CN117165224B - Composite binder and preparation method thereof - Google Patents
Composite binder and preparation method thereof Download PDFInfo
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- CN117165224B CN117165224B CN202310924491.8A CN202310924491A CN117165224B CN 117165224 B CN117165224 B CN 117165224B CN 202310924491 A CN202310924491 A CN 202310924491A CN 117165224 B CN117165224 B CN 117165224B
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- microcrystalline cellulose
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- silicon dioxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011230 binding agent Substances 0.000 title description 16
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 106
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 106
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 106
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004814 polyurethane Substances 0.000 claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 claims abstract description 51
- 239000000853 adhesive Substances 0.000 claims abstract description 49
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 40
- -1 acrylic ester Chemical class 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims abstract description 29
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims abstract description 14
- 229940107700 pyruvic acid Drugs 0.000 claims abstract description 14
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000005543 nano-size silicon particle Substances 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- LQKWPGAPADIOSS-UHFFFAOYSA-N bis(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 LQKWPGAPADIOSS-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 102100026735 Coagulation factor VIII Human genes 0.000 claims description 9
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 7
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims description 6
- 229940041290 mannose Drugs 0.000 claims description 6
- 229960004063 propylene glycol Drugs 0.000 claims description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000006011 modification reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000003522 acrylic cement Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of adhesive preparation, and particularly discloses a composite adhesive and a preparation method thereof, wherein the composite adhesive comprises the following components in parts by weight: modified polyurethane: 20-30 parts of vinyl acetate-acrylic composite emulsion: 70-90 parts of mannose: 0.5-1 part of pyruvic acid: 0.2-0.5 part of propylene glycol: 2-5 parts of microcrystalline cellulose compound: 5-10 parts; the microcrystalline cellulose compound is a compound obtained by the modification reaction of nano microcrystalline cellulose after sulfonation treatment and modified silicon dioxide; the modified polyurethane is a compound obtained by modifying polyurethane through acrylic ester; the invention realizes the enhancement of the adhesiveness of the composite adhesive by adding the modified polyurethane and the microcrystalline cellulose compound.
Description
Technical Field
The invention belongs to the technical field of adhesive preparation, and particularly relates to a composite adhesive and a preparation method thereof.
Background
The adhesive is an important medium for bonding objects, and the acrylic adhesive is widely applied to life due to the excellent performance, and has the following advantages with other adhesives: 1. the acrylic acid ester adhesive is a saturated compound, is not easy to hydrolyze, and has good weather resistance, light resistance and oxidation resistance; 2. the acrylic adhesive has simple formula and little environmental pollution; however, since the adhesive properties and the adhesive film strength of the acrylic adhesive are smaller than those of the solvent-type resin adhesive, there is a need in the market for an acrylic adhesive having high adhesive properties.
The acrylic adhesive can realize the improvement of the adhesiveness by being matched with polyurethane and doping inorganic material particles or fibers; polyurethane and acrylic ester can realize the improvement of the performance of the adhesive through the reaction of the functional groups; the inorganic particles have extremely large specific surface area, surface atoms of the inorganic particles have unsaturation and high surface activity, and the performance of the adhesive can be enhanced.
Disclosure of Invention
Aiming at the situation, the invention provides a composite adhesive and a preparation method thereof for overcoming the defects of the prior art, and the invention provides a technical effect of enhancing the adhesive force of the composite adhesive by adding modified polyurethane and microcrystalline cellulose compound for solving the problem of poor adhesive force of the adhesive.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a composite binder, which comprises the following components in parts by weight: modified polyurethane: 20-30 parts of vinyl acetate-acrylic composite emulsion: 70-90 parts of mannose: 0.5-1 part of pyruvic acid: 0.2-0.5 part of propylene glycol: 2-5 parts of microcrystalline cellulose compound: 5-10 parts.
The vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 98-99 parts of polyvinyl alcohol: 0.2-0.5 part of sodium dodecyl benzene sulfonate: 0.5-0.8 part of diisobutyl terephthalate: 0.005-0.015 part of BYK-025:0.05-0.1 part of nipagin ester: 0.01-0.03 part of sodium persulfate: 0.01-0.03 part of tertiary dodecyl mercaptan: 0.01-0.03 parts.
The preparation method of the vinyl acetate-acrylic composite emulsion comprises the following specific steps:
weighing water and polyvinyl alcohol, adding the water and the polyvinyl alcohol into a reaction kettle, dissolving the polyvinyl alcohol in the water with the addition amount of 0.6-0.75g/mL under the stirring speed of 50 ℃ and 80r/min, heating to 60-65 ℃, adding sodium dodecyl benzene sulfonate, heating to 75 ℃, adding sodium persulfate, adding 60% of vinyl acetate-acrylic emulsion under the stirring speed of 80-100r/min, heating under reflux at 90-95 ℃, adding tert-dodecyl mercaptan, preserving heat for 0.5h, adding diisobutyl terephthalate, BYK-025 and nipagin ester under the stirring speed of 80-120r/min, and cooling to obtain the vinyl acetate-acrylic composite emulsion.
The microcrystalline cellulose compound is a compound obtained by the reaction of nano microcrystalline cellulose after sulfonation treatment and modified silicon dioxide;
the preparation method of the microcrystalline cellulose composite comprises the following specific steps:
(1) weighing microcrystalline cellulose, adding the microcrystalline cellulose into a sulfuric acid solution with the volume fraction of 40%, heating and stirring for reaction, adjusting the pH to 7, washing, and drying in vacuum to obtain pretreated microcrystalline cellulose;
(2) weighing the pretreated microcrystalline cellulose obtained in the step (1), adding the pretreated microcrystalline cellulose into N, N-dimethylformamide, adding a sulfur trioxide-pyridine compound, stirring and heating, adjusting the pH to 7, cleaning by using absolute ethyl alcohol, and drying in vacuum to obtain sulfonated microcrystalline cellulose;
(3) weighing nano silicon dioxide, adding NMP (n-methylpyrrolidone), wherein the addition amount of the nano silicon dioxide in the NMP is 1g/mL, adopting 400W ultrasonic dispersion for 30min, adding APTES which is diluted by the NMP and has the mass fraction of 10%, adopting 400W ultrasonic dispersion for 10min, condensing, refluxing and heating under the protection of nitrogen, carrying out centrifugal precipitation after reaction, wherein the centrifugal rotation speed is 3500-3600r/min, the centrifugal treatment time is 15min, obtaining nano silicon dioxide precipitation, adopting absolute ethyl alcohol to wash the nano silicon dioxide precipitation, adopting the feed liquid ratio of the nano silicon dioxide to the absolute ethyl alcohol to be 1:3, and carrying out vacuum drying and grinding to obtain modified silicon dioxide;
(4) weighing the sulfonated microcrystalline cellulose obtained in the step (2), adding the sulfonated microcrystalline cellulose into N, N-dimethylformamide, adding the modified silicon dioxide obtained in the step (3), adopting 350W ultrasonic for 30min at the temperature of 35-40 ℃, filtering, removing the solvent, drying in vacuum for 20-24h at the temperature of 25-30 ℃, and grinding to obtain the microcrystalline cellulose compound.
Preferably, in the step (1), the microcrystalline cellulose is added to the sulfuric acid solution in an amount of 0.13 to 0.15g/mL; heating at 30-35 deg.c and stirring at 80-120r/min for 5-6 hr; vacuum drying at 50-60deg.C for 4 hr;
preferably, in step (2), the pretreated microcrystalline cellulose is added to the N, N-dimethylformamide in an amount of 0.5 to 0.7g/mL; the mass ratio of the pretreated microcrystalline cellulose to the sulfur trioxide-pyridine compound is 1:5-7, the heating temperature is 40-45 ℃, the stirring speed is 120-150r/min, and the reaction time is 3-3.5h; vacuum drying temperature is 25-30deg.C, drying time is 10-12h;
preferably, in the step (3), the mass ratio of APTES to nano microcrystalline cellulose is 1:1-2; reflux heating temperature is 30-35 ℃, and reaction time is 6-7h; the vacuum drying temperature is 40-45 ℃, and the vacuum drying time is 12h.
The modified polyurethane is a compound obtained by modifying polyurethane through acrylic ester;
the specific steps for preparing the modified polyurethane comprise:
(1) Weighing IPDI (isophorone diisocyanate), dibutyl tin dilaurate and tetrahydrofuran, adding into a three-neck flask, mixing well, adding polyoxypropylene triol, stirring in an oil bath, and heating to obtain a prepolymer;
(2) And (3) adding HEMA (polyhydroxyethyl methacrylate) into the prepolymer obtained in the step (1), stirring and heating in an oil bath, and removing the solvent to obtain the modified polyurethane.
Preferably, in the step (1), the adding amount of the IPDI in the tetrahydrofuran is 0.8-0.85g/mL, the mass ratio of the IPDI to the dibutyltin dilaurate is 83-84:1, and the mass ratio of the polyoxypropylene triol to the IPDI is 3:1; the heating temperature of the oil bath is 68-70 ℃, the stirring speed is 100-120r/min, and the reaction time is 3-4h;
preferably, in the step (2), the mass ratio of the prepolymer to HEMA is 5:1, the heating temperature of an oil bath is 68-70 ℃, the stirring speed is 80-100r/min, and the reaction time is 2h.
The invention also provides a preparation method of the composite binder, which specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 30-35 ℃ at the stirring speed of 100-120r/min to obtain the composite adhesive.
The beneficial effects obtained by the invention are as follows:
the invention realizes the enhancement of the adhesiveness of the composite adhesive by adding the modified polyurethane and the microcrystalline cellulose compound; the nano silicon dioxide is modified by APTES, the APTES contains a plurality of siloxane functional groups and is subjected to condensation reaction with the nano silicon dioxide, so that the hydroxyl number on the surface of the nano silicon dioxide is reduced, the degree of organization is increased, after microcrystalline cellulose is sulfonated, sulfonic acid groups are introduced into the surface of the microcrystalline cellulose, hydrogen bonds are formed between the sulfonic acid groups and the hydroxyl groups on the surface of the modified silicon dioxide, stronger intermolecular force is generated, and the modified silicon dioxide is tightly combined on the sulfonated microcrystalline cellulose to form a microcrystalline cellulose compound; the introduction of APTES on modified silica causes microcrystalline cellulose complex to contain-NH 2 Can react with end group-NCO on polyurethane molecular chain, enhance compatibility between microcrystalline cellulose compound and polyurethane, and increase polymerizationThe crosslinking density of urethane improves the cohesiveness; the microcrystalline cellulose compound is used as a nano material, has extremely large specific surface area and extremely high surface activity, contains modified silicon dioxide, has relatively strong rigidity, and can turn or deflect when a crack is expanded to the microcrystalline cellulose compound in the binder, the crack expansion consumes relatively better energy, the binder is not easy to crack, and the adhesiveness is remarkably enhanced; the microcrystalline cellulose compound can play a role in filling and reinforcing in the adhesive, the density of the adhesive is increased, the intermolecular acting force is reinforced, and the adhesiveness of the adhesive is enhanced; the polyurethane is modified by acrylic ester, the-OH on the polyoxypropylene triol reacts with the-NCO on the isocyanate, a crosslinking structure is introduced into the polyurethane, and the adhesiveness of the modified polyurethane is further enhanced.
Drawings
FIG. 1 is a graph showing the adhesive force results of a composite adhesive and a method for preparing the same;
FIG. 2 is an infrared analysis chart of the microcrystalline cellulose composite obtained in example 1 of the present invention;
FIG. 3 is a flow chart showing the preparation of the modified polyurethane obtained in example 1 of the present invention;
the accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were purchased from commercial sources.
Mannose (CasNo: 69-65-8), available from Beijing enokie technologies Co., ltd., cat# A31968;
pyruvic acid (CasNo: 127-17-3), available from Beijing enokie technologies Co., ltd., cat# A80250;
propylene glycol (CasNo: 57-55-6), available from Beijing enokie technologies Co., ltd., product number A58153;
APTES (CasNo: 919-30-2), available from Beijing Inocai technologies Co., ltd., cat# B51760;
nanocrystalline cellulose (CasNo: 9004-34-6), available from Beijing Inock technologies Co., ltd., cat# A00472;
IPDI (CasNo: 4098-71-9), available from Beijing Inock technologies Co., ltd., cat# A20846;
dibutyl tin dilaurate (CasNo: 77-58-7), available from Beijing Inocai technologies Co., ltd., cat# A77457;
tetrahydrofuran (CasNo: 109-99-9), available from Beijing enokie technologies Co., ltd., product number T2806;
polyoxypropylene triol (CasNo. 25791-96-2), available from Shanghai Michelin Biochemical technology Co., ltd., product number P859203-2.5L;
HEMA (CasNo: 25249-16-5), available from Beijing Inockai technologies Co., ltd., product number B24739;
NMP (CasNo: 872-50-4), available from Beijing enokie technologies Co., ltd., cat# A28738;
absolute ethyl alcohol (CasNo. 64-17-5), available from Beijing enokie technologies Co., ltd., product number G00004;
vinyl acetate-acrylic emulsion (CasNo: 1595290-47-3), available from Shanghai Michelia Biochemical technology Co., ltd., product No. N905568-100mg;
polyvinyl alcohol (CasNo: 9002-89-5), commercially available from Beijing Inock technologies Co., ltd., cat# B20621;
sodium dodecyl benzene sulfonate (CasNo. 25155-30-0), available from Beijing Enoka technologies Co., ltd., product number A56225;
diisobutyl terephthalate (CasNo: 18699-48-4), available from Beijing Inocai technologies Co., ltd., product number D894170-100mg;
nipagin ester (CasNo. 120-47-8), available from Beijing Inocai technologies Co., ltd., cat# A87092;
sodium persulfate (CasNo. 7775-27-1), available from Beijing Inocai technologies Co., ltd., product No. A07130;
tert-dodecyl mercaptan (CasNo: 25103-58-6), available from Shanghai Milin Biochemical technology Co., ltd., product number D807076-2.5L.
Example 1
The composite adhesive comprises the following components in parts by weight: modified polyurethane: 20 parts of vinyl acetate-acrylic composite emulsion: 70 parts of mannose: 0.5 part of pyruvic acid: 0.2 parts of propylene glycol: 2 parts of microcrystalline cellulose complex: 5 parts.
The vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 98 parts of polyvinyl alcohol: 0.2 part of sodium dodecyl benzene sulfonate: 0.5 parts of diisobutyl terephthalate: 0.005 part of BYK-025:0.05 parts of nipagin ester: 0.01 part of sodium persulfate: 0.01 part of tertiary dodecyl mercaptan: 0.01 part.
The preparation method of the vinyl acetate-acrylic composite emulsion comprises the following specific steps:
weighing water and polyvinyl alcohol, adding the water and the polyvinyl alcohol into a reaction kettle, dissolving the polyvinyl alcohol in the water with the addition amount of 0.6g/mL under the stirring speed of 50 ℃ and 80r/min, heating to 60 ℃, adding sodium dodecyl benzene sulfonate, heating to 75 ℃, adding sodium persulfate, adding 60% by mass of vinyl acetate-acrylic emulsion under the stirring speed of 80r/min, heating under reflux at 90 ℃, adding tertiary dodecyl mercaptan, preserving heat for 0.5h, adding diisobutyl terephthalate, BYK-025 and nipagin ester under the stirring speed of 80r/min, and cooling to obtain the vinyl acetate-acrylic composite emulsion.
The microcrystalline cellulose compound is a compound obtained by the modification reaction of nano microcrystalline cellulose after sulfonation treatment and modified silicon dioxide;
the preparation method of the microcrystalline cellulose composite comprises the following specific steps:
(1) weighing microcrystalline cellulose, adding the microcrystalline cellulose into a sulfuric acid solution with the volume fraction of 40%, reacting for 5 hours under the conditions that the heating temperature is 30 ℃ and the stirring speed is 80r/min, adjusting the pH value to be 7, washing, and vacuum drying at 50 ℃ for 4 hours to obtain pretreated microcrystalline cellulose;
(2) weighing pretreated microcrystalline cellulose obtained in the step (1), adding the pretreated microcrystalline cellulose into N, N-dimethylformamide, wherein the adding amount of the pretreated microcrystalline cellulose in the N, N-dimethylformamide is 0.5g/mL, adding a sulfur trioxide-pyridine compound, enabling the mass ratio of the pretreated microcrystalline cellulose to the sulfur trioxide-pyridine compound to be 1:5, reacting for 3h under the condition that the heating temperature is 40 ℃ and the stirring speed is 120r/min, adjusting the pH to 7, cleaning by using absolute ethyl alcohol, and drying for 10h at 25 ℃ to obtain sulfonated microcrystalline cellulose;
(3) weighing nano silicon dioxide, adding NMP (n-methylpyrrolidone), wherein the addition amount of the nano silicon dioxide in the NMP is 1g/mL, adopting 400W ultrasonic dispersion for 30min, adding APTES which is diluted by the NMP and has the mass fraction of 10%, adopting the mass ratio of APTES to nano microcrystalline cellulose to be 1:1, adopting 400W ultrasonic dispersion for 10min, condensing, refluxing and heating under the protection of nitrogen, carrying out reflux heating reaction for 6h at 30 ℃, carrying out centrifugal precipitation after the reaction, adopting the centrifugal rotation speed of 3500r/min, adopting the centrifugal treatment time of 15min to obtain nano silicon dioxide precipitation, adopting absolute ethyl alcohol to wash the nano silicon dioxide precipitation, adopting the feed liquid ratio of the nano silicon dioxide to the absolute ethyl alcohol to be 1:3, carrying out vacuum drying for 12h at 40 ℃, and grinding to obtain modified silicon dioxide;
(4) weighing the sulfonated microcrystalline cellulose obtained in the step (2), adding the sulfonated microcrystalline cellulose into N, N-dimethylformamide, adding the modified silicon dioxide obtained in the step (3), adopting 350W ultrasound at 35 ℃ for 30min, filtering, removing the solvent, drying in vacuum at 25 ℃ for 20h, and grinding to obtain the microcrystalline cellulose compound.
The modified polyurethane is a compound obtained by modifying polyurethane through acrylic ester;
the specific steps for preparing the modified polyurethane comprise:
(1) Weighing IPDI, dibutyl tin dilaurate and tetrahydrofuran, adding the IPDI, the dibutyl tin dilaurate and the tetrahydrofuran into a three-neck flask, uniformly mixing, wherein the adding amount of the IPDI in the tetrahydrofuran is 0.8g/mL, the mass ratio of the IPDI to the dibutyl tin dilaurate is 83:1, adding polypropylene glycol, the mass ratio of the polypropylene glycol to the IPDI is 2:1, and reacting for 3 hours under the condition that the heating temperature of an oil bath is 68 ℃ and the stirring speed is 100r/min to obtain a prepolymer;
(2) Adding HEMA into the prepolymer obtained in the step (1), reacting for 2 hours under the conditions that the heating temperature of an oil bath is 68 ℃ and the stirring speed is 80r/min, and removing the solvent to obtain the modified polyurethane, wherein the mass ratio of the prepolymer to the HEMA is 5:1.
The invention also provides a preparation method of the composite binder, which specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 30 ℃ at the stirring speed of 100r/min to obtain the composite adhesive.
Example 2
The composite adhesive comprises the following components in parts by weight: modified polyurethane: 20 parts of vinyl acetate-acrylic composite emulsion: 70 parts of mannose: 0.5 part of pyruvic acid: 0.2 parts of propylene glycol: 2 parts of microcrystalline cellulose complex: 5 parts.
The vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 99 parts of polyvinyl alcohol: 0.5 part of sodium dodecyl benzene sulfonate: 0.8 parts of diisobutyl terephthalate: 0.015 part of BYK-025:0.1 part of nipagin ester: 0.03 parts of sodium persulfate: 0.03 parts of tert-dodecyl mercaptan: 0.03 parts.
The preparation method of the vinyl acetate-acrylic composite emulsion comprises the following specific steps:
weighing water and polyvinyl alcohol, adding the water and the polyvinyl alcohol into a reaction kettle, dissolving the polyvinyl alcohol in the water with the addition amount of 0.75g/mL under the stirring speed of 50 ℃ and 80r/min, heating to 65 ℃, adding sodium dodecyl benzene sulfonate, heating to 75 ℃, adding sodium persulfate, adding 60% by mass of vinyl acetate-acrylic emulsion under the stirring speed of 100r/min, refluxing and heating at 95 ℃, adding tertiary dodecyl mercaptan, preserving heat for 0.5h, adding diisobutyl terephthalate, BYK-025 and nipagin ester under the stirring speed of 120r/min, and cooling to obtain the vinyl acetate-acrylic composite emulsion.
The microcrystalline cellulose compound is a compound obtained by the modification reaction of nano microcrystalline cellulose after sulfonation treatment and modified silicon dioxide;
the preparation method of the microcrystalline cellulose composite comprises the following specific steps:
(1) weighing microcrystalline cellulose, adding the microcrystalline cellulose into a sulfuric acid solution with the volume fraction of 40%, reacting for 6 hours under the conditions that the heating temperature is 35 ℃ and the stirring speed is 120r/min, adjusting the pH value to be 7, washing, and vacuum drying at 60 ℃ for 4 hours to obtain pretreated microcrystalline cellulose;
(2) weighing pretreated microcrystalline cellulose obtained in the step (1), adding the pretreated microcrystalline cellulose into N, N-dimethylformamide, wherein the adding amount of the pretreated microcrystalline cellulose in the N, N-dimethylformamide is 0.7g/mL, adding a sulfur trioxide-pyridine compound, enabling the mass ratio of the pretreated microcrystalline cellulose to the sulfur trioxide-pyridine compound to be 1:7, reacting for 3.5h under the condition that the heating temperature is 45 ℃ and the stirring speed is 150r/min, adjusting the pH to 7, adopting absolute ethyl alcohol for cleaning, and carrying out vacuum drying at 30 ℃ for 12h to obtain sulfonated microcrystalline cellulose;
(3) weighing nano silicon dioxide, adding NMP (n-methylpyrrolidone), wherein the addition amount of the nano silicon dioxide in the NMP is 1g/mL, adopting 400W ultrasonic dispersion for 30min, adding APTES which is diluted by the NMP and has the mass fraction of 10%, adopting the mass ratio of APTES to nano microcrystalline cellulose to be 1:2, adopting 400W ultrasonic dispersion for 10min, condensing, refluxing and heating under the protection of nitrogen, refluxing and heating for 7h at 35 ℃, carrying out centrifugal precipitation after reaction, wherein the centrifugal rotating speed is 3600r/min, the centrifugal treatment time is 15min, obtaining nano silicon dioxide precipitation, adopting absolute ethyl alcohol to wash the nano silicon dioxide precipitation, adopting the feed liquid ratio of the nano silicon dioxide to the absolute ethyl alcohol to be 1:3, carrying out vacuum drying for 12h at 45 ℃, and grinding to obtain modified silicon dioxide;
(4) weighing the sulfonated microcrystalline cellulose obtained in the step (2), adding the sulfonated microcrystalline cellulose into N, N-dimethylformamide, adding the modified silicon dioxide obtained in the step (3), performing ultrasonic treatment at 40 ℃ for 30min by using 350W, filtering, removing the solvent, performing vacuum drying at 30 ℃ for 24h, and grinding to obtain the microcrystalline cellulose compound.
The modified polyurethane is a compound obtained by modifying polyurethane through acrylic ester;
the specific steps for preparing the modified polyurethane comprise:
(1) Weighing IPDI, dibutyl tin dilaurate and tetrahydrofuran, adding the mixture into a three-neck flask, uniformly mixing, wherein the adding amount of the IPDI in the tetrahydrofuran is 0.85g/mL, the mass ratio of the IPDI to the dibutyl tin dilaurate is 84:1, adding polypropylene glycol, the mass ratio of the polypropylene glycol to the IPDI is 2:1, and reacting for 4 hours under the condition that the heating temperature of an oil bath is 70 ℃ and the stirring speed is 120r/min to obtain a prepolymer;
(2) Adding HEMA into the prepolymer obtained in the step (1), reacting for 2 hours under the conditions that the heating temperature of an oil bath is 70 ℃ and the stirring speed is 100r/min, and removing the solvent to obtain the modified polyurethane, wherein the mass ratio of the prepolymer to the HEMA is 5:1.
The invention also provides a preparation method of the composite binder, which specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 35 ℃ at the stirring speed of 120r/min to obtain the composite adhesive.
Example 3
The composite adhesive comprises the following components in parts by weight: modified polyurethane: 30 parts of vinyl acetate-acrylic composite emulsion: 90 parts of mannose: 1 part of pyruvic acid: 0.5 part of propylene glycol: 5 parts of microcrystalline cellulose complex: 10 parts.
The vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 98 parts of polyvinyl alcohol: 0.2 part of sodium dodecyl benzene sulfonate: 0.5 parts of diisobutyl terephthalate: 0.005 part of BYK-025:0.05 parts of nipagin ester: 0.01 part of sodium persulfate: 0.01 part of tertiary dodecyl mercaptan: 0.01 part.
The specific steps for preparing the vinyl acetate-acrylic composite emulsion are the same as those of the embodiment 1;
the specific procedure for the preparation of the microcrystalline cellulose composite was the same as in example 1;
the specific procedure for the preparation of the modified polyurethane was the same as in example 1;
the invention also provides a preparation method of the composite binder, which specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 30 ℃ at the stirring speed of 100r/min to obtain the composite adhesive.
Example 4
The composite adhesive comprises the following components in parts by weight: modified polyurethane: 30 parts of vinyl acetate-acrylic composite emulsion: 90 parts of mannose: 1 part of pyruvic acid: 0.5 part of propylene glycol: 5 parts of microcrystalline cellulose complex: 10 parts.
The vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 99 parts of polyvinyl alcohol: 0.5 part of sodium dodecyl benzene sulfonate: 0.8 parts of diisobutyl terephthalate: 0.015 part of BYK-025:0.1 part of nipagin ester: 0.03 parts of sodium persulfate: 0.03 parts of tert-dodecyl mercaptan: 0.03 parts.
The specific steps for preparing the vinyl acetate-acrylic composite emulsion are the same as those of the embodiment 2;
the specific procedure for the preparation of the microcrystalline cellulose composite was the same as in example 2;
the specific procedure for the preparation of the modified polyurethane was the same as in example 2;
the invention also provides a preparation method of the composite binder, which specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 35 ℃ at the stirring speed of 120r/min to obtain the composite adhesive.
Comparative example 1
This comparative example provides a composite binder and a method for preparing the same, which is different from example 1 only in that microcrystalline cellulose complex is not included in all components, and the remaining components and the content of components are the same as in example 1.
Comparative example 2
This comparative example provides a composite adhesive and a method for preparing the same, which is different from example 1 only in that modified polyurethane is not contained in all components, and the remaining components and the content of components are the same as example 1.
Experimental example
1. Adhesion Strength experiment
Samples of examples 1-4 and comparative examples 1-2 were taken at 150g/m on a set of (2) boards of the same gauge 2 Coating, namely, superposing and compacting two contact surfaces of a wood board, wherein the specification of the contact surfaces of the wood board is 100 mm-30 mm, applying 1Mpa pressure to the contact surfaces, assembling for 12 hours at room temperature, releasing the pressure, then standing for 12 hours, performing a strength test at room temperature, and recording test results.
2. Infrared analysis
The microstructure of the modified polyurethane obtained in example 1 of the present invention was characterized by KBr method on a Fourier infrared spectrometer, and the modified polyurethane was coated on a potassium bromide sheet with a scanning range of 500-4000cm -1 Resolution of 4cm -1 。
3. Stability test
The storage stability of the binders obtained in examples 1-4 and comparative examples 1-2 according to the present invention was verified by a centrifugal acceleration sedimentation test, specifically by the following procedure: weighing 8g of the adhesive obtained in the examples 1-4 and the comparative examples 1-2 of the invention into a 10mL centrifuge tube, placing the centrifuge tube filled with the adhesive into a high-speed centrifuge, centrifuging for 15min at a rotating speed of 3000r/min, and observing the deposition condition of the adhesive; if no precipitate is formed, the binder is considered to be stable for up to 6 months.
TABLE 1
Analysis of results
FIG. 1 is a graph showing the results of the bonding strength of a composite adhesive according to the present invention, wherein the bonding strength of examples 1-4 is greater than 25MPa, the bonding strength of comparative example 1 is only 21MPa, and the bonding strength of comparative example 2 is only 18MPa; compared with comparative example 1, the nano silicon dioxide is modified by APTES, a siloxane functional group on the APTES and hydroxyl on the surface of the nano silicon dioxide are subjected to condensation reaction, so that the hydroxyl number on the surface of the nano silicon dioxide is reduced, the degree of organization is increased, APTES is introduced into the surface of the nano silicon dioxide, after the microcrystalline cellulose is sulfonated, sulfonic acid groups are introduced into the surface of the microcrystalline cellulose, hydrogen bonds are formed between the sulfonic acid groups and the hydroxyl on the surface of the modified silicon dioxide, stronger intermolecular force is generated, and the modified silicon dioxide is tightly combined on the sulfonated microcrystalline cellulose to form a microcrystalline cellulose compound; the introduction of APTES on modified silica causes microcrystalline cellulose complex to contain-NH 2 The modified polyurethane can react with an end group-NCO on a polyurethane molecular chain, so that the compatibility between a microcrystalline cellulose compound and polyurethane is enhanced, the crosslinking density of the polyurethane is increased, and the cohesiveness is improved; the microcrystalline cellulose compound is used as a nano material, has extremely large specific surface area and extremely high surface activity, contains modified silicon dioxide, has relatively strong rigidity, can effectively prevent crack growth when being added into a binder, and turns or deflects when being expanded to the microcrystalline cellulose compound in the binder, so that the crack growth consumes better energy, the binder is not easy to crack, and the adhesiveness is remarkably enhanced; the microcrystalline cellulose compound can play a role in filling and reinforcing in the adhesive, the density of the adhesive is increased, the intermolecular acting force is reinforced, and the adhesiveness of the adhesive is enhanced; compared with comparative example 2, the polyurethane is modified by acrylic ester, the-OH on the polyoxypropylene triol reacts with the-NCO on the isocyanate, a crosslinking structure is introduced into the polyurethane, the acrylic ester has high adhesiveness, high stability and high weather resistance, the performance of the polyurethane can be effectively improved by adding the acrylic ester, and the adhesiveness of the modified polyurethane is further enhanced.
FIG. 2 shows the present inventionAn infrared analysis chart of the microcrystalline cellulose composite obtained in example 1 was shown, as shown in the figure, 3356cm of the spectrum of the microcrystalline cellulose composite obtained in example 1 -1 The N-H stretching vibration peak appears, 1728cm -1 A stretching vibration peak of c=o, 1545cm, appears -1 C-N stretching vibration peak appears, 1238cm -1 The C-O stretching vibration peak appears at 1248cm -1 The telescopic vibration peak of the sulfonic acid group appears at 910cm -1 The absorption peak is a stretching vibration peak of Si-O at 780cm -1 The absorption peak is a secondary vibration peak of Si-C, which shows that the silane is successfully grafted on the surface of the microcrystalline cellulose; at 3418cm -1 The stretching vibration peak of O-H appears at 2900cm -1 The stretching vibration peak of cellulose C-H is 1186cm -1 C appears at the site 1 -O-C 4 Is 1112cm -1 The expansion vibration peak of the anhydroglucose ring appears at the position of 1056cm -1 C appears at the site 6 -stretching vibration peak of O, according to the above analysis, the desired microcrystalline cellulose complex was successfully prepared.
FIG. 3 is a flow chart showing the preparation of the modified polyurethane obtained in example 1 of the present invention, according to the procedure of the above-mentioned drawing, to obtain a modified polyurethane.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (8)
1. A composite adhesive, characterized in that: the composition specifically comprises the following components in parts by weight: modified polyurethane: 20-30 parts of vinyl acetate-acrylic composite emulsion: 70-90 parts of mannose: 0.5-1 part of pyruvic acid: 0.2-0.5 part of propylene glycol: 2-5 parts of microcrystalline cellulose compound: 5-10 parts; the microcrystalline cellulose compound is a compound obtained by the reaction of nano microcrystalline cellulose after sulfonation treatment and modified silicon dioxide; the modified polyurethane is a compound obtained by modifying polyurethane through acrylic ester;
the preparation method of the microcrystalline cellulose composite comprises the following specific steps:
(1) weighing microcrystalline cellulose, adding the microcrystalline cellulose into a sulfuric acid solution with the volume fraction of 40%, heating and stirring for reaction, adjusting the pH to 7, washing, and drying in vacuum to obtain pretreated microcrystalline cellulose;
(2) weighing the pretreated microcrystalline cellulose obtained in the step (1), adding the pretreated microcrystalline cellulose into N, N-dimethylformamide, adding a sulfur trioxide-pyridine compound, stirring and heating, adjusting the pH to 7, cleaning by using absolute ethyl alcohol, and drying in vacuum to obtain sulfonated microcrystalline cellulose;
(3) weighing nano silicon dioxide, adding NMP, wherein the addition amount of the nano silicon dioxide in the NMP is 1g/mL, adopting 400W ultrasonic dispersion for 30min, adding APTES diluted by NMP and having the mass fraction of 10%, adopting 400W ultrasonic dispersion for 10min, condensing, refluxing and heating under the protection of nitrogen, performing centrifugal precipitation after reaction, wherein the centrifugal rotation speed is 3500-3600r/min, the centrifugal treatment time is 15min, obtaining nano silicon dioxide precipitation, adopting absolute ethyl alcohol to wash the nano silicon dioxide precipitation, the feed liquid ratio of the nano silicon dioxide to the absolute ethyl alcohol is 1:3, and carrying out vacuum drying and grinding to obtain modified silicon dioxide;
(4) weighing the sulfonated microcrystalline cellulose obtained in the step (2), adding the sulfonated microcrystalline cellulose into N, N-dimethylformamide, adding the modified silicon dioxide obtained in the step (3), performing ultrasonic treatment at 35-40 ℃ for 30min by using 350W, filtering, removing the solvent, performing vacuum drying at 25-30 ℃ for 20-24h, and grinding to obtain a microcrystalline cellulose compound;
the specific steps for preparing the modified polyurethane comprise:
(1) Weighing IPDI, dibutyl tin dilaurate and tetrahydrofuran, adding the mixture into a three-neck flask, uniformly mixing, adding polyoxypropylene triol, stirring in an oil bath, and heating to obtain a prepolymer;
(2) And (3) adding HEMA into the prepolymer obtained in the step (1), stirring and heating in an oil bath, and removing the solvent to obtain the modified polyurethane.
2. A composite adhesive according to claim 1, wherein: the vinyl acetate-acrylic composite emulsion comprises the following components in parts by weight: 60% of vinyl acetate-acrylic emulsion: 98-99 parts of polyvinyl alcohol: 0.2-0.5 part of sodium dodecyl benzene sulfonate: 0.5-0.8 part of diisobutyl terephthalate: 0.005-0.015 part of BYK-025:0.05-0.1 part of nipagin ester: 0.01-0.03 part of sodium persulfate: 0.01-0.03 part of tertiary dodecyl mercaptan: 0.01-0.03 parts.
3. A composite adhesive according to claim 2, wherein: the preparation method of the vinyl acetate-acrylic composite emulsion comprises the following specific steps:
weighing water and polyvinyl alcohol, adding the water and the polyvinyl alcohol into a reaction kettle, dissolving the polyvinyl alcohol in the water with the addition amount of 0.6-0.75g/mL under the stirring speed of 50 ℃ and 80r/min, heating to 60-65 ℃, adding sodium dodecyl benzene sulfonate, heating to 75 ℃, adding sodium persulfate, adding 60% of vinyl acetate-acrylic emulsion under the stirring speed of 80-100r/min, heating under reflux at 90-95 ℃, adding tert-dodecyl mercaptan, preserving heat for 0.5h, adding diisobutyl terephthalate, BYK-025 and nipagin ester under the stirring speed of 80-120r/min, and cooling to obtain the vinyl acetate-acrylic composite emulsion.
4. A composite adhesive according to claim 3, wherein: in the step (1), the addition amount of microcrystalline cellulose in the sulfuric acid solution is 0.13-0.15g/mL; heating at 30-35 deg.c and stirring at 80-120r/min for 5-6 hr; the vacuum drying temperature is 50-60 ℃, and the drying is carried out for 4 hours.
5. A composite adhesive according to claim 4, wherein: in the step (2), the addition amount of the pretreated microcrystalline cellulose in the N, N-dimethylformamide is 0.5-0.7g/mL; the mass ratio of the pretreated microcrystalline cellulose to the sulfur trioxide-pyridine compound is 1:5-7, the heating temperature is 40-45 ℃, the stirring speed is 120-150r/min, and the reaction time is 3-3.5h; the vacuum drying temperature is 25-30 ℃ and the drying time is 10-12h.
6. A composite adhesive according to claim 5, wherein: in the step (3), the mass ratio of APTES to nano microcrystalline cellulose is 1:1-2; reflux heating temperature is 30-35 ℃, and reaction time is 6-7h; the vacuum drying temperature is 40-45 ℃, and the vacuum drying time is 12h.
7. A composite adhesive according to claim 6, wherein: in the step (1), the adding amount of the IPDI in tetrahydrofuran is 0.8-0.85g/mL, the mass ratio of the IPDI to the dibutyl tin dilaurate is 83-84:1, and the mass ratio of the polyoxypropylene triol to the IPDI is 3:1; the heating temperature of the oil bath is 68-70 ℃, the stirring speed is 100-120r/min, and the reaction time is 3-4h; in the step (2), the mass ratio of the prepolymer to HEMA is 5:1, the heating temperature of an oil bath is 68-70 ℃, the stirring speed is 80-100r/min, and the reaction time is 2h.
8. A method of preparing a composite adhesive according to any one of claims 1 to 7, wherein: the method specifically comprises the following steps:
mixing the modified polyurethane and the vinyl acetate-acrylic composite emulsion, adding mannose, pyruvic acid, propylene glycol and microcrystalline cellulose composite, and stirring for 1h at 30-35 ℃ at the stirring speed of 100-120r/min to obtain the composite adhesive.
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| CN111363500A (en) * | 2020-04-29 | 2020-07-03 | 佛山市顺德区蓝德堡实业有限公司 | Vinyl acetate-acrylic emulsion adhesive for glass chopped strand mats and preparation method thereof |
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| CN111363500A (en) * | 2020-04-29 | 2020-07-03 | 佛山市顺德区蓝德堡实业有限公司 | Vinyl acetate-acrylic emulsion adhesive for glass chopped strand mats and preparation method thereof |
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