CN114874393B - Flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion and preparation method thereof - Google Patents
Flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 77
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 36
- 239000011574 phosphorus Substances 0.000 title claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000004945 emulsification Methods 0.000 title claims description 9
- 239000003999 initiator Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- -1 diphenyl acrylate-2 hydroxyethyl phosphate Chemical compound 0.000 claims abstract description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- VKRGCVFLYPPMKZ-UHFFFAOYSA-N diphenyl hydrogen phosphate;2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 VKRGCVFLYPPMKZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims 6
- 235000010290 biphenyl Nutrition 0.000 abstract description 16
- 239000004305 biphenyl Substances 0.000 abstract description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 16
- 125000000129 anionic group Chemical group 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 229910021389 graphene Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion, which comprises the following raw materials in parts by weight: diphenyl acrylate-2 hydroxyethyl phosphate: 10-20 parts; acrylic acid: 40-50 parts; butyl acrylate: 30-40 parts; anionic sodium dodecyl sulfonate: 1 to 1.5 portions; emulsifying agent: 2-3 parts; and (3) an initiator: 1 to 1.2 portions; distilled water: 200-250 parts. Firstly, preparing 10wt% of initiator aqueous solution; adding polyvinyl alcohol, anionic sodium dodecyl sulfonate, an emulsifier and sodium bicarbonate, mixing, and adding acrylic acid and butyl acrylate to prepare seed emulsion; dropwise adding acrylic acid, butyl acrylate and an initiator aqueous solution into the seed emulsion to finish the polymerization of the nucleation layer; and then dropwise adding the diphenyl acrylate-2 hydroxyethyl phosphate and an initiator aqueous solution to complete shell polymerization, and finally preparing the flame-retardant phosphorus-containing acrylate core-shell emulsion.
Description
Technical Field
The invention relates to the field of constructional engineering, in particular to a flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion and a preparation method thereof.
Background
The acrylic emulsion is widely used for coating film forming matrix, textile printing and dyeing binder, and is applied to daily chemical industry, chemical power supply, functional film, medical polymer, nano material, water treatment and other aspects. Currently, flame retardant studies on acrylic emulsions are mainly focused on: nitrogen phosphorus and graphene modification, in particular, are as follows.
The invention patent 201710865415.9 relates to a phosphorus-nitrogen synergistic self-flame-retardant acrylic emulsion and a preparation method thereof, and is characterized in that: firstly, synthesizing a phosphorus flame-retardant vinyl monomer, and then, synthesizing a self-flame-retardant acrylic emulsion containing nitrogen and phosphorus elements by performing emulsion copolymerization reaction on a reactive nitrogen-phosphorus flame-retardant vinyl monomer containing vinyl and an acrylic ester monomer; the invention patent application number 201910479486.4 discloses a graphene modified acrylic emulsion and a preparation method thereof, wherein the graphene modified acrylic emulsion comprises the following components: the invention can effectively solve the problems of weak waterproofness, poor hardness, poor corrosion resistance, poor rust resistance and the like of the water-based acrylic emulsion by modifying graphene; the graphene oxide modified water-based fireproof paint provided by the invention with the application number 201911075901.6 comprises the following components: the graphene oxide modified water-based fireproof paint provided by the invention is different from physical modification, graphene is added into the acrylic emulsion in a chemical connection mode and is applied to the preparation of paint, so that the dispersibility of the graphene in a water-based fireproof paint system and the compatibility with other base materials can be improved, and meanwhile, the graphene with a lamellar structure can enhance the strength of a carbon layer after the paint is combusted, so that the purposes of flame retardance and smoke suppression are achieved.
However, the existing self-flame-retardant acrylate emulsion has the following defects: (1) The main flame-retardant products depend on imported products and have higher price; (2) The synthesis steps of the self-flame-retardant monomer are complicated, the self-flame-retardant monomer is prepared by multi-step reaction, the continuous consumption is realized in the reaction process, and the yield is low; (3) In the case of modifying graphene, it is generally necessary to prepare a graphene dispersion solution in order to increase the compatibility of the system, and there is a problem that the cost is high and the grafting rate is not high in the case of chemical modification.
Therefore, a flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion with good flame retardant effect, high conversion rate, simple reaction process and low cost is needed.
Disclosure of Invention
The invention aims to solve the problems of poor flame retardant effect, complex formula, complex reaction steps and higher cost of the traditional flame retardant acrylic acid salt core-shell emulsion.
In order to achieve the above purpose, the invention provides a flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion, which comprises the following raw materials in parts by weight: diphenyl acrylate-2 hydroxyethyl phosphate: 10-20 parts; acrylic acid: 40-50 parts; butyl acrylate: 30-40 parts; anionic sodium dodecyl sulfonate: 1 to 1.5 portions; emulsifying agent: 2-3 parts; and (3) an initiator: 1 to 1.2 portions; distilled water: 200-250 parts.
Preferably, the emulsifier is OP-10.
Preferably, the initiator is selected from any one of ammonium persulfate, sodium persulfate and potassium persulfate serving as persulfate initiators.
Preferably, the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion further comprises 1-2 parts of protective colloid.
Preferably, the protective colloid is selected from any one of polyvinyl alcohol, sodium polyacrylate and hydroxymethyl cellulose.
Preferably, the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion further comprises 0.1-0.15 part of sodium bicarbonate.
The invention also provides a preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion, which comprises the following steps:
step one, preparing an initiator aqueous solution:
1 to 1.2 parts of fresh purified ammonium persulfate is used for preparing an aqueous solution of an initiator with the concentration of 10 weight percent;
Preparing seed emulsion:
Mixing 200-250 parts of distilled water, 1-2 parts of polyvinyl alcohol, 1-1.5 parts of anionic sodium dodecyl sulfonate, 2-3 parts of emulsifier OP-10 and 0.1-0.15 part of sodium bicarbonate uniformly, stirring for 5min at 60 ℃, adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate for emulsification, heating to 70 ℃ after the emulsification is finished, adding one third of the 10wt% of the initiator aqueous solution prepared in the first step, and preserving heat until the emulsion is blue phase to obtain seed emulsion;
Step three, core layer polymerization:
dropwise adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate into the seed emulsion, controlling the completion of dropwise adding within 2-2.5 h, continuously adding one third of 10wt% of aqueous solution of an initiator in the dropwise adding process, and preserving heat for 1h after the completion of the addition, so as to complete nuclear layer polymerization;
step four, shell polymerization:
Heating to 75 ℃, slowly dropwise adding diphenyl acrylate-2-hydroxyethyl phosphate monomer, controlling the dropwise adding speed to ensure that the rest one third of 10wt% of initiator aqueous solution is continuously dropwise added, and keeping the temperature for 30min after finishing dropwise adding within 2-2.5 hours to finish shell polymerization; then heating to 80 ℃, curing for 30min, cooling to 40 ℃ after the reaction is finished, and regulating the pH value to 8-10 by ammonia water to obtain the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion.
Preferably, the emulsifying time is 20-30 min.
Preferably, the heat preservation time is 1 to 1.5 hours.
The invention has the beneficial effects that:
(1) The concentration among different monomers is controlled by adopting a stepwise and sectional dropwise adding mode, and the starvation feeding mode is used for promoting the copolymerization reaction of acrylic monomers in the monomers to form a copolymer structure taking acrylic acid and butyl acrylate as cores and 2-hydroxyethyl acrylate diphenyl phosphate as shells;
(2) The invention uses phosphorus-containing monomer acrylic acid-2 hydroxyethyl diphenyl phosphate, acrylic acid and butyl acrylate to directly react, the double bond of three reactant monomers is directly opened in the reaction process, and is connected into a long chain to form a terpolymer, compared with the traditional grafting mode for reacting, the preparation process is simpler, the conversion rate of the prepared flame-retardant acrylic salt core-shell emulsion is as high as more than 95%, so that the production efficiency is improved, the reactant utilization rate is improved, and the production cost is reduced;
(3) The diphenyl acrylate-2 hydroxyethyl phosphate, acrylic acid and butyl acrylate are polymerized into a terpolymer through monomer emulsion, and the flame-retardant acrylic acid salt core-shell emulsion prepared through the method is higher in stability and better in flame retardant property.
Detailed Description
The technical scheme of the invention is further described below by combining examples.
The invention provides a flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion, which comprises the following raw materials in parts by weight: 10 to 20 parts of acrylic acid-2-hydroxyethyl diphenyl phosphate, 40 to 50 parts of acrylic acid, 30 to 40 parts of butyl acrylate, 1 to 1.5 parts of anionic sodium dodecyl sulfonate, 2 to 3 parts of emulsifying agent, 1 to 1.2 parts of initiator, 1 to 2 parts of protective colloid, 0.1 to 0.15 part of sodium bicarbonate and 200 to 250 parts of distilled water.
The reaction formula of the invention is shown in the formula I, wherein the acrylic acid, butyl acrylate and 2-hydroxyethyl acrylate diphenyl phosphate all contain double bonds, under the action of an initiator ammonium persulfate (Ammonium persulfate, APS) aqueous solution at 70-80 ℃, the double bonds of three reactants are opened to form a long chain, and compared with a grafting mode, the mode of forming the terpolymer can lead the conversion rate of the product to be more than 95%, and the prepared flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion has stronger stability and better flame-retardant effect.
In the embodiment of the invention, the emulsifier is OP-10, the OP-10 belongs to a nonionic emulsifier, and is generally used in combination with anions, and the effect of combining with sodium dodecyl sulfate is better.
Example 1:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
the invention provides a preparation method of flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion, which comprises the following steps:
step one, preparing an initiator aqueous solution:
10g of a 10wt% aqueous initiator solution was prepared using 1 part of freshly purified ammonium persulfate;
Preparing seed emulsion:
Placing a four-neck flask with a stirrer, a reflux condenser, a thermometer and a dropping funnel into a heating jacket with controllable temperature, adding 200g of distilled water, 1g of polyvinyl alcohol, 1g of anionic sodium dodecyl sulfonate, 2g of emulsifier OP-10 and 0.1g of sodium bicarbonate, uniformly mixing, stirring at a high speed for 5min at 60 ℃, adding 20g of acrylic acid and 20g of butyl acrylate, emulsifying for 20-30min, heating to 70 ℃ after emulsification is finished, adding one third (3.3 g) of 10wt% of initiator aqueous solution until the emulsion is blue phase, and preserving heat for 1-1.5 h to prepare the seed emulsion;
Step three, core layer polymerization:
Dropwise adding 20g of acrylic acid and 15g of butyl acrylate into the seed emulsion, controlling the completion of dropwise adding within 2-2.5 h, continuously adding one third (3.3 g) of 10wt% of aqueous solution of an initiator in the dropwise adding process, and preserving heat for 1h after the completion of adding;
step four, shell polymerization:
Heating to 75 ℃, slowly dropwise adding 10g of diphenyl acrylate-2-hydroxyethyl phosphate monomer, strictly controlling the dropwise adding speed, ensuring that the rest (3.4 g) of 10wt% of initiator aqueous solution is continuously dropwise added, preserving heat for 30min after finishing, heating to 80 ℃, curing for 30min, cooling to 40 ℃ after finishing the reaction, and regulating the pH value to 8-10 by ammonia water to obtain the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion.
Example 2:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
The preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion provided by the invention comprises the preparation steps of example 1, wherein the weight of raw materials is different, and the rest steps are the same.
Example 3:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
The preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion provided by the invention comprises the preparation steps of example 1, wherein the weight of raw materials is different, and the rest steps are the same.
The effect of 2-hydroxyethyl acrylate diphenyl phosphate on the properties of the prepared flame retardant phosphorus-containing acrylate core-shell emulsion was investigated on the basis of example 2 by adding no 2-hydroxyethyl acrylate diphenyl phosphate, adding less (7.5 g) of 2-hydroxyethyl acrylate diphenyl phosphate than in example 2, and adding more (22 g) of 2-hydroxyethyl acrylate diphenyl phosphate than in example 2 as comparative examples 1,2 and 3.
Comparative example 1:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
The preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion in the comparative example is as in the preparation step of the example 2, only diphenyl acrylate-2-hydroxyethyl phosphate is not added, and the weight gram of the rest steps and the weight gram of the raw materials are the same.
Comparative example 2:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
the preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion of the comparative example comprises the following preparation steps of example 2, wherein only 7.5g of diphenyl acrylate-2-hydroxyethyl phosphate is added, and the weight gram of the rest steps and the weight gram of raw materials are the same.
Comparative example 3:
the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion comprises the following raw materials in parts by weight:
the preparation method of the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion of the comparative example comprises the following preparation steps of example 2, wherein only 22g of diphenyl acrylate-2-hydroxyethyl phosphate is added, and the weight gram of the rest steps and the weight gram of raw materials are the same.
After the acrylic emulsions of examples 1 to 3 and comparative examples 1 to 3 and the acrylic emulsions purchased conventionally were formulated into clear coats, the storage stability, mechanical stability, freeze-thawing stability, flame resistance time, flame propagation ratio, mass loss and carbonization volume-related properties were tested according to the national standard GB12441-2005, and the test results are shown in Table 1.
TABLE 1 test of related Properties
As shown in Table 1, in comparative example 3, more (22 g) of diphenyl acrylate-2-hydroxyethyl phosphate was added, and the mechanical stability of the prepared flame-retardant phosphorus-containing acrylate core-shell emulsion was not passed, and the mechanical stability, storage stability and freeze-thawing stability of the other examples were all passed.
The comparative example 1 was free of 2-hydroxyethyl acrylate diphenyl phosphate and had a flame resistance time of less than 15 minutes, which was similar to that of commercially available acrylic emulsions, while the remaining examples 1-3 and comparative examples 1-3 all had flame resistances times of greater than 20 minutes, indicating that the addition of 2-hydroxyethyl acrylate diphenyl phosphate greatly increased the flame resistance time.
Comparative example 1 (no added) diphenyl acrylate-2 hydroxyethyl phosphate and commercially available acrylic emulsion had flame spread ratios greater than 20 (25.2 and 24.9, respectively), while the remaining examples were less than 25; the quality loss of the diphenyl acrylate-2 hydroxyethyl acrylate phosphate (not added) of comparative example 1 and the acrylic emulsion purchased in the market is more than 8g (8.4 g and 8.1g respectively), while the other examples are all much less than 8g; the carbonization volume of the diphenyl acrylate-2 hydroxyethyl acrylate phosphate (not added) of comparative example 1 and that of the commercially available acrylic emulsion were each greater than 30cm 3 (31 cm 3 and 32cm 3, respectively), while the remaining examples were each 25cm 3 or less.
Therefore, after the diphenyl acrylate-2-hydroxyethyl phosphate and the acrylic acid are added for reaction, the related performance is obviously optimized, and particularly the flame-retardant time is greatly prolonged, so that the prepared flame-retardant phosphorus-containing acrylate core-shell emulsion is beneficial to widening the application in multiple fields.
Monomer conversion tests were performed on the acrylic emulsions of examples 1 to 3 and comparative examples 1 to 3 described above with those purchased conventionally. Weighing a certain emulsion, adding the emulsion into an accurately weighed weighing bottle, weighing, then dripping 2-3 drops of hydroquinone aqueous solution with the mass fraction of 5%, and drying at 100 ℃ to constant weight, wherein the conversion rate is calculated according to the following formula:
Wherein: y% -conversion; g 0 -sample weight (G); g 1 -constant weight after sample drying (G); w-the non-volatile percentage/% of the polymerization formulation other than monomer; m-percentage of monomer in the formulation.
TABLE 2 testing of monomer conversion
As shown in Table 2, the monomer conversion of the commercially available acrylic emulsion was 92.4% with 95% as an internal control index, but the monomer conversions of examples 1 to 3 and comparative examples 1 to 3 were all 95% or more, and it was found that the monomer conversion was greatly improved by adding diphenyl acrylate-2-hydroxyethyl phosphate, acrylic acid, and butyl acrylate.
According to the flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion, the diphenyl acrylate-2-hydroxyethyl phosphate, acrylic acid and butyl acrylate are added for reaction, the double bonds of the two are opened to form a long chain, and the long chain is directly combined as a monomer to form a terpolymer, so that the flame-retardant type acrylic acid salt emulsion with a core-shell structure is better in flame-retardant effect, higher in conversion rate, simpler and more convenient in preparation process and lower in cost.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (4)
1. The flame-retardant type phosphorus-containing acrylic acid salt core-shell emulsion is characterized by comprising the following raw materials in parts by weight:
2-hydroxyethyl acrylate diphenyl phosphate: 10-20 parts of a lubricant;
Acrylic acid: 40-50 parts of a lubricant;
Butyl acrylate: 30-40 parts of a lubricant;
sodium dodecyl sulfonate: 1-1.5 parts;
Emulsifying agent: 2-3 parts of a lubricant; the emulsifier is OP-10;
And (3) an initiator: 1-1.2 parts;
distilled water: 200-250 parts of a lubricant;
Protective colloid: 1-2 parts of a lubricant; the protective colloid is polyvinyl alcohol;
Sodium bicarbonate: 0.1-0.15 part;
The preparation method comprises the following steps of:
step one, preparing an initiator aqueous solution:
1-1.2 parts of freshly purified ammonium persulfate is used for preparing an aqueous solution of an initiator with the concentration of 10 weight percent;
Preparing seed emulsion:
mixing 200-250 parts of distilled water, 1-2 parts of polyvinyl alcohol, 1-1.5 parts of sodium dodecyl sulfonate, 2-3 parts of emulsifier OP-10 and 0.1-0.15 part of sodium bicarbonate uniformly, stirring for 5min at 60 ℃, adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate for emulsification, heating to 70 ℃ after the emulsification is finished, adding one third of the 10wt% aqueous solution of the initiator prepared in the first step, keeping the emulsion in a blue phase, and preserving the temperature to obtain seed emulsion;
Step three, core layer polymerization:
Dropwise adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate into the seed emulsion, controlling the completion of dropwise adding within 2-2.5 h, continuously adding one third of 10wt% of an aqueous solution of an initiator in the dropwise adding process, and after the completion of adding, preserving heat for 1h to complete nuclear layer polymerization;
step four, shell polymerization:
Heating to 75 ℃, slowly dropwise adding an acrylic acid-2-hydroxyethyl diphenyl phosphate monomer, controlling the dropwise adding speed to ensure that the rest one third of 10wt% of an initiator aqueous solution is continuously dropwise added, and keeping the temperature for 30min after finishing dropwise adding within 2-2.5 hours to finish shell polymerization; and then heating to 80 ℃, curing for 30min, cooling to 40 ℃ after the reaction is finished, and regulating the pH value to 8-10 by ammonia water to obtain the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion.
2. A method for preparing the flame retardant, phosphorous acrylic core-shell emulsion of claim 1, comprising the steps of:
step one, preparing an initiator aqueous solution:
1-1.2 parts of freshly purified ammonium persulfate is used for preparing an aqueous solution of an initiator with the concentration of 10 weight percent;
Preparing seed emulsion:
mixing 200-250 parts of distilled water, 1-2 parts of polyvinyl alcohol, 1-1.5 parts of sodium dodecyl sulfonate, 2-3 parts of emulsifier OP-10 and 0.1-0.15 part of sodium bicarbonate uniformly, stirring for 5min at 60 ℃, adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate for emulsification, heating to 70 ℃ after the emulsification is finished, adding one third of the 10wt% aqueous solution of the initiator prepared in the first step, keeping the emulsion in a blue phase, and preserving the temperature to obtain seed emulsion;
Step three, core layer polymerization:
Dropwise adding 20-25 parts of acrylic acid and 15-20 parts of butyl acrylate into the seed emulsion, controlling the completion of dropwise adding within 2-2.5 h, continuously adding one third of 10wt% of an aqueous solution of an initiator in the dropwise adding process, and after the completion of adding, preserving heat for 1h to complete nuclear layer polymerization;
step four, shell polymerization:
Heating to 75 ℃, slowly dropwise adding an acrylic acid-2-hydroxyethyl diphenyl phosphate monomer, controlling the dropwise adding speed to ensure that the rest one third of 10wt% of an initiator aqueous solution is continuously dropwise added, and keeping the temperature for 30min after finishing dropwise adding within 2-2.5 hours to finish shell polymerization; and then heating to 80 ℃, curing for 30min, cooling to 40 ℃ after the reaction is finished, and regulating the pH value to 8-10 by ammonia water to obtain the flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion.
3. The method according to claim 2, wherein in the second step, the emulsifying time is 20 to 30 minutes.
4. The method according to claim 2, wherein in the second step, the time for heat preservation is 1 to 1.5 hours.
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