CN109422825B - Polymerizable surfactant and emulsion polymerization emulsion - Google Patents
Polymerizable surfactant and emulsion polymerization emulsion Download PDFInfo
- Publication number
- CN109422825B CN109422825B CN201711043192.4A CN201711043192A CN109422825B CN 109422825 B CN109422825 B CN 109422825B CN 201711043192 A CN201711043192 A CN 201711043192A CN 109422825 B CN109422825 B CN 109422825B
- Authority
- CN
- China
- Prior art keywords
- group
- polymerizable surfactant
- alkoxy group
- alkoxy
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 101
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 49
- 239000000839 emulsion Substances 0.000 title claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 51
- -1 o-phenylphenyl group Chemical group 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 19
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 239000000523 sample Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000001879 gelation Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a polymerizable surfactant shown as a formula (I):
R1represents an alkyl group having a branched structure and having 8 to 13 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, an o-phenylphenyl group, a styrenated phenyl group or a styrenated o-phenylphenyl group. S1Represents a single bond or an alkoxy chain segment, and S2Represents an alkoxy segment. The alkoxy segments are each comprised of at least one alkoxy group selected from the group consisting of ethoxy, propoxy, butoxy, and any combination thereof. In S1Or S2In the above formula, the number of the alkoxy groups is 1 to 100. R2Represents an alkyl group having a carbon number of 1 to 4, a phenyl group or a tolyl group. R3Represents an alkenyl group having 2 to 4 carbon atoms. R4Represents a hydrogen atom or an anionic group. x represents an integer of 0 to 3, and y represents an integer of 1 to 3. The prepared polymerizable surfactant has smaller gelling concentration difference.
Description
Technical Field
The invention relates to a polymerizable surfactant, and particularly provides a polymerizable surfactant with a small gelling concentration difference and application thereof.
Background
In order to comply with the international environmental regulations and reduce the emission of Volatile Organic Compounds (VOCs), conventional oil paint resins are gradually replaced by water paint resins. However, some properties of the aqueous coating resin are still not comparable to those of the oily coating resin, such as water resistance or weather resistance. This is because, in the production process of emulsion polymerization, an emulsifier is added to the aqueous coating material, but the emulsifier does not have a functional group reactive with a monomer, and therefore, as the time of use increases, the emulsifier in the resin coating film migrates to the surface of the resin, and the properties (such as water resistance and weather resistance) related to the resin coating film are lowered.
In order to effectively solve this problem, those skilled in the art are working on the development of a polymerizable surfactant. The polymerizable surfactant is a surfactant which has a reactive double bond capable of reacting with a monomer in the structure so as to bond the surfactant and the monomer, so that the residual quantity of the surfactant can be reduced, and the water resistance and the service life of a resin coating film can be further improved.
However, the conventional emulsifiers or polymerizable surfactants have a large difference in gel concentration, and thus have poor dilutability and low-temperature freezing resistance. The term "gelling concentration difference" refers to the difference range of the concentration of the surfactant-containing aqueous solution that does not gel at a specific temperature (i.e., the difference between the highest concentration and the lowest concentration that will gel). In general, the difference in gel concentration is obtained by formulating 10 sample aqueous solutions of the surfactant in such a manner that the difference in gel concentration is gradually increased by 10 weight percent, the minimum concentration is 10 weight percent, and the maximum concentration is 100 weight percent, to evaluate the difference in gel concentration.
In other words, the larger the difference in gelling concentration (i.e., the wider the range of concentration that will produce gelling), the more likely the aqueous solution prepared by the surfactant will be gelled without flowing. Therefore, when the emulsion polymerization reaction is carried out, the surfactant is liable to gel without fluidity and dilutability because the preparation concentration falls within the gel concentration range, and the usability thereof is lowered. Generally speaking, as the operating temperature decreases, the difference of the gelling concentration will also expand, so in countries in high latitudes and frigid zones, the surfactant with larger difference of the gelling concentration is easy to gel and solidify, and is not easy to dilute, thereby further limiting the applicability.
In view of the above, it is desirable to provide a polymerizable surfactant with a low gel concentration difference and its application to improve the defects of the conventional polymerizable surfactant and its application.
Disclosure of Invention
Therefore, one aspect of the present invention is to provide a polymerizable surfactant having a specific structure and a low gel concentration difference.
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 having a structure represented by the following formula (I):
in the formula (I), R1Represents an alkyl group having a branched structure and having 8 to 13 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, an o-phenylphenyl group, a styrenated phenyl group or a styrenated o-phenylphenyl group; s1Represents a single bond or an alkoxy chain consisting of at least one first alkoxy group, S2Represents an alkoxy segment consisting of at least one second 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, respectively, and is represented by1Or S2Wherein the number of the at least one first alkoxy group or the at least one second alkoxy group is 1 to 100, respectively; r2Represents an alkyl group having a carbon number of 1 to 4, a phenyl group or a tolyl group; r3Represents an alkenyl group having 2 to 4 carbon atoms; r4Represents a hydrogen atom or an anionic group; x represents an integer of 0 to 3; and y represents an integer of 1 to 3.
According to an embodiment of the present invention, in the above S1And S2Wherein the at least one first alkoxy group or the at least one second alkoxy group is arranged randomly or blockwise.
According to another embodiment of the present invention, the at least one first alkoxy group or the at least one second alkoxy group is independently selected from a group consisting of ethoxy, propoxy, and any combination thereof.
According to another embodiment of the present invention, the at least one first alkoxy group or the at least one second alkoxy group at least includes an ethoxy group.
According to still another embodiment of the present invention, the aforementioned S1Represents a single bond, and at least one second alkoxy group comprises 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-SO3M、-PO3M2、-PO3MH, -COOM, and any combination thereof, and M represents a hydrogen atom, an alkaline metal atom, an (alkaline earth atom)1/2Ammonium, alkylammonium or alkylammonium with or without alkyl substitution.
According to still another embodiment of the present invention, the aforementioned x represents an integer of 1 to 3.
According to still another embodiment of the present invention, the difference of the gelation concentration of the polymerizable surfactant at 30 ℃ is less than 30% by weight.
According to still another embodiment of the present invention, the difference of the gelation concentration of the polymerizable surfactant at 4 ℃ is less than 30% by weight.
According to another aspect of the present invention, an emulsion polymerization emulsion is provided. The emulsion polymerization emulsion comprises emulsion polymerization monomers and the polymerizable surfactant. Wherein the polymerizable surfactant is used in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the emulsion-polymerized monomer.
The polymerizable surfactant and the application thereof reduce the gelling concentration difference of the polymerizable surfactant by a specific structure, so that the polymerizable surfactant has good dilutability at different operating temperatures, emulsion uniformity during emulsion polymerization can be improved, and polymerization stability of the emulsion polymerization can be improved. Furthermore, the unsaturated double bond structure and the unsaturated double bond group in the emulsion polymerization monomer form a chemical bond, thereby improving the water resistance of the prepared coating.
Detailed Description
The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not 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), R1Represents C8-13 alkyl group having branched structure, C2-5 alkenyl group, phenyl group, o-phenylphenyl group, styrenated phenyl group: (
Wherein "" represents a bond, and m represents an integer of 1 to 3) or a styrenated o-phenylphenyl group. S1Represents a single bond or an alkoxy chain segment consisting of at least one first alkoxy group, and S2Represents an alkoxy segment consisting of at least one second alkoxy group, wherein the at least one first alkoxy group or the at least one second alkoxy group, respectively, may include, but are not limited to, ethoxy, propoxy, butoxy, or any combination thereof, and is substituted at S1Or S2Wherein the number of the at least one first alkoxy group or the at least one second alkoxy group is 1 to 100, respectively; r2Represents an alkyl group having a carbon number of 1 to 4, a phenyl group or a tolyl group; r3Represents an alkenyl group having 2 to 4 carbon atoms; r4Represents 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 of formula (I)1In (b), the alkyl group having a branched structure with a carbon number of 8 to 13 may include, but is not limited to, 2-ethylhexyl, branched nonyl, branched decyl, branched undecyl, branched dodecyl, branched tridecyl, or other suitable alkyl group, or any combination thereof.
If the number of carbons of the alkyl group having a branched structure is greater than 13, the polymerizable surfactant has a large difference in gel concentration and poor dilutability. If the number of carbons of the alkyl group having a branched structure is less than 8, the prepared polymerizable surfactant is difficult to emulsify monomers, and the prepared emulsion has a large particle size, thereby decreasing stability.
In some embodiments, the alkyl group having a branched structure with a carbon number of 8 to 13 may optionally have a substituent. In some embodiments, the branched structure of the alkyl group having a branched structure having a carbon number of 8 to 13 may be a group having a carbon number of 1 to 4. For example, the branched structure may include, but is not limited to, methyl, ethyl, propyl, butyl. Preferably, the branched structure may be a group having 1 to 3 carbon atoms.
The aforementioned alkenyl group having a carbon number of 2 to 5 may include, but is not limited to, ethenyl, propenyl, 2-methylpropenyl, butenyl, 2-butenyl, 3-methyl-3-butenyl, other suitable alkenyl groups, or any combination thereof.
In one embodiment, the alkenyl group having 2 to 5 carbon atoms 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 thereof.
If the polymerizable surfactant of formula (I) lacks R1When the group is used, the prepared compound does not have the interfacial emulsification characteristic and cannot be used as a surfactant.
Preferably, R1Can be propenyl, 2-methylpropenyl, 3-methyl-3-butenyl, branched nonyl, branched decyl, branched undecyl, phenyl, o-phenylphenyl, styrenated phenyl, styrenated o-phenylphenyl, or the like.
In the formula (I), S1First alkoxy of (A) or S2The second alkoxy groups of (a) are arranged randomly or in blocks. In other words, in S1Or S2When the number of alkoxy groups is not less than 3, S1Or S2Respectively, can be random segments or block segments. In some embodiments, S1May be the same as or different from S2。
In some embodiments, the first alkoxy group or the second alkoxy group can include, but is not limited to, ethoxy, propoxy, or any combination of the above alkoxy groups. In some embodiments, the first alkoxy group comprises at least an ethoxy group, or a second alkyl groupThe oxy group contains at least an ethoxy group. In some embodiments, S1May represent a single bond, and S2The second alkoxy group in (1) contains at least an ethoxy group. In such embodiments, when S is the surfactant of formula (I)1Or S2When the surfactant contains at least ethoxy, the hydrophilic-Lipophilic Balance (HLB) value of the obtained polymerizable surfactant can be adjusted, so that emulsion polymerization reaction of the surfactant and the monomer is easy to occur.
In R of formula (I)2In the above, the alkyl group having 1 to 4 carbon atoms may preferably be a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group or an n-butyl group. In some embodiments, R2Preferably ethyl, propyl or butyl.
In some embodiments, R is as described above1Is alkylene group with 2 to 5 carbon atoms, R2Preferably a lipophilic group (e.g., phenyl or tolyl) to balance the hydrophilic-lipophilic balance of the resulting surfactant and limit the difference in gelling concentration of the resulting polymerizable surfactant.
In some embodiments, when x is not 0 (i.e., x is an integer from 1 to 3), by including R2Repeating group of (3) with the aforementioned R1The hydrophilic-lipophilic balance value of the polymerizable surfactant can be properly adjusted, so that the polymerizable surfactant is suitable for emulsion polymerization monomers with different formulas, and the prepared polymerizable surfactant and the emulsion polymerization monomers are promoted to carry out emulsion polymerization reaction.
In some embodiments, x may preferably be an integer from 1 to 3.
In R of formula (I)3In (3), the aforementioned alkenyl group having a carbon number of 2 to 4 may include, but is not limited to, an ethenyl group, a propenyl group, a 2-methylpropenyl group, a butenyl group, a 2-butenyl group, a 3-butenyl group, or other suitable alkenyl group. Preferably, when R is3When having a double bond structure, R3The double bond structure can form chemical covalent bond with unsaturated double bond in the emulsion polymerization monomer, thereby improving the water resistance and weather resistance of the polymerizable surfactant and inhibiting the defect of migration (migration) of the conventional surfactant to the surface of the coating film.
In some embodiments, y may be an integer of preferably 1 to 3, and more preferably 1 to 2.
In the formula (I), when R is4When representing hydrogen atom, the polymerizable surfactant is a nonionic surfactant and has better chemical stability. When R is4When the polymerizable surfactant represents an anionic group, the polymerizable surfactant is an anionic surfactant, and when the polymerizable surfactant and an emulsion polymerization monomer are subjected to emulsion polymerization reaction, emulsion particles in the formed emulsion have smaller particle size and better mechanical stability.
In some embodiments, the aforementioned anionic groups can include, but are not limited to, -SO3M、-PO3M2、-PO3MH, -COOM, other suitable anionic groups, or any combination of the foregoing. Wherein M may represent a hydrogen atom, an alkali metal atom, an (alkali earth atom)1/2Ammonium, alkylammonium, or alkylammonium with or without alkyl substitution.
In some embodiments, the polymerizable surfactant prepared by the present invention has a difference in gelation concentration of less than 30 wt%, preferably not more than 20 wt%, and more preferably not more than 10 wt% in an environment of 30 ℃. In some embodiments, the polymerizable surfactant prepared by the present invention has a difference in gelation concentration of less than 30 wt%, preferably not more than 20 wt%, and more preferably not more than 10 wt% in an environment of 4 ℃.
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 a first intermediate product represented by the following formula (II-2).
R1-OH (II-1)
R1-O-S1-H (II-2)
In the formulae (II-1) and (II-2), R1And S1The definitions of (A) and (B) are as described above and are not described herein.
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, whereby a second intermediate product represented by the following formula (II-5) can be obtained.
In formulae (II-3) to (II-5), R2、R3The definitions of x and y are as described above and are not repeated herein.
Then, the second intermediate product and an alkoxide compound having 2 to 4 carbon atoms are subjected to an addition reaction to obtain the polymerizable nonionic surfactant of the present invention represented by the following formula (II-6-1).
In the formula (II-6-1), S2The definitions of (A) and (B) are as described above and are not described herein.
In one embodiment, the polymerizable nonionic surfactant shown in formula (II-6-1) can be further subjected to esterification reaction with an acid group compound, and then subjected to neutralization reaction, so as to obtain the polymerizable anionic surfactant shown in formula (II-6-2).
In the formula (II-6-2), R4' may represent an anionic group.
In some embodiments, the aforementioned acid group compounds may include, but are not limited to, sulfonic acid compounds, phosphoric acid compounds, carboxylic acid compounds, other suitable acid group compounds, or any mixture of the aforementioned compounds. The neutralizing agent to be added in the neutralization reaction may include ammonia, an alkaline metal compound, an alkaline earth compound, an amine compound, an alkylamine compound, an alkylol amine compound, other suitable basic compounds, or any mixture thereof.
In some embodiments, the anionic group in the foregoing formula (II-6-2) may include, but is not limited to, -SO based on the difference between the acid group compound and the neutralizing agent selected3M、-PO3M2、-PO3MH, -COOM, other suitable anionic groups, or any combination of the foregoing. Wherein M may represent a hydrogen atom, an alkali metal atom, an (alkali earth atom)1/2Ammonium, alkylammonium, or alkylammonium with or without alkyl substitution.
The neutralization reaction can effectively improve the chemical stability of the prepared polymerizable surfactant, and can improve the stability of the applied product.
In one embodiment, the polymerizable surfactant of the present invention can be mixed with an emulsion polymerization monomer and subjected to emulsion polymerization to form an emulsion polymerization emulsion. Wherein, the polymerizable surfactant may be used in an amount of 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight, and more preferably 1.5 to 2.5 parts by weight, based on 100 parts by weight of the emulsion-polymerized monomer.
When the emulsion polymerization reaction is carried out, the double bond structure in the polymerizable surfactant can form chemical bonding with unsaturated double bonds in the emulsion polymerization monomer, so that the defect that the surfactant migrates to the surface or the hydrophilic end of a coating film in the coating film prepared by the conventional emulsion can be avoided, and the water resistance and the weather resistance of the coating film prepared by the emulsion can be further improved.
And secondly, the polymerizable surfactant has lower gelling concentration difference and better dilutability, so that the formed emulsion polymerization emulsion has better low-temperature freeze-thaw stability and can improve the emulsification uniformity in rear-end application.
The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
Preparation of polymerizable surfactant
Example S-1
First, 160g (1.0mole) of isodecanol (a product manufactured by ExxonMobil Chemical Co., Ltd., and having a carbon number distribution of C9: 4%; C10: 89%; C11: 7%), 149g (1.0mole) of butyl glycidyl ether (butyl glycidyl ether) and 114g (1.0mole) of allyl glycidyl ether (allyl glycidyl ether) were charged into a reaction flask and subjected to a ring-opening reaction to produce a second intermediate product. Then, 440g (10.0mole) of ethylene oxide was added to the second intermediate product, and addition reaction was performed. And after the addition reaction is finished, adding sulfamic acid to perform esterification reaction. After the esterification reaction is finished, adding ammonia water, and carrying out neutralization reaction to obtain the polymerizable surfactant shown as the following formula (III-1). The resultant polymerizable surfactant was evaluated in the following manner of evaluation of gelation evaluation, and the results are shown in Table 1-1.
Examples S-2 to S-6
The polymerizable surfactants of examples S-2 to S-6 were prepared by the same synthesis procedure as that of example S-1, except that the species and the amounts of the reactants were changed in examples S-2 to S-6. The polymerizable surfactants prepared in examples S-2 to S-6 have the structures shown in the following formulas (III-2) to (III-6), respectively. The polymerizable surfactants were evaluated in the following manner for gel 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 polymerizable surfactants obtained in examples S-1 to S-6 and the surfactants of comparative examples S '-1(a commercially available product manufactured by ADEKA and having a model number of SR-10) and S' -2 (a commercially available product manufactured by first industry and having a model number of HS-10) were respectively prepared as sample aqueous solutions, wherein the concentration distribution of the sample aqueous solutions was 10 weight percent to 100 weight percent, and the incremental differences of the concentrations were 10 weight percent. Accordingly, 10 sample aqueous solutions can be prepared for each polymerizable surfactant.
Then, these sample aqueous solutions were placed at 30 ℃ or 4 ℃ and after one week, whether the sample aqueous solutions had a gelling phenomenon was visually observed and evaluated on the following criteria:
very good: the aqueous sample solution is in liquid form.
And (delta): the aqueous sample solution is in a colloidal state.
Gamma rays: the aqueous sample solution had gelled to a solid state.
The evaluation results of the gelation evaluation of the polymerizable surfactant are shown in Table 1-1.
TABLE 1-1
According to the evaluation results in table 1-1, the polymerizable surfactant has a low gel concentration difference (less than 30 wt%) at 30 ℃ and 4 ℃, so the polymerizable surfactant prepared in the present invention has better dilutability.
In order to further evaluate the difference in gelling concentration of the polymerizable surfactants, the polymerizable surfactant of example S-1 was prepared as an aqueous solution with a concentration of 75 wt% and 85 wt%, and the polymerizable surfactants of examples S-2 and S-3 were prepared as an aqueous solution with a concentration of 45 wt% and 55 wt%. Then, the aqueous sample solution prepared in example S-1 was placed at 4 ℃ and the aqueous sample solutions prepared in examples S-1 and S-2 were placed at 30 ℃ and 4 ℃. After one week, the evaluation was performed on the basis of the above-described gelation evaluation, and the results obtained are shown in tables 1 to 2.
Tables 1 to 2
As can be seen from the evaluation results shown in Table 1-2, the difference in gel concentration of the example S-1 was reduced to not more than 10% by weight, and the polymerizable surfactant prepared herein had a lower difference in gel concentration. Secondly, at the sample concentrations of 45 wt% and 55 wt%, although the sample aqueous solutions prepared from the polymerizable surfactants of examples S-2 and S-3 are colloidal, the polymerizable surfactants of examples S-2 and S-3 have lower difference in gel concentration (less than 20 wt%) compared to comparative examples S '-1 and S' -2.
Preparation of emulsion polymerization emulsion
The following emulsion polymerization emulsions of application examples 1 to 12 and comparative application examples 1 to 4 were prepared according to table 2.
Application example 1
75.0 g of butyl acrylate (hereinafter, abbreviated as M-2), 75.0 g of methyl methacrylate (hereinafter, abbreviated as M-3), 3.0 g of acrylic acid (hereinafter, abbreviated as M-4), 3.825 g of the polymerizable surfactant obtained in the above-mentioned example S-1 (hereinafter, abbreviated as S-1) and 78 g of water were fed into a mixer, and 0.46 g of Ammonium Persulfate (APS) was added as a starting material. The pre-emulsion of application example 1 was obtained by continuously stirring and mixing the components at room temperature with a stirring apparatus.
Then, 75 g of water and part of the pre-emulsion are added to the reactor and the temperature is raised to a reaction temperature of 75 to 80 ℃. After the reaction temperature is maintained for 30 minutes, the remaining pre-emulsion is dripped into the reactor within 3.0 hours, and the emulsion in the reactor is sequentially subjected to a ripening step, a neutralization step and the like, so that the emulsion polymerization emulsion of application example 1 can be prepared. The emulsion polymerization emulsions thus obtained were evaluated by the following evaluation methods of aggregation, solid content, conversion, average particle size, low-temperature stability, water resistance, etc., and the results are shown in Table 2.
Application examples 2 to 12 and comparative application examples 1 to 4
Application examples 2 to 12 and comparative application examples 1 to 4 were prepared by the same method as the emulsion polymerization emulsion of application example 1, except that the types and the amounts of the emulsion polymerization monomers, the types and the amounts of the polymerizable surfactants, and the amounts of the initiators were changed in application examples 2 to 12 and comparative application examples 1 to 4, and the evaluation results are shown in table 2, respectively, and are not described herein again.
Evaluation item
1. Rate of aggregation
The emulsion polymerization emulsions prepared in the above application examples 1 to 12 and comparative application examples 1 to 4 were filtered using a 100 mesh (mesh) screen, and after washing the aggregates on the screen with water, the collected aggregates were placed in an oven at 105 ℃. After 2 hours had elapsed, the weight of the aggregate was weighed, and the aggregation ratio of the emulsion polymerization emulsion was calculated by the following formula (IV-1).
2. Solid components
Respectively weighing W1The emulsion polymerization emulsions obtained in the aforementioned application examples 1 to 12 and comparative application examples 1 to 4, and added to a weight of W2On an aluminum dish. Then, the aluminum dish was placed in an oven at 130 ℃ for 30 minutes, and after taking out the aluminum dish, the weight (W) thereof was measured3) And the solid content of the emulsion polymerization emulsion was calculated by the following formula (IV-2).
3. Conversion rate
The conversion of the emulsion polymerization emulsion was calculated by dividing the actual solid content calculated in the above application examples 1 to 12 and comparative application examples 1 to 4 by the theoretical solid content.
4. Average particle diameter
The emulsion polymerization emulsions prepared in the above application examples 1 to 12 and comparative application examples 1 to 4 were prepared as aqueous solutions having a concentration of 10% by weight, and the average particle size in the aqueous solutions was measured by a particle size analyzer (model: COULTER LS 230).
5. Low temperature stability
10 g of the emulsion polymerization emulsions prepared in the above application examples 1 to 12 and comparative application examples 1 to 4 were weighed and placed in a 20-ml sample bottle. The sample vial was then placed at-16 ℃. After 2 hours, the sample bottle was taken out, thawed in water at room temperature of 30 ℃, and visually observed whether the emulsion polymerization emulsion in the sample bottle had fluidity or not, and evaluated on the following criteria:
o: the emulsion polymerization emulsion after thawing has fluidity.
Gamma rays: the emulsion polymerization emulsion after thawing had no fluidity.
6. Water resistance
The emulsion polymerization emulsions prepared in the foregoing application examples 1 to 12 and comparative application examples 1 to 4 were uniformly coated on a glass plate with a #4 coating bar to form a coating film having a thickness of 10 μm, and placed in an oven at 50 ℃. After 4 hours, it was taken out. After cooling to room temperature, the mixture was placed in a water-resistant whitening bath at 25 ℃. After 1 day or 7 days, the coating film was visually observed and evaluated on the following criteria:
very good: the coating film was transparent and was adhered to the glass plate.
O: the coating film was cyan and transparent, and was adhered to the glass plate.
□: the coating film was whitened but adhered to the glass plate.
And (delta): the coating film was whitened, but the periphery of the coating film was peeled off.
Gamma rays: the coating film was completely whitened or completely peeled off.
As can be seen from the results in Table 2, the polymerizable surfactant prepared herein has good low temperature stability when used to prepare emulsion polymerization emulsion, and the coating film prepared from the emulsion polymerization emulsion 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 obtained has good low-temperature stability, the surfactant used (comparative example S '-1 or comparative example S' -2) has a higher difference in gel concentration (see table 1-1). Therefore, the surfactants of comparative examples S '-1 and S' -2 are not easily diluted, resulting in uneven emulsification and reduced polymerization stability during emulsion polymerization.
As can be seen from the examples and comparative examples of the present invention, the polymerizable surfactant prepared by the present invention has a low gel concentration difference at room temperature (e.g., 30 ℃) and low temperature (e.g., 4 ℃), and has good dilutability, and can improve the uniformity of the emulsion, thereby improving the polymerization stability during emulsion polymerization.
In addition, the polymerizable surfactant has an unsaturated double bond structure, so that the polymerizable surfactant can form a chemical bond with unsaturated double bond groups in an emulsion polymerization monomer, further the water resistance and the weather resistance of the prepared coating are improved, and the defect that the conventional surfactant migrates to the surface of the coating is inhibited.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A polymerizable surfactant, wherein the polymerizable surfactant has a structure represented by the following formula (I):
in the formula (I), R1Represents a styrenated phenyl or styrenated o-phenylphenyl group; s1Represents a single bond or an alkoxy chain consisting of at least one first alkoxy group, S2Represents an alkoxy segment consisting of at least one second alkoxy group, the at least one first alkoxy group or the at least one second alkoxy group being independently selected from the group consisting of ethoxy, propoxy, butoxy and any combination thereof, and is at S1Or S2Wherein the number of the at least one first alkoxy group or the at least one second alkoxy group is 1 to 100, respectively; r2Represents an alkyl group having a carbon number of 1 to 4, a phenyl group or a tolyl group; r3Represents an alkenyl group having 2 to 4 carbon atoms; r4Represents a hydrogen atom or an anionic group; x represents an integer of 0 to 3; and y represents an integer of 1 to 3.
2. The polymerizable surfactant of claim 1, wherein S is1Or S2Wherein the at least one first alkoxy group or the at least one second alkoxy group is arranged randomly or blockwise.
3. The polymerizable surfactant according to claim 1, 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 any combination thereof.
4. The polymerizable surfactant according to claim 3, wherein the at least one first alkoxy group or the at least one second alkoxy group comprises an ethoxy group.
5. The polymerizable surfactant of claim 1, wherein S is1Represents a single bond, and the at least one second alkoxy group comprises at least an ethoxy group.
6. The polymerizable surfactant according to claim 1, wherein the polymerizable surfactant isCharacterized in that the anionic group is selected from the group consisting of-SO3M、-PO3M2、-PO3MH, -COOM, and any combination thereof, and M represents a hydrogen atom, an alkaline metal atom, an (alkaline earth atom)1/2Ammonium, alkylammonium or alkylammonium with or without alkyl substitution.
7. The polymerizable surfactant according to claim 1, wherein x represents an integer of 1 to 3.
8. The polymerizable surfactant of claim 1, wherein the polymerizable surfactant has a gel concentration difference of less than 30 weight percent at 30 ℃.
9. The polymerizable surfactant of claim 1, wherein the polymerizable surfactant has a gel concentration difference at 4 ℃ of less than 30 weight percent.
10. An emulsion polymerization emulsion, comprising:
emulsion polymerization of monomers; and
the polymerizable surfactant according to any one of claims 1 to 9, wherein the amount used is 100 parts by weight based on the emulsion-polymerized monomer, and the amount used of the polymerizable surfactant is 0.5 to 4.0 parts by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW106129380A TWI648308B (en) | 2017-08-29 | 2017-08-29 | Polymerizable surfactant and emulsion polymerization emulsion |
| TW106129380 | 2017-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109422825A CN109422825A (en) | 2019-03-05 |
| CN109422825B true CN109422825B (en) | 2021-06-08 |
Family
ID=65514357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711043192.4A Active CN109422825B (en) | 2017-08-29 | 2017-10-31 | Polymerizable surfactant and emulsion polymerization emulsion |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109422825B (en) |
| TW (1) | TWI648308B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643380A (en) * | 2012-04-18 | 2012-08-22 | 上海维凯化学品有限公司 | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof |
| CN102676095A (en) * | 2011-03-07 | 2012-09-19 | 顺安涂布科技(昆山)有限公司 | Composition and manufacture method for emulsion type pressure-sensitive adhesive, and protection adhesive tape thereof |
| CN103421183A (en) * | 2013-07-30 | 2013-12-04 | 浙江大学 | Reaction type greasy base degradable surfactant as well as synthetic method and application thereof |
| CN105061665A (en) * | 2015-07-31 | 2015-11-18 | 华南理工大学 | Hydroxypolyacrylate emulsion, and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09311506A (en) * | 1996-05-17 | 1997-12-02 | Nippon Paint Co Ltd | Liquid developer and its production |
| MX356505B (en) * | 2011-08-29 | 2018-05-31 | Ethox Chemicals Llc | New reactive surfactants for emulsion polymerization, pigment dispersion, and uv coatings. |
| WO2014009765A1 (en) * | 2012-07-11 | 2014-01-16 | Omnova Solutions | Rheological agent, preparation methods and uses thereof |
| US20150057389A1 (en) * | 2013-08-23 | 2015-02-26 | University Of Florida Research Foundation, Inc. | Hydrogel and silicone hydrogel devices including polymerized surfactants |
-
2017
- 2017-08-29 TW TW106129380A patent/TWI648308B/en active
- 2017-10-31 CN CN201711043192.4A patent/CN109422825B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676095A (en) * | 2011-03-07 | 2012-09-19 | 顺安涂布科技(昆山)有限公司 | Composition and manufacture method for emulsion type pressure-sensitive adhesive, and protection adhesive tape thereof |
| CN102643380A (en) * | 2012-04-18 | 2012-08-22 | 上海维凯化学品有限公司 | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof |
| CN103421183A (en) * | 2013-07-30 | 2013-12-04 | 浙江大学 | Reaction type greasy base degradable surfactant as well as synthetic method and application thereof |
| CN105061665A (en) * | 2015-07-31 | 2015-11-18 | 华南理工大学 | Hydroxypolyacrylate emulsion, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 不同可聚合乳化剂对丙烯酸酯乳液性能的影响;袁婷婷等;《粘接》;20110110;第68-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201912671A (en) | 2019-04-01 |
| TWI648308B (en) | 2019-01-21 |
| CN109422825A (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105713575B (en) | Anti-fog agent for wind-screen of automobile and preparation method thereof when a kind of long-acting | |
| CN105885739A (en) | Water-based adhesive and preparation method thereof | |
| CN104774293B (en) | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof | |
| CN110760035B (en) | Self-thickening associated acrylate emulsion and preparation method thereof | |
| TW200920766A (en) | Organo-functional silicone in emulsion systems and process for preparing same | |
| CN109651551A (en) | A kind of dope for inner wall of architecture acrylic acid ester emulsion and preparation method thereof and coating | |
| CN104448117B (en) | A kind of aqueous hybrid acrylic acid ester emulsion and preparation method thereof | |
| CN109021182A (en) | Polycarboxylate water-reducer and its preparation method and application from environment-friendly tasteless raw material | |
| CN109422825B (en) | Polymerizable surfactant and emulsion polymerization emulsion | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN112457453A (en) | Formula and preparation method of acrylic emulsion with good compatibility with cement | |
| CN110964212A (en) | Paraffin emulsion and preparation method and application thereof | |
| CN103906769B (en) | Under the existence of polyglycereol polymerization association type acrylic polymer emulsion and in aqueous compositions as the purposes of thickening agent | |
| CN113896827A (en) | Acrylate microemulsion and preparation method thereof | |
| CN108219079B (en) | Polycarboxylic acid water reducing agent, and preparation method and use method thereof | |
| CN110885559B (en) | High-viscosity dimethyl silicone oil emulsion and preparation method thereof | |
| JP6315625B2 (en) | Method for producing surfactant, surfactant and aqueous coating resin | |
| CN111072867A (en) | Solid polycarboxylic acid water reducing agent and preparation method thereof | |
| CN105462428B (en) | A kind of efficiently water-fast aqueous architectural coating emulsion polymer and preparation method thereof | |
| CN106832144B (en) | A kind of polyether-type poly carboxylic acid series water reducer and preparation method thereof and application method | |
| JP2017202480A5 (en) | ||
| KR102101394B1 (en) | Polysiloxane-based copolymer which has high heat-resistant and hydrophobic characteristics, and coating composition comprising thereof | |
| KR102075677B1 (en) | Pre-emulsion composite and water soluble acrylic emulsion resin prepared by using the same | |
| CN109722146A (en) | A kind of Environmental Protective Water-paint and its preparation process | |
| JP4080105B2 (en) | Surfactant composition for emulsion polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |