CN101597470B - Solvent-free bi-component polyurethane adhesive and preparation method thereof - Google Patents
Solvent-free bi-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN101597470B CN101597470B CN2008101142979A CN200810114297A CN101597470B CN 101597470 B CN101597470 B CN 101597470B CN 2008101142979 A CN2008101142979 A CN 2008101142979A CN 200810114297 A CN200810114297 A CN 200810114297A CN 101597470 B CN101597470 B CN 101597470B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 98
- 239000000853 adhesive Substances 0.000 title claims abstract description 96
- 239000004814 polyurethane Substances 0.000 title claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 105
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims description 97
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- 239000004721 Polyphenylene oxide Substances 0.000 claims description 79
- 229920000570 polyether Polymers 0.000 claims description 79
- 229920005906 polyester polyol Polymers 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 31
- 230000003381 solubilizing effect Effects 0.000 claims description 30
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 26
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 24
- 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 description 22
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 22
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004359 castor oil Substances 0.000 claims description 13
- 235000019438 castor oil Nutrition 0.000 claims description 13
- 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 description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- -1 isocyanate group compound Chemical group 0.000 claims description 12
- 229960004063 propylene glycol Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 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 11
- 238000000034 method Methods 0.000 claims description 11
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- 238000001816 cooling Methods 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
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- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical group 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 4
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229910000071 diazene Inorganic materials 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
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- 235000013772 propylene glycol Nutrition 0.000 description 5
- 238000010411 cooking Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
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- 239000003292 glue Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 229920005749 polyurethane resin Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a solvent-free bi-component polyurethane adhesive and a preparation method thereof, relating to an adhesive for composite flexible package in the fields of food, medicine and the like, comprising the following components: the adhesive is prepared by mixing a component A and a component B, wherein the component A is an isocyanate-terminated compound, the component B is a polyhydroxy compound, and the component A and the component B are mixed according to the weight ratio of 2: 1. The adhesive solves the problems that the use effect of the existing solvent-free adhesive is influenced and the use range of the adhesive is limited due to the defects of the existing solvent-free adhesive in the aspects of transparency, viscosity, low-temperature coating property, peeling strength and boiling resistance, the component A and the component B of the adhesive are transparent liquids, are environment-friendly and solvent-free, have low viscosity, have the viscosity of the component A of 2000-5000 mPa.s and the viscosity of the component B of 400-2000 mPa.s at 25 ℃, have good low-temperature coating property, have good peeling strength and maintain good peeling strength after boiling, and are environment-friendly adhesives.
Description
Technical Field
The invention relates to a polyurethane adhesive, in particular to an environment-friendly solvent-free bi-component polyurethane adhesive which can be used as an interlayer adhesive for composite flexible packages in the fields of food, medicine and the like.
Background
The solvent type polyurethane adhesive is widely applied in the composite flexible package industry, however, the organic solvent is flammable and explosive, volatile and smelly, causes air pollution when in use, and has more or less toxicity; with the increasing importance of the sanitary and safety performance of packaging, under the increasing public opinion pressure of protecting the global environment, the green and environment-friendly solvent-free composite adhesive is more and more concerned as one of the substitutes of the solvent-based composite adhesive.
However, the solvent-free adhesives have a high viscosity due to the absence of solvents, and the adhesives have poor coatability during the production process, which is likely to cause problems in appearance or other qualities. In order to ensure the coatability of the adhesive, the viscosity of the adhesive needs to be reduced, and in order to achieve a low viscosity of the adhesive, the molecular weight of the resin contained in the adhesive needs to be reduced as compared with the case of a solvent-based adhesive. When the molecular weight of the resin contained in the adhesive is reduced, the adhesive strength, particularly initial adhesion, is low, and the adhesiveness to a metal-deposited plastic film or metal foil is particularly poor. Therefore, the development of low viscosity, high peel strength, retort resistant solventless glues is a direction of development.
In the CN1277894C patent, japan eastern ink company uses polyester polyol having a high glass transition temperature and a large number average molecular weight, polyester polyol having a low glass transition temperature and a small number average molecular weight, monofunctional alcohol, trifunctional isocyanate, polybasic acid anhydride, silane coupling agent, and the like to prepare a solvent-free adhesive. The solvent-free adhesive can be used for food packaging, medical product packaging, cosmetic packaging materials and the like, has excellent coating property and adhesiveness, and has little reduction of adhesive property after being steamed or used for a long time. Although the adhesive is mentioned as having excellent coatability in the invention, the examples of the invention mention that the viscosity at 70 ℃ is 3000 mPas, which is rather high at 25 ℃, and the low-temperature coatability of the adhesive is poor.
In the patent CN1138077A, Morton International Co., Ltd, Germany invented a solvent-free adhesive, the preparation method of the solvent-free adhesive is: vinyl acetate and/or acrylic acid monomers are polymerized into corresponding polymers in polyether polyol and/or polyester polyol by a free radical method, and then isocyanate group (NCO) -terminated polyurethane prepolymer is added. The solvent-free adhesive has transparency and low viscosity, and the viscosity is 2500mPa & s at 100 ℃. The adhesive can also be applied only at high temperatures, and the viscosity at 25 ℃ is also relatively high.
In order to achieve the purposes of low viscosity and high peel strength, researchers adopt a polyester and polyether mixed type to prepare polyurethane glue. For example, the high molecular weight polyester is synthesized by using aliphatic/aromatic mixed dibasic acid and dihydric alcohol through a melt polycondensation method, the resin and polyether glycol react with different isocyanates to be used as a main agent of the adhesive, and the main agent is matched with the synthesized curing agent, so that the solvent-free polyurethane adhesive can be used for compounding plastic/plastic flexible packages. But the adhesive prepared was opaque in appearance.
The inventors have found that the above prior art has at least the following problems: although the above data have been a lot of research on solvent-free polyurethane adhesives, the requirements for preparing solvent-free polyurethane adhesives with low viscosity and high peel strength cannot be met in terms of transparency, low viscosity, low temperature coatability, high peel strength, and retort resistance of the system.
Disclosure of Invention
The embodiment of the invention provides a solvent-free type bi-component polyurethane adhesive and a preparation method thereof, provides a solvent-free type bi-component polyurethane adhesive with high transparency, low viscosity, high peel strength and boiling resistance, and can be widely applied to flexible package composite films in the fields of food, medicine and the like.
The purpose of the invention is realized by the following technical scheme:
the embodiment of the invention provides a solvent-free type bi-component polyurethane adhesive, which comprises the following components: the component A is an isocyanate-terminated compound, the component B is a polyhydroxy compound, and the component A and the component B are mixed according to the weight ratio of 2: 1 to obtain the bi-component polyurethane adhesive;
wherein, the functionality of at least one raw material compound in the terminal isocyanate group compound of the component A and/or the polyhydroxy compound of the component B is 2.5-3.0; at least one of the component A and the component B comprises a polyester polyol.
The isocyanate-terminated compound of the component A is prepared by reacting polyisocyanate and polyhydroxy compound, wherein the polyhydroxy compound consists of polyether polyol, polyester polyol and micromolecular polyol;
the polyol of component B consists of polyether polyol; or the polyhydroxy compound consists of polyether polyol, polyester polyol and solubilizing resin; alternatively, the polyol is composed of a polyether polyol and a hydroxyl group-containing compound.
The polyisocyanate in the component A is selected from at least one of diphenylmethane diisocyanate (MDI) with molecular weight of more than or equal to 220, isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate (polymeric MDI, also called PAPI) and liquefied MDI; wherein the liquefied MDI is at least one of a mixture of diphenylmethane-4, 4 '-diisocyanate and diphenylmethane-2, 4' -diisocyanate (blend MDI), low molecular polyether modified MDI (U-MDI) or carbodiimide modified MDI (C-MDI); preferably, MDI, C-MDI and IPDI are blended.
The isocyanate group (NCO%) content of the isocyanate group-terminated compound of the component A is 5 to 12% by weight, preferably 8 to 10% by weight; the isocyanate group-terminated compound has a viscosity of 1000 to 20000mPa.s at 25 ℃, preferably a viscosity of 2000 to 5000 mPa.s;
in the component A, the polyether polyol accounts for 5-90% of the total weight of the polyhydroxy compound, and the polyester polyol accounts for 5-90% of the total weight of the polyhydroxy compound; the proportion of the small molecular polyol in the total weight of the polyhydroxy compound is 0.5-10%.
The polyhydroxy compound of the component B is a polyhydroxy compound with a hydroxyl value of 32-200 mg KOH/g, preferably a polyhydroxy compound with a hydroxyl value of 48-120 mg KOH/g; the viscosity of the polyhydroxy compound of the component B is 300-5000 mPa.s at 25 ℃, and the preferred viscosity is 400-2000 mPa.s.
When the polyhydroxy compound of the component B consists of polyether polyol and a hydroxyl-containing compound, the hydroxyl-containing compound is at least one of polycaprolactone diol, polycarbonate diol, castor oil, epoxy resin and hydroxyl-containing polyacrylate.
When the polyhydroxy compound of the component B consists of polyether polyol, polyester polyol and a solubilizing resin, the solubilizing resin is at least one of rosin resin and modified rosin resin.
When the polyhydroxy compound of the component B consists of polyether polyol, polyester polyol, a hydroxyl-containing compound and a solubilizing resin, the weight ratio of each component is as follows: 10-90 parts of polyether polyol, 10-90 parts of polyester polyol and 0.5-5 parts of solubilizing resin;
when the polyhydroxy compound of the component B consists of polyether polyol and hydroxyl-containing compound, the weight ratio of each component is as follows: 50-99 parts of polyether polyol and 1-50 parts of hydroxyl-containing compound.
The polyether polyol in the component A and/or the component B is polyether polyol with the average molecular weight of 400-3000, preferably polyether polyol with the molecular weight of 600-2000; the viscosity of the polyether polyol is 1000-2500 mPa.s at 25 ℃;
the polyester polyol adopted in the component A and/or the component B is polymerized by micromolecular polybasic acid and micromolecular polyol; the micromolecular polybasic acid consists of at least one of adipic acid and sebacic acid and isophthalic acid and/or terephthalic acid, wherein the usage amount of the isophthalic acid and/or the terephthalic acid accounts for 20-90% of the total weight of the micromolecular polybasic acid; the micromolecular polyalcohol consists of 1, 2-propylene glycol and at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and cyclohexanedimethanol, wherein the using amount of the 1, 2-propylene glycol accounts for 1-50% of the total weight of the micromolecular polyalcohol.
The embodiment of the invention also provides a preparation method of the solvent-free type bi-component polyurethane adhesive, which comprises the following steps:
taking the raw materials of the component A and the component B according to the weight percentage:
the component A comprises: polyisocyanates and polyols;
the component B comprises: a polyether polyol; alternatively, polyether polyols, polyester polyols and solubilizing resins; alternatively, a polyether polyol and a hydroxyl group-containing compound;
preparation of the isocyanate-terminated compound of component a: mixing the polyhydroxy compounds at 30-50 ℃, adding polyisocyanate, reacting at 60-80 ℃ for 3-4 hours, and cooling to normal temperature to obtain a component A;
preparation of the polyol of component B:
(1) if polyether polyol is used as a raw material, mixing the polyether polyol at 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare a polyhydroxy compound;
or,
(2) if polyether polyol, polyester polyol and solubilizing resin are used as raw materials, the polyether polyol and the polyester polyol are mixed at the temperature of 30-50 ℃, the solubilizing resin is added, the mixture is heated to 90-100 ℃, the mixture is kept warm and stirred for 1-2 hours until the solubilizing resin is completely dissolved, the system is clear and transparent, and the mixture is cooled to the normal temperature to obtain the polyhydroxy compound of the component B; wherein the initial mixing temperature of the solubilizing resin is more than or equal to 30 ℃;
or,
(3) if polyether polyol and a hydroxyl-containing compound are used as raw materials, mixing the polyether polyol and the hydroxyl-containing compound at the temperature of 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare a polyhydroxy compound;
mixing the prepared component A with the component B prepared by any one method of (1), (2) or (3) according to the weight ratio of 2: 1 to obtain the adhesive.
According to the technical scheme provided by the embodiment of the invention, the isocyanate-terminated compound of the component A and the polyhydroxy compound of the component B are used for preparing the two-component adhesive, and the component A and the component B are transparent liquids, have no solvent and have low viscosity, so that the viscosity of the component A can be 2000-5000 mPa.s and the viscosity of the component B can be 400-2000 mPa.s at 25 ℃, have good low-temperature coating property and good peel strength, and keep good peel strength after cooking. The solvent-free bi-component polyurethane adhesive has good environmental protection effect due to no solvent, and can be used as a composite flexible package interlayer adhesive in the fields of food, medicine and the like.
Detailed Description
The embodiment of the invention provides a solvent-free bi-component polyurethane adhesive and a preparation method thereof, the adhesive can be used for a composite flexible package interlayer adhesive in the fields of food, medicine and the like, and comprises a component A and a component B, wherein the component A is an isocyanate-terminated compound, the component B is a polyhydroxy compound, and the adhesive is obtained after the component A and the component B are mixed according to the weight ratio of 2: 1, wherein the functionality of at least one raw material compound in the isocyanate-terminated compound of the component A and/or the polyhydroxy compound of the component B is 2.5-3.0; at least one of the component A and the component B comprises a polyester polyol.
The adhesive has the advantages that the component A and the component B are solvent-free and have low viscosity, the viscosity of the component A can be 2000-5000 mPa.s at 25 ℃, the viscosity of the component B can be 400-2000 mPa.s, the adhesive has good low-temperature coating property and good peel strength, and the good peel strength is kept after cooking, so that the adhesive is an environment-friendly adhesive.
For the sake of understanding, the following further description will be made with reference to specific examples.
Example one
The present implementation provides a solvent-free two-component polyurethane adhesive, comprising: the composition comprises a component A and a component B, wherein the component A is an isocyanate-terminated compound, and the component B is a polyhydroxy compound;
the component A is formed by reacting polyisocyanate and a polyhydroxy compound, wherein the polyhydroxy compound consists of polyether polyol, polyester polyol and micromolecular polyol; the isocyanate group weight content (NCO%) of the isocyanate group compound at the end of the component A is within the range of 5-12%, preferably 8-10%, the viscosity at 25 ℃ is within the range of 1000-20000 mPa.s, preferably 2000-5000 mPa.s, and the proportion of the polyether polyol is 5-90%, the proportion of the polyester polyol is 5-90%, and the proportion of the micromolecular polyol is 0.5-10% based on the total weight of the polyhydroxy compound in the component A;
mixing the polyhydroxy compounds at 30-50 ℃, adding polyisocyanate, reacting for 3-4 hours at 60-80 ℃, and cooling to normal temperature to obtain a component A-terminal isocyanate group compound;
wherein the hydroxyl value of the polyhydroxy compound of the component B is 32-200 mg KOH/g, preferably 48-120 mg KOH/g, the viscosity at 25 ℃ is within the range of 300-5000 mPa.s, preferably 400-2000 mPa.s, and the polyhydroxy compound can have the following three compositions: (1) the water-soluble polyurethane resin consists of polyether polyol, or (2) the water-soluble polyurethane resin consists of polyether polyol, polyester polyol and solubilizing resin; or, (3) consists of polyether polyol and hydroxyl-containing compound.
If the polyol of component B consists only of polyether polyol (which may be one or more polyether polyols), the total amount of polyether polyol used is 100 parts by weight;
if the polyhydroxy compound of the component B consists of polyether polyol, polyester polyol and solubilizing resin, the weight ratio of each component is as follows: 10-90 parts of polyether polyol, preferably 20-50 parts; 10-90 parts of polyester polyol, preferably 50-80 parts; 0.5-5 parts of solubilizing resin, preferably 0.5-3 parts; in practice, small molecular weight polyol and hydroxyl-containing compound can be added on the basis of the components of polyether polyol, polyester polyol and solubilizing resin, and the specific dosage is as follows: 0-10 parts of small molecular polyol, preferably 0.5-3 parts; 0 to 10 parts of hydroxyl-containing compound, preferably 0.5 to 3 parts;
if the polyol of component B consists of polyether polyol and hydroxyl-containing compound, the weight ratio of the components is as follows: 50-99 parts of polyether polyol, preferably 90-99 parts; 1 to 50 parts of hydroxyl group-containing compound, preferably 1 to 10 parts.
The mixing process of the component B is also divided into the following three cases according to different used raw materials:
(1) if polyether polyol is used as a raw material, mixing the one or more polyether polyols at 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare a polyhydroxy compound;
or,
(2) if polyether polyol, polyester polyol and solubilizing resin are used as raw materials, the polyether polyol and the polyester polyol are mixed at the temperature of 30-50 ℃, the solubilizing resin is added, the mixture is heated to 90-100 ℃, the mixture is kept warm and stirred for 1-2 hours until the solubilizing resin is completely dissolved, the system is clear and transparent, and the mixture is cooled to the normal temperature to obtain the polyhydroxy compound of the component B; wherein the initial mixing temperature of the solubilizing resin is more than or equal to 30 ℃;
or,
(3) if polyether polyol and a hydroxyl-containing compound are used as raw materials, mixing the polyether polyol and the hydroxyl-containing compound at the temperature of 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare a polyhydroxy compound;
mixing the prepared component A with the component B prepared by any one method of (1), (2) or (3) according to the weight ratio of 2: 1 to obtain the adhesive.
In the solvent-free bi-component polyurethane adhesive, the functionality of at least one raw material compound in polyisocyanate and/or polyhydroxy compound is 2.5-3.0; the compound with the functionality in the range can form a crosslinking system in the system, so that the cured adhesive has good mechanical property and good boiling resistance.
In the solvent-free two-component polyurethane adhesive, at least one polyester polyol is used in the component A and/or the component B, so that the adhesive can be endowed with excellent bonding force, namely high peel strength by the polyester polyol.
In the adhesive, the polyisocyanate cyanate in component a is selected from one or more of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate (polymeric MDI, also called PAPI), and liquefied MDI, wherein the liquefied MDI may be a mixture of diphenylmethane-4, 4 '-diisocyanate and diphenylmethane-2, 4' -diisocyanate (blend MDI), low molecular polyether modified MDI (U-MDI), and carbodiimide modified MDI (C-MDI); preferably, MDI, C-MDI and IPDI are mixed; does not contain polyisocyanate with molecular weight less than 220; the polyisocyanates of the types are selected, so that the adhesive system is ensured to have low viscosity, the adhesive is endowed with good low-temperature coating property and good coating quality is obtained, meanwhile, the molecular weight of the selected polyisocyanates is higher than 220, the system is ensured not to have the micromolecular polyisocyanate with strong volatility and high toxicity, and the environment-friendly property is realized.
The polyether polyol in the component A in the adhesive has an average molecular weight of 400-3000, preferably 600-2000; the average molecular weight range is favorable for forming a stable compatible system with the polyester polyol, improving the transparency of the adhesive and simultaneously ensuring the quality and the peel strength of the adhesive.
The polyester polyol in the component A of the adhesive is polymerized by micromolecular polybasic acid and micromolecular polyol; wherein the small molecular polybasic acid consists of isophthalic acid and/or terephthalic acid and at least one of adipic acid and sebacic acid, wherein the weight ratio of the isophthalic acid and/or the terephthalic acid accounts for 20-90% of the total weight of the small molecular polybasic acid, and the ratio range of the isophthalic acid and/or the terephthalic acid is favorable for improving the adhesive property of the adhesive to obtain high peel strength and reducing the crystallinity of the polyester polyol to obtain high transparency of the adhesive; wherein the micromolecular polyhydric alcohol is composed of 1, 2-propylene glycol and at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and cyclohexanedimethanol, wherein the weight ratio of the 1, 2-propylene glycol accounts for 1-50% of the total weight of the micromolecular polyhydric alcohol, and the proportion range of the 1, 2-propylene glycol with the asymmetric structure is favorable for reducing the crystallinity of the polyester polyhydric alcohol so as to ensure that the adhesive has high transparency; the average molecular weight of the polyester polyol is 400-3000, preferably 600-2000, and the molecular weight range of the polyester polyol is favorable for improving the compatibility with the polyether polyol, so that the adhesive has high transparency and high peel strength; the viscosity of the adhesive is 1000-2500 mPa.s at 25 ℃, and the viscosity range of polyester polyol enables the adhesive to have low viscosity and good coating property; the functionality was 2.0.
The polyether polyol in the component B has the average molecular weight of 400-8000, preferably 600-2000; the average molecular weight range is favorable for forming a stable compatible system with the polyester polyol, improving the transparency of the adhesive and simultaneously ensuring the quality and the peel strength of the adhesive.
When the polyol of component B consists of polyether polyol, polyester polyol and solubilizing resin, the polyester polyol is the same as the polyester polyol of component A; wherein, the solubilizing resin can be rosin resin or modified rosin resin; the rosin resin is favorable for promoting the miscibility of the polyester polyol and the polyether polyol and is favorable for the adhesive to obtain high transparency and stability.
If the polyhydroxy compound of component B consists of polyether polyol and hydroxyl-containing compound, the hydroxyl-containing compound can be one or more of polycaprolactone diol, polycarbonate diol, castor oil, epoxy resin and hydroxyl-containing polyacrylate.
In the solvent-free bi-component polyurethane adhesive, the component A and the component B are both transparent liquid; the environment is protected and no solvent is used; the viscosity of the component A is 2000-5000 mPa.s, and the viscosity of the component B is 400-2000 mPa.s at 25 ℃; the coating has good low-temperature coating property; has good peel strength and maintains good peel strength after cooking; the solvent-free bi-component polyurethane adhesive can be used as a composite flexible package interlayer adhesive in the fields of food, medicine and the like.
Example two
The embodiment provides a preparation method of a solvent-free bi-component polyurethane adhesive, which comprises the following specific steps:
raw materials and proportions of polyester polyol:
isophthalic acid/adipic acid/ethylene glycol/1, 2-propanediol (mole ratio) 1/2/3/0.6;
the component A comprises the following raw materials in percentage by weight:
100g of polyester polyol, 500g of polypropylene glycol ether (2000 molecular weight), 5g of 1, 4-butanediol, 350g of MDI and 30g of IPDI;
the characteristics are as follows: clear liquid, viscosity 4000mPa.s at 25 ℃.
The component B comprises the following raw materials in proportion and processes:
720g of polyester polyol, 250g of polypropylene glycol ether (1000 molecular weight), 10g of castor oil and 10g of rosin resin;
mixing polypropylene glycol ether, polyester polyol and castor oil at 40 ℃, adding rosin resin, heating to 90-100 ℃, keeping the temperature and stirring for 2 hours until the rosin resin is completely dissolved, and cooling the whole component B, wherein the component B is clear and transparent.
The characteristics are as follows: clear liquid, viscosity 1900mPa.s at 25 ℃.
The application comprises the following steps: and mixing the component A and the component B according to the weight ratio of 100/50 at room temperature, compounding the BOPP/PE film, and testing the peel strength after curing for 7 days at room temperature, wherein the peel strength can reach 3.0N. After being cooked for 1h at 135 ℃, the peel strength is reduced by less than 5 percent.
EXAMPLE III
The embodiment provides a preparation method of a solvent-free bi-component polyurethane adhesive, which comprises the following specific steps:
raw materials and proportions of polyester polyol:
isophthalic acid/adipic acid/ethylene glycol/1, 2-propanediol (mole ratio) 1/2/3/0.6.
The component A comprises the following raw materials in percentage by weight:
100g of polyester polyol, 500g of polypropylene glycol ether (2000 molecular weight), 6g of 1, 4-butanediol, 350g of blending MDI and 30g of IPDI;
the characteristics are as follows: clear liquid, viscosity 3500 mPas at 25 ℃.
The component B comprises the following raw materials in proportion and processes:
720g of polyester polyol, 250g of polypropylene glycol ether (1000 molecular weight), 10g of castor oil, 10g of epoxy resin and 10g of rosin resin;
mixing polypropylene glycol ether, polyester polyol, castor oil and epoxy resin at 40 ℃, adding rosin resin, heating to 90-100 ℃, keeping the temperature and stirring for 2 hours until the rosin resin is completely dissolved, and cooling the whole component B to be clear and transparent.
The characteristics are as follows: clear liquid, viscosity 1800mPa.s at 25 ℃.
The application comprises the following steps: and mixing the component A and the component B according to the weight ratio of 100/50 at room temperature, compounding the BOPP/PE film, and testing the peel strength after curing for 7 days at room temperature, wherein the peel strength can reach 3.0N. After being cooked for 1h at 135 ℃, the peel strength is reduced by less than 5 percent.
Example four
The embodiment provides a preparation method of a solvent-free bi-component polyurethane adhesive, which comprises the following specific steps:
raw materials and proportions of polyester polyol:
isophthalic acid/adipic acid/ethylene glycol/1, 2-propanediol (mole ratio) 1/2/3/0.6.
The component A comprises the following raw materials in percentage by weight:
100g of polyester polyol, 500g of polypropylene glycol ether (2000 molecular weight), 5g of 1, 4-butanediol, 350g of C-MDI and 30g of IPDI;
the characteristics are as follows: clear liquid, viscosity 3000mPa.s at 25 ℃.
The component B comprises the following raw materials in proportion and processes:
720g of polyester polyol, 250g of polypropylene glycol ether (1000 molecular weight), 10g of polypropylene glycol ether (3000 molecular weight) and 10g of rosin resin;
mixing polypropylene glycol ether, polypropylene glycol ether and polyester polyol at 40 ℃, adding rosin resin, heating to 90-100 ℃, keeping the temperature and stirring for 2 hours until the rosin resin is completely dissolved, and cooling the whole component B to be clear and transparent.
The characteristics are as follows: clear liquid, viscosity 2000mPa.s at 25 ℃.
The application comprises the following steps: and mixing the component A and the component B according to the weight ratio of 100/50 at room temperature, compounding the BOPP/PE film, and testing the peel strength after curing for 7 days at room temperature, wherein the peel strength can reach 3.0N. After being cooked for 1h at 135 ℃, the peel strength is reduced by less than 5 percent.
EXAMPLE five
The embodiment provides a preparation method of a solvent-free bi-component polyurethane adhesive, which comprises the following specific steps:
raw materials and proportions of polyester polyol:
isophthalic acid/adipic acid/ethylene glycol/neopentyl glycol/1, 2-propanediol (mole ratio) 1/2/1/2/0.6.
The component A comprises the following raw materials in percentage by weight:
100g of polyester polyol, 500g of polypropylene glycol ether (2000 molecular weight), 350g of MDI, 30g of IPDI;
the characteristics are as follows: clear liquid, viscosity 4000mPa.s at 25 ℃.
The component B comprises the following raw materials in proportion and processes:
720g of polyester polyol, 250g of polypropylene glycol ether (1000 molecular weight), 10g of castor oil and 10g of rosin resin;
mixing polypropylene glycol ether, polyester polyol and castor oil at 40 ℃, adding rosin resin, heating to 90-100 ℃, keeping the temperature and stirring for 2 hours until the rosin resin is completely dissolved, and cooling the whole component B, wherein the component B is clear and transparent.
The characteristics are as follows: clear liquid, viscosity 1900mPa.s at 25 ℃.
The application comprises the following steps: and mixing the component A and the component B according to the weight ratio of 100/50 at room temperature, compounding the BOPP/PE film, and testing the peel strength after curing for 7 days at room temperature, wherein the peel strength can reach 3.0N. After being cooked for 1h at 135 ℃, the peel strength is reduced by less than 5 percent.
EXAMPLE six
The embodiment provides a preparation method of a solvent-free bi-component polyurethane adhesive, which comprises the following specific steps:
raw materials and proportions of polyester polyol:
isophthalic acid/adipic acid/ethylene glycol/neopentyl glycol/1, 2-propanediol (mole ratio) 1/2/1/2/0.6;
the component A comprises the following raw materials in percentage by weight:
100g of polyester polyol, 500g of polypropylene glycol ether (2000 molecular weight), 350g of MDI and 30g of IPDI.
The characteristics are as follows: clear liquid, viscosity 4000mPa.s at 25 ℃.
The component B comprises the following raw materials in proportion and processes:
720g of polyester polyol, 250g of polypropylene glycol ether (1000 molecular weight), 10g of castor oil and 10g of rosin resin;
mixing polypropylene glycol ether, polyester polyol and castor oil at 40 ℃, adding rosin resin, heating to 90-100 ℃, keeping the temperature and stirring for 2 hours until the rosin resin is completely dissolved, and cooling the whole component B, wherein the component B is clear and transparent.
The characteristics are as follows: clear liquid, viscosity 1900mPa.s at 25 ℃.
The application comprises the following steps: mixing component A and component B at 100/50 weight ratio at room temperature, compounding BOPP/PE film, aging at room temperature for 7 days
The peel strength can reach 3.0N by testing the peel strength. After being cooked for 1h at 135 ℃, the peel strength is reduced by less than 5 percent.
In summary, the adhesive of the embodiment of the invention is composed of the isocyanate-terminated compound (component a) and the polyol (component B) which are transparent liquids, is environment-friendly, solvent-free and low in viscosity, the viscosity of the component a can be 2000-5000 mpa.s and the viscosity of the component B can be 400-2000 mpa.s at 25 ℃, has good low-temperature coating property, good peel strength and good peel strength after cooking, and is an environment-friendly adhesive.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention by any order in the embodiments, and the scope of the present invention is not limited thereto. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A solvent-free bi-component polyurethane adhesive is characterized in that: the adhesive comprises: the component A is an isocyanate-terminated compound, the component B is a polyhydroxy compound, and the component A and the component B are mixed according to the weight ratio of 2: 1 to obtain the bi-component polyurethane adhesive;
wherein, the functionality of at least one raw material compound in the terminal isocyanate group compound of the component A and/or the polyhydroxy compound of the component B is 2.5-3.0; at least one of the component A and the component B comprises a polyester polyol;
the isocyanate-terminated compound of the component A is prepared by reacting polyisocyanate and polyhydroxy compound, wherein the polyhydroxy compound consists of polyether polyol, polyester polyol and micromolecular polyol;
the polyisocyanate in the component A is selected from at least one of isophorone diisocyanate with molecular weight of more than or equal to 220, polymethylene polyphenyl polyisocyanate and liquefied MDI; wherein the liquefied MDI is at least one of a mixture of diphenylmethane-4, 4 '-diisocyanate and diphenylmethane-2, 4' -diisocyanate, low molecular weight polyether modified MDI or carbonized diimine modified MDI;
the isocyanate group content of the isocyanate group-terminated compound of the component A is 5-12% by weight, and the viscosity of the isocyanate group-terminated compound is 1000-20000 mPa.s at 25 ℃;
in the component A, the polyether polyol accounts for 5-90% of the total weight of the polyhydroxy compound, and the polyester polyol accounts for 5-90% of the total weight of the polyhydroxy compound; the proportion of the small molecular polyol in the total weight of the polyhydroxy compound is 0.5-10%;
the polyol of component B consists of polyether polyol; or the polyhydroxy compound consists of polyether polyol, polyester polyol and solubilizing resin; alternatively, the polyol is composed of a polyether polyol and a hydroxyl group-containing compound; the hydroxyl-containing compound is at least one of polycaprolactone diol, polycarbonate diol, castor oil, epoxy resin and hydroxyl-containing polyacrylate;
the polyhydroxy compound of the component B is a polyhydroxy compound with a hydroxyl value of 32-200 mg KOH/g, and the viscosity of the polyhydroxy compound of the component B is 300-5000 mPa.s at 25 ℃;
the polyether polyol in the component A and/or the component B is polyether polyol with the average molecular weight of 400-3000, and the viscosity of the polyether polyol is 1000-2500 mPa.s at 25 ℃;
the polyester polyol adopted in the component A and/or the component B is polymerized by micromolecular polybasic acid and micromolecular polyol.
2. The adhesive of claim 1, wherein: the polyisocyanate in the component A adopts a mixture of diphenylmethane-4, 4 '-diisocyanate and diphenylmethane-2, 4' -diisocyanate, carbonized diimine modified MDI and IPDI.
3. The adhesive of claim 1, wherein: the isocyanate group content of the terminal isocyanate group compound of the component A is 8-10% by weight, and the viscosity is 2000-5000 mPa.s at 25 ℃.
4. The adhesive of claim 1, wherein: the hydroxyl value of the polyhydroxy compound of the component B is 48-120 mg KOH/g; the viscosity of the polyhydroxy compound of the component B is 400-2000 mPa.s at 25 ℃.
5. The adhesive of claim 1, wherein: the component B polyhydroxy compound is composed of polyether polyol, polyester polyol and solubilizing resin, wherein the solubilizing resin is at least one of rosin resin and modified rosin resin.
6. The adhesive of claim 1, wherein: the polyhydroxy compound of the component B consists of polyether polyol, polyester polyol and solubilizing resin, and the weight ratio of each component is as follows: 10-90 parts of polyether polyol, 10-90 parts of polyester polyol and 0.5-5 parts of solubilizing resin;
the polyhydroxy compound of the component B consists of polyether polyol and hydroxyl-containing compound, and the weight ratio of each component is as follows: 50-99 parts of polyether polyol and 1-50 parts of hydroxyl-containing compound; the hydroxyl-containing compound is at least one of polycaprolactone diol, polycarbonate diol, castor oil, epoxy resin and hydroxyl-containing polyacrylate.
7. The adhesive of claim 1, wherein: polyether polyol with the molecular weight of 600-2000 is adopted as polyether polyol in the component A and/or the component B;
in the polyester polyol adopted in the component A and/or the component B, the small molecular polybasic acid is composed of at least one of adipic acid and sebacic acid and isophthalic acid and/or terephthalic acid, wherein the usage amount of the isophthalic acid and/or the terephthalic acid accounts for 20-90% of the total weight of the small molecular polybasic acid; the micromolecular polyalcohol consists of 1, 2-propylene glycol and at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and cyclohexanedimethanol, wherein the using amount of the 1, 2-propylene glycol accounts for 1-50% of the total weight of the micromolecular polyalcohol.
8. A preparation method of a solvent-free bi-component polyurethane adhesive is characterized by comprising the following steps:
taking the raw materials of the component A and the component B according to the formula of any one of claims 1 to 7:
the component A comprises: polyisocyanates and polyols;
the component B comprises: a polyether polyol; alternatively, polyether polyols, polyester polyols and solubilizing resins; alternatively, a polyether polyol and a hydroxyl group-containing compound; the hydroxyl-containing compound is at least one of polycaprolactone diol, polycarbonate diol, castor oil, epoxy resin and hydroxyl-containing polyacrylate;
preparation of the isocyanate-terminated compound of component a: mixing the polyhydroxy compounds at 30-50 ℃, adding polyisocyanate, reacting at 60-80 ℃ for 3-4 hours, and cooling to normal temperature to obtain a component A;
preparation of the polyol of component B:
(1) taking polyether polyol as a raw material, mixing the polyether polyol at 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare a polyhydroxy compound;
or,
(2) taking polyether polyol, polyester polyol and solubilizing resin as raw materials, mixing the polyether polyol and the polyester polyol at the temperature of 30-50 ℃, adding the solubilizing resin, heating to 90-100 ℃, keeping the temperature and stirring for 1-2 hours until the solubilizing resin is completely dissolved, wherein the system is clear and transparent, and cooling to the normal temperature to obtain the polyhydroxy compound of the component B; wherein the initial mixing temperature of the solubilizing resin is more than or equal to 30 ℃;
or,
(3) taking polyether polyol and a hydroxyl-containing compound as raw materials, mixing the polyether polyol and the hydroxyl-containing compound at the temperature of 30-50 ℃, and stirring until the mixture is uniform and transparent to prepare the polyhydroxy compound;
mixing the prepared component A with the component B prepared by any one method of (1), (2) or (3) according to the weight ratio of 2: 1 to obtain the adhesive.
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| US11883557B2 (en) | 2018-08-21 | 2024-01-30 | The Secant Group, Llc | Tunable, controlled-release, urethane-containing elastomers and processes of forming the same |
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| CN101597470A (en) | 2009-12-09 |
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