WO2024050653A1 - Composition and adhesive combined material thereof, and formaldehyde-free artificial board and preparation method therefor - Google Patents

Abstract

The present invention belongs to the technical field of adhesives for formaldehyde-free artificial boards, and particularly relates to a composition and an adhesive combined material thereof, and a formaldehyde-free artificial board and a preparation method therefor. The adhesive combined material comprises a composition A and a composition B, wherein the composition A comprises a component A1 and a component A2, the component A1 comprises metal ions and a tertiary amine type ethylene oxide derivative, and the component A2 is macrocyclic polyether containing a plurality of oxy-methylene structural units. In the present invention, a formaldehyde-free artificial board is prepared from the adhesive combined material, such that the production efficiency of the formaldehyde-free artificial board can be further improved while good adhesive properties and mechanical properties are maintained.

Description

Composition and adhesive composition thereof, aldehyde-free artificial board and preparation method thereof Technical field

The invention belongs to the technical field of adhesives for aldehyde-free artificial boards, and in particular relates to a composition and its adhesive combination, aldehyde-free artificial boards and a preparation method thereof.

Background technique

In recent years, formaldehyde-free artificial boards prepared with isocyanate adhesives as raw materials have shown high brand value in the artificial board market due to their high-quality board performance and environmental protection characteristics. The downstream market has generally responded well and is currently widely used. Used in wood structure construction, furniture, packaging, decoration and decoration industries.

Isocyanate adhesives represented by PMDI were the earliest adhesives used in panels. Because they do not contain formaldehyde and have extremely low volatility, they can greatly avoid harm to the human body caused by chemical substances during the production process. The board produced by MDI adhesive is cured at high temperature to form stable chemical substances. It is an environmentally friendly adhesive board.

Based on this, consumers are also in urgent need of isocyanate adhesives and aldehyde-free sheets. For upstream plate manufacturers, improving the production efficiency of such formaldehyde-free plates and improving the utilization rate of PMDI raw materials will become the core issues for PMDI to move towards large-scale mature application.

At present, most formaldehyde-free panel manufacturers use methods to increase thermal insulation and increase the temperature difference between the surface and core layers to speed up production. However, this does not fundamentally solve the problem of PMDI curing speed in the panels.

The Chinese patent with publication number CN1196374A discloses a preparation method of an adhesive for lignocellulose pressed boards. The adhesive has good detachability during hot pressing and is suitable for the production of lignocellulosic pressed boards. However, the adhesive The system is severely pre-cured, and a large amount of active ingredients in the adhesive have reacted before the board is formed, seriously affecting the improvement of board production efficiency.

The Chinese patent with publication number CN111958746A discloses an adhesive composition that uses polyurethane urea dispersion to improve the problem of poor initial viscosity of isocyanate adhesive in the preparation of ultra-thin high-density fiberboards, which leads to slab breakage. However, the bonding The addition of additives has little effect on improving production efficiency and cannot solve the problem of improving fiberboard production efficiency.

The Chinese patent with publication number CN114181659A discloses an adhesive and its application. The use of compositions including triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives improves the production efficiency of isocyanate adhesives in the preparation of particleboards. During production, The hot pressing factor has been reduced from the conventional 6s/mm to 5s/mm; with the continuous promotion of the awareness of cost reduction and efficiency improvement, this technology can no longer meet the efficiency improvement requirements of plate companies, and there is an urgent need to further improve the production technology to obtain Lower heat pressure factor.

With the substantial increase in market demand, the production methods used by formaldehyde-free panel manufacturers can no longer meet the current efficiency improvements, and have put forward higher requirements for further improvements in production speed. Therefore, how to continue to develop adhesives with faster response and excellent performance for the production of aldehyde-free artificial boards has become a direction worth studying.

Contents of the invention

The object of the present invention is to provide a composition and an adhesive composition thereof in view of the shortcomings of the existing technology. The adhesive composition can further improve the product while maintaining its excellent bonding performance and mechanical properties. The production efficiency of artificial boards without formaldehyde addition (for example, improving the production efficiency of hot pressing).

Another object of the present invention is to provide a formaldehyde-free artificial board prepared from the above-mentioned adhesive composition.

In order to achieve the above-mentioned object of the invention, the technical solutions adopted by the present invention are as follows:

In a first aspect, a composition A for adhesive is provided, which composition includes A1 component and A2 component, wherein:

The A1 component includes metal ions and tertiary amine ethylene oxide derivatives; the metal ions are alkali metal ions; the structure of the tertiary amine ethylene oxide derivative is shown in formula (I):

In formula (I), R ₁ , R ₂ and R ₃ are the same or different, and are each independently selected from C1-C18 alkylene, C1-C18 alkylene, C6-C30 arylene, C6- C30 aralkylene group or C6-C18 aryleneoxy group is preferably selected from C1-C8 alkylene group, C1-C8 alkylene group, C6-C10 arylene group, C6-C10 arylene group Alkyl or C6-C10 aryleneoxy group, more preferably selected from C1-C8 alkylene group, C1-C8 alkyleneoxy group; a, b and c (can be the same or different) are all 1-30 Positive integers (for example, 2, 4, 6, 8, 10, 12, 15, 16, 18, 20, 22, 25, 28);

The A2 component is a macrocyclic polyether containing multiple oxygen-methylene structural units, and its structure is as shown in formula (II):

In formula (II), n is a positive integer from 1 to 10 (for example, 2, 4, 6, 8, 9);

Based on the total weight of the composition, where,

The weight percentage of component A1 is 95 to 99.99% (for example, 95.5%, 96%, 97%, 98.5%, 99%), preferably 98 to 99.99%;

The weight percentage of component A2 is 0.01% to 5% (for example, 0.02%, 0.04%, 0.08%, 0.1%, 0.5%, 1%, 2.5%, 4%), preferably 0.01% to 2%.

According to the composition A provided by the present invention, in some embodiments, the C1-C18 alkylene group is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene and isopropylene. One or more types of butyl.

In some embodiments, the C1-C18 alkyleneoxy group is selected from the group consisting of methyleneoxy, ethyleneoxy, n-propyleneoxy, isopropyleneoxy, n-butyleneoxy and isobutyleneoxy. one or more of them.

In some embodiments, the aryl group mentioned in the C6-C30 arylene group can be, for example, phenyl, and the aralkyl group mentioned in the C6-C30 aralkylene group can be, for example, benzyl. group, phenethyl group; the aryloxy group mentioned in the C6-C18 aryleneoxy group may be, for example, a phenoxy group.

In some embodiments, in formula (I), R ₁ , R ₂ , and R ₃ are the same or different, and each is independently selected from C1-C18 alkylene and C1-C18 alkyleneoxy, preferably selected from C1- C8 alkylene group, C1-C8 alkylene group.

In some embodiments, the molecular weight of the tertiary amine type ethylene oxide derivative is 150-4000g/mol (for example, 180g/mol, 200g/mol, 500g/mol, 800g/mol, 1000g/mol, 2000g/mol , 3000g/mol, 3500g/mol), preferably 400 to 1500g/mol.

For example, by given the types of substituents in structural formula (I) and the values of parameters a, b, and c, the molecular weight of the tertiary amine type ethylene oxide derivative can be determined.

The synthesis process of component A1 can be achieved by conventional means in the art and will not be described again here. For example, the synthesis process of component A1 can be as follows: add the initiator into a stainless steel reactor, replace the reactor with nitrogen several times, add an alkali metal compound as a catalyst, and then add ethylene oxide at 60-100°C. The polymerization reaction takes 1-10 hours; after the polymerization reaction is completed, excess monomers are removed by vacuuming to obtain the A1 component.

In some embodiments, in the A1 component, the metal ion accounts for 0.1 ppm to 0.1% of the mass of the A1 component.

In some embodiments, in the A1 component, the metal ion accounts for 0.01% to 0.1% of the mass of the A1 component (for example, 0.02%, 0.04%, 0.05%, 0.06%, 0.08%).

In some embodiments, the metal ion is an alkali metal ion, such as sodium ion or potassium ion.

In some embodiments, the macrocyclic polyether is selected from one of dioxane, 12-crown ether-4, 15-crown ether-5, 18-crown ether-6 and 24-crown ether-8 or Various.

In a second aspect, an application of the composition A as described above in an adhesive composition is provided.

In a third aspect, an adhesive composition is provided, including component A and component B, wherein,

The A component is composition A as described above;

The B component is polymethylene polyphenyl polyisocyanate and/or its derivatives, and the weight percentage of NCO contained therein is preferably 29-32.8% (for example, 30%, 31%, 32%), Its functionality is preferably 2.9-3.3 (for example, 3.0, 3.1, 3.2), and its viscosity is preferably 150-350cp (for example, 180cp, 200cp, 250cp, 300cp) (under 25°C conditions).

According to the adhesive composition provided by the present invention, in some embodiments, based on the total weight of the adhesive composition, wherein:

The weight percentage of the A component is 10 to 30% (for example, 12%, 15%, 22%, 25%), more preferably 10 to 20%;

The weight percentage of the B component is 70 to 90% (for example, 72%, 76%, 82%, 85%), and more preferably 80 to 90%.

In a fourth aspect, a formaldehyde-free artificial board prepared by using the adhesive composition as described above is provided.

In a fifth aspect, a method for preparing aldehyde-free artificial boards using the adhesive composition as described above is provided, including the following steps:

S1: Adjust the target board-making raw material as the base material to the required moisture content;

S2: According to a certain amount of sizing, apply component A and component B in the adhesive composition to the board-making raw materials through atomization sizing respectively, and mix them to obtain mixture;

S3: Place the above mixture in the mold or on the carrier, and pave and pre-press (according to a certain density or specific assembly method) to form a "pre-slab";

S4: Under the conditions of heating and pressure, the "pre-slab" is compressed to form a plate (of a specific thickness) (in a certain period of time).

According to the method provided by the present invention, in some embodiments, in step S1, the control panel raw materials can be adjusted to the required moisture content through conventional methods in the art. The range of moisture content is a conventional selection and can be determined according to different needs. For example, the moisture content required when preparing the aldehyde-free artificial board may be 1 to 20 wt%, for example, 2 wt%, 4 wt%, 8 wt%, 10 wt%, 15 wt%.

In some embodiments, the board-making raw materials can be conventional wood, including poplar, pine, eucalyptus, etc., which are crushed to produce wood particles and shavings, or can be wheat, rice, flax, bagasse, cotton stalks, reeds, etc. Wood pellets processed from wooden units.

In the present invention, the preparation method of board-making raw materials is a well-known technology in the industry. For example, the manufacturing process of wood fiber disclosed in Chinese patent application CN201811518932.

In step S2, the sizing amount of the adhesive combination (based on the mass of the base material) is 10-30kg/m ³ (for example, 12kg/m ³ , 14kg/m ³ , 15kg/m ³ , 18kg/m ³ , 25kg/ ^m3 ).

In some embodiments, the sizing method is a routine operation in the art; the mixing process can be performed in a glue mixing machine or through high-pressure injection through a discharge pipe. I won’t go into details here.

In step S3, placing the mixture in a mold or on a carrier and paving and pre-pressing it according to a certain density or a specific assembly method are all routine operations in this field and will not be described again here. Heating methods such as microwave preheating and spray steaming can also be used in this operation process, but this is not a necessary process.

In step S4, the suitable temperature for hot pressing when preparing the aldehyde-free artificial board is usually in the range of 100°C to 250°C, such as 120°C to 220°C, or 140°C to 210°C.

The suitable pressure for hot pressing to obtain the desired product size when preparing the aldehyde-free artificial board can be 10 bar to 300 bar, for example, 50 bar, 100 bar, 150 bar, 200 bar, 250 bar.

The time used for hot pressing when preparing the aldehyde-free artificial board will depend on the board type, thickness and density of the product to be produced.

In the present invention, non-limiting examples of the aldehyde-free artificial boards include oriented strand board (OSB), veneerable OSB, structural composite wood (SCL), fiberboard, blockboard, particleboard, plywood, and laminated veneer lumber. wait.

For example, a method for preparing aldehyde-free artificial boards using the adhesive composition as described above includes the following steps:

S1: Use eucalyptus shavings as the base material, control the moisture content of the core layer of eucalyptus shavings at 2%-5%, and control the moisture content of the surface layer of eucalyptus shavings at 15-20%;

S2: Apply component A and component B in the adhesive composition obtained above according to a certain mass and proportion (based on the mass of the base material) directly through atomization sizing, and apply the glue to the base material The surface is mixed with the core wood shavings raw materials in a roller glue mixer to prepare a mixture;

S3: Pave and pre-press the wood shavings containing the adhesive combination (according to a paving density of 600-700kg/m ³ and a paving ratio of surface raw materials to core raw materials of 4:6) through the paving head To form a "pre-slab"; the pressure used for pre-pressing is 0.8-1.5MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a particle board with a thickness of 18mm; the suitable temperature of each pressure frame for hot pressing is 120℃ to 210℃, and the required pressure is 40bar to 200bar .

In the present invention, by selecting a macrocyclic polyether and a tertiary amine type ethylene oxide derivative and using them in combination, not only can the degree of pre-curing be reduced before hot pressing, but the tertiary amine type ethylene oxide derivative can also be utilized The catalytic effect of the polyether chain segment and the active tertiary amine group can build a micro-reaction zone inside the artificial board, and achieve further catalytic effects under the dual effects of interface interaction and activation. specifically:

On the one hand, since the oxygen atoms in the macrocyclic polyether (such as crown ether) rings have unshared electron pairs, the ether ring is negatively charged, and at the same time, the tertiary amine group in the A1 component is positively charged, so before hot pressing Under the low temperature state, the macrocyclic polyether and the tertiary amine group limit the catalytic effect of the tertiary amine group through electrostatic attraction, thereby effectively curbing the curing catalytic reaction before hot pressing, which can reduce the transmission of the board after sizing. , the degree of pre-curing caused during the paving and pre-pressing processes can also effectively reduce adhesion, clogging and other disadvantages to the production equipment, and ultimately ensure that more PMDI will participate in the subsequent hot-pressing process and affect the plate. Adhesion, thereby achieving better internal bonding strength to the board (which further ensures the excellent comprehensive mechanical properties of the board).

On the other hand, when entering the hot pressing process, during the continuous heating process, due to the intensification of chain segment movement, the electrostatic interaction between the macrocyclic polyether and the tertiary amine group is weakened due to thermal activation, and the active tertiary amine can be effectively The catalytic activity of the metal ions contained in the group and A1 component is sufficiently released, and the ether chain of the tertiary amine derivative provides a reaction interface between PMDI and water. The two methods of interfacial interaction and lower activation energy are used to accelerate the reaction between PMDI and water. The reaction of water and hydroxyl group synergistically achieve higher catalytic efficiency, and the plate production efficiency is greatly improved.

In the present invention, the mentioned pre-curing degree is reacted by the residual amount of isocyanate (NCO) in the glue solution PMDI.

Compared with the existing technology, the beneficial effects of the technical solution of the present invention are:

(1) Using the polyether chain segment of the tertiary amine derivative as the reaction interface, the compatibility of PMDI and water is increased, and the interfacial interaction is used to increase the reaction rate, thereby improving the hot pressing production efficiency;

By using the tertiary amine group and metal ions contained in the A1 component as catalytic active centers, the reaction activity is further improved within the interface of the polyether segment, further improving the hot pressing production efficiency;

(2) Under low temperature conditions before hot pressing, the macrocyclic polyether in the component can effectively limit the catalytic activity of the tertiary amine group, greatly reducing the early pre-curing reaction that may occur before hot pressing, thereby effectively reducing the The pre-curing degree under the conditions can reduce the loss of glue used before hot pressing, which can ensure that more PMDI will participate in bonding the board during the hot pressing process, thereby achieving better internal bonding strength and excellent mechanics of the board. performance.

Detailed ways

In order to be able to understand the technical features and content of the present invention in detail, preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the examples, it should be understood that the present invention may be implemented in various forms and should not be limited to the embodiments set forth herein.

<Source of raw materials>

Component B

CW20: a mixture of multifunctional isocyanate and diphenylmethane diisocyanate, NCO content is 31.0wt%, functionality is 3.1, viscosity at 25°C is 205cp, Wanhua Chemical Group Co., Ltd.;

CW30: a mixture of multifunctional isocyanate and diphenylmethane diisocyanate, NCO content is 30.5wt%, functionality is 3.1, viscosity at 25℃ is 225cp, Wanhua Chemical Group Co., Ltd.;

9132FC: Multifunctional isocyanate derivative, NCO content is 29.7wt%, functionality is 2.9, viscosity at 25℃ is 350cp, Wanhua Chemical Group Co., Ltd.;

PM300E: multifunctional isocyanate derivative, NCO content is 30.0wt%, functionality is 3.0, viscosity at 25℃ is 225cp, Wanhua Chemical Group Co., Ltd.;

Each tertiary amine type ethylene oxide derivative in component A1 is homemade; the sources of the main raw materials in the preparation process are as follows:

Triethanolamine, purchased from Shanghai Aladdin, CAS number: 102-71-6;

Triisopropanolamine, purchased from Shanghai Aladdin, CAS number 122-20-3;

Diisopropanolamine, purchased from Beijing Bailingwei, CAS number: 110-97-4;

Diethanol monoisopropanolamine, purchased from Sigma-Aldrich, CAS number 6712-98-7;

2-Amino-1-butanol, purchased from Shanghai McLean, CAS number: 96-20-8;

2-Amino-2-methyl-1-propanol, purchased from Sigma-Aldrich, CAS number: 124-68-5;

Ethylene oxide, purchased from Wanhua Chemical, CAS number 75-21-8;

Potassium hydroxide, purchased from Shanghai Aladdin, CAS number: 1310-58-3;

Sodium hydroxide, purchased from Shanghai Aladdin, CAS number: 1310-73-2;

Macrocyclic polyethers are all commercially available products, including:

Dioxane, purchased from Shanghai Aladdin, CAS number 123-91-1;

12-Crown ether-4, purchased from Sigma-Aldrich, CAS number is 294-93-9;

15-crown ether-5, purchased from Sigma-Aldrich, CAS number is 33100-27-5;

18-crown ether-6, purchased from Shanghai Aladdin, CAS number: 17455-13-9;

24-Crown ether-8 was purchased from Beijing Bailingwei, CAS number is 33089-37-1.

In each of the examples and comparative examples, the main instrument used is: Dieffenbacher continuous hot press production line.

Test Methods

(1) Plate performance testing (such as internal bonding strength, static bending strength, elastic modulus, 2h water absorption thickness expansion rate), tested according to the method specified in the GB17657-2013 standard; among them,

The internal bonding strength, static bending strength and elastic modulus of the plate are tested by the universal testing machine AI-7000S of Gaotie Testing Instrument Co., Ltd.;

The 2h water absorption thickness is tested through the DZKW-C Wolin double-row four-hole stainless steel water bath;

(2) Hot pressing factor, the main control of Dieffenbacher continuous hot pressing production line displays its results;

(3) Test the degree of pre-curing by using an isocyanate (NCO) titrator to measure the amount of isocyanate (NCO) in the base material (such as wood chips) after sizing, and compare it with the amount of isocyanate (NCO) before hot pressing. ) amount; the calculation formula is:

Example 1

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 99.99%, including sodium ions and tertiary amine ethylene oxide derivatives;

Component A2 is dioxane with a content of 0.01%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=18, R ¹ , R ² and R ³ are the same and each is independently an ethyleneoxy group;

The synthesis process of component A1 is: add 15.804 parts by mass of the starter triethanolamine into a stainless steel reactor, replace the reactor with nitrogen 6-8 times, and add 0.03 parts by mass of catalyst sodium hydroxide (accounting for 10% of the mass of component A1 0.03%), then add 84.166 parts by mass of ethylene oxide and perform polymerization reaction at 80-90°C for 4 hours; after the polymerization reaction is completed, excess monomers are removed by vacuuming to obtain the A1 component.

Component B: CW20.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus shavings as the base material, the moisture content of the core layer of eucalyptus shavings is controlled at 5%, and the moisture content of the surface layer of eucalyptus shavings is controlled at 20.5%;

S2: Based on the mass of the base material, apply component A (4.4kg/m ³ ) and component B (15.6kg/m ³ ) of the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shaving raw materials in a drum glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 650kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.0MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a particle board with a thickness of 18mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.

Example 2

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 99.94%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is 12-crown ether-4, content 0.06%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=14, R ₁ , R ₂ , and R ₃ are the same, and each is independently an isopropoxy group;

The synthesis process of component A1 refers to Example 1. The difference is that the starting agent used is triisopropanolamine, and its added amount is 23.658 parts by mass; the catalyst is potassium hydroxide, and its added amount is 0.01 parts by mass; The added amount of ethylene oxide is 76.332 parts by mass.

Component B: CW30.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using poplar wood shavings as the base material, the moisture content of the poplar wood shavings core material is controlled at 4.8%, and the moisture content of the poplar wood shavings surface material is controlled at 19.7%;

S2: Based on the mass of the base material, apply component A (6.6kg/m ³ ) and component B (15.4kg/m ³ ) of the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shaving raw materials in a drum glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 630kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.1MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a particle board with a thickness of 18mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-215°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 44-60bar; the temperature in the third zone is 145-160°C and the pressure is 120-140bar.

Example 3

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 96.5%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is 15-crown ether-5, with a content of 3.50%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=10, _R1 and _R2 are the same, each independently is an isopropoxy group, and _R3 is an ethyleneoxy group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is diisopropanolamine, and the added amount is 23.196 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.015 parts by mass; The mass parts of ethylene oxide are 76.789 parts by mass.

Component B: 9132FC.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus/straw shavings as the base material, the moisture content of the eucalyptus/straw shavings core material is controlled at 3.9%, and the moisture content of the eucalyptus/straw shavings surface material is controlled at 18.6%;

S2: Based on the mass of the base material, apply component A (2.66kg/m ³ ) and component B (16.34kg/m ³ ) of the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shaving raw materials in a drum glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 640 kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head. Form a "pre-slab"; the pressure used for pre-pressing is 1.2MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a 12mm thick particle board; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-220°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 45-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.

Example 4

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 95.190%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is a mixture of dioxane and 15-crown ether-5. The dioxane content is 4.70%; the 15-crown ether-5 content is 0.11%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=25, R ₁ and R ₂ are the same, each independently an ethyleneoxy group, and R ₃ is an isopropoxy group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is diethanol monoisopropanolamine, and the added amount is 12.861 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.045 parts by mass. parts; the mass parts of ethylene oxide are 87.094 parts by mass.

Component B: PM300E.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using poplar wood shavings as the base material, the moisture content of the poplar wood shavings core material is controlled at 4.3%, and the moisture content of the poplar wood shavings surface material is controlled at 18.3%;

S2: Based on the mass of the base material, apply component A (1.2kg/m ³ ) and component B (10.8kg/m ³ ) of the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shaving raw materials in a drum glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 650kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 0.9MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a 15mm thick particle board; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 48-60bar; the temperature in the third zone is 135-155°C and the pressure is 110-125bar.

Example 5

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 99.938%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is 18-crown ether-6, with a content of 0.062%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=17, R ₁ and R ₂ are the same, each independently an ethyleneoxy group, and R ₃ is an n-butoxy group;

The synthesis process of A1 is as in Example 1. The difference is that the starting agent used is 2-amino-1-butanol, and the added amount is 10.633 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.075 parts by mass. ; The mass part of ethylene oxide is 89.292 parts by mass.

Component B: CW30.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus shavings as the base material, the moisture content of the core layer of eucalyptus shavings is controlled at 3.5%, and the moisture content of the surface layer of eucalyptus shavings is controlled at 17.9%;

S2: Based on the mass of the base material, apply component A (2.55kg/m ³ ) and component B (10.95kg/m ³ ) of the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shaving raw materials in a drum glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 620kg/m ³ and the paving ratio of surface raw materials to core raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.0MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a 9mm thick particle board; each frame for hot pressing is divided into three zones: the temperature in the first zone is 205-215°C, and the pressure The temperature in the second zone is 165-185°C and the pressure is 45-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.

Example 6

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 95.0%, including sodium ions and tertiary amine ethylene oxide derivatives;

Component A2 is 24-crown ether-8, with a content of 5.0%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=13, R ₁ is an isobutoxy group, R ₂ and R ₃ are the same and each is independently an ethylene oxide group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is 2-amino-2-methyl-1-propanol, and the amount added is 13.454 parts by mass; the catalyst sodium hydroxide is added The amount is 0.01 parts by mass; the mass part of ethylene oxide is 86.536 parts by mass.

Component B: CW20.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using reed shavings as the base material, the moisture content of the core layer of reed shavings is controlled at 4%, and the moisture content of the surface layer of reed shavings is controlled at 20.2%;

S2: Based on the mass of the base material, the A component (7kg/m ³ ) and B component (18kg/m ³ ) in the adhesive composition obtained above are directly applied through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shavings raw material in a roller glue mixer to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 630kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.0MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a particle board with a thickness of 18mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-215°C, and the pressure The temperature in the second zone is 180-195bar; the temperature in the second zone is 165-180℃, and the pressure is 51-65bar; the temperature in the third zone is 140-160℃, and the pressure is 112-121bar.

Example 7

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 99.10%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is a mixture of 12-crown ether-4 and 15-crown ether-5; the content of 12-crown ether-4 is 0.42%; the content of 15-crown ether-5 is 0.48%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=28, R ₁ and R ₂ are the same, each independently an ethyleneoxy group, and R ₃ is an isopropoxy group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is isopropanolamine, and the added amount is 5.65 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.088 parts by mass; The mass parts of oxyethane are 94.262 parts by mass.

Component B: CW20.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Use eucalyptus fiber as the base material, and control the moisture content of the eucalyptus fiber raw material to 10.3%;

S2: Based on the mass of the base material, sizing component A (5.8kg/m ³ ) and component B (23.2kg/m ³ ) in the adhesive composition obtained above by atomization sizing respectively. , apply glue on the surface of the base material and stir and mix with the wood fiber raw materials in the spray tube to prepare a mixture;

S3: The wood fiber containing the adhesive combination (according to the paving density of 770kg/m ³ ) is paved through the paving head and pre-pressed to form a "pre-slab"; the pressure used for pre-pressing is 1.2 MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a fiber board with a thickness of 20mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 203-214°C, and the pressure The temperature in the second zone is 163-180°C and the pressure is 42-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.

Example 8

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 99.34%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is dioxane with a content of 0.66%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=16, R ₁ , R ₂ , and R ₃ are the same, and each is independently an ethyleneoxy group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is triethanolamine, and the added amount is 17.415 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.053 parts by mass; ethylene oxide The mass parts of alkane are 82.532 parts by mass.

Component B: CW30.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Use poplar fiber as the base material, and control the moisture content of the poplar fiber raw material to 11.9%;

S2: Based on the mass of the base material, sizing component A (3.8kg/m ³ ) and component B (16.2kg/m ³ ) in the adhesive composition obtained above through atomization sizing respectively. , and stir and mix with the wood fiber raw materials in the spray pipe to prepare a mixture;

S3: The wood fiber containing the adhesive combination (according to the paving density of 720kg/m ³ ) is paved through the paving head and pre-pressed to form a "pre-slab"; the pressure used for pre-pressing is 1.1 MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a fiber board with a thickness of 18mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 203-210°C, and the pressure The temperature in the second zone is 163-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 105-120bar.

Example 9

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 98.760%, including potassium ions and tertiary amine ethylene oxide derivatives;

Component A2 is a mixture of dioxane and 18-crown ether-6. The dioxane content is 0.78% and the 18-crown ether-6 content is 0.46%;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=11, R ₁ is an isobutoxy group, R ₂ and R ₃ are the same and each is independently an ethylene oxide group;

The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is 2-amino-2-methyl-1-propanol, and the added amount is 15.507 parts by mass; the catalyst is potassium hydroxide. The added amount is 0.025 parts by mass; the mass part of ethylene oxide is 84.468 parts by mass.

Component B: 9132FC.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Use eucalyptus fiber as the base material, and control the moisture content of the eucalyptus fiber raw material to 8.7%;

S2: Based on the mass of the base material, sizing component A (5.75kg/m ³ ) and component B (17.25kg/m ³ ) in the adhesive composition obtained above by atomization sizing respectively. , and stir and mix with the wood fiber raw materials in the spray pipe to prepare a mixture;

S3: The wood fiber containing the adhesive combination (according to the paving density of 750kg/m ³ ) is paved through the paving head and pre-pressed to form a "pre-slab"; the pressure used for pre-pressing is 1.0 MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a fiber board with a thickness of 12mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 210-220°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 55-68bar; the temperature in the third zone is 140-160°C and the pressure is 110-118bar.

Comparative example 1

(I) In the adhesive composition, component A is not added;

Component B: CW20;

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus shavings as the base material, the moisture content of the core layer of eucalyptus shavings is controlled at 5%, and the moisture content of the surface layer of eucalyptus shavings is controlled at 20.2%;

S2: Based on the mass of the base material, apply component B (20.2kg/m ³ ) in the adhesive composition obtained above directly through atomization sizing, apply the glue to the surface of the base material and mix it in a drum Stir and mix the core layer wood shaving raw materials in the glue machine to prepare a mixture;

S3: The wood shavings containing the adhesive combination (according to the paving density of 650kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.1MPa.

S4: The "pre-slab" is compressed under heat and pressure conditions to form a particle board with a thickness of 18mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.

Comparative example 2

(I) In the adhesive composition, component A is not added;

Component B: CW30;

(II) Preparation steps of aldehyde-free artificial boards:

S1: Use poplar fiber as the base material, and control the moisture content of the poplar fiber raw material to 10.7%;

S2: Based on the mass of the base material, apply component B (28kg/m ³ ) of the adhesive composition obtained above through atomization sizing, and stir and mix it with the wood fiber raw materials in the spray pipe , prepare the mixture;

S3: The wood fiber containing the adhesive combination (according to the paving density of 780kg/m ³ ) is paved through the paving head and pre-pressed to form a "pre-slab"; the pressure used for pre-pressing is 1.0 MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a fiber board with a thickness of 12mm; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C and the pressure is 180-200bar; the temperature in the second zone is 160-180°C, and the pressure is 50-65bar; the temperature in the third zone is 140-160°C, and the pressure is 100-120bar.

Comparative example 3

(I) Each component and its proportion in the adhesive composition

Component A only contains component A1 and does not contain component A2;

The A1 component content is 100%, including sodium ions and tertiary amine ethylene oxide derivatives;

In the structural formula of the tertiary amine type ethylene oxide derivative of component A1, a+b+c=18, R ₁ , R ₂ , and R ₃ are the same, and each is independently an ethyleneoxy group; the synthesis process of component A1 Refer to Example 1;

Component B: CW20;

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus shavings as the base material, the moisture content of the core layer of eucalyptus shavings is controlled at 3.9%, and the moisture content of the surface layer of eucalyptus shavings is controlled at 18.6%;

S2: Based on the mass of the base material, apply component A (2.66kg/m ³ ) and component B (16.72kg/m ³ ) in the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shavings in a drum glue mixer;

S3: The wood shavings containing the adhesive combination (according to the paving density of 640kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.2MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a 12mm thick particle board; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.

Comparative example 4

(I) Each component and its proportion in the adhesive composition

In component A, based on the total weight of component A, each component and its content is:

The A1 component content is 92%, including sodium ions and tertiary amine ethylene oxide derivatives;

Component A2 is dioxane with a content of 8%;

For the synthesis process of component A1 and the structural formula of the tertiary amine type ethylene oxide derivative in component A1, refer to Example 1.

Component B: CW20.

(II) Preparation steps of aldehyde-free artificial boards:

S1: Using eucalyptus shavings as the base material, the moisture content of the core layer of eucalyptus shavings is controlled at 3.9%, and the moisture content of the surface layer of eucalyptus shavings is controlled at 18.6%;

S2: Based on the mass of the base material, apply component A (2.66kg/m ³ ) and component B (16.72kg/m ³ ) in the adhesive composition obtained above directly through atomization sizing. Glue is applied to the surface of the base material and mixed with the core wood shavings in a drum glue mixer;

S3: The wood shavings containing the adhesive combination (according to the paving density of 640kg/m ³ and the paving ratio of surface raw materials to core layer raw materials is 4:6) are paved and pre-pressed through the paving head to form "Pre-slab"; the pressure used for pre-pressing is 1.2MPa;

S4: The "pre-slab" is compressed under heat and pressure conditions to form a 12mm thick particle board; each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C and the pressure is 180-200bar; the temperature in the second zone is 160-180°C, and the pressure is 50-65bar; the temperature in the third zone is 140-160°C, and the pressure is 100-120bar.

The production data and obtained plate properties of each embodiment and comparative example were tested. The results are shown in Table 1.

Among them, the hot pressing factor can be used to judge the hot pressing efficiency, the pre-curing degree can be used to judge the loss of glue before entering the press, the internal bonding strength can be used to judge the bonding strength of the board, static bending strength, elastic modulus and 2h water absorption. Thickness expansion rate can be used to assist in judging mechanical properties.

Table 1 prepared plate performance test data

Attached: In the national standard GB/T 4897-2015 for particleboard and GB/11718-2009 for medium density fiberboard, the physical and chemical performance requirements for each thickness are:

It can be seen from Table 1:

Compared with the adhesive without component A (such as Examples 1-6 and Comparative Example 1, Examples 7-9 and Comparative Example 2), the lowest hot-pressure factor of the adhesive composition with added component A is Significantly reduced, indicating that the hot-pressing time is effectively reduced and the hot-pressing efficiency is significantly improved (for example, compared with Comparative Example 1, the hot-pressing factor of Example 3 is reduced by 1.2s/mm, and the hot-pressing efficiency is increased by 20%). At the same time, various physical and chemical factors The performance can meet the requirements of the standard, indicating that the adhesive added with component A can effectively improve the production efficiency of the board while ensuring comprehensive performance.

Compared with the adhesive without the A2 component (such as Examples 1-6 and Comparative Example 3), the pre-curing degree of the adhesive with the A2 component is greatly reduced, indicating that the pre-curing degree of the adhesive with the A2 component can be effectively reduced. Due to the high degree of pre-curing caused by the use of the A1 component, the minimum pre-curing degree can be reduced to close to the situation without adding the A1 component, that is, the curing agent can be prevented from reacting with the isocyanate in advance before hot pressing; in addition, the use of After the A2 component is added, the internal bonding strength is greatly increased while reducing the pre-curing degree. This shows that the A2 component effectively prevents the A1 component from pre-curing with the PMDI glue before hot pressing, making more glue The liquid participates in the subsequent hot pressing reaction, thereby forming a higher bonding strength.

Compared with Examples 1-6, the adhesives of Comparative Example 3 (without using A2 component) and Comparative Example 4 cannot effectively balance the pre-curing degree and hot pressing efficiency: only adding A1 component without adding A2 component will The degree of pre-curing cannot be significantly reduced, indicating that the use of component A1 alone cannot ensure bonding strength; if the amount of component A2 added is too large, the hot-pressing factor will not be significantly reduced. Although the degree of pre-curing can be reduced, it cannot simultaneously improve the hot-pressing efficiency. .

The adhesives in various embodiments of the present invention can improve the hot pressing efficiency while also ensuring excellent bonding strength and mechanical properties, which benefit from the joint action of the A1 component and the A2 component.

Some embodiments of the present invention have been described above. The above description is illustrative, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A composition A, characterized in that the composition includes component A1 and component A2, wherein:

   The A1 component includes metal ions and tertiary amine ethylene oxide derivatives; the metal ions are alkali metal ions; the structure of the tertiary amine ethylene oxide derivative is shown in formula (I):

   

   In formula (I), R ₁ , R ₂ , and R ₃ are the same or different, and are each independently selected from C1-C18 alkylene, C1-C18 alkylene, C6-C30 arylene, C6- C30 aralkylene group or C6-C18 aryleneoxy group is preferably selected from C1-C8 alkylene group, C1-C8 alkylene group, C6-C10 arylene group, C6-C10 arylene group Alkyl or C6-C10 aryleneoxy group, more preferably selected from C1-C8 alkylene group, C1-C8 alkyleneoxy group; a, b and c are all positive integers from 1 to 30;

   The A2 component is a macrocyclic polyether containing multiple oxygen-methylene structural units, and its structure is as shown in formula (II):

   

   In formula (II), n is a positive integer from 1 to 10;

   Based on the total weight of the composition, where,

   The weight percentage of component A1 is 95-99.99%, preferably 98-99.99%;

   The weight percentage of component A2 is 0.01% to 5%, preferably 0.01% to 2%.
2. The composition A according to claim 1, characterized in that in formula (I), R ₁ , R ₂ and R ₃ are each independently selected from C1-C18 alkylene and C1-C18 alkyleneoxy. ;

   The C1-C18 alkylene group is selected from one or more types of methylene, ethylene, n-propylene, isopropylene, n-butylene and isobutylene;

   The C1-C18 alkyleneoxy group is selected from one of methyleneoxy, ethyleneoxy, n-propyleneoxy, isopropyleneoxy, n-butyleneoxy and isobutyleneoxy or Various.
3. The composition A according to claim 1, characterized in that the molecular weight of the tertiary amine type ethylene oxide derivative is 150-4000g/mol, preferably 400-1500g/mol.
4. The composition A according to claim 1, characterized in that, in the A1 component, the metal ion accounts for 0.1 ppm to 0.1% of the mass of the A1 component, preferably 0.01% to 0.1%;

   The metal ions are sodium ions or potassium ions.
5. The composition A according to claim 1, characterized in that the macrocyclic polyether is selected from dioxane, 12-crown ether-4, 15-crown ether-5, 18-crown ether-6 and 24 -One or more of crown ether-8.
6. An application of the composition A according to any one of claims 1 to 5 in an adhesive composition.
7. An adhesive composition is characterized in that it includes component A and component B, wherein,

   The A component is composition A as described in any one of claims 1-5;

   The B component is polymethylene polyphenyl polyisocyanate and/or its derivatives, the weight percentage of NCO contained in it is preferably 29-32.8%, its functionality is preferably 2.9-3.3, and its viscosity is preferably is 150-350cp.
8. The adhesive composition according to claim 7, characterized in that, based on the total weight of the adhesive composition, wherein:

   The weight percentage of the A component is 10 to 30%, more preferably 10 to 20%;

   The weight percentage of the B component is 70-90%, more preferably 80-90%.
9. A formaldehyde-free artificial board prepared using the adhesive composition according to claim 7 or 8.
10. A method for preparing aldehyde-free artificial boards using the adhesive composition as claimed in claim 7 or 8, characterized in that it includes the following steps:

    S1: Adjust the target board-making raw material as the base material to the required moisture content;

    S2: According to a certain amount of sizing, apply component A and component B in the adhesive composition to the board-making raw materials through atomization sizing respectively, and mix them to obtain mixture;

    S3: Place the above-mentioned mixture in the mold or on the carrier, and perform paving and pre-pressing to form a "pre-slab";

    S4: Compress the "pre-slab" under heating and pressure conditions to form a plate;

    Preferably, in step S2, the sizing amount of the adhesive composition is 10-30kg/m ³ based on the mass of the substrate.