CN117887407A - Solvent-free polyurethane adhesive with high drying speed - Google Patents
Solvent-free polyurethane adhesive with high drying speed Download PDFInfo
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- CN117887407A CN117887407A CN202310938767.8A CN202310938767A CN117887407A CN 117887407 A CN117887407 A CN 117887407A CN 202310938767 A CN202310938767 A CN 202310938767A CN 117887407 A CN117887407 A CN 117887407A
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- 238000001035 drying Methods 0.000 title claims abstract description 36
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 title claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 claims abstract description 48
- 239000000853 adhesive Substances 0.000 claims abstract description 45
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004359 castor oil Substances 0.000 claims abstract description 27
- 235000019438 castor oil Nutrition 0.000 claims abstract description 27
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 27
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 25
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 25
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 61
- 229920002635 polyurethane Polymers 0.000 claims description 42
- 239000004814 polyurethane Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910052726 zirconium Inorganic materials 0.000 claims description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 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 description 24
- 150000002009 diols Chemical class 0.000 claims description 21
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- BMTKGBCFRKGOOZ-UHFFFAOYSA-K cyclopenta-1,3-diene;zirconium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1 BMTKGBCFRKGOOZ-UHFFFAOYSA-K 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 13
- VWOTWOPAYZNLIU-UHFFFAOYSA-L C[SiH]C.Cl[Zr](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[SiH]C.Cl[Zr](Cl)(C1C=CC=C1)C1C=CC=C1 VWOTWOPAYZNLIU-UHFFFAOYSA-L 0.000 description 11
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 6
- ASBGGHMVAMBCOR-UHFFFAOYSA-N ethanolate;zirconium(4+) Chemical compound [Zr+4].CC[O-].CC[O-].CC[O-].CC[O-] ASBGGHMVAMBCOR-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- TUPMGGHTDIFOMI-UHFFFAOYSA-J 2-methylprop-2-enoate;zirconium(4+) Chemical compound [Zr+4].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O TUPMGGHTDIFOMI-UHFFFAOYSA-J 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- -1 alcohol compound Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NZUNWRVHLLQLSX-UHFFFAOYSA-N 2-[2-(6-hydroxyhexanoyloxy)ethoxy]ethyl 6-hydroxyhexanoate Chemical compound OCCCCCC(=O)OCCOCCOC(=O)CCCCCO NZUNWRVHLLQLSX-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a solvent-free polyurethane adhesive with high drying speed, which comprises an A component and a B component, wherein the A component comprises polycaprolactone dihydric alcohol and diisocyanate, and the B component comprises bisphenol A type epoxy resin, diethanolamine and castor oil derivative polyhydric alcohol. The solvent-free polyurethane adhesive adopts a carefully selected and compounded formula, and the combination not only ensures that the adhesive has high adhesiveness and durability, but also obviously improves the drying speed, meets various industrial requirements, and has wide application in a plurality of fields of construction, automobiles, aviation, electronics and the like.
Description
Technical Field
The invention relates to an adhesive, in particular to a solvent-free polyurethane adhesive with high drying speed.
Background
Polyurethane (PUR) is a valuable and widely used adhesive that has found wide application in many industries due to its excellent combination of properties. These industries include, but are not limited to, construction, furniture, packaging, automotive and aerospace, among others, their excellent adhesion, good chemical resistance and excellent abrasion resistance, making polyurethane adhesives an indisputable key material for these industries. Polyurethane adhesives show considerable value, both in heavy industrial production and in precision manufacturing. However, despite these outstanding advantages, polyurethane adhesives present significant challenges in terms of cure speed and cure conditions for some specific industrial application scenarios.
Conventional polyurethane adhesives typically require a longer cure time in a higher temperature and/or humidity environment during curing, which is clearly disadvantageous for certain application scenarios where rapid production is required or where these curing conditions cannot be provided. Some applications requiring rapid curing to improve working efficiency, or some industrial applications that fail to provide constant temperature and humidity environments, pose serious challenges to the traditional polyurethane adhesive cure speed and cure conditions. In addition, conventional polyurethane adhesives often require the use of organic solvents to enhance their flowability and improve their application properties, but these solvents can volatilize during the curing process and can create potential hazards to the environment and human health. This is especially true in the current background of increasingly stringent environmental protection requirements in the production process, as the global environmental awareness is increasingly growing. Therefore, it is necessary to develop a new polyurethane adhesive which can realize the characteristic of quick drying, does not need to use an organic solvent, and can better meet the current industrial production requirements and environmental protection requirements.
In the related art, there have been studies in an attempt to solve these problems by changing the formulation or curing conditions of polyurethane adhesives. For example, the curing reaction is accelerated by using a more reactive polyol or isocyanate, or by introducing a catalyst. However, these solutions often require compromises in other properties of the adhesive, such as bond strength, weatherability or chemical resistance.
Obtaining a quick-drying polyurethane adhesive without solvent is a technical challenge, especially while maintaining other excellent properties of the adhesive. Meanwhile, the quick-drying polyurethane adhesive has a particularly important value for mass production and a quick production line. Therefore, development of a polyurethane adhesive capable of drying rapidly at room temperature without using an organic solvent while maintaining excellent adhesive properties is an important need in the current adhesive technology field.
Disclosure of Invention
In order to solve the technical defects, the invention provides a novel solvent-free polyurethane adhesive with high drying speed.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention provides a solvent-free polyurethane adhesive with high drying speed, which comprises an A component and a B component, wherein the A component comprises polycaprolactone diol and diphenylmethane diisocyanate, and the B component comprises bisphenol A type epoxy resin, diethanolamine and castor oil derivative polyol.
Preferably, the component A comprises the following components in parts by weight:
80-120 parts of polycaprolactone diol;
70-170 parts of diphenylmethane diisocyanate.
Preferably, the component B comprises the following components in parts by weight:
40-90 parts of bisphenol A type epoxy resin;
1-15 parts of diethanolamine;
50-180 parts of castor oil derivative polyol.
Preferably, the weight ratio of the component A to the component B is 1: (0.1-0.9).
Preferably, the solvent-free polyurethane adhesive with high drying speed comprises an A component and a B component,
the component A comprises the following components in parts by weight:
90-110 parts of polycaprolactone diol;
80-150 parts of diphenylmethane diisocyanate;
the component B comprises the following components in parts by weight:
50-80 parts of bisphenol A type epoxy resin;
2-10 parts of diethanolamine;
70-140 parts of castor oil derivative polyol;
the weight ratio of the component A to the component B is 1: (0.2-0.8).
The invention also provides a preparation method of the solvent-free polyurethane adhesive with high drying speed, which comprises the following steps:
the polycaprolactone dihydric alcohol and the diphenylmethane diisocyanate react to obtain a component A;
bisphenol A type epoxy resin, diethanolamine and castor oil derivative polyol react to obtain a component B;
mixing the component A and the component B according to the weight ratio.
Preferably, the preparation method of the solvent-free polyurethane adhesive with high drying speed comprises the following steps:
polycaprolactone diol and diphenylmethane diisocyanate react at 70-80 ℃ for 1-3 hours to obtain a component A;
bisphenol A epoxy resin and diethanolamine react for 30-90 min at 40-60 ℃, castor oil derivative polyol is added, and the reaction is carried out for 20-40 min at 40-60 ℃ to obtain a component B;
mixing the component A and the component B according to the weight ratio.
In order to improve the quick-drying performance of the present invention, the inventors tried to add a catalyst to the formulation, and through a lot of experiments, it was preferable to use a zirconium-containing catalyst.
Therefore, the further improved technical scheme is as follows:
a solvent-free polyurethane adhesive with high drying speed comprises a component A and a component B,
the component A comprises the following components in parts by weight:
90-110 parts of polycaprolactone diol;
80-150 parts of diphenylmethane diisocyanate;
the component B comprises the following components in parts by weight:
50-80 parts of bisphenol A type epoxy resin;
2-10 parts of diethanolamine;
70-140 parts of castor oil derivative polyol;
0.4-1.4 parts of zirconium-containing catalyst;
the weight ratio of the component A to the component B is 1: (0.2-0.8).
The zirconium-containing catalyst is at least one of tetraethoxyzirconium, zirconium tetramethyl acrylate, zirconium n-butoxide, zirconium (IV) tetra-tert-butoxide, cyclopentadienyl zirconium trichloride and dimethylsilyl bis (cyclopentadienyl) zirconium dichloride.
Preferably, the zirconium-containing catalyst is at least one of cyclopentadienyl zirconium trichloride and dimethylsilyl bis (cyclopentadienyl) zirconium dichloride.
The preparation method of the solvent-free polyurethane adhesive with high drying speed is also provided:
the polycaprolactone dihydric alcohol and the diphenylmethane diisocyanate react to obtain a component A;
bisphenol A type epoxy resin, diethanolamine, castor oil derivative polyol and zirconium-containing catalyst react to obtain a component B;
mixing the component A and the component B according to the weight ratio.
The solvent-free polyurethane adhesive adopts a carefully selected and compounded formula, and comprises polycaprolactone dihydric alcohol and diphenylmethane diisocyanate in the component A, and bisphenol A type epoxy resin, diethanolamine and castor oil derived polyhydric alcohol in the component B. The combination not only ensures that the adhesive has high adhesiveness and durability, but also obviously improves the drying speed and meets various industrial requirements. More importantly, the invention realizes the environmental protection and sustainability of the adhesive by introducing the castor oil derivative from renewable resources, improves the product performance, meets the requirements of environmental protection and sustainability development, and has wide application in a plurality of fields such as construction, automobiles, aviation, electronics and the like.
Detailed Description
A solvent-free polyurethane adhesive with high drying speed comprises a component A and a component B,
the component A comprises the following components in parts by weight:
90-110 parts of polycaprolactone diol;
80-150 parts of diphenylmethane diisocyanate;
the component B comprises the following components in parts by weight:
50-80 parts of bisphenol A type epoxy resin;
2-10 parts of diethanolamine;
70-140 parts of castor oil derivative polyol;
the weight ratio of the component A to the component B is 1: (0.2-0.8).
Polycaprolactone diol (Polycaprolactone diol): it is an alcohol compound, has two active hydroxyl groups, and is one of the main participants of the reaction. Such polycaprolactone diols are generally used as main raw materials for polyurethanes because of their good thermal stability, high flexibility and excellent water resistance. In the reaction process, the hydroxyl group of polycaprolactone diol reacts with isocyanate to form urea bond to form polyurethane.
Diphenylmethane diisocyanate (MDI): MDI is a commonly used isocyanate that contains two reactive isocyanate groups that can react with a variety of alcohol compounds to form polyurethanes. This reaction will form a urea linkage between the two reactive groups. The polyurethane formed has higher strength and rigidity due to the rigid cyclic structure of MDI.
Bisphenol a epoxy resin: this is an epoxy compound containing reactive epoxy groups. In this adhesive formulation, the epoxy resin acts primarily as a cross-linking agent, reacting with other ingredients to form a three-dimensional cross-linked structure. Such a crosslinked structure can significantly improve the abrasion resistance and chemical resistance of the adhesive.
Diethanolamine: diethanolamine is a compound having two reactive hydroxyl groups that can react with epoxy resins to promote curing. In addition, it can also play the roles of regulating the viscosity of the formula and improving the fluidity.
Castor oil derivative polyols: the polyol is a polyhydroxy compound obtained by chemical modification of vegetable castor oil. In polyurethane adhesive formulations, its role is mainly to chain extenders and flexibilizers. The hydroxyl groups of the castor oil derivative polyol react with the isocyanate to form new polymer chains, increasing the molecular weight of the polyurethane. The chain structure and flexible ether bond make the newly generated polyurethane chain have good flexibility, and the adhesive property and mechanical property of the adhesive are improved.
Through proper proportion and reaction conditions, the raw materials can react with each other to form the solvent-free polyurethane adhesive with stable structure, good wear resistance and high curing speed.
A preparation method of a solvent-free polyurethane adhesive with high drying speed comprises the following steps:
polycaprolactone diol and diphenylmethane diisocyanate are reacted at 70-80 ℃ for 1-3 hours to obtain the component A. In this process, the hydroxyl group (-OH) of the polycaprolactone diol reacts with the isocyanate group (-NCO) of the diphenylmethane diisocyanate to form a urea linkage (-NHCOO-) and release the diol molecule. This reaction is called an esterification reaction. The purpose of this step is to prepare prepolymers containing reactive isocyanate groups which react with other components in a subsequent preparation step to form polyurethanes.
Bisphenol A epoxy resin and diethanolamine at 40-60 deg.c for 30-90 min, adding 120g of castor oil derivative polyol and reacting at 40-60 deg.c for 20-40 min to obtain component B. In this step, the amino group (-NH 2) of diethanolamine reacts with the epoxy group (-O-) of the epoxy resin to open the epoxy ring and form a new hydroxyl group (-OH). This reaction, known as the epoxy ring opening reaction, increases the crosslink density of the epoxy resin and creates new reactive hydroxyl groups that react with other components in subsequent steps. Then, castor oil derivative polyol is added for reaction. In this step, both the newly formed hydroxyl groups and the hydroxyl groups of the castor oil derivative polyol are likely to react with the remaining epoxy groups to form a more complex network structure.
Mixing the component A and the component B according to the weight ratio. In this step, the prepolymer in the A-component reacts with the hydroxyl groups in the B-component to form polyurethane molecules, thereby forming a more powerful three-dimensional network structure. This complex reaction step further enhances the adhesive properties including its bond strength, flexibility, durability and drying speed.
In order to improve the quick-drying performance of the present invention, the inventors tried to add a catalyst to the formulation, and through a lot of experiments, it was preferable to use a zirconium-containing catalyst. The further improved technical scheme is as follows:
a solvent-free polyurethane adhesive with high drying speed comprises a component A and a component B,
the component A comprises the following components in parts by weight:
90-110 parts of polycaprolactone diol;
80-150 parts of diphenylmethane diisocyanate;
the component B comprises the following components in parts by weight:
50-80 parts of bisphenol A type epoxy resin;
2-10 parts of diethanolamine;
70-140 parts of castor oil derivative polyol;
0.4-1.4 parts of zirconium-containing catalyst;
the weight ratio of the component A to the component B is 1: (0.2-0.8).
The zirconium-containing catalyst comprises at least one compound selected from the group consisting of zirconium tetraethoxide, zirconium tetramethacrylate, zirconium n-butoxide, zirconium (IV) tetra-t-butoxide, cyclopentadienyl zirconium trichloride, and dimethylsilyl bis (cyclopentadienyl) zirconium dichloride. In some preferred embodiments, the zirconium-containing catalyst comprises at least one compound selected from the group consisting of cyclopentadienyl zirconium trichloride and dimethylsilylbis (cyclopentadienyl) zirconium dichloride. In some further preferred embodiments, the zirconium-containing catalyst consists of cyclopentadienyl zirconium trichloride and tetraethoxyzirconium, wherein the mass ratio of cyclopentadienyl zirconium trichloride to tetraethoxyzirconium is from 1:1 to 4:4. In some still further preferred embodiments, the zirconium-containing catalyst consists of cyclopentadienyl zirconium trichloride and zirconium tetraethoxide in a mass ratio of 1:1.
In the following examples:
polycaprolactone diol, CAS number: 36890-68-3, density 1.073g/mL at 25deg.C g/cm3, molecular weight 3000, available from Shandong Wantai chemical Co.
Diphenylmethane diisocyanate, diphenylmethane diisocyanate of the Wanhua brand type MDI50, CAS number: 75-13-8.
Bisphenol A type epoxy resin is adoptedBrand 618 (E51) bisphenol A type liquid epoxy resin.
Diethanolamine, CAS number: 111-42-2, content: 99% or more, provided by Shandong Chuang chemical industry Co., ltd.
Castor oil derivative polyol, polycin brand 2525 castor oil derivative polyol from Vertellus, USA, functionality 3, force 156, viscosity 25000/mPa.s, density 0.969g/cm 3 。
Zirconium tetraethoxide, CAS:18267-08-8.
Zirconium tetramethyl acrylate, CAS:67893-01-0.
Zirconium n-butoxide, CAS:1071-76-7.
Zirconium tetra-tert-butoxide (IV), CAS:2081-12-1.
Dimethylsilylbis (cyclopentadienyl) zirconium dichloride, CAS:86050-32-0.
Cyclopentadienyl zirconium trichloride, CAS:34767-44-7.
Example 1
The preparation method of the solvent-free polyurethane adhesive with high drying speed comprises the following steps:
(1) And (3) preparation of the component A:
100g of polycaprolactone diol and 120g of diphenylmethane diisocyanate are taken and put into a three-neck flask, stirred and reacted for 2 hours at the temperature of 75 ℃, and cooled to room temperature, thus obtaining the component A.
(2) And (3) preparation of a component B:
60g of bisphenol A epoxy resin and 5g of diethanolamine are placed into a three-neck flask, stirred and reacted for 60 minutes at 50 ℃, 120g of castor oil derivative polyol is added, stirred and reacted for 30 minutes at 50 ℃, and cooled to room temperature to prepare the component B.
(3) And (3) composite preparation:
before gluing, the component A and the component B are mixed according to the weight ratio of 1: and 0.5, mixing to obtain the solvent-free polyurethane adhesive with high drying speed.
Example 2
The preparation method of the solvent-free polyurethane adhesive with high drying speed comprises the following steps:
(1) And (3) preparation of the component A:
100g of polycaprolactone diol and 120g of diphenylmethane diisocyanate are taken and put into a three-neck flask, stirred and reacted for 2 hours at the temperature of 75 ℃, and cooled to room temperature, thus obtaining the component A.
(2) And (3) preparation of a component B:
60g of bisphenol A epoxy resin and 5g of diethanolamine are placed into a three-neck flask, stirred and reacted for 60 minutes at 50 ℃, 120g of castor oil derivative polyol and 0.8g of catalyst are added, stirred and reacted for 30 minutes at 50 ℃, and cooled to room temperature, so that the component B is prepared.
(4) And (3) composite preparation:
before gluing, the component A and the component B are mixed according to the weight ratio of 1: and 0.5, mixing to obtain the solvent-free polyurethane adhesive with high drying speed.
The catalyst in this example is cyclopentadienyl zirconium trichloride.
Example 3
The difference from example 2 is that the catalyst is dimethylsilylbis (cyclopentadienyl) zirconium dichloride.
Example 4
The difference from example 2 is that the catalyst is zirconium tetraethoxide.
Example 5
The difference from example 2 is that the catalyst is zirconium tetramethyl acrylate.
Example 6
The difference from example 2 is that the catalyst is zirconium n-butoxide.
Example 7
The difference from example 2 is that the catalyst is composed of cyclopentadienyl zirconium trichloride and tetraethoxyzirconium in a mass ratio of 1:1.
Comparative example 1
The difference from example 2 is that the catalyst is bismuth isooctanoate.
Comparative example 2
The difference from example 2 is that the catalyst is dibutyltin dilaurate.
Comparative example 3
The difference from example 2 is that the catalyst is pentamethyldiethylenetriamine.
Test example 1 shear Strength test
The shear strength of aluminum-aluminum at 25℃was tested as per GB/T7124-2008 determination of tensile shear strength of adhesive (rigid material to rigid material).
Table 1: shear strength test meter for polyurethane adhesive
| Shear strength at 25 ℃ and MPa | |
| Example 1 | 15.0 |
| Example 2 | 14.9 |
| Example 3 | 14.7 |
| Example 4 | 13.2 |
| Example 5 | 13.1 |
| Example 6 | 12.7 |
| Example 7 | 14.2 |
| Comparative example 1 | 12.9 |
| Comparative example 2 | 12.4 |
| Comparative example 3 | 13.4 |
Shear strength is a measure of the physical properties of a material that can withstand shear stress. For adhesives, shear strength is often used as a measure of the strength of their adhesion, i.e., the ability to resist shear stress without breaking.
In the above examples and comparative examples, the effect of the catalyst on the shear strength of the polyurethane adhesive is expressed as: the shear strength of the polyurethane adhesive added with different catalysts is reduced compared with that of the adhesive without the catalysts. This is probably because the catalyst influences the crosslinking density of the polyurethane and thus its mechanical properties.
Specifically, when the zirconium-containing catalyst was added, the shear strength was reduced, but the magnitude of the reduction was relatively small (examples 2 to 6). This is probably because the zirconium catalyst can more effectively catalyze the reaction of isocyanate with alcohol to form a more stable polyurethane network structure and thus has less impact on shear strength. In particular, the effect on the shear strength was even smaller when the catalyst was cyclopentadienyl zirconium trichloride (example 2) or dimethylsilylbis (cyclopentadienyl) zirconium dichloride (example 3). In both zirconium-based catalysts, cyclopentadienyl zirconium trichloride and dimethylsilylbis (cyclopentadienyl) zirconium dichloride, the strong interaction between the zirconium element and the chlorine atom can affect the electron density of the zirconium center, which in turn can alter its ability to activate isocyanates and alcohols. This change can affect the shear strength of the polyurethane adhesive in two ways. On the one hand, the activity of the catalyst influences the rate of the polyurethane forming reaction. If the catalyst activity is too high, the reaction may be too rapid, resulting in a more compact and disordered arrangement of polyurethane molecules in space, which may result in a decrease in the shear strength of the adhesive. On the other hand, if the catalyst activity is moderate, the reaction rate will be moderate, helping the polyurethane molecules to arrange in a more orderly manner, possibly increasing the shear strength of the adhesive. In particular for both cyclopentadienyl zirconium trichloride and dimethylsilylbis (cyclopentadienyl) zirconium dichloride, their particular chemical structure (i.e., the presence of zirconium-chlorine bonds) may provide moderate catalytic activity, which is advantageous for optimizing the rate of formation and the spatial arrangement of polyurethane molecules such that the shear strength of the polyurethane adhesive is reduced to a relatively small extent. That is, the presence of zirconium-chlorine bonds may adjust the activity of both catalysts to a level that is optimal for polyurethane adhesives.
In comparative examples 1-3, however, the addition of the polyurethane adhesive with a non-zirconium catalyst reduced the shear strength more than the adhesive with a zirconium catalyst. This is probably because these catalysts may change the chemical structure and crosslink density of the polyurethane adhesive, resulting in a decrease in the stability of the polyurethane network structure, thereby affecting its shear strength.
Thus, the choice of catalyst has a significant impact on the shear strength of the polyurethane adhesive. By selecting an appropriate catalyst, the performance of the polyurethane adhesive can be optimized to better adapt to specific application requirements.
Test example 2 curing time test
The A component and the B component are rapidly stirred and mixed in a small plastic cup according to the proportion (weight ratio of 1:0.5) and then start timing, and the timing is stopped when the adhesive is observed to start solidification, and the curing time is counted.
Table 2: shear strength test meter for polyurethane adhesive
The cure time is a key parameter in the performance of the adhesive and reflects the time for the adhesive to transition from an initial liquid state to a hardened solid state. The catalyst plays an extremely important role in this process and it can accelerate the rate of polymerization, resulting in a significant reduction in cure time.
Examples 2-6 each had a significant reduction in cure time compared to example 1 without the addition of the catalyst, with the addition of various zirconium-containing catalysts (zirconium tetraethoxide, zirconium tetramethacrylate, zirconium n-butoxide, zirconium (IV) tetra-t-butoxide, cyclopentadienyl zirconium trichloride, and dimethylsilyl bis (cyclopentadienyl) zirconium dichloride). This is because the zirconium-based catalyst is effective in activating the components of the polymerization reaction, particularly the isocyanate and alcohol, to accelerate the reaction rate and thus reduce the curing time.
Examples 2-6 employed zirconium-containing catalysts with significantly less cure time than comparative examples 1-3 employing other catalysts. This is probably due to the superior activation ability of these zirconium-based catalysts, which promote the progress of polymerization more than other catalysts (bismuth isooctanoate, dibutyltin dilaurate and pentamethyldiethylenetriamine). In particular cyclopentadienyl zirconium trichloride and dimethylsilylbis (cyclopentadienyl) zirconium dichloride, may be more advantageous for the activation of isocyanates and alcohols due to their particular chemical structure (e.g. zirconium-chlorine bond), thus allowing shorter curing times.
In addition, the effect of the catalyst on the curing time is also related to their concentration, reaction temperature, and other conditions of the reaction system (such as concentration and ratio of reactants), among others.
In particular, the cure time (48 seconds) for the example 7 formulation with the catalysts cyclopentadienyl zirconium trichloride and tetraethoxyzirconium was effectively reduced compared to the example 2 catalyst cyclopentadienyl zirconium trichloride (57 seconds) and the example 4 catalyst tetraethoxyzirconium (67 seconds) alone. The catalyst cyclopentadienyl zirconium trichloride and tetraethoxyzirconium are compounded, and the quick-drying performance of the catalyst cyclopentadienyl zirconium trichloride and tetraethoxyzirconium are synergistic. This is mainly likely caused by several mechanisms:
(1) Zirconium ion charge density and distribution: the difference in chemical structures of cyclopentadienyl zirconium trichloride and tetraethoxy zirconium results in a different charge distribution of zirconium ions in the system, which in turn affects the strength and manner of interaction with isocyanate groups. By compounding the two catalysts, the charge density and distribution of zirconium ions in the system can be optimized, and a more effective activation environment is formed, so that the efficiency of the whole reaction process is improved.
(2) Different reaction paths and rate control: cyclopentadienyl zirconium trichloride and tetraethoxy zirconium may activate the-NCO groups in different ways and at different rates. By compounding, the two catalysts can simultaneously influence different stages of the reaction, so that possible reaction bottlenecks of a single catalyst are avoided, the whole reaction process is smoothed, and the reaction rate is integrally improved.
(3) Enhanced uniformity effect: the uniformity of the reaction system can be improved by mixing the two catalysts. The more uniform distribution of the catalyst can optimize the contact with the reactant, reduce the possibility of local overheating or overcooling of the reaction, and further improve the reaction rate.
Therefore, through the compounding strategy, obvious synergistic effect can be realized by optimizing charge density and distribution, smoothing reaction paths and speed and improving uniformity of a reaction system, and curing speed of the polyurethane adhesive is greatly improved.
Claims (8)
1. The solvent-free polyurethane adhesive with high drying speed comprises an A component and a B component, and is characterized in that the A component comprises polycaprolactone diol and diisocyanate, and the B component comprises bisphenol A type epoxy resin, diethanolamine and castor oil derivative polyol.
2. The solvent-free polyurethane adhesive with high drying speed according to claim 1, which comprises an A component and a B component, wherein the A component comprises the following components in parts by weight:
80-120 parts of polycaprolactone diol;
70-170 parts of diphenylmethane diisocyanate.
3. The solvent-free polyurethane adhesive with high drying speed according to claim 1 or 2, comprising a component A and a component B, wherein the component B comprises the following components in parts by weight:
40-90 parts of bisphenol A type epoxy resin;
1-15 parts of diethanolamine;
50-180 parts of castor oil derivative polyol.
4. A fast drying solvent free polyurethane adhesive according to any one of claims 1-3 comprising a component a and a component B, wherein the weight ratio of the a component to the B component is 1: (0.1-0.9).
5. A fast drying solvent-free polyurethane adhesive according to claim 4, comprising an A component and a B component, wherein,
the component A comprises the following components in parts by weight:
90-110 parts of polycaprolactone diol;
80-150 parts of diphenylmethane diisocyanate;
the component B comprises the following components in parts by weight:
50-80 parts of bisphenol A type epoxy resin;
2-10 parts of diethanolamine;
70-140 parts of castor oil derivative polyol;
the weight ratio of the component A to the component B is 1: (0.2-0.8).
6. The fast drying solventless polyurethane adhesive of claim 1 wherein the B component further comprises a zirconium catalyst.
7. The method for preparing the solvent-free polyurethane adhesive with high drying speed according to claims 1-6, which is characterized by comprising the following steps:
the polycaprolactone dihydric alcohol and the diphenylmethane diisocyanate react to obtain a component A;
bisphenol A type epoxy resin, diethanolamine and castor oil derivative polyol react to obtain a component B;
mixing the component A and the component B according to the weight ratio.
8. The method for preparing the solvent-free polyurethane adhesive with high drying speed according to claim 7, which is characterized by comprising the following steps:
polycaprolactone diol and diphenylmethane diisocyanate react at 70-80 ℃ for 1-3 hours to obtain a component A;
bisphenol A epoxy resin and diethanolamine react for 30-90 min at 40-60 ℃, castor oil derivative polyol is added, and the reaction is carried out for 20-40 min at 40-60 ℃ to obtain a component B;
mixing the component A and the component B according to the weight ratio.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419714A (en) * | 2014-09-09 | 2016-03-23 | 贵阳时代沃顿科技有限公司 | Epoxy resin two-component polyurethane adhesive and preparation method thereof |
| CN109111892A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | A kind of quick-dry type double component solvent-free polyurethane composite adhesive and its preparation method and application |
| CN112574403A (en) * | 2020-12-07 | 2021-03-30 | 山东一诺威聚氨酯股份有限公司 | Castor oil-based polyol for solvent-free adhesive and preparation method and application thereof |
| CN113388360A (en) * | 2021-06-29 | 2021-09-14 | 杭州之江新材料有限公司 | Two-component polyurethane adhesive capable of being rapidly cured in long opening time |
-
2023
- 2023-07-27 CN CN202310938767.8A patent/CN117887407A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419714A (en) * | 2014-09-09 | 2016-03-23 | 贵阳时代沃顿科技有限公司 | Epoxy resin two-component polyurethane adhesive and preparation method thereof |
| CN109111892A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | A kind of quick-dry type double component solvent-free polyurethane composite adhesive and its preparation method and application |
| CN112574403A (en) * | 2020-12-07 | 2021-03-30 | 山东一诺威聚氨酯股份有限公司 | Castor oil-based polyol for solvent-free adhesive and preparation method and application thereof |
| CN113388360A (en) * | 2021-06-29 | 2021-09-14 | 杭州之江新材料有限公司 | Two-component polyurethane adhesive capable of being rapidly cured in long opening time |
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