CN113969124A - Flame-retardant water emulsion type acrylate pressure-sensitive adhesive - Google Patents
Flame-retardant water emulsion type acrylate pressure-sensitive adhesive Download PDFInfo
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- CN113969124A CN113969124A CN202111311060.1A CN202111311060A CN113969124A CN 113969124 A CN113969124 A CN 113969124A CN 202111311060 A CN202111311060 A CN 202111311060A CN 113969124 A CN113969124 A CN 113969124A
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- emulsifier
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000839 emulsion Substances 0.000 title claims abstract description 57
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 42
- 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 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 57
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 39
- 239000004640 Melamine resin Substances 0.000 claims abstract description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- -1 polysiloxane Polymers 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 claims description 3
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 238000010292 electrical insulation Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 9
- 239000011022 opal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008569 process Effects 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
- 239000012429 reaction media Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a flame-retardant water emulsion type acrylate pressure-sensitive adhesive, and particularly relates to the technical field of pressure-sensitive adhesives, which comprises 50-80 parts of butyl acrylate, 10-30 parts of acrylic acid-2-ethylhexyl ester, 5-20 parts of methyl methacrylate, 1-4 parts of acrylic acid, 0.5-5 parts of acrylic acid-B-hydroxypropyl ester, 1-5 parts of an emulsifier A, 0.1-1 part of an emulsifier B, 0.1-0.8 part of ammonium persulfate, 0-1 part of sodium bicarbonate, 0-0.2 part of dodecyl mercaptan, 1-8 parts of ammonia water in balance, 80 parts of distilled water, 0.5-3 parts of melamine resin, 2-5 parts of a flame retardant, 0.1-1 part of a defoaming agent and 10-13 parts of silicic acid gel. The invention has high chemical activity, good thermal stability, boiling water resistance, chemical resistance and electrical insulation, strong water resistance and high humidity resistance and strong adhesiveness.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a flame-retardant water emulsion type acrylate pressure-sensitive adhesive.
Background
The adhesive is used for connecting the surfaces of homogeneous or heterogeneous objects, has the characteristics of continuous stress distribution, light weight, sealing, low temperature of most processes and the like, is particularly suitable for connecting different materials, different thicknesses, ultrathin specifications and complex components, is the most rapidly developed in recent times, has wide application industries, has a plurality of adhesive classification methods, can be classified into thermosetting type, hot melting type, room temperature curing type, pressure-sensitive type and the like according to the application method, can be classified into structural type, non-structural type or special adhesive according to the application object, can be classified into water-soluble type, water emulsion type, solvent type, various solid types and the like according to the connection form, and is generally favored by synthetic chemists to classify the adhesives according to the chemical components of the adhesive.
The acrylate pressure-sensitive adhesive is the most widely applied pressure-sensitive adhesive at present and is a copolymer of an acrylate monomer and other ethylene monomers. Compared with other pressure-sensitive adhesives, the pressure-sensitive adhesive has the following characteristics: the product has excellent weather resistance and heat resistance almost without adding an anti-aging agent; no phase separation and migration, good transparency and oil resistance.
With increasing importance on safety, energy conservation and the like and continuous expansion of pressure-sensitive adhesive application, the pressure-sensitive adhesive has a trend towards low pollution, energy conservation, high performance and multiple functions. The emulsion type acrylate pressure-sensitive adhesive has the advantages of low cost, safe use, no pollution, short polymerization time, good adhesion to various materials, colorless and transparent coating film and the like, but also has the characteristics of poor water resistance, slow drying rate and the like. The technical development of emulsion type acrylate pressure-sensitive adhesives is centered around improving the performance and overcoming the defects.
The emulsion polymerization is carried out in emulsion prepared by monomer and water under the action of emulsifier, and the system mainly comprises four basic components of monomer, water, emulsifier and initiator dissolved in water.
The water emulsion type acrylate pressure sensitive adhesive in the prior art has poor water resistance, high temperature and high humidity resistance. Therefore, the flame-retardant water emulsion type acrylate pressure-sensitive adhesive is provided.
Disclosure of Invention
The invention aims to provide a flame-retardant water emulsion type acrylate pressure-sensitive adhesive which has the advantages of high chemical activity, good thermal stability, boiling water resistance, chemical resistance and electrical insulation, strong water resistance and high humidity resistance and strong adhesiveness.
In order to achieve the above purpose, the invention provides the following technical scheme: the flame-retardant water emulsion type acrylate pressure-sensitive adhesive comprises, by weight, 50-80 parts of butyl acrylate, 10-30 parts of 2-ethylhexyl acrylate, 5-20 parts of methyl methacrylate, 1-4 parts of acrylic acid, 0.5-5 parts of acrylic acid-B-hydroxypropyl acrylate, 1-5 parts of an emulsifier A, 0.1-1 part of an emulsifier B, 0.1-0.8 part of ammonium persulfate, 0.5-1 part of sodium bicarbonate, 0.1-0.2 part of dodecyl mercaptan, 1-8 parts of ammonia water in balance, 80 parts of distilled water, 0.5-3 parts of melamine resin, 2-5 parts of a flame retardant, 0.1-1 part of a defoaming agent and 10-13 parts of silicic acid gel.
Preferably, the melamine resin is prepared from a melamine resin and a melamine resin in a molar ratio of 1: 6-12 of melamine and formaldehyde.
Preferably, the flame retardant is one or more of 2, 3-dibromopropanol, dibromophenol and tetrabromophthalic anhydride.
Preferably, the defoaming agent is one or more of polyether modified organic silicon, mineral oil mixture and modified polysiloxane emulsion.
The invention also comprises a preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive, which comprises the following specific steps:
the method comprises the following steps: preparing an emulsifier mixed solution: uniformly mixing an emulsifier A, an emulsifier B, sodium bicarbonate, ammonium persulfate, dodecyl mercaptan and distilled water;
step two: preparing monomer mixed liquid: uniformly mixing butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and acrylic acid-B-hydroxypropyl ester;
step three: adding one third of the prepared emulsifier mixed solution into a 250ml four-mouth bottle provided with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel, quickly stirring and emulsifying the monomer mixed solution and the rest emulsifier mixed solution in another three-mouth bottle at room temperature for 15min to obtain an emulsified monomer mixed solution, and injecting the four-fifth emulsified monomer mixed solution into the dropping funnel;
step four: injecting the remaining one fifth of emulsified monomer mixed solution into a four-mouth bottle, stirring and heating, wherein the stirring speed is about 120r/min, reacting for 0.5h at 80 ℃, then dropwise adding the emulsified monomer mixed solution through a dropping funnel, controlling the dropwise adding within 1.5h, continuously reacting for 1-1.5h at 80-85 ℃, then cooling to below 60 ℃, adjusting the pH value to 9 by using ammonia water, discharging, and naturally cooling to the pH value of 7.2 after standing overnight or for several days to obtain the water-emulsion type acrylate emulsion;
step five: synthesis of melamine resin: adding formaldehyde and half amount of melamine into a reaction kettle, adjusting the pH value to 8.5-9, heating to 85-90 ℃, preserving heat for 1h, then cooling to 75-80 ℃, adding the rest melamine, preserving heat, immediately cooling to 40 ℃ when the reaction is finished, adjusting the pH value to 8.5-9, and discharging to obtain melamine resin, wherein the appearance of the product is colorless and precipitate-free transparent liquid;
step six: blending: adding the prepared melamine resin, defoaming agent, flame retardant and silicic acid gel into water emulsion type acrylate emulsion, uniformly stirring, and adjusting the pH value to 7.5-8 to obtain the melamine-formaldehyde resin (MF) modified copolymerized opal glue.
In the technical scheme, the invention provides the following technical effects and advantages:
1. the invention has high polymerization speed and high molecular weight;
2. the invention utilizes various monomers to carry out polymerization and copolymerization, which is beneficial to the modification of emulsion polymer and the development of new products;
3. the invention takes water as a reaction medium, has small viscosity, low cost, easy derivation of reaction heat, stable and safe reaction, and can directly use emulsion products as paint and adhesive;
4. the added melamine resin has high chemical activity, good thermal stability, good boiling water resistance, chemical resistance and electrical insulation, and improves the performances of the pressure-sensitive adhesive in the aspects of thermal stability, boiling water resistance, chemical resistance, electrical insulation and the like;
5. the added silicic acid gel has good chemical stability and heat resistance, has rich porous structure and large specific surface, and a large number of hydroxyl groups exist on the surface of the silicic acid gel, and the hydroxyl groups are compatible with water molecules in the air through the mutual attraction among molecules, so that the water absorption performance is realized, the water resistance and the high humidity resistance of the pressure-sensitive adhesive are improved, and the silicic acid gel has strong adsorption and plays a role in enhancing the adhesion.
Detailed Description
The present invention will be described in further detail below in order to enable those skilled in the art to better understand the technical solution of the present invention.
Example 1
The invention provides a flame-retardant water emulsion type acrylate pressure-sensitive adhesive which comprises the following raw materials (by weight part) of 50 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 5 parts of methyl methacrylate, 1 part of acrylic acid, 0.5 part of acrylic acid-B-hydroxypropyl acrylate, 1 part of emulsifier A, 0.1 part of emulsifier B, 0.1 part of ammonium persulfate, 0.5 part of sodium bicarbonate, 0.1 part of dodecyl mercaptan, 1 part of ammonia water as the balance, 80 parts of distilled water, 0.5 part of melamine resin, 2 parts of flame retardant, 0.1 part of defoaming agent and 10 parts of silicic acid gel.
The melamine resin is prepared from the following components in a molar ratio of 1: 6 melamine and formaldehyde synthesis.
The flame retardant is 2, 3-dibromopropanol.
The defoaming agent is polyether modified organic silicon.
The invention also comprises a preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive, which comprises the following specific steps:
the method comprises the following steps: preparing an emulsifier mixed solution: uniformly mixing an emulsifier A, an emulsifier B, sodium bicarbonate, ammonium persulfate, dodecyl mercaptan and distilled water;
step two: preparing monomer mixed liquid: uniformly mixing butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and acrylic acid-B-hydroxypropyl ester;
step three: adding one third of the prepared emulsifier mixed solution into a 250ml four-mouth bottle provided with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel, quickly stirring and emulsifying the monomer mixed solution and the rest emulsifier mixed solution in another three-mouth bottle at room temperature for 15min to obtain an emulsified monomer mixed solution, and injecting the four-fifth emulsified monomer mixed solution into the dropping funnel;
step four: injecting the remaining one fifth of emulsified monomer mixed solution into a four-mouth bottle, stirring and heating, wherein the stirring speed is about 120r/min, reacting for 0.5h at 80 ℃, then dropwise adding the emulsified monomer mixed solution through a dropping funnel, controlling the dropwise adding within 1.5h, continuing to react for 1h at 80 ℃, then cooling to below 60 ℃, adjusting the pH value to 9 by using ammonia water, discharging, and naturally cooling to the pH value of 7.2 after standing overnight or for several days to obtain the water-emulsion type acrylate emulsion;
step five: synthesis of melamine resin: adding formaldehyde and half amount of melamine into a reaction kettle, adjusting the pH value to 8.5, heating to 85 ℃, preserving heat for 1h, then cooling to 75 ℃, adding the rest melamine, preserving heat, immediately cooling to 40 ℃ at the end of the reaction, adjusting the pH value to 8.5, and discharging to obtain melamine resin, wherein the appearance of the product is colorless and precipitate-free transparent liquid;
step six: blending: and adding the prepared melamine resin, the defoaming agent, the flame retardant and the silicic acid gel into the water emulsion type acrylate emulsion, uniformly stirring, and adjusting the pH value to 7.5 to obtain the melamine-formaldehyde resin (MF) modified copolymerized opal glue.
Example 2
The invention provides a flame-retardant water emulsion type acrylate pressure-sensitive adhesive which comprises the following raw materials (by weight part) 65 parts of butyl acrylate, 20 parts of acrylic acid-2-ethylhexyl ester, 14 parts of methyl methacrylate, 2.5 parts of acrylic acid, 3 parts of acrylic acid-B-hydroxypropyl ester, 3 parts of emulsifier A, 0.5 part of emulsifier B, 0.5 part of ammonium persulfate, 0.75 part of sodium bicarbonate, 0.15 part of dodecyl mercaptan, 5 parts of ammonia water as the balance, 80 parts of distilled water, 1.5 parts of melamine resin, 3.5 parts of flame retardant, 0.5 part of defoaming agent and 11.5 parts of silicic acid gel.
The melamine resin is prepared from the following components in a molar ratio of 1: 9 melamine and formaldehyde synthesis.
The flame retardant is dibromophenol.
The defoaming agent is a mineral oil mixture.
The invention also comprises a preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive, which comprises the following specific steps:
the method comprises the following steps: preparing an emulsifier mixed solution: uniformly mixing an emulsifier A, an emulsifier B, sodium bicarbonate, ammonium persulfate, dodecyl mercaptan and distilled water;
step two: preparing monomer mixed liquid: uniformly mixing butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and acrylic acid-B-hydroxypropyl ester;
step three: adding one third of the prepared emulsifier mixed solution into a 250ml four-mouth bottle provided with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel, quickly stirring and emulsifying the monomer mixed solution and the rest emulsifier mixed solution in another three-mouth bottle at room temperature for 15min to obtain an emulsified monomer mixed solution, and injecting the four-fifth emulsified monomer mixed solution into the dropping funnel;
step four: injecting the remaining one fifth of emulsified monomer mixed solution into a four-mouth bottle, stirring and heating, wherein the stirring speed is about 120r/min, reacting for 0.5h at 80 ℃, then dropwise adding the emulsified monomer mixed solution through a dropping funnel, controlling the dropwise adding within 1.5h, continuing to react for 1.25h at 83 ℃, then cooling to below 60 ℃, adjusting the pH value to 9 by using ammonia water, discharging, and naturally cooling to the pH value of 7.2 after standing overnight or days to obtain the water-emulsion type acrylate emulsion;
step five: synthesis of melamine resin: adding formaldehyde and half amount of melamine into a reaction kettle, adjusting the pH value to 8.75, heating to 88 ℃, preserving heat for 1h, then cooling to 78 ℃, adding the rest melamine, preserving heat, immediately cooling to 40 ℃ at the end of the reaction, adjusting the pH value to 8.75, and discharging to obtain melamine resin, wherein the appearance of the product is colorless and precipitate-free transparent liquid;
step six: blending: and adding the prepared melamine resin, the defoaming agent, the flame retardant and the silicic acid gel into the water emulsion type acrylate emulsion, uniformly stirring, and adjusting the pH value to 7.75 to obtain the melamine-formaldehyde resin (MF) modified copolymerized opal glue.
Example 3
The invention provides a flame-retardant water emulsion type acrylate pressure-sensitive adhesive which comprises the following raw materials (by weight part) of 80 parts of butyl acrylate, 30 parts of acrylic acid-2-ethylhexyl, 20 parts of methyl methacrylate, 4 parts of propylene, 5 parts of acrylic acid-B-hydroxypropyl ester, 5 parts of an emulsifier A, 1 part of an emulsifier B, 0.8 part of ammonium persulfate, 1 part of sodium bicarbonate, 0.2 part of dodecyl mercaptan, 8 parts of ammonia water in balance, 80 parts of distilled water, 3 parts of melamine resin, 5 parts of a flame retardant, 1 part of a defoaming agent and 13 parts of silicic acid gel.
The melamine resin is prepared from the following components in a molar ratio of 1: 12 melamine and formaldehyde synthesis.
The flame retardant is tetrabromo phthalic anhydride.
The defoaming agent is one or more of modified polysiloxane emulsion.
The invention also comprises a preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive, which comprises the following specific steps:
the method comprises the following steps: preparing an emulsifier mixed solution: uniformly mixing an emulsifier A, an emulsifier B, sodium bicarbonate, ammonium persulfate, dodecyl mercaptan and distilled water;
step two: preparing monomer mixed liquid: uniformly mixing butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and acrylic acid-B-hydroxypropyl ester;
step three: adding one third of the prepared emulsifier mixed solution into a 250ml four-mouth bottle provided with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel, quickly stirring and emulsifying the monomer mixed solution and the rest emulsifier mixed solution in another three-mouth bottle at room temperature for 15min to obtain an emulsified monomer mixed solution, and injecting the four-fifth emulsified monomer mixed solution into the dropping funnel;
step four: injecting the remaining one fifth of emulsified monomer mixed solution into a four-mouth bottle, stirring and heating, wherein the stirring speed is about 120r/min, reacting for 0.5h at 80 ℃, then dropwise adding the emulsified monomer mixed solution through a dropping funnel, controlling the dropwise adding within 1.5h, continuing to react for 1.5h at 85 ℃, then cooling to below 60 ℃, adjusting the pH value to 9 by using ammonia water, discharging, and naturally cooling to the pH value of 7.2 after standing overnight or days to obtain the water-emulsion type acrylate emulsion;
step five: synthesis of melamine resin: adding formaldehyde and half amount of melamine into a reaction kettle, adjusting the pH value to 9, heating to 90 ℃, preserving heat for 1h, then cooling to 80 ℃, adding the rest melamine, preserving heat, immediately cooling to 40 ℃ at the end of the reaction, adjusting the pH value to 9, and discharging to obtain melamine resin, wherein the appearance of the product is colorless and precipitate-free transparent liquid;
step six: blending: and adding the prepared melamine resin, the defoaming agent, the flame retardant and the silicic acid gel into the water emulsion type acrylate emulsion, uniformly stirring, and adjusting the pH value to 8 to obtain the melamine-formaldehyde resin (MF) modified copolymerized opal glue.
Performance testing
1. Pressure-sensitive adhesive tape articles were produced from the pressure-sensitive adhesives of examples 1 to 3, and tested for 180 ° peel strength and initial adhesive strength by test method ASTM D3330, and for tack strength by test method ASTM D3654, and three force performance tests were carried out under the same conditions using 3 parts of a common commercially available adhesive tape as comparative examples 1 to 3, and the results are as follows.
TABLE three force Performance test results for examples 1-3 and comparative examples 1-3
From table one, it can be seen that the initial bond strength, tack and 180 ° peel force of the present application are superior to the commercially available conventional packaging tapes.
2. Water and moisture resistance test
The pressure-sensitive adhesives of examples 1-3 were used to make pressure-sensitive adhesive tape articles and tested for water repellency using hydrostatic testing, with the test results shown in table two:
TABLE II test results of water-proof and barrier properties of examples 1 to 3
As can be seen from the table II, the hydrostatic pressure value of the waterproof paint is not less than 51, and the waterproof paint has excellent waterproof, waterproof and moisture-proof performances.
3. High humidity and high temperature test
Uniformly coating the pressure-sensitive adhesive on glass, storing for 48h in an environment with the temperature of 85 ℃ and the relative humidity of 85%, and then peeling off to observe the condition of adhesive residue, wherein the test results are as shown in table III:
TABLE TRI EXAMPLES 1-3 results of high humidity and high temperature resistance test
| Examples | High temperature resistance | High humidity and high temperature resistance |
| Example 1 | No adhesive residue | No adhesive residue |
| Example 2 | No adhesive residue | No adhesive residue |
| Example 3 | No adhesive residue | No adhesive residue |
As can be seen from the third table, the invention has excellent water resistance and temperature resistance, and no adhesive residue is produced after cold tearing after high-temperature baking at 180 ℃.
4. Effect of Melamine resin concentration on Adhesives Performance
Watch four
As can be seen from Table IV, as the content of the melamine resin increases, the initial adhesion of the composite emulsion decreases, and the permanent adhesion and the 180-degree peel strength both increase and decrease. Under the conditions that the common polyacrylate emulsion pressure-sensitive adhesive meets the requirements that the sizing thickness is (20 +/-1) mu m, the initial adhesion is greater than a No. 7 ball and the permanent adhesion is greater than 48h, the 180-degree peel strength is greater than 20N/25mm, and the phenomena of degumming and even transfer exist to different degrees. The melamine resin is introduced into the polyacrylate emulsion by adopting an in-situ emulsion polymerization method, on the basis of slightly reducing the initial adhesion, the 180-degree peel strength can reach more than 25N/25mm without degumming or glue transfer, and the permanent adhesion is also increased.
The composite emulsion system with the melamine resin content of 0.5 percent is subjected to an amplification experiment in a 700L kettle, so that the polymerization reaction can be stably carried out, and no residue or gel is generated. The pressure-sensitive performance of the sample obtained by the amplification experiment is basically consistent with that of a small test sample, and the sample has good performance when being used on BOPP, PET and PE base materials, and can reduce the thickness of glue application to a certain extent and save the cost.
While certain exemplary embodiments of the present invention have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Accordingly, the foregoing description is illustrative in nature and is not to be construed as limiting the scope of the invention as claimed.
Claims (9)
1. The flame-retardant water emulsion type acrylate pressure-sensitive adhesive is characterized in that: the raw materials (by weight portion) include 50-80 portions of butyl acrylate, 10-30 portions of acrylic acid-2-ethylhexyl ester, 5-20 portions of methyl methacrylate, 1-4 portions of acrylic acid, 0.5-5 portions of acrylic acid-B-hydroxypropyl ester, 1-5 portions of emulsifier A, 0.1-1 portion of emulsifier B, 0.1-0.8 portion of ammonium persulfate, 0.5-1 portion of sodium bicarbonate, 0.1-0.2 portion of dodecyl mercaptan, 1-8 portions of ammonia water residue, 80 portions of distilled water, 0.5-3 portions of melamine resin, 2-5 portions of flame retardant, 0.1-1 portion of defoaming agent and 10-13 portions of silicic acid gel.
2. The flame retardant water emulsion acrylate pressure sensitive adhesive of claim 1 wherein: the melamine resin is prepared from the following components in a molar ratio of 1: 6-12 of melamine and formaldehyde.
3. The flame retardant water emulsion acrylate pressure sensitive adhesive of claim 1 wherein: the flame retardant is one or more of 2, 3-dibromopropanol, dibromophenol and tetrabromophthalic anhydride.
4. The flame retardant water emulsion acrylate pressure sensitive adhesive of claim 1 wherein: the defoaming agent is one or more of polyether modified organic silicon, mineral oil mixture and modified polysiloxane emulsion.
5. A process for preparing the flame retardant water emulsion acrylate pressure sensitive adhesive of any one of claims 1-4, wherein: the method comprises the following specific steps:
the method comprises the following steps: preparing an emulsifier mixed solution: uniformly mixing an emulsifier A, an emulsifier B, sodium bicarbonate, ammonium persulfate, dodecyl mercaptan and distilled water;
step two: preparing monomer mixed liquid: uniformly mixing butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and acrylic acid-B-hydroxypropyl ester;
step three: adding one third of the prepared emulsifier mixed solution into a 250ml four-mouth bottle with a dropping funnel, quickly stirring and emulsifying the monomer mixed solution and the rest emulsifier mixed solution in another three-mouth bottle at room temperature for 15min to obtain an emulsified monomer mixed solution, and injecting the four-fifth emulsified monomer mixed solution into the dropping funnel;
step four: injecting the remaining one fifth of the emulsified monomer mixed solution into a four-mouth bottle, stirring and heating for reaction, then dropwise adding the emulsified monomer mixed solution through a dropping funnel, discharging after the reaction, and naturally lowering the pH value to 7.2 after standing overnight or days to obtain the water emulsion type acrylate emulsion;
step five: synthesis of melamine resin: adding formaldehyde and half amount of melamine into a reaction kettle, adjusting the pH value to 8.5-9, heating to 85-90 ℃, preserving heat for 1h, then cooling to 75-80 ℃, adding the rest melamine, preserving heat, immediately cooling to 40 ℃ when the reaction is finished, adjusting the pH value to 8.5-9, and discharging to obtain melamine resin;
step six: blending: and adding the prepared melamine resin, the defoaming agent, the flame retardant and the silicic acid gel into the water emulsion type acrylate emulsion, uniformly stirring, and adjusting the pH value to 7.5-8 to obtain the melamine-formaldehyde resin modified copolymer emulsion glue.
6. The preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive according to claim 5, characterized in that: and an electric stirrer, a reflux condenser and a thermometer are also arranged in the four-mouth bottle in the third step.
7. The preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive according to claim 5, characterized in that: and injecting the rest one fifth of the emulsified monomer mixed solution in the fourth step into a four-mouth bottle, stirring at the speed of about 120r/min, and reacting for 0.5h at the temperature of 80 ℃.
8. The preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive according to claim 5, characterized in that: and in the fourth step, the emulsified monomer mixed solution is dripped into the dropping funnel, the reaction is continued for 1 to 1.5 hours at the temperature of between 80 and 85 ℃, then the temperature is reduced to below 60 ℃, the pH value is adjusted to 9 by ammonia water, and then the material is discharged.
9. The preparation process of the flame-retardant water emulsion type acrylate pressure-sensitive adhesive according to claim 5, characterized in that: the appearance of the product in the fifth step is colorless and precipitate-free transparent liquid.
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|---|---|---|---|---|
| EP0394774A1 (en) * | 1989-04-26 | 1990-10-31 | National Starch and Chemical Investment Holding Corporation | Improved woodworking adhesives based on multistage emulsion polymer |
| CN1368997A (en) * | 1999-08-20 | 2002-09-11 | H·B·富勒许可和金融公司 | Water based pressure sensitive adhesives having enhanced characteristics |
| CN111363504A (en) * | 2020-04-06 | 2020-07-03 | 恩平市盈嘉丰胶粘制品有限公司 | Moisture-absorption curing type acrylate pressure-sensitive adhesive and preparation method thereof |
| CN112143424A (en) * | 2020-09-11 | 2020-12-29 | 陈会杰 | High-performance inorganic flame-retardant acrylic pressure-sensitive adhesive and preparation method thereof |
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2021
- 2021-11-05 CN CN202111311060.1A patent/CN113969124A/en active Pending
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|---|---|---|---|---|
| EP0394774A1 (en) * | 1989-04-26 | 1990-10-31 | National Starch and Chemical Investment Holding Corporation | Improved woodworking adhesives based on multistage emulsion polymer |
| CN1368997A (en) * | 1999-08-20 | 2002-09-11 | H·B·富勒许可和金融公司 | Water based pressure sensitive adhesives having enhanced characteristics |
| CN111363504A (en) * | 2020-04-06 | 2020-07-03 | 恩平市盈嘉丰胶粘制品有限公司 | Moisture-absorption curing type acrylate pressure-sensitive adhesive and preparation method thereof |
| CN112143424A (en) * | 2020-09-11 | 2020-12-29 | 陈会杰 | High-performance inorganic flame-retardant acrylic pressure-sensitive adhesive and preparation method thereof |
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