阅读说明：本技术 人造板用双组分复合胶黏剂及其应用 (Wood-based plate bi-component composite adhesive and its application ) 是由 毛安 李琪 徐伟涛 万辉 于 2019-09-12 设计创作，主要内容包括：本发明公开了一种人造板的制备方法,包括如下步骤：(1)取热塑性酚醛树脂升温至80℃或80℃以上,将加热后的热塑性酚醛树脂涂覆到木材单板上,位于人造板表面的木材单板进行单面涂覆,位于人造板内部的木材单板进行双面涂覆,待其冷却后,热塑性酚醛树脂在单板表面形成一层薄膜；(2)制备人造板时,将异氰酸酯双面涂覆在另外的木材单板上,进行组坯时,使涂覆异氰酸酯和涂覆热塑性酚醛树脂的面依次接触；组坯完成后,压制成型,得到人造板。本发明能够有效解决异氰酸酯与热固性酚醛树脂混合使用时,异氰酸酯基团与热固性酚醛树脂中的水和羟基等活性基团迅速发生反应导致胶黏剂开放期短的问题。(The invention discloses a kind of preparation methods of wood-based plate, include the following steps: that (1) takes thermoplastic phenolic resin to be warming up to 80 DEG C or 80 DEG C or more, thermoplastic phenolic resin after heating is coated on wood single-plate, wood single-plate positioned at artificial plate surface carries out single side coating, wood single-plate inside wood-based plate carries out dual coating, after its cooling, thermoplastic phenolic resin forms thin film on veneer surface；(2) when preparing wood-based plate, by isocyanates dual coating on other wood single-plate, when carrying out assembly, contact the face for coating isocyanates and coating thermoplastic phenolic resin successively；After the completion of assembly, compression moulding obtains wood-based plate.The present invention can effectively solve the problem that isocyanates and when thermosetting phenolic resin is used in mixed way, and the water and hydroxyl isoreactivity group in isocyanate groups and thermosetting phenolic resin react rapidly the problem for causing adhesive open season short.)

1. a kind of preparation method of wood-based plate, which comprises the steps of: (1) take thermoplastic phenolic resin to be warming up to 80 DEG C or 80 DEG C or more, the thermoplastic phenolic resin after heating is coated on wood single-plate, positioned at the timber of artificial plate surface Veneer carries out single side coating, and the wood single-plate inside wood-based plate carries out dual coating, after its cooling, thermoplastic phenolic resin Rouge forms thin film on veneer surface；

(2) when preparing wood-based plate, by isocyanates dual coating on other wood single-plate, when carrying out assembly, make to coat different The face of cyanate and coating thermoplastic phenolic resin successively contacts；After the completion of assembly, compression moulding obtains wood-based plate.

2. preparation method according to claim 1, it is characterised in that: the glue-spread of the thermoplastic phenolic resin is single side 80-150g/m², the glue-spread of isocyanates is single side 100-180g/m²。

3. preparation method according to claim 1, it is characterised in that: the pressure of the compression moulding is 0.5-5.0MPa, It is warming up to glue-line temperature and is greater than or equal to 80 DEG C, hot pressing time 3-6min.

4. preparation method according to claim 1, it is characterised in that: the isocyanates is toluene di-isocyanate(TDI), two Methylenebis phenyl isocyanate, poly- methyl diphenylene diisocyanate, isophorone diisocyanate or polymethylene polyphenyl The combination of one or more of isocyanates.

5. preparation method according to claim 1, it is characterised in that: the thermoplastic phenolic resin is prepared by following steps It forms:

(1) catalyst is added in phenols solution and is stirred and heated to 80-90 DEG C, with acid solution tune pH value to 4.0-5.5；

(2) aldehydes solution is added in the solution made from step (1) and keeps the temperature；

(3) vacuum distillation water removal is carried out again after solution made from step (2) being carried out air-distillation water removal, and cooling is made solid Thermoplastic phenolic resin.

6. preparation method according to claim 5, it is characterised in that: in the aldehydes solution and phenols solution of addition, wherein Aldehyde radical and phenolic hydroxyl group substance amount ratio be 0.85-0.99；

The aldehydes solution be monoaldehyde, the monoaldehyde be one of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, furfural or Several combinations；

The phenols solution is phenol or/and phenol derivatives or/and phenol derivatives, and the phenol derivatives is isophthalic two The combination of one or more of phenol, cresols, xylenol, the phenol derivatives are the natural materials containing phenols, biomass hot tearing Solve the combination of one or more of object, biomass liquefying object.

7. preparation method according to claim 5, it is characterised in that: in step (1), the catalyst is divalent metal oxygen Compound or/and divalent metal salt or/and Divalent metal hydroxide, the divalent metal be beryllium, magnesium, calcium, strontium, barium, chromium, manganese, One or more of iron, cobalt, nickel, copper, zinc, cadmium, mercury, lead, platinum, tin, palladium；

The acid solution is the combination of one or more of sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, boric acid, carbonic acid.

8. preparation method according to claim 5, it is characterised in that: in step (2), aldehydes solution is added in two portions, the The primary amount that aldehydes solution is added accounts for the 60-90% of aldehydes solution total amount, and remaining aldehydes solution is added in second, every time It is added after aldehydes solution and keeps the temperature 30-60min.

9. preparation method according to claim 5, it is characterised in that: in step (3), the temperature of the air-distillation water removal It is 100-110 DEG C；

The temperature of the vacuum distillation water removal is 50-60 DEG C, vacuum degree 10-25mmHg；

The time of air-distillation water removal and vacuum distillation water removal is 1-2h.

10. application of the bi-component composite adhesive being made of thermoplastic phenolic resin and isocyanates in production wood-based plate； Wherein the wood-based plate include glued board, laminated veneer lumber, multi-layer solid wood composite floor, core-board, finger joint lumber, integrated timber, Laminated wood.

Technical field

The present invention relates to based Wood Adhesives technical fields, and in particular to wood-based plate bi-component composite adhesive and its answers With.

Background technique

China's wood-based plate industry development is rapid, and 2018 annual outputs are more than 2.99 billion cubic meters, mainly includes glued board, fiber Plate and particieboard three categories are widely used in the production of the woodworks such as household, floor, door and window, and decorations product packaging, house are built It makes and the fields such as container production.

Glued board is the main wood-based plate kind in China, and yield ranks first.According to national standard GB9846-2015 " normal plywood " Classification, glued board can be divided into weatherability glued board, water-proof plywood and not moisture resistance glued board three grades.Wherein weatherability glue Plywood has the characteristics that durable, resistance to boiling water, high intensity, can be used for outdoor structure, compartment ship, architectural engineering, top-grade furniture and Waterproof floor etc..In addition to this, national standard GB17656-2018 " Plywood for concrete form " also uses concrete blinding More stringent requirements are proposed for glued board, not only wants intensity height, resistance to boiling water, it is also necessary to and it is corrosion-resistant, reach certain reuse time Number requires.Weatherability glued board and Plywood for concrete form generally use thermosetting phenolic resin as adhesive, phenolic aldehyde It is high, water-fast, ageing-resistant, corrosion-resistant, wear-resisting that resin has many advantages, such as bonding strength, but when it is as Artificial Plate Adhesive, solidification Temperature is high, curing time is long, glue-line brittleness is big, and these problems affect its extensive use to a certain degree.

For these problems of phenolic resin, researcher has carried out the modification of various modes to it, for example, by using tannin, The substitute part phenol rich in phenols such as lignin, biological pyrolysis oil, biomass liquefying object prepare phenol-formaldehyde resin modified.But this A little modified resins still have the problems such as viscosity is higher, storage stability is poor, solidification temperature is high.Also there is document report by thermosetting property Phenolic resin and the resin of other types are blended, such as total with epoxy resin, polyurethane, isocyanates, Lauxite etc. It is blended standby composite adhesive, these are blended adhesive there is also component compatibility issue and use technological problems, and thermosetting property When the resin alloys such as phenolic resin and isocyanates, polyurethane, due to containing the water of 40%-50% in thermosetting phenolic resin Point, isocyanate groups contact water can react immediately when blending, cause the adhesive open hour too short, prepare in wood-based plate The normal gluing assembly of Shi Wufa.If be blended using thermoplastic phenolic resin and isocyanates, the hydroxyl in thermoplastic phenolic resin Base can also react with isocyanate groups rapidly, lead to adhesive premature cure, can not carry out practical application.Although using Blocked isocyanate or water-based isocyanate can solve the problems, such as that a certain degree the open hour are short, but the composite adhesive prepared Reactivity is low, higher cost, and needs hot pressing at relatively high temperatures that could solidify, cause energy consumption height and hot pressing efficiency compared with Low, application is not yet received in current this kind of composite adhesive.

Summary of the invention

For the above-mentioned prior art, the object of the present invention is to provide a kind of wood-based plate bi-component composite adhesive and its make Use method.Thermoplastic phenolic resin is first heated up and is coated on wood single-plate, forms one layer of solid film after its cooling, it can be It is not also chemically reacted when saving in 50 DEG C of environment below, and being contacted during assembly with isocyanates for a long time, only Have hot pressing temperature increase when, thermoplastic phenolic resin thawing mixed with isocyanates after can fast reaction curing molding, can have Effect solves isocyanates when mixing with existing phenolic resin, isocyanate groups in phenolic resin water and hydroxyl occur rapidly React the problem for causing adhesive open season short.Wood-based plate of the present invention prepare when, as long as glue-line temperature reach 80 DEG C can with it is different Cyanate reacts rapidly solidification, and the hot pressing temperature needed is low, and hot pressing is high-efficient and energy consumption is effectively reduced.

To achieve the above object, the present invention adopts the following technical scheme:

The first aspect of the present invention provides a kind of preparation method of wood-based plate, includes the following steps:

(1) it takes thermoplastic phenolic resin to be warming up to 80 DEG C or 80 DEG C or more, the thermoplastic phenolic resin after heating is coated Onto wood single-plate, carry out single side coating positioned at the wood single-plate of artificial plate surface, wood single-plate inside wood-based plate into Row dual coating, after its cooling, thermoplastic phenolic resin forms thin film on veneer surface；

(2) when preparing wood-based plate, by isocyanates dual coating on other wood single-plate, when carrying out assembly, make to apply The face for covering isocyanates and coating thermoplastic phenolic resin successively contacts；After the completion of assembly, compression moulding obtains wood-based plate.

After thermoplastic phenolic resin is warming up to 80 DEG C, thermoplastic phenolic resin starts to melt and have preferable mobility, to After cooling, thermoplastic phenolic resin forms one layer of solid film on veneer surface.

Preferably, the glue-spread of the thermoplastic phenolic resin is single side 80-150g/m², the glue-spread of isocyanates is Single side 100-180g/m²。

Preferably, the pressure of the compression moulding is 0.5-5.0MPa, is warming up to glue-line temperature and is greater than or equal to 80 DEG C, heat The conjunction time is 3-6min.

Preferably, the wood single-plate is the various thickness being processed into a manner of rotary-cut, slicing, sawing etc. and moisture content Softwood or broadleaf veneer.

Preferably, the gluing mode is one of showering, spraying, roller coating.

Preferably, the assemble pattern is vertical adjacent veneer texture or adjacent veneer grain parallel or adjacent veneer with it One or more of its align at random angles.

Preferably, compression moulding heating mode is by heating or microwave treatment or high-frequency therapeutic treatment.

Preferably, the isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, poly- diphenyl methane The combination of one or more of diisocyanate, isophorone diisocyanate or polymethylene multi-phenenyl isocyanate.

Preferably, the thermoplastic phenolic resin is prepared by following steps:

(1) catalyst is added in phenols solution and is stirred and heated to 80-90 DEG C, with acid solution tune pH value to 4.0-5.5；

(2) aldehydes solution is added in the solution made from step (1) and keeps the temperature；

(3) vacuum distillation water removal is carried out again after solution made from step (2) being carried out air-distillation water removal, is cooled down and is made solid The thermoplastic phenolic resin of state.

It is to make thermoplastic phenolic resin that solid be presented at normal temperature that water removal is removed water and be evaporated under reduced pressure by air-distillation Form, air-distillation remove most of moisture, and vacuum distillation removes remaining moisture, thermoplastic phenolic resin solid in this way with Isocyanates would not react and premature cure when contacting.

It is furthermore preferred that in the aldehydes solution and phenols solution that are added, the ratio of the amount of aldehyde radical and phenolic hydroxyl group substance therein For 0.85-0.99.

It is furthermore preferred that the aldehydes solution is monoaldehyde, the monoaldehyde in the preparation method of thermoplastic phenolic resin For the combination of one or more of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, furfural；

The phenols solution is phenol or/and phenol derivatives or/and phenol derivatives, and the phenol derivatives is isophthalic The combination of one or more of diphenol, cresols, xylenol, the phenol derivatives are natural materials, biomass thermal containing phenols The combination of one or more of lysate, biomass liquefying object.

Natural materials containing phenols are the combination of one or both of lignin, tannin.

It is furthermore preferred that the catalyst is bivalent metal oxide or/and divalent metal salt or/and divalent in step (1) Metal hydroxides, the divalent metal be beryllium, magnesium, calcium, strontium, barium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, mercury, lead, platinum, One or more of tin, palladium；

The acid solution is the combination of one or more of sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, boric acid, carbonic acid.

It is furthermore preferred that aldehydes solution is added in two portions in step (2), it is molten to account for aldehydes for the amount of addition aldehydes solution for the first time The 60-90% of liquid total amount, remaining aldehydes solution are added in second, are added after aldehydes solution keep the temperature 30- every time 60min。

It is furthermore preferred that the temperature of the air-distillation water removal is 100-110 DEG C in step (3)；

The temperature of the vacuum distillation water removal is 50-60 DEG C, vacuum degree 10-25mmHg；

The time of air-distillation water removal and vacuum distillation water removal is 1-2h.

The second aspect of the present invention provides a kind of bi-component compound adhesive being made of thermoplastic phenolic resin and isocyanates Application of the glutinous agent in production wood-based plate；Wherein the wood-based plate include glued board, laminated veneer lumber, multi-layer solid wood compoundly Plate, core-board, finger joint lumber, integrated timber, laminated wood.

Beneficial effects of the present invention:

(1) preparation method of artificial board of the invention is used, first thermoplastic phenolic resin first heats up and is coated to wood single-plate On, after its cooling after formed one layer of solid film, can be saved for a long time in 50 DEG C of environment below, and during assembly with Isocyanates does not also chemically react when contacting, and only when hot pressing temperature increases, thermoplastic phenolic resin melts and isocyanide Can be fast curing-formed after acid esters mixing, when can effectively solve isocyanates and being mixed with existing thermosetting phenolic resin, isocyanic acid Water and hydroxyl isoreactivity group in ester group and thermosetting phenolic resin react cause adhesive open season short rapidly Problem；

(2) composite adhesive prepared by the present invention, which prepares wood-based plate, can effectively reduce energy consumption, improve hot pressing efficiency；The present invention When prepared by wood-based plate, as long as glue-line temperature, which reaches 80 DEG C, can react with isocyanates and solidify rapidly, existing compound gluing Agent hot pressing temperature is commonly 140-180 DEG C, and the hot pressing temperature that the present invention needs is low, and hot pressing is high-efficient and energy consumption is effectively reduced；

(3) bonding strength that the composite adhesive prepared through the invention is glued glued board can reach national standard GB17657- I class glued board and GB17656-2018 " concrete blinding in 2013 " wood-based plate and face artificial board physicochemical property experimental methods " With glued board " in Plywood for concrete form bonding strength require 4-5 times, bonding strength height；

(4) bi-component composite adhesive technological operation prepared by the present invention is simple, bonding property is excellent, using heat of the invention Plastic phenolic resin and isocyanates preparation bi-component composite adhesive, have curing rate is fast, boiling water resistance is good, be glued The high feature of wood-based plate intensity；

(5) composite adhesive prepared by the present invention can be used for manufacturing weatherability glued board, building template, core-board, list The composite wood boards such as plate laminated material, finger joint lumber, laminated wood, integrated timber are applied to compartment shipbuilding, outdoor structure, building The fields such as engineering, top-grade furniture, waterproof floor.

Specific embodiment

It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.

As background technology part introduction, when being blended due to existing phenolic resin with isocyanates, isocyanate group Group's contact water and hydroxyl can react immediately, cause the adhesive open hour too short, can not normal gluing assembly, although using Blocked isocyanate or water-based isocyanate can solve the problems, such as that a certain degree the open hour are short, but the composite adhesive prepared Reactivity is lower, and needs hot pressing at relatively high temperatures that could solidify, and causes energy consumption higher lower with hot pressing efficiency, so Especially need to develop the application method of a kind of new adhesive and adhesive.

Based on this, the object of the present invention is to provide a kind of using thermoplastic phenolic resin and isocyanates as compound gluing Thermoplastic phenolic resin is first heated up and is coated on wood single-plate by the method that agent prepares wood-based plate, forms one layer after its cooling Solid film does not also chemically react when contacting during assembly with isocyanates, only when hot pressing temperature increases, heat The thawing of plastic phenolic resin can be fast curing-formed after mixing with isocyanates, can effectively solve isocyanates and existing thermosetting property When phenolic resin mixes, isocyanate groups react rapidly with water and hydroxyl isoreactivity group causes adhesive open season short The problem of, it both can solve the short problem of existing adhesive open season, and when wood-based plate of the present invention preparation, as long as glue-line temperature reaches It can solidify rapidly with isocyanates to 80 DEG C, the hot pressing temperature needed is low, and hot pressing is high-efficient.

Test material used in the embodiment of the present invention is the test material of this field routine, can pass through commercial channel It is commercially available.

Thermoplastic phenolic resin described in the embodiment of the present invention the preparation method comprises the following steps:

(1) taking formalin that 169 parts of concentration are 37% (mass concentration) and 235 parts of purity is 99% (mass concentration) benzene Phenol solution is all added reaction kettle, 3 parts of zinc oxide is added, are heated with stirring to 80-90 DEG C, with 20% sulfuric acid by phenol solution Solution tune pH value is to 5.0；

(2) 143 parts of formalins are added, keeps the temperature 45-60min, 26 parts of formalins is then added, keep the temperature 45-60min；

(3) temperature is 100-110 DEG C, distillation removes water 1.5-2h under normal pressure state, then temperature is 50-60 DEG C again, very Reciprocal of duty cycle carries out vacuum distillation water removal 1.5-2h under conditions of being 10-25mmHg, temperature is cooled to room temperature, and obtains solid thermoplasticity Phenolic resin.