CN108864469A - A kind of method that dry method foaming prepares phenol formaldehyde foam - Google Patents
A kind of method that dry method foaming prepares phenol formaldehyde foam Download PDFInfo
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- CN108864469A CN108864469A CN201710333742.XA CN201710333742A CN108864469A CN 108864469 A CN108864469 A CN 108864469A CN 201710333742 A CN201710333742 A CN 201710333742A CN 108864469 A CN108864469 A CN 108864469A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The present invention relates to a kind of methods for preparing phenol formaldehyde foam using thermoplastic phenolic resin dry method foaming.Specific method of the invention is：(1) foaming raw material used is thermoplastic phenolic resin, and powdered foaming agent is used in (2) foaming process and promotes crosslinking agent, (3) raw material to be foamed are added in mold, foamable, it demoulds, the filler in (4) raw material can be any organic or inorganic powdery filler, such as montmorillonite, clay, attapulgite hybrid, inorganic oxide powder, carbon dust, fiber, organic matter powder or their mixture etc..Method production phenolic foam material of the invention is had excellent performance, and cost is relatively low, simple process, low in the pollution of the environment.
Description
Technical field
The present invention relates to foam preparation fields, and in particular to a kind of preparation method of phenol formaldehyde foam.
Background technique
Phenol formaldehyde foam is a kind of novel nontoxic, fire retardant, the low cigarette of fire prevention, low thermal conductivity, distortion resistant to high temperatures insulation guarantor
Adiabator, phenolic foam material also have many excellent performances such as anti-chemical solvent burn into is anti-aging.It overcomes polyphenyl second
The shortcomings that alkene foamed material and polyurethane foamed material have inflammable, thickness, and heat deforms is suitable for building inner-outer wall and protects
Temperature, utilidor and freezer, the fields such as factories and miness workshop and mechanical equipment.
It is that primary raw material foams that foam process traditional at present, which is using thermosetting phenolic resin,.Thermosetting phenolic tree
Rouge is also referred to as resol, first to be synthesized using formaldehydes and phenols chemical substance in the preliminary preparation of foaming
Then resol foams using the phenolic resin of synthesis.The reactivity of this phenolic resin is higher, but first
The stability of rank phenolic resin is poor, and storage cycle is short, can only generally store 1~2 week, with the growth of storage time, phenolic aldehyde tree
Auto polymerization reaction can occur for rouge itself, so generally now preparing current.This also causes each resin synthesis process to produce to final
The quality of product has an impact.
It is low-boiling molten that alkanes and organic fluoride class etc. are added in traditional foam process generally in thermosetting phenolic resin
Additive (such as surfactant) and a variety of processing aids of curing agent is added as foaming agent in agent, agitated, foaming,
The techniques such as curing obtain phenolic foam material.Foaming agent is wrapped in foam, with the passage for using the time, organic foaming agent
Releasing slowly, has not only polluted environment but also has improved the thermal coefficient of phenol formaldehyde foam, reduced the thermal insulation of phenolic foam material
Energy.The most important, existing foam process largely use organic acid or inorganic acid as catalysis during foaming
Agent and curing agent, in subsequent use, these acid chemicals releasing slowly corrodes the contact material of surrounding such as
Metal material, this will lead to serious structure problem, while also pollute environment.
Summary of the invention
Therefore, in order to reduce existing commercial product the shortcomings that, the technical problem to be solved in the present invention is to provide a kind of without molten
Agent, the method that anhydrous dry method foaming preparation has the phenol formaldehyde foam of excellent thermal insulation properties.
The technical scheme is that a kind of method that dry method foaming prepares phenol formaldehyde foam, using thermoplastic phenolic resin
For original material, it is added curing agent, foaming agent, filler after crushing respectively after mixing, or after crushing again after mixing adds
Enter into mold, be heating and curing molding, obtains phenol foam；Curing agent accounts for raw material thermoplastic phenolic resin weight
The 5wt%-55wt% of score；The foaming agent accounts for the 3wt%-40wt% of raw material thermoplastic phenolic resin weight fraction；Institute
State the mass ratio 2-40wt% that filler accounts in raw material phenolic resin.
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the thermoplastic phenolic resin packet
It includes：Thermoplastic phenolic resin of the molar ratio of the aldehydes and phenol that are chemically reacted with phenol and aldehydes less than 1, or
The modified obtained modified thermoplastic phenolic resin with thermoplastic macromolecule material characteristic on this basis.
Thermoplastic phenolic resin is a kind of high molecular material chemically reacted by phenol and aldehydes, in the mistake of preparation
The molar ratio of Cheng Zhong, aldehydes and phenol is less than 1.Phenol may include one or more kinds of phenolic compound, such as phenol,
Resorcinol, bisphenols, cresols, alkyl phenol, phenol ether, tannin acids perhaps lignin or other gone out by phenol derivative
Compound；Aldehydes may include one or more kinds of aldehyde derivatives, such as formaldehyde, acetaldehyde, propionic aldehyde, Aromatic aldehyde compound, ring
Hexane formaldehyde, furtural, aromatic aldehyde, heterocycle aldehydes or other compounds gone out by formaldehyde-derived.Thermoplastic phenolic resin
Molecular weight is between 200 to 100,000.
Further, the modified thermoplastic phenolic resin includes：Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyamide change
Property phenolic resin, epoxy modified phenolic resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, dimethylbenzene modified phenolic
Resin, one of diphenyletherformalde-hyde resin.
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the curing agent includes dioxy penta
Ring, trioxane, paraformaldehyde, hexa, polyphenol, melamine, polyamine, one in resol
Kind or more than one.
Preferably, aromatic hydrocarbons of the polyphenol described in curing agent preferably with multiple phenolic hydroxyl groups.
The solidification blowing temperature of curing agent and thermoplastic phenolic resin is between 120 DEG C -210 DEG C.Phenolic aldehyde steeps in the present invention
In the formula of foam, the ratio of curing agent is 5wt% to the 55wt% of phenolic resin weight score.
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the grain of the smashed powder
Diameter is less than 3 millimeters.
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the foaming agent is polyatomic phenol
Compound or polynary acid compounds.Polyhydric phenols refer to polyphenol compound, are contained in structural formula/strand
The substance of multiple phenol functional groups.Polyphenol compound of the invention is preferably the polyphenol compound with certain acidity.
The aobvious acidity of these polyphenol in aqueous solution, pH value is between 1-6, preferably between 1 and 3.
The effect of foaming agent is so that resin is formed porous foam structure in cross-linking process generating bubble, have simultaneously
The effect of crosslinking accelerator.In the present invention, the foaming agent of fine powder is uniformly scattered in phenolic powder matrix, works as hair
It when infusion is heated, decomposes, generates gas.Due to phenolic powder melt temperature foaming agent decomposition temperature hereinafter, working as
When foaming agent decomposes, foam original unit is generated in the phenolic resin as matrix resin of melting, with the decomposition of foaming agent, foam is original
Unit is gradually grown up, and the foam of certain size size is formed in phenolic resin.Phenolic resin is cured reaction simultaneously, is formed
The phenol formaldehyde foam of excellent thermal insulation properties.
Use polyphenol or polynary acids as solid cross-linking type foaming agent/promotor in the present invention.Polyphenol compound can
It is reacted with the matrix with phenolic resin, improves the mechanical strength of foamed material.Polyphenol compound is structural formula/strand
In contain the substances of multiple phenol functional groups, typical polyphenols has tannic acid, Ellagitannins, theaflavin etc..Polyphenol
Class compound is largely present in nature, can extract from natural plants, such as Chinese gall, the wooden orchid plant, fruit, vegetable
Dish, cereal etc..For example tannic acid, a kind of typical tannins compound, the content in Chinese gall are up to 56%.Polyphenols
It, can also be with chemical synthesis if closing owner to extract from natural material.
Polynary acids refers to may release multiple proton (H in a molecule+) acid, referred mainly in organic compound every
Contain the carboxylic acid of multiple carboxyls in a molecule.Typical polynary acids includes oxalic acid, 2- hydroxysuccinic acid, Cis butene dioic acid, the last of the ten Heavenly stems
Diacid, adipic acid, the third three acid, fourth tetracid, the small molecules such as isoamyl tetracid, or the small-molecular-weight oligomer containing polyacid or big point
Sub- polymer, preferably polyacrylic acid, poly etc..Weight fraction of the polyphenol/acids in phenolic resin from 5wt% to
Between 40wt%.
Further, typical polyphenols has tannic acid, Ellagitannins, theaflavin etc..
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the polynary acid compounds packet
Small molecule polyacid is included, and small-molecular-weight oligomer or macromolecular containing polyacid.
The preferred oxalic acid of small molecule polyacid, the third three acid, fourth tetracid, isoamyl tetracid；Small-molecular-weight oligomerisation containing polyacid
Object or the preferred polyacrylic acid of macromolecular, poly etc..
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that the filler can be it is a kind of or
Perhaps inorganic material is also possible to blending or the composite material of organic-inorganic material to a variety of organic materials of person.
Above-mentioned organic material or the physical pattern of inorganic material can be nanometer perhaps the line nanometer of micro-meter scale or
The particle of micro-meter scale, the nanometer perhaps lamella of micro-meter scale or arbitrary mixing material.
Further, the size range of the organic material or inorganic material is between 5 nanometers to 10 microns.
Due to being foamed using dry method, than wide, filler can be modified the range of the filler in the present invention in phenol formaldehyde foam
The mechanical performance and hot property of phenol formaldehyde foam.Filler can be one or more kinds of organic materials or inorganic material, can also be with
It is blending/composite material of organic-inorganic material.The physical pattern of organic/inorganic materials can be the line of Nano/micron scale,
The particle of Nano/micron scale, the lamella of Nano/micron scale or arbitrary mixing material.The ruler of organic/inorganic materials
Very little range is between 5 nanometers to 10 microns.Ratio of the filler in phenol formaldehyde foam resin is that the 2wt% of phenolic resin is arrived
40wt%.
For inorganic particulate filler, it can choose one or more kinds of materials described below, such as silica dioxide granule, four oxidations three
Iron particle, titanium dioxide granule, carbon particle, calcium carbonate granule, the materials such as aluminum oxide particle.
For natural powder body material, can choose attapulgite hybrid, clay, kaolin, palygorskite, cellulose, metallic fiber or
The materials such as person's metal-oxide fiber.
For stratified material, montmorillonite, layered composite metal hydroxides, graphite, graphene, graphite oxide can choose
Alkene, boron nitride, carbonitride, the materials such as mica splittings.
Organic/inorganic materials are also possible to some chemical products, such as oxalic acid, urea, sodium carbonate, sodium bicarbonate, bicarbonate
Ammonium, ammonium carbonate etc..
For organic powder material, polytetrafluorethylepowder powder can be, with plastics, natural material, the raw material such as fiber are
The powder of basis preparation.
For being also possible to epoxy resin, phenolic resin, rubber tyre for filler, the waste and old material such as other high molecular materials
Material is raw material, obtains the powder of recoverable by processing.
The method that dry method foaming according to the present invention prepares phenol formaldehyde foam, it is preferred that described be heating and curing forms temperature
Between 120 DEG C -210 DEG C.
The beneficial effects of the invention are as follows：
The present invention provides a kind of solvent-free, phenolic aldehyde bubble of the anhydrous dry method foaming preparation with excellent thermal insulation properties
The method of foam.This method does not use the organic solvent of alkanes during preparation, does not use volatile pair of environmental hazard
Big foaming agent, without using the catalyst and curing agent of highly acid, the final ph of product is neutrality, to production equipment and later period
The metal material touched in use is non-corrosive.
The present invention is main raw material(s) using thermoplastic phenolic resin or phenol-formaldehyde resin modified, with the foaming of solid
Agent/promotor is produced, and a variety of organic/inorganic fillers can be added in the product as additive.Production of the invention
Simple process, easy to operate, the excellent performance of product.
Technical process of the invention is simple.The powderous primary material such as thermoplastic phenolic resin for preparing phenol formaldehyde foam, solidification
Agent, foaming agent/promotor, filler etc. after mixing, are added in the mold of certain shapes, and it is Celsius that mold is heated to 120
It spends to curing molding is carried out between 210 degrees Celsius, demoulds to get phenolic foam products.Heating method may be any type of
Heating method, such as baking oven, thermal station or vulcanizing press, hot press etc..
Specific embodiment
Thermoplastic phenolic resin and curing agent, foaming agent/promotor are added in mold, then after filler is blended uniformly
Be heating and curing molding, demoulds to get phenolic foam material is arrived.
Embodiment 1：
Phenolic foam material without filler.100 grams of graininess thermoplastic phenolic resin grinder grind into powder.This
A powder and 12 grams of hexa powder and 15 grams of tannic acid powder after mixing, are injected into mold, and uniform point
It is dispersed in bottom surface.6 inner surfaces of mold cover one layer of brown paper.Then this mold is put into 175 degrees Celsius of convection oven
Middle foamable solidifies 10 minutes.After phenolic resin curing, brown paper is firmly adhered to phenolic foam material surface.Such ox
The phenol formaldehyde foam of mulberry paper package, which is just easily demoulded from mold, to be come out, and 350 millimeters long, 300 millimeters wide, 25 millimeters of thickness is obtained
Phenolic foam board.The density of gained phenolic foam board is 0.048 gram/cc, and thermal coefficient is 0.025W/ (mK).
Embodiment 2：
Phenolic foam material containing inorganic filler.100 grams of graininess thermoplastic phenolic resins, 15 grams of hexas,
20 grams of attapulgite hybrids, 20 grams of tannic acids are blended uses grinder grind into powder afterwards together.Powder after grinding is added in mold.Mould
The inner surface of tool is covered with one layer of aluminium-foil paper.Then this mold is put into 165 degrees Celsius of convection oven and is solidified 20 minutes.
After phenolic resin curing, aluminium-foil paper is firmly adhered to foam surface.The phenol formaldehyde foam of aluminium-foil paper package so just holds very much
It demoulds and comes out in easy slave mold, obtain 350 millimeters long, 300 millimeters wide, thick 25 millimeters of phenolic foam board.Gained phenolic aldehyde bubble
The density of foam plate is 0.059 gram/cc, and thermal coefficient is 0.0314W/ (mK).
Embodiment 3：
The phenolic foam material of the filler containing spent high molecular.115 grams of heat containing 15wt% curing agent hexa
Plastic phenolic toner and 13 grams of oxalic acid are injected into mold after the waste and old Phenolic resin powder of 5g is blended uniformly.Mold it is interior
Surface covers a strata imide membrane.Then this mold is put into two plates of 180 degrees Celsius of vulcanizing press
Between, solidify 15 minutes.After phenolic resin curing, Kapton is adhered to foam surface.Kapton package
Phenol formaldehyde foam just easily demould and come out from mold, obtain 350 millimeters long, 300 millimeters wide, thick 25 millimeters of phenol formaldehyde foams
Plate.The density of gained phenolic foam board is 0.051 gram/cc, and thermal coefficient is 0.0297W/ (mK).
Embodiment 4：
Modified phenolic foam material containing filler.Phenol-formaldehyde resin modified is the homemade silicone-modified thermoplasticity in laboratory
Phenolic resin.After 100 grams of modified thermoplastic phenolic resins and 13 grams of hexas are blended uniformly, it is added 10 grams of oxalic acid, 8
Gram attapulgite hybrid is ground with grinder.Powder after mixing, is injected into mold.The inner surface of mold is covered with one layer of aluminium foil
Paper.Then this mold is put into 170 degrees Celsius of convection oven 20 minutes.After phenolic resin curing, aluminium-foil paper is firm
It is adhered to foam surface.The phenol formaldehyde foam of aluminium-foil paper package in this way, which is just easily demoulded from mold, to be come out, and is grown
It is 350 millimeters, 300 millimeters wide, thick 25 millimeters of phenolic foam board.The density of gained phenolic foam board is 0.050 gram/cube li
Rice, thermal coefficient are 0.0295W/ (mK).
Embodiment 5：
Modified phenolic foam material containing filler.Epoxy modified phenolic resin is laboratory self-control.100 grams epoxy-modified
After thermoplastic phenolic resin and 9 grams of first Jie's Phenolic resin powders are blended uniformly, 8 grams of the third three acid are added, 7 grams of mica splittings are ground
Machine grinding.Powder after mixing, is injected into mold.The inner surface of mold is covered with one layer of aluminium-foil paper.Then this mould
Tool is put into 170 degrees Celsius of convection oven 20 minutes.After phenol-formaldehyde resin modified solidification, aluminium-foil paper is firmly adhered to foam material
Expect surface.The phenol formaldehyde foam of aluminium-foil paper package in this way, which is just easily demoulded from mold, to be come out, and 350 millimeters of length is obtained, wide by 300
Millimeter, thick 25 millimeters of phenolic foam board.The density of gained phenolic foam board is 0.047 gram/cc, and thermal coefficient is
0.0284W/(m·K)。
Embodiment 6：
After the homemade polyamide modified phenolic resin in 100 grams of laboratories and 11 grams of paraformaldehydes are blended uniformly, 8 grams of addition is suitable
Butene dioic acid, 8 grams of celluloses are ground with grinder.Powder after mixing, is injected into mold.The inner surface of mold is covered with
One layer of aluminium-foil paper.Then this mold is put into 180 degrees Celsius of convection oven 25 minutes.After phenolic resin curing, aluminium foil
Paper is firmly adhered to foam surface.The phenol formaldehyde foam of aluminium-foil paper package so just easily demoulds out from mold
Come, obtains 350 millimeters long, 300 millimeters wide, thick 25 millimeters of phenolic foam board.The density of gained phenolic foam board is 0.048
Gram/cc, thermal coefficient is 0.0270W/ (mK).
Embodiment 7：
The homemade polyamide modified phenolic resin in 50 grams of laboratories and 50 grams of boron modified phenolic resins, with 10 gram of six methylene
After urotropine is blended uniformly, 9 grams of polyacrylic acid are added, 2 grams of graphene oxides are ground with grinder.Powder after mixing, is infused
Enter into mold.The inner surface of mold is covered with one layer of aluminium-foil paper.Then this mold is put into 170 degrees Celsius of convection oven
In 20 minutes.After phenolic resin curing, aluminium-foil paper is firmly adhered to foam surface.The phenolic aldehyde bubble of aluminium-foil paper package in this way
Foam is just easily demoulded from mold and is come out, and obtains 350 millimeters long, 300 millimeters wide, thick 25 millimeters of phenolic foam board.Institute
The density for obtaining phenolic foam board is 0.046 gram/cc, and thermal coefficient is 0.0380W/ (mK).
Embodiment 8：
The homemade boron modified phenolic resin in 50 grams of laboratories and 50 grams of dimethylbenzene phenol-formaldehyde resin modifieds are blended, then with more than 12 grams
It is polyoxymethylene blended uniformly after, 8 grams of oxalic acid are added, 9 grams of polytetrafluorethylepowder powders are ground with grinder.Powder after mixing, is infused
Enter into mold.The inner surface of mold is covered with one layer of aluminium-foil paper.Then this mold is put into 180 degrees Celsius of convection oven
In 20 minutes.After phenolic resin curing, aluminium-foil paper is firmly adhered to foam surface.The phenolic aldehyde bubble of aluminium-foil paper package in this way
Foam is just easily demoulded from mold and is come out, and obtains 350 millimeters long, 300 millimeters wide, thick 25 millimeters of phenolic foam board.Institute
The density for obtaining phenolic foam board is 0.049 gram/cc, and thermal coefficient is 0.0290W/ (mK).
The present invention provides the Recipe that a kind of dry method foaming prepares phenolic foam material, this method has technique
Simply, the features such as production cost is small, small pollution of the environment.Make during production without using corrosive highly acid substance
For catalyst, without using alkanes organic solvent as foaming agent, the stability of product is strong.
Claims (10)
1. a kind of method that dry method foaming prepares phenol formaldehyde foam, it is characterised in that：Use thermoplastic phenolic resin for original material,
Be added curing agent, foaming agent, filler, respectively crush after after mixing, or mixing after crush again after, be added in mold,
Be heating and curing molding, obtains phenol foam；Curing agent accounts for raw material thermoplastic phenolic resin weight fraction
5wt%-55wt%；The foaming agent accounts for the 3wt%-40wt% of raw material thermoplastic phenolic resin weight fraction；The filler
Account for the mass ratio 2-40wt% in raw material phenolic resin.
2. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The thermoplastic phenolic
Resin, including：Thermoplastic phenolic resin of the molar ratio of the aldehydes and phenol that are chemically reacted with phenol and aldehydes less than 1
Rouge, or the modified obtained modified thermoplastic phenolic resin with thermoplastic macromolecule material characteristic on this basis.
3. the method that dry method foaming according to claim 2 prepares phenol formaldehyde foam, it is characterised in that：The modified thermoplastic
Phenolic resin includes：Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyamide modified phenolic resin, epoxy modified phenolic resin have
Machine Si modification phenolic resin, boron modified phenolic resin, dimethylbenzene phenol-formaldehyde resin modified, one of diphenyletherformalde-hyde resin.
4. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The curing agent includes
Dioxolanes, trioxane, paraformaldehyde, hexa, polyphenol, melamine, polyamine, resol
One of or more than one.
5. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The smashed powder
The partial size at end is less than 3 millimeters.
6. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The foaming agent is more
First phenolic compound or polynary acid compounds.
7. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The polynary acids
Closing object includes small molecule polyacid, and small-molecular-weight oligomer or macromolecular containing polyacid.
8. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：The filler can be
Perhaps inorganic material is also possible to blending or the composite material of organic-inorganic material to one or more kinds of organic materials.
9. the method that dry method foaming according to claim 8 prepares phenol formaldehyde foam, it is characterised in that：The organic material or
The size range of person's inorganic material is between 5 nanometers to 10 microns.
10. the method that dry method foaming according to claim 1 prepares phenol formaldehyde foam, it is characterised in that：It is described to be heating and curing
Forming temperature is between 120 DEG C -210 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679131A (en) * | 2019-01-05 | 2019-04-26 | 国网山东省电力公司电力科学研究院 | Graphene phenol-formaldehyde resin modified nano film material and preparation method |
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