CN104031514B - The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance - Google Patents
The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance Download PDFInfo
- Publication number
- CN104031514B CN104031514B CN201410324852.6A CN201410324852A CN104031514B CN 104031514 B CN104031514 B CN 104031514B CN 201410324852 A CN201410324852 A CN 201410324852A CN 104031514 B CN104031514 B CN 104031514B
- Authority
- CN
- China
- Prior art keywords
- weight part
- acrylic resin
- flame retardant
- resin coating
- core
- 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
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 39
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 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 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- 230000035484 reaction time Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 238000009413 insulation Methods 0.000 claims abstract description 16
- 229910000085 borane Inorganic materials 0.000 claims abstract description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000004945 emulsification Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- -1 boron alkene Chemical class 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- ZOKWYSXFTXBLSG-UHFFFAOYSA-M dodecyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCC)C1=CC=CC=C1 ZOKWYSXFTXBLSG-UHFFFAOYSA-M 0.000 claims description 5
- OPWAPCOSDAFWFB-UHFFFAOYSA-N 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid Chemical group O1C(C)(C)C(C)(C)OB1C1=CC=CC(C(O)=O)=C1 OPWAPCOSDAFWFB-UHFFFAOYSA-N 0.000 claims description 4
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 claims description 4
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 239000000779 smoke Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZNGINKJHQQQORD-UHFFFAOYSA-N 2-trimethylsilylethanol Chemical compound C[Si](C)(C)CCO ZNGINKJHQQQORD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CPBHJGWJMLDUNB-UHFFFAOYSA-N ethenoxysilane Chemical compound [SiH3]OC=C CPBHJGWJMLDUNB-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance, add water, emulsifying agent, methacrylic acid, A monomer carry out emulsification, start to drip initiator to during temperature 75 DEG C, time for adding 1 ~ 3h, insulation reaction 3 ~ 5h, add quaternary alkylphosphonium salt, reaction times 1 ~ 3h, obtain stratum nucleare emulsion; Drip B monomer and initiator in stratum nucleare emulsion simultaneously, time for adding 1 ~ 3h, 75 ~ 85 DEG C of insulation reaction time 2h, drip borine, insulation reaction 1 ~ 3h, drip linking agent again, insulation reaction time 1 ~ 2h, cools to 50 DEG C, emulsifying agent is added in reaction system, reaction times 30min, adds ammoniacal liquor adjust pH 7 ~ 8, obtains the core-shell type aqueous acrylic resin coating of flame retardant resistance.Gained acrylic resin can reach flame retardant properties and significantly improve, and can improve again the defect of conventional acrylic esters resin " hot sticky cold crisp ".
Description
Technical field
The present invention relates to the resinoid preparation method of a kind of water-and acrylate, particularly the preparation method of the core-shell type aqueous acrylic resin coating of flame retardant resistance.
Background technology
Compared with traditional solvent based coating, water-borne coatings has that price is low, use safety, saving resource and the energy, reduces the advantage such as environmental pollution and public hazards, because becoming the Main way of current development coatings industry.Water soluble acrylic acid esters resin coating is with fastest developing speed in water-borne coatings, that kind is maximum pollution-free coating.
Water soluble acrylic acid esters resin comprises acrylic resin emulsion, acrylic resin water dispersion (also known as water-dilutable vinylformic acid) and the acrylic resin aqueous solution.Emulsion to be mainly emulsified in water under water-based free radical initiator causes synthesis by oiliness vinyl monomer, and resin water dispersion is then by free radical solution polymerization or technique synthesis that progressively solution polymerization etc. is different.From particle diameter: emulsion particle diameter > resin water dispersion particle diameter > aqueous solution particle diameter.The most important with the above two viewed from application.
Acrylic emulsion is mainly used in the base-material of emulsion paint, occupies important application at Building-coating market, and its application is also in continuous expansion at present; The exploitation of acrylic resin water dispersion in recent years, application cause the attention of people day by day, constantly expand in the application of industrial coating, civilian paint field.Usually pure-acrylic emulsion, benzene emulsion, acrylate and vinyl acetate emulsion, organosilicon crylic acid latex, tertiary vinegar (tertiary carbonic ester-vinyl acetate) emulsion, uncle third (tertiary carbonic ester-acrylate) emulsion etc. is divided into according to monomer composition.
Acrylate sort aqueous paint is divided into aqueous dispersion type and water-soluble two large classes, the coating that the former is is matrix with water emulsion or the water-sol.Water-soluble acrylic ester coating adopts the copolymer resins with reactive cross-linkable functional group to make, polyphyly thermosetting coating, additional or do not add cross-linked resin when painting, makes to be cross-linked the paint film forming three dimensional structure between active function groups when film forming.Most of organic volatile solvent under the various characteristic property conditions ensureing acrylate paint, can be replaced by water, thus reach the object significantly reducing topsoil by development Water-borne Acrylic Coating.
The maximum market of acrylic resin coating is car paint, this external light industry, household electrical appliance, metal household implements, aluminum products, coiled material industry, instrument, build, textiles, one's share of expenses for a joint undertaking compound plastics, woodwork, the industry such as papermaking is all widely used.Acrylic resin coating is with the future development in accordance with hydrotropismsization, multifunction and high function.
But acrylic resin be present in hot sticky cold crisp and inflammable defect, hot sticky cold crisp can improve with nucleocapsid polymerization methods, and at present acrylic resin easily burns and adopts phosphorus flame retardant to carry out fire-retardant, but phosphorus can cause the eutrophication of water quality, halogenated flame retardant burning release smog is large, and the Dioxins problem that can cause.
Summary of the invention
The present invention aims to provide the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance, by second boron alkene and second boron alkynes being used for be used in stratum nucleare respectively and shell carries out radical polymerization, be aggregated to the main chain of acrylic resin, and fire-retardant under quaternary alkylphosphonium salt, borine synergistic, improve the flame retardant resistance of acrylic resin coating.
The present invention is by the following technical solutions:
A preparation method for the core-shell type aqueous acrylic resin coating of flame retardant resistance, is characterized in that:
(1) in reaction vessel, add the raw material of following weight proportion: 50 ~ 70 parts, water, emulsifying agent 0.5 ~ 1.8 part, methacrylic acid 0.3 ~ 3.0 part, be warming up to 40 DEG C, stir 15min, add A monomer, emulsification 30 ~ 45min, is warmed up to 70 DEG C and starts logical recirculation water, is incubated after being warmed up to 75 DEG C, drip initiator 0.2 ~ 0.4 weight part, time for adding continues 1 ~ 3h, drips rear stirring reaction 3 ~ 5h, then adds quaternary alkylphosphonium salt 1 ~ 3 weight part, stirring reaction 1 ~ 3h, obtains stratum nucleare emulsion;
Described A monomer be by: butyl acrylate 6 ~ 8 weight part, methyl methacrylate 4 ~ 6 weight part, ethyl propenoate 2.5 ~ 3.5 weight part, second boron alkene 3 ~ 6 weight part mix;
(2) in step (1) gained stratum nucleare emulsion, drip the initiator of B monomer and 0.3 ~ 0.5 weight part simultaneously, time for adding continues 1 ~ 3h, drip rear insulation 75 ~ 85 DEG C of stirring reaction 2h, drip borine 10 ~ 20 weight part again, be incubated 75 ~ 85 DEG C of stirring reaction 1 ~ 3h, drip linking agent 0.5 ~ 1.0 weight part again, be incubated 75 ~ 85 DEG C of stirring reaction time 1 ~ 2h, cool to 50 DEG C, add emulsifying agent 0.3 weight part, reaction times 30min, adds ammoniacal liquor adjust pH to 7 ~ 8, obtains the core-shell type aqueous acrylic resin of described flame retardant resistance;
Described B monomer by: butyl acrylate 3 ~ 5 weight part, methyl methacrylate 3.5 ~ 5.5 weight part, ethyl propenoate 3.5 ~ 6.5 weight part, vinylbenzene 0 ~ 1.5 weight part, second boron alkynes 2 ~ 4 weight part mix form.
Described emulsifying agent is the mixture that Sodium dodecylbenzene sulfonate mixes by weight 2:1 with fatty alcohol-polyoxyethylene ether; Initiator is any one in Potassium Persulphate, ammonium persulphate; Quaternary alkylphosphonium salt is any one in dodecyl triphenyl phosphonium chloride, ten alkyl triphenyl phosphonium phosphonium bromides; Borine is any one in adjacent carborane, a carborane, triphenylborane, five borines, three (dimethylin) borine, three mesityl oxide base borines; Linking agent is 3-Carboxybenzeneboronic acid pinacol ester, N-[4-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-2-base) phenyl] succinamic acid, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, Ethoxylated bisphenol A dimethacrylate any one.
Beneficial effect of the present invention is:
(1) the core-shell type aqueous acrylic resin of the flame retardant resistance prepared by, obviously can improve the defect of conventional propylene acid resin " hot sticky cold crisp ";
(2) select boron-containing compound as borine, 3-Carboxybenzeneboronic acid pinacol ester, N-[4-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-2-base) phenyl] succinamic acid, second boron alkynes, improve the flame retardant resistance of acrylic resin under second boron alkene quaternary alkylphosphonium salt synergistic;
(3) flame retardant resistance improving acrylic resin under stratum nucleare and shell acting in conjunction is selected.
Embodiment
In order to understand better and implement the present invention, further illustrate the present invention below in conjunction with specific embodiment.
example 1
(1) in there-necked flask, adding water 50g, emulsifying agent Sodium dodecylbenzene sulfonate 0.33g and fatty alcohol-polyoxyethylene ether, (model of fatty alcohol-polyoxyethylene ether is OS-15, non-ionic type, be purchased from Jiangsu Hai'an Petrochemical Plant, lower same) 0.17g, methacrylic acid 0.3g, temperature of reaction is risen to 40 DEG C, stir 15min, add A monomer, emulsification times 30min.When temperature is raised to 70 DEG C of logical recirculation waters, to starting dropping 5g water-soluble potassium persulfate solution 5.2g during temperature 75 DEG C, time for adding 1h, insulation reaction 3h, add dodecyl triphenyl phosphonium chloride 1g, stirring reaction time 1h, obtains stratum nucleare emulsion;
A monomer and consumption thereof: A monomer is made up of the mixing of butyl acrylate 6g, methyl methacrylate 4g, ethyl propenoate 2.5g, second boron alkene 3g;
(2) in stratum nucleare emulsion, drip B monomer and with the water-soluble potassium persulfate solution 5.3g of 5g simultaneously, time for adding 1h, 75 DEG C of insulation reaction time 2h, drip adjacent carborane 10g, insulation reaction 1h, drip 3-Carboxybenzeneboronic acid pinacol ester 0.5g again, insulation reaction time 1h, cool to 50 DEG C, emulsifying agent Sodium dodecylbenzene sulfonate 0.2g and fatty alcohol-polyoxyethylene ether 0.1g is joined in there-necked flask, churning time 30min, adds ammoniacal liquor adjust pH 7, obtains the hud typed acrylic resin coating of flame retardant resistance;
B monomer and consumption thereof: B monomer is mixed by butyl acrylate 3g, methyl methacrylate 3.5g, ethyl propenoate 3.5g and second boron alkynes 2g and forms.
example 2
(1) in there-necked flask, add water 70g, emulsifying agent Sodium dodecylbenzene sulfonate 1.2g and fatty alcohol-polyoxyethylene ether 0.6g, methacrylic acid 3.0g, temperature of reaction is risen to 40 DEG C, stir 15min, add A monomer, emulsification times 45min.When temperature is raised to 70 DEG C of logical recirculation waters, to starting dropping 5g water-soluble ammonium persulfate solution 5.4g during temperature 75 DEG C, time for adding 3h, insulated and stirred reaction 5h, add ten alkyl triphenyl phosphonium phosphonium bromide 3g, stirring reaction time 3h, obtains stratum nucleare emulsion;
A monomer and consumption thereof: A monomer is mixed by butyl acrylate 8g, methyl methacrylate 6g, ethyl propenoate 3.5g and second boron alkene 6g and forms;
(2) in stratum nucleare emulsion, drip B monomer and with the water-soluble ammonium persulfate solution 5.5g of 5g simultaneously, time for adding 3h, 85 DEG C of insulation reaction time 2h, carborane 20g between dropping, insulated and stirred reaction 3h, drip N-[4-(4 again, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate-2-base) phenyl] succinamic acid 1.0g, insulated and stirred reaction times 2h, cool to 50 DEG C, emulsifying agent Sodium dodecylbenzene sulfonate 0.2g and fatty alcohol-polyoxyethylene ether 0.1g is joined in there-necked flask, churning time 30min, add ammoniacal liquor adjust pH 8, obtain the hud typed acrylic resin coating of flame retardant resistance,
B monomer and consumption thereof: B monomer is mixed by butyl acrylate 5g, methyl methacrylate 5.5g, ethyl propenoate 6.5g, vinylbenzene 1.5g and second boron alkynes 4g and forms.
example 3
(1) in there-necked flask, add water 60g, emulsifying agent Sodium dodecylbenzene sulfonate 0.8g and fatty alcohol-polyoxyethylene ether 0.4g, methacrylic acid 1.7g, temperature of reaction is risen to 40 DEG C, stir 15min, add A monomer, emulsification times 35min.When temperature is raised to 70 DEG C of logical recirculation waters, to during temperature 75 DEG C with the water-soluble potassium persulfate solution 5.3g of 5g, time for adding 2h, insulated and stirred reaction 4h, add dodecyl triphenyl phosphonium chloride 2g, stirring reaction time 2h, obtains stratum nucleare emulsion;
A monomer and consumption thereof: A monomer is made up of the mixing of butyl acrylate 7g, methyl methacrylate 5g, ethyl propenoate 3.0g, second boron alkene 4.5g;
(2) in stratum nucleare emulsion, drip B monomer and with the water-soluble potassium persulfate solution 5.4g of 5g simultaneously, time for adding 2h, 80 DEG C of insulation reaction time 2h, drip triphenylborane 15g, insulated and stirred reaction 2h, drip trimethylolpropane trimethacrylate 0.75g again, insulated and stirred reaction times 1.5h, cool to 50 DEG C, emulsifying agent Sodium dodecylbenzene sulfonate 0.13g and fatty alcohol-polyoxyethylene ether 0.07g is joined in there-necked flask, churning time 30min, adds ammoniacal liquor adjust pH 8, obtains the hud typed acrylic resin coating of flame retardant resistance;
B monomer and consumption thereof: B monomer is by butyl acrylate 4g, methyl methacrylate weight 4.5g, ethyl propenoate weight 5.0g, and the mixing of vinylbenzene 0.75g and second boron alkynes 3g forms.
example 4
(1) in there-necked flask, water 50g, emulsifying agent Sodium dodecylbenzene sulfonate 0.6g and fatty alcohol-polyoxyethylene ether 0.3g, methacrylic acid 2.0g is added, temperature of reaction is risen to 40 DEG C, stir 15min, add A monomer and 1-phenyl-1-three silyloxy ethene 2.2g, emulsification times 40min.When temperature is raised to 70 DEG C of logical recirculation waters, to starting dropping 5g water-soluble potassium persulfate solution 5.35g during temperature 75 DEG C, time for adding 2.5h, insulated and stirred reaction 4h, add ten alkyl triphenyl phosphonium phosphonium bromide 2g, reaction times 3h, obtains stratum nucleare emulsion;
A monomer and consumption thereof: A monomer is made up of the mixing of butyl acrylate 7g, methyl methacrylate 5g, ethyl propenoate 3.0g and second boron alkene 4g;
(2) in stratum nucleare emulsion, drip B monomer and with the water-soluble potassium persulfate solution 5.45g of 5g simultaneously, time for adding 3h, 85 DEG C of insulation reaction time 2h, drip five borine 15g and 1-methoxyl group-1-(trimethylsiloxy)-2-methyl-1-propylene 2.3g, insulation reaction 3h, drip Ethoxylated bisphenol A dimethacrylate 1.0g again, insulated and stirred reaction times 2h, cool to 50 DEG C, emulsifying agent Sodium dodecylbenzene sulfonate 0.2g and fatty alcohol-polyoxyethylene ether 0.1g is joined in there-necked flask, churning time 30min, add ammoniacal liquor adjust pH 7, obtain the hud typed acrylic resin coating of flame retardant resistance,
B monomer and consumption thereof: B monomer is made up of the mixing of butyl acrylate 5g, methyl methacrylate 5.5g, ethyl propenoate 6.5g, vinylbenzene 0.75g and second boron alkynes 2.5g.
example 5
(1) in there-necked flask, water 55g, emulsifying agent Sodium dodecylbenzene sulfonate 1.0g and fatty alcohol-polyoxyethylene ether 0.5g, methacrylic acid 2.0g is added, temperature of reaction is risen to 40 DEG C, stir 15min, add A monomer and 2-(trimethylsilyl) ethanol 2g, emulsification times 40min.When temperature is raised to 70 DEG C of logical recirculation waters, to starting dropping 5g water-soluble ammonium persulfate solution 5.25g during temperature 75 DEG C, time for adding 2.5h, insulated and stirred reaction 3.5h, drip dodecyl triphenyl phosphonium chloride 2g, reaction times 3h, obtains stratum nucleare emulsion;
A monomer and consumption thereof: A monomer is made up of the mixing of butyl acrylate 6.5g, methyl methacrylate 5.5g, ethyl propenoate 3.0g and second boron alkene 5g;
(2) in stratum nucleare emulsion, drip B monomer and with the water-soluble ammonium persulfate solution 5.45g of 5g simultaneously, time for adding 2h, 80 DEG C of insulation reaction time 2h, drip three mesityl oxide base borine 15g and 3-tertiary butyl dimethylsilyloxy Pyroglutaric acid 1.2g, insulated and stirred reaction 3h, drip Ethoxylated bisphenol A dimethacrylate 1.0g again, insulation reaction time 2h, cool to 50 DEG C, emulsifying agent Sodium dodecylbenzene sulfonate 0.2g and fatty alcohol-polyoxyethylene ether 0.1g is joined in there-necked flask, churning time 30min, add ammoniacal liquor adjust pH 8, obtain the hud typed acrylic resin coating of flame retardant resistance,
B monomer and consumption thereof: B monomer is made up of the mixing of butyl acrylate 4g, methyl methacrylate 3.5g, ethyl propenoate 5.0g, vinylbenzene 1.0g and second boron alkynes 3.5g.
Beneficial effect of the present invention is further illustrated below by relevant experimental data:
Specific examples 1 of the present invention is to the performance of the flame retardant resistance core-shell type aqueous acrylic resin coating institute film forming prepared by example 5.Flame retardant resistance is weighed by smoke density method (maximum smoke density, reach the maximum smoke density time), oxygen index, vertical combustion index (flaming combustion time, glowing time), and elongation at break characterizes its mechanical property.
Table 1 flame retardant resistance hud typed acrylic resin coating institute film forming flame retardant effect index
| Experimental group | Market SB300 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Maximum smoke density | 38 | 30 | 27 | 25 | 22 | 18 |
| Reach maximum smoke density time/s | 180 | 190 | 205 | 200 | 205 | 205 |
| Oxygen index | 18 | 24.3 | 24.3 | 25.3 | 26.3 | 26.4 |
| Flaming combustion time/s | 38.3 | 28.4 | 15.2 | 27.1 | 11.2 | 11.7 |
| Glowing time/s | 38.6 | 0 | 0 | 0 | 0 | 0 |
The detection of table 1 indices is respectively according to following standard: smoke density measures according to GB8323-2008, and oxygen index adopts GB/T5454-1997 " textile combustion performance test-oxygen index method " to measure; Flaming combustion time and glowing time adopt GB/T5455-1997 " textile combustion energy test-normal beam technique " to measure.
As shown in Table 1, the maximum smoke density of acrylic resin institute of the present invention film forming burning significantly reduces, and reach maximum smoke density time significant prolongation, oxygen index significantly improves, and combustion time obviously shortens.
Table 2 flame retardant resistance hud typed acrylic resin coating institute film forming elongation at break
| Experimental group | Market SB300 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Elongation at break/% | 88.06 | 138.67 | 121.5 | 113.69 | 167.38 | 187.25 |
Table 2 middle finger object detection method reference: Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999,82-96.Employ acrylic resin film of the present invention, elongation at break be improved significantly.
Claims (6)
1. a preparation method for the core-shell type aqueous acrylic resin coating of flame retardant resistance, is characterized in that:
(1) in reaction vessel, add the raw material of following weight proportion: 50 ~ 70 parts, water, emulsifying agent 0.5 ~ 1.8 part, methacrylic acid 0.3 ~ 3.0 part, be warming up to 40 DEG C, stir 15min, add A monomer, emulsification 30 ~ 45min; Be warmed up to 70 DEG C and start logical recirculation water, be incubated after being warmed up to 75 DEG C, drip initiator 0.2 ~ 0.4 weight part, time for adding continues 1 ~ 3h, drips rear reaction 3 ~ 5h; Add quaternary alkylphosphonium salt 1 ~ 3 weight part again, stirring reaction 1 ~ 3h, obtain stratum nucleare emulsion;
Described A monomer be by: butyl acrylate 6 ~ 8 weight part, methyl methacrylate 4 ~ 6 weight part, ethyl propenoate 2.5 ~ 3.5 weight part, second boron alkene 3 ~ 6 weight part mix;
(2) in step (1) gained stratum nucleare emulsion, drip the initiator of B monomer and 0.3 ~ 0.5 weight part simultaneously, time for adding continues 1 ~ 3h, drip rear insulation 75 ~ 85 DEG C of stirring reaction 2h, drip borine 10 ~ 20 weight part again, be incubated 75 ~ 85 DEG C of stirring reaction 1 ~ 3h, add linking agent 0.5 ~ 1.0 weight part again, be incubated 75 ~ 85 DEG C of reaction times 1 ~ 2h, cool to 50 DEG C, add emulsifying agent 0.3 weight part, reaction times 30min, adds ammoniacal liquor adjust pH to 7 ~ 8, obtains the core-shell type aqueous acrylic resin coating of described flame retardant resistance;
Described B monomer by: butyl acrylate 3 ~ 5 weight part, methyl methacrylate 3.5 ~ 5.5 weight part, ethyl propenoate 3.5 ~ 6.5 weight part, vinylbenzene 0 ~ 1.5 weight part, second boron alkynes 2 ~ 4 weight part mix form.
2. the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance as claimed in claim 1, is characterized in that, emulsifying agent is the mixture that Sodium dodecylbenzene sulfonate mixes by weight 2:1 with fatty alcohol-polyoxyethylene ether.
3. the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance as claimed in claim 1, is characterized in that, initiator is any one in Potassium Persulphate, ammonium persulphate.
4. the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance as claimed in claim 1, is characterized in that ， quaternary alkylphosphonium salt is any one in dodecyl triphenyl phosphonium chloride, ten alkyl triphenyl phosphonium phosphonium bromides.
5. the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance as claimed in claim 1, it is characterized in that, borine is any one in adjacent carborane, a carborane, triphenylborane, five borines, three (dimethylin) borine, three mesityl oxide base borines.
6. the preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance as claimed in claim 1, it is characterized in that, linking agent is 3-Carboxybenzeneboronic acid pinacol ester, N-[4-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-2-base) phenyl] succinamic acid, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, any one in Ethoxylated bisphenol A dimethacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410324852.6A CN104031514B (en) | 2014-07-09 | 2014-07-09 | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410324852.6A CN104031514B (en) | 2014-07-09 | 2014-07-09 | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104031514A CN104031514A (en) | 2014-09-10 |
| CN104031514B true CN104031514B (en) | 2016-03-02 |
Family
ID=51462519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410324852.6A Active CN104031514B (en) | 2014-07-09 | 2014-07-09 | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104031514B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131761B (en) * | 2015-09-07 | 2017-12-26 | 中国建筑材料科学研究总院 | Fire-resistant fluid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN105482601A (en) * | 2015-12-30 | 2016-04-13 | 段宝荣 | Preparation method of antibacterial flame-retardant acrylate resin paint for buildings |
| CN105778686A (en) * | 2016-03-16 | 2016-07-20 | 郑州航空工业管理学院 | Preparation method for aircraft leather cushion finishing agent and building external wall coating |
| CN105754440A (en) * | 2016-03-16 | 2016-07-13 | 郑州航空工业管理学院 | Preparation method of aviation leather cushion and metal coating |
| CN109423149A (en) * | 2017-07-04 | 2019-03-05 | 南京新莱尔材料科技有限公司 | A kind of fire-type Environmental Protective Water-paint and its manufacturing method |
| CN107903554B (en) * | 2017-12-14 | 2021-07-02 | 蔡豪杰 | Preparation method for modifying acrylate resin by utilizing tanning chromium-containing sludge |
| CN108912929B (en) * | 2018-06-26 | 2021-02-02 | 柳州市安道科技有限公司 | Preparation method of flame-retardant antibacterial water-based core-shell acrylate resin coating and paint |
| CN110295497A (en) * | 2019-05-29 | 2019-10-01 | 安徽华烨特种材料有限公司 | A kind of aging-resistant flame-proof type canvas maceration extract |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0182660B1 (en) * | 1996-06-28 | 1999-04-01 | 한영재 | Aqueous intumescent coating composition for exposure protection and the agent thereof |
| ES2362605B1 (en) * | 2009-12-28 | 2012-05-29 | Universidad De Zaragoza | COMPOSITION OF UREA POLYACRYLATE AS A FLAME RETARDANT. |
| CN102453215B (en) * | 2010-10-28 | 2014-03-26 | 中国石油化工股份有限公司 | Inflaming retarding copolymer latex and preparation method thereof |
| CN102604568A (en) * | 2012-03-20 | 2012-07-25 | 上海应用技术学院 | Flame-retardant polyacrylate emulsion and preparation method thereof |
| CN102850876A (en) * | 2012-08-30 | 2013-01-02 | 青岛保利康新材料有限公司 | Aqueous damping coating having high solid content and high damping performance |
| CN103435743B (en) * | 2013-08-30 | 2015-07-01 | 辽宁鑫兴阿特彩科技有限公司 | Preparation method of flame-retardant and light-resistant paint |
-
2014
- 2014-07-09 CN CN201410324852.6A patent/CN104031514B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104031514A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104031514B (en) | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance | |
| CN104277172B (en) | Water-based waterproof acrylate emulsion and preparation method thereof | |
| CN102875723B (en) | Preparation method of flame-retardant core-shell-type acrylic resin | |
| CN103289010B (en) | Method for preparing core-shell nano SiO2/fluorine-containing polyacrylate soap-free emulsion | |
| CN105085790B (en) | A kind of body flame acrylic acid ester emulsion and its preparation method and application | |
| CN105061666B (en) | Preparation method for organic-phosphorus-modified fluorine-containing polyacrylate flame retarding finishing agent | |
| CN103711033A (en) | Waterproof waterborne glazing oil and preparation method thereof | |
| CN108641033A (en) | A kind of fire-retardant linear thermal expansion microcapsules and preparation method thereof | |
| CN107141394A (en) | A kind of styrene-acrylic emulsion of zero VOC content and preparation method thereof | |
| CN104558383B (en) | Fluorescent complex containing carboxylic acid type high polymer and rare earth, preparation method of fluorescent complex, fluorescent chemical carbon powder and preparation method of fluorescent chemical carbon powder | |
| CN109970905A (en) | Integral ceiling veneer coating aqueous high molecular lotion and preparation method thereof | |
| CN109735192A (en) | A kind of fireproof coating and preparation method thereof based on basic zirconium phosphate and methacrylic acid compound modified acrylic ester core-shell emulsion | |
| CN104448117B (en) | A kind of aqueous hybrid acrylic acid ester emulsion and preparation method thereof | |
| CN106749833A (en) | Vinylidene chloride acrylate Organosiliconcopolymere latex and preparation method thereof | |
| CN103965393A (en) | Water-based acrylic resin | |
| CN103741469A (en) | Antibiotic finishing agent | |
| CN103130950A (en) | Preparation method of fluorine-containing acrylate terpolymer emulsion | |
| CN109423149A (en) | A kind of fire-type Environmental Protective Water-paint and its manufacturing method | |
| CN104140731B (en) | A kind of preparation method of aqueous flame retardant coating | |
| CN104479067A (en) | Amphoteric ionic antistatic agent for acrylonitrile butadiene styrene (ABS) and preparation method of antistatic agent | |
| CN105111876B (en) | Building, the preparation method of the core-shell type aqueous acrylic resin coating of furniture | |
| CN106632876A (en) | Resin for antifouling paint and preparation method thereof | |
| CN103628316A (en) | Novel preparation method of paper fiber fabric coating finishing agent microemulsion | |
| CN102167772A (en) | Fluorine-containing easily processed acrylate rubber and preparation method thereof | |
| CN104087105A (en) | Preparation method of flame-retardant water-based paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Shanjiang Inventor after: Xu Xiaodong Inventor after: Dong Lizhi Inventor after: Jing Wang Inventor after: Liu Hongliang Inventor before: Duan Baorong |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170316 Address after: 072550 Hebei city of Baoding province Xushui Chenyang Street No. 1 Patentee after: Hebei Chenyang IndustrialL&trade Group Co., Ltd. Patentee after: Hebei Chenyang water paint Co. Ltd. Address before: 264005 Shandong Province, Yantai city Laishan District Road No. 30 spring Patentee before: Duan Baorong |
|
| TR01 | Transfer of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20200929 Granted publication date: 20160302 |
|
| PP01 | Preservation of patent right | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20210902 Granted publication date: 20160302 |
|
| PD01 | Discharge of preservation of patent |