is included in the aqueous emulsion and is helping under the situation of controlled polymerization.The control polycoordination of alkene described in the article that deliver in the recent period (Macromolecules 2003,36,3085) such as Coates etc. (Angew.Chem., Int.Ed.2002,41,2236) and Gottfried.Chen Yichun (Organometallics 2001,20, reference in 1285-1286 and the literary composition) such as (transliteration) has described the control copolymerization of alpha-olefin and carbon monoxide.(Angew.Chem.Int.Ed.Engl.2002,41,545 such as Bauers; Macromolecules2003,36,6711) and (Prog.Polym.Sci.2003,28,619) article of delivering in the recent period such as Claverie summarized the progress in moisture polycoordination field.

Ring-opening metathesis polymerization (ROMP)

Olefin metathesis is the universal method of exchange alkylidene group between the different alkene.Described permutoid reaction is (to be M=CR by multiple metal alkylidene complex ₂) carry out catalyticly, its mechanism is set up fully.When olefin metathesis is applied to ring-type strain (strained) alkene, the open loop and the controlling polymers chainpropagation of " activity " polymeric feature that it can cause occurring having tradition.The generally acknowledged mechanism of ROMP describes in diagram 6.

Diagram 6

The ROMP control agent is a metal alkylidene group catalyzer, and it can directly add in the monomer, or produces from containing metal pre-catalyst original position.When using preformed metal alkylidene group catalyzer (M=CR for example ₂) time, ROMP can spontaneous initiation.But when not using preformed catalyzer, active catalyst must come original position to produce by containing metal pre-catalyst and suitable initiator for reaction.

The most general ROMP catalyzer is based on VIII group 4 transition metal alkylidene complex, and described complex compound is by exploitations (PCT International Application No. WO 0279127, PCT International Application No. WO 0220535, PCT International Application No. WO 0058322, PCT International Application No. WO 0056785, PCT International Application No. WO 9922865, PCT International Application No. WO 9842665, PCT International Application No. WO 9842665, PCT International Application No. WO 9821214, PCT International Application No. WO 9842665, PCT International Application No. WO 9706185, PCT International Application No. WO 9604289) such as Grubbs.The existing regularly detailed summary of the state-of-art of ROMP (referring to Claverie, Prog Polym.Sci.2003,28,619; Grubbs etc., Acc.Chem.Res.2001,34,18).The effort of also splitting hair-cream liquid ROMP system in relevant document is described (referring to Lynn etc., J.Am.Chem.Soc.2000,122,6601; Love etc., J.Am.Chem.Soc.2003,125,10103; Trnka etc., J.Am.Chem.Soc.2003,125,2546; Choi etc., Angew.Chem.Int.Ed.Engl.2003,42,1743).

Acyclic dienes metathesis polymerization (ADMET)

ADMET has a lot of similarities with ROMP on mechanism, and many ROMP catalyzer also can be used for ADMET.As ROMP, causing ADMET polymeric chemical reaction is the catalytic olefin metathesis of metal alkylidene group.But different with the ROMP of the chain polymerization that relates to cyclic monomer is that ADMET takes place by the monomeric progressively polymerization of linearity.The dominant mechanism feature of ADMET describes in diagram 7.

Diagram 7

Usually, the ADMET polymerization does not have ROMP so attractive, because monomer of every consumption just produces the little alkene (for example ethene) of a molecule.This of ADMET on the one hand and other aspects discussion (referring to Courchay etc., Macromolecules 2003,36,8231 and reference wherein) is arranged in recent publication.

Organic tellurium mediation active free radical polymerization (TERP)

TERP is the new class control radical polymerization that occurs in the recent period.This system is showing some unique feature aspect versatility, molecular weight controllability, functional group's compatibility and the polymer terminal group conversion easiness.Control with ATRP, NMP and RAFT that free radical system is different to be, TERP can be undertaken by two competitive approach: thermal dissociation (TD) and degradation chain transfer (DT).

Yamago etc. have described the general mechanism and the application of TERP system in a series of articles.(L.Am.Chem.Soc.2002,124,2874; J.Am.Chem.Soc.2002,124,13666; J.Am.Chem.Soc.2003,125,8720; And Macromolecules 2003,36,3793).

Control agent

Controlled polymerization needs energy controlled polymerization process, can reduce the reagent existence of unwanted side reaction (as end stopping of chain) simultaneously again as far as possible.These reagent are called " control agent ", and their feature greatly depends on polymeric each side details, comprise polymerization mechanism, used monomeric type, cause type, solvent system and reaction conditions.The control agent of number of different types is studied.These control agents are the materials that can keep the running balance between reactivity (activity) polymer chain and the slumber chain.In some embodiments of the present invention, described control agent can be the polymerization process that is used to follow free radical mechanism, as ATRP, NMP, DT, RAFT, or is used to relate to the control agent of the polymerization process of stabilized radical mechanism.In other embodiments, described control agent can be the polymerization process that is used to follow ionic mechanism, as the control agent of positively charged ion or anionic polymerisation process.For ROMP or ADMET controlled polymerization, control agent is an olefin metathesis catalyst.In the situation of control polycoordination, control agent is to come the catalysis chainpropagation by monomeric insertion in the coordination sphere of control agent.

Control agent can be incorporated in the emulsion system by multiple different methods, and preferable methods greatly depends on practiced specific embodiments.In some embodiments, the form that activity control agent can pure compound or directly join in the reaction vessel as the component of solution or mixture.In other embodiments, activity control agent can by occur in before the emulsification, chemical reaction original position central or afterwards produces.

No matter how to introduce or to produce control agent, being fit to control agent of the present invention can provide one or more and the relevant benefit of " activity " polymerization kinetics.These benefits comprise: (1) polymerization degree is as the linear dependence of the function of time; (2) number-average molecular weight (M _n) with the linear dependence of extent of polymerization; (3) polymer molecule that does not obviously rely on transformation efficiency and the active centre of constant number; (4) range of molecular weight distributions is narrow, M _w/ M _nUsually less than 4, preferably between 1.1 and 2.0, often be lower than 1.5; (5) monomer is converted into polymkeric substance basically fully, can proceed polymerization again when adding more monomer; (6) have by adding monomer according to the order of sequence and prepare the ability of segmented copolymer; And/or (7) have the ability of producing the chain end functionalized polymeric with high yield.

Initiator

All polyreactions must cause.For some monomer such as vinylbenzene, reagent that need not be other heat can occur from causing.For many other monomers, initiation will trigger one or more final generations by interpolation reagent can make the chemical reaction of the intermediate of polymerization growth realize.These reagent are commonly called " initiator ".

The type that is fit to initiator of the present invention greatly depends on polymeric each side details, comprises polymerization mechanism, used monomeric type, control agent type, solvent system and reaction conditions.The initiator of number of different types is studied.

In some embodiments of the present invention, described initiator can be the polymerization process that is used to follow free radical mechanism, as ATRP, NMP, DT, RAFT, or is used to relate to the initiator of the polymerization process of stabilized radical mechanism.Usually, suitable radical polymerization initiator is the reagent or the agent combination that can produce free radical.Produce the additive method of free radical, comprise being exposed to ionizing rays (electron beam, X-radiation, gamma-rays radiation etc.), photochemical reaction and sonication, it is apparent to those skilled in the art as the appropriate method that causes radical polymerization.

In some embodiments, described initiator can be the polymerization process that is used to follow ionic mechanism, as the initiator of positively charged ion or anionic polymerisation process.For ROMP or ADMET controlled polymerization, initiator can be the reagent that produces the metal alkylidene group catalyzer of catalyzed alkene transposition.In the situation of control polycoordination, the common and containing metal pre-catalyst reaction generation active catalyst of initiator, described active catalyst comes the catalysis chainpropagation by insert monomer in the coordination sphere of metal.

In some embodiments of the present invention, initiator can be the compound that also can be used as the control agent source.For example in the situation of NMP, initiator can be the initiator shown in the formula I-control agent adducts:

Formula I

R wherein ¹And R ²Independently be selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, assorted alkyl, Heterocyclylalkyl, substituted heterocycle alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl and combination thereof; Optional R ¹And R ²In ring structure, link together.In context, Y is atom or one group of atom that can cause radical polymerization when Y-O key homolysis.Suitable Y group comprises for example alkyl, substituted alkyl, alkoxyl group, substituted alkoxy, cycloalkyl, substituted cycloalkyl, assorted alkyl, Heterocyclylalkyl, substituted heterocycle alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl substituting group.When initiator was formula I compound, control agent can be regulated by add extra free radical or control agent from other sources (comprising other chemical reactions) with the ratio of initiator.

In some embodiments of the present invention, initiation can and realize for polymerization process provides the chemical reaction of the pre-catalyst of control agent by monomer.For example in the situation of polycoordination, preformed metal alkyl and metal hydride complex compound are once contact initiated polymerization immediately with monomer.In the situation of ROMP or ADMET, when for example control agent is introduced with the form of the active catalyst of olefin metathesis, also spontaneous initiated polymerization can appear.

Initiator can be introduced in the emulsion system by multiple diverse ways, and preferable methods greatly depends on practiced specific embodiments.In some embodiments, initiator can be present in water or the organic phase before emulsification.In other embodiments, initiator can join in the reaction vessel after emulsification, or initiator can be before the emulsion process, one or more chemical reaction original positions central or that occur afterwards produce.In some embodiments, initiator can add in the different time in polymerization process at twice or repeatedly.Polymeric causes can be before the emulsification program, central or take place afterwards.

Macromole evocating agent and macromole control agent

The present invention is widely used in the controlled polymerization in the aqueous emulsion.In some embodiments, preferred only from low molecular weight compositions production polymkeric substance.For example the styrene polymerization that is undertaken by NMP can be lower than 400 one-tenth with formula weight and assigns to realize.In other embodiments, initiator, control agent or both can be derived from the mixtures of compound with higher amount or compound.Term " macromole evocating agent " has the initiator of higher formula weight in this article in order to description, term " macromole control agent " has the control agent of higher formula weight in this article in order to description.

Much be suitable as existing description of art methods of the compound or the material of macromole evocating agent of the present invention or macromole control agent in order to preparation.Described known method for example comprises: (i) initiator or control agent functional group are grafted on the preformed polymkeric substance; (ii) stoichiometry ground can cause or the reagent of the end group of controlled polymerization stops solution polymerization by another mechanism with introducing; (iii) " activity " polymkeric substance of solution synthesizing stable or oligopolymer are used as " seed " of other controlled polymerization methods subsequently.Produce these methods of multipolymer and additive method by Davis and Matyjaszewski (Adv.Polym.Sci.2002 by controlled polymerization, 159,1-168) (for radical polymerization) and Grubbs (Aq.Phase Organometal.Catal.1998,466-76 page or leaf) (for ROMP) summarize.

The surface modified granules that contains the polymerization starter of chemisorption or control agent also is suitable as macromole evocating agent and the macromole control agent is used for the present invention, and condition is that described particle can not disturb emulsion process.Functions of use silicon-dioxide and goldc grains cause controlled polymerization from the surface be known.Other embodiments it will be apparent to those skilled in the art that.

Promotor, inhibitor and other additives

Term " promotor " in order to describe such material in general sense, when it adds in the polymerization system when relatively small amount ground, can be given higher activity, improved selectivity or better stable in this article.Term " inhibitor " in order to describe such material in general sense, when it adds in the polymerization system when relatively small amount ground, can cause active the attenuating in this article.For particular of the present invention, adding optional promotor or inhibitor can provide actual benefit, for example comprises that control better causes, more favourable reaction times, catalyst life prolongs and selectivity improves.Add other optional, materials, comprise for example buffer composition, cosurfactant and frostproofer, further benefit can be provided.

For example in NMP polymeric situation, a spot of some acid can be accelerated rate of polymerization (referring to Hawker etc., Tetrahedron 1997,53,15225) significantly.These acid are the promotors of NMP with relevant acid.Also known acid can promote ROMP (referring to J.Am.Chem.Soc.2000 such as Grubbs, 122,6601).In the situation of polycoordination and ROMP, the part of adding can by competition on the control agent the coordination position or by the stable state concentration that reduces the unsaturated intermediate of coordination rate of rise is relaxed (referring to Acc.Chem.Res.2001 such as Grubbs, 34,18; Chien, Coordination Polymerization, Academic Press, NY, 1975).

Monomer

Can use the inventive method to carry out polymeric monomer (and the material that can derive monomer M) and comprise that at least one is selected from following monomer: vinylbenzene, substituted phenylethylene, alkyl acrylate, the substitutional crylic acid alkyl ester, alkyl methacrylate, the substituent methyl alkyl acrylate, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, the N-alkyl acrylamide, N-alkyl methyl acrylamide, N, N-dialkyl group acrylamide, N, N-dialkyl methyl acrylamide, isoprene, 1,3-butadiene, ethene, vinyl acetate, vinylchlorid, vinylidene chloride, oxygenant, lactone, lactan, cyclic anhydride, cyclosiloxane and combination thereof.Also can use these monomeric functionalized form.Can be used for the present invention and concrete monomer or the comonomer of the M that can therefrom derive comprise methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate (all isomer), butyl methacrylate (all isomer), methacrylic acid 2-ethylhexyl, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methyl styrene, methyl acrylate, ethyl propenoate, propyl acrylate (all isomer), butyl acrylate (all isomer), 2-EHA, isobornyl acrylate, vinylformic acid, benzyl acrylate, phenyl acrylate, vinyl cyanide, vinylbenzene, glycidyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, Rocryl 410 (all isomer), methacrylic acid hydroxy butyl ester (all isomer), methacrylic acid N, the N-dimethylaminoethyl, methacrylic acid N, the N-lignocaine ethyl ester, the methacrylic acid triethyleneglycol ester, itaconic anhydride, methylene-succinic acid, glycidyl acrylate, vinylformic acid 2-hydroxyl ethyl ester, Propylene glycol monoacrylate (all isomer), vinylformic acid hydroxy butyl ester (all isomer), vinylformic acid N, the N-dimethylaminoethyl, vinylformic acid N, the N-lignocaine ethyl ester, the vinylformic acid triethyleneglycol ester, Methacrylamide, N methacrylamide, N,N-DMAA, N-tertiary butyl Methacrylamide, N-normal-butyl Methacrylamide, the N-methylol methacrylamide, the N-hydroxyethyl methacrylamide, N tert butyl acrylamide, N-normal-butyl acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl benzoic acid (all isomer), diethylin vinylbenzene (all isomer), Alpha-Methyl vinyl benzoic acid (all isomer), diethylin alpha-methyl styrene (all isomer), right-vinylbenzenesulfonic acid, right-the vinylbenzenesulfonic acid sodium salt, methacrylic acid trimethoxysilyl propyl ester, methacrylic acid triethoxysilyl propyl ester, methacrylic acid three butoxy silyl propyl ester, dimethylaminoethyl acrylate methyl oxygen ylmethyl silyl propyl ester, methacrylic acid diethoxymethyl silyl propyl ester, methacrylic acid dibutoxy methyl-silicane base propyl ester, methacrylic acid diisopropoxy methyl-silicane base propyl ester, dimethylaminoethyl acrylate methyl oxygen base silyl propyl ester, methacrylic acid diethoxy silyl propyl ester, methacrylic acid dibutoxy silyl propyl ester, methacrylic acid diisopropoxy silyl propyl ester, vinylformic acid trimethoxysilyl propyl ester, vinylformic acid triethoxysilyl propyl ester, vinylformic acid three butoxy silyl propyl ester, vinylformic acid dimethoxy-methyl silyl propyl ester, vinylformic acid diethoxymethyl silyl propyl ester, vinylformic acid dibutoxy methyl-silicane base propyl ester, vinylformic acid diisopropoxy methyl-silicane base propyl ester, vinylformic acid dimethoxy silyl propyl ester, vinylformic acid diethoxy silyl propyl ester, vinylformic acid dibutoxy silyl propyl ester, vinylformic acid diisopropoxy silyl propyl ester, maleic anhydride, N-phenylmaleimide, the N-butyl maleimide, chloroprene, ethene, vinyl acetate, vinylchlorid, vinylidene chloride, 2-methyl-2-vinylformic acid 2-(2-oxo-1-imidazolidyl) ethyl ester, 1-[2-[2-hydroxyl-3-(2-propyl group) propyl group] amino] ethyl]-the 2-imidazolidone, the N-vinyl pyrrolidone, the N-vinyl imidazole, Ba Dousuan, vinyl sulfonic acid and combination thereof.

Some can be used for ROMP polymeric representative monomers and comprise norbornylene, norbornadiene, cyclopentenes, Dicyclopentadiene (DCPD), suberene, cyclooctene, 7-oxa-norbornylene, 7-oxa-norbornadiene and ring dodecylene.Can be used for the normally non-conjugated α of ADMET polymeric monomer, ω-diene, as 1, the 9-decadiene.Non-conjugated α like this, ω-diene contain 5 usually to about 20 carbon atoms.

Tensio-active agent, dive tensio-active agent and tensio-active agent activator

Tensio-active agent is absolutely necessary for purposes of the invention, and suitable tensio-active agent comprises can make the stable any compound of colloid aqueous emulsion or the mixture of compound.In general, tensio-active agent is the surface tension that can reduce liquid, or reduces between two kinds of liquid or the amphipathic molecule of the interfacial tension between liquid and the solid.Tensio-active agent can be small molecules or polymkeric substance, can form micella or not form micella, can be anionic, cationic, amphoteric ion type or nonionic surface active agent.In some embodiments of the present invention, used surfactant mixtures.The consumption of tensio-active agent with respect to monomer usually between about 200% weight of about 0.01-, more preferably between about 8% weight of about 0.1-, more clearly preferably between about 3% weight of about 0.5-.Those skilled in the art will consider multiple factor usually when being application-specific purpose option table surface-active agent, comprise economic factors.

The emulsifying agent of McCutcheon and sanitising agent handbook (Emulsifiers ﹠amp; DetergentsHandbook, McCutcheon Division, Manufacturing Confectioner PublishingCo, Glen Rock, NJ, 1999) multiple suitable tensio-active agent described.Suitable aniorfic surfactant comprises and replacing or unsubstituted sulfovinate, sulfonate, carboxylate salt, phosphonic acid ester and phosphoric acid ester that its each anionic functional group has 6-30 carbon atom.Suitable cationic surfactant comprises and replacing or unsubstituted alkyl ammonium salt that its each Cationic functional groups has 6-30 carbon atom.Suitable nonionic surface active agent comprises the amphiphilic acid amides, and its each hydrocarbon acyl group has 6-30 carbon atom, and each alkyl amino (hydrocarbyl amine group) has 2-30 carbon atom.For every kind of tensio-active agent, another atom that one or more hydrogen on its alkyl or carbon atom can be selected from N, S, O, Si, F, Cl, Br and I replaces.One or more hydrogen on the described alkyl or carbon atom also can be replaced by the functional group such as ketone, ester, acid amides, ether, thioether, hydroxyl etc., and described alkyl can be the part of ring texture.

In some embodiments, useful tensio-active agent comprises for example an alkali metal salt and the ammonium salt of following material: (i) alkyl-sulphate (alkyl: C ₈-C ₁₈); (ii) alkyl aryl sulfonic acid (alkyl: C ₉-C ₁₈); (iii) alkansulfonic acid (alkyl: C ₈-C ₁₈); (v) alkylamine succsinic acid half amide (alkyl: C ₈-C ₁₈); (v) alkanol succinic acid half-ester (alkyl: C ₈-C ₁₈); (vi) paraffinic acid (alkyl: C ₈-C ₁₈); (vii) alkyl phosphate (alkyl: C ₁-C ₁₈); (viii) phosphonate ester (alkyl: C ₁-C ₁₈); (ix) acidylate sarkosine and taurine (acyl group: C ₈-C ₁₈); (x) sulfosuccinic acid diesters and diamide (alkyl: C ₄-C ₁₈).In other embodiments, useful tensio-active agent for example comprises: (i) alkanolamide (alkyl: C ₂-C ₁₈); (ii) quaternized amine (alkyl: C ₁-C ₁₈), comprise the amine oxide derivative; Quaternized nitrogen heterocyclic ring (the alkyl: C that (iii) has the side alkyl ₄-C ₁₈); (iv) betanin derivative (alkyl: C ₈-C ₁₈); (v) amphiphilic block copolymer.

An importance of the present invention is original position emulsification, and this is by " dive tensio-active agent " and " tensio-active agent activator " reaction being generated be used to the tensio-active agent of controlling letex polymerization to be realized.Term used herein " dive tensio-active agent " refers to the such compound or the mixture of compound: (i) dissolve in can not with the water-soluble mixed monomer solution that contains; (ii) on the tensio-active agent level of routine with the mixture of described compound or compound with contain monomer solution and water simply leniently mixes, can not independently generate stable colloid microemulsion.Term " tensio-active agent activator " is in this article in order to describe the such compound or the mixture of compound: (i) water soluble; (ii) on the tensio-active agent level of routine with the mixture of described compound or compound with contain monomer solution and water simply leniently mixes, can not independently generate stable colloid microemulsion.For the present invention, water can be the reactant of original position emulsion reaction, but water can not be separately the tensio-active agent activator.Under any circumstance, emulsifying agent all is by making " tensio-active agent of diving " and " tensio-active agent activator " (original position in the aqueous polymerization medium) reaction in water-bearing media come synthetic.

Prokopov and Gritskova (Russ.Chem.Rev.2001,70,791) ultimate principle of original position microemulsified has been described, summarized the purposes of original position microemulsified in cinnamic conventional radical polymerization, described vinylbenzene radical polymerization is used by in the lipid acid and the alkali metal soap of in-situ preparing.Explain as Prokopov and Gritskova, in the emulsion process on vinylbenzene-water termination the preparation of carboxylic soap can generate tiny microemulsion because a large amount of emulsifying agents that interfacial tension has been generated on the interface reduce greatly.By changing the carboxylic acid that in interface upper surface promoting agent synthetic, uses and the character of metal gegenion, might control the dispersity and the stability of emulsion and the polystyrene latex by the conventional radical polymerization generation.In the present invention, the principle of original position microemulsified is expanded greatly, adopts conventional soap level, need not add hydrophobic materials or not want special emulsifying device, just can produce the emulsion that is applicable to the controlled polymerization that is undertaken by several different methods.

In some embodiments, the tensio-active agent that is used for controlled polymerization can be produced by the acid on the monomers/water interface/alkali neutralization reaction.For the aniorfic surfactant of some type, this can be for example reaction by monomeric acid of solubilized and alkali aqueous solution realize that the monomeric acid of wherein said solubilized is the tensio-active agent of diving, described alkali is for being used for original position emulsive tensio-active agent activator.The monomeric acid of suitable solubilized comprises for example palmitinic acid, oleic acid, Witco 1298 Soft Acid, dodecyl sulfate, hexadecyl sulfonic acid, double hexadecyl phosphonic acids, hexadecyl succinic acid half-ester and mono succinate hexadecyl acid amides.Suitable alkali comprises for example oxyhydroxide, carbonate and the supercarbonate of alkalimetal ion and quaternary ammonium ion; Replace and unsubstituted amine and alkaline nitrogen heterocyclic ring.Its pK _bPK less than about solvable monomeric acid _aAny alkali aqueous solution also be fit to use, this is apparent to those skilled in the art.It is evident that equally, the oxyhydroxide that original positions such as the compound of moisture-sensitive such as sodium methylate, sodium amide, potassium hydride KH produce also is suitable as the tensio-active agent activator by hydrolysis.

Cats product for some types, synthetic can for example the reaction by monomeric alkali of solubilized and aqueous acids of its original position in emulsion process realized, the monomeric alkali of wherein said solubilized is the tensio-active agent of diving, and described acid is the tensio-active agent activator.The monomeric alkali of solubilized that is fit to comprises for example hexadecyl dimethylamine, cetyl dimethyl amine oxide and amphiphilic nitrogen heterocyclic ring.Suitable acid comprises for example mineral acid, sulfonic acid and phosphonic acids.Its pK _bPK less than about monomeric alkali of solubilized _aAny aqueous acid also be fit to use, this is apparent to those skilled in the art.It is evident that equally, the acid that original positions such as the compound of moisture-sensitive such as Lewis acid, carboxylic acid halides, acid anhydrides, inorganic acid anhydrides, hydrolyzable transition metal halide, main group halogenide produce also is suitable as the tensio-active agent activator by hydrolysis.

In some embodiments, tensio-active agent can produce by the chemical reaction original position that hydrophilic functional groups can be connected to functionalized hydrophobic materials.For these embodiments, functionalized hydrophobic materials is the tensio-active agent of diving, and connects one or more required reagent of hydrophilic functional groups as the tensio-active agent activator.For the tensio-active agent of some type, this can for example react by the monomeric electrophile and moisture nucleophile of solubilized realizes.Suitable electrophile for example comprising: (i) hydrocarbon acyl halide; (ii) hydrocarbon acyl ester; (iii) hydrocarbon acyl anhydrides; (iv) alkyl isocyanic ester; (v) alkyl halogen; (the vi) hydrocarbyl carbonate of sulfonic acid.Suitable tensio-active agent activator for example comprises: (i) amine-functionalized sulfovinate, hydrocarbon carboxylic acids salt, alkyl phosphate, alkyl ammonium salt; (ii) diethanolamine; (iii) diethylenetriamine and other amino amine; (iv) amino polyoxyethylene glycol and polyglycol ether; (v) aminoglycoside; (vi) amido betaine; (the vii) oxyhydroxide of alkalimetal ion and quaternary ammonium ion; (viii) alkylamine.

For the tensio-active agent of some type, original position is synthetic can be realized by monomeric nucleophile of solubilized and moisture electrophile reaction with emulsification.Suitable nucleophile comprises for example cetylamine and hexadecyl dimethylamine.Suitable electrophile for example succinyl oxide, methyl-sulfate and 1, the 3-N-morpholinopropanesulfonic acid lactone of comprising.

Many other reactions can be used for the original position synthetic surfactant, and the specific embodiments of more than giving an example does not have a mind to get rid of any latent surfactant/surfactant activator combination that can produce tensio-active agent in emulsion process.It will be apparent for a person skilled in the art that when synthetic chemical process with controlled polymerization when tensio-active agent is compatible that other latent surfactant/surfactant activator combinations also are suitable.

Polymerization system

Polymerization system of the present invention is the combination or the mixture of various compositions, and described composition comprises water, tensio-active agent, control agent and at least a monomer.In polymerization system, add initiator and choose wantonly, but this is normally preferred concerning embodiment of the present invention.Tensio-active agent original position in emulsion process is synthetic, and normally dive tensio-active agent and at least a monomeric solution and tensio-active agent activator aqueous solution finish together by containing for this.Control agent, initiator, promotor and inhibitor can be present in one of above-mentioned two kinds of solution or both before mixing, perhaps they can original position produce in emulsion process, perhaps can add after emulsification.Polymerization system takes place under the polymerizing condition of realizing at least a monomer polymerization.For random copolymers or high order (high order) interpolymer, can simultaneously two or more monomers be added in the polymerization system.For segmented copolymer, monomer on demand order usually adds, so that make the block growth that needs.For emulsion polymerization systems, polymerization system can be thought to stand the material composition that polymerizing condition is handled.The product of such polymerization system is an emulsion itself, is perhaps separating or dried polymkeric substance.

The ratio of each composition in the polymerization system (for example initiator, tensio-active agent, monomer, control agent etc.) is very important, depends on practiced particular, and described ratio can be greatly for a change.Monomer can be used to definite molecular weight of controlling the polymkeric substance of emulsion polymerisation process production with the present invention with the ratio of control agent.According to these polymerization processs, the number-average molecular weight of resulting polymers depends on the number and the monomeric quality of polymer chain linearly.Suppose that each growing chain contains a residue derived from control agent, can offer an opportunity for the molecular weight of controlling polymers (or polymerization degree) in advance the selection of monomer and the ratio of control agent.But as a rule, between actual molecular weight and the predicted molecular weight relative constant percentage difference is arranged, when the product of preparation desired molecule amount, this difference will be taken into account.In typical embodiment, the ratio of monomer and control agent can be at about 10: 1 to about 10,000: in 1 the scope, more preferably at about 50: 1 to about 10,000: in 1 the scope, most preferably at about 100: 1 to about 5000: 1 scope.

Another important ratio is an initiator and the ratio of control agent equivalent.For many controlled polymerization, comprise for example ROMP, NMP, positively charged ion and anionoid polymerization, the number of the polymeric chain that is caused should equal the number of control agent molecule in principle.For the controlled polymerization of following transfer mechanism, comprise for example RAFT, DT and ATRP, only need the initiator of catalytic amount to realize transforming fully in principle.In practice, the efficient of initiator change is very big, needs to adjust the result of ratio need to obtain of initiator and control agent usually.

The ratio of may command tensio-active agent and monomer, this ratio usually about 0.0001: 1 to about 2: 1 scope, more preferably 0.001: 1 to about 0.2: 1 scope, most preferably at about 0.01: 1 to about 0.1: 1 scope.In case emulsion is formed by the in-situ surface promoting agent is synthetic, tensio-active agent can further be adjusted by adding other tensio-active agent with the ratio of monomer.Described other tensio-active agent can be identical tensio-active agent, or needs not to be the different tensio-active agent of original position synthetic.

The solid per-cent of emulsion about 0.01% to the scope of about 95% weight.In some preferred practical application, generating solids content is 40% weight or higher emulsion.The useful solids content that is applicable to other purposes is about 0.5% to about 40% weight.The polymeric water consumption is selected according to the required solids content of aqueous polymer emulsions to be prepared.

Polymerizing condition comprises general known other conditions of composition ratio, system temperature, pressure, atmosphere (atmosphere) type, reaction times and those skilled in the art.Polymerization temperature can be approximately between-40 ℃ to 250 ℃.For many embodiments, polymerization temperature can be between about 0 ℃ to about 200 ℃, more preferably between about 25 ℃ to about 150 ℃, most preferably between about 40 ℃ to about 110 ℃.In other embodiment preferred, the temperature of polymerization system is controlled at and is lower than about 100 ℃, more preferably less than about 90 ℃, even more preferably less than about 80 ℃, is lower than concerning some embodiment or is about 70 ℃.Polymerizing condition also is included in about environmental stress to the pressure that reaches as high as between about 200 normal atmosphere.Atmosphere type above the emulsion also can be one of polymerizing condition, and described atmosphere can be air, nitrogen, argon gas or other suitable atmosphere.Polymerizing condition also comprises the reaction times, and it can be between about 0.5 hour to about 72 hours, preferably about 1 hour to about 24 hours scope, more preferably at about 2 hours to about 12 hours scope.

Emulsion system

On wide significance, letex polymerization is any multi-phase polymerization process under the aqueous conditions.Usually, the product of these polymerization systems is polymer beads.Those skilled in the art can discern the many multi-form of these polymerization processs, are divided into polymerization, the polymerization in the microemulsion, the polymerization in the miniemulsion, the polymerization in the suspension and the polymerization in the dispersion liquid in the genuine milk liquid usually.These different methods are normally distinguished according to method, composition or result's difference, and concrete Consideration comprises whether the tensio-active agent of needs exists, amount and type; Whether initiator exists, amount and type; Monomeric type and amount comprise the monomer solvability; Polymerization kinetics; Temperature; The interpolation of each composition comprises the joining day of each composition (for example monomer) in proper order; The solvability of polymerisate; Stirring condition; Whether cosolvent and hydrophobic materials exist; The particulate size that generates; In the polymerization system particle solidify or precipitation aspect stability; And well known to a person skilled in the art other factors.

System of the present invention may be not exclusively in the scope of the common employed any traditional definition (for example comparison of genuine milk liquid and microemulsion) of those skilled in the art.These systems of the present invention may have the peculiar character of system of one or more traditional classifications simultaneously again between traditional definition.Therefore, can think that polymerization process of the present invention included conventional emulsion (or genuine milk liquid) polymerization, microemulsion and mini-emulsion polymerization and suspension and dispersion liquid polymerization.The feature that can be used to distinguish these heterophase polymerization systems is listed in following table 2.

Table 2

Character	Conventional emulsion	Miniemulsion	Microemulsion	Suspension	Dispersion liquid
						The polymerization place	Particle	Drop	Particle	Drop	Water
Monomer distribution	Drop/particle	Drop	Particle	Drop	Drop/water
						Distribution of polymer	Particle	Drop	Particle	Drop	Particle
Monomeric water-soluble	In paramount	In being low to moderate	In	In being low to moderate	High
						The importance that stirs	In to low	High (during beginning)	Low	High	High
Typical gained granular size (nm)	10-200	50-500	10-100	500-5000	500-5000
						The exemplary particles size distribution	Narrow	Extensively	Narrow	Extensively	Extensively
The ratio of exemplary surfactants and amount of monomer	0-5％	0.1-10％	～100％	0-5％	0-5％
						Thermodynamic stability before the polymerization	Unstable	Unstable	Stable	Unstable	Unstable
Typical maximum solids content	50％	20％	＜10％	40-50％	40-50％

Some is subjective the setting in these scopes, and its extremum only obtains usually under special circumstances.Term such as low, neutralization is high is a subjective determination, is intended to explanation and well known to a person skilled in the art classificatory difference.Each method of the present invention is distinguished as discussed herein like that.

A concrete preferred embodiment of the present invention is the control heterophase polymerization reaction in the emulsion, it is characterized in that granular size in the scope of 10-150nm (hydrodynamic radius), preferably in the scope of 15-100nm or in the scope of 20-70nm.The polymerization technique parameter of this embodiment is similar to " tradition " discussed above or " very " emulsion polymerisation process.These emulsions are stable (not observing coalescent or deposited phenomenon in a plurality of months greatly), but it prepares 2% weight of the amount of used tensio-active agent less than amount of monomer.The characteristics of these emulsions are particle size dispersion evenly (ununiformity of polymer beads radius distribution---as the root-mean-square deviation of average polymer particle radius less than about 50%).

The control granular size is as the feature of the controlled polymerization emulsion of some embodiments of the present invention, for many practical applications provide multiple benefit.The active character of polymerization process of the present invention provides new means for the granular size and the distribution of polymer emulsion that control becomes.It is normally highly stable to have more short grained emulsion, and has useful processed edge, as reaction kinetics faster with have more the preparation of scalability and reproducibility.Such emulsion has useful optical property (as low turbidity), high viscosity, bigger surface-area, more even or the thinner film of the coalescent formation of energy, all these characteristics will be very favourable in typical practical application such as tackiness agent, dispersion agent, coating and separating medium.In other embodiments at different practical applications, may need bigger particle, it can use inhomogeneous moisture free radical polymerisation process of the present invention to obtain.

The required character of macrobead emulsion comprises the isolating accessibility of opacity, low viscosity and polymkeric substance.Having emulsion even or wide particle size dispersion can obtain from the inventive method, and it has the various advantages that well known to a person skilled in the art the particle size dispersion aspect.For example, wider particle size dispersion can derive from correct selective polymerization condition, maybe can mix by the particle with narrower size distribution that will obtain from several different polymerization processs to obtain.

Unless otherwise, otherwise heterogeneity index or PDI refer to the intermediate value ratio that distributes, or more specifically, for the situation of molecular weight determination, heterogeneity index known in this field be M _w/ M _n, M wherein _wBe the weight-average molecular weight of polymer samples, M _nIt is the number-average molecular weight of polymer samples.PDI value in this specification sheets is 1.0 or higher, the sample of the relative monodispersity of value representation near 1.0.

Under the emulsion condition, use the nitroxide control agent that other benefits (for example the linear growth of molecular weight be the function of transformation efficiency) relevant with active kinetics are provided.Control free-radical emulsion polymerization of the present invention provide to molecular weight especially high molecular (high to＞50,000, or even＞100,000) height control, and the narrower (polymolecularity (M of molecular weight distribution usually _w/ M _n) generally be lower than 4, preferably between 1.1 and 2.0, also can be lower than 1.5).

Although, the amount that depends on monomer and tensio-active agent, the typical granular size of non-control free-radical emulsion polymerization is in about scope of 50 to about 200nm, but show that polymerization process of the present invention can provide has the more emulsion of small particle size under similar tensio-active agent and monomer concentration condition.For example, the particle radius of cinnamic non-control letex polymerization (1% tensio-active agent, 20% solid, target Mw are 100,000) generation is in about scope of 50 to about 75nm.In contrast, emulsion polymerisation process of the present invention can easily be produced the emulsion polymer that granular size is lower than 40nm.

In emulsion polymerisation process of the present invention, combine with the control agent and the water of group (radical) form, tensio-active agent, initiator (or initiating radical), at least a monomer and optional promotor and/or with reagent that control agent reacts under polymerizing condition.The letex polymerization condition comprises the condition of above discussion, but most preferably is being lower than under about 95 ℃ temperature.

Polymkeric substance (comprising segmented copolymer)

Can implement the inventive method to produce new polymkeric substance.In a preferred embodiment, " activity " oligopolymer of the present invention or polymkeric substance can be described with formula 1:

(formula 1)

Wherein Q is the residue derived from the material of initiated polymerization; M is one or more monomers (as above discussing); CA is the residue that controlled polymerization is increased derived from control agent; N is the integer greater than 1, is preferably greater than 10, more preferably greater than 100.For the embodiment of using multifunctional initiator, polymkeric substance can be described with formula 2, and wherein m1 represents the number of the polymer chain that each multifunctional initiator causes.For the embodiment of using multifunctional control agent, polymkeric substance can be described with formula 3, and wherein m2 represents to be connected to the number derived from the polymer chain of the residue of control agent.

Formula 2 formulas 3

For using the embodiment that can produce crosslinked monomer (Dicyclopentadiene (DCPD) under divinyl under for example radical polymerization situation and Vinylstyrene or the ROMP situation) in the controlled polymerization process, formula 1-3 can be used to describe the single polymer molecule in the cross-linked polymer.

The described polymkeric substance of formula 1-3 has shown the residue derived from control agent that is connected to polymkeric substance.These residues can be removed or modification with the method for well known to a person skilled in the art.The available concrete grammar depends on the type derived from the residue of control agent, for example can comprise from the polymkeric substance residue that dissociates.

" activity " character of polymerization process of the present invention makes those skilled in the art can create the almost required polymer architecture of any kind, and optional majority kind monomer.Therefore, the present invention includes segmented copolymer derived from two or more monomeric control copolymerizations.Some such segmented copolymers are in following examples illustrated.Though some may prepare by additive method in the segmented copolymer of these types, the invention provides the control synthetic method in emulsion, described method has the kinetics of active type, can cause occurring new character.New property comprises higher molecular weight (M for example _wBe higher than 50,000), to the better control of granular size, the lower required tensio-active agent level of latex.The molecular weight of polymkeric substance (or following discussion for block of realize assembling molecular weight) can be 2,000 and higher, preferred 50,000 and higher, more preferably 100,000 and higher.Can derive other character from these character, this elsewhere at this specification sheets has discussion.For some practical applications, polymkeric substance can use in its heterogeneous preparation medium, and in other practical applications, polymkeric substance can be separated from emulsion.Depend on concrete practical application, polymkeric substance can separate with multiple known technology, comprises the chemical modification of for example coating, drying, spraying drying, coalescent (with salt, solvent, thermal cycling, shearing etc.), solvent extraction, polymkeric substance etc.

For specific practical application, no matter whether in emulsion, properties-correcting agent, stablizer or other additives can be added in the polymkeric substance, this is known for a person skilled in the art.

Term used herein " segmented copolymer " refers to comprise at least two different segmental polymkeric substance of forming; It has multiple different structure any, and monomer wherein is not so that statistical way or non-control mode are attached in the polymer architecture completely.Though can have three kinds, four kinds or multiple monomer in single block type polymer structure, described polymer architecture still is called segmented copolymer in this article.In some embodiments, segmented copolymer has A-B structure (" A " and " B " represents monomer).Other structures that are included within the definition of segmented copolymer comprise A-B-A, A-B-A-B, A-B-C, A-B-C-A, A-B-C-A-B, A-B-C-B, A-B-A-C (" C " represents the third monomer), and conspicuous for a person skilled in the art other combinations.

In another embodiment, segmented copolymer of the present invention comprises the block of one or more random copolymerss and the block of one or more single monomer.Therefore, this paper comprises polymer architectures such as A-R, R-R ', A-R-B, A-B-R, A-R-B-R-C, and wherein R is the random block of monomer A and B or is the random block of monomers B and C.In addition, with respect to whole segmented copolymer, random block can change aspect composition or the content to some extent.For example in some embodiments, random block R accounts for the 5-80% of segmented copolymer weight.In other embodiments, depend on concrete practical application, it is more or less that random block R accounts for the ratio of segmented copolymer weight.

In addition, in the random block a kind of monomer to another monomer (as A: B) composition gradient is arranged, described gradient changes along random block with certain algorithmic approach, and such algorithm can be the linear algorithm with slope of needs, index (as the numeral of 0.1-5) exponentiation algorithm or the Logarithmic Algorithm with needs.Random block can be subjected to being present in the domination of the same kinetic effect (as forming drift (drift)) of any other corresponding non-control copolymerization, and it is formed and big I is subjected to the effect of kinetics such as Markov.The listed any monomer of this specification sheets elsewhere all can be used in the segmented copolymer of the present invention.

" block " in the scope of segmented copolymer of the present invention comprises the monomer (as described above, random block recently defines according to its composition and/or weight percent) of about 10 or more single type usually.In preferred embodiments, monomeric number can be about 15 or more in the single block, and about 20 or more, or about 50 or more.But in another selectable embodiment, segmented copolymer of the present invention comprises such block, and described block is by being defined at the elsewhere of multipolymer non-existent both or multiple monomer.This definition is had a mind to forgive in the one or both ends of the polymkeric substance of homopolymerization basically and is added a spot of second kind of this layer of monomer meaning.Can select in the embodiment this another, same copolymer structure discussed above also is suitable for.Therefore this definition has a mind to comprise telechelic polymer, described telechelic polymer comprise can with one or more end functional groups of other molecular reactions.Therefore, generally speaking, telechelic polymer is to belong to the present invention to define interior segmented copolymer.Functional group on the one or both ends of telechelic polymer well known to a person skilled in the art functional group, comprises for example oxyhydroxide, aldehyde, carboxylic acid or carboxylicesters, halogen, amine etc., and they have the ability that combines or form key with another molecule.Equally, segmented copolymer of the present invention has a mind to forgive the telechelic polymer that contains bifunctional, the telechelic polymer of allyl capped or ethenyl blocking for example, they are called as macromonomer sometimes, because they have the ability that participates in polyreaction by its functional end-group.

Merge above-mentioned embodiment, for the design segmented copolymer provides special effective means.For example, segmented copolymer can have the structure of F-A-B-F, wherein functional group's (so the F-A-B-F structure can be forgiven F-A-B-F ' structure) that the F representative can be identical or different in single F-A-B-F structure.Other block copolymer structures within the scope of the present invention comprise A-R-B-F and F-A-R-B-F.Other structures will be conspicuous concerning them after those skilled in the art have consulted this specification sheets.Really, although do not want to be limited to any concrete theory, the active character of emulsion of the present invention provides even also can make the ability of these novel block copolymers just.

In one embodiment, segmented copolymer assembles (assembled) by different monomers and monomer mixture are added in the living polymerization in turn.In another embodiment, be that functionalized block (as telechelic oligoner or polymkeric substance) with assembled in advance adds in the active free radical polymerization mixture and produces segmented copolymer.It is desirable to, the growth of each block takes place with high conversion.Transformation efficiency is measured by gravimetry.For each block, typical transformation efficiency can reach 50% to 100%.Medium transformation efficiency can cause occurring having the segmented copolymer of the block of random copolymer that separates two or more homopolymer blocks, and this depends on the relative rate that polymerization and monomer add.Under high conversion, this random block proportion is very little, to such an extent as to it less has influence on the character of polymkeric substance, as be separated, thermal behavior and mechanical modulus.Can have a mind to make full use of this fact, to improve the polymerization time of some practical application, the not obvious again performance characteristic that influences resulting polymers.Segmented copolymer also can be made by grafted monomer, monomer mixture, the oligopolymer with multiple available functional groups or polymkeric substance.

In other embodiments, the preparation of the preparation that segmented copolymer can be by grafting method, telechelic polymer, macromonomer waits and prepares.In these embodiments, at least a polymer segment is derived from activity of the present invention or control method, other segments can be derived from any polymerization process simultaneously, for example comprise control or non-control radical polymerization, condensation polymerization, ionic polymerization, surface modification or grafting, or other additions or growing method progressively.

Heterogeneous (particularly emulsion) condition combines with the polymerization kinetics of active type, and the height control to composition, structure, phase morphology and the microstructure of polymkeric substance produced according to the invention can be provided.Practicable these methods to form new polymkeric substance, except that novel homopolymer, also comprise for example both arms, three arms, gasoline arm (poly-arm), multi-arm, starlike and graft block copolymer.Can also carry out these methods,, comprise the polymer network and the polymer modification surface of nanoscale to form multiple crosslinking polymer network, interpenetrating polymer networks and polymer modification surface.

Segmented copolymer makes and possible various polymer property (for example hard/soft and/or hydrophilic/hydrophobic (amphiphilic) block) can be attached in the middle of the single polymer chain.Firmly/soft block copolymers will have visibly different second-order transition temperature (T _g) segment combine.Firmly typical/soft multipolymer makes relatively, and the block of " firmly " (as vinylbenzene) is combined together with the block (as butyl acrylate) of relative " soft ".The gained material can have its any composition segment the performance characteristic that do not embody.The existence of microphase-separated and various phase morphologies is relevant with the special performance feature of many segmented copolymers in the segmented copolymer.For example, by the hardness of hard material or the flexibility of rigidity characteristic and soft material are combined, segmented copolymer can show favorable properties, as depend on and make the creeping characteristic (being equivalent to the ability that material keeps its shape outside under the stress) of the workability under melting condition, elasticity, wear resistance and the anti-fragility and the needs of its form them be suitable as and to extrude loose material, coating and separating medium.Firmly/the definite character of soft multipolymer significantly depends on the poor of second-order transition temperature that it respectively forms block; Therefore, the different monomers of selecting to have the second-order transition temperature of particular difference value can obtain to have specific required feature firmly/soft block copolymers.Therefore, though for certain practical application, each block of 20 ℃ combines to suit to differ its second-order transition temperature for example, and this practical application is depended in the selection of Tg (and thereby material).Can be (referring to No. the 5th, 755,540, United States Patent (USP) for example) well known in the art in conjunction with the monomer that forms hard block and soft segment.

Equally, amphiphilic block copolymer produced according to the invention has both hydrophobic and hydrophilic nmature, and these two kinds of character make such material be suitable as tensio-active agent or dispersion agent, scavenging agent, surface treatment agent etc.Contain the different block content of all monomer ratio and molecular weight, cause occurring all kinds of novel cpds, for example thermoplastics, elastomerics, tackiness agent and polymeric micelle.

The existence of segmented copolymer of the present invention can be determined by well known to a person skilled in the art method.For example, those skilled in the art can consider segmented copolymer is carried out nucleus magnetic resonance (NMR) research.Those skilled in the art are adding second kind of monomer so that first kind of monomeric living polymerization increased chain, also will consider the increase of determining molecular weight.Block copolymer structure can be observed by the microphase-separated method, comprises that long-range (long range order) in order (X-ray diffraction is determined), micro-and/or birefringence measurement infer.The additive method of determining the existence of segmented copolymer comprise mechanical properties measure (as firmly/elasticity of soft block copolymers), heat analyzes and stratographic analysis (as no homopolymer).

Measurement to optical property such as absorbancy (color and transparency) can provide the phase morphology of relevant polymer emulsion and the information of microstructure.Therefore, for example birefringence measurement can show the optically anisotropic existence that microphase-separated caused in the hard/soft block copolymers of vinylbenzene and butyl acrylate.Equally, the distinct color profile in the optical microscopy map of annealing polymer film can show the existence of block copolymer structure orderly, microphase-separated.

The sufficiently high segmented copolymer of molecular weight is separated in the micro-scale scope, forms spaced microcell, and described microcell mainly comprises certain or another kind of polymkeric substance usually.These microcells can thin slice, right cylinder, spheroid and other more complicated forms such as form occur, the size of microcell and at interval usually in the 10-100nm scope.This microphase-separated can detect with several different methods, comprises electron microscopy, X ray or scattering of neutrons or reflection, optically anisotropic measurement and rheology measurement.Not existing microstructure at interval not prove does not have segmented copolymer synthetic, because non-existent reason may be because molecular weight is low, molecular interaction deficiency of time and kinetics weak or the microphase-separated effect is slow.But the existence of the interval microstructure of 10-100nm yardstick can think to form the very convictive evidence of segmented copolymer of the present invention.

The new property of multipolymer and emulsion---for example comprise: (i) high molecular and relatively low polymolecularity; (ii) the control phase morphology and the microstructure of multipolymer; (iii) controllable particle size dispersion; (iv) high-optical-purity---make them be applicable in the multiple practical applications, comprise tackiness agent (adhesive), tackiness agent (binder), coating, dispersion agent, scavenging agent, rheology improving agent, can extrude loose material and health and personal-care supplies.Therefore, for example pressure sensitive adhesive can be with the preparation of emulsion of the present invention or dispersion, and described tackiness agent comprises tackifier well known in the art and/or softening agent (referring to for example: United States Patent (USP) the 4th, 879, No. 333, it is attached to herein by reference).

The present invention describes by following examples.These embodiment can not think the restriction to the scope of the invention or embodiment just for purpose of explanation.Except have specifically in addition and indicate, otherwise part or per-cent by weight.

Embodiment 1

Be used for vinylbenzene original position emulsive surfactant system

Carry out a series of reaction, to be identified for the latent surfactant/surfactant activator combination of original position emulsive.In typical reaction, prepared solution and tensio-active agent activator the solution in water (5 milliliter) of latent tensio-active agent (～0.2 gram) in vinylbenzene (5 milliliters), subsequently aqueous solution mild stirring is joined in the styrene solution, produce emulsion.The latent surfactant/surfactant activator combination of the generation emulsion of selecting is summarized in following table:

Sequence number	Latent tensio-active agent	The tensio-active agent activator
			1	Palmityl chloride	KOH
2	Palmityl chloride	Diethanolamine/KOH
			3	Palmityl chloride	Glycine/KOH
4	Palmityl chloride	3-aminopropyl phosphonic acids/KOH
			5	Palmityl chloride	3-aminopropanesulfonic acid/KOH
6	Palmityl chloride	(2-amino-ethyl) trimethyl ammonium chloride hydrochloride/KOH
			7	Cetylamine	Succinyl oxide
8	Cetylamine	1,3-N-morpholinopropanesulfonic acid lactone/KOH
			9	Cetylamine	HCl
10	Isocyanic acid n-Hexadecane ester	Diethanolamine/KOH
			11	Isocyanic acid n-Hexadecane ester	Glycine/KOH
12	Isocyanic acid n-Hexadecane ester	(2-amino-ethyl) trimethyl ammonium chloride hydrochloride/KOH
			13	The 4-4-dodecylphenol	KOH
14	Dodecanol	Maleic anhydride/KOH

Embodiment 2

Control M by the RAFT method _nPolymerization with the polystyrene of PDI

1, the 000 gram vinylbenzene, 60.0 of at first packing in 2 gallons of reaction vessels restrains oleic acid and 7.2 gram trithiocarbonic acid dibenzyl esters.Use the nitrogen purging reactor then, of short duration emptying, packing into comprises the aqueous solution of 4,000 gram RO water, 40.0 gram Potassium Persulphates, 40.0 gram Tripotassium phosphates and 16.4 gram potassium hydroxide.One mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 65 ℃.Just be converted into stable slight yellow polystyrene latex fully less than 1.5 hours.The solid that obtains behind the stripping is 20.6%.The gpc analysis of final polymkeric substance shows its M _nBe 54,000, PDI is 1.17.

Embodiment 3

The polymerisable surfactant that uses original position to produce passes through the RAFT method

Control M _nPolymerization with the polystyrene of PDI

1, the 000 gram vinylbenzene, 60.0 of at first packing in 2 gallons of reaction vessels restrains the hexadecyl half ester and the 7.2 gram trithiocarbonic acid dibenzyl esters of toxilic acids.Use the nitrogen purging reactor then, of short duration emptying, packing into comprises the aqueous solution of 4,000 gram reverse osmosis (RO) water, 40.0 gram Potassium Persulphates, 40.0 gram Tripotassium phosphates and 16.4 gram potassium hydroxide.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 65 ℃.Just be converted into stable slight yellow polystyrene latex fully less than 3 hours.The solid that obtains behind the stripping is 23.7%.The gpc analysis of final polymkeric substance shows its M _nBe 48,000, PDI is 1.17.

Embodiment 4

Prepare the triblock copolymer emulsion from seed latex

With pack into one quart of heavy wall polymerization " soft drink (pop) " bottle of the seed PS latex of difference amount, add in the isoprene, divinyl of RO water and different amounts or 77/23 divinyl and the styrene mixture a kind of then.This bottle purging is removed air, and tight with the crown cap lid that seal washer is housed, the metal part of described crown cap can supply take a sample to solid in the polymerization process towards porose.Pack into thing and selected aggregated data in each independent bottle show in following table.Transparent latex cast film is easy to just prepare, and it shows suitable intensity and elastic recovery.The SPM Photomicrograph is clear to be shown, all has the homogeneous phase of very little (about 80nm) to separate territory, hard area (polystyrene) in all samples, shows to have formed the block structure with thermoplastic elastomer (TPE) feature.

	A	B	C	D	E	F
RO water	200	200	200	200	200	200
							The latex of embodiment 2	167	167	167	120	120	120
Isoprene	100	--	--	100	--	--
							Divinyl	--	100	77.15	--	100	77.15
Vinylbenzene	--	--	22.85	--	--	22.85
The % transformation efficiency	100	97	100	98.6	100	100
							Time (hour)	14	14	9	12	12	9
Final solid %	28.6	27.7	28.6	28.8	29.8	29.5
							The ratio of HB: SB	18.8∶81.2	18.8∶81.2	18.8∶81.2	24.4∶75.6	24.4∶75.6	24.4∶75.6
Polymerization temperature (Fahrenheit)	149	149	149	149	149	149

● HB: SB=hard block: the ratio of soft segment

● the solid %=20.6 of embodiment 2 latex does not proofread and correct (uncorr.)

● bottle coefficient=1.2 gram/parts

Transparent latex cast film is easy to just prepare, and it shows suitable intensity and elastic recovery.

Embodiment 5

Prepare S-NBR-S triblock copolymer emulsion from seed latex

By with the similar mode of above embodiment 4, in one quart of bottle, prepare a series of S-NBR-S triblock copolymer latex from the PS seed latex.

	A	B	C	D	E	F
RO water	241	197.1	84.7	241	197.1	160.5
							The latex of embodiment 2	63.8	128	227.5	--	--	--
The latex of embodiment 3	--	--	--	56	112.3	168.7
							Divinyl	80.4	71.3	72.1	80.4	71.3	60.9
AN	39.6	35.2	35.5	39.6	35.2	29.8
The % transformation efficiency	100	100	100	ND *	ND *	ND *
							Time (hour)	6	2	2	ND	ND	ND
Final solid %	31.0	31.0	35.6	ND	ND	ND
							The ratio of HB: SB	10∶90	20∶80	30∶70	10∶90	20∶80	30∶70
Polymerization temperature (Fahrenheit)	149	149	149	149	149	149

^*Though these polymeric transformation efficiency height are coalescent very sensitive to shearing.Before the separation, add 0.6phr K/ oleate soap solution, to recover the stability of latex.

● HB: SB=hard block: the ratio of soft segment

● the solid %=20.6 of embodiment 2 latex (not proofreading and correct)

● the solid %=23.7 of embodiment 3 latex (not proofreading and correct)

● bottle coefficient=1.3 gram/parts

Embodiment 6

(PBN) undertaken by the NMP method with the phenyl tert-butylnitrone

Control M _nPolymerization with the polystyrene of PDI

1,000 gram vinylbenzene, 60.0 gram oleic acid and 10.0 gram PBN at first pack in 2 gallons of reaction vessels.Use the nitrogen purging reactor then, of short duration emptying, packing into comprises the aqueous solution of 4,000 gram RO water, 40.0 gram Potassium Persulphates, 40.0 gram Tripotassium phosphates and 16.4 gram potassium hydroxide.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.Just be converted into stable white polystyrene latex fully less than 2 hours.The solid that obtains behind the stripping is 22.7%.The gpc analysis of final polymkeric substance shows its M _nBe 25,000, PDI is 1.80.

Embodiment 7

Prepare S-I Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock emulsion from seed latex

By with the similar mode of above embodiment 4, in one quart of bottle, prepare a series of S-I Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock latex from the PS seed latex.

	A	B	C	D	E
RO water	241	197.1	84.7	241	197.1
						The latex of embodiment 6	58.2	116.2	166.5	206.7	254.1
Isoprene	120	106.5	89	71	58.2
						The % transformation efficiency	89	98	99	98	99
Time (hour)	21	13	12	12	12
						Final solid %	28.4	31.1	30	27.8	27.7
The ratio of HB: SB	10∶90	20∶80	30∶70	40∶60	50∶50
						Polymerization temperature (Fahrenheit)	149	149	149	149	149

● HB: SB=hard block: the ratio of soft segment

● the solid %=22.7 of embodiment 6 latex (not proofreading and correct)

● bottle coefficient=1.3 gram/parts

Transparent latex cast film is easy to just prepare, and it shows suitable intensity and elastic recovery.

Embodiment 8

Pass through the NMP method at 65 ℃ with phenyl tert-butylnitrone (PBN)

Control M _nPolymerization with the polystyrene of PDI

50 gram (0.48 mole) vinylbenzene, 3.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar (pot) thermometer and nitrogen inlet are housed restrain (0.0106 mole) oleic acid and 0.44 gram (0.002485 mole) phenyl tert-butylnitrone (PBN).Use the nitrogen purging flask, packing into then comprises the aqueous solution of 200 gram distilled water, 2.06 gram (0.00762 mole) Potassium Persulphates, 2.13 gram (0.01 mole) Tripotassium phosphates and 0.9 gram (0.014 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 65 ℃.In about 7 hours, be converted into stable white polystyrene latex fully.The gpc analysis of final polymkeric substance shows its M _nBe 35,000; M _wBe 61,000, PDI is 1.74.

Comparing embodiment 9

It should be noted that, adopt the condition identical, but carry out cinnamic controlled polymerization without nitrone, the M of the polymkeric substance that obtains with embodiment 8 _nBe 440,000; M _wBe 860,000, PDI is 1.95.

Embodiment 10

Pass through the NMP method at 75 ℃ with phenyl tert-butylnitrone (PBN)

Control M _nPolymerization with the polystyrene of PDI

200 gram (1.923 moles) vinylbenzene, 12.0 of at first packing in one liter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain (0.0424 mole) oleic acid and 2.0 gram (0.0113 mole) phenyl tert-butylnitrones (PBN).Then use the nitrogen purging flask, packing into then comprises the aqueous solution of 500 gram distilled water, 8.0 gram (0.296 mole) Potassium Persulphates, 8.0 gram (0.0377 mole) Tripotassium phosphates and 3.6 gram (0.056 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 3.5 hours, be converted into stable white polystyrene latex fully.The gpc analysis of final polymkeric substance shows its M _nBe 39,000; M _wBe 48,000, PDI is 1.22.

Embodiment 11

Pass through the NMP method at 65 ℃ with propyloxy phenyl base nitrone (PIN)

Control M _nPolymerization with the polystyrene of PDI

Use the step identical with above embodiment 8, just the PIN replacement PBN of molar equivalent such as usefulness grade carries out same polymerization process.This polymerization was also finished in about 7 hours.Molecular weight analyse shows the M of final polymkeric substance _nBe 41,000; M _wBe 70,000, PDI is 1.70.

Embodiment 12

Control M with " seed " latex by the NMP method at 65 ℃ _nWith PDI's

The polymerization of the positive butyl ester segmented copolymer of styrene-propene acid

100 grams of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed are about 22% latex derived from the solids content of embodiment 10.When at room temperature slowly purging, in the latex that stirs, add the solution of 0.5 gram (0.00184 mole) Potassium Persulphate in 100 ml distilled waters, add 22.0 gram (0.171 mole) n-butyl acrylates then with nitrogen.To about 65 ℃, can notice faint exothermic phenomenon this moment, makes temperature rise to about 70 ℃ with the gained mixture heating up.In about 2 hours, reach fully and transform.Molecular weight analyse shows the M of final polymkeric substance _nBe 45,000; M _wBe 77,000, PDI is 1.70.

It should be noted that, these results effectively illustrated on the formation of segmented copolymer and polystyrene " seed " chain can the active alkoxylamine of re-initiation polymeric functional group existence.

Embodiment 13

" original position " preparation with PIN is undertaken by the NMP method

Control M _nPolymerization with the polystyrene of PDI

3.0 gram (0.0106 mole) oleic acid, 0.31 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain 15% aqueous solution of (0.00292 mole) phenyl aldehyde and 1.4 gram (0.0028 mole) N-isopropylhydroxylas.Then use the nitrogen purging flask, at room temperature stirred 1 hour, add 50.0 gram (0.48 mole) vinylbenzene then, reinstall the aqueous solution that comprises 200 gram distilled water, 2.06 gram (0.00762 mole) Potassium Persulphates, 2.13 gram (0.01 mole) Tripotassium phosphates and 0.9 gram (0.014 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 4 hours, reach fully and transform.The gpc analysis of final polymkeric substance shows its M _nBe 31,000; M _wBe 55,000, PDI is 1.76.

It should be noted that this result of experiment is approaching with the result of the embodiment 11 that uses preformed PIN.

Embodiment 14

" original position " with nitrogen oxide generates by the NMP method

Control M _nPolymerization with the polystyrene of PDI

50.0 gram (0.48 mole) vinylbenzene, 3.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain (0.0092 mole) Witco 1298 Soft Acid and 1 ml distilled waters.Under agitation add 0.171 gram (0.002485 mole) Sodium Nitrite then to the gained mixture.Very fast vinylbenzene almost becomes pale bluish green mutually, takes off again for light yellow in several minutes.Then use the nitrogen purging flask, packing into then comprises the aqueous solution of 200 gram distilled water, 2.06 gram (0.00762 mole) Potassium Persulphates, 2.13 gram (0.01 mole) Tripotassium phosphates and 0.74 gram (0.0115 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Under agitation the gained mixture is heated rapidly to 75 ℃ then.In about 3 hours, reach fully and transform.Molecular weight analyse shows the M of final polymkeric substance _nBe 97,000; M _wBe 147,000, PDI is 1.51.

It should be noted that, it is reported from (J.Org.Chem.1964,29,1937) such as J.F.Brown Jr. (J.Am.Chem.Soc.1957,79,2480) and L.V.Phillips, nitrogen oxide can with multiple alkene such as isobutene reaction, generate separable alkoxylamine derivative.

Embodiment 15

With 1, the 1-toluylene is controlled M _nPolymerization with the polystyrene of PDI

50 gram (0.48 mole) vinylbenzene, 3.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain (0.0106 mole) oleic acid and 0.448 gram (0.002485 mole) 1,1-toluylene (DPE).Then use the nitrogen purging flask, packing into then comprises the aqueous solution of 200 gram distilled water, 2.06 gram (0.00762 mole) Potassium Persulphates, 2.13 gram (0.01 mole) Tripotassium phosphates and 0.92 gram (0.0143 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 2 hours, be converted into stable white polystyrene latex fully.The gpc analysis of final polymkeric substance shows its M _nBe 51,000; M _wBe 92,000, PDI is 1.80.

Embodiment 16

Control by RAFT method high solid/low KPS

M _nPolymerization with the polystyrene of MWD

2, the 240 gram vinylbenzene, 134.4 of at first packing in 2 gallons of reaction vessels restrain oleic acid and 16.0 gram trithiocarbonic acid dibenzyl esters.Use the nitrogen purging reactor then, of short duration emptying, packing into comprises the aqueous solution of 3,808 gram RO water, 13.44 gram Potassium Persulphates, 89.6 gram Tripotassium phosphates and 36.96 gram potassium hydroxide.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 65 ℃.Just be converted into stable slight yellow polystyrene latex (38.9% solid) fully less than 3 hours.The gpc analysis of final polymkeric substance shows its M _nBe 45,500, PDI is 1.11.

Embodiment 17

Control M by the NMP method _nLetex polymerization with the polystyrene of PDI:

Generate nitrogen oxide with acetate " original position "

0.69 gram (0.01 mole) Sodium Nitrite, 3.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrains (0.0106 mole) oleic acid and 50 gram (0.48 mole) vinylbenzene.The disposable then solution of 1.0 gram (0.0167 mole) spirit acids in 2 gram water that in this stirred mixture, adds.Very fast vinylbenzene almost becomes pale bluish green mutually, takes off again for light yellow in 15 minutes.Then use the nitrogen purging flask, packing into then comprises the aqueous solution of 160 gram distilled water, 2.0 gram (0.00739 mole) Potassium Persulphates, 2.0 gram (0.01 mole) Tripotassium phosphates and 2.35 gram (0.0367 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture under agitation is heated rapidly to 75 ℃.Transforming (26.1% solid) fully less than just reaching in about 2.5 hours.The molecular weight analyse of final polymkeric substance shows its M _nBe 96,300; M _wBe 135,000, PDI is 1.4.

Embodiment 18

With thick 1-chloro-1, the 1-diphenylethane carries out cinnamic control letex polymerization

50 gram (0.48 mole) vinylbenzene, 3.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain (0.0106 mole) oleic acid and about 0.01 mole of thick 1-chloro-1, the 1-diphenylethane, described thick 1-chloro-1, the 1-diphenylethane prepared by at room temperature 2 gram (about 0.01 mole) methyl-diphenyl-carbinol acutely being mixed with 10 milliliters of dense HCl and 5 milliliters of toluene separately in 30 minutes.Taking-up contains 1-chloro-1 then, and the top organic layer of 1-diphenylethane joins in vinylbenzene/oleic acid mixture.Then use the nitrogen purging flask, packing into then comprises the aqueous solution of 200 gram distilled water, 2.0 gram (0.0074 mole) Potassium Persulphates, 2.0 gram (0.0094 mole) Tripotassium phosphates and 1.55 gram (0.0242 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 4 hours, be converted into stable white polystyrene latex (22.7% solid) fully.The gpc analysis of final polymkeric substance shows its M _nBe 40,000, PDI is 1.37.

Embodiment 19

With thick 1-chloro-1, the 1-diphenylethane carries out cinnamic

Control letex polymerization: high solid prescription

1,300 gram (12.5 moles) vinylbenzene, 78.0 of at first packing in 5 liter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrains (0.2756 mole) oleic acid and the thick 1-chloro-1 of 39.0 grams, 1-diphenylethane.Then use the nitrogen purging flask, pack into then and comprise the aqueous solution of 2,470 gram deionization reverse osmosis (RO) water, 50.7 gram (0.1875 mole) Potassium Persulphates, 50.7 gram (0.2388 mole) Tripotassium phosphates and 29.5 gram (0.602 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 5.5 hours, be converted into stable white polystyrene latex (38.6% solid) fully.The gpc analysis of final polymkeric substance shows its M _nBe 32,000, PDI is 1.85.

Embodiment 20

The ATRP emulsion copolymerization of n-butyl acrylate and 1-hexene

On the other hand, for making great efforts to enlarge the scope and the application of CFR microemulsion technology, attempted carrying out the copolymerization of n-butyl acrylate and 1-hexene by the microemulsion ATRP scheme of CFR.It should be noted that, under conventional free radical emulsion condition, even will make ethene and acrylic acid copolymer close all very difficulty.But existing reporting adopted homogeneous phase ATRP condition, and 1-alkene can close (J.Am.Chem.Soc., 2001,123,12738) with methyl acrylate copoly.In this case, the mixtures of 25 gram 1-hexenes, 25 gram n-butyl acrylates, 0.38 gram dipyridyl, 4.0 gram oleic acid and 0.47 gram 2-isobutyl ethyl bromide are packed into be equipped with in 500 milliliter of three neck round-bottom reaction flask of nitrogen inlet, oar propeller agitator, jar thermometer and condenser.Under agitation using slowly, nitrogen gas stream purges the gained homogeneous phase solution.Add the solution of 1.7 gram 85%KOH in 139 ml distilled waters subsequently.Begin to form uniform emulsion immediately.After about 2 minutes, add 60.9 grams, the 1% cupric sulfate pentahydrate aqueous solution, make white emulsion become sky blue emulsion.Add 2 hydrazine hydrates in this emulsion, this moment, mixture became dark red brown.To about 65 ℃ of maintenances 1.5 hours, solid reached 10.9% o'clock stopped reaction with mixture heating up.Under reduced pressure latex emulsion is carried out stripping then, to remove unreacted monomer.Then latex is coalescent in excessive cold HCl dilute solution.It should be noted that, brown disappearance, water becomes transparent light blue (Cu (II) ion).Separating the polymkeric substance that obtains is the heavy-gravity low molecular weight material.With this material dichloromethane extraction, evaporating solvent obtains 27.8 gram liquid polymerses.Then this material is carried out NMR and analyze, wherein ¹³C-NMR determines that the 1-hexene of existing 5.5 moles of % mainly is incorporated in the multipolymer with the form of separating unit.

Embodiment 21

With the N of terephthalaldehyde, N '-two sec.-propyl nitrones

Carry out cinnamic control letex polymerization

100 gram (0.96 mole) vinylbenzene, 6.0 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain the N of (0.02124 mole) oleic acid and 0.62 gram (0.0025 mole) terephthalaldehyde, N '-two sec.-propyl nitrones (BIN).Use the nitrogen purging flask, packing into then comprises the aqueous solution of 250 gram distilled water, 4.0 gram (0.0148 mole) Potassium Persulphates, 4.0 gram (0.02 mole) Tripotassium phosphates and 1.8 gram (0.028 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 75 ℃.In about 3 hours, be converted into stable white polystyrene latex (31.4% solid) fully.The gpc analysis of final polymkeric substance shows its M _nBe 54,600; M _wBe 85,900, PDI is 1.57.

Embodiment 22

With the N of terephthalaldehyde, N '-two sec.-propyl nitrones

Carry out the control letex polymerization of methyl methacrylate

104 gram (1.04 moles) methyl methacrylate monomers, 6.24 of at first packing in 500 milliliter of three neck round-bottom reaction flask that oar propeller agitator, condenser, jar thermometer and nitrogen inlet are housed restrain the N of (0.02213 mole) oleic acid and 1.1 gram (0.00443 mole) terephthalaldehydes, N '-two sec.-propyl nitrones (BIN).Use the nitrogen purging flask, pack into the then water that comprises 210 gram reverse osmosis method purifying, the aqueous solution that 4.95 gram (0.0183 mole) Potassium Persulphates, 4.95 restrain (0.0233 mole) Tripotassium phosphates and 1.87 gram (0.0292 mole) 87.5% pure cerium hydroxide potassium.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 60 ℃.6.5 after hour, latex solid reaches 33.6% (transformation efficiency about 91%).The gpc analysis of final polymkeric substance shows its M _nBe 91,000; M _wBe 156,700, PDI is 1.72.

Embodiment 23

Prepare PS-SIR segmented copolymer latex with the phenyl tert-butylnitrone as control agent list still

The 680 gram vinylbenzene, 40.8 of at first packing in 2 gallons of reaction vessels restrain oleic acid and 6.8 gram phenyl tert-butylnitrones (PBN).Use the nitrogen purging reactor then, of short duration emptying, pack into the water that comprises 2,720 gram reverse osmosis method purifying, the aqueous solution that 27.2 gram Potassium Persulphates, 27.2 restrain Tripotassium phosphates and 11.15 gram potassium hydroxide.It should be noted that one mixes the aqueous solution with the organic substance of front, just form tiny microemulsion.Then the gained mixture is heated rapidly to 65 ℃.Reaction process is measured by the percent solids of measuring latex with gravimetry.After 4 hours, the percent solids of latex has reached 13.6%.Then reaction mixture is cooled to room temperature rapidly, the water of 1, the 020 other gram reverse osmosis method purifying of then packing into, 1, the 360 gram isoprene of packing into again subsequently.Under agitation will react and be heated to 65 ℃ once more, proceed reaction, in 20 hours, obtain the solid (36.1% total solids) of constant basis.This solid level is represented about 99% transformation efficiency.

Embodiment 24

Synthesize with the control agent of RAFT type and the initiator of persulphate type

Positive butyl ester-the styrene triblock copolymer of styrene-propene acid

In used step, with 3.37 gram K ₂S ₂O ₈, 0.89 the gram KOH and 3.2 the gram K ₃PO ₄The aqueous solution in 64.4 gram water joins in 1.27 gram trithiocarbonic acid dibenzyl esters, 3.0 gram oleic acid and the cinnamic mixture of 23 grams of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With the jolting 3 hours in 65 ℃ of water-baths of gained emulsion.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 34.9%, M _nBe 12,300, M _wBe 14,400, heterogeneity index (PDI) is 1.17.

Subsequently, 14.7 gram n-butyl acrylates and 27 gram water are joined in the 34.3 gram polystyrene latexs.This mixture purged and jolting 4 hours in 62 ℃ of water-baths.The M of analysis revealed latex _nBe 34,800, M _wBe 40,500, PDI is 1.16.

Embodiment 25

Synthesize with the control agent of RAFT type and the initiator of persulphate type

N-butyl acrylate-positive butyl ester the triblock copolymer of styrene-propene acid

In used step, with 1.56 gram K ₂S ₂O ₈, 0.69 the gram KOH and 1.69 the gram K ₃PO ₄The aqueous solution in 60.0 gram water joins in the mixture of 0.4 gram trithiocarbonic acid dibenzyl ester, 2.0 gram oleic acid and the 35.2 gram n-butyl acrylates of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With the jolting 3 hours in 65 ℃ of water-baths of gained emulsion.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 40.0%, M _nBe 26,000, M _wBe 32,000, PDI is 1.2.

Subsequently, with 2.73 gram vinylbenzene and 0.01 gram K ₂S ₂O ₈Join in the positive butyl ester latex of 25.0 gram polyacrylic acid.This mixture purged and jolting 20 hours in 65 ℃ of water-baths.The M of analysis revealed latex _nBe 36,800, M _wBe 53,100, PDI is 1.44.

Embodiment 26

At room temperature use the control agent of RAFT type and iron-EDTA/ROOH type

Initiator synthesizing styrene-isoprene-styrene triblock copolymer

In used step, with 0.12 gram sodium formaldehyde sulphoxylate hydrate, 0.64 gram KOH and 0.14 gram K ₃PO ₄The aqueous solution in 60.0 gram water joins in 0.32 gram trithiocarbonic acid dibenzyl ester, 6.0 gram oleic acid and the cinnamic mixture of 25 grams of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With this emulsion N ₂Purged 15 minutes, and added 1.0 gram 1.0%Fe-EDTA complex solutions, add 0.1 gram pinane hydroperoxide (44% solution) then, gained emulsion jolting at room temperature 3 hours.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 35.2%, M _nBe 29,000, M _wBe 45,000, PDI is 1.57.

Subsequently, 8.0 gram isoprene, 12 gram water, 0.7 gram Fe-EDTA complex compound and 0.05 gram sodium formaldehyde sulphoxylate hydrate are joined in the 34.3 gram polystyrene latexs.With this mixture N ₂Purge, add 0.25 gram pinane hydroperoxide (44% solution) then.With gained emulsion jolting at room temperature 4 hours.The solids content of analysis revealed latex is 33.0%, M _nBe 72,000, M _wBe 125,700, PDI is 1.7.

Embodiment 27

At room temperature use the control agent of RAFT type and iron-EDTA/ROOH type

Initiator synthesizing styrene-n-butyl acrylate-styrene block copolymer

In used step, 19.1 gram n-butyl acrylates, 40 gram water, 0.8 gram Fe-EDTA complex compound and 0.07 gram sodium formaldehyde sulphoxylate hydrate are joined in the 30 gram polystyrene latexs.With gained mixture N ₂Purge, add 0.25 gram pinane hydroperoxide (44% solution) then.With gained emulsion jolting at room temperature 4 hours.The solids content of analysis revealed latex is 31.0%, M _nBe 87,000, M _wBe 113,000, PDI is 1.3.

Embodiment 28

Control agent and persulfate initiator synthetic polystyrene seed with the BIN type

Synthetic with the initiator of iron-EDTA/ROOH type subsequently

Positive butyl ester-the styrene triblock copolymer of styrene-propene acid

In used step, with 1.28 gram K ₂S ₂O ₈, 0.83 the gram KOH and 1.25 the gram K ₃PO ₄The aqueous solution in 66.6 gram water joins in 0.315 gram BIN, 2.92 gram oleic acid and the cinnamic mixture of 26 grams of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With the jolting 3 hours in 65 ℃ of water-baths of gained emulsion.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 25.0%, M _nBe 45,000, M _wBe 60,000, PDI is 1.33.

Subsequently, 18.85 gram n-butyl acrylates, 1.0 gram 1%Fe-EDTA solution, 0.07 gram sodium formaldehyde sulphoxylate hydrate and 40 gram water are joined in the above-mentioned polystyrene latex of 30.34 grams.With this mixture N ₂Purge, add 0.5 gram pinane hydroperoxide (44% solution) then and jolting 2.5 hours in room temperature (20 ℃) water-bath.The M of analysis revealed latex _nBe 125,000, M _wBe 200,000, PDI is 1.63.

Embodiment 29

At room temperature with phenyl tert-butylnitrone (PBN) and 1,1-toluylene (DPE) is a control agent

Initiator synthetic polystyrene latex with iron-EDTA/ROOH type

PBN：

In used step, with 0.1 gram sodium formaldehyde sulphoxylate hydrate, 0.316 gram KOH and 0.172 gram K ₃PO ₄The aqueous solution in 55.2 gram water joins in 0.22 gram PBN, 2.46 gram oleic acid and the cinnamic mixture of 25.5 grams of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With this emulsion N ₂Purged 15 minutes, and added 1.0 gram 1.0%Fe-EDTA complex solutions, add 0.1 gram pinane hydroperoxide (44% solution) then, gained emulsion jolting at room temperature 3 hours.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 34.2%, M _nBe 70,700, M _wBe 100,000, PDI is 1.43.

DPE：

With 0.125 gram sodium formaldehyde sulphoxylate hydrate, 0.307 gram KOH and 0.182 gram K ₃PO ₄The aqueous solution in 52.3 gram water joins in 0.23 gram DPE, 2.53 gram oleic acid and the cinnamic mixture of 24.6 grams of jolting in heavy wall soft drink bottle, and moment just forms emulsion.With this emulsion N ₂Purged 15 minutes, and added 1.0 gram 1.0%Fe-EDTA complex solutions, add 0.1 gram pinane hydroperoxide (44% solution) then, gained emulsion jolting at room temperature 3 hours.Make latex filter glass cotton, coalescent, for gpc analysis.The solids content of analysis revealed latex is 35%, M _nBe 51,000, M _wBe 75,700, PDI is 1.48.

Embodiment 30

To being control agent with phenyl tert-butylnitrone (PBN) and being initiator with the Potassium Persulphate

Styrene polymerization carry out molecular weight control

With Potassium Persulphate is initiator, is control agent with the different PBN that measure, and carries out a series of styrene polymerization reaction.In typical reaction, with vinylbenzene (100 grams; 962mmol), oleic acid (6.0 grams; 21.2mmol) and PBN join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), KOH (1.64 the gram; 29.3mmol) and K ₂S ₂O ₈(2.62 moles of every mole of PBN) solution in water (400 gram).In all cases, all form emulsion immediately.With champagne bottle N ₂Purge, tightly and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) with " Mi Feng (sure seal) fully " crown cap lid.Each hour following detection extent of polymerization: from each bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.In all cases, vinylbenzene all is substantially completely to the conversion of polystyrene.Following acquisition supplies to carry out subsequently the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The GPC data of the polymkeric substance for preparing with the PBN of difference amount are compiled in following table.M _nWith the relation curve of vinylbenzene/PBN molar ratio be linear, this is consistent with the controlled polymerization method.

PBN(g)	PBN(mmol)	Vinylbenzene (g)	Vinylbenzene (mmol)	Vinylbenzene/PBN	Mn
						0.75	4.24	100	962	227	52300
0.75	4.24	100	962	227	45290
						1	5.65	100	962	170	37200
1	5.65	100	962	170	33060
						1.25	7.06	100	962	136	32300
1.25	7.06	100	962	136	27300
						1.7	9.6	100	962	100	20860

Embodiment 31

To with phenyl tert-butylnitrone (PBN) being control agent and, 4-azo two (4-cyanopentanoic acid) with 4

(ABCV) carry out molecular weight control for the styrene polymerization of initiator

With 4,4-azo two (4-cyanopentanoic acid) is an initiator, is control agent with the different PBN that measure, and carries out a series of styrene polymerization reaction.In typical reaction, with vinylbenzene (100 grams; 962mmol), oleic acid (6.0 grams; 21.2mmol) and PBN join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), KOH (the every ABCV of 29.3mmol+2mmol KOH) and ABCV (every mole of PBN of the 2.62-3.50 mole) solution in water (400 gram).In all cases, all form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from each bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.In all cases, vinylbenzene all is substantially completely to the conversion of polystyrene.Following acquisition supplies to carry out subsequently the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The GPC data of the polymkeric substance for preparing with the PBN of difference amount are compiled in following table.M _nWith the relation curve of vinylbenzene/PBN molar ratio be linear, this is consistent with the controlled polymerization method.

PBN(g)	PBN (mmol)	ABCV/PBN	Vinylbenzene (g)	Vinylbenzene (mmol)	Vinylbenzene/PBN	M n
							0.75	4.24	3.50	100	962	227	53780
1	5.65	3.50	100	962	170	39910
							1	5.65	3.50	100	962	170	39050
1.25	7.06	3.50	100	962	136	31490
							1.25	7.06	3.50	100	962	136	30950
0.75	4.24	2.62	100	962	227	59840
							1	5.65	2.62	100	962	170	40370

Embodiment 32

To N with terephthalaldehyde, N '-two sec.-propyl nitrones (BIN) be control agent and

The styrene polymerization that with the Potassium Persulphate is initiator carries out molecular weight control

With Potassium Persulphate is initiator, is control agent with the different BIN that measure, and carries out a series of styrene polymerization reaction.In typical reaction, with vinylbenzene (100 grams; 962mmol), oleic acid (6.0 grams; 21.2mmol) and BIN join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), KOH (1.64 the gram; 29.3mmol) and K ₂S ₂O ₈(2.62 moles of every mole of BIN) solution in water (400 gram).In all cases, all form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from each bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.In all cases, vinylbenzene all is substantially completely to the conversion of polystyrene.Following acquisition supplies to carry out subsequently the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The GPC data of the polymkeric substance for preparing with the BIN of difference amount are compiled in following table.M _nWith the relation curve of vinylbenzene/BIN molar ratio be linear, this is consistent with the controlled polymerization method.

BIN(g)	BIN(mmol)	Vinylbenzene (g)	Vinylbenzene (mmol)	Vinylbenzene/PBN	M n
						0.53	2.14	100	962	450	92270
0.7	2.82	100	962	341	50630
						0.88	3.55	100	962	271	41970
1.06	4.28	100	962	225	42300
						1.19	4.8	100	962	200	37100

Embodiment 33

With 1,1-toluylene (DPE) be control agent, Potassium Persulphate be initiator,

Witco 1298 Soft Acid is the tensio-active agent activator for dive tensio-active agent and KOH

Carry out styrene polymerization

With vinylbenzene (100 grams; 962mmol), Witco 1298 Soft Acid (9.9 grams, 70% aqueous isopropanol; 21.2mmol) and DPE (0.9 gram; 5.0mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), KOH (1.64 the gram; 29.3mmol) and K ₂S ₂O ₈(4.0 grams, 14.8mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 5 hours, vinylbenzene is to the conversion of polystyrene (22.7% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 69,500, PDI is 1.48.

Embodiment 34

With 1,1-toluylene (DPE) be control agent, Potassium Persulphate be initiator,

Oleic acid carries out styrene polymerization for dive tensio-active agent and KOH for the tensio-active agent activator

With vinylbenzene (100 grams; 962mmol), oleic acid (6.0 grams; 21.2mmol) and DPE (0.9 gram; 5.0mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), KOH (1.64 the gram; 29.3mmol) and K ₂S ₂O ₈(4.0 grams, 14.8mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 5 hours, vinylbenzene is to the conversion of polystyrene (22.1% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 66,900, PDI is 1.60.

Embodiment 35

With 1,1-toluylene (DPE) be control agent, Potassium Persulphate be initiator,

Palmityl chloride is the tensio-active agent activator for dive tensio-active agent and KOH/ glycine

Carry out styrene polymerization

With vinylbenzene (100 grams; 962mmol), palmityl chloride (5.8 grams; 21.1mmol) and DPE (0.9 gram; 5.0mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), glycine (1.57 the gram; 20.9mmol), KOH (2.82 the gram; 50.4mmol) and K ₂S ₂O ₈(4.0 grams, 14.8mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 4 hours, vinylbenzene is to the conversion of polystyrene (21.2% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 90,500, PDI is 1.32.

Embodiment 36

With phenyl tert-butylnitrone (PBN) be control agent, Potassium Persulphate be initiator,

Palmityl chloride is the tensio-active agent activator for dive tensio-active agent and KOH/ glycine

Carry out styrene polymerization

With vinylbenzene (100 grams; 962mmol), palmityl chloride (5.8 grams; 21.1mmol) and PBN (1.0 grams; 5.65mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding K ₃PO ₄(4.0 grams; 18.8mmol), glycine (1.57 the gram; 20.9mmol), KOH (2.82 the gram; 50.4mmol) and K ₂S ₂O ₈(4.0 grams, 14.8mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 4 hours, vinylbenzene is to the conversion of polystyrene (21.4% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 177,500, PDI is 1.44.

Embodiment 37

With 1,1-toluylene (DPE) be control agent, Potassium Persulphate be initiator,

Myristyl chloride for dive tensio-active agent and NaOH/ sarkosine is

The tensio-active agent activator carries out styrene polymerization

With vinylbenzene (100 grams; 962mmol), myristyl chloride (5.21 grams; 21.1mmol) and DPE (0.9 gram; 5.0mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding Na ₃PO ₄(3.1 grams; 18.9mmol), sarkosine (1.87 the gram; 21.0mmol), NaOH (1.71 the gram; 42.8mmol) and Na ₂S ₂O ₈(3.5 grams, 14.7mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 12 hours, vinylbenzene is to the conversion of polystyrene (21.2% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 67,300, PDI is 1.7.

Embodiment 38

With phenyl tert-butylnitrone (PBN) be control agent, Potassium Persulphate be initiator,

Myristyl chloride is the tensio-active agent activator for dive tensio-active agent and NaOH/ sarkosine

Carry out styrene polymerization

With vinylbenzene (100 grams; 962mmol), myristyl chloride (5.21 grams; 21.1mmol) and PBN (1.0 grams; 5.65mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding Na ₃PO ₄(3.1 grams; 18.9mmol), sarkosine (1.87 the gram; 21.0mmol), NaOH (1.71 the gram; 42.8mmol) and Na ₂S ₂O ₈(3.5 grams, 14.7mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 4 hours, vinylbenzene is to the conversion of polystyrene (21.9% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 179,400, PDI is 1.84.

Embodiment 39

With 1,1-toluylene (DPE) be control agent, Potassium Persulphate be initiator,

N-myristoyl-N-methylaminoacetic acid (Hamposyl M) for dive tensio-active agent and

NaOH carries out styrene polymerization for the tensio-active agent activator

With vinylbenzene (100 grams; 962mmol), Hamposyl M (6.32 grams; 21mmol) and DPE (0.9 the gram; 5.0mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding Na ₃PO ₄(3.1 grams; 18.9mmol), NaOH (0.87 the gram; 21.8mmol) and Na ₂S ₂O ₈(3.5 grams, 14.7mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 4 hours, vinylbenzene is to the conversion of polystyrene (22.4% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 66,980, PDI is 1.59.

Embodiment 40

With phenyl tert-butylnitrone (PBN) be control agent, Potassium Persulphate be initiator,

N-myristoyl-N-methylaminoacetic acid (Hamposyl M) for dive tensio-active agent and

NaOH carries out styrene polymerization for the tensio-active agent activator

With vinylbenzene (100 grams; 962mmol), Hamposyl M (6.32 grams; 21mmol) and PBN (1.0 the gram; 5.65mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding Na ₃PO ₄(3.1 grams; 18.9mmol), NaOH (0.87 the gram; 21.8mmol) and Na ₂S ₂O ₈(3.5 grams, 14.7mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (75 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 5 hours, vinylbenzene is to the conversion of polystyrene (22.2% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 49,170, PDI is 1.22.

Embodiment 41

With the perfluoro-hexyl iodide is control agent, 4, and 4-azo two (4-cyanopentanoic acid) (ABCV)

For initiator, oleic acid are the tensio-active agent activator for dive tensio-active agent and NaOH

Carry out cinnamic degradation iodine transfer polymerization

With vinylbenzene (100 grams; 962mmol), oleic acid (6.0 grams; 21.2mmol) and perfluoro-hexyl iodide (1.74 grams; 3.9mmol) join in 750 milliliters of champagne bottles.Use N ₂Behind the purging, stir adding Na ₃PO ₄(3.5 grams; 21.3mmol), NaOH (0.92 the gram; 23mmol) and ABCV (0.2 gram, 0.71mmol) solution in water (400 gram).Form emulsion immediately.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (70 ℃) to use up hermetic crown cap lid.Each hour following detection extent of polymerization: from bottle, take out the aliquots containig (～5 milliliters) of latex, be placed in the aluminum pan 140 ℃ and be evaporated to constant weight.After 5 hours, vinylbenzene is to the conversion of polystyrene (21.2% solid) substantially fully.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 36,130, PDI is 1.24.

Embodiment 42

With trithiocarbonic acid dibenzyl ester (DBTTC) be control agent, Potassium Persulphate be initiator,

Oleic acid is controlled M for dive tensio-active agent and KOH for the tensio-active agent activator _n

The polymerization of vinylbenzene-vinylidene chloride/methyl methacrylate-styrene block copolymer

Method by embodiment 2 contains 22.6% solid, M from 1020 gram vinylbenzene, 60 gram oleic acid, 9.5 gram DBTTC and 18 gram KOH preparations _nBe 29,600 and PDI be 1.6 polystyrene latex.From then on take out 150 grams in the latex, with water (275 gram), vinylidene chloride (28 grams; 0.29mol), methyl methacrylate (7 the gram; 0.070mol) and Potassium Persulphate (0.2 gram) in 750 milliliters of champagne bottles, merge.With champagne bottle N ₂Purge, it is tight and be placed on the swiveling wheel in the water bath with thermostatic control (50 ℃) to use up hermetic crown cap lid.A polymerase 17 hour generation contains 12.5% solid latex.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes 100 milliliters of latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 35,600, PDI is 1.44.

Embodiment 43

With 1,1-toluylene (DPE) is for control agent and mix ethene subsequently

Control M _nThe polymerization of polystyrene

Prepare M by method similar to Example 15 _nBe 51,000 and PDI be 1.29 polystyrene latex.The part (14.85 gram) of this latex is placed the phial of being furnished with the lid that contains consent.This bottle is fixed in the high-pressure reaction vessel that contains  inch hydrostatic.The following ethene purge of using: the ethene with 50psig pressurizes to reactor, and exhaust is then so carried out three times.Seal after making reactor slowly be forced into 400psig with ethene.When reactor was heated to 250 ℃, its internal pressure increased to more than the 1000psi.Reactor is chilled to 25 ℃ after keeping 4 hours under 250 ℃, make pressure reduce to about 300psi.After making the reactor emptying, the quality of measuring in the bottle that contains latex has increased 0.151g.Following acquisition supplies the solid polymerization matter sample of gpc analysis: makes latex coalescent with rare HCl aqueous solution, filters, wash with water, and air-dry at 25 ℃.The gpc analysis (THF, 25 ℃) of final polymkeric substance shows its M _nBe 30,500, PDI is 1.73.

Embodiment 44

With trithiocarbonic acid dibenzyl ester (DBTTC) be control agent, Potassium Persulphate be initiator,

Oleic acid is the tensio-active agent activator for dive tensio-active agent and KOH

Control the polymerization of the styrene-butadiene-styrene block copolymer of Mw and PDI

Method by embodiment 2 contains 22.6% solid, M from 1020 gram vinylbenzene, 60 gram oleic acid, 9.5 gram DBTTC and 18 gram KOH preparations _nBe 31,400 and PDI be 1.1 polystyrene latex.From then on take out 2,480 grams in the latex, in 2 gal reactor, merge with water (2,640 gram) and 1,3-butadiene (1,090 gram).With reactor N ₂Purging also is heated to 50 ℃.Monitor extent of polymerization by the aliquots containig (50 milliliters) of taking out latex from reactor.In each sample, add a spot of Carax, to suppress further reaction.Each sample get about 5 milliliters in the aluminum pan 25 ℃ be evaporated to constant weight.Each sample remainder is coalescent with rare HCl aqueous solution, produces solid polymer, with its filtration, wash with water, 25 ℃ air-dry, carry out gpc analysis (THF, 25 ℃).The experimental data of each sample of collecting in 9.5 hours time period comes together in the following table.The relation curve in % butadiene conversion and reaction times and M _nAs follows with the relation curve in reaction times.As desired to the DBTTC controlled polymerization, the M of latex _nWith the % solid in time with the increase of butadiene conversion and increase.Butadiene conversion is 50% when following, and resulting polymers dissolves in THF (25 ℃), its PDI also low (1.1-1.5).Under higher transformation efficiency, the PDI of polymkeric substance increases, and it is insoluble in or is insoluble to THF, and this is crosslinked consistent with divinyl segmental free yl induction.

Time (hour)	The % solid	The % butadiene conversion	Solubleness under 25 ℃ in THF	M n	PDI
						0	8.87	0	Solvable	31,400	1.1
1	11.7	16.2	Solvable	45,500	1.1
						2	12.1	18.5	Solvable	47,900	1.1
4	14	29.4	Solvable	51,100	1.2
						6	18	52.4	Solvable	94,100	1.5
8	23.3	82.8	Part is solvable	216,800	2.0
						8.5	24.1	87.4	Usually soluble	--	--
9	25.1	93.1	Soluble	--	--
						9.5	26.3	99.3	Soluble	--	--

Embodiment 45

In emulsion, use this (Grubbs) catalyzer of croup to carry out the ROMP polymerization

0.172 gram (0.0008 mole) K at first packs in 100 milliliter of two neck round-bottom reaction flask of magnetic stirring apparatus, condenser and nitrogen inlet is housed ₃PO ₄With the solution of 0.085 gram (0.0015 mole) KOH in 40 ml waters.Preparation 4.2 gram (0.0385 mole) cyclooctene and the solution of 0.92 gram (0.002 mole) Witco 1298 Soft Acid (70%2-propanol solution) in 2 milliliters of toluene join gained solution in the above-mentioned aqueous solution, form emulsion immediately.In this emulsion, stir to add the solution of 0.1 gram (0.00012 mole) two (tricyclohexyl phosphine) chloro-benzal ruthenium (IV) (this catalyzer of croup) in 2 milliliters of toluene, 20 ℃ of following stirred reaction mixtures 17 hours.The M of resulting polymers _nBe 42,000, PDI is 1.45.

In this latex, add the solution of 2.63 gram (0.028 mole) norbornylenes in 1 milliliter of toluene, at N ₂Further again stirred reaction mixture is 3 hours under the atmosphere, obtains M _nBe 108,000, PDI is 1.7 segmented copolymer (4.3 gram).

Embodiment 46

In emulsion, use this catalyzer of croup to carry out the ADMET polymerization

0.12 gram (0.00057 mole) K at first packs in 25 milliliter of two neck round-bottom reaction flask of magnetic stirring apparatus, condenser and nitrogen inlet is housed ₃PO ₄With the solution of 0.038 gram (0.00068 mole) KOH in 10 ml waters.Preparation 2.2 gram (0.016 moles) 1,9-decadiene and the solution of 0.3 gram (0.00065 mole) Witco 1298 Soft Acid (70%2-propanol solution) in 1 milliliter of toluene join gained solution in the above-mentioned aqueous solution, form emulsion immediately.In this emulsion, stir and add the solution of 0.1 gram (0.00012 mole) two (tricyclohexyl phosphine) chloro-benzal ruthenium (IV) (this catalyzer of croup) in 0.5 milliliter of toluene, 20 ℃ of following stirred reaction mixtures 60 hours, obtain poly-1,9-decadiene latex, according to Wagener etc. at macromolecules2002,35,48 describe ¹H-NMR measures transformation efficiency and reaches 60%.

Though for the purpose of illustrating the invention, some representative embodiment and details have been provided, but it will be apparent for a person skilled in the art that and to carry out various changes and correction to above-mentioned representative embodiment and details, but this does not depart from the scope of the present invention.

Claims (10)

1. emulsion polymerisation process, described method comprises: (1) preparation aqueous polymerization medium, described medium by (a) at least a monomer, (b) polymerization control agent, (c) emulsifying agent and (d) water forms, wherein said emulsifying agent reacts and in-situ preparing by latent tensio-active agent and tensio-active agent activator in the monomer solution that by described monomer, described polymerization control agent and (d) water is formed; (2) in described aqueous polymerization medium, cause described monomeric polymerization.

2. the emulsion polymerisation process of claim 1, wherein said polymerization carry out the sufficiently long time with the preparation polymkeric substance, and make described aqueous polymerization medium not have unreacted initiator basically.

3. the emulsion polymerisation process of claim 2, wherein polyreaction causes with first kind of initiators for polymerization in the step (2); And wherein polyreaction causes with second kind of initiators for polymerization subsequently.

4. the emulsion polymerisation process of claim 3, wherein said first kind of initiators for polymerization used the mechanism that is selected from following kind: atom transfer radical polymerization, nitroxide-mediated polymerization, reversible addition fracture are shifted, degradation transfer, anionoid polymerization, cationoid polymerisation, polycoordination, ring-opening metathesis polymerization, acyclic dienes metathesis polymerization and other relate to the polyreaction of stabilized radical; And the mechanism that wherein said second kind of initiators for polymerization used is different with the mechanism that described first kind of initiator used.

5. claim 1 or 2 emulsion polymerisation process, wherein polymerization adopts at least two kinds of different control agents that are used for following reaction that independently are selected to realize: radical polymerization, anionoid polymerization, cationoid polymerisation, polycoordination, ring-opening metathesis polymerization (ROMP), acyclic dienes metathesis polymerization (ADMET) and other relate to the polyreaction of stabilized radical (SFR).

6. the emulsion polymerisation process of claim 5, wherein first kind of monomer in described aqueous polymerization medium with second kind of monomer copolymerization, and wherein after all described first kind of monomers and described second kind of monomer are converted into polymkeric substance substantially, the described first kind of monomer of being selected from of additional quantity, described second kind of monomer and other monomeric monomers are joined in the described polymerisation medium, and wherein said polymerization has prepared segmented copolymer.

7. the emulsion polymerisation process of claim 6 wherein saidly is polymerized to radical polymerization, and wherein said control agent is the reagent that is used to control radical polymerization.

8. the emulsion polymerisation process of claim 6, wherein said emulsifying agent in described aqueous polymerization medium by acid/alkali neutralization procedure in-situ preparing.

9. emulsion polymerisation process, described method comprises: (1) preparation monomer solution, described solution is by (a) at least a monomer and (b) pK _aThe conjugate acid of tensio-active agent less than 14 and (c) the radical polymerization control agent form; (2) preparation water-bearing media, described medium by (a) water and (b) the faintly acid conjugate base form the pK of wherein said alkali _bLess than 14; (3) described monomer solution is mixed under the condition that can cause original position formation emulsifying agent with described water-bearing media; (4) cause radical polymerization.

10. the emulsion polymerisation process of claim 9, the pK of the conjugate acid of wherein said tensio-active agent _aIn the scope of 0-7, and the pK of wherein said faintly acid conjugate base _bIn the scope of 0-7.