CN107446538B - Silanol-based double-component waterborne polyurethane wood adhesive and preparation method thereof - Google Patents
Silanol-based double-component waterborne polyurethane wood adhesive and preparation method thereof Download PDFInfo
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- CN107446538B CN107446538B CN201610377121.7A CN201610377121A CN107446538B CN 107446538 B CN107446538 B CN 107446538B CN 201610377121 A CN201610377121 A CN 201610377121A CN 107446538 B CN107446538 B CN 107446538B
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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
- 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
- C09J1/00—Adhesives based on inorganic constituents
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a silanol-based two-component waterborne polyurethane wood adhesive and a preparation method thereof. The adhesive comprises a main agent and a cross-linking agent, wherein the main agent is mainly prepared from the following components in parts by weight: 9-15 parts of polyvinyl alcohol; 6-12 parts of compound polyol; 15-25 parts of silica sol; 0.2-0.4% of propylene glycol; 0.03-0.06 wt% of polyacrylamide; 50-65 parts of water; 0.05-0.2% of a surfactant; 0-0.15% of defoaming agent; 0-0.2% of preservative; 8-15 parts of a filler; the composite polyol is prepared from soybean oil polyol, polyether polyol and dibutyl phthalate or dioctyl phthalate, wherein the weight ratio of the soybean oil polyol to the polyether polyol is 6-15: 1-4: mixing the components in a weight ratio of 30-60; the cross-linking agent is prepared from the following components in parts by weight: 5-8 parts of vegetable oil; 20-30 parts of polyol benzoate; 65-75% of isocyanate. The adhesive has high adhesive strength, good water resistance and weather resistance and environmental protection.
Description
Technical Field
The invention relates to a wood adhesive, in particular to a silanol-based two-component waterborne polyurethane wood adhesive and a preparation method thereof.
Background
The existing wood adhesives are various in types, but urea-formaldehyde resin glue and phenolic resin glue are mainly used in production, and as formaldehyde is used as a main raw material of the glue, free formaldehyde is continuously released in a considerable period of time in the production and use processes, so that the environment and the health of users are influenced.
With the enhancement of environmental awareness of people, the environmental protection requirement on the adhesive is higher and higher. The development of a wood adhesive which is suitable for the requirements of plywood production process, has high adhesive strength and good water and weather resistance, and is environment-friendly has become the key point of research.
Disclosure of Invention
The invention aims to solve the technical problem of providing the silanol-based two-component waterborne polyurethane wood adhesive which is suitable for the production process requirement of plywood, has high adhesive strength and good water and weather resistance and is environment-friendly and the preparation method thereof.
The invention relates to a silanol-based two-component waterborne polyurethane wood adhesive, which comprises a main agent and a cross-linking agent, wherein:
the main agent is mainly prepared from the following components in parts by weight:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0-0.15% of defoaming agent;
0-0.2% of preservative;
8-15 parts of a filler;
the composite polyol is prepared from soybean oil polyol, polyether polyol and dibutyl phthalate or dioctyl phthalate, wherein the weight ratio of the soybean oil polyol to the polyether polyol to the dibutyl phthalate or the dioctyl phthalate is 6-15: 1-4: mixing the components in a weight ratio of 30-60;
the cross-linking agent is prepared from the following components in parts by weight:
5-8 parts of vegetable oil;
20-30 parts of polyol benzoate;
65-75% of isocyanate.
According to the invention, the composite polyol is added into a polyvinyl alcohol and silica sol system, so that the solid content of the adhesive is improved, the compatibility of the polyvinyl alcohol and the silica sol is enhanced, the flexibility and the storage stability of the adhesive are enhanced, the working life of the adhesive after the main agent and the cross-linking agent are combined can be prolonged, and the plate making process is improved; the addition of propylene glycol can make the obtained adhesive have frost resistance and reduce its film-forming temperature, and the addition of polyacrylamide has a certain thickening action.
In order to make the reaction of the components of the main agent more uniform and improve the properties of the final product, such as adhesive strength, water resistance and weather resistance, the weight ratio of the components in the main agent is preferably:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0.05-0.15% of defoaming agent;
0-0.2% of preservative;
8-15 parts of filler.
On the basis of ensuring the performances of the finally obtained product such as bonding strength, water resistance, weather resistance and the like, in order to further improve the shelf life of the finally obtained product, the weight ratio of the components in the main agent is further preferably as follows:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0.08-0.15% of defoaming agent;
0.05-0.2% of preservative;
8-12 parts of filler.
In the composition of the cross-linking agent in the technical scheme of the invention, the vegetable oil is preferably castor oil.
In the composition of the cross-linking agent according to the technical scheme of the present invention, the isocyanate may specifically be polyphenyl polymethylene polyisocyanate (polymeric MDI) and/or diphenylmethane diisocyanate (pure MDI).
In the technical scheme of the invention, the weight ratio of the main agent to the cross-linking agent is 100: 6-30, preferably 100: 6 to 25.
In the technical scheme of the invention, the type and the granularity of the filler are selected to be the same as those of the prior art, and specifically, the type of the filler can be one or the combination of more than two of kaolin, titanium dioxide, calcium carbonate and talcum powder; when the filler is selected from a combination of two or more of the above substances, the compounding ratio thereof may be any ratio. The particle size of the filler is preferably 325 mesh or more, more preferably 800 mesh or more.
In the technical scheme of the invention, the surfactant is an anionic surfactant, and preferably sodium dodecyl benzene sulfonate is adopted.
In the technical scheme of the invention, the selection of the defoaming agent is the same as that of the prior art, and specifically, the defoaming agent can be n-butyl alcohol and/or tributyl phosphate.
In the technical scheme of the invention, the selection of the preservative is the same as that of the prior art, and specifically the preservative can be isothiazolinone.
The invention also provides a preparation method of the silanol-based two-component waterborne polyurethane wood adhesive, which comprises the preparation of a main agent and the preparation of a cross-linking agent, wherein the preparation method comprises the following steps:
the method for preparing the main agent comprises the following steps:
firstly, placing water into a reaction container, adding polyvinyl alcohol, keeping the system at 55-70 ℃ after the polyvinyl alcohol is dissolved, adding a surfactant, then adding silica sol, stirring for reaction, adjusting the pH value of the system to be 6.0-7.0 by using a pH regulator, then adding composite polyol, uniformly stirring, cooling the system to be less than or equal to 50 ℃, adding propylene glycol and a filler, stirring for 30-40 minutes, then adding polyacrylamide, uniformly stirring (about stirring for 30-40 minutes), filtering and discharging to obtain a main agent;
when the main agent contains the defoaming agent and the preservative, the defoaming agent is added at the same time of adding water or after adding water; the preservative is added before or simultaneously with or after the filler is added, and the mixture is stirred uniformly after the addition;
the method for preparing the cross-linking agent comprises the following steps:
placing isocyanate in a reaction container, heating to 60-70 ℃ under the protection of gas, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 5-15 minutes, keeping the system at 65-80 ℃, adding polyol benzoate, carrying out heat preservation reaction for 100-150 minutes at 65-80 ℃, cooling and discharging to obtain the cross-linking agent.
In the method for preparing the main agent, preferably, the surfactant is added, stirred and reacted for 20-40 minutes, and then the silica sol is added;
in the above method for preparing the base compound, the dissolution of the polyvinyl alcohol is preferably carried out under heating, and more preferably at 90 to 95 ℃. When the surfactant is added, the temperature of the system is preferably kept at 60-80 ℃. The pH regulator can be an acidic substance or an alkaline substance, and is specifically selected according to the pH value of a system after silica sol is added, stirred and reacted for 30-45 minutes; the acidic substance is preferably formic acid; the alkaline substance is preferably sodium hydroxide.
The above-mentioned method for preparing the crosslinking agent is usually carried out under the protection of inert gas (such as nitrogen, argon, helium, etc.), and the crosslinking agent prepared by the above-mentioned method is preferably preserved by introducing nitrogen gas.
After the main agent is prepared, in specific application, according to different water resistance and weather resistance requirements of the bonding material, the main agent and the curing agent are mixed according to the proportion of 100: 5-30 parts by weight of the silicone-based double-component waterborne polyurethane wood adhesive.
The silanol-based double-component waterborne polyurethane wood adhesive disclosed by the invention can be applied to bonding of structural laminated wood, bonding of novel engineering wood materials, splicing of solid wood, production of solid wood composite floors, production of structural plywood, indoor and outdoor plywood, bamboo-wood composite boards, production of laminated wood boards, bonding of wooden furniture, kitchen cabinets and wooden doors and the like.
The invention adopts silanol group polymer as main agent, the main agent mainly contains silanol group polymer and various high-activity hydroxyl groups, no large amount of carboxyl exists, the length of the working life can be adjusted, no negative reaction is generated in the working life, corresponding isocyanate cross-linking agent (such as pure MDI or polymeric MDI) can be added to generate carbamate and urea bond compounds, the isocyanate cross-linking agent and the hydroxyl groups in the main agent, the hydroxyl groups penetrating into glue inside the wood and the hydroxyl groups contacting the glue in the lignin inside and outside the wood are subjected to cross-linking reaction to form a multidimensional network structure and strong glue nails, and silicon atoms are uniformly distributed in the adhesive, so that the wet bonding strength, water resistance, weather resistance and aging resistance of the glue bonding part are greatly enhanced. The applicant proves through experiments that the main agent and the cross-linking agent are mixed according to the ratio of 100: 6-8, the dry strength and the wet strength of the prepared plywood are more than or equal to 1.0MPa and more than or equal to 0.7MPa, namely the plywood reaches the national standard of the class II common plywood; mixing the main agent and the cross-linking agent according to the ratio of 100: 10-12, the produced plywood can be dipped in boiling water at 100 ℃ without degumming, and the tensile shear strength is more than or equal to 1.2MPa in dry strength and more than or equal to 1.0MPa in wet strength; mixing the main agent and the cross-linking agent according to the ratio of 100: 12-15, the plywood produced can be circularly dipped in boiling water at 100 ℃ for multiple times without degumming, the tensile shear strength dry strength is more than or equal to 1.2MPa, the wet strength is more than or equal to 1.0MPa, and the requirements of LY/T1601-type 2011 type I standard in China are met; mixing the main agent and the cross-linking agent according to the ratio of 100: 15-20 parts by weight of the adhesive, and the structural laminated wood produced by Pinus densiflora and spruce can meet the national standard requirements of GB/T26899-2011 structural laminated wood; mixing the main agent and the cross-linking agent according to the ratio of 100: 25, the adhesive is used for beech wood as a test material, and the dry compression shear strength is 15.28mpa, and the wet compression shear strength is 5.83 mpa; mixing the main agent and the cross-linking agent according to the ratio of 100: 30, the adhesive is used for beech wood as a test material, the dry compression shear strength is 16.19mpa, the wet compression shear strength is 5.46mpa, and the normal-temperature water immersion stripping performance and the repeated immersion stripping performance in boiling water at 100 ℃ both meet the highest standard requirement of GB/T26899-2011 structure laminated wood. All main performance indexes and environmental protection indexes of the wood adhesive are higher than those of the existing aqueous high-molecular isocyanate wood adhesive.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
The parts described in the following examples are parts by weight.
Example 1
1. The adhesive formula comprises:
the main agent is prepared from the following components in parts by weight:
9 parts of polyvinyl alcohol;
11 parts of compound polyol (prepared by mixing soybean oil polyol, polyether polyol and dibutyl phthalate in a weight ratio of 10: 1: 40);
15 parts of silica sol;
0.4 part of propylene glycol;
0.05 part of polyacrylamide;
65 parts of water;
0.05 part of a surfactant (sodium dodecyl benzene sulfonate);
0.08 part of defoaming agent (n-butyl alcohol);
0 part of preservative (isothiazolinone);
15 parts of a filler (calcium carbonate);
the cross-linking agent is prepared from the following components in parts by weight:
7 parts of castor oil;
28 parts of polyol benzoate;
65 parts of isocyanate (polyphenyl polymethylene polyisocyanate (polymeric MDI)).
The weight ratio of the main agent to the cross-linking agent is 100: 10.
2. the preparation method comprises the following steps:
1) weighing the components according to the formula for later use;
2) adding water into a reaction kettle with a heating stirrer, adding polyvinyl alcohol and a defoaming agent, heating to 90 ℃, keeping the temperature until the polyvinyl alcohol is completely dissolved, then cooling the system to 70 ℃, adding a surfactant, keeping the temperature, stirring and reacting for 40 minutes, then cooling the system to 60-65 ℃, adding silica sol, stirring and reacting for 30 minutes, adjusting the pH of the system to 6.5 by using a pH regulator (formic acid), then adding composite polyol, stirring and reacting for 40 minutes, then cooling the system to 50 ℃, then adding propylene glycol, stirring for 25 minutes, cooling to below 40 ℃, adding a filler and polyacrylamide, stirring uniformly, filtering and discharging to obtain the main agent.
3) Placing isocyanate in another reaction kettle with a heating stirrer, heating to 60 ℃ under the protection of nitrogen, adding castor oil under stirring, carrying out polymerization reaction for 10 minutes, heating the system to 65 ℃, adding polyol benzoate, carrying out heat preservation reaction for 150 minutes at 65 ℃, cooling, discharging, and filling nitrogen for storage to obtain the cross-linking agent;
4) the obtained main agent and the cross-linking agent are mixed according to the proportion of 100: 10 to obtain the silanol-based double-component waterborne polyurethane wood adhesive.
The main agent and the cross-linking agent prepared in the above examples are sent to a detection department for performance test according to relevant standards, and the test results are respectively shown in the following table 1:
table 1:
example 2
1. The adhesive formula comprises:
the main agent is prepared from the following components in parts by weight:
10 parts of polyvinyl alcohol;
10 parts of composite polyol (prepared from 14 parts of soybean oil polyol, 4 parts of polyether polyol and 50 parts of dioctyl phthalate);
25 parts of silica sol;
0.35 part of propylene glycol;
0.06 part of polyacrylamide;
55 parts of water;
0.08 part of surfactant (sodium dodecyl benzene sulfonate);
0.10 part of defoaming agent (tributyl phosphate);
0.05 part of preservative (isothiazolinone);
8 parts of a filler (talcum powder);
the cross-linking agent is prepared from the following components in parts by weight:
5 parts of castor oil;
20 parts of polyol benzoate;
75 parts of isocyanate (polyphenyl polymethylene polyisocyanate (polymeric MDI)).
The weight ratio of the main agent to the cross-linking agent is 100: 6.
2. the preparation method comprises the following steps:
1) weighing the components according to the formula for later use;
2) adding water into a reaction kettle with a heating stirrer, adding polyvinyl alcohol and a defoaming agent, heating to 95 ℃, keeping the temperature until the polyvinyl alcohol is dissolved, then cooling the system to 65 ℃, adding a surfactant, keeping the temperature, stirring and reacting for 25 minutes, then cooling the system to 60 ℃, adding silica sol, stirring and reacting for 40 minutes, adjusting the pH of the system to 6.0 by using a pH regulator (formic acid), then adding composite polyol, propylene glycol and a preservative, cooling to 30 ℃ after uniformly stirring, adding a filler and polyacrylamide, uniformly stirring, filtering and discharging to obtain a main agent;
3) placing isocyanate in another reaction kettle with a heating stirrer, heating to 70 ℃ under the protection of nitrogen, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 10 minutes, heating the system to 75 ℃, adding polyol benzoate, carrying out heat preservation reaction for 120 minutes at 80 ℃, cooling, discharging, filling nitrogen, and storing to obtain the cross-linking agent;
4) the obtained main agent and the cross-linking agent are mixed according to the proportion of 100: 6, and then obtaining the silanol-based double-component waterborne polyurethane wood adhesive.
The main agent and the cross-linking agent prepared in the above examples are sent to relevant departments for performance test according to relevant standards, and the test results are respectively shown in the following table 2:
table 2:
example 3
1. The adhesive formula comprises:
the main agent is prepared from the following components in parts by weight:
15 parts of polyvinyl alcohol;
9 parts of composite polyol (obtained by mixing 15 parts of soybean oil polyol, 2 parts of polyether polyol, and 30 parts of dibutyl phthalate and dioctyl phthalate in parts by weight);
18 parts of silica sol;
0.3 part of propylene glycol;
0.04 part of polyacrylamide;
60 parts of water;
0.2 part of surfactant (sodium dodecyl benzene sulfonate);
0 part of defoaming agent (n-butanol);
0.08 part of preservative (isothiazolinone);
12 parts of filler (comprising kaolin and talcum powder according to the weight ratio of 2: 1);
the cross-linking agent is prepared from the following components in parts by weight:
6 parts of vegetable oil (castor oil);
30 parts of polyol benzoate;
72 parts of isocyanate (diphenylmethane diisocyanate (pure MDI)).
The weight ratio of the main agent to the cross-linking agent is 100: 20.
2. the preparation method comprises the following steps:
1) weighing the components according to the formula for later use;
2) adding water into a reaction kettle with a heating stirrer, adding polyvinyl alcohol and a defoaming agent, heating to 92 ℃, keeping the temperature until the polyvinyl alcohol is dissolved, then cooling the system to 70 ℃, adding a surfactant, keeping the temperature, stirring and reacting for 30 minutes, then cooling the system to 55 ℃, adding silica sol, stirring and reacting for 30 minutes, adjusting the pH of the system to 6.3 by using a pH regulator (formic acid), then adding composite polyol, propylene glycol and a preservative, stirring and reacting for 35 minutes, then cooling the system to 35 ℃, adding a filler and polyacrylamide, stirring uniformly, filtering and discharging to obtain a main agent;
3) placing isocyanate in another reaction kettle with a heating stirrer, heating to 65 ℃ under the protection of nitrogen, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 10 minutes, then heating the system to 70 ℃, adding polyol benzoate, carrying out heat preservation reaction for 100 minutes at 75 ℃, cooling, discharging, filling nitrogen for storage, and obtaining the cross-linking agent;
4) the obtained main agent and the cross-linking agent are mixed according to the proportion of 100: 20, and then obtaining the silanol group double-component waterborne polyurethane wood adhesive.
The test results of the performance of the beech samples prepared from the base compound prepared in the above examples and the final product adhesive according to relevant standards are respectively shown in the following table 3:
table 3:
example 4
1. The adhesive formula comprises:
the main agent is prepared from the following components in parts by weight:
11 parts of polyvinyl alcohol;
7 parts of composite polyol (prepared by mixing 13 parts of soybean oil polyol, 3 parts of polyether polyol and 45 parts of dibutyl phthalate in a weight ratio);
20 parts of silica sol;
0.25 part of propylene glycol;
0.035 parts of polyacrylamide;
63 parts of water;
0.18 part of surfactant (sodium dodecyl benzene sulfonate);
0.15 part of defoaming agent;
0.10 part of preservative (tributyl phosphate);
10 parts of filler (titanium dioxide);
the cross-linking agent is prepared from the following components in parts by weight:
7.0 parts of vegetable oil (castor oil);
26.0 parts of polyol benzoate;
67 parts of isocyanate consisting of diphenylmethane diisocyanate (pure midi) and polyphenyl polymethylene polyisocyanate (polymeric midi) in a 1: 1 weight ratio.
The weight ratio of the main agent to the cross-linking agent is 100: 15.
2. the preparation method comprises the following steps:
1) weighing the components according to the formula for later use;
2) adding water into a reaction kettle with a heating stirrer, adding polyvinyl alcohol and a defoaming agent, heating to 92 ℃, keeping the temperature until the polyvinyl alcohol is completely dissolved, then cooling the system to 70 ℃, adding a surfactant, keeping the temperature, stirring and reacting for 20 minutes, then cooling the system to 60 ℃, adding silica sol, stirring and reacting for 35 minutes, adjusting the pH of the system to 6.6 by using a pH regulator (formic acid), adding composite polyol, propylene glycol and a preservative, uniformly stirring, cooling the system to 35 ℃, adding a filler and polyacrylamide, uniformly stirring, filtering and discharging to obtain a main agent;
3) placing isocyanate in another reaction kettle with a heating stirrer, heating to 62 ℃ under the protection of nitrogen, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 10 minutes, then heating the system to 70 ℃, adding polyol benzoate, carrying out heat preservation reaction for 110 minutes at 78 ℃, cooling, discharging, filling nitrogen for storage, and obtaining the cross-linking agent;
4) the obtained main agent and the cross-linking agent are mixed according to the proportion of 100: 15, and then obtaining the silanol-based double-component waterborne polyurethane wood adhesive.
The main agent and the cross-linking agent prepared in the above examples are sent to a detection department for performance test according to relevant standards, and the test results are respectively shown in the following table 4:
table 4:
example 5
1. The adhesive formula comprises:
the main agent is prepared from the following components in parts by weight:
12 parts of polyvinyl alcohol;
5 parts of composite polyol (prepared by mixing 11 parts of soybean oil polyol, 2 parts of polyether polyol and 30 parts of dioctyl phthalate by weight);
24 parts of silica sol;
0.2 part of propylene glycol;
0.03 part of polyacrylamide;
60 parts of water;
0.10 part of surfactant (sodium dodecyl benzene sulfonate);
0.15 part of defoaming agent (tributyl phosphate).
0.20% of preservative
11 parts of a filler (calcium carbonate);
the cross-linking agent is prepared from the following components in parts by weight:
8 parts of castor oil;
24 parts of polyol benzoate;
the isocyanate was 68 parts of polyphenyl polymethylene polyisocyanate (polymeric MDI).
The weight ratio of the main agent to the cross-linking agent is 100: 25.
2. the preparation method comprises the following steps:
1) weighing the components according to the formula for later use;
2) adding water into a reaction kettle with a heating stirrer, adding polyvinyl alcohol and a defoaming agent, heating to 94 ℃, keeping the temperature until the polyvinyl alcohol is completely dissolved, then cooling the system to 70 ℃, adding a surfactant, keeping the temperature, stirring and reacting for 30 minutes, then cooling the system to 63 ℃, adding silica sol, stirring and reacting for 30 minutes, adjusting the pH of the system to 6.7 by using a pH regulator (formic acid), then adding composite polyol, propylene glycol and a preservative, stirring and reacting for 40 minutes, adding the preservative, stirring uniformly, cooling the system to 35 ℃, adding a filler and polyacrylamide, stirring uniformly, filtering and discharging to obtain a main agent;
3) placing isocyanate in another reaction kettle with a heating stirrer, heating to 65 ℃ under the protection of nitrogen, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 5 minutes, heating the system to 75 ℃, adding polyol benzoate, carrying out heat preservation reaction for 120 minutes at 80 ℃, cooling, discharging, filling nitrogen, and storing to obtain the cross-linking agent;
4) the obtained main agent and the cross-linking agent are mixed according to the proportion of 100: 25 to obtain the silanol-based double-component waterborne polyurethane wood adhesive.
The test results of the test of the properties of the beech samples prepared from the base compound prepared in the above examples and the final product adhesive according to relevant standards are respectively shown in the following table 5:
table 5:
Claims (10)
1. a silanol-based double-component waterborne polyurethane wood adhesive is composed of a main agent and a cross-linking agent, and is characterized in that:
the main agent is prepared from the following components in parts by weight:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0-0.15% of defoaming agent;
0-0.2% of preservative;
8-15 parts of a filler;
the composite polyol is prepared from soybean oil polyol, polyether polyol and dibutyl phthalate or dioctyl phthalate, wherein the weight ratio of the soybean oil polyol to the polyether polyol to the dibutyl phthalate or the dioctyl phthalate is 6-15: 1-4: mixing the components in a weight ratio of 30-60;
the cross-linking agent is prepared from the following components in parts by weight:
5-8 parts of vegetable oil;
20-30 parts of polyol benzoate;
65-75% of isocyanate.
2. The silanol two-component aqueous polyurethane wood adhesive according to claim 1, characterized in that: the main agent is prepared from the following components in parts by weight:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0.05-0.15% of defoaming agent;
0-0.2% of preservative;
8-15 parts of filler.
3. The silanol two-component aqueous polyurethane wood adhesive according to claim 1, characterized in that: the main agent is prepared from the following components in parts by weight:
9-15 parts of polyvinyl alcohol;
6-12 parts of compound polyol;
15-25 parts of silica sol;
0.2-0.4% of propylene glycol;
0.03-0.06 wt% of polyacrylamide;
50-65 parts of water;
0.05-0.2% of a surfactant;
0.08-0.15% of defoaming agent;
0.05-0.2% of preservative;
8-12 parts of filler.
4. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: in the composition of the cross-linking agent, the vegetable oil is castor oil.
5. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: in the composition of the cross-linking agent, the isocyanate is polyphenyl polymethylene polyisocyanate and/or diphenylmethane diisocyanate.
6. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: the weight ratio of the main agent to the cross-linking agent is 100: 6 to 30.
7. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: the filler is one or the combination of more than two of kaolin, titanium dioxide, calcium carbonate and talcum powder.
8. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: the surfactant is an anionic surfactant.
9. The silanol two-component aqueous polyurethane wood adhesive according to any one of claims 1 to 3, wherein: the defoaming agent is n-butyl alcohol and/or tributyl phosphate.
10. The preparation method of the silanol-based two-component waterborne polyurethane wood adhesive disclosed by claim 1 comprises the steps of preparing a main agent and preparing a cross-linking agent, and is characterized in that:
the method for preparing the main agent comprises the following steps:
firstly, placing water into a reaction container, adding polyvinyl alcohol, keeping the system at 55-70 ℃ after the polyvinyl alcohol is dissolved, adding a surfactant, then adding silica sol, stirring for reaction, adjusting the pH value of the system to be 6.0-7.0 by using a pH regulator, then adding composite polyol, uniformly stirring, cooling the system to be less than or equal to 50 ℃, adding propylene glycol and a filler, stirring for 30-40 minutes, then adding polyacrylamide, uniformly stirring, filtering and discharging to obtain a main agent;
when the main agent contains the defoaming agent and the preservative, the defoaming agent is added at the same time of adding water or after adding water; the preservative is added before or simultaneously with or after the filler is added, and the mixture is stirred uniformly after the addition;
the method for preparing the cross-linking agent comprises the following steps:
placing isocyanate in a reaction container, heating to 60-70 ℃ under the protection of gas, adding vegetable oil under the stirring condition, carrying out polymerization reaction for 5-15 minutes, keeping the system at 65-80 ℃, adding polyol benzoate, carrying out heat preservation reaction for 100-150 minutes at 65-80 ℃, cooling and discharging to obtain the cross-linking agent.
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| CN115093819B (en) * | 2022-07-01 | 2024-03-15 | 张家港飞腾复合新材料股份有限公司 | Adhesive for connecting composite boards and application method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912041A (en) * | 2006-08-23 | 2007-02-14 | 河北北方绿野居住环境发展有限公司 | Environmental protection type adhesion agent for wood industry |
| CN102807833A (en) * | 2012-08-28 | 2012-12-05 | 东莞市山力高分子材料科研有限公司 | Water-based inorganic silicon-organic silicon-polyurethane adhesive and preparation method thereof |
| CN104861896A (en) * | 2014-12-22 | 2015-08-26 | 王玉燕 | Environmentally-friendly wood adhesive and preparation method thereof |
| CN105219307A (en) * | 2015-11-06 | 2016-01-06 | 江苏奇艳丽涂料有限公司 | Environment-friendly constant-pressure type timber assembling tackiness agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912041A (en) * | 2006-08-23 | 2007-02-14 | 河北北方绿野居住环境发展有限公司 | Environmental protection type adhesion agent for wood industry |
| CN102807833A (en) * | 2012-08-28 | 2012-12-05 | 东莞市山力高分子材料科研有限公司 | Water-based inorganic silicon-organic silicon-polyurethane adhesive and preparation method thereof |
| CN104861896A (en) * | 2014-12-22 | 2015-08-26 | 王玉燕 | Environmentally-friendly wood adhesive and preparation method thereof |
| CN105219307A (en) * | 2015-11-06 | 2016-01-06 | 江苏奇艳丽涂料有限公司 | Environment-friendly constant-pressure type timber assembling tackiness agent |
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