CN111171217A - Preparation process and application of composite glass fiber mesh cloth tackifying adhesive - Google Patents
Preparation process and application of composite glass fiber mesh cloth tackifying adhesive Download PDFInfo
- Publication number
- CN111171217A CN111171217A CN202010051729.7A CN202010051729A CN111171217A CN 111171217 A CN111171217 A CN 111171217A CN 202010051729 A CN202010051729 A CN 202010051729A CN 111171217 A CN111171217 A CN 111171217A
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- China
- Prior art keywords
- monomer
- monomers
- nano
- acrylate
- glass fiber
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 239000004744 fabric Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000003365 glass fiber Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims description 194
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- -1 acrylic ester Chemical class 0.000 claims description 53
- 239000012874 anionic emulsifier Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000012875 nonionic emulsifier Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000012986 chain transfer agent Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- 230000001804 emulsifying effect Effects 0.000 claims description 19
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 15
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002086 nanomaterial Substances 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011152 fibreglass Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 9
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 19
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- 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
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a composite glass fiber mesh fabric tackifying adhesive, a preparation process and application thereof. The adhesive disclosed by the invention has unique advantages in the aspects of initial adhesion, permanent adhesion and peeling strength, and can still enable a product to keep excellent performances under the environments of high temperature, low temperature and the like.
Description
Technical Field
The invention relates to an adhesive, and in particular relates to a composite glass fiber mesh fabric tackifying adhesive, a preparation process and application. Belongs to the technical field of adhesives.
Background
The gridding cloth is glass fiber woven by medium-alkali or alkali-free glass fiber yarn and coated by alkali-resistant polymer emulsion, and is widely applied to wall reinforcing materials (GRC wallboards, EPS internal and external wall insulation boards), reinforced plastics, framework materials of rubber products, fire-proof boards, grinding wheel base cloth and the like. The adhesive has two characteristics of initial adhesiveness and permanent adhesiveness, and the characteristics of the mesh cloth are realized by the tackifying adhesive of the glass fiber mesh cloth.
If the initial adhesion retentivity is poor, the mesh cloth is easy to fall off, and the purpose of adhesion cannot be achieved; if the holding power is too small, the bonded object and the bonded object are liable to be detached when a small force is applied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite type fiberglass mesh cloth tackifying adhesive, a preparation process and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylate soft monomers and acrylate hard monomers, and the dosage of the acrylate soft monomers and the acrylate hard monomers is 42-48% and 6-12% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 1-2.5%, 0.5-1.2%, 0.1-0.2%, 0.2-0.5% and 0.01-0.05% of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.4-8.6.
Preferably, the acrylate soft monomer comprises the following components in a mass ratio of 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), wherein the acrylic ester hard monomer comprises the following components in a mass ratio of 1.8-2: 1 of Styrene (ST) and Methyl Methacrylate (MMA), wherein the functional monomers comprise the following components in a mass ratio of 1.8-2: 5.5: 2.5-2.7: 1-1.5 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), wherein the mass ratio of the anionic emulsifier to the anionic emulsifier is 1.1: 0.5-0.9: 0.7-1.4 of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (A-102 (without APEO)), wherein the nonionic emulsifier comprises the following components in a mass ratio of 0.3-0.5: 0.2-0.4 polyoxyethylene octyl phenol ether (OP-10) and ethyl phenyl polyethylene glycol (NP-40), wherein the initiator comprises the following components in a mass ratio of 1.3-2.7: 0.4-1.4 of ammonium persulfate and sodium persulfate, wherein the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
Preferably, the monomer is modified by the following specific method: the preparation method comprises the steps of firstly adding nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate into toluene, conducting ultrasonic dispersion treatment for 20-30 minutes, then adding methacryloxypropyltrimethoxysilane, continuing to conduct ultrasonic dispersion treatment for 5-8 minutes, reacting at 85-95 ℃ for 6-8 hours, cooling to room temperature (25 ℃), centrifuging, drying to obtain an organic modified nano material, finally mixing the organic modified nano material with nano silicon dioxide sol and a monomer, and conducting ultrasonic dispersion for 25-35 minutes to achieve modification treatment on the monomer.
Preferably, the mass ratio of the nano lanthanum hexaboride, the nano chromium oxide, the nano aluminum silicate, the toluene, the methacryloxypropyl trimethoxy silane, the nano silica sol with the mass concentration of 10% to the monomer is 0.02-0.03: 0.03 to 0.04: 0.01-0.02: 1.5-2: 0.1-0.15: 0.05-0.08: 100.
still more preferably, the nano silica sol is prepared by the following method: ethanol, deionized water, ethyl orthosilicate and concentrated ammonia water with the mass concentration of 28% are mixed according to the volume ratio of 250: 20: 55: 1.7, stirring uniformly, heating to 63 ℃ for reaction for 5 hours, removing ethanol by rotary evaporation, filtering by using 0.22 mu m filter paper, adding deionized water, and mixing to prepare the nano silicon dioxide sol with the mass concentration of 10%.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding 1/3-1/2 formula amount of deionized water, 1/3-1/2 formula amount of anionic emulsifier, and formula amount of nonionic emulsifier, monomer and functional monomer into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 82-88 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4-5 hours, and reacting for 1 hour under heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
Preferably, in the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 30-40 minutes.
Preferably, in the step (1), after the feeding is finished, the high-speed shearing is carried out at 10000-12000 rpm for 10-15 minutes. The low shear rate or short treatment time can lead to insufficient emulsification, and the high shear rate or long treatment time can lead to excessive emulsification to cause layering, which can affect various indexes of viscosity, viscosity retention and the like of the product.
Preferably, in the step (4), the residual monomer is eliminated by a boiling blowing method, and the residual monomer is carried away by nitrogen gas boiling blowing.
The adhesive is applied to the composite glass fiber mesh cloth.
Preferably, the glass fiber mesh cloth is wholly soaked in the adhesive, stands for 10-15 minutes, is taken out and is dried at 130 ℃, and then the composite glass fiber mesh cloth is obtained.
The invention has the beneficial effects that:
the composite fiberglass mesh fabric tackifying adhesive is prepared from monomers, functional monomers, anionic emulsifiers, nonionic emulsifiers, initiators, chain transfer agents, pH regulators, deionized water and the like, wherein the monomers are a combination of acrylate soft monomers and acrylate hard monomers. The adhesive disclosed by the invention has unique advantages in the aspects of initial adhesion, permanent adhesion and peeling strength, and can still enable a product to keep excellent performances under the environments of high temperature, low temperature and the like.
1. The soft monomer has lower glass transition temperature and mainly provides initial viscosity for the product, and the soft monomer adopts the combination of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA). The hard monomer is used to increase its cohesive strength and rigidity, and the hard monomer of the present invention employs a combination of Methyl Methacrylate (MMA) and Styrene (ST). The functional monomer can obviously improve the adhesive property and cohesive strength of the product, and the invention adopts the combination of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA) and 2-acrylamide-2-methyl propanesulfonic Acid (AMPS).
2. The applicant screens the factors such as the proportion of soft and hard monomers, the dosage of functional monomers, the dosage of emulsifying agents, the types and dosage of initiators, the polymerization reaction time, the polymerization reaction temperature and the like, and considers the influence on the performances such as the conversion rate, the viscosity, the initial adhesion, the permanent adhesion, the peel strength and the like of the product, thereby obtaining the polymerization process and the basic formula with better comprehensive performance. The conversion rate of the invention is more than 99%. The dosage of the adhesive is determined by testing the appearance, viscosity, pH value, solid content, bonding performance and the like of the product. The alternating temperature and thermal property resistance analysis test is carried out on the obtained adhesive, and the adhesive has excellent initial adhesion, lasting adhesion and alternating temperature resistance.
3. During preparation, fully emulsifying part of deionized water, part of anionic emulsifier, the non-ionic emulsifier, the monomer and the functional monomer according to the formula amount to obtain a pre-emulsified material, adding the rest of deionized water and the anionic emulsifier according to the formula amount into a reaction kettle, heating, adding part of the pre-emulsified material, carrying out heat preservation reaction for a short time, slowly dropwise adding the rest of the pre-emulsified material, continuing to react, and finally adjusting the pH value to obtain the adhesive. Except for the control of the feeding sequence, the dripping speed of the residual pre-emulsified materials is very critical, and the residual pre-emulsified materials can be quickly dispersed after being dripped if the speed is too low, so that technical problems of over-emulsification, layering and the like are caused, and various indexes of the product such as viscosity and the like are further influenced; the coated state can be presented microscopically too fast, the emulsification effect is influenced, the emulsification is insufficient, and various indexes of the product can be influenced.
4. The monomer is modified before feeding, and the method comprises the steps of modifying nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate by methacryloxypropyltrimethoxysilane to prepare an organic modified nano material, and mixing the organic modified nano material with nano silicon dioxide sol and the monomer to realize the modification treatment of the monomer. The nanometer lanthanum hexaboride, the nanometer chromium oxide and the nanometer aluminum silicate have nanometer particle sizes and have certain reflection and barrier effects on heat, and after the nanometer lanthanum hexaboride, the nanometer chromium oxide and the nanometer aluminum silicate are compounded, the reflection and barrier effects on heat are stronger, cold and heat are effectively insulated, and the stability of the adhesive is improved. Moreover, the introduction of the nano material further improves the initial adhesion, the permanent adhesion and the like of the product. However, the compatibility of the nano materials with organic monomers is poor, so that the stability advantage of the nano materials is influenced, the applicant utilizes methacryloxypropyltrimethoxysilane for modification treatment, introduces double bonds, can polymerize with monomers containing the double bonds, and fundamentally avoids the separation of organic and inorganic materials. The invention also introduces nano-silica sol which has an interface effect, promotes the full fusion of all components in the system and ensures the product performance.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylate soft monomers and acrylate hard monomers, and the dosage of the monomers is 42% and 12% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 1 percent, 1.2 percent, 0.1 percent, 0.5 percent and 0.01 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.6.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.8: 1 Styrene (ST) and Methyl Methacrylate (MMA), the functional monomers comprising, in a mass ratio of 2: 5.5: 2.5: 1.5 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.5: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, disodium fatty alcohol polyoxyethylene ether sulfosuccinate (A-102 (no APEO)), and the nonionic emulsifier comprises, in a mass ratio of 0.3: 0.4 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 1.3: 1.4 of ammonium persulfate and sodium persulfate, wherein the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding 1/3 formula amount of deionized water, 1/2 formula amount of anionic emulsifier, and formula amount of nonionic emulsifier, monomer and functional monomer into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 82 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 5 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 30 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 10 minutes at 12000 rpm.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Example 2:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylate soft monomers and acrylate hard monomers, and the dosage of the monomers is 48% and 6% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2.5 percent, 0.5 percent, 0.2 percent and 0.05 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to be 8.4.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), wherein the acrylate hard monomer comprises a copolymer of 2: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.8: 5.5: 2.7: 1 Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.9: 0.7 of sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (A-102 (no APEO)), wherein the nonionic emulsifier comprises a mixture of sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.5: 0.2 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2.7: 0.4 of ammonium persulfate and sodium persulfate, wherein the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding 1/2 formula amount of deionized water, 1/3 formula amount of anionic emulsifier, formula amount of nonionic emulsifier, monomer and functional monomer into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 88 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 40 minutes.
In the step (1), after the feeding is finished, shearing at a high speed of 10000 rpm for 15 minutes.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Example 3:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylic ester soft monomers and acrylic ester hard monomers, and the dosage of the two monomers is 45% and 10% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2 percent, 1 percent, 0.15 percent, 0.4 percent and 0.03 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.5.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.9: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.9: 5.5: 2.6: 1.2 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.7: 1 sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (a-102 (without APEO)), wherein the nonionic emulsifier comprises a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.4: 0.3 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2: 1, the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding deionized water with the formula amount of 1/2, an anionic emulsifier with the formula amount of 1/2, a nonionic emulsifier, a monomer and a functional monomer with the formula amount into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 85 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 35 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 12 minutes at 11000 r/min.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Example 4:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylic ester soft monomers and acrylic ester hard monomers, and the dosage of the two monomers is 45% and 10% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2 percent, 1 percent, 0.15 percent, 0.4 percent and 0.03 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.5.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.9: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.9: 5.5: 2.6: 1.2 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.7: 1 sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (a-102 (without APEO)), wherein the nonionic emulsifier comprises a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.4: 0.3 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2: 1, the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The monomer is modified, and the specific method comprises the following steps: the preparation method comprises the steps of firstly adding nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate into toluene, conducting ultrasonic dispersion treatment for 20-30 minutes, then adding methacryloxypropyltrimethoxysilane, continuing to conduct ultrasonic dispersion treatment for 5-8 minutes, reacting at 85-95 ℃ for 6-8 hours, cooling to room temperature (25 ℃), centrifuging, drying to obtain an organic modified nano material, finally mixing the organic modified nano material with nano silicon dioxide sol and a monomer, and conducting ultrasonic dispersion for 25-35 minutes to achieve modification treatment on the monomer.
The mass ratio of the nano lanthanum hexaboride, the nano chromium oxide, the nano aluminum silicate, the toluene, the methacryloxypropyl trimethoxy silane, the nano silicon dioxide sol with the mass concentration of 10 percent to the monomers is 0.02-0.03: 0.03 to 0.04: 0.01-0.02: 1.5-2: 0.1-0.15: 0.05-0.08: 100.
the nano-silica sol is prepared by the following method: ethanol, deionized water, ethyl orthosilicate and concentrated ammonia water with the mass concentration of 28% are mixed according to the volume ratio of 250: 20: 55: 1.7, stirring uniformly, heating to 63 ℃ for reaction for 5 hours, removing ethanol by rotary evaporation, filtering by using 0.22 mu m filter paper, adding deionized water, and mixing to prepare the nano silicon dioxide sol with the mass concentration of 10%.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding deionized water with the formula amount of 1/2, an anionic emulsifier with the formula amount of 1/2, a nonionic emulsifier, a monomer and a functional monomer with the formula amount into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 85 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 35 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 12 minutes at 11000 r/min.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Example 5:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylic ester soft monomers and acrylic ester hard monomers, and the dosage of the two monomers is 45% and 10% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2 percent, 1 percent, 0.15 percent, 0.4 percent and 0.03 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.5.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.9: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.9: 5.5: 2.6: 1.2 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.7: 1 sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (a-102 (without APEO)), wherein the nonionic emulsifier comprises a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.4: 0.3 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2: 1, the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The monomer is modified, and the specific method comprises the following steps: the preparation method comprises the steps of firstly adding nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate into toluene, conducting ultrasonic dispersion treatment for 20-30 minutes, then adding methacryloxypropyltrimethoxysilane, continuing to conduct ultrasonic dispersion treatment for 5-8 minutes, reacting at 85-95 ℃ for 6-8 hours, cooling to room temperature (25 ℃), centrifuging, drying to obtain an organic modified nano material, finally mixing the organic modified nano material with nano silicon dioxide sol and a monomer, and conducting ultrasonic dispersion for 25-35 minutes to achieve modification treatment on the monomer.
The mass ratio of the nano lanthanum hexaboride, the nano chromium oxide, the nano aluminum silicate, the toluene, the methacryloxypropyl trimethoxy silane, the nano silicon dioxide sol with the mass concentration of 10 percent to the monomers is 0.02-0.03: 0.03 to 0.04: 0.01-0.02: 1.5-2: 0.1-0.15: 0.05-0.08: 100.
the nano-silica sol is prepared by the following method: ethanol, deionized water, ethyl orthosilicate and concentrated ammonia water with the mass concentration of 28% are mixed according to the volume ratio of 250: 20: 55: 1.7, stirring uniformly, heating to 63 ℃ for reaction for 5 hours, removing ethanol by rotary evaporation, filtering by using 0.22 mu m filter paper, adding deionized water, and mixing to prepare the nano silicon dioxide sol with the mass concentration of 10%.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding deionized water with the formula amount of 1/2, an anionic emulsifier with the formula amount of 1/2, a nonionic emulsifier, a monomer and a functional monomer with the formula amount into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 85 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 35 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 12 minutes at 11000 r/min.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Example 6:
a composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylic ester soft monomers and acrylic ester hard monomers, and the dosage of the two monomers is 45% and 10% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2 percent, 1 percent, 0.15 percent, 0.4 percent and 0.03 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.5.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.9: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.9: 5.5: 2.6: 1.2 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.7: 1 sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (a-102 (without APEO)), wherein the nonionic emulsifier comprises a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.4: 0.3 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2: 1, the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The monomer is modified, and the specific method comprises the following steps: the preparation method comprises the steps of firstly adding nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate into toluene, conducting ultrasonic dispersion treatment for 20-30 minutes, then adding methacryloxypropyltrimethoxysilane, continuing to conduct ultrasonic dispersion treatment for 5-8 minutes, reacting at 85-95 ℃ for 6-8 hours, cooling to room temperature (25 ℃), centrifuging, drying to obtain an organic modified nano material, finally mixing the organic modified nano material with nano silicon dioxide sol and a monomer, and conducting ultrasonic dispersion for 25-35 minutes to achieve modification treatment on the monomer.
The mass ratio of the nano lanthanum hexaboride, the nano chromium oxide, the nano aluminum silicate, the toluene, the methacryloxypropyl trimethoxy silane, the nano silicon dioxide sol with the mass concentration of 10 percent to the monomers is 0.02-0.03: 0.03 to 0.04: 0.01-0.02: 1.5-2: 0.1-0.15: 0.05-0.08: 100.
the nano-silica sol is prepared by the following method: ethanol, deionized water, ethyl orthosilicate and concentrated ammonia water with the mass concentration of 28% are mixed according to the volume ratio of 250: 20: 55: 1.7, stirring uniformly, heating to 63 ℃ for reaction for 5 hours, removing ethanol by rotary evaporation, filtering by using 0.22 mu m filter paper, adding deionized water, and mixing to prepare the nano silicon dioxide sol with the mass concentration of 10%.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding deionized water with the formula amount of 1/2, an anionic emulsifier with the formula amount of 1/2, a nonionic emulsifier, a monomer and a functional monomer with the formula amount into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 85 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 35 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 12 minutes at 11000 r/min.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Comparative example 1
A composite glass fiber mesh fabric tackifying adhesive is prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylic ester soft monomers and acrylic ester hard monomers, and the dosage of the two monomers is 45% and 10% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 2 percent, 1 percent, 0.15 percent, 0.4 percent and 0.03 percent of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.5.
The acrylic ester soft monomer comprises the following components in percentage by mass 3: 57: 100 of Ethyl Acrylate (EA), Butyl Acrylate (BA) and isooctyl acrylate (2-EHA), said acrylate hard monomers comprising, in a mass ratio of 1.9: 1 Styrene (ST) and Methyl Methacrylate (MMA), said functional monomers comprising, in a mass ratio of 1.9: 5.5: 2.6: 1.2 of Acrylamide (AM), Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), the anionic emulsifier comprising, in a mass ratio of 1.1: 0.7: 1 sodium lauryl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester (a-102 (without APEO)), wherein the nonionic emulsifier comprises a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester in a mass ratio of 0.4: 0.3 polyoxyethylene octyl phenol ether (OP-10), ethyl phenyl polyethylene glycol (NP-40), the initiator comprising the following components in a mass ratio of 2: 1, the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
The preparation process of the composite glass fiber mesh fabric tackifying adhesive comprises the following specific steps:
(1) firstly, adding deionized water with the formula amount of 1/2, an anionic emulsifier with the formula amount of 1/2, a nonionic emulsifier, a monomer and a functional monomer with the formula amount into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 85 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4 hours, and reacting for 1 hour under the condition of heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
In the step (1), the monomer is fed in a continuous dropwise adding mode, and the dropwise adding time is 35 minutes.
In the step (1), after the feeding is finished, high-speed shearing is carried out for 12 minutes at 11000 r/min.
In the step (4), the residual monomers are eliminated by a boiling method, and the residual monomers are taken away by adopting nitrogen gas boiling.
Comparative example 1
In the preparation process, the residual pre-emulsified material in the step (3) is dripped into the reaction kettle for 3.5 hours.
The rest is the same as example 1.
Comparative example 2
In the preparation process, the residual pre-emulsified material in the step (3) is dripped into the reaction kettle for 5.5 hours.
The rest is the same as example 1.
Test examples
The adhesives obtained in examples 1-6 and comparative examples 1 and 2 were subjected to performance tests, and the results are shown in tables 1 and 2.
Wherein, the solid content refers to GB/T2793-1995, the glass transition temperature Tg adopts a DSC method, the viscosity, the freeze-thaw stability and the mechanical stability refer to GB/T11175-2002, and the peel strength refers to GB/T2792-1998.
The method for detecting the viscosity retention property comprises the following steps:
1. test strip instrument
(1) Holding the adhesion tester: the device consists of a base, a bracket for hanging and fixing a test board and a gravity timing switch. The working face of the test panel was held in a vertical orientation.
(2) Test panel: the selection and treatment of the test plate are required to generate the adhesive force, and the test plate is 2-3.5 mm thick, 60-65 mm wide and 80-100 mm long. The test plate is made of stainless steel.
(3) Standard press rolls: the press roll was a rubber coated steel wheel of about 84mm diameter (excluding the rubber layer) and about 60mm width, the mass of the rubber coated hard press roll being 1000g + -10 g.
(4) Weight: 1000 g. + -. 5g
2. Test procedure
2-1: 6 samples (8-10 g of dry glue per square meter) with the size of 5mm by 7.5mm are cut according to the standard. The sample is placed at the center of two test steel plates, and under the condition of not applying pressure, the grid cloth sample is uniformly rolled and stuck within an area range of 5mm multiplied by 7.5mm by the weight of a compression roller.
2-2: the sample was rolled back and forth three times lengthwise from the area of the stick test. Speed 200 mm/min.
2-3: the test sample is stuck on a plate and placed, then the weight is hung at the position of a connected sample hook, the whole test stand is arranged under the test environment adjusted to the required test environment, and the test starting time is recorded.
2-4: and recording the time for the sample to fall off from the test plate, wherein the time is more than or equal to 1h, min is taken as a unit, and s is taken as a unit less than 1 h.
2-5: the test is carried out at the temperature of-10 ℃, 25 ℃, 35 ℃, 40 ℃ and the relative humidity of 65% +/-5%.
TABLE 1 Performance index
Note: "- -" indicates an unmeasured item.
TABLE 2 Hold-tack Performance at different temperatures
The adhesive of embodiments 1-6 has high solid content, high viscosity, excellent viscosity-holding performance, high peel strength, and excellent mechanical stability, chemical stability, and alternating temperature resistance. Examples 4, 5 and 6, in which the monomer was modified, were better than examples 1 to 3 in each property, and in examples 4 and 5, compared with example 6, the nano aluminum silicate and the nano silica sol were omitted, respectively, and the properties of examples 4 and 5 were slightly inferior to example 6. Comparative examples 1 and 2 were prepared by adjusting the dropping rate in step (3) of the preparation process, and the respective properties were remarkably deteriorated.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (10)
1. The compound type glass fiber mesh cloth tackifying adhesive is characterized by being prepared from the following raw materials: the composite material comprises a monomer, a functional monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a chain transfer agent, a pH regulator and deionized water, wherein the total weight percentage of the raw materials is 100%; wherein the monomers comprise acrylate soft monomers and acrylate hard monomers, and the dosage of the acrylate soft monomers and the acrylate hard monomers is 42-48% and 6-12% of the total weight of the raw materials in sequence; the dosage of the functional monomer, the anionic emulsifier, the nonionic emulsifier, the initiator and the chain transfer agent is 1-2.5%, 0.5-1.2%, 0.1-0.2%, 0.2-0.5% and 0.01-0.05% of the weight of the monomer in sequence, and the pH regulator is dripped in the form of aqueous solution to regulate the pH value to 8.4-8.6.
2. The compound type glass fiber mesh fabric tackifying adhesive as claimed in claim 1, wherein the acrylate soft monomers comprise, by mass, 3: 57: 100 of ethyl acrylate, butyl acrylate and isooctyl acrylate, wherein the acrylic ester hard monomer comprises the following components in a mass ratio of 1.8-2: 1, and the functional monomer comprises the following components in a mass ratio of 1.8-2: 5.5: 2.5-2.7: 1-1.5 of acrylamide, acrylic acid, hydroxyethyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid, wherein the anionic emulsifier comprises the following components in a mass ratio of 1.1: 0.5-0.9: 0.7-1.4 of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and disodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester, wherein the nonionic emulsifier comprises the following components in a mass ratio of 0.3-0.5: 0.2-0.4 of polyoxyethylene octyl phenol ether and ethyl phenyl polyethylene glycol, wherein the initiator comprises the following components in a mass ratio of 1.3-2.7: 0.4-1.4 of ammonium persulfate and sodium persulfate, wherein the chain transfer agent is n-dodecyl mercaptan, and the pH regulator is sodium hydroxide.
3. The compound fiberglass gridding cloth tackifying adhesive according to claim 1, wherein the monomer is modified by the specific method comprising the following steps: adding nano lanthanum hexaboride, nano chromium oxide and nano aluminum silicate into toluene, performing ultrasonic dispersion treatment for 20-30 minutes, adding methacryloxypropyltrimethoxysilane, continuing the ultrasonic dispersion treatment for 5-8 minutes, reacting at 85-95 ℃ for 6-8 hours, cooling to room temperature, centrifuging, drying to obtain an organic modified nano material, mixing the organic modified nano material with nano silicon dioxide sol and a monomer, and performing ultrasonic dispersion for 25-35 minutes to realize the modification treatment on the monomer.
4. The composite glass fiber mesh fabric tackifying adhesive as claimed in claim 3, wherein the mass ratio of the nano lanthanum hexaboride, the nano chromium oxide, the nano aluminum silicate, the toluene, the methacryloxypropyl trimethoxy silane, the nano silica sol with the mass concentration of 10% to the monomers is 0.02-0.03: 0.03 to 0.04: 0.01-0.02: 1.5-2: 0.1-0.15: 0.05-0.08: 100.
5. the composite glass fiber mesh fabric tackifying adhesive according to claim 4, wherein the nano silica sol is prepared by the following method: ethanol, deionized water, ethyl orthosilicate and concentrated ammonia water with the mass concentration of 28% are mixed according to the volume ratio of 250: 20: 55: 1.7, stirring uniformly, heating to 63 ℃ for reaction for 5 hours, removing ethanol by rotary evaporation, filtering by using 0.22 mu m filter paper, adding deionized water, and mixing to prepare the nano silicon dioxide sol with the mass concentration of 10%.
6. The preparation process of the composite glass fiber mesh fabric tackifying adhesive as claimed in any one of claims 1 to 5, which is characterized by comprising the following specific steps:
(1) firstly, adding 1/3-1/2 formula amount of deionized water, 1/3-1/2 formula amount of anionic emulsifier, and formula amount of nonionic emulsifier, monomer and functional monomer into an emulsifying kettle, and fully emulsifying to obtain a pre-emulsified material;
(2) adding the rest amount of deionized water and the anionic emulsifier into the reaction kettle, heating to 82-88 ℃, adding 1/4 volume of the pre-emulsified material obtained in the step (1) into the reaction kettle, and carrying out heat preservation reaction for 5 minutes;
(3) dropwise adding the rest pre-emulsified material into the reaction kettle within 4-5 hours, and reacting for 1 hour under heat preservation;
(4) and finally, removing residual monomers, cooling to 45 ℃, and adding 0.5mol/L sodium hydroxide solution to adjust the pH value to obtain the compound fiberglass mesh fabric tackifying adhesive.
7. The preparation process according to claim 6, wherein in the step (1), the monomer is fed in a continuous dropwise manner, and the dropwise addition time is 30-40 minutes.
8. The preparation process according to claim 6, wherein in the step (1), after the feeding is finished, the high-speed shearing is carried out at 10000-12000 rpm for 10-15 minutes.
9. The process according to claim 6, wherein in step (4), the elimination of residual monomers is carried out by a boiling method, in particular by nitrogen boiling.
10. The application of the adhesive of any one of claims 1-5 in composite glass fiber mesh cloth.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113699794A (en) * | 2020-05-21 | 2021-11-26 | 南通碧辉石业有限公司 | Modification method for toughened marble back-adhered fiber mesh cloth |
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| US4845149A (en) * | 1986-08-22 | 1989-07-04 | S. C. Johnson & Son, Inc. | Pressure sensitive adhesive compositions |
| CN1715228A (en) * | 2004-06-14 | 2006-01-04 | 日信化学工业株式会社 | Glass fiber adhesive composition and glass fiber felt |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| US20180142118A1 (en) * | 2016-11-22 | 2018-05-24 | Nan Ya Plastics Corporation | Low-voc-emission waterborne coating having high hardness and good adhesion and process for producing the same |
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| JPS60226433A (en) * | 1984-04-24 | 1985-11-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Water-based binder for glass fiber |
| US4845149A (en) * | 1986-08-22 | 1989-07-04 | S. C. Johnson & Son, Inc. | Pressure sensitive adhesive compositions |
| CN1715228A (en) * | 2004-06-14 | 2006-01-04 | 日信化学工业株式会社 | Glass fiber adhesive composition and glass fiber felt |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| US20180142118A1 (en) * | 2016-11-22 | 2018-05-24 | Nan Ya Plastics Corporation | Low-voc-emission waterborne coating having high hardness and good adhesion and process for producing the same |
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| CN113699794A (en) * | 2020-05-21 | 2021-11-26 | 南通碧辉石业有限公司 | Modification method for toughened marble back-adhered fiber mesh cloth |
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