CN112048278B - Steaming-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof - Google Patents
Steaming-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof Download PDFInfo
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention relates to the technical field of polyurethane adhesives, in particular to a steaming-resistant bi-component solvent-free polyurethane laminating adhesive and a preparation method thereof. The boiling-resistant bi-component solvent-free polyurethane laminating adhesive consists of a component A and a component B according to the mass ratio of 100-200; the component A is a prepolymer with 15-20wt% of NCO content prepared by the reaction of high temperature resistant polyester polyol and polyisocyanate; the component B consists of castor oil modified polyester polyol, polyether polyol B and an anti-hydrolysis modifier. The boiling-resistant bi-component solvent-free polyurethane laminating adhesive has the advantages of environmental protection, low viscosity, high peel strength and high-temperature boiling resistance, still has very high peel strength after being boiled by 135 ℃ steam, and is particularly suitable for the adhesive for compounding the flexible packaging film which needs long-time high-temperature sterilization and disinfection; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, in particular to a steaming-resistant bi-component solvent-free polyurethane laminating adhesive and a preparation method thereof.
Background
Along with the continuous improvement of living standard of people, the requirement on the packaging material is higher and higher, the attractive appearance of the packaging material is emphasized, and higher requirements on the practicability and the environmental protection are also provided. At present, the adhesive for flexible packaging in China is the two-component solvent type polyurethane laminating adhesive with the most use and the best performance. However, the solvent-based laminating adhesives have the following problems: 1) The solvent is inflammable and explosive, and potential safety hazards exist in the production, storage and use processes; 2) The solvent has strong smell and toxicity, and does not meet the requirement of environmental protection. Therefore, the green and environment-friendly solvent-free laminating adhesive is more and more valued by people to replace a solvent-based laminating adhesive.
Although the solvent-free laminating adhesive has more advantages, the solvent-free laminating adhesive has a plurality of problems in the popularization process, because the solvent-free laminating adhesive does not contain a solvent, has higher viscosity, is difficult to coat uniformly, has low cohesive force and poor steaming resistance. In order to ensure good coating properties of the solvent-free laminating adhesives, the viscosity of the laminating adhesives must be reduced. In addition, the laminating adhesive is applied to the field of food packaging, particularly for packaging cooked food, and in order to prevent the food from deteriorating, the packaged food must be sterilized at high temperature, so that the food is not deteriorated in the storage process, and the packaging material is required to withstand the damage of high-temperature and high-humidity environment. Therefore, the development of a solvent-free polyurethane adhesive with low viscosity, high strength and high temperature and humidity resistance is an urgent research subject to be solved in the field.
The patent CN2013100893651 discloses a low-viscosity solvent-free polyurethane laminating adhesive, which comprises a component A and a component B, wherein the component A is polyester polyol, and an isocyanate-terminated compound obtained by reacting polyether polyol, vegetable oil polyol and isocyanate, and the component B is a hydroxyl-terminated mixture obtained by mixing vegetable oil polyol, modified vegetable oil polyol, micromolecular polyol and a bonding force promoter; the component A and the component B are prepared according to the following steps of: the molar ratio of the hydroxyl groups is 1.3-1.75, and the two-component polyurethane adhesive is obtained after mixing. The low-viscosity solvent-free polyurethane laminating adhesive has the advantages of low viscosity, high curing speed, high peel strength and 100 ℃ high-temperature steaming resistance, but the normal-temperature viscosity is high, and the operation temperature and the curing temperature are high.
Disclosure of Invention
The invention aims to provide a boiling-resistant bi-component solvent-free polyurethane laminating adhesive which has the advantages of environmental protection, low viscosity, high peel strength and high-temperature boiling resistance, still has high peel strength after being boiled by 135 ℃ steam, and is particularly suitable for adhesives for compounding flexible packaging films which need long-time high-temperature sterilization and disinfection; the invention also provides a preparation method of the composition.
The boiling-resistant bi-component solvent-free polyurethane laminating adhesive disclosed by the invention consists of a component A and a component B according to a mass ratio of 100-200;
the component A is a prepolymer with 15-20wt% of NCO content prepared by the reaction of high temperature resistant polyester polyol and polyisocyanate;
the component B consists of castor oil modified polyester polyol, polyether polyol B and an anti-hydrolysis modifier;
the high-temperature-resistant polyester polyol is prepared by carrying out esterification-polycondensation reaction on micromolecule dibasic acid, micromolecule dihydric alcohol containing lateral methyl and polyether polyol A and adding a nano filler, and the hydroxyl value is 100-200mgKOH/g;
the castor oil modified polyester polyol is prepared by mixing and reacting high-temperature resistant polyester polyol and castor oil according to the mass ratio of 100.
The polyisocyanate is one or more of toluene diisocyanate and diphenylmethane diisocyanate; preferably one or more of MDI-100, MDI-50, liquefied MDI, TDI-80 and TDI-100.
The dosage of the high-temperature resistant polyester polyol is as follows: the mol ratio of the side methyl-containing micromolecular dihydric alcohol to the micromolecular dibasic acid is 1.28-1.52, the polyether polyol A accounts for 9-21% of the mass of the micromolecular dihydric alcohol, and the nano filler accounts for 0.05-0.1% of the total mass of the raw materials.
The micromolecular dibasic acid consists of aliphatic dibasic acid and aromatic dibasic acid according to a molar ratio of 10-20; the aliphatic dibasic acid is one or more of succinic acid, adipic acid, glutaric acid and sebacic acid; the aromatic dibasic acid is one or more of phthalic anhydride, isophthalic acid and terephthalic acid.
The small molecular dihydric alcohol is one or more of 1, 2-propylene glycol, methyl propylene glycol and neopentyl glycol.
The polyether polyol A is one or more of PEG-400, DL-400, PTMG-650, MN500 and MN700, and the molecular weight thereof is less than 1000.
The nano filler is one or more of nano silicon dioxide, nano calcium carbonate, nano titanium dioxide, nano zinc oxide, nano montmorillonite and nano kaolin.
The component B comprises the following raw materials in parts by mass:
100 parts of castor oil modified polyester polyol,
10-20 parts of polyether polyol B,
10-20 parts of an anti-hydrolysis modifier.
The polyether polyol B is a polypropylene oxide polyol, and preferably is one or more of DL-400, DL-1000, DL-2000, MN500, MN700 and MN 1000.
The hydrolysis-resistant modifier is prepared by reacting monomer carbodiimide or polymeric carbodiimide with high-temperature-resistant polyester polyol, and the method comprises the following steps: mixing high-temperature-resistant polyester polyol with monomer carbodiimide or polymeric carbodiimide according to the mass ratio of 100 to 5-10, and reacting for 1-2h under the protection of nitrogen at the temperature of 150-200 ℃ to obtain the polyester polyol.
The preparation method of the boiling-resistant bi-component solvent-free polyurethane laminating adhesive comprises the following steps:
(1) Preparing high-temperature-resistant polyester polyol: adding nano filler into micromolecular dibasic acid, micromolecular dihydric alcohol containing lateral methyl and polyether polyol A, and performing esterification-polycondensation reaction for 10-15h at 200-230 ℃ under the vacuum condition of-0.09 MPa to-0.1 MPa to obtain high-temperature-resistant polyester polyol;
preparing the castor oil modified polyester polyol: mixing high-temperature-resistant polyester polyol with castor oil according to the mass ratio of 100 to 10-50, and reacting for 2-4h at 200-220 ℃ and-0.065-0.080 MPa to obtain castor oil modified polyester polyol;
(3) Preparing a component A: reacting high-temperature resistant polyester polyol with polyisocyanate at the temperature of 70-90 ℃ for 1-3h to obtain a prepolymer with the NCO content of 15-20wt%, namely a component A;
(4) Preparing a component B: mixing the castor oil modified polyester polyol, polyether polyol and an anti-hydrolysis modifier at the temperature of 80-100 ℃ according to the mass ratio of 100;
(5) Preparing laminating adhesive: and mixing the component A and the component B according to the mass ratio of 100-200.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the component A, high-temperature-resistant polyester polyol is adopted, and micromolecular alcohol containing lateral methyl and aromatic dibasic acid are introduced into a system, so that the heat resistance of the polyester polyol is improved; meanwhile, micromolecular polyether polyol is introduced into the system, so that the viscosity of the polyester polyol is reduced, and the hydrolysis resistance of the polyester polyol is improved; the heat resistance of the polyester polyol is further improved by adding the nano filler, so that the high temperature resistance and hydrolysis resistance of the adhesive are substantially improved;
(2) The component B adopts castor oil modified high-temperature resistant polyester polyol, and realizes the intersolubility of polyester and polyether by introducing a nonpolar chain on a polar polyester molecular chain through introducing the castor oil; the castor oil modified polyester polyol and the polyether polyol are mixed, and the prepared adhesive has the high bonding strength performance of polyester type and excellent hydrolysis resistance of polyether type; by introducing polyether, the viscosity of the system is greatly reduced, and the problem of uneven sizing in downstream use is solved;
(3) According to the invention, the hydrolysis-resistant modifier is added into the component B, so that the laminating adhesive has excellent hydrolysis resistance;
(4) The adhesive prepared by the invention has the advantages of environmental protection, low viscosity, high peel strength and high-temperature cooking resistance, still has high peel strength after being steamed and cooked by 135 ℃ steam, is particularly suitable for the adhesive for compounding flexible packaging films which need long-term high-temperature sterilization and disinfection, and has great market potential in the field of high-end flexible packaging laminating adhesives.
Detailed Description
The present invention is further illustrated by the following examples.
Some of the raw material manufacturers used in the following examples and comparative examples were as follows:
PEG-400: shanghai east polyurethane Co., ltd;
DL-400, MN500: shandong-Nowev New materials, inc.;
PTMG-650: (ii) Shanghai Basff;
DL-400, DL-1000, DL-2000, MN500: shandong-Nowei New materials Co., ltd;
MN700, MN1000: shandong Lanxing Dongda, inc.
Example 1
The boiling-resistant bi-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: 909g of adipic acid, 103g of isophthalic acid, 790g of methyl propylene glycol, 89.5g of DL-400 and 0.9g of nano silicon dioxide are added, and the esterification-polycondensation reaction is carried out for 10 hours at 220 ℃ under the vacuum-0.1 MPa condition to obtain the high-temperature resistant polyester polyol with the hydroxyl value of 108 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 50g of castor oil, and reacting for 3 hours at 220 ℃ and-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 71.5g of T-80 at the temperature of 80 ℃ for 2 hours to obtain a prepolymer with the NCO content of 15wt%, namely a component A, and the normal-temperature viscosity of the prepolymer is 1230cps;
(4) Preparing a component B: firstly, 100g of high-temperature resistant polyester polyol and 5g of monomer carbodiimide react for 1-2h at 150-200 ℃ under the protection of nitrogen to prepare an anti-hydrolysis modifier, and then 100g of castor oil modified polyester polyol, 20g of polyether polyol MN305 and 10g of anti-hydrolysis modifier are uniformly mixed at 80-100 ℃ to obtain a component B with the normal-temperature viscosity of 560cps;
(5) Preparing laminating adhesive: and in parts by mass, 194 parts of the component A and 100 parts of the component B are fully mixed at 35 ℃, then coating is carried out, the compounded film is cured at 35-45 ℃, and after full curing is carried out for 48 hours, the T peel strength of the film is tested.
The peel strength between BOPP and the aluminum foil film is 7.5N/15mm, and the peel strength after steam boiling at 135 ℃ for 3h is 7.4N/15mm.
Example 2
The boiling-resistant double-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: 923g of adipic acid, 77g of phthalic anhydride, 415g of methyl propylene glycol, 480g of neopentyl glycol and 94.5g of MN500 are added with 1.6g of nano titanium dioxide, and the esterification-polycondensation reaction is carried out for 12 hours at the temperature of 200 ℃ and under the vacuum-0.092 MPa condition to obtain the high-temperature resistant polyester polyol with the hydroxyl value of 135 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 40g of castor oil, and reacting for 3h at 220 ℃ and-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 103.8g of MDI-50 and 50.9g of liquefied MDI at 70 ℃ for 3 hours to obtain a prepolymer with 16wt% of NCO, namely a component A, and the normal-temperature viscosity is 1108cps;
(4) Preparing a component B: firstly, 100g of high-temperature resistant polyester polyol and 6g of monomer carbodiimide react for 1-2h at 150-200 ℃ under the protection of nitrogen to prepare an anti-hydrolysis modifier, and then 100g of castor oil modified polyester polyol, 10g of polyether polyol DL-400 and 15g of anti-hydrolysis modifier are uniformly mixed at 80-100 ℃ to obtain a component B, wherein the normal-temperature viscosity is 610cps;
(5) Preparing laminating adhesive: and (2) fully mixing 180 parts of the component A and 100 parts of the component B at 35 ℃, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 7.9N/15mm, and the peel strength after steam boiling at 135 ℃ for 3h is 7.7N/15mm.
Example 3
The boiling-resistant double-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: carrying out esterification-polycondensation reaction on 937g of adipic acid, 71g of isophthalic acid, 1005g of neopentyl glycol and 100.5g of PEG400 and 1.26g of nano silicon dioxide at 215 ℃ under the vacuum-0.098 MPa for 13h to obtain high-temperature resistant polyester polyol with a hydroxyl value of 163 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 30g of castor oil, and reacting for 3h at 220 ℃ and-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 139.2g of MDI-50 at 85 ℃ for 1h to obtain a prepolymer with 17wt% of NCO content, namely a component A, and the normal-temperature viscosity of 1050cps;
(4) Preparing a component B: firstly, 100g of high-temperature-resistant polyester polyol and 8g of monomer carbodiimide react for 1-2 hours at 150-200 ℃ under the protection of nitrogen to prepare an anti-hydrolysis modifier, and then 100g of castor oil modified polyester polyol, 15g of polyether polyol MN1000 and 20g of anti-hydrolysis modifier are uniformly mixed at 80-100 ℃ to obtain a component B with the normal-temperature viscosity of 650cps;
(5) Preparing laminating adhesive: and (2) fully mixing 150 parts of the component A and 100 parts of the component B at 35 ℃ by mass, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 7.8N/15mm, and the peel strength is 7.7N/15mm after the BOPP and the aluminum foil film are steamed and boiled in steam at 135 ℃ for 3 hours.
Example 4
The boiling-resistant bi-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: 941g sebacic acid, 59g isophthalic acid, 340g methyl propylene glycol, 393g neopentyl glycol, 86.7g DL-400 and 1.8g nano calcium carbonate are added, and esterification-polycondensation reaction is carried out for 12h at 225 ℃ under the vacuum-0.095 MPa condition to obtain high temperature resistant polyester polyol with the hydroxyl value of 175 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 20g of castor oil, and reacting for 3 hours at 220 ℃ and-0.065-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 215.9g of liquefied MDI at 75 ℃ for 2.5h to obtain a prepolymer with 18wt% of NCO content, namely a component A, and the normal-temperature viscosity of 1020cps;
(4) Preparing a component B: firstly, 100g of high-temperature-resistant polyester polyol and 10g of monomer carbodiimide react for 1-2 hours at 150-200 ℃ under the protection of nitrogen to prepare an anti-hydrolysis modifier, and then 100g of castor oil modified polyester polyol, 18g of polyether polyol DL-1000 and 10g of the anti-hydrolysis modifier are uniformly mixed at 80-100 ℃ to obtain a component B with the normal-temperature viscosity of 630cps;
(5) Preparing laminating adhesive: and (2) fully mixing 100 parts of the component A and 100 parts of the component B at 35 ℃, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 8.2N/15mm, and the peel strength after being cooked for 3 hours in steam boiling water at 135 ℃ is 8.1N/15mm.
Example 5
The boiling-resistant double-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: 952g succinic acid, 48g phthalic anhydride, 1050g methyl propylene glycol, 100g PTMG-650 and 1.07g nano silicon dioxide are added, and esterification-polycondensation reaction is carried out for 12h under the conditions of 210 ℃ and vacuum-0.093 MPa to obtain high temperature resistant polyester polyol with the hydroxyl value of 186 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 10g of castor oil, and reacting for 3 hours at 220 ℃ and-0.065-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 180.8g of MDI-50 and 31.5g of TDI-80 for 1 hour at the temperature of 90 ℃ to obtain a prepolymer with 19wt% of NCO, namely a component A, and the normal-temperature viscosity of the prepolymer is 950cps;
(4) Preparing a component B: firstly, 100g of high-temperature resistant polyester polyol and 10g of polymerized carbodiimide react for 1-2h under the protection of nitrogen and at the temperature of 150-200 ℃ to prepare an anti-hydrolysis modifier, and then 100g of castor oil modified polyester polyol, 20g of polyether polyol DL-1000 and 12g of anti-hydrolysis modifier are uniformly mixed at the temperature of 80-100 ℃ to obtain a component B, wherein the normal-temperature viscosity is 575cps;
(5) Preparing laminating adhesive: and (2) fully mixing 110 parts of the component A and 100 parts of the component B at 35 ℃, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 8.5N/15mm, and the peel strength after steam boiling at 135 ℃ for 3h is 8.3N/15mm.
Example 6
The boiling-resistant bi-component solvent-free polyurethane laminating adhesive is prepared by the following method:
(1) Preparing high-temperature-resistant polyester polyol: carrying out esterification-polycondensation reaction on 947g of adipic acid, 53g of terephthalic acid, 900g of methyl propanediol and 95g of MN500 and 2.0g of nano calcium carbonate at 230 ℃ under the vacuum-0.1 MPa for 15h to obtain high-temperature-resistant polyester polyol with the hydroxyl value of 197 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of high-temperature-resistant polyester polyol with 30g of castor oil, and reacting for 3h at 220 ℃ and-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 256g of MDI-50 at 85 ℃ for 1.5h to obtain a prepolymer with 20wt% of NCO content, namely a component A, wherein the normal-temperature viscosity is 890cps;
(4) Preparing a component B: firstly, reacting 100g of high-temperature-resistant polyester polyol with 9g of polycarbodiimide under the protection of nitrogen at the temperature of between 150 and 200 ℃ for 1 to 2 hours to prepare an anti-hydrolysis modifier, and then uniformly mixing 100g of castor oil modified polyester polyol, 20g of polyether polyol DL-2000 and 10g of anti-hydrolysis modifier at the temperature of between 80 and 100 ℃ to obtain a component B with the normal-temperature viscosity of 558cps;
(5) Preparing laminating adhesive: and (2) fully mixing 100 parts of the component A and 100 parts of the component B at 35 ℃, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 7.6N/15mm, and the peel strength is 7.5N/15mm after the BOPP and the aluminum foil film are steamed and boiled in steam at 135 ℃ for 3 hours.
Comparative example 1
The comparative example adopts conventional polyester polyol to replace high-temperature-resistant polyester polyol to prepare the two-component solvent-free polyurethane laminating adhesive:
(1) Preparation of conventional polyester polyols: carrying out esterification-polycondensation reaction on 900g of adipic acid and 917g of diethylene glycol for 12 hours at 220 ℃ under the vacuum-0.1 MPa condition to obtain polyester polyol with a hydroxyl value of 195 mgKOH/g;
(2) Preparing the castor oil modified polyester polyol: mixing 100g of conventional polyester polyol with 30g of castor oil, and reacting for 3h at 220 ℃ and-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol with transparent appearance;
(3) Preparing a component A: reacting 100g of conventional polyester polyol with 250g of MDI-50 at 85 ℃ for 1.5h to obtain a prepolymer with 19.8wt% of NCO content, namely a component A, wherein the normal-temperature viscosity is 878cps;
(4) Preparing a component B: uniformly mixing 100g of castor oil modified polyester polyol and 20g of polyether polyol DL-2000 at the temperature of 80-100 ℃ to obtain a component B, wherein the normal-temperature viscosity is 546cps;
(5) Preparing laminating adhesive: and (2) fully mixing 100 parts of the component A and 100 parts of the component B at 35 ℃, coating, curing the compounded film at 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 4.6N/15mm, and the peel strength is 3.5N/15mm after the BOPP and the aluminum foil film are steamed and boiled in steam at 135 ℃ for 3 hours.
As can be seen from comparative example 1, the laminating adhesive prepared by using the conventional polyester polyol instead of the high-temperature-resistant polyester polyol has low peel strength and is not resistant to high-temperature cooking.
Comparative example 2
The component B of the comparative example adopts castor oil to prepare two-component solvent-free polyurethane laminating adhesive:
(1) Preparing high-temperature-resistant polyester polyol: 947g of adipic acid, 53g of terephthalic acid, 900g of methyl propylene glycol, 95g of MN500 and 2.0g of nano calcium carbonate are added, and esterification-polycondensation reaction is carried out for 15h at 230 ℃ and under the vacuum-0.1 MPa condition to obtain high-temperature resistant polyester polyol with the hydroxyl value of 197 mgKOH/g;
(2) Preparing a component A: reacting 100g of high-temperature-resistant polyester polyol with 256g of MDI-50 at 85 ℃ for 1.5h to obtain a prepolymer with 20wt% of NCO content, namely a component A, wherein the normal-temperature viscosity is 890cps;
(3) Preparing a component B: castor oil is used as a raw material, and moisture is removed at the temperature of 100-110 ℃ to obtain a component B with the normal-temperature viscosity of 530cps;
(4) Preparing laminating adhesive: and (2) fully mixing 100 parts of the component A and 100 parts of the component B at the temperature of 35 ℃ in parts by mass, then coating, curing the compounded film at the temperature of 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 5.4N/15mm, and the peel strength is 3.3N/15mm after the BOPP and the aluminum foil film are steamed and boiled in steam at 135 ℃ for 3 hours.
As can be seen from comparative example 2, the component B only adopts conventional castor oil polyol, and the prepared laminating adhesive has low peel strength and is not resistant to high temperature cooking.
Comparative example 3
According to the comparative example, the component A adopts conventional polyester polyol to replace high-temperature-resistant polyester polyol, the component B adopts castor oil, and the two-component solvent-free polyurethane laminating adhesive is prepared:
(1) Preparation of conventional ester polyols: carrying out esterification-polycondensation reaction on 900g of adipic acid and 917g of diethylene glycol for 12 hours at 220 ℃ under the vacuum-0.1 MPa condition to obtain polyester polyol with a hydroxyl value of 195 mgKOH/g;
(2) Preparing a component A: reacting 100g of conventional polyester polyol with 250g of MDI-50 at 85 ℃ for 1.5h to obtain a prepolymer with 19.8wt% of NCO content, namely a component A, wherein the normal-temperature viscosity is 878cps;
(3) Preparing a component B: castor oil is used as a raw material, and moisture is removed at the temperature of 100-110 ℃ to obtain a component B, wherein the normal-temperature viscosity is 530cps;
(5) Preparing laminating adhesive: and (2) fully mixing 100 parts of the component A and 100 parts of the component B at the temperature of 35 ℃ in parts by mass, then coating, curing the compounded film at the temperature of 35-45 ℃, and testing the T peel strength after fully curing for 48 hours.
The peel strength between BOPP and the aluminum foil film is 3.4N/15mm, and the peel strength is 2.1N/15mm after the BOPP and the aluminum foil film are steamed and boiled in steam at 135 ℃ for 3 hours.
As can be seen from comparative example 3, the composite film adhesive prepared by using the conventional polyester polyol to replace the high-temperature-resistant polyester polyol as the component A and using the conventional castor oil polyol as the component B has low peel strength and poor high-temperature cooking resistance.
Claims (5)
1. The boiling-resistant double-component solvent-free polyurethane laminating adhesive is characterized by comprising the following components in parts by weight: the paint consists of a component A and a component B according to the mass ratio of 100-200;
the component A is a prepolymer with 15-20wt% of NCO content prepared by the reaction of high temperature resistant polyester polyol and polyisocyanate; the high-temperature-resistant polyester polyol is prepared by carrying out esterification-polycondensation reaction on micromolecule dibasic acid, micromolecule dihydric alcohol containing lateral methyl and polyether polyol A and adding a nano filler, and the hydroxyl value is 100-200mgKOH/g; the mol ratio of the side methyl-containing micromolecule dihydric alcohol to the micromolecule dibasic acid is 1.28-1.52, the polyether glycol A accounts for 9-21% of the mass of the micromolecule dihydric alcohol, and the nano filler accounts for 0.05-0.1% of the total mass of the raw materials; the micromolecular dibasic acid consists of aliphatic dibasic acid and aromatic dibasic acid according to a molar ratio of 10-20; the polyether polyol A is one or more of PEG-400, DL-400, PTMG-650, MN500 and MN700, and the molecular weight of the polyether polyol A is less than 1000;
the component B comprises the following raw materials in parts by mass: 100 parts of castor oil modified polyester polyol, 10-20 parts of polyether polyol B and 10-20 parts of hydrolysis-resistant modifier; the castor oil modified polyester polyol is prepared by mixing and reacting high-temperature resistant polyester polyol and castor oil according to the mass ratio of 100; the polyether polyol B is polypropylene oxide polyol;
the nano filler is one or more of nano silicon dioxide, nano calcium carbonate, nano titanium dioxide, nano zinc oxide, nano montmorillonite and nano kaolin;
the hydrolysis-resistant modifier is prepared by reacting monomer carbodiimide or polymeric carbodiimide with high-temperature-resistant polyester polyol, and the method comprises the following steps: mixing high-temperature-resistant polyester polyol with monomer carbodiimide or polymeric carbodiimide according to the mass ratio of 100 to 5-10, and reacting for 1-2h under the protection of nitrogen at the temperature of 150-200 ℃ to obtain the polyester polyol.
2. The steam-resistant two-component solvent-free polyurethane laminating adhesive as claimed in claim 1, wherein: the polyisocyanate is one or more of toluene diisocyanate and diphenylmethane diisocyanate.
3. The steam-resistant two-component solvent-free polyurethane laminating adhesive as claimed in claim 1, wherein: the aliphatic dibasic acid is one or more of succinic acid, adipic acid, glutaric acid and sebacic acid; the aromatic dibasic acid is one or two of isophthalic acid and terephthalic acid.
4. The steam-resistant two-component solvent-free polyurethane laminating adhesive as claimed in claim 1, wherein: the small molecular dihydric alcohol is one or more of 1, 2-propylene glycol, methyl propylene glycol and neopentyl glycol.
5. A method for preparing a steam-resistant two-component solvent-free polyurethane laminating adhesive according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
(1) Preparing high-temperature-resistant polyester polyol: adding a nano filler into micromolecular dibasic acid, micromolecular dihydric alcohol containing lateral methyl and polyether polyol A, and carrying out esterification-polycondensation reaction for 10-15h at the temperature of 200-230 ℃ under the vacuum condition of-0.09 to-0.1 MPa to obtain high-temperature-resistant polyester polyol;
(2) Preparing the castor oil modified polyester polyol: mixing high-temperature-resistant polyester polyol with castor oil according to the mass ratio of 100-50, and reacting for 2-4h at 200-220 ℃ and under the conditions of-0.065 to-0.080 MPa to obtain castor oil modified polyester polyol;
(3) Preparing a component A: reacting high-temperature resistant polyester polyol with polyisocyanate at the temperature of 70-90 ℃ for 1-3h to obtain a prepolymer with the NCO content of 15-20wt%, namely a component A;
(4) Preparing a component B: mixing the castor oil modified polyester polyol, polyether polyol and an anti-hydrolysis modifier at the temperature of 80-100 ℃ according to the mass ratio of 100;
(5) Preparing laminating adhesive: and mixing the component A and the component B according to the mass ratio of 100-200.
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| CN112724916B (en) * | 2020-12-28 | 2022-09-20 | 上海华峰新材料研发科技有限公司 | Solvent-free adhesive for electrical insulation composite material and preparation method and application thereof |
| CN113527694B (en) * | 2021-08-04 | 2022-08-05 | 合肥安利聚氨酯新材料有限公司 | Preparation method of solvent-free polyurethane resin and application of solvent-free polyurethane resin in textile coating |
| CN113583611A (en) * | 2021-09-07 | 2021-11-02 | 广东和润新材料股份有限公司 | Bi-component solvent-free polyurethane adhesive and preparation method thereof |
| CN113980635B (en) * | 2021-11-30 | 2024-03-22 | 湖北回天新材料(宜城)有限公司 | Adhesive for steaming-resistant food flexible package composite film, and preparation method and application thereof |
| CN114752340B (en) * | 2021-12-20 | 2024-04-05 | 上海都昱新材料科技有限公司 | High-temperature steaming type medium-resistant solvent-free double-component polyurethane adhesive and preparation method thereof |
| CN115521749A (en) * | 2022-10-17 | 2022-12-27 | 山东逸飞新材料有限公司 | Bi-component solvent-free steaming-resistant polyurethane composite adhesive and preparation method thereof |
| CN115651156A (en) * | 2022-11-07 | 2023-01-31 | 合肥安利聚氨酯新材料有限公司 | Solvent-free polyurethane resin and preparation method and application thereof |
| CN116445121B (en) * | 2023-06-16 | 2023-09-05 | 山东一诺威聚氨酯股份有限公司 | Bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and preparation method thereof |
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