CN101134801A - Polymerisation particles, entirety of the polymerisation particles or mixture and rubber latex - Google Patents
Polymerisation particles, entirety of the polymerisation particles or mixture and rubber latex Download PDFInfo
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- CN101134801A CN101134801A CNA2006101011935A CN200610101193A CN101134801A CN 101134801 A CN101134801 A CN 101134801A CN A2006101011935 A CNA2006101011935 A CN A2006101011935A CN 200610101193 A CN200610101193 A CN 200610101193A CN 101134801 A CN101134801 A CN 101134801A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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Abstract
A process for the emulsion polymerization in the presence of a stable free radical of at least one monomer which can be polymerized by the radical route, which emulsion comprises a liquid aqueous phase and a liquid organic phase, the aqueous phase comprising at least 50% by weight of water and the liquid organic phase comprising more than 50% by weight of monomer(s) to be polymerized. The invention results, by a rapid controlled polymerization process, in a latex of polymer particles, it being possible for the polymer to comprise acrylate and/or methacrylate blocks.
Description
The application is that application number is dividing an application of the female case of CN03145856.4.The applying date of this mother's case is on July 10th, 1999; Denomination of invention is " overall or the mixture and the latex of polymer beads, polymer beads ".
Technical field
The latex that the present invention relates to the overall or mixture (combination) of polymer beads, these polymer beads and contain the overall or mixture of these polymer beads.
Summary of the invention
The present invention about at least-kind through free radical in other words the radical approach can the polymeric monomer emulsion polymerisation process in the presence of-kind of stable free radical, it comprises a liquid water and a liquid organic phase, described water contains the water of at least 50% (weight), described liquid organic phase contain 50% (weight) above want polymeric monomer (one or more).With the method for quick controlled polymerization, the present invention makes a kind of polymer beads latex.The polymkeric substance polymolecularity that obtains (ratio of weight-average molecular weight and number-average molecular weight, Mw/Mn) low.If number-average molecular weight linearly raises with the transforming degree that monomer is transformed into polymkeric substance, polymerization process is controlled.Leave linearity, then control is bad more.The paradigmatic system of control is the paradigmatic system of a work equally, therefore can obtain segmented copolymer.The present invention can make the sequential polymerization thing that contains vinylformic acid and/or methacrylate type block especially.
Emulsion contains a water order and an organic phase.Water contains the water of at least 50% (weight).The liquid organic phase all contains wait polymeric monomer more than 50% (weight) in each polymerization moment.
Emulsion contains a kind of emulsifying agent and best a kind of radical polymerization initiator equally.
Water is an emulsion external phase, so organic phase is in the dispersed of droplet form.
Emulsion comprises-kind of stable free radical.
Stable free radical is not mixed the free radical that the latter obtains as the initiator as superoxide, oxyhydroxide and azo-type by polymerization starter commonly used mutually with the free radical in short-lived (a few second).The polymerization starter free radical trends towards quickening polymerization.On the contrary, stable free radical trends towards slowing down polymerization usually.Usually can say that on meaning of the present invention, if if not polymerization starter with under use condition of the present invention, free radical is stable, free radical mean lifetime at least 5 minutes.In this life, stable free radical molecule replaces the free radical state always and is connected in the state of the base on the polymer chain by covalent linkage.Certainly, all be satisfactory stability in the whole within the scope of the present invention use of preferably stable free radical.Usually, at ambient temperature, stable free radical can separate at the free radical state.Stable free radical is enough stable so that its free radical state can characterize with spectrography.
Stable free radical generates a polymer chain reversible key with growth in polymerization.At the polymkeric substance end of the chain, stable free radical alternately is connected in the state of the base on the described chain and the stable free radical state that leaves from described chain by covalent linkage always, and back one book attitude is in order to press following process embedding-individual monomeric unit:
2)-M·+M+Y·→·M-M-Y
Wherein, the list of-M representative-individual chainpropagation is ashamed, and M representative-individual unit Y representative is free radical (F stable under the situation of simple function for the latter
SFR=1, F
SFRRepresent the functionality of stable free radical, i.e. positional number on the same stable free radical molecule that is the free radical state).It is to embed monomer to increase polymer chain between growing chain and stable free radical that this process repeats purpose.
The notion of submitting to annotate 45 free radicals that spread to is for known to the professional, be meant continue to air in the environment around and humidity anergy like that-kind of base, pure base can use and store at ambient temperature, need not more take care (about this problem is seen D.Gtiller et K. lngold than most of commodity chemical, A.ocounts of Chemioal Re.search, 1976,9,13-19, perhaps Orgallio Chemiqtty of StableFroo Raaicals, A.foneoster et Coll., Academic Press, 1968).
Stable free radical series obviously comprises for monomer stores as the compound of radical polymerization inhibitor and stable nitroxyl, promptly contains=the N-O base.
Can use the base represented by following formula as stable free radical:
Wherein n represents an integer (non-zero), R1, R2, R3, R4, R ' 1 and R ' 2 can be identical or different, represent a hydrogen atom, a halogen atom is (as chlorine, bromine or iodine), a collinear, ramose or annular, saturated or unsaturated alkyl, as alkyl or phenyl, or an ester group-COOR or an alkoxyl group-OR, a phosphonate group-PO (OR) 2, or a polymer chain for example can be poly-(methyl) alkyl acrylate chain such as polymethylmethacrylate, polydiene chain such as polyhutadiene, polyolefin chain such as polyethylene or polypropylene, but preferred polystyrene chain, R5 wherein, R6, R7, R8, R9 and R10 can be identical or different, can be selected from R1, R2, R3, R4, the base of R ' 1 and R ' 2 same item in addition also can representation hydroxy-OH, acidic group as-COOH or-PO (OH)
2Perhaps-SO
3H.
Particularly, stable free radical can be Ciba fine chemicals company provide 2,2,5,5-tetramethyl--1-pyrrolidyl oxygen (PROXYL), 2,2,6,6-tetramethyl--piperidino oxygen (TEMPO), 4-hydroxyl-2,2,6,6-tetramethyl--piperidino oxygen (4-hydroxyl TEMPO) or two (1-hydroxyl-2,2,6,6-tetramethyl piperidine-4-yl) sebate (CXA5415).
Stable free radical is selected from following compounds equally:
-N-the tertiary butyl-1-phenyl-2-methyl-propyl nitro oxide or title nitrogen oxygen base (meaning nitroxide),
-N-the tertiary butyl-1-(2-naphthyl)-2-methyl-propyl nitro oxide,
-N-the tertiary butyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide,
-N-the tertiary butyl-1-dibenzyl phosphono-2,2-dimethyl propyl nitro oxide,
-N-phenyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide,
-N-phenyl-1-diethyl phosphonyl-1-methylethyl nitro oxide,
-N-(1-phenyl-2-methyl-propyl)-1-diethyl phosphonyl-1-methylethyl nitro oxide,
-4-oxo-2,2,6,6-tetramethyl--piperidino oxygen,
-2,4,6-three-tertiary butyl phenoxy group.
Stable free radical preferably contains the connection chain of following formula:
R wherein
LBase represents molecular weight greater than 15.R for example
LBase can be selected from the front to R
1, R
2, R
3, R
4, R '
1And R '
2The base of being considered (representing molecular weight greater than 15) from them.For the nitrogen-atoms of nitrooxy, univalent R
LBasis representation is in the β position.The residual valence of carbon atom and nitrogen-atoms can link with various bases in the formula (1), for example hydrogen atom, alkyl, the aryl or aralkyl of alkyl as containing 1～10 carbon atom.Be not precluded within the formula (1) between the carbon atom and nitrogen-atoms with continuous in the middle of the divalent radical, form a ring.Yet residual valence preferably is connected on some monad radicals between middle carbon atom of formula (1) and the nitrogen-atoms.Preferably, R
LBase represents molecular weight greater than 30.For example, the RL base can be between the molecular weight 40～450.For example, R
LBase can be a base that contains phosphoryl, described R
LCan represent with following:
R wherein
11And R
12Can be identical or different, can be selected from alkyl, cycloalkyl, alkoxyl group, aryloxy, aryl, aralkoxy, perfluoroalkyl, aralkyl and 1～20 carbon atom can be arranged.R
11And R
12Can be a halogen atom such as chlorine or bromine or fluorine or iodine equally.R
LCan contain an aromatic ring equally at least as phenyl or naphthyl, the latter can for example be replaced by the alkyl that contains 1～4 carbon atom.
Stable free radical can feed so that (SFR) * F
(SFR)By 110
-1To 110
-3The moles/mole monomer, (SFR) mole number of representative stable free radical in emulsion, F
(SFR)Represent the functionality of stable free radical, i.e. the position number on same stable free radical molecule of the state of expression base.
As functionality F
SFREqual 1 stable free radical example, can point out by
Represented molecule, its R1, R2, R3, R4, R5, R6, R7 and R8 represent alkyl.
As functionality F
SFREqual 2 stable free radical example, can point out by
Represented molecule, its R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8It is integer (non-zero) that base is represented alkyl, n.
Preferably, according to 0.1g/l and 1g/l water are better at least, stable freedom is based in 25 ℃ of following water solubles.
All polymerization starters, as organic superoxide and hydroperoxide, for example dibenzoyl superoxide or dicumyl peroxide or 3,3-two (tert-pentyl peroxide)-ethyl butyrate all is an available.Following compound equally also can be proposed as initiator:
-following azo derivative:
Azo two (isopropyl cyanide),
4,4 '-azo two (4-cyanopentanoic acid),
2, two (2-amidine propane) dihydrochlorides of 2 '-azo,
-mistake salt, particularly persulphate such as Potassium Persulphate (K
2S
2O
8) or ammonium persulphate,
-redox couple such as Fe
2+/ H
2O
2, POH/Ce
4+(R is organic radical such as alkyl or aryl herein), K
2S
2O
8/ Fe
2+, K
2S
2O
8/ Na
2S
2O
5
Preferred initiator is can be water-soluble, and promptly its solubleness at aqueous phase is at least 1g/l under 25 ℃.When emulsion is not microemulsified, even more important for this condition of initiator solubleness.Can add the third material so that improve the solubleness of initiator at aqueous phase at described aqueous phase.For example, if initiator is 4,4 '-azo two (4-cyanopentanoic acid), the third material can be sodium hydroxide, potassium hydroxide or ammonia.The third material can exist in aqueous phase according to the amount of one mole of the third material/mole initiator.
Initiator can be fed so that make (AMO) * F
AMOBy 110
-4To 110
-1The moles/mole monomer (AMO) is represented the mole number of initiator, F
AMOBe the functionality of initiator, promptly present the position number of various initiator molecules energy regenerated free radical states.
As functionality F
AMOBe 2 initiator example, can propose K
2S
2O
8
As functionality F
AMOBe 4 initiator, can propose 3,3-two (uncle-amyl peroxy)-ethyl butyrate can be expressed from the next:
Respectively can generate two connection chain-O-O-that are the position of free state because it contains two, be exactly-O '.
Preferred [F
SFR* (SFR)]/[F
AMO* (AMO)] be 0.1～5.
Stable free radical can be with among stable radical form or the molecular form feeding polymerisation medium, and molecule contains the group that can generate stable free radical when polymerization.
For example, for when in polymerisation medium, feed contain can situation with the molecule of-base that A Y represents under, described base can generate stable free radical Y when polymerization; Must consider the whole-A-Y base of feeding when beginning, within definite scope of on top described (SFR) quantity.In any case within this routine scope, if when generating Y ' ,-A base is a kind of polymerization starter, should consider equally at the whole-A-Y base that begins to feed within definite scope of above-mentioned (AMO) quantity.
Such-A-Y based compound that can generate stable free radical Y when polymerization can be an emulsifying agent itself.Such a kind of have stable free radical generate base emulsifying agent can a kind of stable free radical and can take off a proton on the hydrocarbon chain radical initiator in the presence of, the emulsifying agent that will contain the hydrocarbon chain that preferably has 5 carbon atoms at least is heat-treated and is obtained.Such thermal treatment for example can contain 410
-3～110
-2The emulsifying agent, 410 of mole
-3～110
-2Mole initiator, 410
-2～110
-1In 70～150 ℃, carry out under preferred 80～125 ℃ on a kind of medium of mole solvent.
Such initiator can be a kind of organo-peroxide or hydroperoxide, for example can be selected from following compounds.
The sec.-propyl list peroxidation carbonic acid tert-butyl ester,
2-ethylhexyl list peroxidation carbonic acid tertiary butyl ester,
Dicumyl peroxide,
Tert-butyl peroxide,
1,1 two (tert-butyl hydroperoxide) hexanaphthene,
1,1 two (tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane,
The tert-butyl hydroperoxide acetic ester,
The cumyl tert-butyl peroxide,
Tert butyl peroxy benzoate,
Tert-butyl hydroperoxide-2 ethylhexoate.
Preferably, the stable free radical that feeds polymerisation medium links to each other with emulsifying agent at least partially, and promptly emulsifying agent preferably at least partly is the base that band generates stable free radical.
Therefore, stable free radical is effective especially, and making it might be than with emulsifying agent not with the same quadrat method feeding amount of stable free radical not still less.
Hydrocarbon chain belongs to the hydrophobic part of emulsifying agent.This chain can be the alkyl type, polystyrene type, perhaps can be an aliphatic chain.
Emulsifying agent is a kind of tensio-active agent of energy stable emulsion.Any emulsifying agent commonly used in this class emulsion all can use.
Emulsifying agent can be negatively charged ion, positively charged ion or non-ionic.Emulsifying agent can be amphoteric or connect four carbon atom or quaternary salt or fluorine-containing tensio-active agent.It can be selected from alkyl or aryl vitriol, alkyl or aryl sulfonate, soap, polyvinyl alcohol, many fatty alcohol ethoxylates.As an example, emulsifying agent can be selected from following compounds:
-Sodium Lauryl Sulphate BP/USP,
-Sodium dodecylbenzene sulfonate,
-sodium stearate,
The many ethoxylates of-nonylphenol,
-dihexyl sodium sulfosuccinate,
-dioctyl sodium sulphosuccinate,
-bromination lauryl dimethyl ammonium,
-lauryl amido betaine,
-mistake fluorine octyl group potassium acetate.
Emulsifying agent can be block or statistics or grafted amphipathic copolymer equally, as Sodium styrene sulfonate multipolymer, particularly polystyrene-embedding-poly-(Sodium styrene sulfonate).
The total amount that emulsifying agent feeds in the polymerisation medium is 1～10% for monomeric amount.
Emulsion can be a kind of microemulsion, and promptly organic phase forms diameter less than 2 μ m among the emulsion, is generally dripping of 100～1000nm.
Because the existence of shearing stress that medium is enough and hydrophobic polymer and solubility promoter obtains microemulsion.
Hydrophobic polymer should be dissolved in organic phase, is better than under 25 ℃ the solubleness in water most less than 110
-6G/l and weight-average molecular weight equal 100000 at least, for example between 100000～400000.As an example, hydrophobic polymer can be polystyrene, polymethylmethacrylate, butyl polyacrylate.
For wanting the polymeric monomer, it is 0.5～2% (weight) that hydrophobic polymer can feed the emulsion amount.
Solubility promoter has the hydrocarbon connection chain of at least 6 carbon atoms, and the solubleness under 25 ° in water is lower than 110
-6And under polymerization temperature liquid.
If solubility promoter is contain fluorine atoms not, the hydrocarbon connection chain preferably contains 12 carbon atoms.
As an example, solubility promoter can be:
-n-Hexadecane,
-stearyl methacrylate,
-methacrylic dodecyl gallate,
-methacrylic acid perfluor monooctyl ester.
For obtain the enough shearing stress of microemulsion state can by for example ultrasonic reach firmly to stir realize.Usually when keeping the microemulsion state, shearing stress might be got back to common emulsion shearing stress and reduce shearing stress.
The monomer meaning be meant any can polymerization or the monomer of copolymerization through the free radical method." monomer " speech comprises several monomeric mixtures certainly.
Monomer can be selected from vinyl, vinylidene, dialkylene and olefines, allylic monomers.
Vinyl monomer refers to (methyl) CALCIUM ACRYLATE, ethenyl aromatic yl monomer, vinyl ester, (methyl) vinyl cyanide, (methyl) acrylamide and one and two-(alkyl of 1～18 carbon atom)-(methyl) acrylamide, and an ester and the diester of maleic anhydride and toxilic acid.
(methyl) acrylate is respectively the following formula especially person:
R wherein
0Be selected from and contain 1～18 carbon atom, line style or ramose, primary, the second month in a season or tertiary alkyl; the alkyl that contains-1～18 carbon atom of cycloalkyl (alkoxyl group of 1-18 carbon atom) of 5～18 carbon atoms; alkyl, aryl and the aralkyl of (alkylthio of 1～18 carbon atom)-1～18 carbon atom; these bases can be replaced by at least one halogen atom (as fluorine) and/or at least one hydroxyl; after this hydroxyl protection, abovementioned alkyl be line style or ramose: (methyl) glycidyl acrylate, norborneol ester, isobornyl thiocyanoacetate.
As useful methacrylic ester example, methyl methacrylate, ethyl ester, 2 can be proposed, 2, the 2-trifluoro ethyl ester, n-propyl, isopropyl ester, positive butyl ester, secondary butyl ester, the tert-butyl ester, n-pentyl ester, isopentyl ester, just own ester, 2-ethylhexyl, cyclohexyl, monooctyl ester, different monooctyl ester, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, lauryl, stearyl ester, phenyl ester, benzene methyl, beta-hydroxy ethyl ester, isobornyl thiocyanoacetate, hydroxy propyl ester, hydroxyl butyl ester.
Vinylformic acid example as above-mentioned formula, methyl acrylate, ethyl ester, n-propyl, isopropyl ester, positive butyl ester, secondary butyl ester, the tert-butyl ester, own ester, 2-ethylhexyl, different monooctyl ester, 3 can be proposed, 3, the own ester of 5-trimethylammonium, the ninth of the ten Heavenly Stems ester, isodecyl ester, lauryl, octadecyl ester, cyclohexyl, phenyl ester, methoxyl group methyl esters, methoxyl group ethyl ester, oxyethyl group methyl esters, ethoxy ethyl ester, perfluor monooctyl ester, 20 diester.
From meaning vinyl aromatic monomers of the present invention, the meaning is the undersaturated aromatic monomer of alkene such as vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-vinyl toluene, 3-vinyl toluene, 4-methoxy styrene, 2-(hydroxymethyl) vinylbenzene, 4-ethyl styrene, 3,4-dimethyl styrene, 2-chloro-styrene, 3-chloro-styrene, 4-chloro-3-vinyl toluene, 3-t-butyl styrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 1-vinyl naphthalene.
As vinyl ester, vinyl-acetic ester, propionate, vinylchlorid and vinyl fluoride can be proposed.
As vinylidene monomer, vinylidene fluoride can be proposed.
The diene monomers meaning is by line style or cyclic, the diene of selecting in conjugated or the unconjugated diene, as an example as divinyl, 2, the 3-dimethylbutadiene, isoprene, 1, the 3-pentadiene, 1, the 4-pentadiene, 1, the 4-hexadiene, 1, the 5-hexadiene, 1, the 9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornylene, 2-alkyl-2, the 5-norbornadiene, 5-ethylidene-2-norbornene, 5-(2-propenyl)-2-norbornylene, 5-(5-hexenyl)-2-norbornylene, 1, the 5-cyclooctadiene, dicyclo [2,2,2] suffering-2, the 5-diene, cyclopentadiene, 4,7,8,9-tetrahydroindene and isopropylidene tetrahydroindene.
As olefinic monomer, ethene, butylene, hexene and 1-octene can be proposed.Equally also the Fluorine containing olefine monomer can be proposed.
Can make block polymer by the inventive method.In fact, with the inventive method first kind of monomer polymerization obtained polymer blocks alive.Place second kind of monomeric polymerisation medium might on first block, connect another kind of polymer blocks the polymer blocks of first kind of work.Might obtain segmented copolymer like this, the multipolymer that for example contains one or several polystyrene block and one or several polybutadiene block perhaps contains the multipolymer of the block of the block of one or several polystyrene block and one or several methyl acrylic ester and one or several esters of acrylic acid.
In practice, can be in same set of equipment, after some other obtain block.So that when obtaining first kind of block, it is just enough to feed the second kind of monomer that is used to make second kind of block, does not stop to stir first kind of monomer consumption, need not cool off or other interruption.Certainly, according to monomeric character, can be with the formation condition of each block, as emulsion temperature.
Certainly, placing the living polymerization thing in the monomer polymerization medium of hope formation block might link and the block of wishing to be connected in as much on the living polymerization thing.
Therefore, the present invention is equally about a kind of preparation method of block polymer, this method had at least according to a step of the present invention, obtain the block of first kind of work, described block alive is placed at has at least in addition-kind wish to constitute connects the monomer of the block on the-kind of the block to exist down, so that it is form the diblock of living,, continuous like this according to the block number that hope obtains.
Therefore, specification sheets of the present invention is equally about a kind of preparation method of diblock polymer, comprise by the present invention the-kind of monomer polymerization-step, so that obtain the block of-kind of work, then one go on foot, the make the block of kind living place under second kind of monomer exist therein, second kind of monomer polymerization so that generate be attached at the-kind, second kind of block on embedding is good.
Specification sheets of the present invention is included under the existence of the diblock that makes according to the method described above equally about a kind of preparation method of triblock polymer, and the king plants a step of monomer polymerization, to generate the 3rd block that connects on the diblock polymer.
As an example, can obtain following block polymer:
Polyphenyl alkene-block--poly-methylpropanoic acid methyl esters,
Polystyrene-block-polyphenyl sulphonate,
Polystyrene-block-polyacrylamide,
Polystyrene second block. PMAm,
Polymethylmethacrylate-block-polyacrylic acid second is indulged in,
Polystyrene-block-butyl polyacrylate,
Polyhutadiene-block-polymethylmethacrylate,
Polyisoprene-block-polystyrene-copolymerization-vinyl cyanide,
Polyhutadiene-block-polystyrene-copolymerization-vinyl cyanide,
Polystyrene-copolymerization-butyl acrylate-block-polymethyl methyl esters,
Polystyrene-block-poly-third vinyl acetate between to for plastic,
Polystyrene-block-polyacrylic acid 2-ethylhexyl,
Polystyrene-block-poly-methyl methacrylate mole at tenth of the twelve Earthly Branches Hydroxyethyl acrylate,
Polystyrene-block-polyhutadiene-block-polymethylmethacrylate,
Polyhutadiene-embedding is wished-polystyrene ethene-polymethylmethacrylate.
Polystyrene-block-butyl polyacrylate-block-polystyrene,
Polystyrene-block-polyhutadiene-block-polystyrene,
Polystyrene-block-polyisoprene-block-polystyrene,
Polyacrylic acid perfluor monooctyl ester-block-polymethylmethacrylate,
Get vinylformic acid perfluor monooctyl ester-block-polystyrene,
Polyacrylic acid perfluor monooctyl ester-block-polyacrylic acid 20 diester,
Polyacrylic acid perfluor monooctyl ester-block-polymethyl acrylic acid stearyl,
Polyacrylic acid n-octyl-block-polymethylmethacrylate.
For the system segmented copolymer, and with the situation of the emulsifying agent that has the base that generates stable free radical, might work as the new monomer of adding, with the raising polymerization velocity, adding quantity is F
AMO* (AMO) between 0～2.510
-2The initiator of the monomer that moles/mole is new (this amount is not included as the quantity that obtains the used initiator of preceding one or more blocks)." new monomer ", the meaning be meant the new block of in sequential polymerization thing generation (because of rather than first block) monomer of usefulness.
Within the scope of the present invention, its general meaning got in polymkeric substance one speech, therefore comprises homopolymer, multipolymer, trimer and mixture of polymers.Its general meaning also got in polymerization one speech.
Polymkeric substance when the polymerized unit that will obtain containing acrylate or methyl acrylic ester (i.e. " (methyl) acrylate "), particularly when when acrylic ester unit begins to aggregate into multipolymer, as previously mentioned, the preferred especially stable free radical that contains the following formula connection chain that uses.
In order to improve the chemical stability of emulsion, particularly the monomer degraded reduces to minimum in acidic medium, and " PH buffer reagent " compound that preferably feeds sufficient amount in emulsion is 5～8.5 to keep pH value, is preferably between 6～7.Such a kind of compound for example can be Sodium phosphate dibasic (Na
2HPO
4) or sodium bicarbonate (NaHCO
3), perhaps K
2CO
3
Stable free radical for nitro oxide that hydrolysis trend is arranged or nitrogen oxygen base (nitroxide) class, according to acid PH or alkaline PH situation, PH buffer reagent compound can be used for avoiding this decomposition equally or draw to become degraded in the mode of control if necessary.
If PH is lower, promptly PH is lower than 7, compares greater than the polymerization of carrying out under 7 the situation with PH, and polymerization is carried out in mode faster.Therefore, talk about faster if wish polymerization velocity, might be lower than below 7 at PH, for example carry out polymerization between 2～4, known this effect is poorly showed by polymerization control equally.
To contain:
-water,
-initiator,
-emulsifying agent may be the band basic person's that generates stable free radical a water and contain:
-monomer,
-optional organic solvent,
-stable free radical (if emulsifying agent does not have)
-the organic phase of optional solubility promoter mixes and can obtain emulsion.
Can be at least partially under 50～140 ℃ according to method of the present invention, carry out under preferred 85～130 ℃.The inventive method is to be enough to avoid emulsion to be seethed with excitement mutually and its various components remain essentially under the pressure of (minimally reduces each component and becomes vapour phase) in the emulsion and carry out.
Therefore, the inventive method can be partly, for example is lower than under 95 ℃ and carries out being lower than 100 ℃ fully even.
The method according to this invention obtains a kind of polymer latex.Within this latex, the mean diameter of the overall or mixture of polymer beads is less than 2 μ m, usually between 20～1000nm.
Polymer beads can comprise by at least two kinds of different monomers (one of them kind is acrylate or methacrylic ester) polymeric unit.Such polymkeric substance can comprise that equally some are by at least a vinyl aromatic monomers and/or at least a diene monomers polymeric unit.
Therefore polymer beads can comprise by at least a acrylate and/or methacrylic ester polymeric unit with by neither acrylate is not again the unit of the monomer polymerization of methacrylic ester.Constitute these particulate polymkeric substance and can be a kind of in the listed polymkeric substance of a kind of block polymer, particularly front.
The particle that makes according to the inventive method contains with radical form or with a kind of stable free radical of form of the base that can generate stable free radical.
Stable free radical maybe can generate stable free radical base have a thermostability that helps improve polymkeric substance.
Embodiment
In following example, used following characterization technique:
-monomer becomes the transformation efficiency of polymkeric substance: by measuring in amount of dry matter, and with the amount of monomer report that adds,
-average diameter of particles: with light diffraction approach (equipment Malvem Zeta Sizer 4),
-polymericular weight and polymolecularity: after water-soluble substances is removed in washing, use spatial exclusion chromatography at polymkeric substance.With " water " chromatographic instrument, tetrahydrofuran (THF) (THF) is made eluant.Chromatographic instrument is equipped with four PLgel
10 μ m (poly-(vinylbenzene) Vinylstyrene) post (100,500,1000 and 100000 ) and two detections (analysing the ultraviolet ray of penetrating instrument and 254nm).Calibrate with the polystyrene standard sample.With 10mg/ml, flow is 1ml/ minute following injection of polymer.
Example 1 and 2
In a double jacket glass reactor that stirring system and temperature control be housed, under agitation feed 199g (promptly 11.1 moles) water, add 0.1245g (promptly 1.48 * 10 then
-3Mole) NaHCO
3Work as NaHCO
3Complete when soluble in water, the solution that obtains with the nitrogen bubbling degassing 30～45 minutes to remove micro amount of oxygen.90 ℃ of temperature of reactor add 0.427g (promptly 2.07 * 10
-3Mole) Sodium styrene sulfonate (SSNa) adds the N-tertiary butyl-1-diethyl phosphono-2 that 23g (promptly 0.22 mole) sneaks into following structural formula then, the vinylbenzene of 2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxode),
Quantity be [(SFR) * F
SFR/ [(AMO) * F
AMO] ratio be equivalent to numerical value shown in the table 1, add 0.182g (i.e. 9.6 * 10-4 mole) then and be dissolved in the Na2S2O5 in the 5g water, add 0.254g (promptly 9.4 * 10 again
-4Mole) be dissolved in K in the 5g water
2S
2O
8, last adding shows polymerization time 0.For:
-observed molecular weight is along with the variation of transformation efficiency,
-come assaying reaction kinetics by gravimetry, in entire reaction course, sampling (5ml) is several times.
Table 1 is collected the result.In example 2 situations, after the nucleation period, observe be varied to the basically linear fashion growth of number-average molecular weight with percent conversion.
| Example n ° | SFRxF SFRAMOxF AMO | Time (h) | Transformation efficiency (%) | Mn | Mw/Mn | Particle diameter (nm) |
| 1 | 0 | 2 | 99.3 | 48357 | 2.97 | 108 |
| 2 | 0.6 | 567816 | 21.128.537.944.176.8 | 1511136101947624954 | 1.271.91.661.692.47 | 350 |
Table 1
Example 3 and 4
Except with 0.156g (promptly 1.86 * 10
-3Mole) NaHCO3 and with 0.307g (promptly 1.07 * 10
-3Mole) Sodium Lauryl Sulphate BP/USP (SDS) replaces outside the SSNa, and operation is as example 1 and 2.
Table 2 is collected the result.
In the situation of example 4, after the coring phase, the variation number-average molecular weight of observing with percent conversion is the line style growth basically, arrives about 80% up to percent conversion.
In the situation of example 4, observed transformation efficiency at about 80% o'clock, pH reaches 4.6 from beginning 6.7 in polymerization.
| Example n | SFRxF SFRAMOxF AMO | Time | Transformation efficiency (%) | Mn | Mw/Mn | Particle diameter (nm) |
| 3 | 0 | 1 hour 30 minutes | 100 | 145000 | 4 | 140 |
| 4 | 0.6 | 1 hour 30 minutes 2 hours 2 hours 30 minutes 3 hours 4 hours 30 minutes | 11.823.251.476.496.8 | 34606762850013086 | 2.512.232.882.763.46 | 115.2 |
Table 2
Example 5 and 6
To on the one hand:
-23g (promptly 0.22 mole) vinylbenzene,
-N-the tertiary butyl-1-diethyl phosphonyl-2, (the SFR) * F of 2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxide) quantity such as table 3
SFR/ (AMO) * F
AMOShown in, perhaps 0 mole (example 5) and 3.12 * 10
-4Mole (example 6).
-0.28g molecular-weight average is 300000 polystyrene,
-1.152g (promptly 1.08 * 10
-3The mole) n-Hexadecane mixed a kind of organic solution,
To on the other hand:
-121.1g water
-0.792g (promptly 2.75 * 10
-3Mole) Sodium Lauryl Sulphate BP/USP,
-0.049g (promptly 2.6 * 10
-4Mole) Na
2S
2O
5,
-0.069g (promptly 2.6 * 10
-4Mole) K
2S
2O
8Be mixed with the aqueous solution.
Then, be stirred in 10 minutes two kinds of solution mixing by means of magnetic.Use the ultrasound probe (the 400W ultrasonic disintegrator is with reference to the 370th page of diagram of the OSI1996/1997 of international standard office directory A 65.900.10) of extra-heavy power that mixture was placed strong turbulence following 10 minutes again, be the emulsion of 100nm so that obtain dripping size.Make the emulsion degassing remove micro amount of oxygen in 10 minutes with the nitrogen bubbling again.
Then emulsion is placed in the double jacket glass reactor that is heated to 90 ℃ and the 250ml under stirring (400 rev/mins) in advance.Time 0 is equivalent to the moment in the emulsion feeding thermal reactor.A few sub-sampling 5ml in entire reaction course so that;
-observed molecular weight is along with the variation of transformation efficiency,
-come assaying reaction kinetics by gravimetry.
Table 3 has been collected the result.
| Example n ° | SFRxFSFRAMOxFAMO | Time (h) | Transformation efficiency (%) | Mn | Mw/Mn | Particle diameter (nm) |
| 5 | 0 | 1 | 92 | 127400 | 4 | 213 |
| 6 | 0.6 | 13579 | 1441.655.671.887.9 | 2255039540567007100088750 | 3.482.552.292.823.04 | 100 |
Table 3
Example 7
A, preparation have the emulsifying agent of the base that generates stable free radical
A) poly-(Sodium styrene sulfonate) block of preparation
Be equipped with stir and thermoregulator 250ml double jacket glass reactor in put into 23.9g water and 71.7g ethylene glycol, dissolve 28.72g (promptly 0.14 mole) styrene sulfonic acid then therein and receive monomer, add 0.1835gNa again
2HPO
4, add 0.44g (promptly 1.57 * 10 again
-3Mole) 4,4 ' azo two (4-cyanopentanoic acids) (ACVA) adds 0.8g (promptly 2.72 * 10 again
-3Mole) the N-tertiary butyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxide) add 0.106g caustic soda or sodium hydroxide then.Outgas 10 minutes to remove micro amount of oxygen with the nitrogen bubbling subsequently.
Reactor reached 125 ℃ at 48 hours then, then cooling.The polymkeric substance that generates precipitates twice in methyl alcohol, refilter and in 50 ℃ of vacuum-dryings 24 hours.
B) preparation polystyrene-block-poly-(Sodium styrene sulfonate) segmented copolymer:
With a) same reactor in, put into the mixture of 7.5g water and 22.5g ethylene glycol, add the polymkeric substance that 5g makes again in a), dissolving adds 1g (promptly 9.6 * 10 again
-3Mole) vinylbenzene adds 0.8g (promptly 2.72 * 10 again
-3Mole) the N-tertiary butyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide or nitrogen oxygen base (mitrxide).The solution that obtains was removed micro amount of oxygen in 10 minutes with the degassing of nitrogen bubbling then.
Reactor reached 125 ℃ then in 24 hours, cooling again is with 20g de-salted water dilution content.Under envrionment temperature, solution is fed vacuum then and rotate vaporizer to remove the styrene monomer of the remnants that may exist.4 days (filtration yield 100 (1000g/ mole) of the general membrane filtration of the solution that obtains.Final copolymer separates with rotating the complete evaporating solvent of vaporizer (water-ethylene glycol) under 50 ℃ of vacuum, then in 50 ℃ of following vacuum-dryings 24 hours.
B is through emulsion polymerizing preparation vinylbenzene-block-butyl polyacrylate segmented copolymer
In the reactor identical with the front, put into the emulsifying agent (by base that generates stable free radical of emulsifying agent chain belt) that 104.7g water, 0.26g make at A, add 0.0135g (promptly 9.5 * 10 then
-5Mole) Na
2HPO
4(PH buffer compounds) adds 0.065g (promptly 6.25 * 10 then
-4Mole) vinylbenzene.
The solution that obtains outgases 10 minutes to remove micro amount of oxygen through the nitrogen bubbling.
Reactor was warming up to 90 ℃ in 7 hours then, and this causes styrene polymerization.Reactor keeps 90 ℃, adds 22.5g (promptly 0.176 mole) butyl acrylate and 0.045g (promptly 2.36 * 10
-4Mole) K
2S
2O
8And under 90 ℃, let alone polymerization 18 hours.
Steric exclusion chromatography analysis revealed butyl acrylate block is connected on the polystyrene block well.
Example 8
Except K with same mole number
2CO
3Replace NaHCO
3Outside, operation is with example 4.Polymerase 17 hour obtains 8.4% transformation efficiency.Obtain the latex that average particulate diameter is 375nm.When transformation efficiency reaches 8.4%, observe PH and 7.5 reach 8.6 by what polymerization began.Can be with this example and example 4 contrasts.Therefore observing pH value remains on and shows more than 7 that polymerization velocity is slower.
Example 9
A) the preparation band generates the polystyrene of the base of stable free radical
Under stirring, in the 100ml three-necked bottle, puts into magnetic
-50g (promptly 0.48 mole) vinylbenzene,
-0273g (1.66 * 10
-3Mole) Diisopropyl azodicarboxylate (AIBN),
-0.694g (promptly 2.36 * 10
-3Mole) the N-tertiary butyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxide).
At ambient temperature, with the nitrogen degassing 1 hour, 90 ℃ of heating 4 and a half hours under stirring again.The product that obtains precipitates in methyl alcohol, filters then and 50 ℃ of following vacuum-dryings.Polymkeric substance number-average molecular weight Mn is 5200, and polymolecularity is 1.45.
B) at A) in the band that makes generate micro-emulsion polymerization in the presence of the polystyrene of base of stable free radical:
On the one hand, incite somebody to action:
-23g (promptly 0.22 mole) vinylbenzene,
-1.104g (promptly 4.88 * 10
-3Mole) n-Hexadecane,
The band that-13g makes in A generates the N-tertiary butyl-1,1-diethyl phosphonyl-2, the polystyrene of the base of 2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxide), (total synteny 2.5 * 10
-4Stable free radical),
-0.01g (promptly 3.4 * 10
-5Mole) the N-tertiary butyl-1-diethyl phosphonyl-2,2-dimethyl propyl nitro oxide or nitrogen oxygen base (nitroxide) mix, and make a kind of organic solution.
On the other hand, incite somebody to action:
-207g (promptly 11.5 moles) water,
-0.936g (promptly 3.25 * 10
-3Mole) Sodium Lauryl Sulphate BP/USP
-0.156g (promptly 1.86 * 10
-3Mole) NaHCO
3Mix, prepare a kind of aqueous solution.
These two kinds of solution stir by means of magnetic then and mixed 10 minutes.Use the ultrasound probe (the 400W ultrasonic disintegrator is with reference to the 370th page of diagram of the OSI1996/1997 of international standard office directory A 65.900.10) of extra-heavy power that mixture was placed strong turbulence following 10 minutes again, be the emulsion of 100nm so that obtain dripping size.Make the emulsion degassing remove micro amount of oxygen in 10 minutes with the nitrogen bubbling again.
Then emulsion is placed on and is heated to 90 ℃ and place it in the double jacket glass reactor of the 250ml under the stirring (400 rev/mins) in advance.Time 0 is equivalent to the moment in the emulsion feeding thermal reactor.Several sub-samplings (5ml) are with example in the whole reactor process:
-observed molecular weight is with the variation of transformation efficiency,
-come assaying reaction kinetics by gravimetry.
Table 4 has been collected the result.
Observe when transformation efficiency is 4.8%, PH 8.1 reaches 8.8 from what polymerization began.
| Example n ° | Time (h) | Transformation efficiency (%) | Mn | Mw/Mn | Particle diameter (nm) |
| 9 | 7 | 4.8 | 7020 | 1.48 | 137 |
Table 4
Example 10
A) the N-tertiary butyl-N-(1-diethyl phosphonyl-2,2-dimethyl propyl)-O-(1-phenylethyl) oxyamine (1) is synthetic:
In a 100ml Schlenk pipe that purifies with nitrogen, feed 0.57g (4mmol) CuBr and 1.25g (8mmol) 2,2 '-two pyridines.Add 0.74g (4mmol) (1-bromotrifluoromethane) benzene and the solution of 0.68g (2mmol) DEPN86% in the 9ml dry toluene.Under agitation, make it to react at ambient temperature 48 hours.Reaction mixture is gone up at cellulose acetate (celite) and is filtered.Leach thing 5% copper-bath, wash with water then.At the thousands of dry organic phases of sal epsom, evaporating solvent then.Pass through silicon-dioxide column chromatography purified product with pentane/ether eluant (6/4).Obtain the compound (1) (yield=95%) of 0.75g diastereoisomer form, by 23.14 and signal integration mensuration ratio on crude mixture 31P spectrum of 2436ppm (I/II=64/36) be 64/36.
B) at A) preparation alkoxylamine in the presence of micro-emulsion polymerization:
Block PABu's (butyl polyacrylate) is synthetic:
On the one hand, incite somebody to action:
-17.5g (promptly 0.134 mole) butyl acrylate,
-0.17g weight-average molecular weight is 300000 polystyrene (as hydrophobic polymer),
-0.7g (promptly 6.56 * 10
-4Mole) n-Hexadecane,
-0.686g (promptly 1.72 * 10
-3Mole) alkoxylamine for preparing in A is mixed with a kind of organic solution.
On the other hand, incite somebody to action:
-173.8g (i.e. 9.66 moles water),
-0.566g (promptly 1.97 * 10
-3Mole) Sodium Lauryl Sulphate BP/USP,
-0.686g (promptly 1.29 * 10
-3Mole) the perfluoro capryl potassium acetate mixes, and prepares a kind of aqueous solution.
These two kinds of solution stir by means of magnetic and mixed in 10 minutes then.With extra-heavy power ultrasound probe mixture was placed strong turbulence following 10 minutes again, be the emulsion of 100nm so that obtain dripping size.Make the emulsion degassing remove micro amount of oxygen in 10 minutes with the nitrogen bubbling again.
Then emulsion is placed on ability 5 bar pressures at least, is equipped with in the 250ml stainless steel double jacket reactor of stirring and thermoregulating system.After stirring (400 rev/mins) and nitrogen deaeration stage, feed 3 crust excess nitrogen pressure in the reactor to avoid 125 ℃ of water boilings.The temperature given value of reactor is 120 ℃, and double jacket is 125 ℃.Time 0 is equivalent to reactor and reaches 125 ℃ of moment.After 125 ℃ were reacted 5 hours down, reaction mixture was also taken out the latex that obtains.The results are shown in following table.
| Transformation efficiency (%) | Mn | Mw/Mn |
| 84.5 | 10810 | 2.5 |
The synthetic polystyrene block that is attached on the PABu block in front;
The latex that-121g front obtains is retained in the reactor.Stirring reaches 400 rev/mins again, and then adds
-5.3g (promptly 5.1 * 10
-2Mole) vinylbenzene
-0.176g (promptly 6.13 * 10
-4Mole) Sodium Lauryl Sulphate BP/USP.
Mixture stir and envrionment temperature under one night of reservation so that in the latex that vinylbenzene is entered formed.
After the nitrogen deaeration stage, feed 3 crust excess nitrogen pressure in the reactor.The temperature of reactor set-point reaches 120 ℃ more then, and double jacket is 125 ℃.After 125 ℃ of reactions 6 hours, the reaction mixture cooling is also taken out sample.
Collection is in following table:
| Transformation efficiency (%) | Mn | Mw/Mn |
| 83.4, all | 19630 | 1.8 |
The displacement explanation styrene block at steric exclusion chromatography peak is connected on the butyl polyacrylate well.
Claims (9)
1. polymer beads wherein contains the polymerized unit of at least two kinds of different monomers, described monomeric at least a be acrylate or methacrylic ester.
2. according to the particle of claim 1, it is characterized in that described polymkeric substance contains the polymerized unit of at least a vinyl aromatic monomers and/or at least a diene monomers.
3. according to the particle of claim 1 or 2, it is characterized in that it contains the monomeric polymerized unit of not only non-acrylate but also non-methacrylic ester.
4. according to the particle of claim 1 or 2, it is characterized in that described polymkeric substance is a kind of block polymer.
5. according to the particle of claim 1, it is characterized in that described polymkeric substance is the wherein a kind of of following polymers:
Polystyrene-block-polymethylmethacrylate,
Polymethylmethacrylate-block-polyethyl acrylate,
Polystyrene-block-butyl polyacrylate,
Polyhutadiene-block-polymethylmethacrylate,
Polystyrene-copolymerization-butyl acrylate-block-polymethylmethacrylate,
Polystyrene-block-polyacrylic acid 2-ethylhexyl,
Polystyrene-block-polymethylmethacrylate-copolymerization-Hydroxyethyl acrylate,
Polystyrene-block-polyhutadiene-block-polymethylmethacrylate,
Polyhutadiene-block-polystyrene-block-polymethylmethacrylate,
Polystyrene-block-butyl polyacrylate-block-polystyrene,
Polyacrylic acid perfluor monooctyl ester-block-polymethylmethacrylate,
Polyacrylic acid perfluor monooctyl ester-block-polystyrene,
Polyacrylic acid perfluor monooctyl ester-block-polyacrylic acid 22 ester,
Polyacrylic acid perfluor monooctyl ester-block-polymethyl acrylic acid stearyl,
Polyacrylic acid n-octyl-block-polymethylmethacrylate.
6. according to the particle of claim 1 or 2, it is characterized in that it contains a kind of stable free radical or a kind of base that generates stable free radical.
7. the overall or mixture according to the particulate of claim 1 is characterized in that described particulate mean diameter is lower than 2 μ m.
8. the overall or mixture according to the particulate of claim 7 is characterized in that described particulate mean diameter is between 20～1000nm.
9. the latex that contains the overall or mixture of the particulate of claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR98/08916 | 1998-07-10 | ||
| FR9808916A FR2781486B1 (en) | 1998-07-10 | 1998-07-10 | EMULSION POLYMERIZATION IN THE PRESENCE OF A STABLE FREE RADICAL |
| FR99/03941 | 1999-03-30 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031458564A Division CN1478802A (en) | 1998-07-10 | 1999-07-10 | Polymer granue, polymer granule ensemble or mixture and cream of latex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101134801A true CN101134801A (en) | 2008-03-05 |
Family
ID=9528543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101011935A Pending CN101134801A (en) | 1998-07-10 | 1999-07-10 | Polymerisation particles, entirety of the polymerisation particles or mixture and rubber latex |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101134801A (en) |
| FR (1) | FR2781486B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483514A (en) * | 2013-09-17 | 2014-01-01 | 常州大学 | Amphiphilic acrylate copolymers and preparation method thereof |
| CN113677993A (en) * | 2019-03-29 | 2021-11-19 | 积水医疗株式会社 | Immunoassay reagent and immunoassay method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU571240B2 (en) * | 1983-07-11 | 1988-04-14 | Commonwealth Scientific And Industrial Research Organisation | Alkoxy-amines, useful as initiators |
| US5322912A (en) * | 1992-11-16 | 1994-06-21 | Xerox Corporation | Polymerization processes and toner compositions therefrom |
-
1998
- 1998-07-10 FR FR9808916A patent/FR2781486B1/en not_active Expired - Fee Related
-
1999
- 1999-07-10 CN CNA2006101011935A patent/CN101134801A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483514A (en) * | 2013-09-17 | 2014-01-01 | 常州大学 | Amphiphilic acrylate copolymers and preparation method thereof |
| CN103483514B (en) * | 2013-09-17 | 2015-07-01 | 常州大学 | Amphiphilic acrylate copolymers and preparation method thereof |
| CN113677993A (en) * | 2019-03-29 | 2021-11-19 | 积水医疗株式会社 | Immunoassay reagent and immunoassay method |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2781486B1 (en) | 2000-09-08 |
| FR2781486A1 (en) | 2000-01-28 |
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