CN117736689A - Solvent-free modified polyurethane adhesive and preparation method thereof - Google Patents
Solvent-free modified polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN117736689A CN117736689A CN202311741540.0A CN202311741540A CN117736689A CN 117736689 A CN117736689 A CN 117736689A CN 202311741540 A CN202311741540 A CN 202311741540A CN 117736689 A CN117736689 A CN 117736689A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 117
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000002156 mixing Methods 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 33
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 13
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims abstract description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- MTYHLWRUYCUTPA-UHFFFAOYSA-L zinc;naphthalene-1-carboxylate Chemical compound [Zn+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 MTYHLWRUYCUTPA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims abstract description 7
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims abstract description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 24
- 239000004115 Sodium Silicate Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 235000010333 potassium nitrate Nutrition 0.000 claims description 14
- 239000004323 potassium nitrate Substances 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- -1 aluminum sulfate octadecanoate hydrate Chemical compound 0.000 claims 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 abstract description 10
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
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- 206010068319 Oropharyngeal pain Diseases 0.000 description 1
- 201000007100 Pharyngitis Diseases 0.000 description 1
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- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a solvent-free modified polyurethane adhesive and a preparation method thereof, and belongs to the technical field of polyurethane adhesives. The preparation of the adhesive comprises the following steps: mixing and heating abietic acid, terephthalic acid and diglycol, and introducing maleic acidAdding zinc naphthalate into anhydride, and reacting to obtain a material A; mixing the material A with polyether glycol, heating and stirring, adding a stabilizer, and grinding to obtain a material B; mixing and reacting the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate to obtain a material C; mixing the material C with epoxy resin, and reacting to obtain a material D; mixing polyether glycol and water absorbent BF-5, filtering, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, stirring, and adding hexahydrophthalic anhydride to obtain a material E; the material D and the material E are mixed according to the mass ratio of 1-1.2:2-4, and obtaining the solvent-free polyurethane adhesive with excellent bonding strength and wear resistance.
Description
Technical Field
The invention belongs to the technical field of polyurethane adhesives, and particularly relates to a solvent-free modified polyurethane adhesive and a preparation method thereof.
Background
At present, composite materials, such as a mixture of rubber particles and adhesives, are commonly used as a base material for paving indoor stadium sites. Constructors can evenly lay the base raw materials on the field, and compact and level by utilizing professional equipment, so that the flatness and compactness of the base are ensured. Wherein the adhesive is mainly solvent polyurethane adhesive.
The polyurethane adhesive is an adhesive containing carbamate groups or isocyanate groups in the molecular chain, and is obtained by reacting isocyanate with hydroxyl-containing compounds or other polyols. The adhesive has the characteristics of excellent performance, strong molecular designability, wide physical property, wide bonding application range and the like, and is one of important varieties in synthetic adhesives. The solvent type polyurethane adhesive has mature technology and shows unique advantages in the field of field paving, but the volatilization of the organic solvent not only wastes resources, but also threatens the environment and the production safety. The organic solvent volatilized into the air is inhaled by human body to cause headache, nausea, sore throat, debilitation and other poisoning symptoms, and long-term contact can cause cancer, teratocarcinoma, damage to liver, kidney, central nerve and the like. Therefore, the preparation of the solvent-free polyurethane adhesive has very important significance.
However, when the solvent-free polyurethane adhesive is paved on an indoor stadium field, the solvent-free polyurethane adhesive is cured by reacting isocyanate with water vapor in the air when the solvent-free polyurethane adhesive is cured. However, the cohesive force of the adhesive is reduced due to the fact that the isocyanate reacts with water, so that the adhesive strength of the solvent-free polyurethane adhesive is poorer than that of the solvent-free polyurethane adhesive, a large amount of loads generated by movement friction such as people flow and balls can be born in the use process of a stadium, the adhesive strength of the solvent-free adhesive is insufficient to resist the action of external force, and the field paving material is cracked and even scrapped very quickly under the action of high-load friction.
Disclosure of Invention
The invention discloses a solvent-free modified polyurethane adhesive and a preparation method thereof, and belongs to the technical field of polyurethane adhesives. The preparation of the adhesive comprises the following steps: mixing and heating abietic acid, terephthalic acid and diglycol, introducing maleic anhydride, adding zinc naphthalate, and reacting to obtain a material A; mixing the material A with polyether glycol, heating and stirring, adding a stabilizer, and grinding to obtain a material B; mixing and reacting the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate to obtain a material C; mixing the material C with epoxy resin, and reacting to obtain a material D; mixing polyether glycol and water absorbent BF-5, stirring, filtering, adding 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, stirring, and adding hexahydrophthalic anhydride to obtain a material E; the material D and the material E are mixed according to the mass ratio of 1-1.2:2-4, and obtaining the solvent-free polyurethane adhesive with excellent bonding strength and wear resistance.
The invention aims to solve the technical problems: the solvent-free polyurethane adhesive with excellent bonding strength and wear resistance is prepared.
The aim of the invention can be achieved by the following technical scheme:
a solvent-free modified polyurethane adhesive and a preparation method thereof are provided, wherein the preparation of the adhesive comprises the following steps:
(1) Mixing abietic acid, terephthalic acid and diglycol in a reaction kettle in a nitrogen atmosphere, heating the reaction kettle to 170-175 ℃ under vacuum condition, introducing maleic anhydride, heating to 220 ℃ for 1-2h, adding zinc naphthalate, heating to 240-250 ℃ for reacting for 7-9h, cooling to 180 ℃ for 1.5-2h, cooling to 100 ℃, discharging to obtain a material A;
(2) Placing the material A and polyether glycol into a mixing kettle, stirring for 1.5-2h at 110-115 ℃, cooling to 45-55 ℃, adding a stabilizer, performing ultrasonic dispersion for 15-25min, and grinding to obtain a material B;
(3) Mixing the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, heating to 65-68 ℃ and stirring for 2-3 hours at constant temperature to obtain a material C;
(4) Mixing the material C and the epoxy resin, stirring for 1-2h, heating to 75 ℃ for reacting for 2-3h, cooling to room temperature to obtain a material D, and sealing for later use;
(5) Placing polyether glycol and water absorbent BF-5 into a material kettle, mixing and stirring for 30-40min, filtering, taking liquid phase, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, stirring for 1-1.5h at 85 ℃, cooling to room temperature, adding hexahydrophthalic anhydride, vacuumizing and sealing for standby to obtain a material E;
(6) The application method comprises the following steps: and (3) mixing the materials D and E according to the mass ratio of 1-1.2:2-4, and rapidly and uniformly stirring and then applying.
As a preferable technical scheme of the invention, in the step (1), the mass ratio of the rosin acid, the terephthalic acid, the diglycol, the maleic anhydride and the zinc naphthalate is 75-110:45-60:150:100-120:2-3; the vacuum refers to the vacuum pumping to the vacuum degree of 40-60kPa.
As a preferable technical scheme of the invention, in the step (2), the mass ratio of the material A to the polyether glycol is 1-2:2-3.
In the step (3), the mass ratio of the material B to the toluene diisocyanate to the 4,4' -diphenylmethane diisocyanate is 5-8:3-4:4-6.
As a preferable technical scheme of the invention, in the step (4), the mass ratio of the material C to the epoxy resin is 1:0.5-0.8.
As a preferable embodiment of the present invention, in the step (5), the polyether glycol, the water absorbing agent BF-5, 3 ′ -dichloro-4, 4 ′ -diaminodiphenylmethane, hexahydrophthalic anhydride in a mass ratio of 2-4:0.4-0.6:0.5-0.7:1-1.2.
As a preferred technical solution of the present invention, the polyether glycol includes at least one of PPG204, PPG210, and PPG 220.
As a preferable technical scheme of the invention, the preparation of the stabilizer comprises the following steps:
s1, weighing cetyl trimethyl ammonium bromide, sodium silicate and deionized water, mixing, and stirring for 0.5-1h to obtain a material F;
s2, weighing sodium silicate, deionized water and silica sol, mixing, adding the mixture into the material F, stirring for 1-2h, adding aluminum sulfate octadecabydrate and ferric nitrate nonahydrate, and stirring for 0.5-1h to obtain a material G;
s3, adjusting the pH value of the material G to 10-11, crystallizing at 150-175 ℃ for 24-36h, washing the crystallized material G with a potassium nitrate solution until the pH value is 8, filtering, taking a solid phase, drying at 60 ℃ for 10-12h, and roasting at 550 ℃ for 8-10h to obtain the stabilizer.
As a preferable technical scheme of the invention, the mass ratio of the cetyl trimethyl ammonium bromide, the sodium silicate weighed in the step S1, the deionized water weighed in the step S1, the sodium silicate weighed in the step S2, the deionized water weighed in the step S2, the silica sol, the aluminum sulfate octadeca hydrate and the ferric nitrate nonahydrate is 0.2-0.4:0.8-1:80-100:0.1-0.2:100-120:1-2:0.54-0.63:0.3-0.4.
As a preferable technical scheme of the invention, the mass fraction of silicon dioxide in the silica sol is 30%; the mass fraction of potassium nitrate in the potassium nitrate solution is 10%.
A polyurethane adhesive prepared by the preparation method.
The invention has the beneficial effects that:
(1) According to the solvent-free modified polyurethane adhesive and the preparation method thereof, the modified alcohol prepared from the rosin acid, the terephthalic acid, the diglycol and the maleic anhydride and the polyether glycol are used for providing hydroxyl groups of an adhesive system together, and a large number of ester groups are introduced into the modified alcohol to improve a loose structure in the polyether glycol, so that the tensile strength and the peeling strength of the adhesive are improved, and the adhesive property of the adhesive is improved.
(2) According to the solvent-free modified polyurethane adhesive and the preparation method thereof, the alkaline stabilizer is prepared, the stabilizer adsorbs gas generated by the reaction of isocyanate and water and provides an alkaline environment for the curing of the adhesive to promote the reaction process of curing, on the other hand, the porous structure of the stabilizer enables alcohol molecules to creep into the pores of the stabilizer to enhance the adhesive force, so that the cohesive force of the adhesive is improved, and the adhesive strength of the solvent-free polyurethane adhesive is improved.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
Preparing a solvent-free modified polyurethane adhesive:
(1) Mixing abietic acid, terephthalic acid and diglycol in a reaction kettle in a nitrogen atmosphere, heating the reaction kettle to 170 ℃ under vacuum condition, introducing maleic anhydride, heating to 220 ℃ and preserving heat for 1h, adding zinc naphthalate, heating to 240 ℃ and reacting for 7h, cooling to 180 ℃ and preserving heat for 1.5h, cooling to 100 ℃, discharging to obtain a material A;
the mass ratio of the rosin acid to the terephthalic acid to the diglycol to the maleic anhydride to the zinc naphthalate is 75:45:150:100:2;
the vacuum condition refers to that the reaction kettle is vacuumized until the vacuum degree is 40kPa;
(2) Placing the material A and polyether glycol into a mixing kettle, stirring for 1.5h at 110 ℃, cooling to 45 ℃, adding a stabilizer, performing ultrasonic dispersion for 15min, and grinding to obtain a material B; the mass ratio of the material A to the polyether glycol is 1:2;
(3) Mixing the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, heating to 65 ℃ and stirring for 2 hours at constant temperature to obtain a material C; the mass ratio of the material B to the toluene diisocyanate to the 4,4' -diphenylmethane diisocyanate is 5:3:4, a step of;
(4) Mixing the material C and the epoxy resin, stirring for 1h, heating to 75 ℃ for reaction for 2h, cooling to room temperature to obtain a material D, and sealing for later use; the mass ratio of the material C to the epoxy resin is 1:0.5;
(5) Placing polyether glycol and water absorbent BF-5 into a material kettle, mixing and stirring for 30min, filtering, taking liquid phase, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, stirring for 1h at 85 ℃, cooling to room temperature, adding hexahydrophthalic anhydride, vacuumizing and sealing for standby to obtain a material E; the polyether glycol, the water absorbent BF-5, 3 ′ -dichloro-4, 4 ′ The mass ratio of diaminodiphenylmethane to hexahydrophthalic anhydride is 2:0.4:0.5:1, a step of;
(6) And (3) mixing the materials D and E according to the mass ratio of 1:2, mixing the materials in proportion, rapidly stirring uniformly, and then applying; the polyether glycol comprises at least one of PPG204, PPG210 and PPG 220.
Preparation of the stabilizer:
s1, weighing cetyl trimethyl ammonium bromide, sodium silicate and deionized water, mixing, and stirring for 0.5h to obtain a material F;
s2, weighing sodium silicate, deionized water and silica sol, mixing, adding the mixture into the material F, stirring for 1h, adding aluminum sulfate octadecabydrate and ferric nitrate nonahydrate, and stirring for 0.5h to obtain a material G;
s3, adjusting the pH value of the material G to 10, crystallizing at 150 ℃ for 24 hours, washing the crystallized material G with a potassium nitrate solution until the pH value is 8, filtering, taking a solid phase, drying at 60 ℃ for 10 hours, and roasting at 550 ℃ for 8 hours to obtain the stabilizer;
the mass ratio of the cetyl trimethyl ammonium bromide to the sodium silicate weighed in the step S1 to the deionized water weighed in the step S1 to the sodium silicate weighed in the step S2 to the deionized water weighed in the step S2 to the silica sol to the aluminum sulfate octadecatried and ferric nitrate nonahydrate is 0.2:0.8:80:0.1:100:1:0.54:0.3; the mass fraction of silicon dioxide in the silica sol is 30%; the mass fraction of potassium nitrate in the potassium nitrate solution is 10%.
Example 2
Preparing a solvent-free modified polyurethane adhesive:
(1) Mixing abietic acid, terephthalic acid and diglycol in a reaction kettle in a nitrogen atmosphere, heating the reaction kettle to 172 ℃ under vacuum condition, introducing maleic anhydride, heating to 220 ℃ and preserving heat for 1.5h, adding zinc naphthalate, heating to 245 ℃ and reacting for 8h, cooling to 180 ℃ and preserving heat for 1.8h, cooling to 100 ℃, discharging to obtain a material A;
the mass ratio of the rosin acid to the terephthalic acid to the diglycol to the maleic anhydride to the zinc naphthalate is 90:50:150:110:2.5;
the vacuum condition refers to that the reaction kettle is vacuumized until the vacuum degree is 50kPa;
(2) Placing the material A and polyether glycol into a mixing kettle, stirring for 1.8 hours at 112 ℃, cooling to 50 ℃, adding a stabilizer, performing ultrasonic dispersion for 20 minutes, and grinding to obtain a material B; the mass ratio of the material A to the polyether glycol is 1.5:2.5;
(3) Mixing the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, heating to 66 ℃ and stirring for 2.5 hours at constant temperature to obtain a material C; the mass ratio of the material B to the toluene diisocyanate to the 4,4' -diphenylmethane diisocyanate is 6:3.5:5, a step of;
(4) Mixing the material C and the epoxy resin, stirring for 1.5 hours, heating to 75 ℃ for reaction for 2.5 hours, cooling to room temperature to obtain a material D, and sealing for later use; the mass ratio of the material C to the epoxy resin is 1:0.65;
(5) Placing polyether glycol and water absorbent BF-5 into a material kettle, mixing and stirring for 35min, filtering, taking liquid phase, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, stirring for 1.2h at 85 ℃, cooling to room temperature, adding hexahydrophthalic anhydride, vacuumizing and sealing for standby to obtain a material E; the polyether glycol, the water absorbent BF-5, 3 ′ -dichloro-4, 4 ′ The mass ratio of diaminodiphenylmethane to hexahydrophthalic anhydride is 3:0.5:0.6:1.1;
(6) And (3) mixing the materials D and E according to the mass ratio of 1:2.5, mixing and rapidly stirring uniformly, and then applying; the polyether glycol comprises at least one of PPG204, PPG210 and PPG 220.
Preparation of the stabilizer:
s1, weighing cetyl trimethyl ammonium bromide, sodium silicate and deionized water, mixing, and stirring for 0.8h to obtain a material F;
s2, weighing sodium silicate, deionized water and silica sol, mixing, adding the mixture into the material F, stirring for 1.5 hours, adding aluminum sulfate octadecabydrate and ferric nitrate nonahydrate, and stirring for 0.8 hour to obtain a material G;
s3, adjusting the pH value of the material G to 10.5, crystallizing at 165 ℃ for 28 hours, washing the crystallized material G with a potassium nitrate solution until the pH value is 8, filtering, taking a solid phase, drying at 60 ℃ for 11 hours, and roasting at 550 ℃ for 9 hours to obtain the stabilizer;
the mass ratio of the cetyl trimethyl ammonium bromide to the sodium silicate weighed in the step S1 to the deionized water weighed in the step S1 to the sodium silicate weighed in the step S2 to the deionized water weighed in the step S2 to the silica sol to the aluminum sulfate octadecatried and the ferric nitrate nonahydrate is 0.3:0.9:90:0.15:110:1.5:0.58:0.35; the mass fraction of silicon dioxide in the silica sol is 30%; the mass fraction of potassium nitrate in the potassium nitrate solution is 10%.
Example 3
Preparing a solvent-free modified polyurethane adhesive:
(1) Mixing abietic acid, terephthalic acid and diglycol in a reaction kettle in a nitrogen atmosphere, heating the reaction kettle to 175 ℃ under vacuum condition, introducing maleic anhydride, heating to 220 ℃ and preserving heat for 2 hours, adding zinc naphthalate, heating to 250 ℃ and reacting for 9 hours, cooling to 180 ℃ and preserving heat for 2 hours, cooling to 100 ℃, discharging to obtain a material A;
the mass ratio of the rosin acid, the terephthalic acid, the diglycol, the maleic anhydride and the zinc naphthalate is 110:60:150:120:3, a step of;
the vacuum condition refers to that the reaction kettle is vacuumized until the vacuum degree is 60kPa;
(2) Placing the material A and polyether glycol into a mixing kettle, stirring for 2 hours at 115 ℃, cooling to 55 ℃, adding a stabilizer, performing ultrasonic dispersion for 25 minutes, and grinding to obtain a material B; the mass ratio of the material A to the polyether glycol is 2:3, a step of;
(3) Mixing the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, heating to 68 ℃ and stirring for 3 hours at constant temperature to obtain a material C; the mass ratio of the material B to the toluene diisocyanate to the 4,4' -diphenylmethane diisocyanate is 8:4:6, preparing a base material;
(4) Mixing the material C and the epoxy resin, stirring for 2 hours, heating to 75 ℃ for reaction for 3 hours, cooling to room temperature to obtain a material D, and sealing for later use; the mass ratio of the material C to the epoxy resin is 1:0.8;
(5) Placing polyether glycol and water absorbent BF-5 into a material kettle, mixing and stirring for 40min, filtering, taking liquid phase, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, stirring for 1.5h at 85 ℃, cooling to room temperature, adding hexahydrophthalic anhydride, vacuumizing and sealing for standby to obtain a material E; the polyether glycol, the water absorbent BF-5, 3 ′ -dichloro-4, 4 ′ -diaminodiphenylmethane and hexahydrophthalic anhydride in a mass ratio of 4:0.6:0.7:1.2;
(6) And (3) mixing the materials D and E according to the mass ratio of 1:3, mixing in proportion, rapidly stirring uniformly, and then applying; the polyether glycol comprises at least one of PPG204, PPG210 and PPG 220.
Preparation of the stabilizer:
s1, weighing cetyl trimethyl ammonium bromide, sodium silicate and deionized water, mixing, and stirring for 1h to obtain a material F;
s2, weighing sodium silicate, deionized water and silica sol, mixing, adding the mixture into the material F, stirring for 2 hours, adding aluminum sulfate octadecabydrate and ferric nitrate nonahydrate, and stirring for 1 hour to obtain a material G;
s3, adjusting the pH value of the material G to 11, crystallizing at 175 ℃ for 36 hours, washing the crystallized material G with a potassium nitrate solution until the pH value is 8, filtering, taking a solid phase, drying at 60 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours to obtain the stabilizer;
the mass ratio of the cetyl trimethyl ammonium bromide to the sodium silicate weighed in the step S1 to the deionized water weighed in the step S1 to the sodium silicate weighed in the step S2 to the deionized water weighed in the step S2 to the silica sol to the aluminum sulfate octadecatried and the ferric nitrate nonahydrate is 0.4:1:100:0.2:120:2:0.63:0.4; the mass fraction of silicon dioxide in the silica sol is 30%; the mass fraction of potassium nitrate in the potassium nitrate solution is 10%.
Comparative examples 1 to 2
The difference from example 1 is the dosing ratio of aluminum sulfate octadecatydrate, ferric nitrate nonahydrate in the preparation of the stabilizer, as shown in Table 1.
TABLE 1
Comparative examples 3 to 5
The difference from example 1 is the pH of the material G after crystallization in step S3 after washing with potassium nitrate solution in the preparation of the stabilizer, as shown in table 2.
TABLE 2
| pH after washing | |
| Comparative example 3 | 9.2 |
| Comparative example 4 | 7.5 |
| Comparative example 5 | 7 |
Comparative example 6
The difference from example 1 is that no stabilizer is added in the preparation of the polyurethane adhesive.
Comparative examples 7 to 8
The difference from example 1 is the ratio of the amounts of material A and polyether glycol in the preparation of the polyurethane adhesives, as shown in Table 3.
TABLE 3 Table 3
Performance testing
Tensile strength testing is carried out according to the standard GB/T1040.2-2006;
peel strength testing was performed according to standard GB/T7122-1996;
carrying out wear resistance test according to the standard GB 3960-83;
the polyurethane adhesives prepared in examples 1 to 3 and comparative examples 1 to 8 were subjected to performance tests according to the above criteria, and the test results are shown in Table 4 below.
TABLE 4 Table 4
As is clear from Table 4, in comparative examples 1 to 2, the adhesive has a reduced abrasion resistance due to the difference in the mixing ratio of aluminum sulfate octadecabydrate and ferric nitrate nonahydrate; in comparative examples 3 to 5, the reaction of the adhesive was inhibited due to the difference in pH, so that the tensile strength, peel strength and abrasion resistance of the adhesive were reduced to different extents; the comparative example 6 was free of a stabilizer, which resulted in a decrease in cohesive force during the curing process of the adhesive, resulting in a significant decrease in tensile strength, peel strength and abrasion resistance of the adhesive; in the comparative example 7, only the material A is added, so that the inside of the adhesive system is more viscous, the inside of the adhesive is more tightly combined, the tensile strength is overlarge, but the flowing wettability of the adhesive system is poor, and the peeling strength is greatly reduced; only polyether glycol was added to comparative example 8, which resulted in a looser interior of the adhesive system, resulting in a reduction in tensile strength and peel strength over example 1.
Note that: the sources of some of the materials involved in the present invention are shown in Table 5 below.
TABLE 5
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the solvent-free modified polyurethane adhesive is characterized by comprising the following steps of:
(1) Mixing abietic acid, terephthalic acid and diglycol in a nitrogen atmosphere, heating in vacuum, introducing maleic anhydride, preheating, adding zinc naphthalate, reacting at a controlled temperature, cooling, discharging to obtain a material A;
(2) Mixing the material A and polyether glycol, heating, stirring, cooling, adding a stabilizer, performing ultrasonic dispersion, and grinding to obtain a material B;
(3) Mixing the material B, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, and performing temperature control reaction to obtain a material C;
(4) Mixing the material C and the epoxy resin, stirring, performing temperature control reaction, cooling to obtain a material D, and sealing for later use;
(5) Mixing polyether glycol and water absorbent BF-5, filtering, adding 3,3 ′ -dichloro-4, 4 ′ -diaminodiphenyl methane, heating, stirring, cooling, adding hexahydrophthalic anhydride, vacuumizing, and sealing for standby to obtain a material E;
(6) And (3) mixing the materials D and E according to the mass ratio of 1-1.2:2-4, and rapidly and uniformly stirring and then applying.
2. The preparation method of the solvent-free modified polyurethane adhesive according to claim 1, wherein in the step (1), the mass ratio of the rosin acid, the terephthalic acid, the diglycol, the maleic anhydride and the zinc naphthalate is 75-110:45-60:150:100-120:2-3; the vacuum refers to the vacuum pumping to the vacuum degree of 40-60kPa.
3. The preparation method of the solvent-free modified polyurethane adhesive according to claim 1, wherein in the step (2), the mass ratio of the material A to the polyether glycol is 1-2:2-3.
4. The preparation method of the solvent-free modified polyurethane adhesive according to claim 1, wherein in the step (3), the mass ratio of the material B to the toluene diisocyanate to the 4,4' -diphenylmethane diisocyanate is 5-8:3-4:4-6.
5. The preparation method of the solvent-free modified polyurethane adhesive according to claim 1, wherein in the step (4), the mass ratio of the material C to the epoxy resin is 1:0.5-0.8.
6. The method for preparing a solvent-free modified polyurethane adhesive according to claim 1, wherein in the step (5), the polyether glycol, the water absorbent BF-5, 3 ′ -dichloro-4, 4 ′ -diaminodiphenylmethane, hexahydrophthalic anhydride in a mass ratio of 2-4:0.4-0.6:0.5-0.7:1-1.2.
7. The method for preparing the solvent-free modified polyurethane adhesive according to claim 1, wherein the polyether glycol comprises at least one of PPG204, PPG210 and PPG 220.
8. The method for preparing the solvent-free modified polyurethane adhesive according to claim 1, wherein the preparation of the stabilizer comprises the following steps:
s1, weighing cetyl trimethyl ammonium bromide, sodium silicate and deionized water, mixing and stirring to obtain a material F;
s2, weighing sodium silicate, deionized water and silica sol, mixing, adding the mixture into the material F, stirring, adding aluminum sulfate octadecanoate hydrate and ferric nitrate nonahydrate, and stirring to obtain a material G;
s3, adjusting the pH value of the material G to 10-11, crystallizing, washing the crystallized material G with a potassium nitrate solution until the pH value is 8, filtering, taking a solid phase, drying, and roasting to obtain the stabilizer.
9. The preparation method of the solvent-free modified polyurethane adhesive according to claim 8, wherein the mass ratio of cetyl trimethyl ammonium bromide to sodium silicate weighed in the step S1 to deionized water weighed in the step S1 to sodium silicate weighed in the step S2 to deionized water weighed in the step S2 to silica sol to aluminum sulfate octadecatried to ferric nitrate nonahydrate is 0.2-0.4:0.8-1:80-100:0.1-0.2:100-120:1-2:0.54-0.63:0.3-0.4.
10. A polyurethane adhesive obtainable by the process of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102212172A (en) * | 2011-02-17 | 2011-10-12 | 安徽淮河化工股份有限公司 | Resin special for anchoring agent and preparation method thereof |
| CN107312166A (en) * | 2017-06-28 | 2017-11-03 | 郑善 | A kind of modified PET polyester and its preparation method and application |
| CN113372872A (en) * | 2021-07-21 | 2021-09-10 | 浙江禾欣科技有限公司 | Solvent-free polyurethane adhesive with high bonding fastness and preparation method thereof |
| CN114163946A (en) * | 2022-01-13 | 2022-03-11 | 罗剑 | Preparation process of high-toughness composite hot melt adhesive for carpet |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212172A (en) * | 2011-02-17 | 2011-10-12 | 安徽淮河化工股份有限公司 | Resin special for anchoring agent and preparation method thereof |
| CN107312166A (en) * | 2017-06-28 | 2017-11-03 | 郑善 | A kind of modified PET polyester and its preparation method and application |
| CN113372872A (en) * | 2021-07-21 | 2021-09-10 | 浙江禾欣科技有限公司 | Solvent-free polyurethane adhesive with high bonding fastness and preparation method thereof |
| CN114163946A (en) * | 2022-01-13 | 2022-03-11 | 罗剑 | Preparation process of high-toughness composite hot melt adhesive for carpet |
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