JPS5981302A - Polymerization - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Book 'R'. lil fj enalene series nonj+jl sum unit t1. rI′1 combined water 1′l f spun from the body
Easy dispersion in AI quality or Radex mourning 3? h method, and furthermore, R'i'< 7. 111 of a dispersion to avoid and where stabilization of the dispersed phase results in the production of a dispersion that is entirely steric.
Regarding the 4 construction methods. The illegal feature is the use of a redox polymerization initiator system based on hydrogen peroxide.

This results in a number of advantages, including the ease of obtaining aqueous dispersions of certain polymers that would otherwise not be easily prepared.

The so-called aqueous emulsion polymerization of ethylenically unsaturated monomers is a very well-known process. Although most of the monomers to be polymerized are initially present as droplets emulsified in the aqueous medium used, the actual polymerization initially takes place within the aqueous medium rather than within these droplets, and therefore takes time. It is misunderstood as aqueous emulsion polymerization.

A significant amount of dissolved monomer in the aqueous medium is maintained throughout the process and is incorporated into the polymer particles formed therein. For this reason, aqueous emulsion polymerization techniques are only suitable for monomers with unacceptably low solubility in water. ! No. What arises from this scenario is that the method requires the presence of a surfactant dissolved in an aqueous medium in the PIl-, whereby as the polymerization proceeds, the 'I' M dissolved in the aqueous medium is
Second, the method stabilizes the entire emulsified droplet of monomers, since it does not actually create a reservoir to replenish the monomers; secondly, the method reduces the amount of dissolved Q' 11 rather than polymerizing the emulsified monomers. : a free radical type soluble in aqueous media to cause polymerization of the body?
i Requires the presence of a synthesis initiator. It is useful to use ionizable compounds for both of these functions on the oil side. That is, as a surfactant, dotesyl is commonly used with anionic substances such as sodium, dioctyl sulfosuccinic acid, and alkali chlorite or ammonium salts of sulfonated fatty alcohols. As a polymerization initiator, a water-soluble decompound such as ammonium or potassium persulfate is commonly used as a polymerization initiator. The presence of electrically charged substances derived from possible surface activators and/or initiators on the polymer particles stabilizes them from agglomerating into large particles. However, this stability of the dispersed phase can be quite easily disturbed by external influences that the dispersion may undergo, such as by shear forces on the 11" star, by the introduction of multiply charged ions, by freeze-thaw conditions or by Disturbed by changes in pH.

GB 1,196.247 discloses that both polymer particles have the ability to form a protective surrounding wall of polymer chains which are solvated by an aqueous medium around each polymer particle, i.e. by a different steric structure. Is it possible to make large grains by including a polymeric stabilizer for toughness and medium in the dispersion? ■; 1! An aqueous dispersion of a synthetic polymer in which the polymer particles are stabilized to prevent 4fi aggregation. It has already been proposed to expand. Although this conventional method avoids the presence of stimulants derived from conventional ionic surfactants on the polymer particles, it does not address the desirability of avoiding the use of ionic initiators. Although not emphasized in the above specification, it is actually suggested that materials such as ammonium persulfate or potassium persulfate be used.

In British Patent No. 1,544,635,
In the presence of a catalyst and also when polymeric blocks of nigga are observed,
Block copolymer dispersion chamber 7i containing at least two polymeric blocks that are aqueous and the other hydrophobic has already been described, and the 4"1'1 niblock serves to create a stabilizing surrounding wall around the polymer particles.

and N, but surface activation for sweet 11'i 1'1: Loading by using agent? If the introduction of li and q substances is avoided, it is noted that it is desirable to have a nonionic starting point ff+. Among the initiators described as being suitable are polymerization initiators of the -f-on type with poly(lj<).

The appearance of Honde Rinto! - British Office %'f 13, No. 8.2' + No. 4,675 and No. 312,212 (!, No. 312,212 Meiji: Book 11) states that the entire synthetic addition polymer is not charged. An emulsion polymerization method to form a sterically stabilized aqueous dispersion or latex has been described, which uses a water-soluble and non-ionizable azo polymerization initiator. According to a method recently discovered by the present inventor, a redox type polymerization initiator system containing hydrogen peroxide is used in combination with a nonionic water-soluble activation compound, instead of an azo polymerization initiator. It has many advantages.

According to the present invention, a water-insoluble polymer having a solubility in water in the range of 0.08 to 8-80% is emulsified in water to form at least one ethylenic compound. (b) in the presence of a redox-type polymerization initiation system containing hydrogen peroxide in combination with a nonionic water-soluble activator compound, and (b) in the molecule (1) a polymeric chain having at least 400 molecular moieties and which is itself soluble in the aqueous phase; and (11) an unsaturated group copolymerizable with one or more monomers to be polymerized. There is provided a method for producing ethylenically unsaturated monomers in aqueous emulsion, which comprises carrying out the above polymerization in the presence of a precursor compound containing

Preferably, the precursor compound (7 in bJ) (combined chain (1)) has at least 10,000 molecules -pf Yf.

By the method of the present invention, V combination I'f ethylenic unsquared single star bodies include, for example, 1. m-forms in f acrylic, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methoxyzobutylmethacrylate, cyclohexyl methacrylate, benzyl methacrylate. , hydroxyethyl acrylate 1/-t.

Hydroxyethyl methacrylate, hydroxyisopropyl methacrylate, benzyl acrylate, dimethylaminoethyl methacrylate, ethyl acrylate, butyl acrylate, hydroxybutyl acrylate, N
-butoxymethyl methacrylamide, N-butoxymethyl acrylamide, acrylonitrile, acrylic acid and methacrylic acid, anhydrous maleic anhydride, itaconic anhydride, vinyl 1ij 'jr''r form e.g. (3'F
l'1'2 vinyl, vinyl propionate, styrene, vinyltoluene, t-butylstyrene.

Examples include mel-xystyrene and vinylpyridine and single vinyl halides such as vinyl chloride and vinylidene chloride. All of these il'4-4a bodies exhibit a required minimum solubility in water of F11 degrees. If desired, together with one or more of such monomers, a single IA' which cannot be polymerized by itself by an aqueous emulsion polymerization process and which has a negligible amount in water is added.
A llj, jii form having +'r degrees, such as 2-etherhexyl acrylate or stearyl methacrylate, can be used as low as [4°]. As explained in detail 1 below, water hydration is a compound containing a significant proportion of qhf forms that are easily affected by water, such as grindyl acrylate, glycidyl methacrylate, and r-methacryloxypropyltrimethoxysilane. It has the additional advantage of facilitating the polymerization of the polymer mixture.

Polymerized monomers can also include monomers that are polyfunctional with respect to the polymerization reaction, and the resulting aqueous component K
7)1. Made of polymer.

, Suitable polyfunctional monomers V,1 include, for example, allyl meccrylate, ethylene glycol dimethacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and divinylbenzene.

Although the process of the present invention can be carried out to the fullest using any of the FJ'J r412 monomers or a combination thereof, the inventor has disclosed that the resulting polymer or The polymer has a relatively low ambient glass transition temperature 1) t(
When the latex has a Tg), the resulting latex has a finer particle size. That is, it is preferable that the polymer or ζ/Y copolymer V has a Tg of 60°C or less;
The present invention is not limited to making a dispersion of a polymer as described above. Dispersions of higher TF polymers are also easily formed, but the grain size of the grains is relatively thicker.

Activator compounds include, for example, ascorbic acid, thiourine, yellow compounds, amines such as hydroxylamine, triethylamine and ethanolamine, 1% base agents such as glycolic acid and tartaric acid,
There are benzylic acid and benzyl alcohol.

The hl of the hydrogen peroxide and activator compounds used in this I) may vary widely depending on factors such as the particular monomer being polymerized, the molecular weight sought to be achieved, and the desired rate of polymerization. Oxide peroxide, e.g. polymerized II'
Used in jii- of 0.006 to 6.0 heavy sleeves of H1 body.

■・1 (activator compound t, 1 e.g. 0.01 to 11)
Used in a 7.5-wt.
□Substantial excess of 1 or more 11: (e.g. ro 3 chi) to'
:, 17 moles of M4 can be as low as 25)^, and in the case of Gonagi, especially with a high ratio of C to the monomer (1)! When hydrogen dihydride is used, 11↓;il<j:111 of two substances such as 8 and 1) can be easily measured by the simple practical formula 1). .

In addition to the initiator system, the polymerization process of the present invention contains in the aqueous phase a polymer chain with a total of 400 IJ small molecules that is itself bath-compatible and a copolymerizable unsaturated 11-group in the molecule. The entire presence of the compounds contained in the product should be removed by mixing. This compound is thought to function as a precursor for the in-situ production of a graft copolymer that stabilizes the 5i form of the copolymer. One polymer chain 1j', : min is soluble in the aqueous phase, nQ Y4 polymerizes slowly, so N*; Well, in addition to this, the enclosing wall with -C prevents the U prefecture of the polymer particles +), and L ; This other polymerization 1
r: a chain component, grafted onto the first component and assumed to have an affinity for the polymer particles by having a similar monomer composition as the polymer particles themselves; be done.

Regarding the former compounds, the polymers soluble in the aqueous phase can be derived from the older water-soluble polymers, but the monoalgyl ethers thereof (
(wherein the alkyl group has 1 to 4 carbon atoms), poly(ethylene oxide)-poly(propylene oxide) copolymers containing at least 40% ethylene oxide, and monoalkyl ethers of such copolymers. , polyvinylpyrrolidone, 7J polymethacrylamide, polymethacrylamide and polyvinylalcohol are particularly suitable. Other water-soluble -i that can have the polymer series <1'i as the core
For the combination,; silica (ethyleneimine), poly[N-
acetylethyleneimine) and the corresponding N-propionyl spindles and their hydrolysis products and BoIJ CN-(
(diethyl hydromethyl)-N-metalumenal acrylamide]. Preferably, the molecule "tA7" of this polymer component is at least 1000, and preferred bamboo-soluble polymers include polyethylene glycols or Q or their monomethyls having a molecular composition ranging from 2[]OO to 4D f30. The process of the present invention can be operated with water-soluble polymeric series 7iM of molecular weight up to a minimum value of 40n, which is an ether, but is much lower than these preferred values, and Using molecular weight polymer chains, the above-mentioned British Patent Application Nos. 8,214,675 and 8,3
12,212 cannot be carried out; this difference is due to the fact that when using an azo initiator, generally a higher degree of polymerization is required, e.g. in the range of 75-80°C. It is possible. At such temperatures, the ability of relatively short water-soluble polymer chains to provide a sterically stabilizing enveloping wall is known;
j: Ability is not impaired.

The unsaturated groups that are also required to be present in the precursor molecules can be obtained by esterifying such glycols or ethers with copolymerizable unsaturated acids such as methacrylic acid, itaconic acid or maleic acid. Serve it conveniently and wait.

An example of 4 bodies is the molecule) ii, 20 n O
Meccryl I'+,\ ester of monomethyl ether of polyethylene glycol.

Esterification of glycol or C or ether is not f1
q 71'I'l' can be carried out by transesterification of 4 with 11 (primary alkyl esters such as methacrylic C1), or by transesterification of glycols or their ethers in the presence of a hydrogen hydride acceptor. It can be further reacted with a suitable acid chloride such as methacrylic chloride.

What's more...Glycol also has it, that ether V soil, H mouth 1'jβ and direct 1? (Jyi Li-, esters can be obtained by dilution of esters, or ξ, which can be reacted with hydrate to form semi-Nisdels. Other suitable precursors can be (r, 1-ruboxyl JI% polyvinylpyrrolidone at the end (UK special Q'l'gH
's 1. [Refer to No. 196,912, Meiho 1)] with glycidyl methacrylate. Yet another suitable precursor can be obtained by the method described in applicant's UK Patent Application No. 2,051,096A; , by reacting the monoalkyl ether with an aliphatic carboxyl acetate (hydrate) and then reacting the resulting half ester with an epoxy compound containing a double bond of poly(oJ[B)]. For example, reacting the monoethyl ether of polyethylene glycol with succinic anhydride and condensing the product with dalicidyl methacrylate yields a +3iJl precursor containing a terminal vinyl group.

As explained in the above-mentioned British patent application, this method is well suited for preparing precursors in the form of J', J', and J'.

This is because there is no need to remove excess reactants, by-products, or excess reactants that may interfere with subsequent use of the 1.11J precursor in the method. (as occurs in most of the other methods mentioned above). Another suitable precursor t:dvinylbenzyl chloride 2;J
By reacting monomethyl ether of 4'-retelene glycol with a sodium conductor, I1no et al! It is also monomethyl 1,000-novinyl benzyl ether of polyx5-L/linker. Before the above 1! (The 4-body contains one or more unsaturated I+ groups in the molecule -'FT [
, IEIru.

The proportion of preform compounds added to the polymerization mixture in carrying out the process of the invention is determined to the extent that the particular dispersion polymer being produced and the dispersion particles obtained are comprised of the desired dispersion particles 1F. Although varying, the optimum ratio for any individual case can be easily found by simple experimentation. Typical proportions of precursors range from 0.5 to jp weighing weight to be polymerized.
20%, more particularly in the range of 5-10%.

The first step in carrying out the method of the invention is before attempting to induce not only water but also stabilizers! It consists in emulsifying one or more monoisomers to be polymerized in the aqueous phase of the polymerization mixture, which usually also contains monomers. The aforementioned polymerization 6)-compound is subjected to high shear treatment or ultrasonic treatment to form an emulsion of monomer droplets with a sufficient degree of 111 concentration.
It is usually desirable to include in the polymerization mixture a surfactant that can assist in emulsification. Not only surfactants, but also ionic substances or carriers! le
It must be of non-ionic type in order to meet the objective of the present invention of producing a polymer dispersion containing no /Jyt. Examples of suitable nonionic surfactants include ethylene oxide condensates of alkylphenols, such as 1 mole nonylphenol and 20 moles ethylene oxide (commercially available as "Level'an" P 20 B), or molecular weight 400 polyethylene glycol oleic acid ester (''Eth?Ia
(commercially available as n"A4) ("Le
velan'' and Ethylan'' are registered trademarks)
.

However, instead of using conventional nonionic surfactants such as 1f, it is also possible to use a substance that combines the surfactant adhesion ability and the functions of a 1f (4-component compound) in one molecule.

That is, according to another embodiment of the invention: (i) 0.0
8-8 duet% 9・i゛1. (8) at least one ethylenically unsaturated monomer yielding a water-insoluble polymer having a solubility in water of 117°C, but having a molecular weight of at least 4000 molar mass, which is itself soluble in the aqueous phase; Q minute and (bl single 1
(C) an unsaturated group capable of copolymerizing with one or more hand groups with said intermediate soluble component; emulsified in water in the presence of a nonionic surface-active compound containing in its molecule a bonded or integrated unsaturated group; A polymerization method is provided in which the polymerization is carried out in the further presence of a redox-type polymerization initiator system containing a water-soluble activator compound and π[1 wood peroxide together.

Emulsification of the monomers can be promoted by subjecting the polymerization mixture to high-speed shearing or sonication, as with conventional nonionic surfactants, but usually in the presence of surfactant precursor compounds. The conventional 1't41' action is sufficient.

As previously mentioned, the surfactant compound contains six distinct features in its molecule.

εI31 contains at least 400. (preferably at least 1000 molecules)1
1 component is present. Add appropriate ingredients &:t tp
Pure precursor compounds (i.e. 010 without surface active properties)
There is an ingredient that has already been determined to be suitable as a similar ingredient to ``Ni-Kyu''.

Second, 15 is itself soluble in the monolithic phase of the polymerization mixture.
Components with molecular weights ranging from 0 to 1000 are present; i.e. IF
) The first listed component t/itI' is hydrophilic, but
This second component has hydrophobic properties. Suitable components include chains derived from the self-condensation or co-condensation of propylene oxide, butylene oxide or styrene oxide, or hydrocarbon chains such as those derived from higher fatty acids or fatty alcohols. .

These first and second components together provide the compound with the surface active HEW properties required for one or more single body emulsifications. Preferably, the first component, hydrophilic component, and the second component, hydrophobic component, are present in a ratio of 4, tj;, Jj, ranging from 20:1 to 1:1.

Said second component, i.e. I bend water 1<4. Surfactant 1Q1 <
The sixth 11-character moiety of the 71j compound is an unsatisfactory A- compound capable of copolymerizing with the second monomer.
8 This unsaturated group is preferably bonded to the portion of the hydrophobic component farthest from the hydrophilic component or is integrated with and.tL.1. When the hydrophobic component is a polymer chain containing a hydroxyl group, for example a poly(oxybutylene) chain having a group at the end,
The single radical is methacrylic acid, itacon t゛・η or (f
Conveniently, the component may be in the form of an ester of the component with a copolymerizable unsaturated acid, such as maleic acid. Such esters can be produced by combining lower alkyl esters of military oxy-acids, such as methyl methacrylate, with compounds forming the remainder of the pre-β1z molecules, such as the monomethyl ether of IF (oxyethylene)-poly(oxybutylene) copolymers. It may be possible to carry out a transesterification reaction between. 1) IJ
Examples of suitable surface cleaner precursor compounds of this ester type include the following formula: (wherein X and y are, for example, values corresponding to the molecular weight for poly(oxyethylene) and oxybutylene blocks of 2ooo and 700, respectively).

These materials do not contain methanol! It is easily obtained by condensation with ethylene oxide in a proportion of 9 and then with butylene oxide and then reacting this product with meccryl chloride, or the above-mentioned compound in the presence of the catalyst β1 of tetra-isopropyltitanate. It is easily obtained by performing a transesterification reaction between the product and methyl methacrylate.

Another polymerization includes a suitable surfactant precursor compound tit,
It is obtained by condensation of a hydroxyl compound already containing the required co-combinable hydroxyl group with, for example, butylene oxide and ethyleneoxy F.

For example, by continuously condensing allyl alcohol with ethylene oxide, a block copolymer of the following formula: ) can be done. Other useful compounds of this type include the triaryl ether of tantaerythritol with butylene oxide and ethylene oxide in molar ratios such as 1:2:35.1:/l:35°1:4:46 and 1:4:65. It is obtained by continuous condensation.

In yet another case, the hydrophobic component of the surfactant compound is provided by a hydrocarbon chain which may also include unsaturated groups. An example of such a linkage is an undecylenic acid linkage, which can be converted into the required surfactant precursor by direct condensation with ethylene oxide, for example in a 1:650 molar ratio.

When practicing the invention using conventional surfactants and simple precursor compounds, the f? C depends on the particular monomer or monomers to be emulsified and the desired fineness of the emulsion as well as the efficiency of the desired surfactant. Optimal ratio of agent to surface activity 41 rj', -'': I
'+ can now be more easily established, but usually used r)i
It is in the range of 0.5 to 10 weight of l4 body. In front of the self-activator! jf, the same situation applies when using a tetramer compound, provided that the proportion used is sufficient to produce the necessary graft copolymer to effect steric stabilization of the polymer particles. . Therefore, the proportion of surfactant precursor used preferably has the same order of magnitude as the proportion of the simple (non-surfactant) precursor used in the first case, with the proportion of the surfactant precursor used in the PIJ being between 0.5 and It is preferably in the range of 20% by weight, more particularly 5 to 10% by weight. Although not usually safe, the present invention may be practiced using conventional surfactants in addition to surfactant precursor compounds.

What are the main concrete examples of 1MfJ? 1. In carrying out the method of the present invention, one or more mono-At
Treat the entire body at once with aqueous IJ1. fR; this is conveniently referred to as the "one-shot" method. As mentioned above, this JY'hua f71 was emulsified in an aqueous medium. L forms a container from which the carapace is gradually removed as the polymerization progresses until all of the carapace is converted into dispersed claw aggregates. Another and more convenient method is to initially add only a portion of the 111 to the aqueous medium, i.e.
are emulsified and combined to form a dispersion of fine "seed" polymer particles, after which the remainder of the It-■ monomer is added gradually or in small portions to effect growth of the particles. this is"
Seed +'1nd feed
(seed and feed) process; its main advantage is that it achieves a good control of the particle size of the polymer dispersion.
It is to be. At that time, on the 11th day of the single silk body, the
It is also possible to change the configuration, i.e.
i] At the beginning, by vJ (i
Adding the rli size of Q or a mixture of multiple monomers IJ
Ru. In this way, the polymer particles of the latex are constructed to have a layered structure consisting of a single core and one or more surrounding jackets of different compositions.
obtain. For example, by including a polyfunctional monomer, monomer, in only the initial feed, the crosslinked core and non-jr.
Particles containing an outer 1i11 envelope of t2-bridged polymer are obtained77. In another case, the outer layer (God alone came from a Q'+-1.1 body with all 411 functional groups such as human cogyl or epoxide groups) )
-7 can be made more compatible.

The redox-type polymerization initiator system of ζjj′, reacts with one or more tri i+4 +I<117. In the case of the ``Kyot'' method, the entire required initiator system can be introduced in 1U of hydrogen peroxide and a non-ionic activator of the system, separately dissolved in a small amount of water. . When using the "insert and feed" method, add one or more mediums, stitches (addition of books;
75 (preferably) by adding +, 'I, -1x initiators corresponding to )).

Polymerization) 1? 1 Water-soluble 1 chain transfer agent present in the compound 4
Then you can do it. Examples of suitable chain transfer agents are mercaptoethanol and thioglycolic acid. Ren g, 7H
, transfer agent is JI'I, Ii, j, body weight + 0.1 of tt
It can be used with h↑ of ~2゜. 1 for the effects of stimulants
1 min ha lr, Φ conjunction (i) is the nLj1 clause of the molecule F'f + H, and in the end, the finer #ll in the min jj ri 411
It decreases the proportion of particles per catty and thus reduces the average particle IIV gold monk.

In general, ■ Legal d, emulsion polymerization 4) In the town <l'i (〆 11 times may be the same '') Procedures well known to each person l) - to 1
・There are two devices ((filk, gas container and 4
1. Stirring 1. 1.1-4) Is the polymerizable J-1 polymerizable?
) to: 1ft, J'lJ starting yarn resistance and)
(+ to the polymerization rate of j, t-1, then (1p of warm-
So, make the actual M11 sea 3. As if cjii was stored, j;・i
The stabilizer is solvated hψ1 min 7) 1 effectively dissolved by the aqueous phase 1.1. It should be so high that it won't be 11th - i7 DJ. However, if the polymerization is generally initiated using the azo type (f11), the temperature of water (1.1°) is considerably higher than the required temperature IW (If: This is the II stone modification of the polymerization method that uses l:ij starting cutting system.
X1λ box (・J, need to exceed 50℃ (1 not required)

However, the method of the present invention is advantageous in that the mixture is free of any polymeric substances and the method of the present invention is different from the fact that a relatively low polymerization temperature can be used. ;〈
J,
F, (water 1゛) and Jl'rl 7j'+ 'η can be obtained as a single unit, ; body and °C with a very small amount of other units (, + '14-) (only as a component of 11) I' jl
,! li, l'+9', 'AX Iノ'I, ip,'
Emulsified into standard water 1' using agent C, it is possible to emulsify it into standard water 1' using technical pressure. t3ii i・, -1, i1''', j
, il・i: I hope that this method will allow for successful polymerization (
A-et al., [the polymer or co-41 polymer of the ji+,

That is to say, it is made as much as possible! thickening of the proboscis and important feeding) (5 to 6'1' without mu
: ;lE % or more of glycidyl methacrylate +, ij : fi7 body mixed heat insulation (゛tsu semi-technical),
Rito I) - 01 things to do and 31+ things to do. 7) - Φ (azoamidine salt j'; Yushio is used to obtain 7) - 0kuhu + :t1
Contains 5% glycidyl methacrylate,
Φ: () 111j successes were achieved in copolymerizing a quaternary polymer (
Chem.

Abs, 95 (14), 116276k). '
711! To KM'J, the inventor has added 25:1% or 4:i5
Among the 0-weight J4 glycidyl meccrylate containing λ-0 glycidyl meccrylate, the water mixture was found to be difficult to copolymerize illegally. Thus, the "water-sensitive" reactive molecules that polymerize successfully in substantial proportions include glycidyl methacrylate, glycidyl methacrylate, and γ-methacrylate dipropyltrimethoxysilane 75S.
be.

Of these six reactive monomers, Ji↓ is listed later.
As an alternative to using all monomers, it is possible to include a H1-=loxyl compound such as H1-loxyl methacrylate in the illegally polymerized mono-Fa mixture.
By containing the PJi body and supplying tetraethyl silicate together with this mixture, "C1) Corn Ihi-1
Tetraethyl silicate (1-3-reacts with hydroxyl group during polymerization and silica-containing irq is bonded to 111 polymerized molecules); ) Z,.il under certain conditions of illegality
The hydrolysis of detraethersilicate and the formation of a precipitate throughout life do not occur all at once.

(a) In addition to the advantage of having great latitude in choosing the shoulder body composition and having great latitude in choosing the sterically safe γ′, 13 min,
10. Easily obtainable initiator and 11.
,,'t: It has ten advantages over the conventional R4 of British Patent No. 8,214,675 and No. 8,312,212 in that only hot cutting is required. The aforementioned British patent pile 1
Furthermore, water-soluble, monomer-insoluble azo initiators are not widely available1-7.

Yet another advantage of the present invention is that the polymer obtained in latex form is stabilized in its entirety by steric means, but, if desired, at a temperature at which the water-soluble polymer chains cease to exert their stabilizing effect. j', ij that latex love is added to
'-j) It is possible to collect and separate the scum from the aqueous phase by one means. For example, when converting water-soluble chains from methoxypolyethylene glycol with a molecular weight of 2000, the dispersion polymer IJf clustering can occur upon heating to 92°C or higher. With 600 chain molecules m, the critical aggregation temperature is 60-70°C.

At temperatures below the critical flocculation value, the illegally obtained latinx is stable indefinitely and is unaffected by changes in pH, addition of multiply charged ions or freeze-thaw conditions, all of these factors This has a disadvantageous effect on the stability of latex stabilized by electrical charge. Illicit and cleared latexes are useful as bases for water-borne aqueous coating compositions for which a high degree of formulation flexibility is available; for example, ionic materials may be included in other components of the composition such as pigments. It is not necessary to take into account all the points that exist.

The present invention will be explained with reference to the following examples, but is not limited thereto.
H%. Regarding the obtained polymer latex, gt
s; 1 ton of nanosizer sold by 11 companies in the country, Coulter Electronic
Particle size and dispersion measurements are carried out by ZER) J®. This measurement result is represented by two numerical analogies PI,')
: Represented by 361; only the first (character 1 + Ji [
+ (-Qi-dispersion) ~ 11 degree measure of the latex particles on an arbitrary scale of 10, the second number being the average size of the particles (nanometers).

In all of the following examples, the polymerization 9;j was carried out using a 1"1" 1st stirrer (7 pots) of the anchor type or non-ferrous turbine type with means for intermixing a nitrogen atmosphere, a reflux condenser and polytetrafluoroethylene vanes. "Culture vessel 2: ÷" (i.e., a reaction vessel with a flat bottom and a vertical 11111)
Do this at a temperature of 5 + ” inside.

A unitary mass fed by either a lettuce was introduced into the aqueous reaction mixture, directed into the vortex created by a mulch; the hydrogen peroxide initiator and activator were separately dissolved in water, and the solution was The same is true with the help of a pre-demand pump.
, V! Add to one stream in proportions that correspond to each other depending on the direction (=J).

The following examples all illustrate the "seed and feed"method;
ji Example 1-121J, 11. In the pure case, the use of a reliable surfactant together with the main body is shown, whereas the actual examples 1 to 11 show the use of an Ilk form before the surfactant.

1 (Iiij This actual rolling example is 2 [15°C Tg (Glass rolling 'Jl', i
The production of a latex of a 48/42/10 co-conjugate of methyl methacrylate, bubur acrylate and hydroxyl impropyl methacrylate is described.

First dust-filled month 1, 2 Salt water
2002 nonylphenol and 2
0 moles of eterenio) 11 go '1 course*2.
2F molecule P182000, I! □Lyethylene glycol monoethyl ether methacrylate ether+
2.21*Hereinafter, it will be referred to as "1 Surfactant A".

Below 10, "precursor" will be written as "J".

Methyl methacrylate 9.61 Bunal acrylate 8.32 Methyl methacrylate) 69.135'
Butyl acrylate 6 o, 8
S'hyaloxyisopropyl methacrylate
16+8y clothes and life 1・H:, fill A,
5.99 Oil!・J Pa, I ((
Δ B, 8゜Methyl methacrylate 17.2y Butyl acrylate-1, 14.2y Hydroxyinpropyl methacrylate 6.62
Surfactant A 1.4f The first aqueous charge is heated to 50° C. under a wet bed and the “seed” monomer charge is added with stirring. The "seed" initiator solution is then added; after forming a fine seed one-stage latex, the first "feed" charge and initiator are gradually introduced over a period of 6 hours. The second "feed" charge and initiator are then fed over a period of 1 hour; finally the initiator "spike" is added and the reaction mixture is cooled after heating for 20 minutes.

The latex obtained after removing about 1y of coagulum is
The test result of ``Nanosizer'' was 0:169, which was fully confirmed. The latex has a solids content of 48.5 inches and a monomer conversion of 98 inches. A total of 9 stable dosage forms were used.
: and the total loss of surfactant is 5.5% and 4.7%, respectively, based on the monomer required.
The amounts of initiator and activator were respectively [1,006%
and ml, 135%. Latex has a pH (9
The latex has unparalleled electrophoretic mobility and undergoes coagulation when heated in a vortex TW at 92°C.

Both of these observations indicate the absence of ionic material and indicate that the stabilizing morphology of the polymer particles is steric.

EXAMPLE 2 This example uses the same copolymer latex as in Example 1, except that a lower 1+g emulsifier and slightly lower concentrations of peroxide and ascorbic acid activator are used. Indicates manufacture.

The method of Example 1 is repeated using the same lubricants, except as follows: "Seed" initiator Methyl methacrylate 69.8f Butyl acrylate) 6r1.8 Glycyisopropyl methacrylate 1/
+, 8F surfactant A 1.48
S' Precursor A 8.8f
Methyl methacrylate 17.2 ffi, acri2) 1/1.
2yHyF Roxyisobuvir methacrylate
Ro, 69 Surfactant A O, Ro 5
7. The final initiator "spike" is not used in this case.

The resulting latex contains approximately 42 coagulums.

After removing this coagulum, the latex is processed with a "nanosizer" ([eta]jIt: then a result of 2:175f is obtained.

jpa・1 type 5'J containing 111, T45, monomer mothization rate (d92 ratio. Before stabilizer'!L< body and Table 1
iii Activation 1 (The total amount of L agent is 5.5 and 2.0 yen, respectively, based on all the IF speaking bodies used, and the total amount of initiator and activator is fL (1,005 yen, respectively) on the same basis. % and O, f) 4%.

``'': ti'j 'I'l) 5 The same conjugate as in Examples 1 and 2 except that the lower molecule than j uses the A form before the stabilizer Z) latex school 47: ', j is explained.

-17,:f,>f#,l The method of 1 is repeated using the same substance in 1:1, but instead of the methacrylic acid of the monomethyl needle of bonoetelene glycol of R2000. A methacrylic ester of monomethyl ether of polyethylene glycol having a molecular weight of 50 [1] is used as the same.

(1'q J Before the start +j'?j l・,?Hydrogen hydride, 20 volumes Jft
/j-8Sl'J''@first ``feed'' initiator J'1 1 1 1 Ni] No initiator ``spike'' is used during this digging.

After removing a small amount of coagulum at edge d), the borrowed latex is
:151 result a). Solid content included: 11 □:t 44
．． 7% and ji'+, , 'From the integral conversion rate t, it is 4.8
Chi C Chiru. 111 of the agent (+, 1. agent) are all 1 (−, 1.5 and 6, respectively)
．． 71r, 9s, initiator and excipient 1'+', +' rjl
, l]1I-f', l-1 are respectively [1,6chi and 0.9ヅ, and all j, r3. Based on a single hI compound. Latex Ti172-7 (when heated directly, it turned into B).

1. This article describes the production of a stable latex of a co-conjugate containing a substantial proportion of a "reactive" resin, ie, glycidyl methacrylate.

Repeat the method of Example 1 with the following charges: 11゛First charge! i# Deionized water 2nDV, ll mojim) Bovine formula A 2.2 before 1 ((X
Body 7% 2.21i' [
Inuki Q J, Q4. ,j,',: Sumitomo methyl methacrylate 102 Bual acrylate 87 ", T17-1 initiator 11 strokes hydrogen monoxide, 2 (l regret 4.
87 methyl methacrylate/-) 48 gup”fur acrylate 652
Glycidi A/Methacrylate Ro8F Surfactant^ 6ri Precursor A
Initiator hydrogen peroxide, 20 volumes 12F Methyl methacrylate 1nF Butyl acrylate 132 Glycidyl methacrylate F Surfactant A 1.2F to Al4. ', /')3
Mebul methacrylate/butyl acrylate V = )
/ glycidyl methacrylate) lf1 formation J (hand 1
These are latex socks. After dispensing a very small amount of coagulum, this latex gives a result of 1:166 when measured with a Nanosizer. Solid content &:J:
46.7, and the monomer conversion rate was 95.5%. The balances of stabilizer precursor, surfactant, initiator, and activator are 5.6%, 4.75%, 0.65%, and 0.9%, respectively, based on the total monomers.

This example repeats Example 4 on a larger scale and using a different surface active agent in the feed-1 charge.

Repeat the method of Example 1 with the following charge: 11↓
First charge de-oiled water 100
0f Table j C1 Activator A
Before jig, ql body A,
111F "(in heavy-1," jt monolithic methyl methacrylate) 5
[]f Butyl acrylate-1-40f [Kami] Initiator hydrogen peroxide, 10 otifN
4.8 f/ascorhinic acid
2.07 (Wed)
5.01 Initial 1-Feed” Feed Methyl Methacrylate 240
Sibutyl acrylate 62
5 taglycidyl methacrylate 1
90! /molecule 111400 polyethylene glycol olein 6'sal
Ro02 precursor A
452" or less, d, surfactant B, 100 volumes f (j:
12ri (water)
187 Ascorbic acid
57 (Wednesday)
251F-kun 2 [I11, Feed-1 Charge methyl methacrylate 1/-t 5
11-butyl acrylate
652 Glycidyl Methacrylate-1・
Filter 51 Surfactant 116 g Second r II; Initiator: 11. i Hydrogen oxide, 100 stir h457 (water
10F ascorbic acid
21 (Wednesday)
132 The resulting latex contains some "1 bit", which is removed by filtration. When a p-filtered substance is tested with a 1 nanosizer, a result of 2:162 is obtained. The solids content and the conversion rate per mouse are 48% and 95.6%, respectively. The total amounts of stabilizer precursor, surfactant, initiator, and activator are 5.6%, 4.75%, 1.15%, and 1.4%, respectively, based on total monomers.

Example 6 In 11 cases, the initiator concentration C'>%Examples 4 and 5
The composition of the co-offshore body remains unchanged.

Repeat the method of Example 4 except that the initiator charge is changed as follows: [One] Initiator hydrogen peroxide, 20 vol liter O
,04FIF(Wed 2
．． 02 Ascorbic acid
0. [] 04 F (Wed 2
．． 1) f first "feed" initiator hydrogen peroxide, 20 vol. 0.12
F (Wednesday 202
After removing a very small amount of clot? ! 1: By testing with the latex li:l-nanosizer
171 results are shown. The solid content is 41.2%, and the dead conversion rate is 87.8%. The concentrations of stabilizer precursor and surfactant were as in Example 4 and 5, but at 3 degrees of initiator and activator.

All rjjfA, Jll in i-body, each 0.006
% and [1, OD 9%.

911 (f, l indicates that a chain transfer agent is included in the polymerization mixture.

The procedure of Example 4 is repeated except that some of the charge is substituted for: Methyl methacrylate) 48
17'butyl-acrylate
65yglymethyl methacrylate
682 Surfactant A
6f ago! 1st body A
9y Ethyl 2-bromo-2-methylpropionate 0.839 Initial 1 Feed Initiator Hydrogen Peroxide, 20 Volume 12I/
water
isg ascorbic acid
5v water
152 2nd 1 Feed - 1 Charge Methyl Methacrylate 10f
Butyl acrylate 13
rGlycidyl methacrylate −
Surface activity rill-A
I, 2y Ebul 2-bromo-2-methylpropionate 0.17 fn (1 of 2,
Initiator peracid F1, water level, 20 volumes
5.02 (Wed)
5.07 Ascorbic acid
2.01 (Wed)
i o, o ii' The latex obtained contains a very small amount of coagulum; after separating this, the latex gives a result of i:164 when tested with a "Bunozizer". Latex has a solids content of 42 to 17
, Rod: 11: Body: jl, g, and ≧+<1, so there are three bodies. Initiator and activator r7. ``4 degree is 0.65% and 4.5% based on the total type h) body, respectively;
It's the same as rp.

Example 8 Honjitsu/lα (the example is different from those shown in Examples 4 to 7)
The incorporation of four reactants ('I-1) into a latex polymer will be explained.

Repeat the method of Example 1 with the following charges: Initial Charge Deionized Water 2001
Surfactant A2・27 nil! , tus body A2・22 fltrJ monomer methyl methacrylate 9
．． 6y butyl acrylate
8.31 "(Φ") Initiator hydrogen peroxide, 20 volumes 1T14.8S' Ascorbic acid
0.4v (water
5.021 (, λ first "feed" charge methyl methacrylate 8 [
〕7butyl acrylate
B (1r-methacryloxyzulovir trimethoxysilane 82 surfactant A6/72 da precursor A,
9.24 f'1% hydrogen chloride, 20 volumes: i? :
12 y (water)
87 Ascorbic acid
1ri (water)
192 methyl methacrylate
157 Butyl Acryle-1-15f γ-Meccryloxyglobil Trimethoxysilane
0, 0 surfactant A1゜261 µs ρ-moon table eave'1
52 (Wednesday)
101 Ascorbic acid
D047 (Water)
The latex containing about 10% of coagulum contains about 11 coagulum; after removal of this coagulum, the latex gives a result of 1:159 when tested with a nanosizer.

The solids content was 47.8% and the monomer conversion was 97.8%.
This is Section 9. The total amounts of stabilizer precursor and surfactant are 5.2% and 4.7%, respectively, and the total amount of initiator and activator is 0.59'4 and +-+, 8%, respectively, and all The latex polymer has a composition of 48//l 715 of methyl methacrylate/butyl acrylate-1./γ-mecrylogyciglopyr l.rimethoxysilane.

This example shows that the outer 4111 shell having 411 functional groups derived from the [reactive] monomer 111 present in the second "II Feed" charge and the -711 r (, lli supply-
Illustrating the production of a latex polymer with a crosslinked core by incorporating a polyfunctional monoM: body in one charge 4 Repeating the method of Example 1 with the following charges = 1
1Σ first charge deionized water 2002
Surfactant A
Before 2.29, frame A,
2.21i'1 year old/do' monomer butyl methacrylate 9
%vButyl acrylate
8.32 “God 1 initiator, il,, (12 f1. water ζ!” = , 2 07
．． -! ;,'
[1,0249(Wed)
1.07 Ascorbic acid
o, o ir (water)
1.07 first 1-supply], low methyl methacrylate 1.71.71 butyl acrylate 7
1.7F allyl methacrylate-1-4, Of surfactant A 5
．． 9 f front jq4 bodies A,
8.8 f Initial [Feed-1 Initiator Hydrogen Peroxide, 20 volumes 0.
12 f (water)
110 mio1 ascorbine self-n
Skin 051 (Water)
10. Of 2nd 1 feed' charge methyl methacrylate) 1
0. y-butyl acrylate
152 Glycidyl methacrylate
107 Surface 1 Oxygen A-1, 4f 2nd 1-Supply Initiator Hydrogen Peroxide, 20 Volume 0
．． 0485? ( water
1 (1,0? Ascorbic acid
0.021/( water
10. Or the obtained latex polymer is 46/4
It has an overall composition of methyl methacrylate/butyl acrylate-1/glycidyl meccrylate of 7/2/5 and has a T1 of 15°C. After removing approximately 27% of coagulum, this latex was tested with a 1-nanosizer and a result of 1:194 was obtained.
The body conversion rates are 46.5% and 98%, respectively. Total amount of stabilizer precursor, surfactant, initiator and activator required VJ5, all based on total monomers, 5.5 cm each 4.
7%, 0.006% and 0.05%.

Example 10 This example is shown in Example 9.1. The following describes the use of different multifunctional monomers; in this case also the resulting polymer particles have a core-shell structure.

The method of Example 9 is repeated except that some of the charges are substituted as follows:
1.5y butyl acrylate
71°521:6-hexanediol diacrylate) 4. Of surface a fortune telling A 1 all at once A

5.9ft2fl! u<rt;:A

8.8 y) + 4 acetic acid I hydrogen, 20 volumes 0.144
t( water
12 guascorbine (li72
' 0.06 f( water
12 The resulting latex contains a very small amount of coagulum: after separating the scum, the latex gives a result of 1:218 in the Nanosizer-1 test. The solids content was 44.6% and the monomer conversion was 91%. The surfactant precursor, surfactant, initiator and activator tails used are substantially the same as in Example 9. The latex polymer has a methysifthacrylate/butyl acrylate/hexanediol diacrylate/glycidyl methacrylate phase composition of 46/47/215 and a T1 of 15°C.

Cold suit A upper t-1 This example shows the method of Example 9 and the method of
The material of the particles has hydroxyl groups and carboxyl groups instead of epoxide groups.

Repeat the method of Example 1 using the following charges: Initial charge deionized water 2
[,] Ov Surfactant AO・91 Precursor A
0057 “Woodman” Methyl Methacrylate 1
．． 94f butyl acrylate
2.101 "Weigh" initiator Jj hydrogen hydride, 20 volumes (・J',
0. Q24f (Wednesday)
1. Oy first 1 feed' charge methyl methacrylate filtration 1
゜92 Butyl acrylate)
33.9 f allyl methacrylate
2.161 Surfactant A
2.7 S'mfl! (<
Rest A4/5' Initial 1-i4I supply' Initiator n'-hydrogen peroxide, 20 volumes jii: 0.12f (water
10. Of ascorbic acid
0.05! i'( water
10. Or methacrylate, f
2.979 hydroxy ethyl acrylate 4.247 butyl acrylate 13.97 y surfactant A,
Q. 91i' Second "II, Supply" Initiator Hydrogen peroxide, 20 volumes Skin 0
482 (Wednesday)
1.01 ascorbine ft
O, 02f (water)
1.02 Initial Initiator 1-Spike' Hydrogen Peroxide, 20 Volume Armpit 0.
[124f(Wed)
1. +3S'ascorbic acid
n, o i It'( water
1.02 In this case, 30 minutes after adding the first 1-spike, a second initiator 1-spike is added to the polymerization mixture and heating at 5°C is continued for a further 2.5 hours.

The latex produced contains almost no coagulum,
Testing with ``Nanosizer'' yields a result of 1:175. Solid content is 29. It is Ochi and the conversion rate of single needle is 93
．． It is 9%. Before the stabilizer used! The total amounts of 814 and surfactant were 5°4 and ri 4.8, respectively, and the total amounts of initiator and activator were 0.016% and 0, respectively.
．． 11%, all based on total monomer. The latex polymer has a methyl methacrylate/butyl acrylate/allyl methacrylate/methacrylic acid/hydroxyethyl acrylate composition of 36/54/2/3/5.

Example 12 This Example C demonstrates the preparation of a siliconized latex polymer by the use of tetraethyl silicate in combination with a hydroxyl group-containing monomer.

Replicate the method of Example 1 with the following charges: Initial Charge Deionized Water 200f Surfactant A2.2 Gourd p j I!i-j, r-methyl methacrylate 9.6
y-butyl acrylate)
8.3 r "seed" initiator harsh hydrogen, 2o volume R'+, -4,8F methyl methacrylate -) 69.8 W butyl
Acrylate 60.8 f Hydroxyinpropyl Methacrylate-1-16,13
f Tetraethyl silicate 7
．． 57 Surfactant C (nonylphenol and 60 mol R
Condensate of i with ethylene oxide 1 5.9S'
Before, f((S body A,
8.8y hydrogen peroxide, 20 vol';il
12.0? ( water
8. Ofmethyl methacrylate
17.2F butyl ac 1 liter/t
14.2ghydroxyinglovir methacrylate 5.6vtetraethyl silicate
2.5y Surfactant C1,4f 2nd 1 Supply” Initiator: +17! rri': hydrogen hydride, 20 volume f, t
5. or (water)
5.07 Ascorbic acid
0.47 (Water i
o, o y (4) The leaking latex contains a very small amount of coagulum, which is removed by filtration. The material that has passed through the sea was examined using the F Nanosizer and a result of 1:164 was obtained. The total amount of stabilizer precursors, surfactants, initiators and ll+·f', liη agents used (d is 5.2%, 4.5%, 0.75% and 0.75%, respectively, based on total monomers). It is 1.05%.

Composition of latex polymer based on raw materials 46/39/10
15 methyl methacrylate/butyl acrylate/
Bitroxyisopropyl methacrylate-1/tetraethyl silicate.

Example 13 This example describes the preparation of a latex of a 48/d 2/10 copolymer of methyl meccrylate, butyl acrylate, and hydroxyisopropyl methacrylate having a 'j17 of 15'0.

Initial charge de-tempered water 20Of
Surfactant precursor r) (see below) 4.
4E1 surfactant precursor
IJ allyl ether with 4 moles of butylene oxide and 4
It is the product of continuous condensation with 6 moles of ethylene oxide.

“Seed” simple substance methyl methacrylate 9.6
7butyl acrylate) 8
．． 5 yl type” initiator hydrogen peroxide, 20 volumes 0.02
4 F (Wed 1
．． Of ascorbic acid
0.01? (Water 1
．． Of the first "feed" charge meboul methacrylate 69.
8 F-butyl acrylate 6
0.8 F hydroxyinpropyl methacrylate
16.8! Surfactant precursor D
14.7 J f methyl methacrylate)
17.2 F-butyl acrylate
14.2 f Hydroxyisopropyl methacrylate 3.6y Surfactant Precursor D 1.75S' Water
1.07 Heat the initial aqueous charge to 50"C in a nitrogen sieve and
Add the single batch charge with stirring. Then +-J
Add 'li J initiator solution; 71. After producing the Q-fine seed one-stage latex, the first 1-feed" charge and initiator are gradually charged over a 6 hour period.

The second "feed" charge and initiator were then fed over a period of 30 minutes; finally the reaction mixture was allowed to rise for a further 60 minutes.
℃ and then cooled.

After removing extremely old coagulum by filtration, the resulting latex was examined with a 1-nanosizer-1 to give a
: 137 results. Latex υ2 46.2%
The conversion rate of the isomorphic component-containing plate to a polymer of yellow monomer 111 is 93.3. Used surfactant type 1 (14 types,
The total amount of initiator and activator is the total 1iR of Jlj Fi1 body.
10.4%, 0.006% and 0 based on t, respectively.
．． I am in charge of 04.

Example 14 Honjitsu 77 is the same copolymer as in Example 13, except that a surfactant precursor and a slightly higher proportion of peroxyhydrogen initiator and ascorbic acid activator are used. Figure 2 shows the production of a coalescent latex.

The method of Example 13 is repeated using the same amounts of materials with the following exceptions: (i) In each case 1.2 of surfactant precursor E is substituted for surfactant precursor E. It is the product of the sequential condensation of IJt triallyl ether with 2 moles of butylene oxide and 65 moles of ethylene oxide.

(11) The second 1-feed initiator has the following composition: (
ii+) After addition of the second 1-feed initiator, the following composition: Hydrogen peroxide, 20 vol) J: o
, o 4 B g ( water
Another initiator "spike" of 1° is added to the reaction mixture. The resulting latex was filtered to remove a very small amount of the same substance, and then tested with a Nanosizer (
I get a result of 2:136 from somewhere. Solid content is 44.
8%, and the conversion rate of mono-h(isomer) is 91.6%.

The total amounts of surfactant precursor, initiator and activator used were 10 and 4, respectively, based on the degeneracy percent of the 11jfa form.
H, 0.01 ratio and 0.07%.

Example 15 This example describes the formation of a polymeric latex similar to that of Example 16 except with a higher Ty.

Repeat the method of Example 1 with the following charges: Initial charge deionized water 200.
9 Surfactant Front, main body D4゜48〃 "Seed" 11 U) Single body methyl methacrylate)
9.6g butyl acrylate
8.5, & “seed” initiator methyl methacrylate ioa
! j-butyl acrylate
27. ! /Hydroxyinpropyl methacrylate 30.9 Surfactant Precursor D
16.5j? Methyl methacrylate
21. qButyl acrylate 5g Pidroxisoglobil methacrylate 6
The resulting latex contains a small amount of MF solids, which are removed by filtration. When a substance with P No. 1 is tested with a ``nanosizer'', a result of 4:202 is obtained.

The solids content is 46% and the monomer conversion is 91%. All the surfactants used were precursors, initiators, and activators with 10.
Section 5, Section 006 and Section [1,04]. The monomeric composition of the latex polymer is 66/19/16 methyl methacrylate/butyl acrylate/hydroxyisozorobyl methacrylate;
! It has a temperature of 1-52°C.

Example 16 This example illustrates the use of another different surfactant precursor and the inclusion of water-sensitive "reactive" monomers in the polymerization mixture.

Repeat the method of Example 13 with the following charge: fi
Shi's first charge deionized water 20
0.9 Surfactant Precursor F (see below)
4.49 Surfactant Precursor F is the product of the sequential condensation of pentaerythritol triallyl needle with 4 moles of petite/oxide and 35 moles of ethylene oxide.

"Weight J J4 (-j'i%, body methyl methacrylate 10,
qButyl acrylate 9
gr fITIJ initiator methyl methacrylate 55g butyl acrylate 55g glycidyl methacrylate 42g surface active agent precursor F' 14. #7
Methyl methacrylate 11g Butyl acrylate 11g Glycidyl methacrylate 89 Surface viscosity agent Under precursor 1.
The latex polymer obtained in 75 g had a monomer composition of methyl methacrylate/butyl acrylate/glycidyl methacrylate of 8/37/25 and a Tg of 15°C, and the conversion of monomer to polymer was 91 factors. be. After stripping off a very small amount of coagulum, the latex gives a reading of 1:135 when tested with a "nanosizer". The solids content is 45.6%.

All of the surfactant precursors, initiators and activators used were J1.
10,4 h, respectively, based on the total weight of l'J monomers,
It is 0.006% and 0.04%.

EXAMPLE 17 This example demonstrates the incorporation of even higher proportions of monoreactive monomers into latex polymers than the monomers of Example 16.

Reverse the method of Example 15 using the following charges: Initial Charge Deionized Water 200g Surfactant Precursor G (see below) 4.4
g Surfactant precursor G is the product of the sequential condensation of pentaerythritol triallyl ether with 4 moles of butylene oxide and 65 moles of ethylene oxide.

Type 1” monomer methyl methacrylate 9.6
g-butyl acrylate 8.
3g "seed" initiator hydrogen peroxide, 20 volumes 0.0
24 g (water)
1.0g ascorbic acid
[River] 1g (water 1
．． I) jj Initial "feed" charge Methyl methacrylate 25g Butyl ° Acrylate 43.9
Glycidyl methacrylate-1-84, '7 Surfactant Precursor Q 14.7 i Methyl
Methacrylate 5g Butyl acrylate 9g Grindyl
Methacrylate 16g surface activity 111-
In front of the drug, senryu (J 1.75
．． ! 7 Thus i! The added latex gives a reading of 16 on the F Nanosizer-1 of 2:124. The solid content is 48.4%, and the body composition of the polymer is 20%.
/ro D150 methyl methacrylate/butyl acrylate/glycidyl methacrylate-1. The total amounts of surfactant precursor, initiator, and activator used were IO, 4%, 0.005%, and 0.04%, respectively, based on the total weight of monomers.

EXAMPLE 18 This example shows that the functional groups derived from the appropriate functional monomer present in the second "feed" charge, along with the side skins, having 41 1 illustrates the production of latex polymers with crosslinked cores by incorporating multifunctional monomers in the charge.

First charge deionized water 1ooo! ? Surfactant precursor F 6g
My monomer methyl methacrylate) 9.
7g butyl acrylate 10.5g "God" initiator hydrogen peroxide, 20 volume fan: 0
．． 12g (water
2.0g ascorbic acid
0.059 (water 2.
0 g7i) First “Feed-4 Charge Methyl Methacrylate 159.5
g-butyl acrylate 169.
4.9 allyl methacrylate i
o, ag surfactant precursor F
34.9 Initial feed - 1 initiator hydrogen peroxide, 20 vol.
．． 2g (40g water)
Ascorbic acid 0.5
g (water 40.
q Second “feed” charge Butyl acrylate 69.8
g hydroxyethyl acrylate) 2
1.2g methacrylic f”・2
14.9. 'i' surfactant preform type body
4.5 g hydrogen peroxide, 20 volumes
0.24 F (water 5.
01' ascorbic acid
0.11 (water 5
．． After removing the Shobang coagulum by Oy filtration, the resulting latex gives a 1 nanosizer'' reading of 2:111. The single-chamber 9-body composition of the polymer is 36154/2/3
15, methyl methacrylate/butyl acrylate/allyl methacrylate/methacrylic acid/hydroxyethyl acrylate, and the monomer conversion rate t is 6q6. The solids content of the latex is 30.7%. The total amounts of surfactant precursor, initiator and activator used were 9.6%, D, D 1 B and 0.13%, respectively, based on the degeneracy M of the monomers.

Claims (1)

[Claims] 1, 0. [] Emulsifying in water at least one ethylenically unsaturated polymer having a water solubility in the range of 88 to 8 weight but insoluble in water, and carrying out the polymerization in this state. However, with the exception of non-ionic water-soluble 1'1. (1) in the molecule in the presence of a redox-type polymerization initiator system containing hydrogen peroxide in combination with an activator compound.
a precursor compound containing a polymeric chain having a molecular weight of at least 400 and itself soluble in an aqueous phase; and (11) an unsaturated chain capable of copolymerizing with one or more QI bodies to be polymerized. An aqueous emulsion polymerization method for ethylenically unsaturated monomers, characterized in that the above polymerization is carried out in the presence of. 2. The monomer to be polymerized should be such that the resulting polymer has a glass transition temperature of 60°C or less. 6. The method according to claim 2151 or 2, wherein the nonionic water-soluble activator compound is ascorbic acid. 4. Based on the composition of the monomers being polymerized, hydrogen peroxide is 0.
．． 003 to 6,0% by weight of the activator compound 1-
Claim 91 (The method according to any one of paragraphs 1 to 6.
5. A method according to any one of claims 1 to 4, having a molecular weight of at least 10,000. 6. The above polymer chain is polyethylene glycol or its monoalkyl ether (however, the alkyl group is 1.
6. A method according to claim 5, wherein the method is derived from a compound having .about.4 carbon atoms. 7. The method of claim 6, wherein the polymer chain Z is derived from polyethylene glycol or its monomethyl ether having a molecular weight in the range of 2,000 to 4,000. 8. The method of claim 7, wherein said precursor compound is a methacrylic acid ester of monomethyl ether of polyethylene glycol having a molecular weight of 2[]00. 9 The precursor compound of 6C is present in a proportion of 0.5 to 20 f) of the weight of the monomers to be polymerized
The method described in C.11 in any of Items 1 to 8. 10. The method according to any one of claims 1 to 9, wherein the one or more monomers to be polymerized are emulsified in the presence of a conventional nonionic surfactant. 11. The method according to claim 10, wherein the surfactant is used in a proportion of 0.5 to 10 parts by weight of the monomer to be polymerized. 12, if! jl< compound has the properties of a surfactant and, in addition to a polymeric chain and a terminal unsaturated group that are soluble in aqueous 1'1 phase, has 150 to 10
00 nip, contains another component with a molecular weight in the range,
Claim 1, wherein said compound is present during emulsification of the monomer in water. 12. The method according to claim 12, wherein the component of the surfactant precursor which is itself soluble in the monolayer is a poly(oxybutylene) chain. 14 The surfactant precursor compound has the following formula: % formula % (where X and yt are poly(oxyethylene) and poly(
14. The method of claim 13, wherein the unsaturated block copolymer is an unsaturated block copolymer of oxybutylene) having values corresponding to 2000 and 7000 molecules per block, respectively. 15. The surfactant precursor compound has the following formula: % formula %) (where X and y It.J are each 20
17. A method according to claim 16, wherein the unsaturated block copolymer is an unsaturated block copolymer having a molecular weight of 0.00 and 7000. 16, surfactant precursor compound 1:2:35. Claim r) Scope 13 which is the product of the sequential condensation of the triallyl ether of nithaerythritol with butylene oxide and ethylene oxide in a molar ratio of 12/1:35,1:A:46 or 1:4:65. Method described. 1Z The surfactant precursor compound is a condensation product of 5 moles of undecylenic acid: j1' with ethylene oxide.
'ri self-posting method. 1B, surface active 1'lE agent, precursor compound was used. 18. The method according to any one of claims 12 to 17, wherein the mercury is used in a proportion of [], 5 to 2 D Jjκ. 19 0 of a monolayer body using a water-soluble ill transport agent
．． 1 to 2 layers; 11. % hl of any of claims 13J'1 to 18. 20. The monomer to be polymerized is glycidyl acrylate.
}・Reaction 1′L selected from glycidyl acrylate and γ-methacrylogyciprovir)・rimethoxysilane
The method according to any one of Items 1 to 19 of the scope of patent R, which involves a monochorus.