CN114716624A - Modified polyacrylate flame-retardant emulsion, modified polyacrylate flame-retardant pressure-sensitive adhesive containing emulsion and preparation method of modified polyacrylate flame-retardant pressure-sensitive adhesive - Google Patents
Modified polyacrylate flame-retardant emulsion, modified polyacrylate flame-retardant pressure-sensitive adhesive containing emulsion and preparation method of modified polyacrylate flame-retardant pressure-sensitive adhesive Download PDFInfo
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- CN114716624A CN114716624A CN202210150222.6A CN202210150222A CN114716624A CN 114716624 A CN114716624 A CN 114716624A CN 202210150222 A CN202210150222 A CN 202210150222A CN 114716624 A CN114716624 A CN 114716624A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 93
- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- 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 81
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 75
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004945 emulsification Methods 0.000 title abstract description 4
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 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 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 12
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 12
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 239000000779 smoke Substances 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- COAPBYURHXLGMG-UHFFFAOYSA-N azane;1,3,5-triazine-2,4,6-triamine Chemical compound N.NC1=NC(N)=NC(N)=N1 COAPBYURHXLGMG-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Abstract
The invention discloses a modified polyacrylate flame-retardant emulsion, a modified polyacrylate flame-retardant pressure-sensitive adhesive containing the emulsion and a preparation method thereof, wherein the preparation method of the modified polyacrylate flame-retardant emulsion comprises the following steps: firstly, mixing epoxy resin and acrylic acid mixed monomer, adding an emulsifier solution for pre-emulsification to obtain a pre-emulsion, and then dropwise adding an initiator solution into the pre-emulsion for semi-continuous seed initiation polymerization to obtain a seed emulsion, namely the modified polyacrylate flame-retardant emulsion. The modified polyacrylate emulsion has good fire resistance, and also has excellent caking property, weather resistance and film-forming property of the polyacrylate emulsion. The main component of the pressure-sensitive adhesive is modified polyacrylate flame-retardant emulsion, melamine-ammonium polyphosphate-dipentaerythritol is used as an expansion flame-retardant system, and titanium dioxide, zinc oxide, graphene and diatomite are added to reduce smoke generation amount and improve carbon layer strength, so that the flame-retardant performance of the pressure-sensitive adhesive is improved.
Description
Technical Field
The invention relates to the technical field of flame-retardant acrylic adhesives, in particular to a modified polyacrylate flame-retardant emulsion and a preparation method thereof, and a modified polyacrylate flame-retardant pressure-sensitive adhesive containing the emulsion and a preparation method thereof.
Background
In recent years, the demand of acrylate pressure-sensitive adhesives in China is getting larger and larger, and the requirement of certain special fields on the flame retardant performance is strict. The existing pressure-sensitive adhesive products use environment-friendly brominated flame retardants, but halogen itself can cause serious harm to human bodies, and the burning of halogen can bring a large amount of toxic and harmful gases to the environment, so that metabolic disorders of nervous systems, respiratory systems, digestive systems, circulatory systems and the like in human bodies are directly or indirectly caused.
A simple method for improving the flame retardance of the acrylate pressure-sensitive adhesive is realized by adding various halogen-free flame retardants. However, the halogen-free flame retardant may affect the pressure-sensitive properties of the acrylic pressure-sensitive adhesive, such as initial adhesion and peel strength, and may also affect the overall thickness of the product.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a preparation method of modified polyacrylate flame-retardant emulsion, wherein thermosetting epoxy resin is modified into thermoplastic polyacrylate emulsion, so that the emulsion has good fire resistance; the second purpose of the invention is to provide a modified polyacrylate flame-retardant emulsion which can be used as a raw material of a pressure-sensitive adhesive to improve the fire resistance of the pressure-sensitive adhesive; the invention also aims to provide a modified polyacrylate flame-retardant pressure-sensitive adhesive, which is not added with a halogen-free flame retardant, is added with a flame-retardant emulsion as a substrate, and is supplemented with a filler to reduce the smoke amount, improve the strength of a carbon layer and improve the flame retardant property of a coating; the fourth purpose of the invention is to provide a preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive, which has simple steps and is suitable for industrial large-scale use.
One of the purposes of the invention is realized by adopting the following technical scheme:
a preparation method of modified polyacrylate flame-retardant emulsion comprises the following steps:
1) weighing an emulsifier, adding water for mixing, and stirring for dissolving to obtain an emulsifier solution;
2) dissolving epoxy resin in an acrylic acid mixed monomer, adding half of the emulsifier solution, mixing, and pre-emulsifying to obtain a pre-emulsion; wherein, the acrylic acid mixed monomer is butyl acrylate, methyl methacrylate and styrene;
3) mixing part of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, heating while stirring, dropwise adding an initiator solution into the mixed solution when the temperature is raised to a certain temperature, continuously heating, obtaining a seed emulsion after a system is blue, and continuously keeping the reaction; adding the rest of the pre-emulsion, and continuing the heat preservation reaction;
4) and after the reaction is finished, cooling, adding a pH regulator to regulate the pH to 7-8, and thus obtaining the modified polyacrylate flame-retardant emulsion.
Further, the emulsifier is polyethylene glycol octyl phenyl ether and/or sodium dodecyl sulfate; the mass fraction of the emulsifier solution is 5-8%.
Still further, the mass ratio of the epoxy resin to the acrylic mixed monomer is 1: (4-5); the mass ratio of the epoxy resin to the emulsifier is (5-6): 1; the acrylic acid mixed monomer is prepared from (1-2) by mass: 1: 1 butyl acrylate, methyl methacrylate and styrene.
Further, the pH regulator is sodium bicarbonate; the initiator solution is a potassium persulfate aqueous solution with the mass fraction of 1-2%; the mass ratio of the initiator solution to the pre-emulsion is 25-30%.
Further, in the step 3), mixing one fourth of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, stirring and heating, heating to 50-60 ℃, dropwise adding an initiator solution into the mixed solution, continuously heating to 70-80 ℃, obtaining a seed emulsion after the system is blue, and continuously keeping the reaction for 1-2 hours; and (4) finishing dripping the residual pre-emulsion and the initiator within 2-3 h, and continuing to perform heat preservation reaction for 3-4 h.
The second purpose of the invention is realized by adopting the following technical scheme:
the modified polyacrylate flame-retardant emulsion is prepared by the preparation method of the modified polyacrylate flame-retardant emulsion.
The third purpose of the invention is realized by adopting the following technical scheme:
the modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following raw materials in parts by mass:
30-40 parts of the modified polyacrylate flame-retardant emulsion, 10-15 parts of melamine, 15-20 parts of ammonium polyphosphate, 15-20 parts of dipentaerythritol, 1-5 parts of titanium dioxide, 1-5 parts of zinc oxide, 1-5 parts of graphene, 1-5 parts of kieselguhr, 0.1-0.5 part of a dispersing agent and 0.1-0.5 part of an antifoaming agent.
The fourth purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following steps:
1) mixing and dispersing the modified polyacrylate flame-retardant emulsion, the dispersing agent and the dispersing agent to obtain a mixed solution;
2) and grinding melamine, dipentaerythritol, titanium dioxide, zinc oxide and diatomite, adding the mixed solution, uniformly stirring, and adding ammonium polyphosphate and graphene to obtain the modified polyacrylate flame-retardant pressure-sensitive adhesive.
Further, in the step 1), dispersing for 10-20 min at the rotating speed of 1000-2000 r/min.
Further, in the step 1), the melamine, the dipentaerythritol, the titanium dioxide, the zinc oxide and the diatomite are ground to the fineness of 50-100 μm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the modified polyacrylate flame-retardant emulsion comprises the steps of mixing epoxy resin and an acrylic acid mixed monomer, adding an emulsifier solution for pre-emulsification to obtain a pre-emulsion, and then dropwise adding an initiator solution into the pre-emulsion for semi-continuous seed initiation polymerization to obtain a seed emulsion, namely the modified polyacrylate flame-retardant emulsion. The polyacrylate emulsion modified by the epoxy resin overcomes the technical problems of low adhesive force, poor solvent resistance, high-temperature stickiness and the like of the polyacrylate emulsion, has good fire resistance, and also has excellent cohesiveness, weather resistance and film-forming property of the polyacrylate emulsion.
(2) The invention relates to a modified polyacrylate flame-retardant emulsion, belonging to intumescent fire-retardant coating, the fire-retardant mechanism of which is as follows: the expanding fireproof coating can generate an expanding carbon layer in the heating process, and the expanding carbon layer can reduce heat to the base material, transfer and seal the protected object so as to play a fireproof role. The modified polyacrylate flame-retardant emulsion is modified by epoxy resin to delay the thermal decomposition of a film forming substance (polyacrylate), the three-dimensional network structure of the epoxy resin also locally limits the melt flow, and released gas can effectively expand a carbon layer, so that a fireproof coating has excellent expansion foaming capacity, and the flame-retardant property of the flame-retardant emulsion is realized.
(3) The main component of the modified polyacrylate flame-retardant pressure-sensitive adhesive is modified polyacrylate flame-retardant emulsion, and melamine (gas source) -ammonium polyphosphate (acid source) -dipentaerythritol (carbon source) is used as an expansion flame-retardant system; the acid source plays a role in dehydration and catalytic carbonization, the carbon source mainly has a function of generating an esterification reaction with a product decomposed by the acid source to dehydrate and generate a nonflammable porous carbon layer in a combustion process, the gas source refers to a non-combustible or inert gas capable of inhibiting flame from continuously spreading when heated at high temperature, water vapor generated by dehydration and carbonization of the acid source and the carbon source can promote expansion of the carbon layer, and titanium dioxide, zinc oxide, graphene and diatomite are added to reduce smoke generation and improve the strength of the carbon layer, so that the flame retardant property of the pressure sensitive adhesive is improved.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
Example 1
The modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following raw materials in parts by mass:
35 parts of modified polyacrylate flame-retardant emulsion, 13 parts of melamine, 16 parts of ammonium polyphosphate, 18 parts of dipentaerythritol, 3 parts of titanium dioxide, 4 parts of zinc oxide, 2 parts of graphene, 1.5 parts of kieselguhr, 0.2 part of dispersing agent and 0.3 part of defoaming agent.
The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following steps:
1) mixing the modified polyacrylate flame-retardant emulsion, the dispersing agent and the dispersing agent, and dispersing for 15min at the rotating speed of 1500r/min to obtain a mixed solution;
2) and grinding melamine, dipentaerythritol, titanium dioxide, zinc oxide and diatomite to the fineness of 60 mu m, adding the mixed solution, stirring uniformly, and adding ammonium polyphosphate and graphene to obtain the modified polyacrylate flame-retardant pressure-sensitive adhesive.
The preparation method of the modified polyacrylate flame-retardant emulsion comprises the following steps:
1) weighing an emulsifier, adding water for mixing, and stirring for dissolving to obtain an emulsifier solution;
2) dissolving epoxy resin in an acrylic acid mixed monomer, adding half of emulsifier solution, mixing, and pre-emulsifying to obtain a pre-emulsion; wherein, the acrylic acid mixed monomer is butyl acrylate, methyl methacrylate and styrene;
3) mixing one fourth of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, stirring and heating, dripping an initiator solution into the mixed solution when the temperature is raised to 55 ℃, continuously heating to 75 ℃, obtaining a seed emulsion after a system is blue, and continuously keeping the reaction for 2 hours; dripping the rest of pre-emulsion and initiator within 2-3 h, and continuing to perform heat preservation reaction for 3 h;
4) and after the reaction is finished, cooling, and adding a pH regulator to regulate the pH to 7-8 to obtain the modified polyacrylate flame-retardant emulsion.
Specifically, the emulsifier is prepared from the following components in a mass ratio of 1: 3 polyethylene glycol octyl phenyl ether and sodium dodecyl sulfate; the mass fraction of the emulsifier solution is 7%. The mass ratio of the epoxy resin to the acrylic mixed monomer is 1: 4; the mass ratio of the epoxy resin to the emulsifier is 5: 1; the acrylic acid mixed monomer is prepared from the following components in a mass ratio of 2: 1: 1 butyl acrylate, methyl methacrylate and styrene. The pH regulator is sodium bicarbonate; the initiator solution is a potassium persulfate aqueous solution with the mass fraction of 1.5%; the mass ratio of the initiator solution to the pre-emulsion is 28%.
Example 2
The modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following raw materials in parts by mass:
30 parts of modified polyacrylate flame-retardant emulsion, 10 parts of melamine, 15 parts of ammonium polyphosphate, 15 parts of dipentaerythritol, 1 part of titanium dioxide, 1 part of zinc oxide, 1 part of graphene, 1 part of kieselguhr, 0.1 part of dispersing agent and 0.1 part of defoaming agent.
The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive of the embodiment is the same as that of the embodiment 1.
Example 3
The modified polyacrylate flame-retardant pressure-sensitive adhesive comprises the following raw materials in parts by mass:
40 parts of modified polyacrylate flame-retardant emulsion, 15 parts of melamine, 20 parts of ammonium polyphosphate, 20 parts of dipentaerythritol, 5 parts of titanium dioxide, 1-5 parts of zinc oxide, 1-5 parts of graphene, 1-5 parts of diatomite, 0.1-0.5 part of dispersing agent and 0.1-0.5 part of defoaming agent.
The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive of the embodiment is the same as that of the embodiment 1.
Example 4
The modified polyacrylate flame-retardant pressure-sensitive adhesive of example 4 is prepared in the same way as example 1, except that: the method of preparing the modified polyacrylate flame retardant emulsion of example 4, comprising the steps of:
1) weighing an emulsifier, adding water for mixing, and stirring for dissolving to obtain an emulsifier solution;
2) dissolving epoxy resin in an acrylic acid mixed monomer, adding half of emulsifier solution, mixing, and pre-emulsifying to obtain a pre-emulsion; wherein, the acrylic acid mixed monomer is butyl acrylate, methyl methacrylate and styrene;
3) mixing one fourth of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, stirring and heating, dripping an initiator solution into the mixed solution when the temperature is raised to 50 ℃, continuously heating to 70 ℃, obtaining a seed emulsion after a system is blue, and continuously keeping the reaction for 1 h; dripping the rest of pre-emulsion and initiator within 2-3 h, and continuing to perform heat preservation reaction for 3 h;
4) and after the reaction is finished, cooling, and adding a pH regulator to regulate the pH to 7-8 to obtain the modified polyacrylate flame-retardant emulsion.
Specifically, the emulsifier is polyethylene glycol octyl phenyl ether; the mass fraction of the emulsifier solution is 5%. The mass ratio of the epoxy resin to the acrylic mixed monomer is 1: 4; the mass ratio of the epoxy resin to the emulsifier is 5: 1; the acrylic acid mixed monomer is prepared from the following components in a mass ratio of 1: 1: 1 butyl acrylate, methyl methacrylate and styrene. The pH regulator is sodium bicarbonate; the initiator solution is a potassium persulfate aqueous solution with the mass fraction of 1%; the mass ratio of the initiator solution to the pre-emulsion is 25%.
Example 5
The modified polyacrylate flame-retardant pressure-sensitive adhesive of example 5 is prepared in the same way as example 1, except that: the method of preparing the modified polyacrylate flame retardant emulsion of example 5, comprising the steps of:
1) weighing an emulsifier, adding water for mixing, and stirring for dissolving to obtain an emulsifier solution;
2) dissolving epoxy resin in an acrylic acid mixed monomer, adding half of the emulsifier solution, mixing, and pre-emulsifying to obtain a pre-emulsion; wherein, the acrylic acid mixed monomer is butyl acrylate, methyl methacrylate and styrene;
3) mixing one fourth of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, stirring and heating, dripping an initiator solution into the mixed solution when the temperature is raised to 60 ℃, continuously heating to 80 ℃, obtaining a seed emulsion after a system is blue, and continuously keeping the reaction for 2 hours; dripping the rest of the pre-emulsion and the initiator within 3 hours, and continuing to perform heat preservation reaction for 4 hours;
4) and after the reaction is finished, cooling, and adding a pH regulator to regulate the pH to 7-8 to obtain the modified polyacrylate flame-retardant emulsion.
Specifically, the emulsifier is polyethylene glycol octyl phenyl ether and/or sodium dodecyl sulfate; the mass fraction of the emulsifier solution is 8%. The mass ratio of the epoxy resin to the acrylic mixed monomer is 1: 5; the mass ratio of the epoxy resin to the emulsifier is 6: 1; the acrylic acid mixed monomer is prepared from the following components in a mass ratio of 1.5: 1: 1 butyl acrylate, methyl methacrylate and styrene. The pH regulator is sodium bicarbonate; the initiator solution is a potassium persulfate aqueous solution with the mass fraction of 2%; the mass ratio of the initiator solution to the pre-emulsion is 30%.
Comparative example 1
Comparative example 1 differs from example 1 in that: the flame retardant emulsion of comparative example 1 was not modified with epoxy resin, and the remaining components and preparation method of the pressure sensitive adhesive were the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that: the pressure sensitive adhesive of comparative example 2 was not added with melamine, ammonium polyphosphate and dipentaerythritol.
Comparative example 3
Comparative example 3 differs from example 1 in that: the pressure sensitive adhesive of comparative example 3 was not added with titanium dioxide, zinc oxide, graphene, and diatomaceous earth.
Evaluation and test of Effect
Firstly, testing mechanical properties
The pressure-sensitive adhesives of examples 1 to 5 and comparative examples 1 to 3 were coated on a cellulose acetate cloth having a size of 320mm × 320mm, the thickness of the pressure-sensitive adhesive layer (after solvent evaporation) was 30 μm, and finally the whole piece of cellulose acetate cloth was dried in an oven at 150 ℃ for 10 min. After being taken out, the 180-degree peel strength is detected, and the appearance of the rubber surface is observed. Wherein, the test piece of the acetate fiber cloth cut into 200mm multiplied by 25m m is carried out 180 DEG peeling strength test according to GB/T2792-1998; the initial tack test was performed by cutting the test pieces into 40 mm by 100 mm. A minimum of 3 replicates were averaged for each performance test. Specific data are shown in table 1.
TABLE 1 mechanical Property Effect of pressure-sensitive adhesives of each group
Second, testing the flame retardant property
The pressure-sensitive adhesives of examples 1 to 5 and comparative examples 1 to 3 were coated on a 30cm × 30 cm-sized acetate cloth, the thickness of the pressure-sensitive adhesive layer (after solvent evaporation) was 30 μm, and finally the entire acetate cloth was dried in an oven at 150 ℃ for 10 min. After being taken out, the test piece is subjected to a vertical burning test, a smoke density test and a limited oxygen index test, which are specifically shown in table 2.
TABLE 2 flame retardancy data for various groups of pressure sensitive adhesives
As can be seen from Table 1, the pressure-sensitive adhesives of examples 1-5 and comparative examples 1-3 have better mechanical properties, wherein the polyacrylate flame-retardant emulsion of comparative example 1 has reduced mechanical properties because it is not modified by epoxy resin. The mechanical properties of comparative example 2 and comparative example 3 are not much different from those of example 1, which shows that melamine, ammonium polyphosphate, dipentaerythritol, titanium dioxide, zinc oxide, graphene and diatomite are not main factors influencing the mechanical properties of the pressure-sensitive adhesive.
As can be seen from Table 2, the flame retardant performance of examples 1 to 5 is better than that of comparative examples 1 to 3, which shows that the modified polyacrylate flame retardant emulsion, the flame retardant expansion system (melamine, ammonium polyphosphate and dipentaerythritol) and the filler (titanium dioxide, zinc oxide, graphene and diatomite) are all important factors influencing the pressure sensitive adhesive, wherein in comparative example 3, the smoke generation amount is remarkably increased because no filler is added, and the smoke generation amount can be reduced because of the titanium dioxide, the zinc oxide, the graphene and the diatomite.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified polyacrylate flame-retardant emulsion is characterized by comprising the following steps of:
1) weighing an emulsifier, adding water for mixing, and stirring for dissolving to obtain an emulsifier solution;
2) dissolving epoxy resin in an acrylic acid mixed monomer, adding half of emulsifier solution, mixing, and pre-emulsifying to obtain a pre-emulsion; wherein, the acrylic acid mixed monomer is butyl acrylate, methyl methacrylate and styrene;
3) mixing part of the pre-emulsion with the other half of the emulsifier solution, adding a pH regulator to obtain a mixed solution, heating while stirring, dropwise adding an initiator solution into the mixed solution when the temperature is raised to a certain temperature, continuously heating, obtaining a seed emulsion after a system is blue, and continuously keeping the reaction; adding the rest of the pre-emulsion, and continuing the heat preservation reaction;
4) and after the reaction is finished, cooling, adding a pH regulator to regulate the pH to 7-8, and thus obtaining the modified polyacrylate flame-retardant emulsion.
2. The method for preparing the modified polyacrylate flame retardant emulsion according to claim 1, wherein the emulsifier is polyethylene glycol octyl phenyl ether and/or sodium dodecyl sulfate; the mass fraction of the emulsifier solution is 5-8%.
3. The method for preparing the modified polyacrylate flame retardant emulsion according to claim 1, wherein the mass ratio of the epoxy resin to the acrylic mixed monomer is 1: (4-5); the mass ratio of the epoxy resin to the emulsifier is (5-6): 1; the acrylic acid mixed monomer is prepared from (1-2) by mass: 1: 1 butyl acrylate, methyl methacrylate and styrene.
4. The method of claim 1, wherein the pH modifier is sodium bicarbonate; the initiator solution is a potassium persulfate aqueous solution with the mass fraction of 1-2%; the mass ratio of the initiator solution to the pre-emulsion is 25-30%.
5. The preparation method of the modified polyacrylate flame-retardant emulsion according to claim 1, wherein in the step 3), one quarter of the pre-emulsion is mixed with the other half of the emulsifier solution, a pH regulator is added to obtain a mixed solution, the temperature is raised while stirring, an initiator solution is dropwise added into the mixed solution when the temperature is raised to 50-60 ℃, the temperature is continuously raised to 70-80 ℃, a seed emulsion is obtained after the system is blue, and the reaction is continuously maintained for 1-2 hours; and (4) finishing dripping the residual pre-emulsion and the initiator within 2-3 h, and continuing to perform heat preservation reaction for 3-4 h.
6. A modified polyacrylate flame-retardant emulsion is characterized by being prepared by the preparation method of the modified polyacrylate flame-retardant emulsion according to any one of claims 1-5.
7. The modified polyacrylate flame-retardant pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by mass:
the modified polyacrylate flame-retardant emulsion as claimed in claim 6, which comprises 30-40 parts of modified polyacrylate flame-retardant emulsion, 10-15 parts of melamine, 15-20 parts of ammonium polyphosphate, 15-20 parts of dipentaerythritol, 1-5 parts of titanium dioxide, 1-5 parts of zinc oxide, 1-5 parts of graphene, 1-5 parts of diatomite, 0.1-0.5 part of dispersing agent and 0.1-0.5 part of defoaming agent.
8. The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive of claim 7, which is characterized by comprising the following steps:
1) mixing and dispersing the modified polyacrylate flame-retardant emulsion, the dispersing agent and the dispersing agent to obtain a mixed solution;
2) and grinding melamine, dipentaerythritol, titanium dioxide, zinc oxide and diatomite, adding the mixed solution, uniformly stirring, and adding ammonium polyphosphate and graphene to obtain the modified polyacrylate flame-retardant pressure-sensitive adhesive.
9. The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive according to claim 8, wherein in the step 1), the dispersion is performed for 10-20 min at a rotation speed of 1000-2000 r/min.
10. The preparation method of the modified polyacrylate flame-retardant pressure-sensitive adhesive according to claim 8, wherein in the step 1), melamine, dipentaerythritol, titanium dioxide, zinc oxide and diatomite are ground to a fineness of 50-100 μm.
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| CN202210150222.6A CN114716624A (en) | 2022-02-18 | 2022-02-18 | Modified polyacrylate flame-retardant emulsion, modified polyacrylate flame-retardant pressure-sensitive adhesive containing emulsion and preparation method of modified polyacrylate flame-retardant pressure-sensitive adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124940A (en) * | 2022-07-21 | 2022-09-30 | 安洁利德科技(江苏)有限公司 | Multilayer composite cotton for automobile air duct and preparation method thereof |
| CN115621660A (en) * | 2022-09-08 | 2023-01-17 | 阜阳隆能科技有限公司 | Composite diaphragm for lithium battery core, lithium battery core and lithium battery |
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- 2022-02-18 CN CN202210150222.6A patent/CN114716624A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124940A (en) * | 2022-07-21 | 2022-09-30 | 安洁利德科技(江苏)有限公司 | Multilayer composite cotton for automobile air duct and preparation method thereof |
| CN115124940B (en) * | 2022-07-21 | 2023-11-03 | 安洁利德科技(江苏)有限公司 | Multilayer composite cotton for automobile air duct and preparation method thereof |
| CN115621660A (en) * | 2022-09-08 | 2023-01-17 | 阜阳隆能科技有限公司 | Composite diaphragm for lithium battery core, lithium battery core and lithium battery |
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