CN113461888B - Hyperbranched urea-polyamine-formaldehyde copolycondensation resin and preparation method thereof - Google Patents
Hyperbranched urea-polyamine-formaldehyde copolycondensation resin and preparation method thereof Download PDFInfo
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- CN113461888B CN113461888B CN202110895937.XA CN202110895937A CN113461888B CN 113461888 B CN113461888 B CN 113461888B CN 202110895937 A CN202110895937 A CN 202110895937A CN 113461888 B CN113461888 B CN 113461888B
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
Abstract
The invention discloses a hyperbranched urea-polyamine-formaldehyde copolycondensation resin and a preparation method thereof, wherein the resin is prepared by copolycondensation of urea, polyamino compounds and formaldehyde, and the preparation of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps: the synthetic preparation comprises deamination, addition and polycondensation processes. The preparation method comprises the steps of firstly preparing a hyperbranched polymer with urea end groups, and then preparing an initial polymer of the hyperbranched resin through an addition polycondensation reaction. Compared with the traditional urea-formaldehyde resin, the adhesive has more excellent gluing performance and lower formaldehyde release amount, and is suitable for the production and manufacture of various artificial boards such as plywood, shaving board, fiberboard and the like.
Description
Technical Field
The invention belongs to the technical field of artificial board manufacturing, and particularly relates to hyperbranched urea-polyamine-formaldehyde copolycondensation resin and a preparation method thereof.
Background
Urea-formaldehyde resin is the most important adhesive in the artificial board industry and is widely used for the production and manufacture of artificial boards such as plywood, chipboard, fiberboard and the like. The main defect of urea-formaldehyde resin is that the glued product has poor water resistance and has hidden trouble of formaldehyde release. In recent years, in order to reduce formaldehyde emission of urea-formaldehyde resin, a low molar ratio synthesis technology is generally adopted, namely, the formaldehyde dosage in a synthesis formula is reduced, so that the overall performance of the urea-formaldehyde resin is deteriorated and the production efficiency is reduced.
The main causes of urea formaldehyde resin defects are in two aspects: firstly, the addition reaction of urea-formaldehyde resin is a reversible reaction, and a part of free formaldehyde remains in the final resin, and the part of formaldehyde still exists in the artificial board after the resin is solidified; secondly, the chemical structure stability of the urea-formaldehyde resin is poor, and the cured urea-formaldehyde resin is gradually depolymerized in a humid environment, so that the dimensional stability of the artificial board is reduced, and formaldehyde is released in the use process of the artificial board product.
And a proper amount of formaldehyde scavenger is added into the urea-formaldehyde resin, so that the formaldehyde release amount of the artificial board can be reduced to a certain extent. For example, the patent "a preparation method of formaldehyde scavenger and its application in urea formaldehyde resin (publication No. CN 102627726B)" discloses a copolymer formaldehyde scavenger synthesized from acrylamide, vinyl acetate and styrene as main raw materials. The patent No. CN102580282A discloses a formaldehyde scavenger formula which takes urea, dicyandiamide, caprolactam, hydroxyl-containing water-soluble polymer, glass powder and the like as raw materials. The formula design of the formaldehyde scavenger is based on the higher reactivity to formaldehyde. Analysis from the chemical reaction equilibrium point of view, the scavenger reacts with free formaldehyde, which also causes dissociation of hydroxymethyl groups on the resin molecules, and even causes depolymerization of the polymer and a decrease in branching degree, resulting in a decrease in resin properties.
The most common method for improving the hydrolytic stability of urea-formaldehyde resins is to use modified urea-formaldehyde resins such as melamine, including blending and copolycondensation. For example, the patent "melamine-urea-formaldehyde copolycondensation resin wood adhesive, ZL 200810058522.1", discloses a method for synthesizing melamine-urea-formaldehyde copolycondensation resin, which increases the content of copolycondensation components, and since the melamine functionality is 3, the crosslinking degree of the resin after curing is still limited, and the improvement of the overall performance of urea-formaldehyde resin is limited.
At present, a branched urea-polyamine-formaldehyde copolycondensation resin with low formaldehyde release amount and high bonding strength and a preparation method thereof are lacking.
Disclosure of Invention
The invention aims to provide branched urea-polyamine-formaldehyde copolycondensation resin with low formaldehyde release amount and high bonding strength and a preparation method thereof.
Meanwhile, in order to solve the problems in the prior art, the invention provides the following technical scheme: the invention relates to a preparation method of hyperbranched urea-polyamine-formaldehyde copolycondensation resin, which comprises the following steps:
(1) Accurately weighing hyperbranched urea-polyamine-formaldehyde copolycondensation resin, copolycondensing urea, polyamino compound and formaldehyde, adding the polyamino compound into a reaction kettle at one time, adding urea under stirring, wherein the molar ratio of the polyamino compound to the urea is 1:2 to 20; gradually heating the reactant to 100-130 ℃, preserving heat for 7-13 hours, cooling to obtain a hyperbranched urea-like compound UL, and preparing the hyperbranched urea-like compound UL into a 60% aqueous solution for later use;
(2) Adding formaldehyde F into the reaction kettle at one time, and adjusting the pH value to 9.0-9.5; adding urea U1 and hyperbranched urea-like compound UL1 water solution UL1 for the first time under stirring, wherein the dosage of the UL1 water solution is 20-30% of that of the U1, and gradually heating to 80-90 ℃ after the reaction time is 10-30 minutes;
(3) After the heat preservation reaction is carried out for 20 to 60 minutes at the temperature of 80 to 90 ℃, the pH value is adjusted to be between 4.1 and 6.0, and the heat preservation reaction is carried out for 90 to 150 minutes;
(4) Adjusting the pH value to 8.5-9.5, controlling the temperature of the system to 55-90 ℃, adding the second urea U2 and the UL aqueous solution UL2, wherein the dosage of the UL2 aqueous solution is 20-30% of that of the second urea U2, and performing heat preservation reaction for 10-30 minutes;
(5) Cooling the mixture under stirring, stopping the reaction after the temperature reaches below 30 ℃, and discharging and storing the mixture to obtain the hyperbranched urea-polyamine-formaldehyde copolycondensation resin.
Further, in the step (1), the polyamino compound is an organic compound of three or more fatty amino groups
Further, in the step (1), the molar ratio of the polyamino compound to urea is 1:2-20.
Further, in the step (1), the polyamino compound is any one of tri (2-aminoethyl) amine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine or polyamide-amine.
Further, in the step (2), the molar ratio of urea U1 to formaldehyde F is 1:2.0.
Further, in step (4), the molar ratio of urea (U1+U2) to formaldehyde after adding U2 is 1:1.2.
Furthermore, the hyperbranched urea-polyamine-formaldehyde copolycondensation resin is prepared by copolycondensation of urea, polyamino compounds and formaldehyde.
The beneficial effects are that: the copolycondensation resin can replace the traditional urea-formaldehyde resin, can form a compact reticular cross-linked structure after solidification, has more excellent gluing performance and basically no formaldehyde release, and is suitable for the production and manufacture of various artificial boards such as plywood, shaving board, fiberboard and the like. The resin is water-soluble resin, has a highly branched molecular structure, has similar reactivity with the conventional urea-formaldehyde resin, and is suitable for the prior production technology system.
Compared with the prior art, the invention has the following advantages:
(1) The method is simple to operate, and the existing synthesis method and synthesis device of urea formaldehyde resin are not changed. Fatty amino (-CH) in the molecular structure of resin 2 ～NH 2 ) Can seal hydroxyl and urea end groups (-NH-CO-NH) on the surface of wood 2 ) The free formaldehyde can be captured and can also participate in the curing reaction, so that the resin after curing has lower formaldehyde release amount and more excellent bonding strength.
(2) The invention provides a technical method for modifying a urea resin hyperbranched structure, which improves the overall performance of resin from three aspects by introducing polyfunctional monomers to participate in copolycondensation, and firstly ensures the hyperbranched degree of initial resin and compact crosslinking of the cured resin; secondly, introducing functional groups capable of chemically reacting with the surface of the wood into a resin molecular structure, and improving the bonding strength and the water resistance of a bonded product by forming new chemical bonds; thirdly, functional groups capable of reacting with formaldehyde are introduced into the molecular structure of the resin, so that formaldehyde is removed, and the full-cycle near-zero formaldehyde release of the glued product is ensured.
(3) The molecular chain contains polyamino compound molecular chain segment (-NH-CH) 2 ～CH 2 -N-), urea chain segment (NH-CO-NH-), and formaldehyde chain segment (CH) 2 To) and at the same time, the molecular chain end of the resin comprises fatty amino (-CH) 2 ～NH 2 ) Urea end group (-NH-CO-NH) 2 ) And hydroxymethyl functional groups (-CH) 2 OH)。
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the present invention will be further described with reference to the following examples, which include, but are not limited to, the following examples. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Example 1
The preparation method of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps:
(1) Accurately weighing all the components, adding triethylenetetramine into a reaction kettle at one time, adding urea under stirring, controlling the molar ratio of the triethylenetetramine to the urea to be 1:4.5, gradually heating to 130 ℃, keeping the temperature for 13 hours, cooling to obtain a hyperbranched urea-like compound UL, and preparing the highly branched urea-like compound UL into a 60% aqueous solution for later use;
(2) Adding formaldehyde into the reaction kettle at one time, and adjusting the pH value to 9.0; adding urea (U1) and an UL aqueous solution (UL 1) for the first time under stirring, controlling the molar ratio (U1: F) of the urea (U1) to formaldehyde (F) to be 1:2.1, wherein the dosage of the U1 aqueous solution is 25% of that of the U1, and gradually heating to 85 ℃ after the reaction time is 10 minutes;
(3) After the reaction is carried out for 40 minutes at 80 ℃, the pH value is adjusted to be between 4.1, and the reaction is carried out for 90 minutes at the temperature;
(4) Adjusting the pH value to 8.9, controlling the temperature of the system to 80 ℃, adding urea (U2) and an UL aqueous solution (UL 2) for the second time, controlling the molar ratio (F (U1 + U2)) of the urea to formaldehyde to be 1:1.2, controlling the dosage of the U2 aqueous solution to be 25% of U2, and performing heat preservation reaction for 10 minutes;
(5) Cooling the mixture under stirring, stopping the reaction after the temperature reaches below 30 ℃, and discharging and storing the mixture to obtain the hyperbranched urea-polyamine-formaldehyde copolycondensation resin.
Example 2
Example 2 differs from example 1 in that: the preparation method of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps:
in the step (1), adding tetraethylenepentamine compound into a reaction kettle at one time, adding urea under stirring, controlling the molar ratio of the tetraethylenepentamine compound to the urea to be 1:6.0, gradually heating to 120 ℃, keeping the temperature for 7 hours, and cooling to obtain a hyperbranched urea-like compound UL;
in the step (2), formaldehyde is added into the reaction kettle at one time, and the pH value is adjusted to 9.5; adding urea (U1) and an UL aqueous solution (UL 1) for the first time under stirring, controlling the molar ratio (U1: F) of the urea (U1) to formaldehyde (F) to be 1:2.3, wherein the dosage of the U1 aqueous solution is 30% of that of the U1, and gradually heating to 90 ℃ after the reaction time is 30 minutes;
in the step (3), after the reaction is carried out for 20 minutes at 90 ℃, the pH value is adjusted to be between 6.0, and the reaction is carried out for 150 minutes at the temperature;
in the step (4), the pH value is regulated to 9.5, the temperature of the system is controlled to be 90 ℃, the urea (U2) and the UL aqueous solution (UL 2) for the second time are added, the molar ratio (F (U1 + U2)) of the urea to the formaldehyde is controlled to be 1:1.0, the dosage of the U2 aqueous solution is 30 percent of U2, and the thermal insulation reaction is carried out for 30 minutes;
in the step (5), cooling is carried out under the stirring state, and after the temperature reaches below 30 ℃, the reaction is stopped, and the material is discharged and stored, so that the hyperbranched urea-polyamine-formaldehyde copolycondensation resin is prepared.
Example 3
Example 3 differs from example 1 in that: the preparation method of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps:
in the step (1), a pentaethylenehexamine compound is added into a reaction kettle at one time, urea is added under stirring, the molar ratio of the polyhexamethylene amine compound to the urea is controlled to be 1:7.5, the temperature is gradually increased to 100 ℃, the reaction time is kept for 12 hours, and then the mixture is cooled to obtain a hyperbranched urea-like compound UL;
in the step (2), formaldehyde is added into the reaction kettle once, and the pH value is adjusted to 9.3; adding urea (U1) and an UL aqueous solution (UL 1) for the first time under stirring, controlling the molar ratio (U1: F) of the urea (U1) to formaldehyde (F) to be 1:2.5, wherein the dosage of the U1 aqueous solution is 20% of the dosage of the U1, and gradually heating to 80 ℃ after the reaction time is 20 minutes;
in the step (3), after the reaction is carried out for 60 minutes at 86 ℃, the pH value is adjusted to be between 5.0, and the reaction is carried out for 130 minutes at the temperature;
in the step (4), the pH value is regulated to 8.5, the temperature of the system is controlled to 55 ℃, the second urea (U2) and the UL aqueous solution (UL 2) are added, the molar ratio (F (U1 + U2)) of urea to formaldehyde is controlled to be 1:0.9, the dosage of the U2 aqueous solution is 20% of U2, and the thermal insulation reaction is carried out for 20 minutes;
in the step (5), cooling is carried out under the stirring state, and after the temperature reaches below 30 ℃, the reaction is stopped, and the material is discharged and stored, so that the hyperbranched urea-polyamine-formaldehyde copolycondensation resin is prepared.
Example 4
Example 4 differs from example 1 in that: the preparation method of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps: in the step (1), accurately weighing hyperbranched urea-polyamine-formaldehyde copolycondensation resin, copolycondensation of urea, polyamino compound and formaldehyde, adding the polyamino compound into a reaction kettle at one time, adding urea under stirring, wherein the molar ratio of the polyamino compound to the urea is 1:20, a step of; gradually heating the reactant to 110 ℃, preserving heat for 10 hours, and then cooling to obtain a hyperbranched urea-like compound UL, and preparing the hyperbranched urea-like compound UL into a 60% aqueous solution for later use;
in the step (3), after the incubation reaction is carried out at 86 ℃ for 60 minutes, the pH value is adjusted to be between 6.0, and the incubation reaction is carried out for 150 minutes.
Example 5
Example 5 differs from example 1 in that: the preparation method of the hyperbranched urea-polyamine-formaldehyde copolycondensation resin comprises the following steps: in the step (1), accurately weighing hyperbranched urea-polyamine-formaldehyde copolycondensation resin, copolycondensation of urea, polyamino compound and formaldehyde, adding the polyamino compound into a reaction kettle at one time, adding urea under stirring, wherein the molar ratio of the polyamino compound to the urea is 1:2; gradually heating the reactant to 100-130 ℃, keeping the temperature for 13 hours, cooling to obtain a hyperbranched urea-like compound UL, and preparing the hyperbranched urea-like compound UL into a 60% aqueous solution for later use;
in the step (3), after the reaction is carried out for 20 minutes at 90 ℃, the pH value is adjusted to be between 6.0, and the reaction is carried out for 150 minutes at the temperature.
Test example 1
The adhesive prepared in example 1 and the conventional UF adhesive (F: u=1.2) were taken separately, a three-layer plywood was produced from a poplar veneer having a thickness of 2mm, and appliedThe glue amount is 200g/m 2 (amount of double-sided glue applied to the core plate) the physical and mechanical properties of the plate are tested according to national standard GB/T17657-2013 method for testing the physical and chemical properties of artificial boards and veneers artificial boards, and the water resistance of the plate is mainly tested. The specific results are as follows:
when the hot pressing temperature is 140 ℃ and the hot pressing time is 5 minutes, after the test piece is soaked in cold water for 24 hours, the wet bonding strength of the plywood manufactured by the adhesive of the example 1 is 1.78Mpa, and the wet bonding strength of the plywood manufactured by the conventional UF adhesive is 1.40Mpa.
Respectively taking the two adhesives, manufacturing a three-layer plywood by using a poplar veneer with the thickness of 2mm, checking the formaldehyde release amount of the board according to a dryer method specified in national standard GB/T17657-2013, method for testing the physicochemical properties of artificial boards and veneer artificial boards, and displaying the checking result: the formaldehyde emission of the plywood prepared with the adhesive of example 1 was 0.38mg/L and the formaldehyde emission of the plywood prepared with the conventional UF adhesive was 1.79mg/L.
It should be noted that the use of a catalyst having both aliphatic amine terminal amino groups (-NH) 2 ) And terminal amide (-CONH) 2 ) A similar effect is also possible with the substitution of the highly (hyper) branched polymer of the urea-like polymer UL of the invention. The urea-like polymer can react with formaldehyde to obtain urea-polyamine-formaldehyde copolycondensation resin, and can be used as a modifier of traditional amino resins such as urea-formaldehyde resin, melamine-formaldehyde resin and the like.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing embodiments and description merely illustrates the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, the scope of which is defined in the appended claims, specification and their equivalents.
Claims (4)
1. A preparation method of hyperbranched urea-polyamine-formaldehyde copolycondensation resin is characterized by comprising the following steps:
(1) Accurately weighing urea, polyamino compound and formaldehyde for copolycondensation, adding the polyamino compound into a reaction kettle at one time, adding the urea under stirring, wherein the molar ratio of the polyamino compound to the urea is 1: 2-20 parts of a base; gradually heating the reactant to 100-130 ℃, preserving heat for 7-13 hours, and cooling to obtain a hyperbranched urea-like compound UL, and preparing the hyperbranched urea-like compound UL into a 60% aqueous solution for later use; the polyamino compound is any one of tri (2-aminoethyl) amine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylene polyamine or polyamide-amine;
(2) Adding formaldehyde F into the reaction kettle at one time, and adjusting the pH value to 9.0-9.5; adding urea U1 and a hyperbranched urea-like compound UL1 water solution UL1 for the first time under stirring, wherein the dosage of the UL1 water solution is 20-30% of that of the U1, and gradually heating to 80-90 ℃ after the reaction time is 10-30 minutes;
(3) After the heat preservation reaction is carried out for 20-60 minutes at the temperature of 80-90 ℃, the pH value is adjusted to be 4.1-6.0, and the heat preservation reaction is carried out for 90-150 minutes;
(4) Adjusting the pH value to 8.5-9.5, controlling the system temperature to 55-90 ℃, adding the second urea U2 and the UL aqueous solution UL2, wherein the dosage of the UL2 aqueous solution is 20-30% of that of the second urea U2, and performing heat preservation reaction for 10-30 minutes;
(5) Cooling under stirring, stopping the reaction after the temperature reaches below 30 ℃, discharging and storing to obtain the hyperbranched urea-polyamine-formaldehyde copolycondensation resin.
2. The process for the preparation of hyperbranched urea-polyamine-formaldehyde copolycondensation resins according to claim 1, characterized in that: in the step (1), the polyamino compound is an organic compound of three or more fatty amino groups.
3. The process for the preparation of hyperbranched urea-polyamine-formaldehyde copolycondensation resins according to claim 1, characterized in that: in step (4), the molar ratio of urea (U1+U2) to formaldehyde described after the addition of U2 is 1:1.2.
4. A hyperbranched urea-polyamine-formaldehyde copolycondensation resin obtainable by the process according to any one of claims 1 to 3, characterized in that: the hyperbranched urea-polyamine-formaldehyde copolycondensation resin is prepared by copolycondensation of urea, polyamino compounds and formaldehyde.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674971A (en) * | 1995-06-06 | 1997-10-07 | Georgia-Pacific Resins, Inc. | Urea-formaldehyde resin composition and method of preparation thereof |
| CN101302412A (en) * | 2008-06-13 | 2008-11-12 | 西南林学院 | Melamine-urea-methyl aldehyde copolycondensation resin lumber adhesive and preparation thereof |
| CN102675574A (en) * | 2012-04-12 | 2012-09-19 | 西南林业大学 | Copolycondensation resin type formaldehyde catching agent and preparation method thereof |
| CN103333651A (en) * | 2013-07-02 | 2013-10-02 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
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- 2021-08-05 CN CN202110895937.XA patent/CN113461888B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674971A (en) * | 1995-06-06 | 1997-10-07 | Georgia-Pacific Resins, Inc. | Urea-formaldehyde resin composition and method of preparation thereof |
| CN101302412A (en) * | 2008-06-13 | 2008-11-12 | 西南林学院 | Melamine-urea-methyl aldehyde copolycondensation resin lumber adhesive and preparation thereof |
| CN102675574A (en) * | 2012-04-12 | 2012-09-19 | 西南林业大学 | Copolycondensation resin type formaldehyde catching agent and preparation method thereof |
| CN103333651A (en) * | 2013-07-02 | 2013-10-02 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
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