TWI648308B - Polymerizable surfactant and emulsion polymerization emulsion - Google Patents

Abstract

The present invention relates to a polymerizable surfactant as shown in formula (I):

R ₁ represents an alkyl group having a branched structure having 8 to 13 carbons, an olefin group having 2 to 5 carbons, a phenyl group, an o-phenylphenyl group, a (meth) styrylphenyl group, or a (methyl group) ) Styrenated o-phenylphenyl. S ₁ represents a single bond or an alkoxy segment, and S ₂ represents an alkoxy segment. These alkoxy segments are each composed of at least one alkoxy group, and the alkoxy group is selected from the group consisting of ethoxy, propoxy, butoxy, and any combination thereof. In S ₁ or S ₂ , the number of alkoxy groups is 1 to 100, respectively. R ₂ represents an alkyl group, a phenyl group or a tolyl group having a carbon number of 1 to 4. R ₃ represents an alkenyl group having 2 to 4 carbon atoms. R ₄ represents a hydrogen atom or an anionic group. x represents an integer from 0 to 3, and y represents an integer from 1 to 3.

Description

Polymerizable surfactant and emulsion polymerization emulsion

The present invention relates to a polymerizable surfactant, and particularly to a polymerizable surfactant having a small difference in gelation concentration and application thereof.

In order to comply with current international environmental protection regulations and reduce the emission of environmental volatile organic compounds (VOCs), traditional oil-based coating resins have been gradually replaced by water-based coating resins. However, some properties of water-based coating resins cannot be compared with oil-based coating resins, such as water resistance or weather resistance. The reason is that in the process of emulsion polymerization, an emulsifier must be added to the aqueous coating, but the emulsifier does not have a functional group that can react with the monomer. Therefore, the emulsifier in the resin coating film will migrate with the use of time. To the resin surface and reduce the related physical properties (such as water resistance or weather resistance) of the resin coating film.

In order to effectively solve this problem, those with ordinary knowledge in the technical field to which this case belongs are committed to developing polymerizable surfactants. Polymerizable surfactant refers to the reaction of the surfactant with the monomer in the structure of the surfactant The double bond is used to bond the surfactant to the monomer, which can reduce the residual amount of the surfactant and further improve the water resistance and life of the resin coating film.

However, the difference in gelation concentration between conventional emulsifiers and polymerizable surfactants is large, so they all have poor dilution and low-temperature freeze resistance. Among them, the "gelatinization concentration difference" mentioned here refers to the difference range of the concentration of gelled and non-flowable solution (that is, the highest concentration of gelatinization) at a certain temperature in an aqueous solution containing a surfactant. Difference from lowest concentration). In general, the difference in gelation concentration is a method of increasing the concentration difference by 10% by weight, with 10% by weight as the lowest concentration and 100% by weight as the highest concentration. The surfactant is formulated into 10 sample aqueous solutions to evaluate its gel. Chemical concentration difference.

In other words, the larger the gelation concentration difference (that is, the wider the gelation concentration range), the more the aqueous solution prepared by this surfactant is more likely to cause gelation and non-flowing. Therefore, when the emulsification polymerization reaction is performed, the surfactant tends to be gelled without flowability and dilubility because the disposition concentration falls within the gelation concentration range, thereby reducing its usability. Generally speaking, as the operating temperature decreases, the difference in gelation concentration will also increase. Therefore, in high-latitude cold zone countries, surfactants with large gelation concentration differences are easy to gel and solidify, but not easy to dilute. Limit its applicability.

In view of this, there is an urgent need to provide a polymerizable surfactant having a lower difference in gelation concentration and its application in order to improve the drawbacks of the conventional polymerizable surfactant and its application.

Therefore, one aspect of the present invention is to provide a polymerizable surfactant, which has a specific structure and a lower difference in gelation concentration.

Another aspect of the present invention is to provide an emulsion polymerization emulsion comprising the aforementioned polymerizable surfactant.

According to one aspect of the present invention, a polymerizable surfactant is provided. The polymerizable surfactant has a structure represented by the following formula (I):

In formula (I), R ₁ represents an alkyl group having a branched structure having 8 to 13 carbons, an olefin group having 2 to 5 carbons, phenyl, o-phenylphenyl, (meth) styrene Phenyl or (meth) styrene-o-phenylphenyl; S ₁ represents a single bond or an alkoxy segment composed of at least one first alkoxy group, and S ₂ represents an alkoxy group composed of at least one second alkoxy group The composed alkoxy segments, at least one first alkoxy group or at least one second alkoxy group are respectively selected from the group consisting of ethoxy, propoxy, butoxy and any combination thereof, In S ₁ or S ₂ , the number of at least one first alkoxy group or at least one second alkoxy group is 1 to 100, respectively; R ₂ represents an alkyl group, phenyl group, or toluene having 1 to 4 carbon atoms. group; R ₃ represents a carbon atoms, an alkenyl group of 2 to 4; R ₄ represents a hydrogen atom or an anionic group; X represents an integer of 0 to 3; and y represents an integer of 1-3.

According to an embodiment of the present invention, in the aforementioned S ₁ and S ₂ , at least one first alkoxy group or at least one second alkoxy group is arranged randomly or in blocks.

According to another embodiment of the present invention, the at least one first alkoxy group or the at least one second alkoxy group are independently selected from the group consisting of ethoxy, propoxy, and any combination of the foregoing. .

According to another embodiment of the present invention, the at least one first alkoxy group or the at least one second alkoxy group includes at least an ethoxy group.

According to another embodiment of the present invention, the aforementioned S ₁ represents a single bond, and at least one second alkoxy group includes at least an ethoxy group.

According to yet another embodiment of the present invention, the aforementioned anionic group is selected from the group consisting of -SO ₃ M, -PO ₃ M ₂ , -PO ₃ MH, -COOM, and any combination thereof, and M represents a hydrogen atom, an alkali gold group atom, (alkaline earth group atom) _1/2 , an ammonium group, an alkylammonium group, or an alcohol ammonium group having an alkyl substitution or unsubstitution.

According to still another embodiment of the present invention, the aforementioned x represents an integer of 1 to 3.

According to yet another embodiment of the present invention, the gelation concentration difference of the polymerizable surfactant at 30 ° C. is less than 30 weight percent.

According to yet another embodiment of the present invention, the gelation concentration difference of the polymerizable surfactant at 4 ° C is less than 30 weight percent.

According to another aspect of the present invention, an emulsion polymerization emulsion is proposed. This emulsion polymerization emulsion contains an emulsion polymerization monomer and the aforementioned polymerizable surfactant. The amount of the emulsified polymerizable monomer is 100 parts by weight, and the amount of the polymerizable surfactant is 0.5 to 4.0 parts by weight.

The polymerizable surfactant of the present invention and its application are used to reduce the gelation concentration difference of the polymerizable surfactant by a specific structure, so that it can have good dilution at different operating temperatures, and can be Improve the homogeneity of emulsion during emulsion polymerization, and improve the polymerization stability of emulsion polymerization. Furthermore, it forms a chemical bond with the unsaturated double bond group in the emulsified polymerized monomer through the unsaturated double bond structure, thereby improving the water resistance of the resulting coating film.

The manufacture and use of the embodiments of the invention are discussed in detail below. It is understood, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific content. The specific embodiments discussed are for illustration only and are not intended to limit the scope of the invention.

The polymerizable surfactant of the present invention has a structure represented by the following formula (I):

In the formula (I), R ₁ represents a carbon atoms of 8 to 13 alkyl group having a branched structure, the carbon number of the olefin group of 2 to 5, phenyl, o-phenylphenyl (meth) styrene Phenyl ( , Where "*" represents the bond and m represents an integer from 1 to 3) or (meth) styrenated o-phenylphenyl. S ₁ represents a single bond or an alkoxy segment composed of at least one first alkoxy group, and S ₂ represents an alkoxy segment composed of at least one second alkoxy group, at least one first alkoxy group or The at least one second alkoxy group may include, but is not limited to, an ethoxy group, a propoxy group, a butoxy group, or any combination thereof, and in S ₁ or S ₂ , at least one first alkoxy group or The number of at least one second alkoxy group is 1 to 100 respectively; R ₂ represents an alkyl group, phenyl group or tolyl group having 1 to 4 carbon atoms; R ₃ represents an alkenyl group having 2 to 4 carbon atoms; R ₄ Represents a hydrogen atom or an anionic group; x represents an integer of 0 to 3; and y represents an integer of 1 to 3.

In R ₁ of formula (I), the alkyl group having a branched structure having 8 to 13 carbon atoms may include, but is not limited to, 2-ethylhexyl, branched nonyl, branched decyl, and branched undecane Group, branched dodecyl group, branched tridecyl group, or other suitable alkyl group or any combination thereof.

If the number of carbons of the aforementioned alkyl group having a branched structure is greater than 13, the gelation concentration difference of the polymerizable surfactant obtained will be large, and it will have poor dilution. If the carbon number of the aforementioned alkyl group having a branched structure is less than 8, it is difficult for the obtained polymerizable surfactant to emulsify the monomer, and the particle size of the obtained emulsion is large, thereby reducing the stability.

In some embodiments, the alkyl group having a branched structure having 8 to 13 carbon atoms may optionally have a substituent. In some embodiments, a branched structure of an alkyl group having a branched structure having 8 to 13 carbons may be a group of 1 to 4 carbons. For example, this branched structure may include, but is not limited to, methyl, ethyl, propyl, and butyl. Preferably, the branched structure may be a group having 1 to 3 carbon atoms.

The aforementioned olefin group having a carbon number of 2 to 5 may include, but is not limited to, vinyl, propenyl, 2-methylpropenyl, butenyl, 2-butenyl, 3-butenyl, 3-methyl-3 -Butenyl, other suitable alkenyl or any combination thereof.

In an embodiment, the olefin group having a carbon number of 2 to 5 may optionally have a substituent. In this embodiment, the substituent may include, but is not limited to, methyl, ethyl, other suitable substituents, or any combination of the foregoing groups.

If the polymerizable surfactant represented by formula (I) lacks the R ₁ group, the compound obtained will not have interfacial emulsification properties and cannot be used as a surfactant.

Preferably, R ₁ may be propenyl, 2-methylpropenyl, 3-methyl-3-butenyl, branched nonyl, branched decyl, branched undecyl, phenyl, ortho Phenylphenyl, (meth) styrenated phenyl, or (meth) styrenated o-phenylphenyl, and the like.

In Formula (I), the first alkoxy group of S ₁ or the second alkoxy group of S ₂ is arranged randomly or in blocks. In other words, in S ₁ or S ₂ , when the number of alkoxy groups is not less than 3, S ₁ or S ₂ may be a random segment or a block segment, respectively. In some embodiments, S ₁ may be the same as or different from S ₂ .

In some embodiments, the first alkoxy group or the second alkoxy group may include, but is not limited to, an ethoxy group, a propoxy group, or any combination thereof. In some embodiments, the first alkoxy group includes at least an ethoxy group, or the second alkoxy group includes at least an ethoxy group. In some embodiments, S ₁ may represent a single bond, and the second alkoxy group in S ₂ includes at least an ethoxy group. In these embodiments, when S ₁ or S _{2 of the} surfactant shown in formula (I) contains at least an ethoxy group, the hydrophilic lipophilic balance of the polymerizable surfactant is obtained. ; HLB) value can be adjusted, which can make the emulsification polymerization reaction of surfactant and monomer easier to occur.

In R ₂ of formula (I), the aforementioned alkyl group having 1 to 4 carbon atoms may preferably be methyl, ethyl, propyl, isopropyl, isobutyl or n-butyl. In some embodiments, R ₂ may preferably be ethyl, propyl or butyl.

In some embodiments, when R ₁ is an olefin group having 2 to 5 carbon atoms, R _{2 is} preferably a lipophilic group (for example, phenyl or tolyl, etc.) to balance the surfactant produced. The hydrophilic-lipophilic balance value can limit the difference in gelation concentration of the polymerizable surfactant produced.

In some embodiments, when x is not 0 (that is, x is an integer from 1 to 3), the hydrophilic-lipophilic balance value of the polymerizable surfactant by using the repeating group containing R ₂ and the aforementioned R ₁ It can be adjusted appropriately, and is suitable for emulsified polymerized monomers of different formulas, and then promotes the polymerized surfactants and emulsified polymerized monomers to undergo an emulsification polymerization reaction.

In some embodiments, x may be an integer of 1 to 3.

In R ₃ of formula (I), the aforementioned alkenyl group having 2 to 4 carbon atoms may include, but is not limited to, vinyl, propenyl, 2-methpropenyl, butenyl, 2-butenyl, 3- Butenyl or other suitable alkenyl. Preferably, when R ₃ has a double bond structure, the double bond structure of R ₃ can form a chemical covalent bond with an unsaturated double bond in the emulsion polymerization monomer, and the water resistance of the polymerizable surfactant can be improved. And weather resistance, and inhibit the migration of conventional surfactants to the surface of the coating film.

In some embodiments, y may preferably be an integer of 1 to 3, and more preferably may be an integer of 1 to 2.

In formula (I), when R ₄ represents a hydrogen atom, the polymerizable surfactant is a nonionic surfactant, and it has better chemical stability. When R ₄ represents an anionic group, the polymerizable surfactant is an anionic surfactant, and when the polymerizable surfactant is subjected to an emulsion polymerization reaction with an emulsion polymerization monomer, the latex particles in the formed emulsion have Small particle size and better mechanical stability.

In some embodiments, the aforementioned anionic group may include, but is not limited to, -SO ₃ M, -PO ₃ M ₂ , -PO ₃ MH, -COOM, other suitable anionic groups, or any combination of the foregoing groups. Among them, M may represent a hydrogen atom, an alkali gold group atom, (alkaline earth group atom) _1/2 , an ammonium group, an alkylammonium group, or an alcohol ammonium group having an alkyl substitution or unsubstitution.

In some embodiments, in a 30 ° C environment, the gelation concentration difference of the polymerizable surfactant prepared by the present invention is less than 30% by weight, preferably not more than 20% by weight, and more preferably not more than 10 weight percent. In some embodiments, in a 4 ° C environment, the gelation concentration difference of the polymerizable surfactant prepared by the present invention is less than 30% by weight, preferably not more than 20% by weight, and more preferably not more than 10 weight percent.

The polymerizable surfactant of the present invention can first perform an addition reaction on an alcohol compound represented by the following formula (II-1) and a first epoxy compound having 2 to 4 carbon atoms to obtain the following formula (II -2) The first intermediate product shown.

R ₁ -OH (II-1)

R ₁ -OS ₁ -H (II-2)

In formulae (II-1) and (II-2), the definitions of R ₁ and S ₁ are as described above, and are not repeated here.

Then, the aforementioned first intermediate product and the epoxy compound represented by the following formula (II-3) and formula (II-4) are mixed to perform a ring-opening reaction to obtain the following formula (II-5) Shown as the second intermediate.

In the formulae (II-3) to (II-5), the definitions of R ₂ , R ₃ , x, and y are as described above, and are not repeated here.

Next, the aforementioned second intermediate product is subjected to an addition reaction with an alkoxy compound having a carbon number of 2 to 4 to obtain a polymerizable nonionic interface activity of the present invention represented by the following formula (II-6-1): Agent.

In formula (II-6-1), the definition of S ₂ is as described above, and is not repeated here.

In one embodiment, the polymerizable non-ionic surfactant as shown in formula (II-6-1) can be further subjected to an esterification reaction with an acid-based compound, followed by a neutralization reaction, to obtain the following formula (II-6-2) The polymerizable anionic surfactant according to the present invention is shown.

In the formula (II-6-2), R ₄ ′ may represent an anionic group.

In some embodiments, the aforementioned acid-based compound may include, but is not limited to, a sulfonic acid compound, a phosphoric acid compound, a carboxylic acid compound, other suitable acid-based compounds, or any combination of the aforementioned compounds. The neutralizing agent added to the neutralization reaction may include ammonia, alkali metal compounds, alkaline earth compounds, amine compounds, alkylamine compounds, alcohol amine compounds having alkyl substitution or non-substitution, other suitable basic compounds, or Any combination of the above materials.

In some embodiments, based on the difference between the selected acid-based compound and the neutralizing agent, the anionic group in the aforementioned formula (II-6-2) may include, but is not limited to, -SO ₃ M, -PO ₃ M ₂ ,- PO ₃ MH, -COOM, other suitable anionic groups or any combination of the above groups. Among them, M may represent a hydrogen atom, an alkali gold group atom, (alkaline earth group atom) _1/2 , an ammonium group, an alkylammonium group, or an alcohol ammonium group having an alkyl substitution or unsubstitution.

The aforementioned neutralization reaction can effectively improve the chemical stability of the polymerizable surfactant, and can improve the stability of the applied product.

In a specific example, the polymerizable surfactant of the present invention can be mixed with an emulsion polymerization monomer and subjected to an emulsion polymerization reaction to form an emulsion polymerization emulsion. Wherein, the used amount based on the emulsified polymerization monomer is 100 parts by weight, and the used amount of the polymerizable surfactant may be 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight, and more preferably 1.5 Part by weight to 2.5 parts by weight.

When carrying out the emulsion polymerization reaction, the double bond structure in the polymerizable surfactant can form a chemical bond with the unsaturated double bond in the emulsion polymerization monomer, and can avoid the interfacial activity in the coating film prepared by the conventional emulsion. The defect that the agent migrates to the surface of the coating film or the hydrophilic end can further improve the water resistance and weather resistance of the coating film prepared by this emulsion.

Secondly, the polymerizable surfactant of the present invention has a lower difference in gelation concentration and can have better dilutability, so the emulsion polymerized emulsion formed has better low-temperature freeze-thaw stability and can improve the back end. Emulsification uniformity during application.

The following uses examples to illustrate the application of the present invention, but it is not intended to limit the present invention. Any person skilled in the art can make various changes and decorations without departing from the spirit and scope of the present invention.

Preparation of polymerizable surfactant Example S-1

First, 160 g (1.0 mole) of isodecanol (product of ExxonMobil Chemical Company, model No. Exxal 10, the carbon number distribution is C9: 4%; C10: 89%; C11: 7%) mole) of butyl glycidyl ether and 114 g (1.0 mole) of allyl glycidyl ether were added to a reaction flask, and a ring-opening reaction was performed to obtain a second intermediate product . Then, 440 g (10.0 mole) of ethylene oxide was added to the second intermediate product, and an addition reaction was performed. After the addition reaction is completed, aminosulfonic acid is added to perform the esterification reaction. After the esterification reaction is completed, ammonia water is added and in progress And a reaction to obtain a polymerizable surfactant represented by the following formula (III-1). The obtained polymerizable surfactant was evaluated by the following evaluation method of gelatinization evaluation, and the results are shown in Table 1-1.

Examples S-2 to S-6

The method for preparing the polymerizable surfactant of Examples S-2 to S-6 uses the same synthetic steps as the method of preparing the polymerizable surfactant of Example S-1, except that Example S- 2 to S-6 change the type and amount of reactants. Among them, the polymerizable surfactants prepared in Examples S-2 to S-6 have structures represented by the following formulae (III-2) to (III-6), respectively. The obtained polymerizable surfactants were evaluated by the following evaluation methods for gelation evaluation, and the results are shown in Table 1-1.

In the formulae (III-4) to (III-5), p represents an integer of 1 to 3.

The evaluation method of the aforementioned gelation evaluation is a polymerizable surfactant prepared in Examples S-1 to S-6, and Comparative Example S'-1 (manufactured by ADEKA and model SR-10) Products sold) and Comparative Example S'-2 (a commercial product manufactured by Daiichi Industries and model HS-10) are configured as sample aqueous solutions, wherein the concentration distribution of these sample aqueous solutions is between 10 weight The percentage is from 100 to 100 weight percent, and the difference in increasing concentration is 10 weight percent. According to this, each polymerizable surfactant can be formulated into 10 sample aqueous solutions.

Then, the sample aqueous solution was left at 30 ° C or 4 ° C. After one week, the sample aqueous solution was visually observed for gelation, and evaluated based on the following criteria:

：: The sample aqueous solution was liquid.

△: The sample aqueous solution was in a colloidal state.

╳: The sample aqueous solution has gelled to a solid state.

The evaluation results of the gelation evaluation of the aforementioned polymerizable surfactant are shown in Table 1-1 on the following page.

According to the evaluation results in Table 1-1, it can be known that the polymerizable surfactants in this case have lower gelation concentration differences (less than 30% by weight) at 30 ° C and 4 ° C. Therefore, the polymerizable surfactants prepared in this case Type surfactants have better dilution properties.

Among them, in order to further evaluate the gelation concentration difference of the polymerizable surfactant in this case, the polymerizable surfactant of the foregoing Example S-1 was configured as an aqueous solution having a concentration of 75 wt% and 85 wt%, and implemented The polymerizable surfactants of Examples S-2 and S-3 were configured as aqueous solutions having a concentration of 45 weight percent and 55 weight percent. Then, the sample aqueous solution prepared in Example S-1 was placed at 4 ° C, and the sample aqueous solutions prepared in Example S-1 and Example S-2 were placed at 30 ° C and 4 ° C. After one week, the evaluation was performed on the basis of the aforementioned gelation evaluation, and the results obtained are shown in Table 1-2.

According to the evaluation results in Tables 1-2, it can be known that the difference in gelation concentration of Example S-1 can be reduced to not more than 10% by weight. Therefore, the polymerizable surfactant prepared in this case has a lower gel Chemical concentration difference. its Second, when the sample concentration is 45 weight percent and 55 weight percent, although the sample aqueous solution prepared by the polymerizable surfactants of Examples S-2 and S-3 is already colloidal, it is compared with the comparative example. The polymerizable surfactants of S'-1 and Comparative Example S'-2, Examples S-2 and S-3 still have a lower difference in gelation concentration (less than 20% by weight).

Preparation of emulsion polymerization emulsion

The following are the emulsion polymerization emulsions of Application Examples 1 to 12 and Comparative Application Examples 1 to 4 based on Table 2.

Application example 1

75.0 grams of butyl acrylate (hereinafter referred to as M-2), 75.0 grams of methyl methacrylate (hereinafter referred to as M-3), 3.0 grams of acrylic acid (hereinafter referred to as M-4), and 3.825 grams of the foregoing The polymerizable surfactant (hereinafter referred to as S-1) and 78 grams of water prepared in Example S-1 were added to the mixer, and 0.46 grams of ammonium persulfate (APS) was added as a starting material. Starting agent. The pre-emulsion of Application Example 1 can be obtained by continuously stirring and mixing with a stirring device at room temperature.

Then, 75 grams of water and a part of the pre-emulsion were added to the reactor, and the temperature was raised to a reaction temperature of 75 to 80 ° C. After the reaction temperature is maintained for 30 minutes, the remaining pre-emulsion is added dropwise to the reactor within 3.0 hours, and the emulsion in the reactor is sequentially matured and neutralized, and the application can be obtained. The emulsified polymeric emulsion of Example 1. The obtained emulsion polymerization emulsion was evaluated by the following evaluation methods, such as the coagulation rate, solid content, conversion rate, average particle diameter, low-temperature stability, and water resistance. The results are shown in Table 2 below.

Application Examples 2 to 12 and Comparative Application Examples 1 to 4

Application Examples 2 to 12 and Comparative Application Examples 1 to 4 use the same preparation method as the production method of the emulsion polymerization emulsion of Application Example 1, except that Application Examples 2 to 12 and Comparative Application Examples 1 to 4 change the emulsion polymerization. The types and usage amounts of the monomers, the types and usage amounts of the polymerizable surfactants, and the usage amounts of the initiators, and the evaluation results are shown in Table 2, respectively, and are not repeated here.

Evaluation item Agglutination rate

The emulsion polymerization emulsions prepared in the aforementioned Application Examples 1 to 12 and Comparative Application Examples 1 to 4 were filtered using a 100 mesh screen, and the aggregates on the screen were washed with water, and the collected aggregates were placed in 105 ℃ in an oven. After 2 hours, the weight of the aggregate was measured, and the aggregation ratio of the emulsion polymerization emulsion was calculated by the following formula (IV-1).

2. Solid content

They were weighed the weight W ₁ of Application Example 1 to 12 and Comparative Application Examples 1 to 4 prepared by emulsion polymerization of the emulsion, and added to the weight W ₂ of the aluminum plate. Then, the aluminum dish was placed in an oven at 130 ° C. After 30 minutes, the aluminum dish was taken out, the weight (W ₃ ) was measured, and the solid content of the emulsion polymerization emulsion was calculated by the following formula (IV-2).

3. Conversion rate

The conversion ratio of the emulsion polymerization emulsion can be calculated by dividing the actual solid content calculated in the aforementioned Application Examples 1 to 12 and Comparative Application Examples 1 to 4 by its theoretical solid content.

4. Average particle size

The emulsion polymerization emulsions prepared in the aforementioned Application Examples 1 to 12 and Comparative Application Examples 1 to 4 were configured as an aqueous solution having a concentration of 10% by weight, and the average particle diameter in the aqueous solution was measured with a particle size analyzer (model: COULTER LS230). .

5. Low temperature stability

10 g of the emulsified polymerized emulsion prepared in the aforementioned Application Examples 1 to 12 and Comparative Application Examples 1 to 4 were weighed and placed in a 20 ml sample bottle. The vial was then placed at -16 ° C. After 2 hours, the sample bottle was taken out, and it was placed in a 30 ° C normal temperature hydrolytic freeze to visually observe whether the emulsified polymer emulsion in the sample bottle had fluidity, and evaluated based on the following criteria:

○: The emulsified polymerized emulsion after thawing has fluidity.

╳: The emulsion polymerization emulsion after thawing does not have fluidity.

6. Water resistance

The emulsion polymerization emulsions prepared in the aforementioned Application Examples 1 to 12 and Comparative Application Examples 1 to 4 were evenly coated on a glass plate with a # 4 coating rod to form a coating film having a thickness of 10 μm, and then placed at 50 ° C. In the oven. After 4 hours, it was removed. After cooling to room temperature, put it into a water-resistant whitening tank with a water temperature of 25 ° C. After 1 or 7 days, the coating film was visually observed and evaluated based on the following criteria:

：: The coating film is transparent and adheres to the glass plate.

○: The coating film is cyan and transparent, and adheres to the glass plate.

□: The coating film is whitened, but adheres to the glass plate.

△: The coating film was whitened, but the periphery of the coating film was peeled off.

╳: The coating film is completely whitened or peeled off completely.

According to the results in Table 2, it can be known that when the polymerizable surfactant prepared in this case is used to make an emulsion polymerization emulsion, it can have good low-temperature stability, and the coating film prepared by using this emulsion polymerization emulsion is also Has good stability. Among them, according to the evaluation results of Comparative Application Example 1 and Comparative Application Example 2, although the emulsion polymerization emulsion prepared by them has good low-temperature stability, the surfactants used by them (Comparative Example S'-1 or Comparative Example S '-2) has a higher gelation concentration difference (please refer to Table 1-1). Therefore, the surfactants of Comparative Example S'-1 and Comparative Example S'-2 are not easy to dilute, making the emulsification uneven, and further reducing the polymerization stability during the emulsion polymerization.

It can be known from the examples and comparative examples of the present invention that the polymerizable surfactant prepared by the present invention has a lower gelation concentration difference at room temperature (for example, 30 ° C) and low temperature (for example, 4 ° C), and It has better dilution, and can improve the homogeneity of the emulsion, thereby improving the polymerization stability during emulsion polymerization.

In addition, the polymerizable surfactant of the present invention has an unsaturated double bond structure, so it can form a chemical bond with the unsaturated double bond group in the emulsion polymerization monomer, thereby improving the water resistance and weather resistance of the prepared coating film. And inhibits the defects of conventional surfactants from migrating to the surface of the coating film.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application.

Claims (10)

A polymerizable surfactant has a structure represented by the following formula (I): In formula (I), R ₁ represents an alkyl group having a branched structure having 8 to 13 carbons, an olefin group having 2 to 5 carbons, phenyl, o-phenylphenyl, or (meth) benzene Vinyl phenyl or (meth) styrenated o-phenylphenyl; S ₁ represents a single bond or an alkoxy segment composed of at least one first alkoxy group, and S ₂ represents an at least one second An alkoxy segment composed of an alkoxy group, the at least one first alkoxy group or the at least one second alkoxy group is selected from the group consisting of ethoxy, propoxy, butoxy, and any combination thereof. Form a group, and in the S ₁ or the S ₂ , the number of the at least one first alkoxy group or the at least one second alkoxy group is 1 to 100, respectively; the R ₂ represents a carbon number of 1 Alkyl, phenyl or tolyl to 4; the R ₃ represents an alkenyl having 2 to 4 carbons; the R ₄ represents a hydrogen atom or an anionic group; the x represents an integer from 0 to 3, where x is When 0, the R ₁ does not represent an alkyl group having a branched structure having 8 to 13 carbons, an olefin group having 2 to 5 carbons, or a (meth) styryl group; and y represents 1 to 3 Integer. According to the polymerizable surfactant described in item 1 of the patent application scope, in the S ₁ or the S ₂ , the at least one first alkoxy group or the at least one second alkoxy group is randomly or block-wise. To arrange. The polymerizable surfactant according to item 1 of the application, wherein the at least one first alkoxy group or the at least one second alkoxy group is independently selected from the group consisting of ethoxy, propoxy, and A group of any combination of the above. The polymerizable surfactant according to item 3 of the application, wherein the at least one first alkoxy group or the at least one second alkoxy group includes at least an ethoxy group. The polymerizable surfactant according to item 1 of the application, wherein S ₁ represents a single bond, and the at least one second alkoxy group includes at least an ethoxy group. The polymerizable surfactant according to item 1 of the application, wherein the anionic group is selected from the group consisting of -SO ₃ M, -PO ₃ M ₂ , -PO ₃ MH, -COOM, and any combination thereof. A group consisting of M, and M represents a hydrogen atom, an alkali gold group atom, (alkaline earth group atom) _1/2 , an ammonium group, an alkylammonium group, or an alcohol ammonium group having an alkyl substitution or unsubstitution. The polymerizable surfactant according to item 1 of the patent application range, wherein x represents an integer of 1 to 3. The polymerizable surfactant according to item 1 of the scope of the patent application, wherein the difference in gelation concentration of the polymerizable surfactant at 30 ° C. is less than 30% by weight. The polymerizable surfactant according to item 1 of the scope of the patent application, wherein the difference in gelation concentration of the polymerizable surfactant at 4 ° C is less than 30 weight percent. An emulsion polymerization emulsion, comprising: an emulsion polymerization monomer; and the polymerizable surfactant as described in any one of claims 1 to 9 of the scope of application for a patent, wherein the amount based on the emulsion polymerization monomer is 100 The weight of the polymerizable surfactant is 0.5 to 4.0 parts by weight.