CN112708386A - Solvent-free single-component moisture-curing polyurethane adhesive for paper-plastic compounding and preparation method thereof - Google Patents
Solvent-free single-component moisture-curing polyurethane adhesive for paper-plastic compounding and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention belongs to the technical field of polyurethane adhesives, relates to two polyester polyols with special structures and a preparation method thereof, and particularly relates to a paper-plastic composite adhesive and a preparation method thereof. The paper-plastic composite adhesive adopts two polyester polyols with special structures, and is composed of the following components in parts by weight: polyester polyol 1: 15-20 parts of a solvent; polyester polyol 2: 20-25 parts; polyether polyols: 30-40 parts; isocyanates: 20-30 parts of a solvent; catalyst: 0.01-0.05 part. According to the invention, two polyester polyols with special structures are adopted, so that the initial adhesion of the solvent-free single-component polyurethane adhesive can be improved and improved, and the method is particularly suitable for the field of paper-plastic composite packaging with good initial adhesion, high adhesion strength and high composite speed.
Description
Technical Field
The invention belongs to the technical field of adhesives, relates to two polyester polyols with special structures and a preparation method thereof, and relates to a paper-plastic composite adhesive and a preparation method thereof.
Background
With the increasing strictness of national environmental protection policies, solvent-free adhesives are coming to a rapid development period. In the preparation process and the use process, the solvent-free single-component polyurethane adhesive does not relate to a solvent, so the application in the field of paper-plastic composite is more and more extensive.
As an adhesive in the field of paper-plastic compounding, the adhesive is widely applied to the aspects of packaging materials, hardcover books, decorative building materials and the like, enables the surface of printed matters to be smoother and brighter, and has the stereoscopic impression, and meanwhile, has the effects of moisture prevention, soil resistance, counterfeiting resistance, folding resistance and the like. At present, the adhesives for paper-plastic compounding in the market are various in types, and are unsatisfactory in initial adhesion, bonding strength and compounding speed.
The solvent-free single-component moisture curing polyurethane adhesive mainly comprises polyester polyol (polyester for short) with the molecular weight of 1000-5000g/mol and isocyanate compound, and is reacted to generate isocyanate-terminated polyurethane prepolymer. The prepolymer has thermal fluidity, is coated on the surface of an adhesive through composite equipment after being heated, and is crosslinked by depending on moisture in the air to form good adhesion.
Because the solvent-free single-component moisture curing polyurethane adhesive has the characteristic of coating after heating, the hot melt viscosity of the adhesive is an important index and is a precondition for improving the compounding speed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a solvent-free single-component moisture-curing polyurethane adhesive for paper-plastic compounding and a preparation method thereof.
The technical scheme of the invention is as follows:
the solvent-free single-component moisture curing polyurethane adhesive for paper-plastic compounding is characterized by comprising the following components in parts by weight:
polyester polyol 1: 15-20 parts of a solvent;
a, B, C, D, wherein A is at least one long straight chain dibasic acid, the long straight chain dibasic acid is straight chain dibasic acid with at least more than 6 carbon atoms in the carbon chain, and the weight percentage is 25-40%; b is at least one dicarboxylic anhydride, including aliphatic and aromatic carboxylic anhydrides, 15-30% by weight; c is at least one long straight chain dihydric alcohol, the long straight chain dihydric alcohol is straight chain dihydric alcohol with at least more than 5 carbon atoms in the carbon chain, and the weight percentage is 20-35%; d is at least one branched diol, wherein the branched diol is diol with a linear straight carbon chain and at least one branched chain structure, and the weight percentage is 10-25%; the alkyd ratio of the A, B, C, D four monomers is less than 1.3.
A, B, C, D, the ratio of alcohol to acid of the four monomers involved in the polyester polyol 1 is 1.05-1.20, the molar ratio of the hydroxyl substance to the carboxyl substance (alcohol to acid ratio for short) is properly adopted, and the hydroxyl value of the system is continuously measured in the reaction process to obtain the polyester product with similar molecular weight, and in order to obtain the polyester product with higher molecular weight, the ratio of alcohol to acid is less than 1.3, preferably 1.05-1.20.
Specifically, A is at least one of 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid and 1, 11-undecanedioic acid; b is at least one of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride; c is at least one of 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol; d is 1, 5-pentanediol;
a method for preparing polyester polyol 1, comprising the steps of: under the protection of nitrogen, all the components in the proportion are added into a reaction kettle, stirred and heated to 130-150 ℃, and the temperature is kept for 2 +/-0.5 h, and the system is drained; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 20-70mgKOH/g through heat preservation reaction to obtain the polyester polyol 1.
The concentration of the polyester polyol 1 auxiliary agent in the reaction liquid is 10-500 ppm; the auxiliary agent is selected from one or more of stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate and tetraisopropyl titanate.
Polyester polyol 2: 20-25 parts;
the polyester polyol 2 for synthesizing the solvent-free single-component moisture curing polyurethane adhesive is prepared from E, F, G, H, I five monomers through esterification condensation reaction. Wherein E is at least one long straight chain dibasic acid, the long straight chain dibasic acid is straight chain dibasic acid with at least more than 6 carbon atoms in the carbon chain, and the weight percentage is 30-50%; f is at least one dicarboxylic anhydride, including aliphatic and aromatic carboxylic anhydrides, the weight percentage is 2-20%; g is at least one polyether polyol, the molecular weight of the polyether polyol is 200-1000G/mol, and the weight percentage is 5-25%; h is at least one branched diol, the branched diol is diol with a linear straight carbon chain and at least one branched chain structure, and the weight percentage is 10-30%; i is at least one linear dihydric alcohol, and the weight percentage is 5-25%; the alkyd ratio of the E, F, G, H, I five monomers is less than 1.3.
The alkyd ratio of E, F, G, H, I monomers involved in the polyester polyol 2 is 1.05-1.20, the appropriate molar ratio of hydroxyl substances to carboxyl substances (alcohol-acid ratio for short) is adopted, and the hydroxyl value of the system is continuously measured in the reaction process to obtain a polyester product with similar molecular weight, and in order to obtain a polyester product with higher molecular weight, the alkyd ratio is less than 1.3, preferably 1.05-1.20.
Specifically, E is at least one of 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid and 1, 11-undecanedioic acid; f is at least one of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride; g is at least one of polyethylene glycol, polypropylene oxide glycol and polytetrahydrofuran glycol; h is at least one of 2-methyl-1, 3-propanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol and 2-butyl-2-ethyl-propanediol; i is at least one of ethylene glycol, 1, 4-butanediol and diethylene glycol.
A method for preparing polyester polyol 2, comprising the steps of: under the protection of nitrogen, all the components in the proportion are added into a reaction kettle, stirred and heated to 130-150 ℃, and the temperature is kept for 2 +/-0.5 h, and the system is drained; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 40-100mgKOH/g through heat preservation reaction to obtain the polyester polyol 2.
The concentration of the auxiliary agent of the polyester polyol 2 in the reaction liquid is 10-500 ppm; the auxiliary agent is selected from one or more of stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate and tetraisopropyl titanate.
Polyether polyols: 30-40 parts; the polyether polyol is at least one of polyethylene glycol, polypropylene oxide glycol and polytetrahydrofuran glycol, and the molecular weight is 600-3000 g/mol.
Isocyanates: 20-30 parts of a solvent; the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
Catalyst: 0.01-0.05 part of a catalyst, wherein the catalyst is at least one of stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate, tetraisopropyl titanate, dimorpholinyl diethyl ether and dimorpholinyl triethyl ether.
The preparation method of the solvent-free single-component moisture curing polyurethane adhesive for paper-plastic compounding is characterized by comprising the following steps of:
preparing a polyurethane adhesive, namely respectively adding polyester polyol 1, polyester polyol 2 and polyether polyol into a reaction kettle, heating to 40-60 ℃, uniformly stirring, sampling, and testing the moisture content, wherein the moisture content is controlled to be 0-500 ppm; adding isocyanate raw materials in corresponding weight parts, controlling the system temperature, gradually heating to 75-85 ℃, and preserving heat for 2-3.5 h; and cooling to 70-80 ℃, adding a catalyst, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive.
By the scheme, the invention at least has the following advantages:
the polyester polyol 1 related by the invention adopts long straight chain dibasic acid, and the long straight chain dibasic acid has low density of polyester ester group obtained after reaction with alcohols due to more number of carbon atoms between two terminal carboxyl groups, so the polyester polyol has lower viscosity; long straight chain dihydric alcohol is adopted, and because the number of carbon atoms between two terminal hydroxyl groups is large, the polyester ester group obtained after the reaction with acid has low density, the viscosity is low; 1, 5-pentanediol is preferably used, and since 1, 5-pentanediol has a carbon chain structure with an uneven number of carbon atoms, a polyester with lower crystallinity can be synthesized, thereby obtaining a polyester with lower viscosity. The polyester polyol can be used for obtaining the solvent-free single-component moisture curing polyurethane adhesive for paper-plastic compounding, which has lower viscosity of a finished product.
According to the polyester polyol 2, micromolecular polyether polyol and diol containing side groups are introduced, the compatibility and hydrolysis resistance of the micromolecular polyether polyol and the diol are improved, the polyester polyol with low viscosity, high reaction activity, good compatibility and hydrolysis resistance is prepared, and the selectivity of raw materials in the development of solvent-free single-component polyurethane adhesives is widened. The solvent-free single-component polyurethane adhesive for paper-plastic compounding is prepared by adopting two polyester polyols with special structures, and is particularly suitable for the field of paper-plastic compound packaging with good initial adhesion, high bonding strength and high compounding speed.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Synthesis of polyester polyol 1
Example 1
33.01 parts by weight of adipic acid, 20.61 parts by weight of phthalic anhydride, 17.72 parts by weight of neopentyl glycol and 28.67 parts by weight of 1, 6-hexanediol were added to a reaction vessel in an alcohol-to-acid ratio of 1.09, based on 100 parts by weight of the total weight of the raw materials, and stirring was started while raising the temperature. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 20-70mgKOH/g through heat preservation reaction to obtain the polyester polyol P1. The polyester polyol has a molecular weight of about 2500g/mol and a viscosity of 1200 mPas at 80 ℃.
Example 2
Based on 100 parts by weight of the total weight of the raw materials, 32.93 parts by weight of adipic acid, 20.56 parts by weight of phthalic anhydride, 17.76 parts by weight of neopentyl glycol and 28.74 parts by weight of 1, 6-hexanediol were added to a reaction vessel in an alcohol-to-acid ratio of 1.14, and stirring was started while raising the temperature. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 20-70mgKOH/g through heat preservation reaction to obtain the polyester polyol P2. The polyester polyol has a molecular weight of about 2500g/mol and a viscosity of 1100 mPas at 80 ℃.
Synthesis of polyester polyol 2
Example 3
Based on 100 parts by weight of the total weight of the raw materials, 38.06 parts by weight of adipic acid, 9.65 parts by weight of phthalic anhydride, 16.27 parts by weight of PPG-400, 8.45 parts by weight of neopentyl glycol, 17.30 parts by weight of diethylene glycol and 10.27 parts by weight of 2-methyl-1, 3-propanediol are added into a reaction kettle, the ratio of the alcohol to the acid is 1.10, and stirring is started while heating. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 40-100mgKOH/g through heat preservation reaction to obtain the polyester polyol P3. The polyester polyol has a molecular weight of about 1700g/mol and a viscosity of 1300 mPas at 50 ℃.
Example 4
Based on 100 parts by weight of the total weight of the raw materials, 38.06 parts by weight of adipic acid, 9.30 parts by weight of phthalic anhydride, 16.27 parts by weight of PPG-400, 8.45 parts by weight of neopentyl glycol, 17.65 parts by weight of diethylene glycol and 10.27 parts by weight of 2-methyl-1, 3-propanediol are added into a reaction kettle, the ratio of the alcohol to the acid is 1.12, and stirring is started while heating. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 40-100mgKOH/g through heat preservation reaction to obtain the polyester polyol P4. The polyester polyol has a molecular weight of about 1700g/mol and a viscosity of 1200 mPas at 50 ℃.
Comparative example 1
34.79 parts by weight of adipic acid, 20.61 parts by weight of phthalic anhydride, 19.48 parts by weight of neopentyl glycol and 21.12 parts by weight of 1, 6-hexanediol were added to a reaction vessel in an alcohol-to-acid ratio of 1.05, and stirring was started while raising the temperature, based on 100 parts by weight of the total raw materials. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 20-70mgKOH/g through heat preservation reaction to obtain the polyester polyol P5. The polyester polyol has a molecular weight of about 4500g/mol and a viscosity of 3200 mPas at 80 ℃.
Comparative example 2
According to the total weight of 100 parts by weight of raw materials, 36.06 parts by weight of adipic acid, 9.30 parts by weight of phthalic anhydride, 18.27 parts by weight of PPG-400, 8.45 parts by weight of neopentyl glycol, 17.65 parts by weight of diethylene glycol and 10.27 parts by weight of 2-methyl-1, 3-propanediol are added into a reaction kettle, the alcohol-acid ratio is 1.17, and stirring is started while heating. Stirring and heating to 130-150 ℃ under the protection of nitrogen, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; and continuously heating to 230 ℃ and adding the auxiliary agent, and stopping the reaction when the acid value is less than 2mgKOH/g and the hydroxyl value is 40-100mgKOH/g through heat preservation reaction to obtain the polyester polyol P4. The polyester polyol has a molecular weight of about 1200g/mol and a viscosity of 800 mPas at 50 ℃.
The results of the performance tests of the polyester polyols synthesized in examples 1 to 4 and comparative examples 1 and 2 are shown in Table 1.
Synthesis of paper-plastic composite adhesive
Example 5
Respectively adding 16.12 parts by weight of polyester polyol P1, 19.88 parts by weight of polyester polyol P3 and 35.78 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; 28.22 parts by weight of 4, 4' -diphenylmethane diisocyanate is added into the mixture, the temperature of the system is controlled, the temperature is gradually increased to 75-85 ℃, and the temperature is kept for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.02 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was 4.82% by titration and the viscosity at 100 ℃ was 700 mPas.
Example 6
Respectively adding 16.12 parts by weight of polyester polyol P1, 19.88 parts by weight of polyester polyol P4 and 35.65 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; adding 28.35 parts by weight of 4, 4' -diphenylmethane diisocyanate, controlling the temperature of the system, gradually heating to 75-85 ℃, and keeping the temperature for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.02 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was determined to be 4.87% by titration and the viscosity at 100 ℃ was 630 mPas.
Example 7
Respectively adding 16.25 parts by weight of polyester polyol P2, 19.75 parts by weight of polyester polyol P3 and 35.55 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; adding 28.45 parts by weight of 4, 4' -diphenylmethane diisocyanate, controlling the temperature of the system, gradually raising the temperature to 75-85 ℃, and keeping the temperature for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.03 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was determined to be 4.86% by titration and the viscosity at 100 ℃ was 650 mPas.
Example 8
Respectively adding 16.42 parts by weight of polyester polyol P2, 19.98 parts by weight of polyester polyol P4 and 35.32 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; adding 28.45 parts by weight of 4, 4' -diphenylmethane diisocyanate, controlling the temperature of the system, gradually raising the temperature to 75-85 ℃, and keeping the temperature for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.03 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was 4.92% by titration and the viscosity at 100 ℃ was 600 mPas.
Comparative example 3
Respectively adding 17.23 parts by weight of polyester polyol P5, 20.62 parts by weight of polyester polyol P3 and 35.57 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; then adding 26.58 parts by weight of 4, 4' -diphenylmethane diisocyanate, controlling the temperature of the system, gradually raising the temperature to 75-85 ℃, and preserving the heat for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.03 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was 4.41% by titration and the viscosity at 100 ℃ was 1800 mPas.
Comparative example 4
Respectively adding 17.25 parts by weight of polyester polyol P1, 20.60 parts by weight of polyester polyol P6 and 33.69 parts by weight of polyether polyol PPG-1000 into a reaction kettle according to 100 parts by weight of the total weight of the raw materials, heating to 40-60 ℃, uniformly stirring, sampling, and carrying out moisture content test, wherein the moisture content is controlled to be 0-500 ppm; adding 28.46 parts by weight of 4, 4' -diphenylmethane diisocyanate, controlling the temperature of the system, gradually heating to 75-85 ℃, and keeping the temperature for 2-3.5 hours; and cooling to 70-80 ℃, adding 0.03 weight part of catalyst dimorpholinyl diethyl ether, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive. The NCO value was determined to be 4.70% by titration, and the viscosity at 100 ℃ was 400 mPas.
The method for testing the polyester polyol parameter index comprises the following steps:
1) acid value measurement: tested according to HG/T2708-;
2) hydroxyl value determination: tested according to HG/T2709-;
3) and (3) viscosity measurement: tested according to the GB/T2794-2013 standard (rotational viscometer method).
The method for testing the parameter indexes of the paper-plastic composite adhesive comprises the following steps:
1) and (3) water content determination: testing according to GB/T6283-;
2) and (3) viscosity measurement: testing according to the GB/T2794-2013 standard (rotational viscometer method);
3) determination of NCO: tested according to HG/T2409-.
The paper-plastic composite adhesive prepared in the above examples 5 to 8 can achieve the following performances after the on-machine test of a nodeme solvent-free compound machine: initial adhesion: the initial adhesion can be completed after the machine is taken off for 2 hours; bonding strength: after the film material after the compounding is placed at 45 ℃ for 24 hours, the complete transfer of the paper fiber can be completed; viscosity at 100 ℃: 500-1000 mPas; compounding speed: the speed of 200-400m/min can be achieved by using Nodemeik solvent-free compound equipment; storage stability: more than 6 months; no foaming, and can completely meet the requirements of paper-plastic composite packaging customers. After the paper-plastic composite adhesive prepared according to the proportion 3 and the proportion 4 is tested on a machine of a Nuode Meike solvent-free compound machine, the viscosity of the proportion 3 is too high, the machine cannot run at a high speed, the compounding speed is only 100-plus 150m/min, the initial adhesion of the proportion 4 is not high, the initial adhesion still does not exist after the machine is started for 2 hours, and the paper fiber does not transfer after the film material after the compounding is placed at 45 ℃ for 24 hours, so that the requirements of paper-plastic composite packaging customers cannot be met.
TABLE 1 polyester polyol Property test results synthesized in examples 1-4 and comparative examples 1 and 2
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The solvent-free single-component moisture curing polyurethane adhesive for paper-plastic compounding is characterized by comprising the following components in parts by weight:
polyester polyol 1: 15-20 parts of a solvent;
a, B, C, D is prepared by esterification and condensation reaction of four monomers, A is at least one of 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid and 1, 11-undecanedioic acid; b is at least one of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride; c is at least one of 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol; d is 1, 5-pentanediol;
polyester polyol 2: 20-25 parts;
the polyester polyol 2 is prepared from E, F, G, H, I five monomers through esterification condensation reaction, and E is at least one of 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid and 1, 11-undecanedioic acid; f is at least one of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride; g is at least one of polyethylene glycol, polypropylene oxide glycol and polytetrahydrofuran glycol; h is at least one of 2-methyl-1, 3-propanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol and 2-butyl-2-ethyl-propanediol; i is at least one of ethylene glycol, 1, 4-butanediol and diethylene glycol;
polyether polyols: 30-40 parts;
isocyanates: 20-30 parts of a solvent;
catalyst: 0.01-0.05 part.
2. The solvent-free one-component moisture-curing polyurethane adhesive for paper-plastic composite according to claim 1, wherein: the polyether polyol is at least one of polyethylene glycol, polypropylene oxide glycol and polytetrahydrofuran glycol, and the molecular weight is 600-3000 g/mol.
3. The solvent-free one-component moisture-curing polyurethane adhesive for paper-plastic composite according to claim 1, wherein: the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
4. The solvent-free one-component moisture-curing polyurethane adhesive for paper-plastic composite according to claim 1, wherein: the catalyst is at least one of stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate, tetraisopropyl titanate, dimorpholinyl diethyl ether and dimorpholinyl triethyl ether.
5. The preparation method of the solvent-free one-component moisture-curing polyurethane adhesive for paper-plastic composite according to any one of claims 1 to 4, characterized by comprising the following steps:
preparing polyester polyol 1, adding A, B, C, D four monomers in the proportion into a reaction kettle under the protection of nitrogen, stirring and heating to 130-150 ℃, and keeping the temperature for 2 +/-0.5 h to obtain system water; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; continuously heating to 230 ℃ and adding the auxiliary agent, keeping the temperature and reacting until the acid value is less than 2mgKOH/g and the hydroxyl value is 20-70mgKOH/g, and stopping the reaction to obtain the polyester polyol 1;
preparing polyester polyol 2, adding E, F, G, H, I monomers in the proportion into a reaction kettle under the protection of nitrogen, stirring and heating to 130-150 ℃, and keeping the temperature for 2 +/-0.5 h to obtain system effluent; continuously heating to 190 ℃ and 210 ℃, and keeping the temperature for 2 +/-0.5 h; continuously heating to 230 ℃ and adding the auxiliary agent, keeping the temperature and reacting until the acid value is less than 2mgKOH/g and the hydroxyl value is 40-80mgKOH/g, and stopping the reaction to obtain polyester polyol 2;
preparing a polyurethane adhesive, namely respectively adding polyester polyol 1, polyester polyol 2 and polyether polyol into a reaction kettle, heating to 40-60 ℃, uniformly stirring, sampling, and testing the moisture content, wherein the moisture content is controlled to be 0-500 ppm; adding isocyanate raw materials in corresponding weight parts, controlling the system temperature, gradually heating to 75-85 ℃, and preserving heat for 2-3.5 h; and cooling to 70-80 ℃, adding a catalyst, and vacuumizing and defoaming to obtain the paper-plastic composite adhesive.
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