阅读说明：本技术 一种酚醛泡沫复合板材及其制备方法 (A kind of phenolic foam composite board and preparation method thereof ) 是由 杨准 杨峰 陈晨 王春 刘俊泽 鞠鹏达 董雅君 于 2019-09-18 设计创作，主要内容包括：本发明提供了一种酚醛泡沫复合板材及其制备方法,属于复合板技术领域。本发明提供的酚醛泡沫复合板材,包括依次层叠的第一不饱和树脂层、第一中碱性玻纤网层、酚醛泡沫芯层、第二中碱性玻纤网层和第二不饱和树脂层；所述酚醛泡沫芯层的制备原料包括：废旧酚醛泡沫、骨架材料、纤维、高分子抗裂材料、粘结剂和水。本发明提供的酚醛泡沫复合板材以废旧酚醛泡沫为主要材料,配合使用骨架材料、纤维、高分子抗裂材料、粘结剂和水,提高了酚醛泡沫芯层的耐久性、安全稳定性和耐火性质；中碱性玻纤网层和不饱和树脂层作为防护层,进一步强化了酚醛泡沫复合板材的力学性能、整体性、耐候性和密度。(The present invention provides a kind of phenolic foam composite boards and preparation method thereof, belong to composite plate technical field.Phenolic foam composite board provided by the invention, including the first unsaturated-resin layer, the first neutral and alkali glass stratum reticulare, phenol formaldehyde foam sandwich layer, the second neutral and alkali glass stratum reticulare and the second unsaturated-resin layer stacked gradually；The raw material for preparing of the phenol formaldehyde foam sandwich layer includes: waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water.Phenolic foam composite board provided by the invention is used cooperatively framework material, fiber, macromolecule anticracking material, binder and water, improves the durability, security and stability and refractory properties of phenol formaldehyde foam sandwich layer using waste and old phenol formaldehyde foam as main material；Neutral and alkali glass stratum reticulare and unsaturated-resin layer further enhance mechanical property, globality, weatherability and the density of phenolic foam composite board as protective layer.)

1. a kind of phenolic foam composite board, which is characterized in that the first unsaturated-resin layer including stacking gradually, alkali in first Property glass stratum reticulare, phenol formaldehyde foam sandwich layer, the second neutral and alkali glass stratum reticulare and the second unsaturated-resin layer；

The phenol formaldehyde foam sandwich layer prepare raw material include: waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, Binder and water.

2. phenolic foam composite board according to claim 1, which is characterized in that the preparation of the phenol formaldehyde foam sandwich layer is former In material, waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water mass ratio be (25~55): (9~14): (0.5~2): (3.5~6): (3~5): (10~20).

3. phenolic foam composite board according to claim 1 or 2, which is characterized in that the waste and old phenol formaldehyde foam makes With preceding being pre-processed；The pretreated mode is to mix after being crushed waste and old phenol formaldehyde foam with surfactant, is washed to The pH value of gained washing lotion is 6~7, is then filtered and dry.

4. phenolic foam composite board according to claim 1 or 2, which is characterized in that the framework material includes oxidation Magnesium and magnesium chloride；The mass ratio of the magnesia and magnesium chloride is (3~4): (2~3)；

The fiber includes plant fiber and/or glass fibre；

The macromolecule anticracking material includes ethylene-vinyl acetate copolymer；

The binder includes styrene-acrylic emulsion.

5. phenolic foam composite board according to claim 1 or 2, which is characterized in that the thickness of the phenol formaldehyde foam sandwich layer Degree is 5~20mm.

6. useless phenolic foam composite board according to claim 1, which is characterized in that the first unsaturated-resin layer and Unsaturated-resin in second unsaturated-resin layer includes 191^#Resin.

7. phenolic foam composite board according to claim 1, which is characterized in that the first neutral and alkali glass stratum reticulare and The thickness of two neutral and alkali glass stratum reticulares independently is 20~150mm；

The thickness of the first unsaturated-resin layer and the second unsaturated-resin layer independently is 0.5~1mm.

8. according to claim 1, phenolic foam composite board described in 2,6 or 7, which is characterized in that the phenol formaldehyde foam is compound The density of plate is 90~140kg/m³。

9. the preparation method of any one of claim 1~8 phenolic foam composite board, which is characterized in that including following step It is rapid:

Waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water are mixed, phenol formaldehyde foam core is obtained Material liquid；

It is sequentially placed into neutral and alkali glass fiber net, the phenol formaldehyde foam core raw material liquid and neutral and alkali glass fiber net in a mold, is cold-pressed It is demoulded after molding, obtains plate semi-finished product；

The upper and lower surfaces of the plate semi-finished product are sprayed into unsaturated-resin, obtain phenolic foam composite board.

10. preparation method according to claim 9, which is characterized in that the temperature of the cold moudling is 5~40 DEG C, when Between be 45~50h, pressure be 150~250MPa.

Technical field

The present invention relates to composite plate technical fields, and in particular to a kind of phenolic foam composite board and preparation method thereof.

Background technique

Phenol formaldehyde foam has the characteristic of fire retardant, low cigarette, distortion resistant to high temperatures, is widely used in space flight and aviation, defence and military neck Domain, the stringent place of the fire protection requirements such as civil aircraft, ship, station, oil well, and set applied to skyscraper, hospital, sport The construction material etc. applied.However being widely used for phenol formaldehyde foam also produces a large amount of waste phenolic foam.

Existing waste and old phenolic foam board is mainly used in battenboard, charing powder additive and resin and returns surface side filler. Wherein, waste and old phenol formaldehyde foam as sandwich board core material in use, need to cut waste and old phenolic foam board it is regular after carry out spelling, Abundant residues material is generated, the secondary discarding of waste and old phenol formaldehyde foam is caused, utilization can not be imitated entirely；Waste and old phenol formaldehyde foam is as carbonization power Last additive is in use, need waste and old phenolic sheet being broken into powder completely, by high temperature carbonization, washing, filtering, drying etc. Process is activated into adding ingredient, however the additional amount of waste and old phenol formaldehyde foam is excessive, and the quality that will lead to product reduces, thus in order to Guarantee that the quality of product, the dosage of waste and old phenol formaldehyde foam are less；Waste and old phenol formaldehyde foam as resin backfill material in use, need by Waste and old phenol formaldehyde foam is broken into powder completely, is added in resin to be foamed, however in order to guarantee the foam structure of finished product plate And internal uniformity, additive amount is very limited, and utilization rate is not also high.

Summary of the invention

The purpose of the present invention is to provide a kind of phenolic foam composite board and preparation method thereof, phenolic aldehyde provided by the invention Foam composite board mechanical property, has excellent weather resistance at globality, and significantly improves the utilization rate of waste and old phenol formaldehyde foam.

In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:

The present invention provides a kind of phenolic foam composite board, including stack gradually the first unsaturated-resin layer, first Neutral and alkali glass stratum reticulare, phenol formaldehyde foam sandwich layer, the second neutral and alkali glass stratum reticulare and the second unsaturated-resin layer；

The phenol formaldehyde foam sandwich layer prepare raw material include: waste and old phenol formaldehyde foam, surfactant, framework material, fiber, Macromolecule anticracking material, binder and water.

Preferably, the phenol formaldehyde foam sandwich layer is prepared in raw material, waste and old phenol formaldehyde foam, framework material, fiber, macromolecule The mass ratio of anticracking material, binder and water is (25~55): (9~14): (0.5~2): (3.5~6): (3~5): (10~ 20)。

Preferably, the waste and old phenol formaldehyde foam is pre-processed before use；The pretreated mode is by waste and old phenol It is mixed after aldehyde bubble collapse with surfactant, the pH value for being washed to gained washing lotion is 6~7, is then filtered and dry.

Preferably, the framework material includes magnesia and magnesium chloride；The mass ratio of the magnesia and magnesium chloride is (3 ~4): (2~3)；

The fiber includes plant fiber and/or glass fibre；

The macromolecule anticracking material includes ethylene-vinyl acetate copolymer；

The binder includes styrene-acrylic emulsion.

Preferably, the phenol formaldehyde foam sandwich layer with a thickness of 5~20mm.

Preferably, the unsaturated-resin in the first unsaturated-resin layer and the second unsaturated-resin layer includes 191^#Tree Rouge.

Preferably, the thickness of the first neutral and alkali glass stratum reticulare and two neutral and alkali glass stratum reticulares independently be 20~ 150mm；

The thickness of the first unsaturated-resin layer and the second unsaturated-resin layer independently is 0.5~1mm.

Preferably, the density of the phenolic foam composite board is 90~140kg/m³。

The present invention provides the preparation methods of phenolic foam composite board described in above-mentioned technical proposal, comprising the following steps:

Waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water are mixed, phenolic aldehyde bubble is obtained Foam core raw material liquid；

It is sequentially placed into neutral and alkali glass fiber net, the phenol formaldehyde foam core raw material liquid and neutral and alkali glass fiber net in a mold, carries out It is demoulded after cold moudling, obtains plate semi-finished product；

The upper and lower surfaces of the plate semi-finished product are sprayed into unsaturated-resin, obtain phenolic foam composite board.

Preferably, the temperature of the cold moudling is 5~40 DEG C, and the time is 45~50h, and pressure is 150~250MPa.

The present invention provides a kind of phenolic foam composite board, including stack gradually the first unsaturated-resin layer, first Neutral and alkali glass stratum reticulare, phenol formaldehyde foam sandwich layer, the second neutral and alkali glass stratum reticulare and the second unsaturated-resin layer；The phenol formaldehyde foam The raw material for preparing of sandwich layer includes: waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water.This hair The phenolic foam composite board of bright offer significantly improves the utilization of waste and old phenol formaldehyde foam using waste and old phenol formaldehyde foam as main material Rate；Waste and old phenol formaldehyde foam is used cooperatively framework material, fiber, macromolecule anticracking material, binder and water, obtained phenol formaldehyde foam Durability, security and stability and the refractory properties of sandwich layer are good；Neutral and alkali glass stratum reticulare and unsaturated-resin layer as protective layer, into One step enhances mechanical property, globality, weatherability and the density of phenolic foam composite board.

Preparation method provided by the invention does not need to carry out modifying to waste and old phenol formaldehyde foam to cut, and does not generate waste foam yet Secondary discarding, the utilization rate of waste and old phenol formaldehyde foam is high, and easy to operate, suitable for scale production.

Detailed description of the invention

Fig. 1 is the preparation process schematic diagram of phenol formaldehyde foam core raw material liquid；

Fig. 2 is the preparation process flow schematic diagram of phenolic foam composite board.

Specific embodiment

The present invention provides a kind of phenolic foam composite board, including stack gradually the first unsaturated-resin layer, first Neutral and alkali glass stratum reticulare, phenol formaldehyde foam sandwich layer, the second neutral and alkali glass stratum reticulare and the second unsaturated-resin layer；

The raw material for preparing of the phenol formaldehyde foam sandwich layer includes: waste and old phenol formaldehyde foam, framework material, fiber, macromolecule cracking resistance Material, binder and water.

In the present invention, the waste and old phenol formaldehyde foam is preferably pre-processed using preceding, and the pretreated mode is excellent It is selected as mixing after being crushed waste and old phenol formaldehyde foam with surfactant, the pH value for being washed to gained washing lotion is 6~7, is then filtered And drying.

The present invention is not particularly limited described be crushed, and can guarantee that the waste and old phenol formaldehyde foam is cotton-shaped.

In the present invention, the surfactant is preferably methyl-silicone oil.In the present invention, the waste and old phenol formaldehyde foam and The amount ratio of surfactant is preferably (10~15): (3~5), and the quality of water used in the washing is preferably the waste and old phenol 4.5~8 times of aldehyde foam.In the present invention, the washing preferably carries out under agitation, and the time of the stirring is preferably 25~35min；The present invention is not particularly limited the mixing speed, using mixing speed well known in the art.In In the present invention, preferably gained washing lotion is stood before detecting the pH value of the washing lotion；The time of the standing is preferably 45~ 60min.The present invention is not particularly limited the number of the washing, can guarantee that the pH value of gained washing lotion after washing is 6~7 .In the present invention, the surfactant is conducive to the waste and old phenol formaldehyde foam and is sufficiently soaked, and then is conducive to give up Acid in old phenol formaldehyde foam removes, the compatibility of enhancing gained pretreated waste and old phenol formaldehyde foam and other raw materials, and then improves Durability, security and stability and the refractory properties of phenol formaldehyde foam sandwich layer.

The present invention is not particularly limited the filtering, using filter operation well known in the art.In the present invention In, the temperature of the drying is preferably 45~55 DEG C；The present invention is not particularly limited the time of the drying, can guarantee Moisture content < 20wt% of the solid material.

In the present invention, the framework material preferably includes magnesia and magnesium chloride；The matter of the magnesia and magnesium chloride Amount is than being preferably (3~4): (2~3).The present invention is by adding framework material in waste and old phenol formaldehyde foam, in being total to for other raw materials Under same-action, the intensity of phenol formaldehyde foam sandwich layer can be improved.

In the present invention, the fiber preferably includes plant fiber and/or glass fibre, more preferably plant fiber or glass Glass fiber；The present invention is not particularly limited the length and fineness of the fiber, using fiber well known in the art.This Invention is by adding fiber in waste and old phenol formaldehyde foam, under the collective effect of other raw materials, can be improved phenol formaldehyde foam sandwich layer Intensity.

In the present invention, the macromolecule anticracking material is preferably ethylene-vinyl acetate copolymer；The ethyl vinyl acetate The mass fraction of vinyl acetate is preferably 5~15% in ethylene copolymer.The present invention is high by adding in waste and old phenol formaldehyde foam Molecule anticracking material can be improved the intensity of phenol formaldehyde foam sandwich layer under the collective effect of other raw materials.

In the present invention, the binder preferably includes styrene-acrylic emulsion (i.e. styrene-acrylate emulsion)；The phenylpropyl alcohol The solid content of lotion is preferably 5~10%.In the present invention, the styrene-acrylic emulsion have adhesive force is good, water-fast, oil resistant, it is heat-resisting, Ageing-resistant performance is good, is used cooperatively with other raw materials, can be improved the intensity, weatherability and resistance to ag(e)ing of phenol formaldehyde foam sandwich layer Energy.

In the present invention, the phenol formaldehyde foam sandwich layer is prepared in raw material, waste and old phenol formaldehyde foam, framework material, fiber, height The mass ratio of molecule anticracking material, binder and water is preferably (25~55): (9~14): (0.5~2): (3.5~6): (3~ 5): (10~20), more preferably (30~50): (9.5~13.3): (0.9~1.8): (3.8~5.7): (2.5~5): (12~ 20), most preferably (35~50): (10~13): (1~1.5): (4~5): (3~4.5): (15~20).It is provided by the invention Phenolic foam composite board significantly improves the utilization rate of waste and old phenol formaldehyde foam using waste and old phenol formaldehyde foam as main material；It is waste and old Phenol formaldehyde foam is used cooperatively framework material, fiber, macromolecule anticracking material, binder and water, improves phenol formaldehyde foam sandwich layer Durability, security and stability and refractory properties.

In the present invention, the thickness of the phenol formaldehyde foam sandwich layer is preferably 5~20mm, more preferably 8~20mm, most preferably For 10~15mm.

In the present invention, the thickness of the first neutral and alkali glass stratum reticulare and two neutral and alkali glass stratum reticulares is independently preferably 20~150mm, more preferably 30~120mm, most preferably 50~100mm.The present invention does not have the neutral and alkali glass fiber net Particular determination, using commercially available neutral and alkali fiberglass gridding cloth；The neutral and alkali glass fiber net be preferably dimensioned to be 5mm × The surface density of 5mm, the neutral and alkali glass fiber net are preferably 125g/m².The neutral and alkali glass fiber net chemical stability that the present invention uses Good, the caking property between resin is strong, good stability of the dimension；The present invention is using neutral and alkali glass stratum reticulare as protective layer, further Enhance mechanical property, globality, weatherability and the density of phenolic foam composite board.

In the present invention, the unsaturated-resin in the first unsaturated-resin layer and the second unsaturated-resin layer preferably wraps Include 191^#Resin.In the present invention, the thickness of the first unsaturated-resin layer and the second unsaturated-resin layer is independently preferred For 0.5~1mm, more preferably 0.6~0.9mm, most preferably 0.7~0.8mm.Phenolic foam composite board provided by the invention Play the role of protection and leveling with unsaturated-resin layer, the mechanical property, whole of phenolic foam composite board can be further increased Body and weatherability and density.

In the present invention, the density of the phenolic foam composite board is preferably 90~140kg/m³, more preferably 120~ 140kg/m³。

In the present invention, if without specified otherwise, all raw material components are commercially available quotient well known to those skilled in the art Product.

The present invention provides the preparation methods of phenolic foam composite board described in above-mentioned technical proposal, comprising the following steps:

Waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water are mixed, phenolic aldehyde bubble is obtained Foam core raw material liquid；

It is sequentially placed into neutral and alkali glass fiber net, the phenol formaldehyde foam core raw material liquid and neutral and alkali glass fiber net in a mold, carries out It is demoulded after cold moudling, obtains plate semi-finished product；

The upper and lower surfaces of the plate semi-finished product are sprayed into unsaturated-resin, obtain phenolic foam composite board.

The present invention mixes waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water, obtains Phenol formaldehyde foam core raw material liquid.

In the present invention, the waste and old phenol formaldehyde foam, framework material, fiber, macromolecule anticracking material, binder and water are mixed Framework material, fiber, macromolecule anticracking material and part water are preferably carried out the first mixing by the sequence of conjunction, obtain slurry；It will Waste and old phenol formaldehyde foam, slurry, binder and remaining water carry out the second mixing, obtain phenol formaldehyde foam core raw material liquid, process flow chart As shown in Figure 1.

In the present invention, the waste and old phenol formaldehyde foam is preferably pre-processed using preceding.In the present invention, the pre- place Reason is preferably identical as the pretreated mode of phenol formaldehyde foam waste and old in above-mentioned technical proposal, and details are not described herein.

In the present invention, the mass ratio of the part water and remaining water is preferably 1:(0.5~2), more preferably 1:1.In In the present invention, first mixing and the second mixed mode are preferably stirred, and the present invention is stirred for described Speed be not particularly limited, using mixing speed well known in the art.In the present invention, first mixing and second The mixed time is independently preferably 45~60min.

After obtaining phenol formaldehyde foam core raw material liquid, the present invention is sequentially placed into neutral and alkali glass fiber net, phenolic aldehyde bubble in a mold Foam core raw material liquid and neutral and alkali glass fiber net demould after carrying out cold moudling, obtain plate semi-finished product.

The present invention is not particularly limited the type of the mold, using mold well known in the art.The present invention The size of the mold is not particularly limited, is preferably determined as needed.

In the present invention, the release agent is preferably water glass adhesive gel material.In the present invention, described to spread into neutral and alkali glass It is preferably also included in the mold inner-cavity before fibre web and smears release agent and drying.In the present invention, the release agent is preferably water Glass cement.In the present invention, the temperature of the drying is preferably 25~35 DEG C, and the time is preferably 1~2h, the drying Release agent solidifies in the process.

In the present invention, the temperature of the cold moudling is preferably 5~40 DEG C, in an embodiment of the present invention preferably room Temperature；The time of the cold moudling is preferably 45~50h, more preferably 48h；The pressure of the cold moudling is preferably 150~ 250MPa, more preferably 200~250MPa.

In the present invention, the release agent smeared in the mold is conducive to subsequent demoulding.

After completing the demoulding, it is also preferable to include gained semi-finished product are carried out deburring shaping by the present invention.The present invention is for institute The mode for stating deburring shaping is not particularly limited, using deburring Training system well known in the art.

After obtaining plate semi-finished product, the present invention sets the upper and lower surfaces spraying unsaturation of the plate semi-finished product Rouge obtains phenolic foam composite board.

The present invention is not particularly limited the mode of the spraying, using spraying method well known in the art.This Invention sprays unsaturated-resin on the surface of the plate semi-finished product, plays the role of cover and leveling, can be improved phenol formaldehyde foam Surface impact, water resistance and the weatherability of composite board.

The preparation method of phenolic foam composite board provided by the invention does not need to carry out finishing sanction to waste and old phenol formaldehyde foam It cuts, does not also generate the secondary discarding of waste and old phenol formaldehyde foam, the utilization rate of waste and old phenol formaldehyde foam is high, and easy to operate, proper scale Metaplasia produces.

Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to In the scope of protection of the invention.