Long-activation-period hydroxypropyl emulsion for plate splicing glue as well as preparation method and application of long-activation-period hydroxypropyl emulsion

Abstract

The invention relates to the technical field of hydroxypropyl emulsions, and discloses a long-activation-period hydroxypropyl emulsion for plate splicing glue as well as a preparation method and application of the long-activation-period hydroxypropyl emulsion. Through a two-step polymerization and post-dispersion method, methyl methacrylate, butyl acrylate and styrene are polymerized to prepare a hydrophobic inner core layer, hydroxyethyl methylacrylate, acrylic acid, sulfonate-modified epoxy resin and adamantane-modified phosphate-modified phenolic resin are added for continuous polymerization to prepare a hydrophilic shell layer, and the hydrophobic outer core layer and the hydrophilic shell layer are compounded to prepare a hydrophobic core layer. Dimethylethanolamine is added to neutralize carboxyl in the shell layer, water is added for dispersion, and the long-activation-period hydroxypropyl emulsion for the plate splicing glue is obtained. A long side chain group in a hydrophilic shell has hydrophobicity, interaction with a core molecular chain can be increased when water is added for dispersion, a tighter core-shell structure is formed, certain steric hindrance of the long side chain group can wrap a part of hydroxyl groups, the hydroxypropyl emulsion is prevented from reacting with a curing agent too early, the activation period is prolonged, and the curing effect is improved. And a good high-temperature-resistant effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of hydroxypropylene emulsions, in particular to a hydroxypropylene emulsion with a long activation period for plywood glue and a preparation method and application thereof. Background Art

[0002] Panel glue refers to an adhesive used to splice wood products such as integrated materials. At present, most of the adhesives used in this area in China are two-component panel glues composed of a main agent and a curing agent. The curing agent is generally isocyanate. Hydroxypropylene emulsion is an acrylic emulsion containing hydroxyl functional groups. It is polymerized by hydroxyl acrylic monomers and acrylic monomers or vinyl monomers. The two-component panel glue composed of hydroxypropylene emulsion as the main agent and isocyanate as the curing agent needs to be packaged separately before use. When used, the two components are mixed to produce a chemical reaction. The viscosity continues to rise during the reaction and finally gels. During the period from mixing to gelling, the glue will maintain a certain fluidity and bonding performance. This period is called the activation period. During the activation period, the adhesive performance of the glue is the best and it is suitable for bonding operations. Many two-component panel glues have the problem of too short activation period, which affects their application. In addition, due to the insufficient cross-linking density of hydroxypropylene emulsion, its high temperature resistance is not very ideal. Therefore, it is of great significance to solve the problem of short activation period of hydroxypropylene emulsion after encountering isocyanate and to improve the high temperature resistance of hydroxypropylene emulsion. In the document "Development of Two-Component Panel Glue", a two-component panel glue was synthesized with water-based polymer emulsion as the main agent and isocyanate as the curing agent. Its characteristics are room temperature curing, high bonding strength, water resistance, heat resistance, aging resistance and other properties, but its activation period needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a hydroxypropylene emulsion with a long activation period for panel glue, and a preparation method and application thereof. The panel glue synthesized using the hydroxypropylene emulsion prepared by the present invention as a main agent and toluene diisocyanate as a curing agent has a longer activation period and better high temperature resistance.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a long activation period for a panel glue, comprising the following weight components: 5-8 weight parts of methyl methacrylate, 16-20 weight parts of hydroxyethyl methacrylate, 10-12 weight parts of acrylic acid, 3-6 weight parts of sulfonate-modified epoxy resin, and 2-5 weight parts of adamantane-modified phosphate-modified phenolic resin.

[0007] Preferably, the method for preparing the sulfonate-modified epoxy resin comprises the following steps:

[0008] (1) Add 8-12 g of 1-naphthol-5-sulfonic acid and 15-20 g of phosphorus oxychloride to a single-necked flask, heat and reflux for 7-8 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.05-0.07 g of triethylamine catalyst at 0-5° C., add 8-10 g of 3-butene-1-ol after the addition is complete, react at 25-28° C. for 10-12 h, filter and distill under reduced pressure to obtain intermediate 1;

[0009] (2) Add intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stir and mix at 90-98° C. to form a homogeneous phase, add ethyltriphenylphosphonium bromide as a catalyst, heat to 150-160° C. at a rate of 2-4° C. / min, and react for 50-70 min. After the reaction is completed, cool, wash and dry to obtain a sulfonate-modified epoxy resin.

[0010] Preferably, the temperature of the reflux reaction in step (1) is 72-80°C.

[0011] Preferably, in step (2), the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.4-3.6:0.04-0.08.

[0012] Preferably, the method for preparing the adamantane-modified phosphate-modified phenolic resin comprises the following steps:

[0013] S1. Add 15-18 g of 3-hydroxy-1-adamantyl methacrylate, 7-9 g of ethylene (chloromethyl) dimethoxysilane, 0.03-0.06 g of potassium hydroxide catalyst, and 0.05-0.07 g of 4-methoxyphenol inhibitor to tetrahydrofuran solvent, stir and mix, react for 2-2.5 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0014] S2. Add 10-14 g of phenol, 22-30 g of formaldehyde aqueous solution, and 0.08-0.1 g of oxalic acid catalyst to deionized water, stir and mix, react at 88-92 ° C for 3-4 h, add 1.5-2 g of 2-amino-5-methylphenyl phosphoric acid, and continue to react for 1.5-2 h. After the reaction is completed, add deionized water, wash with water for 40-50 min, and then stand for 20-24 h. After stratification, pour out the upper water to obtain an amino-modified phosphate-modified phenolic resin;

[0015] S3. Add 7-9 g of amino-modified phosphate-modified phenolic resin, 12-14 g of intermediate 2, and 0.02-0.05 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stir and mix, react at 30-35° C. for 2-4 h, and after the reaction, filter, wash and dry to obtain adamantane-modified phosphate-modified phenolic resin.

[0016] Preferably, the reaction temperature in S1 is 40-48°C.

[0017] Preferably, the mass fraction of the formaldehyde aqueous solution in S2 is 36%-38%.

[0018] Preferably, the method for preparing the long-activation-period hydroxypropyl emulsion for the panel glue comprises the following steps:

[0019] Step 1: Add ethylene glycol butyl ether solvent to the reactor, heat to 110-120° C., mix 18-22 parts by weight of methyl methacrylate, 7-10 parts by weight of butyl acrylate, 4-6 parts by weight of styrene, 0.2-0.6 parts by weight of benzoyl peroxide initiator, and 0.1-0.3 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled at 2.5-3 hours. After the dropping is completed, keep the temperature for reaction for 50-70 minutes.

[0020] Step 2: Mix 16-20 parts by weight of hydroxyethyl methacrylate, 10-18 parts by weight of acrylic acid, 3-6 parts by weight of sulfonate-modified epoxy resin, 2-5 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.3-0.8 parts by weight of benzoyl peroxide initiator, and 0.2-0.4 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the reaction solution of step 1. The dropping time is controlled at 1-1.5 hours. After the dropping is completed, keep warm for reaction for 1.5-2 hours. After the reaction is completed, evaporate the solvent, add 0.3-0.6 parts by weight of dimethylethanolamine as a neutralizer and stir for 15-20 minutes, add deionized water to disperse, and obtain a hydroxypropyl emulsion with a long activation period for puzzle glue.

[0021] (III) Beneficial technical effects

[0022] The invention prepares a long-activation-period hydroxypropyl emulsion for panel glue with a core-shell structure by a two-step polymerization and post-dispersion method. Methyl methacrylate, butyl acrylate and styrene are polymerized to prepare a hydrophobic inner core layer, and then hydroxyethyl methacrylate, acrylic acid, sulfonate-modified epoxy resin and adamantane-modified phosphate-modified phenolic resin are added for further polymerization to prepare a hydrophilic outer shell layer, and dimethylethanolamine is added to neutralize the carboxyl groups in the hydrophilic outer shell layer and water is added for dispersion to obtain the long-activation-period hydroxypropyl emulsion for panel glue.

[0023] The sulfonic acid group in 1-naphthol-5-sulfonic acid reacts with phosphorus oxychloride to undergo chlorination reaction, and then reacts with the hydroxyl group in 3-butene-1-ol to introduce a sulfonate group to obtain intermediate 1. The phenolic hydroxyl group in intermediate 1 reacts with the epoxy group in bisphenol A epoxy resin to obtain a sulfonate modified epoxy resin. The hydroxyl group in 3-hydroxy-1-adamantyl methacrylate reacts with the chlorine in ethylene (chloromethyl) dimethoxysilane to obtain intermediate 2. Phenol and formaldehyde undergo polycondensation reaction to obtain a phenolic resin. The phenolic hydroxyl group in the phenolic resin reacts with the phosphoric acid group in 2-amino-5-methylphenyl phosphoric acid to obtain an amino-modified phosphate ester modified phenolic resin. The amino group in the amino-modified phosphate ester modified phenolic resin undergoes Michael addition reaction with intermediate 2 to obtain an adamantane modified phosphate ester modified phenolic resin.

[0024] In sulfonate-modified epoxy resin, the bond energy between the sulfur atom and the oxygen atom of the sulfonate group is relatively high, and the bond energy is relatively high, so the bond energy has relatively high thermal stability, which improves the high temperature resistance of the hydroxypropylene emulsion. The naphthyl group is formed by the fusion of two benzene rings, and has a highly stable conjugated system, which exhibits relatively high thermal stability and enhances the high temperature resistance of the hydroxypropylene emulsion. The epoxy resin forms a dense cross-linked network during the curing process, which further enhances the high temperature resistance of the hydroxypropylene emulsion. In adamantane-modified phosphate-modified phenolic resin, the highly symmetrical rigid structure of adamantane has extremely high thermal stability, which enhances the high temperature resistance of the hydroxypropylene emulsion. The phenolic resin molecule contains a large number of benzene rings and methylene groups, and these structural units have relatively high bond energy, so that the phenolic resin can maintain relatively good stability at high temperatures, thereby enhancing the high temperature resistance of the hydroxypropylene emulsion. The POC bond generated by the reaction of 2-amino-5-methylphenylphosphonic acid and phenolic resin has a sealing effect on the phenolic hydroxyl groups in the phenolic resin, which reduces the oxidation sensitivity of the resin at high temperatures and increases the content of benzene rings in the resin, thereby improving the thermal stability of the phenolic resin and enhancing the high temperature resistance of the hydroxypropylene emulsion.

[0025] In the core-shell structured hydroxypropyl emulsion, the core is completely obtained by polymerization of hydrophobic monomers, and the hydrophilic units are gathered in the outer shell. The long side chain groups in the hydrophilic outer shell are hydrophobic. When dispersed with water, they can increase the interaction between the outer shell and the inner core molecular chains, entangle and curl up with each other to form a tighter core-shell structure. The certain steric hindrance of the long side chain groups can wrap around a part of the hydroxyl groups, preventing the hydroxypropyl emulsion from reacting with the curing agent too early, thereby prolonging the activation period. DETAILED DESCRIPTION

[0026] Example 1

[0027] (1) Add 8 g of 1-naphthol-5-sulfonic acid and 15 g of phosphorus oxychloride to a single-necked flask, heat to 72° C., reflux for 7 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.05 g of triethylamine catalyst at 0° C., add 8 g of 3-butene-1-ol after the addition is complete, react at 25° C. for 10 h, filter and distill under reduced pressure to obtain intermediate 1;

[0028] (2) adding intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stirring and mixing at 90° C. to form a homogeneous phase, adding ethyl triphenyl phosphonium bromide catalyst thereto, wherein the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.4:0.04, heating to 150° C. at a rate of 2° C. / min and reacting for 50 min. After the reaction is completed, cooling, washing, and drying are performed to obtain a sulfonate-modified epoxy resin;

[0029] (3) Add 15 g of 3-hydroxy-1-adamantyl methacrylate, 7 g of ethylene (chloromethyl) dimethoxysilane, 0.03 g of potassium hydroxide catalyst, and 0.05 g of 4-methoxyphenol inhibitor to tetrahydrofuran solvent, stir and mix, react at 40° C. for 2 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0030] (4) adding 10 g of phenol, 22 g of formaldehyde aqueous solution, and 0.08 g of oxalic acid catalyst to deionized water, wherein the mass fraction of the formaldehyde aqueous solution is 36%, stirring and mixing, reacting at 88° C. for 3 h, adding 1.5 g of 2-amino-5-methylphenylphosphoric acid thereto, and continuing the reaction for 1.5 h. After the reaction is completed, adding deionized water, washing with water for 40 min, and then standing for 20 h. After separation, pouring out the upper layer of water to obtain an amino-modified phosphate ester modified phenolic resin;

[0031] (5) adding 7 g of amino-modified phosphate-modified phenolic resin, 12 g of intermediate 2, and 0.02 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stirring and mixing, reacting at 30° C. for 2 h, and filtering, washing and drying after the reaction to obtain adamantane-modified phosphate-modified phenolic resin;

[0032] (6) Add ethylene glycol butyl ether solvent to the reactor, heat to 110° C., mix 18 parts by weight of methyl methacrylate, 7 parts by weight of butyl acrylate, 4 parts by weight of styrene, 0.2 parts by weight of benzoyl peroxide initiator, and 0.1 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled within 2.5 hours. After the dropping is completed, keep the temperature for reaction for 50 minutes;

[0033] (7) 16 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of acrylic acid, 3 parts by weight of sulfonate-modified epoxy resin, 2 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.3 parts by weight of benzoyl peroxide initiator, and 0.2 parts by weight of dodecyl mercaptan chain transfer agent are mixed and added dropwise to the reaction solution of step (6). The addition time is controlled to be 1 hour. After the addition is completed, the mixture is kept warm for reaction for 1.5 hours. After the reaction is completed, the solvent is evaporated, 0.3 parts by weight of dimethylethanolamine as a neutralizer is added and stirred for 15 minutes, and deionized water is added to disperse the mixture to obtain a hydroxypropyl emulsion with a long activation period for the plywood glue.

[0034] Example 2

[0035] (1) Add 12 g of 1-naphthol-5-sulfonic acid and 20 g of phosphorus oxychloride to a single-necked flask, heat to 80° C., reflux for 8 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.07 g of triethylamine catalyst at 5° C., add 10 g of 3-butene-1-ol after the addition is complete, react at 28° C. for 12 h, filter and distill under reduced pressure to obtain intermediate 1;

[0036] (2) adding intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stirring and mixing at 98° C. to form a homogeneous phase, adding ethyl triphenyl phosphonium bromide catalyst thereto, wherein the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.6:0.08, heating to 160° C. at a rate of 4° C. / min for 70 min, and after the reaction is completed, cooling, washing, and drying to obtain a sulfonate-modified epoxy resin;

[0037] (3) Add 18 g of 3-hydroxy-1-adamantyl methacrylate, 9 g of ethylene (chloromethyl) dimethoxysilane, 0.06 g of potassium hydroxide catalyst, and 0.07 g of 4-methoxyphenol inhibitor to tetrahydrofuran solvent, stir and mix, react at 48° C. for 2.5 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0038] (4) adding 14 g of phenol, 30 g of formaldehyde aqueous solution, and 0.1 g of oxalic acid catalyst to deionized water, wherein the mass fraction of the formaldehyde aqueous solution is 38%, stirring and mixing, reacting at 92° C. for 4 h, adding 2 g of 2-amino-5-methylphenylphosphoric acid thereto, and continuing the reaction for 2 h. After the reaction is completed, adding deionized water, washing with water for 50 min, and then standing for 24 h. After separation, pouring out the upper layer of water to obtain an amino-modified phosphate ester modified phenolic resin;

[0039] (5) adding 9 g of amino-modified phosphate-modified phenolic resin, 14 g of intermediate 2, and 0.05 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stirring and mixing, reacting at 35° C. for 4 h, and filtering, washing and drying after the reaction to obtain adamantane-modified phosphate-modified phenolic resin;

[0040] (6) Add ethylene glycol butyl ether solvent to the reactor, heat to 120° C., mix 22 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 6 parts by weight of styrene, 0.6 parts by weight of benzoyl peroxide initiator, and 0.3 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled within 3 hours. After the dropping is completed, keep the temperature for reaction for 70 minutes;

[0041] (7) 20 parts by weight of hydroxyethyl methacrylate, 18 parts by weight of acrylic acid, 6 parts by weight of sulfonate-modified epoxy resin, 5 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.8 parts by weight of benzoyl peroxide initiator, and 0.4 parts by weight of dodecyl mercaptan chain transfer agent are mixed and added dropwise to the reaction solution of step (6). The addition time is controlled to be 1.5 hours. After the addition is completed, the mixture is kept warm for 2 hours. After the reaction is completed, the solvent is evaporated, 0.6 parts by weight of dimethylethanolamine as a neutralizer is added and stirred for 20 minutes, and deionized water is added to disperse the mixture to obtain a hydroxypropyl emulsion with a long activation period for the plywood glue.

[0042] Example 3

[0043] (1) Add 10 g of 1-naphthol-5-sulfonic acid and 17.5 g of phosphorus oxychloride to a single-necked flask, heat to 76° C., reflux for 7.5 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.06 g of triethylamine catalyst at 2° C., add 9 g of 3-butene-1-ol after the addition is complete, react at 26° C. for 11 h, filter and distill under reduced pressure to obtain intermediate 1;

[0044] (2) adding intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stirring and mixing at 94° C. to form a homogeneous phase, adding ethyl triphenyl phosphonium bromide catalyst thereto, wherein the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.5:0.06, heating to 155° C. at a rate of 3° C. / min for 60 min, and after the reaction is completed, cooling, washing, and drying to obtain a sulfonate-modified epoxy resin;

[0045] (3) Add 16.5 g of 3-hydroxy-1-adamantyl methacrylate, 8 g of ethylene (chloromethyl) dimethoxysilane, 0.04 g of potassium hydroxide catalyst, and 0.06 g of 4-methoxyphenol polymerization inhibitor to tetrahydrofuran solvent, stir and mix, react at 44° C. for 2.3 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0046] (4) adding 12 g of phenol, 26 g of formaldehyde aqueous solution, and 0.09 g of oxalic acid catalyst to deionized water, wherein the mass fraction of the formaldehyde aqueous solution is 37%, stirring and mixing, reacting at 90° C. for 3.5 h, adding 1.8 g of 2-amino-5-methylphenylphosphoric acid thereto, and continuing the reaction for 1.8 h. After the reaction is completed, adding deionized water, washing with water for 45 min, and then standing for 22 h. After separation, pouring out the upper layer of water to obtain an amino-modified phosphate ester modified phenolic resin;

[0047] (5) adding 8 g of amino-modified phosphate-modified phenolic resin, 13 g of intermediate 2, and 0.03 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stirring and mixing, reacting at 32° C. for 3 h, and after the reaction is completed, filtering, washing and drying to obtain adamantane-modified phosphate-modified phenolic resin;

[0048] (6) Add ethylene glycol butyl ether solvent to the reactor, heat to 115° C., mix 20 parts by weight of methyl methacrylate, 9 parts by weight of butyl acrylate, 5 parts by weight of styrene, 0.4 parts by weight of benzoyl peroxide initiator, and 0.2 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled within 2.7 hours. After the dropping is completed, keep the temperature for reaction for 60 minutes;

[0049] (7) 18 parts by weight of hydroxyethyl methacrylate, 14 parts by weight of acrylic acid, 5 parts by weight of sulfonate-modified epoxy resin, 3 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.6 parts by weight of benzoyl peroxide initiator, and 0.3 parts by weight of dodecyl mercaptan chain transfer agent are mixed and added dropwise to the reaction solution of step (6). The addition time is controlled to be 1.2 hours. After the addition is completed, the mixture is kept warm for reaction for 1.7 hours. After the reaction is completed, the solvent is evaporated, 0.4 parts by weight of dimethylethanolamine as a neutralizer is added and stirred for 18 minutes, and deionized water is added to disperse the mixture to obtain a hydroxypropyl emulsion with a long activation period for the panel glue.

[0050] Example 4

[0051] (1) Add 8 g of 1-naphthol-5-sulfonic acid and 15 g of phosphorus oxychloride to a single-necked flask, heat to 72° C., reflux for 7 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.05 g of triethylamine catalyst at 0° C., add 8 g of 3-butene-1-ol after the addition is complete, react at 25° C. for 10 h, filter and distill under reduced pressure to obtain intermediate 1;

[0052] (2) adding intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stirring and mixing at 90° C. to form a homogeneous phase, adding ethyl triphenyl phosphonium bromide catalyst thereto, wherein the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.4:0.04, heating to 150° C. at a rate of 2° C. / min and reacting for 50 min. After the reaction is completed, cooling, washing, and drying are performed to obtain a sulfonate-modified epoxy resin;

[0053] (3) Add 18 g of 3-hydroxy-1-adamantyl methacrylate, 9 g of ethylene (chloromethyl) dimethoxysilane, 0.06 g of potassium hydroxide catalyst, and 0.07 g of 4-methoxyphenol inhibitor to tetrahydrofuran solvent, stir and mix, react at 48° C. for 2.5 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0054] (4) adding 14 g of phenol, 30 g of formaldehyde aqueous solution, and 0.1 g of oxalic acid catalyst to deionized water, wherein the mass fraction of the formaldehyde aqueous solution is 38%, stirring and mixing, reacting at 92° C. for 4 h, adding 2 g of 2-amino-5-methylphenylphosphoric acid thereto, and continuing the reaction for 2 h. After the reaction is completed, adding deionized water, washing with water for 50 min, and then standing for 24 h. After separation, pouring out the upper layer of water to obtain an amino-modified phosphate ester modified phenolic resin;

[0055] (5) adding 8 g of amino-modified phosphate-modified phenolic resin, 13 g of intermediate 2, and 0.03 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stirring and mixing, reacting at 32° C. for 3 h, and after the reaction is completed, filtering, washing and drying to obtain adamantane-modified phosphate-modified phenolic resin;

[0056] (6) Add ethylene glycol butyl ether solvent to the reactor, heat to 115° C., mix 20 parts by weight of methyl methacrylate, 9 parts by weight of butyl acrylate, 5 parts by weight of styrene, 0.4 parts by weight of benzoyl peroxide initiator, and 0.2 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled within 2.7 hours. After the dropping is completed, keep the temperature for reaction for 60 minutes;

[0057] (7) 18 parts by weight of hydroxyethyl methacrylate, 14 parts by weight of acrylic acid, 5 parts by weight of sulfonate-modified epoxy resin, 3 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.6 parts by weight of benzoyl peroxide initiator, and 0.3 parts by weight of dodecyl mercaptan chain transfer agent are mixed and added dropwise to the reaction solution of step (6). The addition time is controlled to be 1.2 hours. After the addition is completed, the mixture is kept warm for reaction for 1.7 hours. After the reaction is completed, the solvent is evaporated, 0.4 parts by weight of dimethylethanolamine as a neutralizer is added and stirred for 18 minutes, and deionized water is added to disperse the mixture to obtain a hydroxypropyl emulsion with a long activation period for the panel glue.

[0058] Example 5

[0059] (1) Add 12 g of 1-naphthol-5-sulfonic acid and 20 g of phosphorus oxychloride to a single-necked flask, heat to 80° C., reflux for 8 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.07 g of triethylamine catalyst at 5° C., add 10 g of 3-butene-1-ol after the addition is complete, react at 28° C. for 12 h, filter and distill under reduced pressure to obtain intermediate 1;

[0060] (2) adding intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stirring and mixing at 98° C. to form a homogeneous phase, adding ethyl triphenyl phosphonium bromide catalyst thereto, wherein the mass ratio of intermediate 1, bisphenol A epoxy resin, and ethyl triphenyl phosphonium bromide is 1:3.6:0.08, heating to 160° C. at a rate of 4° C. / min for 70 min, and after the reaction is completed, cooling, washing, and drying to obtain a sulfonate-modified epoxy resin;

[0061] (3) Add 16.5 g of 3-hydroxy-1-adamantyl methacrylate, 8 g of ethylene (chloromethyl) dimethoxysilane, 0.04 g of potassium hydroxide catalyst, and 0.06 g of 4-methoxyphenol polymerization inhibitor to tetrahydrofuran solvent, stir and mix, react at 44° C. for 2.3 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2;

[0062] (4) adding 12 g of phenol, 26 g of formaldehyde aqueous solution, and 0.09 g of oxalic acid catalyst to deionized water, wherein the mass fraction of the formaldehyde aqueous solution is 37%, stirring and mixing, reacting at 90° C. for 3.5 h, adding 1.8 g of 2-amino-5-methylphenylphosphoric acid thereto, and continuing the reaction for 1.8 h. After the reaction is completed, adding deionized water, washing with water for 45 min, and then standing for 22 h. After separation, pouring out the upper layer of water to obtain an amino-modified phosphate ester modified phenolic resin;

[0063] (5) adding 7 g of amino-modified phosphate-modified phenolic resin, 12 g of intermediate 2, and 0.02 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stirring and mixing, reacting at 30° C. for 2 h, and filtering, washing and drying after the reaction to obtain adamantane-modified phosphate-modified phenolic resin;

[0064] (6) Add ethylene glycol butyl ether solvent to the reactor, heat to 110° C., mix 18 parts by weight of methyl methacrylate, 7 parts by weight of butyl acrylate, 4 parts by weight of styrene, 0.2 parts by weight of benzoyl peroxide initiator, and 0.1 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled within 2.5 hours. After the dropping is completed, keep the temperature for reaction for 50 minutes;

[0065] (7) 16 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of acrylic acid, 3 parts by weight of sulfonate-modified epoxy resin, 2 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.3 parts by weight of benzoyl peroxide initiator, and 0.2 parts by weight of dodecyl mercaptan chain transfer agent are mixed and added dropwise to the reaction solution of step (6). The addition time is controlled to be 1 hour. After the addition is completed, the mixture is kept warm for reaction for 1.5 hours. After the reaction is completed, the solvent is evaporated, 0.3 parts by weight of dimethylethanolamine as a neutralizer is added and stirred for 15 minutes, and deionized water is added to disperse the mixture to obtain a hydroxypropyl emulsion with a long activation period for the plywood glue.

[0066] Comparative Example 1

[0067] Compared with Example 5, the difference in this comparative example is that no adamantane-modified phosphate-modified phenolic resin is added.

[0068] Comparative Example 2

[0069] Compared with Example 5, the difference in this comparative example is that no sulfonate-modified epoxy resin is added.

[0070] The hydroxypropyl emulsion prepared in Example 1-5 and Comparative Example 1-2 was mixed with toluene diisocyanate at a ratio of 8:1 at 600 rpm for 3-5 minutes to obtain a panel glue.

[0071] The panel glue was placed in a 35°C / 60%RH constant temperature and humidity test chamber for an activation period test. The test results are shown in Table 1.

[0072] Table 1: Pot life test.

[0073] project Activation period (min) Example 1 63 Example 2 70 Example 3 68 Example 4 74 Example 5 66 Comparative Example 1 42 Comparative Example 2 47

[0074] It can be seen from Table 1 that the plywood glue made from the hydroxypropylene emulsion in Examples 1-5 has a longer activation period than the plywood glue made from the hydroxypropylene emulsion in Comparative Examples 1-2.

[0075] Apply the glue to the base material, which is solid wood, and the glue application amount is 180g / m 2 , place for 1.5 hours, boil in 100℃ water for 6 hours, and then bake in 80℃ oven for 20 hours. If there is no debonding after baking for 20 hours, the glue of the board is qualified; if it debonds after baking for 20 hours, the glue of the board is unqualified. The test results are shown in Table 2:

[0076] Table 2: High temperature resistance test.

[0077] project High temperature resistance Example 1 qualified Example 2 qualified Example 3 qualified Example 4 qualified Example 5 qualified Comparative Example 1 Failure Comparative Example 2 Failure

[0078] It can be seen from Table 2 that the test results of the jigsaw glue made from the hydroxypropylene emulsion in Examples 1-5 are qualified; the test results of the jigsaw glue made from the hydroxypropylene emulsion in Comparative Examples 1-2 are unqualified, indicating that the jigsaw glue prepared with the hydroxypropylene emulsion with a long activation period has better high temperature resistance.

[0079] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A long-activation-period hydroxypropyl emulsion for plywood glue, characterized in that: The invention comprises the following components by weight: 18-22 parts by weight of methyl methacrylate, 7-10 parts by weight of butyl acrylate, 4-6 parts by weight of styrene, 16-20 parts by weight of hydroxyethyl methacrylate, 10-18 parts by weight of acrylic acid, 3-6 parts by weight of sulfonate-modified epoxy resin, and 2-5 parts by weight of adamantane-modified phosphate-modified phenolic resin.

2. The long-activation-period hydroxypropyl emulsion for panel glue according to claim 1, characterized in that: The preparation method of the sulfonate modified epoxy resin comprises the following steps: (1) Add 8-12 g of 1-naphthol-5-sulfonic acid and 15-20 g of phosphorus oxychloride to a single-necked flask, heat and reflux for 7-8 h, remove the remaining phosphorus oxychloride under reduced pressure, dropwise add 0.05-0.07 g of triethylamine catalyst at 0-5° C., add 8-10 g of 3-butene-1-ol after the addition is complete, react at 25-28° C. for 10-12 h, filter and distill under reduced pressure to obtain intermediate 1; (2) Add intermediate 1 and bisphenol A epoxy resin to a three-necked flask, stir and mix at 90-98° C. to form a homogeneous phase, add ethyltriphenylphosphonium bromide as a catalyst, heat to 150-160° C. at a rate of 2-4° C. / min, and react for 50-70 min. After the reaction is completed, cool, wash and dry to obtain a sulfonate-modified epoxy resin.

3. The long-activation-period hydroxypropyl emulsion for plywood glue according to claim 2, characterized in that: The temperature of the reflux reaction in step (1) is 72-80°C.

4. The long-activation-period hydroxypropyl emulsion for plywood glue according to claim 2, characterized in that: In the step (2), the mass ratio of the intermediate 1, bisphenol A epoxy resin and ethyl triphenyl phosphonium bromide is 1:3.4-3.6:0.04-0.

08.

5. The long-activation-period hydroxypropyl emulsion for plywood glue according to claim 1, characterized in that: The method for preparing the adamantane-modified phosphate-modified phenolic resin comprises the following steps: S1. Add 15-18 g of 3-hydroxy-1-adamantyl methacrylate, 7-9 g of ethylene (chloromethyl) dimethoxysilane, 0.03-0.06 g of potassium hydroxide catalyst, and 0.05-0.07 g of 4-methoxyphenol inhibitor to tetrahydrofuran solvent, stir and mix, react for 2-2.5 h, and after the reaction is completed, filter, wash and dry to obtain intermediate 2; S2. Add 10-14 g of phenol, 22-30 g of formaldehyde aqueous solution, and 0.08-0.1 g of oxalic acid catalyst to deionized water, stir and mix, react at 88-92 ° C for 3-4 h, add 1.5-2 g of 2-amino-5-methylphenyl phosphoric acid, and continue to react for 1.5-2 h. After the reaction is completed, add deionized water, wash with water for 40-50 min, and then stand for 20-24 h. After stratification, pour out the upper water to obtain an amino-modified phosphate-modified phenolic resin; S3. Add 7-9 g of amino-modified phosphate-modified phenolic resin, 12-14 g of intermediate 2, and 0.02-0.05 g of sodium ethoxide catalyst to tetrahydrofuran solvent, stir and mix, react at 30-35° C. for 2-4 h, and after the reaction, filter, wash and dry to obtain adamantane-modified phosphate-modified phenolic resin.

6. The long-activation-period hydroxypropyl emulsion for plywood glue according to claim 5, characterized in that: The reaction temperature in S1 is 40-48°C.

7. The long-activation-period hydroxypropyl emulsion for plywood glue according to claim 5, characterized in that: The mass fraction of the formaldehyde aqueous solution in S2 is 36%-38%.

8. A long-activation-period hydroxypropyl emulsion for plywood glue as claimed in claim 1, characterized in that: The method for preparing the long-activation-period hydroxypropyl emulsion for the panel glue comprises the following steps: Step 1: Add ethylene glycol butyl ether solvent to the reactor, heat to 110-120° C., mix 18-22 parts by weight of methyl methacrylate, 7-10 parts by weight of butyl acrylate, 4-6 parts by weight of styrene, 0.2-0.6 parts by weight of benzoyl peroxide initiator, and 0.1-0.3 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the ethylene glycol butyl ether solvent. The dropping time is controlled at 2.5-3 hours. After the dropping is completed, keep the temperature for reaction for 50-70 minutes. Step 2: Mix 16-20 parts by weight of hydroxyethyl methacrylate, 10-18 parts by weight of acrylic acid, 3-6 parts by weight of sulfonate-modified epoxy resin, 2-5 parts by weight of adamantane-modified phosphate-modified phenolic resin, 0.3-0.8 parts by weight of benzoyl peroxide initiator, and 0.2-0.4 parts by weight of dodecyl mercaptan chain transfer agent, and add dropwise to the reaction solution of step 1. The dropping time is controlled at 1-1.5 hours. After the dropping is completed, keep warm for reaction for 1.5-2 hours. After the reaction is completed, evaporate the solvent, add 0.3-0.6 parts by weight of dimethylethanolamine as a neutralizer and stir for 15-20 minutes, add deionized water to disperse, and obtain a hydroxypropyl emulsion with a long activation period for puzzle glue.