CN1694905A - Dispersions containing living radicals - Google Patents
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- CN1694905A CN1694905A CN 03824029 CN03824029A CN1694905A CN 1694905 A CN1694905 A CN 1694905A CN 03824029 CN03824029 CN 03824029 CN 03824029 A CN03824029 A CN 03824029A CN 1694905 A CN1694905 A CN 1694905A
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Abstract
The present invention relates to a dispersion of polymer particles, the particle containing, on average, more than 1 living radicals each, the radicals not being chemically protected. The invention is also directed to a free radical polymerization process resulting in a dispersion containing polymer particles having on average one or more living radicals. The process involves carefully regulating the polymerization conditions to produce small size particles under monomer-starved conditions containing, on average, more than one living radical in every particle. These living polymer radicals can be further reacted to form polymers with a controlled architecture.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
The application requires the rights and interests of the U.S. Provisional Application No 60/404,557 of submission on August 19th, 2002.
Technical field
The present invention relates to a kind of dispersion of polymer particle, wherein polymer particle contains, average above living radical of each particle, and these living radicals are protected without chemical mode.Living radical can be used for forming the polymkeric substance with control texture subsequently.
Background technology
In many polymkeric substance were synthetic, radical polymerization was a kind of preferred technology.A shortcoming of radical polymerization is to lack control for the polymer architecture that is generated.The type of initiator and quantity, temperature and delay monomer feed all have been used for controlling final structure and polymer particle size.
Reactive polymer gives certain control to polymer architecture.Reactive polymer is the polymkeric substance that has activity/growth terminal (nonterminated polymer chain) at polymer chain.Prevailing is that reactive terminal forms by carry out anionoid polymerization in non-polar solvent, perhaps relates to end-blocking mechanism the free radical of growth is stopped growing, and resets polymer growth by reversible removal end group then.
Be known in the art with chemical trapping agent as by reversible means with the end-blocked measure of reactive polymer free radical.Unfortunately, this method needs additional purification costs so that remove trapping agent from product.Trapping agent also increases the restriction of kinetics aspect, and this is relevant with the concrete trapping agent that uses.
United States Patent (USP) 5,173,551 and " carrying out the research of methacrylic acid polymeric " by means of the contrary precipitation polymerization technology of free radical, J.Applied Polymer Science, the 62nd volume, 2039-2051 (1996) has narrated the application of free radical reverse polymerization technology as the means of controlling polymers molecular weight distribution.In the method, the monomer mixture in the solvent cause to generate free polymer readical by the radical initiator that dissolves in solvent, and the latter is deposited in the polymer-rich phase in solvent.Above-mentioned patent also relates to the ability of FRRPP controlling polymers free radical activity and produces multipolymer with them.In addition, provide about original process, made possible the equipment of this technology operation, by change temperature and adding or remove monomer or being described in detail of the means of inert diluent conditioned reaction speed.
U.S. Patent application 10/045881 and 10/045725 has been narrated can be by the free radical dispersion and the multipolymer of the contrary precipitation preparation of free radical.The shortcoming of FRRPP is that it need make the poor solvent of polymer precipitation more than lower critical solution temperature.
Need a kind of controlling polymers structure and method that do not have the shortcoming of prior art existence.
Be surprisingly found out that, a kind ofly contain average each particle and have the stable particle dispersion of the particle of an above living radical, can be under the condition that does not have chemical end-capping reagent or amboceptor (mediation) and do not need by free radical to produce under the contrary condition of the described free radical of precipitation polymerization explained hereafter.
Summary of the invention
The present invention relates to a kind of dispersion of polymer particle, described particle contains, average above living radical of each particle, and described free radical is protected without chemical mode.The invention still further relates to a kind of free radical polymerization process, its generation contains the dispersion of the polymer particle that on average has one or more living radicals.This technology comprises that careful adjusting polymerizing condition is to lacking under the monomeric condition, so that generate the small size particles that contains an average above living radical.These reactive polymer free radicals can be again react with other monomer, and perhaps identical monomer is to increase polymericular weight, and perhaps other one or more monomers are to form segmented copolymer, the composition of tapered block copolymer or control texture.Being aggregated under the condition that does not need other initiator in addition carried out.
Description of drawings
Fig. 1 granularity evolution
The GPC curve of six different samples of Fig. 2
The GPC curve of six different samples of Fig. 3
The GPC curve of four different samples of Fig. 4
The GPC curve of four different samples of Fig. 5
Embodiment
Term used herein " dispersion " is used to refer to the external phase that disperse phase is wherein arranged.Disperse phase exists under zone of dispersion or particle shape, if must stablize by tensio-active agent or stablizer.Dispersion is used for being applied to many possible material compositions, includes, but not limited to emulsion, ultra-fine emulsion, microemulsion, precipitation, colloidal dispersion and colloidal suspension.
Term used herein " stablizer " means tensio-active agent, stablizer and other dispersing auxiliary.
Under situation about not being bound by any particular theory, think that small grain size adds careful control initiator and monomeric adding, produce the particle that stable having is trapped in inboard free radical.Because granularity is little,, cause termination speed to descend to the full extent so that free radical is subjected to is sterically hindered.
The method of production polymeric dispersions of the present invention comprises: careful telo merization condition is so that generation and maintenance contain the small-particle of holding back free radical.This concentration by careful adjusting initiator, monomer and stablizer realizes.These are adjusted to the maximization of particle nucleation and minimization of particle size creates conditions.Polymeric dispersions of the present invention generally contains water as external phase.Water-containing solvent external phase that also can application mix is as water/mixable alcohol.In addition, also can use inverse emulsion technology.Hereinafter general narration and embodiment mainly narrate water continuous phase.Those skilled in the art can be applied to other paradigmatic system with identical notion and technology.
In the polymeric the first step, in reactor, add entry, stablizer and radical initiator, and adjusting condition is so that produce free radical.Free radical can produce by heat, redox, uv-radiation, gamma-radiation or other method, depends on selected initiator system.After free radical forms, add raw material monomer, the situation that keeps monomer to lack.Reaction always lacks the monomer that becomes initial reaction phase from initiator and lacks.
The polymeric fs is created in the dispersion of polymer particle in the dispersion medium, preferably in water.Each polymer particle on average contains one or more reactive polymer free radicals.Preferred particle on average contains at least 2 reactive polymer free radicals, more preferably at least 5 reactive polymer free radicals, also more preferably at least 10 reactive polymer free radicals, most preferably at least 20 reactive polymer free radicals.Having produced each polymer particle contains and surpasses 100,1000 or even 10,000 and the particle of more reactive polymer free radical.Reactive polymer particle of the present invention exists under the condition that does not have chemical end-capping reagent known in the art, that add for the temporary protection living radical.Later on temporary transient chemical end-capping reagent is reversible and living radical is exposed.
The living radical of holding back in dispersion particle under the thermal initiation condition keeps the time longer than seven half-lives of initiators, and preferred 15hr at least is most preferably more than several days.The living radical of holding back in redox and other initiator system also has the long life-span, keeps 10min at least.
In case the dispersive monomer reaction to being bordering on 100%, generally is up to 5-10 half-lives of initiators, can add other monomer then in the polymer particle that contains many living radicals.Under the situation that adds same monomer, can form higher molecular weight polymer.Because the termination of particle is controlled, can the controlling polymers molecular weight to the molecular weight that produces any requirement, greater than 3,000,000 molecular weight can produce.Other monomer also can be one or more different monomers, thereby forms segmented copolymer.The inventive method can be produced pure segmented copolymer, because in fact before adding second monomer, all monomers of the first step all should consume.Second the step monomer can advantageously be different from the first step monomer fully, for example, a kind of monomer be hydrophilic and another kind of be hydrophobic situation.Use the inventive method, can access the segmented copolymer and the new segmented copolymer combination of hydrophilic and oleophilic.Present method is not subjected to the restriction of reactivity ratio, only is subjected to the restriction of diffusion and would rather say so.By controlling in the reaction that provides in the inventive method, also can production tapered polymers composition.
Adding other monomeric technology can proceed in any step, and need not add other initiator.
The monomer of Ying Yonging comprises any monomer that can carry out radical chain polymerization in the present invention.Specifically, applied monomer is an ethylenically unsaturated monomers.Example comprises (methyl) acrylate, maleic acid ester, vinyl ester, itaconic ester, vinyl ether, styrenic, unsaturated hydrocarbons, nitrogenous functional group monomer such as vinyl cyanide, alkyl acrylamide, N-vinyl formamide, V-Pyrol RC, zwitterionic monomer or ampholytic monomer, the hydroxyl functional group monomer, macromonomer, (methyl) vinylformic acid and N-hexanolactam.The term of Ying Yonging (methyl) acrylate refers to the derivative of acrylate and methacrylate monomer both and they in this article.Similarly, term (methyl) vinylformic acid refers to vinylformic acid, methacrylic acid and their derivative.As known in the art, also can use low-level cross-linking monomer, to improve some performance of polymkeric substance.
Initial charge can be chosen wantonly and contain polymer latex seed.Think that the using polymer latex seed can be favourable for the free polymer readical of holding back initiation.These seeds can form on the spot by being added to small amounts of monomer in the initial charge and making described monomer carry out polymerization before the delay monomer feed begins.
Dispersion can be by means of tensio-active agent, stablizer, other dispersing auxiliary and dispersion agent, or its mixture is stablized.Useful in the present invention tensio-active agent comprises negatively charged ion, nonionic, positively charged ion and amphoterics.Preferred surfactants is a nonionogenic tenside, as alkylphenol ethoxylate, alkylethoxylate or other ethoxylate.Other tensio-active agent comprises, but is not limited to alkylphenol, alkyl sodium sulfate ester, ether sulfate, phosphoric acid ester and similar anion surfactant.Stablizer can be or polymkeric substance or non-polymer to include but not limited to polyvinyl alcohol and hydrophilic and oleophilic block copolymer stabilizers.Polymeric dispersant includes but not limited to the multipolymer of polymaleic acid and toxilic acid and compatible alkene chain type unsaturated monomer, the monoesters of the latter such as toxilic acid and diester, (methyl) vinylformic acid, (methyl) acrylic acid alkyl ester, (methyl) acrylic acid hydroxy alkyl ester, alpha-methyl styrene, vinylbenzene and derivative, vinyl acetate between to for plastic, butenoic acid, crotonate and acrylamide, with and derivative.Other suitable linear polymer dispersion agent includes but not limited to the polystyrolsulfon acid ester, it typically obtains by the multipolymer sulfonation with polystyrene or vinylbenzene and compatible ethylenically unsaturated monomers, and described unsaturated monomer includes but not limited to the monoesters and the diester of (methyl) vinylformic acid, (methyl) acrylate, toxilic acid and toxilic acid; Condenses includes but not limited to naphthene sulfonic acid-formaldehyde condensation products and melamine-formaldehyde condensation products.In the present invention some of Ying Yonging natural or natural derived polymers include but not limited to tannin, lignin, lignosulfates, alginate, dispersion or soluble starch and treated starch and cellulose polymer compound.But other stabilization aid and dispersing auxiliary can comprise the compound of copolymerization, sodium vinyl sulfonate for example, and it can help stabilization.The mixture of one or more tensio-active agents, stablizer, dispersion agent, or the combination of tensio-active agent and stablizer also can be applicable to the present invention.
Because of polymerization takes place in free radical.Radical-forming agent can generate free radical polymerization such as following mechanism by using one or more, for example photochemistry initiation, thermal initiation, redox initiation, degraded initiation, ultrasonic initiation, ultraviolet ray initiation or gamma-rays initiation etc.Preferably, initiator is selected from azo-type initiator, peroxide type initiator or its mixture.The example of suitable peroxide initiator comprises, but be not limited to, peroxidation two acyls, peroxyester, ketal peroxide, dialkyl peroxide and hydroperoxide, specifically, benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, cumene hydroperoxide, t-butyl peroxy-acetate, 2,2-two (t-butylperoxy) butane, peroxidation diallyl, peroxidation cumyl or its mixture.Suitable and the example of azo-type initiator include, but not limited to Diisopropyl azodicarboxylate (AIBN), 1,1 '-azo two (1-cyclohexane nitrile), sour official can the azo-type initiator as 4,4 '-azo two (4-cyanopentanoic acid).Preferred dispersants is a water, and radical-forming agent is a water soluble starter, as 2, and two (N, N '-amidine propane) two hydrochloric acid or 2 of 2 '-azo, two (N, N '-dimethylene isobutyl amidine) two hydrochloric acid of 2 '-azo.Free radical and the monomer reaction formation polymer chain that exists with equal amount at aqueous phase.
The present invention's reaction is not limited by reactor geometries.Reaction can be batchwise polymerization, semi-batch polymerization or successive polymerization such as tubular reactor.Polymerization can be carried out under normal atmosphere or high pressure.
The polymeric control mechanism does not have strict influence to the second-order transition temperature of polymer product.
Granularity can be controlled by employed and the tensio-active agent during manufacturing and processing dispersion or the type and the quantity of stablizer.Granularity keeps very little state.Be not subjected to the constraint of any particular theory, think because free radical in small-particle, be subjected to sterically hindered, so free radical retaining part activity.Be preferably 1-200nm in the first step mean particle size, more preferably 10-150nm.Size-grade distribution can be approximate unimodal distribution from the multimodal profile adjustment than broad.Granularity in second step is generally more than the 100nm, can be up to several microns.
The solids content of copolymer dispersion can be 5-50wt%, is preferably 10-30wt%.
The termination of free polymer readical can be finished by a step or a few step, for example reduce reaction chamber temperature, increase chamber pressure, the appropriate solvent that adds resulting polymers, (for example add suitable chain-transfer agent, the thioalcohol type chain-transfer agent) in system, perhaps by adding suitable radical scavenger (as oxygen).
Can use polymerization process and produce high-molecular weight homopolymer, and block copolymer structure, comprise diblock, three blocks and alternation block.The composition of block can be formed and meets the demands by regulating monomer feed.Other polymer architecture that can produce includes, but not limited to many blocks, comb shaped structure, block graft, two sense initiated polymerization thing and radial polymers.
The polymeric dispersions of producing by the inventive method can be applied to tackiness agent, paint, industrial coating, ink, membrane-forming agent, polymeric surface active agent, stablizer, toughner, base-material, nonwoven material, the property additive, rheology modifier, thermoplastic elastomer, the polymkeric substance compatibilizing agent, biological adhesive, be used to control the encapsulant of peeling off, nano particle, nanogel, redispersible powder, film, composite organic-inorganic material, porous-film, structural polymer, engineering plastics, air-permeable envelope, the medical thing of imbedding, bioavailable polymer and various other industrial application.
The inventive method is difficult to create condition with the multipolymer that other means obtain for producing economically, for example, but be not limited to Vinyl Acetate Copolymer-block-polystyrene, polyvinyl ether-block-polystyrene, polyvinyl ester-block-poly-(methyl) acrylate such as polyvinyl acetate (PVA)-block-polymethylmethacrylate.
Now provide following embodiment to be used for further illustrating and explain the present invention, but should be as the restriction to any aspect.The gained emulsion is at room temperature stable, even also do not occur conspicuous layering or sedimentation after 1 year.The feature of gained multipolymer adopts heat to analyze (dsc) and fractionation/solvent extraction to carry out its block structure and check and characterize.
Example I
The first step: will be in water (150ml), the tensio-active agent (sodium lauryl sulphate in the four neck round-bottomed flasks, Rhodia) (3g) and initiator (0.3g) (2; 2 " two (N, N '-amidine propane) two hydrochloric acid or the V-50 of-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene monomers (33ml) in slow feed hopper is with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃, stirs 20min simultaneously.Under 50 ℃, slowly add styrene monomer (7ml) and last 5min, slowly add all the other monomers again and last 3hr.
Second step: reaction mixture is cooled to 60 ℃.Prepare pre-emulsion by following step: will not hinder poly-butyl acrylate (78.3ml) and be added drop-wise to and water (25ml) and tensio-active agent be housed (sodium lauryl sulphate Rhodia) in the beaker of (2.1g), adopts simultaneously that mixing tank is fierce to be mixed.Slowly use nitrogen purging gained pre-emulsion 30min in the feed hopper, and under 60 ℃, lasted 1hr its slow adding.Reaction mixture is stirred 3hr, cool to room temperature then down at 60 ℃.
Example II
The first step: will be in water (150ml), the tensio-active agent (sodium lauryl sulphate in the four neck round-bottomed flasks, Rhodia) (3g) and initiator (0.3g) (2; 2 " two (N, N '-amidine propane) two hydrochloric acid or the V-50 of-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene monomers (33ml) in slow feed hopper is with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃, stirs 20min simultaneously.Under 50 ℃, slowly add styrene monomer (7ml) and last 5min, slowly add all the other monomers again and last 3hr.
Second step: reaction mixture is cooled to 60 ℃.Prepare pre-emulsion by following step: will not hinder poly-vinylbenzene (77.0ml) and be added drop-wise to and water (25ml) and tensio-active agent be housed (sodium lauryl sulphate Rhodia) in the beaker of (2.1g), adopts simultaneously that mixing tank is fierce to be mixed.Slowly use nitrogen purging gained pre-emulsion 30min in the feed hopper, and under 60 ℃, lasted 1hr its slow adding.Reaction mixture is stirred 3hr, cool to room temperature then down at 60 ℃.
EXAMPLE III
The first step: the water (150ml) in four neck round-bottomed flasks, tensio-active agent (sodium lauryl sulphate, Rhodia) (3g) and initiator (0.3g) (2; 2 " two (N, N '-amidine propane) two hydrochloric acid or the V-50 of-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene in slow feed hopper and methacrylic acid monomer mixture (35ml) are with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃, stirs 20min simultaneously.Under 50 ℃, slowly add monomer mixture (7ml) and last 5min, slowly add all the other monomers again and last 3hr.
Second step: reaction mixture is cooled to 60 ℃.Prepare pre-emulsion by following step: will not hinder poly-butyl acrylate (78.3ml) and be added drop-wise to and water (25ml) and tensio-active agent be housed (sodium lauryl sulphate Rhodia) in the beaker of (2.1g), adopts simultaneously that mixing tank is fierce to be mixed.Slowly use nitrogen purging gained pre-emulsion 30min in the feed hopper, and under 60 ℃, lasted 1hr its slow adding.Reaction mixture is stirred 3hr, cool to room temperature then down at 60 ℃.
EXAMPLE IV
The first step: will be in water (150ml), the tensio-active agent (sodium lauryl sulphate in the four neck round-bottomed flasks, Rhodia) (3g) and initiator (0.3g) (2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] two hydrochloric acid or the VA-044 of 2 '-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene monomers (35ml) in slow feed hopper is with nitrogen purging 30min under the surface.Reaction mixture is heated to 65 ℃, stirs 20min simultaneously.Under 50 ℃, slowly add styrene monomer (7ml) and last 5min, slowly add all the other monomers again and last 3hr.
Second step: reaction mixture is cooled to 60 ℃.Prepare pre-emulsion by following step: will not hinder poly-butyl acrylate (78.3ml) and be added drop-wise to and water (25ml) and tensio-active agent be housed (sodium lauryl sulphate Rhodia) in the beaker of (2.1g), adopts simultaneously that mixing tank is fierce to be mixed.Slowly use nitrogen purging gained pre-emulsion 30min in the feed hopper, and under 60 ℃, lasted 1hr its slow adding.Reaction mixture is stirred 3hr, cool to room temperature then down at 60 ℃.
EXAMPLE V
The first step: will be in the water (203ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (2.9g) and initiator (0.2g) (2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] two hydrochloric acid or the VA-044 of 2 '-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene (31ml) in slow feed hopper is with nitrogen purging 30min under the surface.It is slowly reinforced at room temperature to begin to carry out styrene monomer, 3ml vinylbenzene is slowly added last 5min.Reaction mixture is heated to 75 ℃, stirs 15min simultaneously.All the other monomers are lasted 1.5hr slow the adding.When vinylbenzene slowly added end, stirred reaction mixture 1.5hr was cooled to 60 ℃ simultaneously.
Second step: slowly do not hindering polystyrene (30ml) with nitrogen purging 30min in the feed hopper, under 60 ℃, lasted 2hr its slow adding.At 60 ℃ of following stirred reaction mixture 1hr, cool to room temperature then.
Example VI
The first step: will be in the water (200ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (3.9g) and initiator (0.1g) (2; 2 " two (the N of-azo, N '-amidine propane) two hydrochloric acid or V-50, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene (21ml) in slow feed hopper is with nitrogen purging 30min under the surface.It is slowly reinforced at room temperature to begin to carry out styrene monomer.Reaction mixture is heated to 80 ℃, stirs 10min simultaneously, 5ml vinylbenzene is slowly added last 10min, temperature of reaction reaches 80 ℃ then, slowly adds basic surplus monomer again and lasts 1.5hr.When vinylbenzene slowly adds end, at 80 ℃ of following stirred reaction mixture 1.5hr.Measure transformation efficiency and molecular weight with irregular time sampling.
Second step: reaction mixture is cooled to 60 ℃.Slowly do not hinder poly-vinylbenzene (36ml) 30min with nitrogen purging in the feed hopper, and under 60 ℃, lasted 2hr its slow adding.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.Timing sampling is measured transformation efficiency and molecular weight.
Example VII A (25D)
The first step: will be in water (175ml), the tensio-active agent (sodium lauryl sulphate in the four neck round-bottomed flasks, Rhodia) (2.5g) and initiator (0.5g) (2; 2 " two (N, N '-amidine propane) two hydrochloric acid or the V-50 of-azo, Wako chemicals) uses nitrogen purging 45min.Not resistance polystyrene (55ml) in slow feed hopper is with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃, stirs 20min simultaneously.Under 50 ℃, monomer mixture (7ml) is lasted 5min slow the adding, slowly add all the other monomers again and last 3hr.
Second step: reaction mixture is cooled to 60 ℃.Slowly do not hinder polystyrene (55ml) with nitrogen purging 30min in the feed hopper, under 60 ℃, lasted 1hr its slow adding.At 60 ℃ of following stirred reaction mixture 3hr, cool to room temperature then.
Example VII A I (108)
The first step: will be in the water (200ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (3.9g) and initiator (0.1g) (2; 2 " two (the N of-azo, N '-amidine propane) two hydrochloric acid or V-50, Wako chemicals) use nitrogen purging 45min, the not resistance polystyrene (20.7ml) in slow feed hopper is with nitrogen purging 30min under the surface.It is slowly reinforced at room temperature to begin to carry out styrene monomer, is heated to 80 ℃ simultaneously, slowly adds 5ml vinylbenzene and lasts 20min, and later temperature of reaction reaches 80 ℃, slowly adds all the other monomers again and lasts 1.5hr.When vinylbenzene slowly adds end, at 80 ℃ of following stirred reaction mixture 30min.
Second step: reaction mixture is cooled to 60 ℃.Slowly do not hinder polystyrene (35ml) 30min with nitrogen purging in the feed hopper, and under 60 ℃, lasted 2hr its slow adding.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.
Example I X (137)
The first step: will be in the water (200ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (3.9g) and initiator (0.19g) (2; 2 " two (the N of-azo, N '-amidine propane) two hydrochloric acid or V-50, Wako chemicals) use nitrogen purging 45min, the not resistance Vinyl Acetate Copolymer (21ml) in slow feed hopper is with nitrogen purging 30min under the surface.At room temperature begin to carry out slow the feeding in raw material of Vinyl Acetate Monomer and be heated to 80 ℃ simultaneously.The 5ml vinyl acetate between to for plastic is lasted 20min slow the adding, and temperature of reaction reaches 80 ℃ then, slowly adds all the other monomers again and lasts 1.5hr.When monomer slowly adds end, at 80 ℃ of following stirred reaction mixture 30min.
Second step: reaction mixture is cooled to 60 ℃.Slowly do not hinder poly-vinylbenzene (41ml) 30min with nitrogen purging in the feed hopper, and under 60 ℃, lasted 2hr its slow adding.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.
Embodiment X
The first step: will be in water (200ml), the tensio-active agent (sodium lauryl sulphate in the four neck round-bottomed flasks, Rhodia) (5.1g) and initiator (0.3g) (2; 2 " two (N, N '-amidine propane) two hydrochloric acid or the V-50 of-azo, Wako chemicals) uses nitrogen purging 45min.The methyl methacrylate (33ml) that not resistance in slow feed hopper gathers is with nitrogen purging 30min under the surface.It is slowly reinforced at room temperature to begin to carry out methyl methacrylate (MMA) monomer, is heated to 80 ℃ simultaneously.Add 3ml MMA and last 5min in flask, temperature reaches 80 ℃ then, slowly adds all the other monomers again and lasts 2.5hr.When monomer slowly adds end, at 80 ℃ of following stirred reaction mixture 30min.
Second step: reaction mixture is cooled to 60 ℃.In slow feed hopper, do not hinder the positive butyl ester of polyacrylic acid (78ml) 30min and under 60 ℃, it is slowly added and last 1hr with nitrogen purging.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.
Embodiment XI and XII show, from monomeric residual inhibitor the second step conversion of monomer are exerted an influence.The monomeric level of inhibitor that embodiment XI uses is than embodiment XII height.As seen, do not find that in embodiment XI second step transformed (Table I).
Embodiment XI
The first step: will be in the water (200ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (4.2g) and initiator (0.1g) (2; 2 " two (the N of-azo, N '-amidine propane) two hydrochloric acid or V-50, Wako chemicals) uses nitrogen purging 45min.The vinylbenzene (21ml) that not resistance in slow feed hopper gathers is with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃ stirs 20min simultaneously.It is slowly reinforced at room temperature to begin to carry out styrene monomer, slowly adds 5ml vinylbenzene and lasts 10min, and later temperature of reaction reaches 80 ℃, slowly adds all the other monomers again and lasts 1.5hr.When vinylbenzene slowly feeds in raw material end, at 80 ℃ of following stirred reaction mixture 30min.
Second step: reaction mixture is cooled to 60 ℃.In slow feed hopper, do not hinder butyl polyacrylate (36ml) 30min and under 60 ℃, it is slowly added and last 2hr with nitrogen purging.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.
Embodiment XII
The first step: will be in the water (200ml) in the four neck round-bottomed flasks, tensio-active agent (IgepalCA-897 octylphenol ethoxylate, Rhodia) (4.2g) and initiator (0.1g) (2; 2 " two (the N of-azo, N '-amidine propane) two hydrochloric acid or V-50, Wako chemicals) uses nitrogen purging 45min.The vinylbenzene (21ml) that not resistance in slow feed hopper gathers is with nitrogen purging 30min under the surface.Reaction mixture is heated to 80 ℃ stirs 20min simultaneously.It is slowly reinforced at room temperature to begin to carry out styrene monomer, slowly adds 5ml vinylbenzene and lasts 10min, and later temperature of reaction reaches 80 ℃, slowly adds all the other monomers again and lasts 1.5hr.When vinylbenzene slowly feeds in raw material end, at 80 ℃ of following stirred reaction mixture 30min.
Second step: reaction mixture is cooled to 60 ℃.In slow feed hopper, do not hinder butyl polyacrylate (36ml) 30min and under 60 ℃, it is slowly added and last 2hr with nitrogen purging.At 60 ℃ of following stirred reaction mixture 2hr, cool to room temperature then.
All embodiment that provide are sampling regularly all, measures transformation efficiency, granularity and molecular weight.Transformation efficiency adopts weight analysis determining, and molecular weight is measured with size exclusion chromatography, with the Waters Associates system that adopts Waters styragel post and polystyrene standards.Brookhaven Instruments BI90 is all adopted in the particle size measurement of these embodiment or the BI90plus particle-size analyzer carries out.Transformation efficiency, molecular weight and granularity data are listed in the Table I.
In order to extract homopolymer and to contain a lot of polymkeric substance of a kind of monomer,, adopt two kinds of different solvents that dry polymer is imposed Soxhlet extractron based on the solvability of every kind of polymeric constituent.The second-order transition temperature of all residues adopts the thermal instrument dsc to measure.Adopt Bruker NMR spectrometry instrument to impose composition measuring mutually with residue with all extraction phases of proton NMR spectrometry.The Soxhlet extractron of EXAMPLE III the results are shown in Table II.The granularity of example I differentiation curve in time is shown in figure I.The GPC color atlas of example II, I, VII and VIII is shown in respectively among figure II, III, IV and the V.
Table I. each embodiment transformation efficiency and molecular weight data
| Embodiment | Total conversion rate | The % solid 1 | Granularity (nm) | Molecular weight (Mn) 2 | |||
| The I step | Finally | The I step | Finally | The I step | Finally | ||
| ??I | ??83.21 | ??95.93 | ??36 | ??36 | ??45 | ??28,000 | ??1,136,000 |
| ??II | ??73.56 | ??66 | ??25 | ??127 | ??61 | ??25,000 | ??120,000 |
| ??III | ??75.7 | ??64.38 | ??23 | ??- | ??84 | ??18,000 | ??2,476,000 |
| ??IV | ??80.47 | ??96.99 | ??34 | ??153 | ??144 | ??l35,000 | ??138,000 |
| ??V | ??80.14 | ??69.12 | ??16 | ??78 | ??149.5 | ??58,000 | ??116,000 |
| ??VI | ??82.54 | ??86.36 | ??20 | ??63.7 | ??553.8 | ??1,539,000 | ??1,580,000 |
| ??VII | ??70.57 | ??66.93 | ??22 | ??273 | ??127 | ??9,000 | ??40,000 |
| ??VIII | ??83.2 | ??96 | ??21 | ??59 | ??105 | ??41,000 | ??135,000 |
| ??IX | ??76.4 | ??81.5 | ??23 | ??53 | ??88 | ??11,000 | ??1,458,000 |
| ??X | ??94.2 | ??81.9 | ??30 | ??21 | ??67 | ??15000 | ??25,000 |
| ??XI | ??89.75 | ??36.66 | ??9 | ??57.7 | ??91 | ??77,000 | ??52,000 |
| ??XII | ??85.96 | ??68.03 | ??16 | ??58.4 | ??141.2 | ??103,000 | Do not analyze |
Table II. the Soxhlet extractron result
| Weight % | ??????????????T g℃ | NMRmol% forms | |||||
| ??BA | ??MMA | Vinylbenzene | |||||
| EXAMPLE III (dry polymer) | ??- | ??-55.98 | ??-25.07 | ??104 | ??48.05 | ??51.95 | |
| EXAMPLE III (Soxhlet extractron in acetone): | |||||||
| Flask | ??53 | ??-54.7 | ??- | ??103 | ??54.8 | ??45.2 | ??- |
| Sleeve pipe | ??- | ??-52.89 | ??- | ??101 | ??51.04 | ??48.96 | ??- |
| EXAMPLE III (Soxhlet extractron in ethyl acetate): | |||||||
| Flask | ??38.8 | ??-54.09 | ??- | ??117 | ??48.33 | ??51.67 | ??- |
| Sleeve pipe | ??8.2 | ??-51.7 | ??- | ??110 | ??51.81 | ??48.19 | ??- |
1Be rounded up to immediate %
2Be rounded up to immediate 1000 dalton
Claims (28)
1. one kind comprises the dispersion that is dispersed in the copolymer particle in the dispersion medium, wherein said each polymer particle contains, 1 above living radical in each polymer particle, and wherein said dispersion do not contain chemical end-capping reagent, do not need organic solvent to make polymer precipitation.
2. the dispersion of claim 1, wherein said each polymer particle contains, on average 3 above living radicals in each polymer particle.
3. the dispersion of claim 2, wherein said each polymer particle contains, on average 5 above living radicals in each polymer particle.
4. the dispersion of claim 3, wherein said each polymer particle contains, on average 20 above living radicals in each polymer particle.
5. the dispersion of claim 4, wherein said each polymer particle contains, on average 100 above living radicals in each polymer particle.
6. the dispersion of claim 5, wherein said each polymer particle contains, on average 1000 above living radicals in each polymer particle.
7. the dispersion of claim 1, the mean particle size of wherein said polymer particle is 10-10,000nm.
8. the dispersion of claim 7, the mean particle size of wherein said polymer particle is 10-1000nm.
9. the dispersion of claim 8, the mean particle size of wherein said polymer particle is 20-400nm.
10. the dispersion of claim 1, wherein said polymer particle has unimodal or the multimodal size-grade distribution.
11. the dispersion of claim 1, wherein said dispersion medium comprises water.
12. the dispersion of claim 1, wherein said dispersion also contains organic thinner.
13. the dispersion of claim 1, wherein said polymer particle comprises block polymer.
14. the dispersion of claim 1, wherein said polymer particle comprises tapered block copolymer.
15. a production has the method for the polymkeric substance of control texture, comprising:
A) form the first step stabilising dispersions, its method comprises:
In dispersion medium, adopt the radical source initiated polymerization to make one or more monomer polymerizations, and randomly use tensio-active agent, stablizer or dispersion agent with the stabilization of polymer dispersion, and do not use chemical polymerization conditioning agent or end-capping reagent, wherein said particle contains, on average 1 above living radical of each particle; With
B) other monomer is joined in the first step dispersion, expand the polymer chain that is pre-existing in by other monomer and the living radical reaction that in step a), produces.
16. the method for claim 15, wherein said dispersion medium is a water.
17. the method for claim 15, wherein said the first step dispersion by regulate described granularity, monomer and/or solvent strength in described particle forms.
18. the method for claim 15, wherein said radical-forming agent is a water soluble starter.
19. the method for claim 15 also comprises: in step (b) afterwards, at least a other monomer joined describedly have activity and hold back in the polymer dispersion of free radical.
20. the method for claim 15, wherein the other monomer in step (b) comprises and monomer identical in the first step polymerization.
21. the method for claim 15, wherein the other monomer in step (b) comprises at least a monomeric monomer of the first step that is different from, and forms segmented copolymer.
22. the method for claim 15, wherein said dispersion medium (a) is two or more mixtures of liquids.
23. the method for claim 15, wherein said stablizer are a kind of colloids.
24. the method for claim 15, wherein said glass or plastic containers.
25. the method for claim 15, wherein said segmented copolymer are pure segmented copolymers.
26. the method for claim 15, wherein said the first step monomer and the described second step monomer comprise at least a hydrophobic monomer and at least a hydrophilic monomer.
27. a segmented copolymer dispersion, wherein said dispersion does not contain chemical end-capping reagent or organic solvent.
28. comprise tackiness agent, coating or the encapsulant of claim 27 segmented copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40455702P | 2002-08-19 | 2002-08-19 | |
| US60/404,557 | 2002-08-19 | ||
| US10/632,764 | 2003-08-01 |
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| CN2008101693897A Division CN101386652B (en) | 2002-08-19 | 2003-08-14 | Dispersions containing living radicals |
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| CN1694905A true CN1694905A (en) | 2005-11-09 |
| CN100549033C CN100549033C (en) | 2009-10-14 |
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| CNB038240297A Expired - Fee Related CN100549033C (en) | 2002-08-19 | 2003-08-14 | The dispersion that contains living radical |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5627248A (en) * | 1995-09-26 | 1997-05-06 | The Dow Chemical Company | Difunctional living free radical polymerization initiators |
| CA2229978A1 (en) * | 1996-06-04 | 1997-12-11 | Elf Atochem S.A. | Method for preparing telechelic 1,3-diene oligomers by the controlled free radical polymerization of 1,3-dienes in presence of a stable free radical |
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| Publication number | Publication date |
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| CN101386652B (en) | 2011-12-07 |
| CN101386652A (en) | 2009-03-18 |
| CN100549033C (en) | 2009-10-14 |
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