CN101602275A - Phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof - Google Patents
Phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof Download PDFInfo
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Abstract
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate of good toughness, by last, following metal covering color steel and middle Phonelic foam sandwich board are formed, the compositing formula of Phonelic foam sandwich board is (all representing with weight portion in the prescription): phenolic resins 100, levelling agent 2-8, blowing agent 3-9, catalyst 1-5, stabilizing agent 0.5-1.5, curing agent 20-30, its production technology comprises the steps: at first to add phenol in reactor, 37% formalin and 20% baryta water begin to stir, be warming up to 85 ℃, reaction is 4-5 hour under this temperature, add the aqueous hydrochloric acid solution adjust pH till the 6.8-7, be warming up to 100 ℃ of backflows, add oxalic acid, the thickening of reducing pressure again, it is 2500-3000MPa (25 ℃) that sampling makes discharging viscosity, this is a reaction end, and cooling discharging promptly gets phenolic resins.
Description
Technical field
The present invention relates to a kind of chromatic steel sandwich plate and production technology thereof, relate in particular to a kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof.
Background technology
Phenol formaldehyde foam is a kind of foamed plastics that is obtained by foaming by phenolic resins, with the polystyrene foam that accounts for the market leading position in early days, polyvinyl chloride foam, materials such as polyurethane foam are compared, it has special premium properties aspect fire-retardant, it is in light weight, rigidity is big, dimensional stability is good, chemical resistance is strong, good heat resistance, difficult combustion, from putting out, low smog, flame resistant penetrates, meet fire and do not have unrestrained thing, cheap, be electrical equipment, instrument, building, the insulation heat-insulation and heat-preservation material that industries such as petrochemical industry are comparatively desirable, thereby be subjected to people's extensive attention.At present, phenol formaldehyde foam has become one of kind with fastest developing speed in the foamed plastics, and consumption figure constantly increases, and range of application constantly enlarges, and research and development is all quite active both at home and abroad.Yet the weakness of phenol formaldehyde foam maximum is that fragility is big, the percent opening height.
Summary of the invention
The phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and the continuous production technology thereof that the purpose of this invention is to provide a kind of good toughness.
For achieving the above object, the technical solution used in the present invention is:
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is made up of upper and lower metal covering color steel and middle Phonelic foam sandwich board, and it is characterized in that: the compositing formula of described Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 2-8
Blowing agent 3-9
Catalyst 1-5
Stabilizing agent 0.5-1.5
Curing agent 20-30
More than be all weight portion in the prescription.
According to described phenolic aldehyde foam double-metal-face chromatic steel sandwich plate, it is characterized in that: the compositing formula of described Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 5
Blowing agent 6
Catalyst 3
Stabilizing agent 1
Curing agent 25
More than be all weight portion in the prescription.
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate production technology is characterized in that: comprise the steps:
At first prepare phenolic resins, in the reactor that has agitator, reflux condenser, thermometer, according to phenol: the ratio of formaldehyde=1: 1.0-4.8 adds phenol, 37% formalin and 20% baryta water and begins to stir, be warming up to 85 ℃, reaction is 4-5 hour under this temperature, adding aqueous hydrochloric acid solution transfers pH value till the 6.8-7, be warming up to 100 ℃ of backflows, add oxalic acid, the thickening of reducing pressure again, it is 2500-3000mPa (25 ℃) that sampling makes discharging viscosity, this is a reaction end, cooling discharging promptly gets phenolic resins;
Then according to above-mentioned Phonelic foam sandwich board compositing formula, phenolic resins, levelling agent, blowing agent, catalyst, stabilizing agent are added thermal agitation according to ratio separately in retort, add curing agent then, by mixing bunker mixing debugging, form and mix stoste, promptly get the Phonelic foam sandwich board constitutive material, mix stoste and be sprayed onto in the color steel polymerization reaction take place in 30-60 ℃ one-tenth press by muzzle.
Serialization phenolic aldehyde foam double-metal-face chromatic steel sandwich plate material belongs to the organic rigid foam metal of macromolecule sintetics, be to form through die mould with color steel by the thermosetting phenolic resin foaming, it have lightweight, fire prevention, chance naked light do not burn, smokeless, nontoxic, do not have under drippage, serviceability temperature scope wide (196～+ 200 ℃), the low temperature environment do not shrink, advantage, especially good toughness such as not embrittlement.
The specific embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further described:
Embodiment one:
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is made up of upper and lower metal covering color steel and middle Phonelic foam sandwich board, and the compositing formula of Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 2
Blowing agent 3
Catalyst 1
Stabilizing agent 0.5
Curing agent 20
More than be all weight portion in the prescription.
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate production technology comprises the steps:
At first prepare phenolic resins, in the reactor that has agitator, reflux condenser, thermometer, according to phenol: the ratio of formaldehyde=1: 1.0-4.8 adds phenol, 37% formalin and 20% baryta water and begins to stir, be warming up to 85 ℃, reaction is 4-5 hour under this temperature, adding aqueous hydrochloric acid solution transfers pH value till the 6.8-7, be warming up to 100 ℃ of backflows, add oxalic acid, the thickening of reducing pressure again, it is 2500-3000mPa (25 ℃) that sampling makes discharging viscosity, this is a reaction end, cooling discharging promptly gets phenolic resins;
Then according to above-mentioned Phonelic foam sandwich board compositing formula, phenolic resins, levelling agent, blowing agent, catalyst, stabilizing agent are added thermal agitation according to ratio separately in retort, add curing agent then, by mixing bunker mixing debugging, form and mix stoste, promptly get the Phonelic foam sandwich board constitutive material, mix stoste and be sprayed onto in the color steel polymerization reaction take place in 30-60 ℃ one-tenth press by muzzle.
Embodiment two:
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is made up of upper and lower metal covering color steel and middle Phonelic foam sandwich board, and the compositing formula of Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 8
Blowing agent 9
Catalyst 5
Stabilizing agent 1.5
Curing agent 30
More than be all weight portion in the prescription.
The phenolic aldehyde foam double-metal-face chromatic steel sandwich plate production technology is with embodiment one.
Embodiment three:
A kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is made up of upper and lower metal covering color steel and middle Phonelic foam sandwich board, and the compositing formula of Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 5
Blowing agent 6
Catalyst 3
Stabilizing agent 1
Curing agent 25
More than be all weight portion in the prescription.
The phenolic aldehyde foam double-metal-face chromatic steel sandwich plate production technology is with embodiment one.
Embodiment recited above is described preferred implementation of the present invention; be not that design of the present invention and scope are limited; under the prerequisite that does not break away from design concept of the present invention; common engineers and technicians make technical scheme of the present invention in this area various modification and improvement; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection all is documented in claims.
Resin viscosity is very big to foaming condition and foaming quality influence, and viscosity is too big, and each component is difficult for mixing during foaming, and since mobile poor, cause towards the film difficulty, and viscosity is crossed and is easy to when hanging down escape, and bubble appears, the bubble phenomenon of collapsing, so viscosity should be controlled between the 2500-3000mPa (25 ℃).When the water content in the resin was too high, owing to steam causes that lather quickness is slow, expansion ratio was little in foaming and the maturing process, otherwise, reduce water content because resin viscosity increases, cause the foaming operation difficulty, discover that the water yield should be controlled at about about 5%.
On, following color steel is respectively by last, unreeling of following unreeling machine, according to the different templates of different client's needs through on different, following press embossing, the stirring of in different retort, heating respectively of phenolic resins and curing agent, work by the resin pump is in order to 2-6: 1 ratio is mixed in stirring-head and is ejected on the molded following colour film, go up then, following colour film outer rim is alignd in the make-up machine that enters 30-60 ℃, through a series of chemical reaction and last, following colour film is bonded together through the high strength die mould and passes through forming press, the size different according to customer requirement, cut by cutting machine again, become finished product.
Serialization is produced phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and is belonged to the New Building Materials industry, be that country greatly develops the project that the energy-saving and environmental protection policy is given special assistance to, be mainly used in insulation, building partition, exterior wall composite plate, suspended ceiling, abatvoix of industrial pipelines such as the cold insulation of freezer and petrochemical industry and equipment etc.
Serialization phenolic aldehyde foam double-metal-face chromatic steel sandwich plate material belongs to the organic rigid foam metal of macromolecule sintetics, be to form through die mould with color steel by the thermosetting phenolic resin foaming, it have lightweight, fire prevention, chance naked light do not burn, smokeless, nontoxic, do not have under drippage, serviceability temperature scope wide (196～+ 200 ℃), the low temperature environment do not shrink, not embrittlement, be the desirable heat-insulating material of HVAC Refrigeration Engineering.Because phenol formaldehyde foam rate of closed hole height, then thermal conductivity factor is low, and heat-proof quality is good, and has a water resisting property and water vapour permeability, is desirable heat insulating energy saving material.Because phenolic aldehyde has benzene ring structure, thus dimensionally stable, rate of change＜1%, and chemical composition stability, anticorrosion anti-aging, particularly ability organic solution, strong acid, weak base corrosion.
In production technology foaming, make blowing agent, meet international environmental protection standard without freon, and contain hydrogen in its molecular structure, oxygen, carbon, during pyrolytic, the gas that overflows is nontoxic, tasteless, and is all harmless to human body, environment, meets national environment protection requirement.Therefore, phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is optimal fire prevention, thermal insulation, environment-friendly and green insulation material energy-conservation, attractive in appearance
Phenol formaldehyde foam and common macromolecule resin rely on and add the material that fire retardant obtains the different of essence are arranged, in fire, do not burn, do not melt, can not distribute toxic smog yet, and have the insulation of light weight, nontoxic, no burn into, energy-conservation, sound insulation, an advantage such as inexpensive, and foam without freon, non-environmental-pollution, good, the easy construction of processability, its combination property is that present various insulation material is incomparable, it is undesirable to have solved other organic material fire protecting performance, and the inorganic material water absorption rate is big, problem such as skin urtication when " dewfall ", construction easily.
Below with regard to used blowing promotor, foaming mechanism in the phenol formaldehyde foam preparation with foam is toughness reinforcing is introduced.
One, blowing promotor
1, catalyst/curing agent
Phenol formaldehyde foam generally is to prepare under room temperature or low-heat condition, therefore needs with acid as catalyst, when acid as catalyst, acid can be quickened the polycondensation reaction between molecular resin, the reaction liberated heat impels blowing agent sharply to gasify, and emulsifying resins is swelled, simultaneously resin solidification.Catalyst for reaction also is the curing agent of resin.The type of curing agent and quantity are extremely important to obtaining good quality froth at ambient temperature.The selection of curing agent should make the curing rate and the expansion rate coupling of polymer.Therefore, require used curing agent that curing rate is changed in very wide scope, curing reaction itself can carry out under lower temperature again.
Curing agent divides inorganic acid and organic acid, inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid etc.Organic acid has oxalic acid, adipic acid, benzene nitric acid, phenol nitric acid, toluenesulfonic acid, benzene sulfonic acid, mahogany acid etc.The inorganic acid price is low, but curing rate is too fast, and metal is had very strong corrosiveness, the therefore anticorrosion a great problem that becomes in the phenol formaldehyde foam use.Studies show that, can utilize dilution inorganic acids such as methyl alcohol, ethanol, propyl alcohol to reach inhibition, also can add corrosion inhibitor such as calcium oxide, iron oxide, calcium carbonate, borax anhydrous, alkali metal and alkaline earth metal carbonate and zinc, aluminium etc.Someone has considered to handle foam with the alkali nertralizer, but the validity of this method still is confirmed at the end.The research of relevant this respect is also underway.Document was once reported, and used acid naphthalene sulfonic acids phenolic aldehyde not only to play catalytic action but also participated in the condensation reaction of phenolic aldehyde, had reduced sour permeability, and was also just very little to corrosion of metal.Also mention other in the document and reduce foamed material corrosivity method, at first remove volatile matter in the shaped article when making curing agent, use NH again with vacuum method with hydrochloric acid
3Remove remaining acid or heat treatment under 80-130 ℃ of condition, or add nertralizer etc. at resin formula, these methods make complex manufacturingization, and increase cost.
The curing agent that present employing aromatic sulfonic acid is the basis is very general.This is because its corrosivity is little, and has plasticization.Also have organic acid and inorganic acid are mixed use.For guaranteeing to be uniformly dispersed, solid-state organic sulfonic acid should be made into the aqueous solution of high concentration during use, the concentration of general solution is advisable at 40-65%.
2, blowing agent
Blowing agent is that the plastic foamed method in source of foaming power in the plastic foamed moulding generally is divided into mechanical foaming, physical blowing and chemical blowing.Mechanical foaming is the strong agitation by means of machinery, gas is sneaked into equably form bubble in the resin.Physical blowing then is by means of the change that is dissolved in the blowing agent physical state in the resin, forms a large amount of bubbles.More than two kinds of foaming be physical process fully, any chemical change does not take place.Chemical blowing is to make CBA generation chemical change in the foaming process, thereby decomposes and produce a large amount of gases, and foaming process is carried out.The kind and the consumption of blowing agent have material impact to foaming effect.It directly influences foam density, and then has influence on physics, the mechanical performance of product.In addition, use blowing agent to make foam have a large amount of spherical micropores, foam flame resistance and toughness improve.
According to phenolic resins foamable reaction mechanism, great majority carry out with physical foaming method.Physical blowing agent divides inert gas and low-boiling point liquid two classes.The blowing agent that phenol formaldehyde foam is commonly used is the volatile liquids of various boiling points between 30-60 ℃, as freon, chlorinated hydrocabon, pentane etc.The blowing agent overwhelming majority who uses in present scientific research and the plant produced remains HCFC, and is wherein the most extensive with (mol) mixture use in 1: 4 of freon-21 with freon 1.Fluorochlorohydrocarbon blowing agent effect is very good, but fluorochlorohydrocarbon can destroy the ozone layer of atmosphere, so limited use and begun to select substitute.In recent patent,, selected to endanger little fluorochlorohydrocarbon,, be called as the blowing agent that does not consume ozone as CF32CF2CHC12, HCF2CF2CEt for reducing harm to atmospheric ozone layer.The somebody adopts the use amount that reduces the fluoride blowing agent, adds the part substitute, mixes use as F-11 and pentane.The most promising inert gas blown agent carbon dioxide, the nitrogen etc. of surely belonging in new substitute.They are nontoxic, pollution-free, and ozone-depleting coefficient (ODP) is zero, and (GwP) is very little for the greenhouse effects coefficient, does not fire, and be cheap and easy to get, be the focus of freon substitute research, but difficulty is higher.The good news is bibliographical information, the researcher of the Asahi chemical company of Japan uses CO
2Replace fluorochlorohydrocarbon to make to produce the blowing agent of phenolic foam material, respond well.They are by phenolic aldehyde copolymer resins (containing methylolurea) and blowing agent CO
2Reach the awake foamed material of phenol that catalyst mixture makes.Its airtight air vent content is 96.0%, and hole diameter is 190 μ m, and thermal conductivity (JISA1412) is 0.0231Kcal/m.h. ℃, CO
2Content is 5.2%, and brittleness (JIS A9511) is 11%.The most frequently used with carrene in the chlorinated hydrocabon, its chemical property is comparatively stable, gas forming amount also is higher than fluorochlorohydrocarbon, so the replacements fluorochlorohydrocarbon that existing in recent years many producers use or the two usefulness also.In plastic foamed industry, select for use low boiling aliphatic alkane G4-G7 mixture such as pentane as blowing agent, but its effect is undesirable, also has inflammable danger.Sometimes the way by several blowing agents and usefulness solves the problem that blowing agent vapourizing temperature and resin solidification reaction speed are complementary, and blowing agent is when vaporization like this, and resin has had suitable viscosity, thereby helps the formation of foam structure and stable.
CBA also has application, and as blowing agent H (N, N one dinitroso five methine tetramines), it meets acid decomposition strongly, discharges nitrogen, thereby makes resin expanded.
3, surfactant
Contain hydrophilic-structure and hydrophobic structure in the molecule of surfactant, capillary effect with interface trend and reduction liquid resin, make the emulsifying raw material that hydrophily and hydrophobicity differ greatly in the foamed plastics become homogeneous system, each component fully contacts, and various reactions can be carried out more evenly.Though the consumption of surfactant is little, be the 2-6% of resin only, it is very big to foam process and properties of product influence.It can guarantee that each component fully mixes in the foaming process, forms evenly fine many foam structures and stable rate of closed hole, can also accelerate course of reaction, shortens hardening time, and to the compression strength of foamed product, abscess-size etc. all have bigger influence.
The foam plastic foaming moulding divides three phases usually.Phase I is to form a large amount of evenly fine and closely woven nuclei of bubbles in the melt of foaming matrix or liquid, and then expand into the foam with requirement foam structure, and by heating, solidifying and setting obtains foam plastic product at last.Foaming is that will to make with the blowing agent be that decentralized photo, resin are the emulsion of continuous phase the phase I, in resin, form be evenly distributed in a large number, blowing agent drop (nuclei of bubbles) that particle diameter is small.As with high-speed stirred blowing agent being distributed in the resin merely, this dispersion is extremely unstable, destroys easily.Surfactant can reduce interfacial tension, makes dispersion stable on thermodynamics.At this moment surfactant has played the effect of emulsifying agent or foam stabilizer.When under high-speed stirred, when adding curing agent in the emulsion of phenolic resins and blowing agent, the phenolic foam moulding has entered second stage.A-stage resin generation condensation reaction under the curing agent effect, be converted into the B-stage resin stage, final curing is a C-stage resin, a large amount of reaction heat that the while resin condensation discharges make the blowing agent droplets vaporize, and foamed material is in retrogradation, and volume increases rapidly, original emulsion has been transformed into foam, this foam is unsettled, and established bubble can continue to expand, and also may merge, subsides or break.There is not solidifying and setting front surface activating agent to play a part stable foam at phenol formaldehyde foam.
Compatibility between each component of phenolic foam is relatively poor, so select for use surfactant more will consider its emulsifiability.The good emulsifying performance can improve the uniformity coefficient that each component is mixed, and helps forming evenly fine foam structure, and can accelerate course of reaction, shortens hardening time.This external surfactants also must keep stable to the highly acid of curing agent.Although it is a lot of to be used for the kinds of surfactants of phenolic foam, the nonionic surface active agent effect is best, than 1. aliphatic alcohol polyethenoxy, the polyoxypropylene ethers of having commonly used; 2. APES class is as the addition product of nonyl phenol and oxirane; 3. the block copolymer of polysiloxanes, polyoxyethylene, polyoxypropylene, this class surfactant not only has good foam stabilization performance, and extremely strong emulsification is arranged.
Also there is the researcher to adopt the kinds of surface active agent intermixture to obtain having the foam of particular characteristic in recent years, makes the high-hydroscopicity foam as the surfactant that usefulness silicone such as Ikeda justice is grand mix with neopelex.
Two, foam Research on Toughening
The structural weak link of phenolic resins is the easy oxidation of phenolic hydroxyl group and methylene.Its foam percentage elongation is low, and matter is crisp, and hardness is big, not anti-bending.This has limited the application of phenol formaldehyde foam greatly, so be very necessary to the toughness reinforcing of foam.Phenol formaldehyde foam toughness reinforcing, can realize by following several approach: 1. flexibilizer outside system adds, the mode by blend reaches toughness reinforcing purpose; 2. by the chemical reaction of resol and flexibilizer, reach toughness reinforcing purpose; 3. replace phenol synthetic resin with the modified phenol that is partly with the toughness chain.
1, adds outer flexibilizer
This modification mode requires resin and toughened system must have certain compatibility, could improve its fragility, improves toughness and compressive property, can be according to the compatibility between the solubility parameter δ prediction organic compound.The enforcement of this modification mode generally is to carry out as follows.At first synthetic common resol adds modifier then in system, dehydration, foaming.This class modifier is commonly used three classes.
The first kind is a rubber elastomer modifier.Rubber toughened phenolic resins belongs to physics blending modification, but because elastomer has active end group (as carboxyl, hydroxyl etc.) and two key usually, can take place with the methylol in the resol in various degree connect the school or block copolymerization is reacted.These rubber-like elastomeric segments generally can be separated out from matrix in resin solidification and foaming process, form the island two phase structure physically.The fracture toughness of this rubber toughened thermosetting resin and foam has by a relatively large margin raising compared with not toughness reinforcing resin and foam.Rubber commonly used has butyronitrile, butylbenzene, natural rubber and nbr carboxyl terminal and other to contain the rubber of active group.Toughness reinforcing effect is also relevant with blend ratio etc., and rubber mass does not reach effect very little, but if rubber content is higher, influence hear resistance, and the while also can influence the compatibility between phenolic aldehyde rubber.The addition of rubber generally should be controlled between the 5-20%.
Second class is a thermoplastic resin.The polyvinyl alcohol that has that is used for the phenol formaldehyde foam modification, polyethylene glycol etc.Hydroxyl in the polyvinyl alcohol molecule might with the methylol generation chemical reaction in the phenol-aldehyde condensation polyme, form graft copolymer.Polyvinyl alcohol modification phenolic resins can improve the compressive strength of foam.According to the literature, foam compression intensity is relevant with the addition of polyvinyl alcohol.The amount that adds polyvinyl alcohol very little, compressive strength improves not obvious; The polyvinyl alcohol that added volume can cause sticking pot, makes reaction be difficult to proceed.The addition of polyvinyl alcohol is that the 1.5-3% of phenol weight is comparatively suitable.
Polyethylene glycol also is the effective flexibilizer of phenolic resins.OH in the polyethylene glycol may combine with the OH in the resin, but reaction is difficult under alkali condition.OH in the polyethylene glycol and the OH in the resin also may form the part hydrogen bond, make to import long flexible ether chain in the resin, thereby play toughness reinforcing effect.Human different molecular weight polyethylene glycol such as Ge Dongbiao series is come toughness reinforcing foam, finds that modified effect increases along with the increase of molecular weight polyethylene glycol, and molecular weight is to reach peak value at 1000 o'clock, and the increase along with molecular weight polyethylene glycol then reduces.Given conclusion is: along with the increase of molecular weight, the polyethers flexible chain that imports in the phenolic resins is long earlier, helps hot strength and elongation at break and increases; But molecular weight polyethylene glycol was greater than 1000 o'clock, because it is certain adding the quality of people's polyethylene glycol, the shared ratio of its strand two terminal hydroxy groups reduces relatively, makes the probability of methylol reaction of hydroxyl and phenolic resins reduce, and has influenced the modified effect of polyethylene glycol.The foam toughness of cetomacrogol 1000 that molecular weight is moderate and 800 modifications is best.
The phenol formaldehyde foam of polyethylene glycol toughening modifying is compared with pure phenol formaldehyde foam, and not only dimensional stability is good, compressive strength is high, apparent density is moderate, and the abscess rate of closed hole is higher, the size is even, fine and close, and easily processing cutting, and section does not have or few chip.Haloflex (CPE), polyvinyl chloride (PVC) toughened resin and foam also have report in addition.
The 3rd class is small-molecule substance such as ethylene glycol.After the toughness reinforcing foam of ethylene glycol is novolak resin, adds ethylene glycol by a certain percentage and mix, add stabilizing agent, blowing agent, equal infusion successively, stir, add curing agent, vigorous stirring then, pour in the ready mould group's mould foaming rapidly into, treat its completion of cure after the demoulding get final product.
Someone infers that according to the difference of the infrared spectrogram of pure phenol formaldehyde foam and glycol-modified phenol formaldehyde foam (ethylene glycol content is phenol amount 15%) ethylene glycol may partly or entirely generate the derivative of glycerine alcohols under the acid catalysis effect, has participated in main reaction.The adding of ethylene glycol can improve the performance of phenol formaldehyde foam to a certain extent, improves its compressive strength, improves its fragility, and don't loses its anti-flammability too much, and optimum amount is 10-15 part/100 part resins.This moment, its oxygen index (OI) was 37-38, and compressive strength is 0.40MPa, and density is 0.059g/cm3, and is as shown in table 1.
Table 1 foaming properties and ethylene glycol addition
| A | B | C | D | E | F | |
| Ethylene glycol/w% | 25 | 20 | 15 | 10 | 5 | 0 |
| Density/g.cm 3 | 0.064 | 0.06 | 0.059 | 0.058 | 0.056 | 0.062 |
| Compressive strength/MPa | 0.30 | 0.35 | 0.40 | 0.37 | 0.38 | 0.31 |
| Oxygen index (OI) | 35 | 37 | 37 | 38 | 38 | 40 |
Adding chopped glass fiber also is outer toughness reinforcing a kind of method.Chopped glass fiber belongs to inorganic material, and is colourless under the normal temperature, tasteless, nontoxic, easy and phenolic resins mixing.Chopped glass fiber is after with coupling agent treatment, and with the phenolic resins blend, phenolic foam is made in foaming then.Chopped glass fiber content sees Table 2 to the influence of modified phenolic foam plastic main performance.
Short fine content and the phenol formaldehyde foam performance of cutting brokenly of table 2
| Chopped glass fiber/w% | 0 | 3 | 4 | 5 | 6 | 8 | 10 |
| Unit weight/kg.cm 3 | 60 | 60 | 60 | 60 | 62 | 68 | 80 |
| Fragility mass loss/% | 40.0 | 28.0 | 25.0 | 22.0 | 21.0 | 17.7 | 15.0 |
| Oxygen index (OI) | 45 | 45 | 46 | 48 | 48 | 50 | 50 |
| Compressive strength/MPa | 0.20 | 0.25 | 0.26 | 0.28 | 0.31 | 0.39 | 0.43 |
As shown in Table 2, increase along with chopped glass fiber content, the compressive strength of phenolic foam obviously improves, unit weight increases, fragility reduces, and oxygen index (OI) raises, but the viscosity of blend raises along with the increase of chopped glass fiber content, make foam process be difficult to control, so the content of chopped glass fiber generally is controlled at below 10%.It is toughness reinforcing that document has reported that also organic substances such as dioctyl phthalate, tricresyl phosphate are used for foam.
2, chemical toughness reinforcing resol
The chemistry toughening modifying method is to add modifier when synthetic A-stage resin, by flexible chain in the chemical reaction grafting of phenolic hydroxyl group and methylol, thereby obtains the modification A-stage resin of intrinsic toughening, and this method of modifying will be got well than the effect of blend method.
Polyurethane-modified phenol formaldehyde foam is a kind of good chemical method for toughening, has carried out series of studies in Japan, the U.S., has obtained achievement preferably.See following 2 kinds of modes from the method that adopts: 1. with furfuryl alcohol resin, arylamine polyalcohol etc. as the polyol the polyurethane component, phenolic resins, polyisocyanates (MDI, PAPI) and above-mentioned various polyalcohol are mixed, and auxiliary agents such as adding blowing agent carry out composite foamed.2. polyethers, the synthetic end of the pure and mild isocyanates of polyester polyols are the performed polymer of a NCO group, mix with phenolic resins, blowing promotor again, carry out composite foamed.
In polyurethane-modified phenol formaldehyde foam preparation process, no matter adopt which kind of method of modifying, its reaction mechanism is consistent.Mainly contain two kinds of reactions and take place, 1. the hydroxyl of the polyol in isocyanate groups and the component carries out crosslinked or chain extending reaction; 2. the methylol in isocyanate groups and the resol carries out cross-linking reaction.The result of two kinds of reactions has introduced the pliability segment in phenolic aldehyde rigid molecule structure, fundamentally changed the rigid molecule structure of phenolic resins, thereby has improved the toughness of foamed product, has reduced fragility; Introduced the characteristic of polyurethane simultaneously, as improving rate of closed hole, reduced water imbibition, accelerated curing reaction speed, moulding is fast, has also improved the intensity of goods.
With TDI and molecular weight is the reaction of 1000 polyethylene glycol, the synthetic performed polymer modified phenolic foam that has a NCO group, and its performance is as shown in table 3.
Table 3 TDI modified poly (ethylene glycol) toughening metlbond foam performance
| Compressive strength/MPa | Density/kg.cm 3 | Water absorption rate/% | Oxygen index (OI) |
| 0.288 | 0.1771 | 14.39 | 38.3 |
3, replace phenol synthetic resin with the modified phenol that is partly with the toughness chain
The 3rd class method of modifying is to replace phenol and formaldehyde condensation with the toughness material part that contains with the similar functional group of phenol, thereby reaches toughness reinforcing purpose.Modifications such as bibliographical information resorcinol, orthoresol, paracresol, hydroquinones are arranged.Addition is controlled at 0.2-10%, can reduce foam brittleness, improves the intensity and the toughness of goods.Alkyl phenol and cashew nut oil modified report arranged all also.With the monoene or the diolefin long-chain of 15 carbon, so feature of the existing phenolic compound of cashew nut shell oil has the flexibility of aliphatic compound again to the cashew nut shell oil primary structure, uses its modified phenolic foam on position between phenol, and toughness has clear improvement.
Attempt with tung oil and modification of flax oil phenol also someone, the conjugated triene in the tung oil under acid catalysis with the reaction of phenol generation kation alkyl, wherein residual two keys are because empty inhibition effect, the probability of participating in reaction is very little.Product under base catalysis further with formolite reaction, generated tung oil-modified resol.Linseed oil is the octatecatrienoic acid glyceride, and three two keys are all arranged in its molecular structure.Under the effect of catalyst, alkylated reaction takes place in the carbon atom on the ortho para of phenol on two keys of linseed oil, synthesis modification phenol, modification phenol and formaldehyde copolymerization then, submissive alkyl chain has linked the phenolic aldehyde strand of fragility not, has improved phenol formaldehyde foam fragility effectively.
Claims (3)
1, a kind of phenolic aldehyde foam double-metal-face chromatic steel sandwich plate is made up of upper and lower metal covering color steel and middle Phonelic foam sandwich board, and it is characterized in that: the compositing formula of described Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 2-8
Blowing agent 3-9
Catalyst 1-5
Stabilizing agent 0.5-1.5
Curing agent 20-30
More than be all weight portion in the prescription.
2, phenolic aldehyde foam double-metal-face chromatic steel sandwich plate according to claim 1 is characterized in that: the compositing formula of described Phonelic foam sandwich board is as follows:
Phenolic resins 100
Levelling agent 5
Blowing agent 6
Catalyst 3
Stabilizing agent 1
Curing agent 25
More than be all weight portion in the prescription.
3, the described phenolic aldehyde foam double-metal-face chromatic steel sandwich plate production technology of claim 1 is characterized in that: comprise the steps:
At first prepare phenolic resins, in the reactor that has agitator, reflux condenser, thermometer, according to phenol: the ratio of formaldehyde=1: 1.0-4.8 adds phenol, 37% formalin and 20% baryta water and begins to stir, be warming up to 85 ℃, reaction is 4-5 hour under this temperature, adding aqueous hydrochloric acid solution transfers pH value till the 6.8-7, be warming up to 100 ℃ of backflows, add oxalic acid, the thickening of reducing pressure again, it is 2500-3000mPa (25 ℃) that sampling makes discharging viscosity, this is a reaction end, cooling discharging promptly gets phenolic resins;
Then according to the described Phonelic foam sandwich board compositing formula of claim 1, phenolic resins, levelling agent, blowing agent, catalyst, stabilizing agent are added thermal agitation according to ratio separately in retort, add curing agent then, by mixing bunker mixing debugging, form and mix stoste, promptly get the Phonelic foam sandwich board constitutive material, mix stoste and be sprayed onto in the color steel polymerization reaction take place in 30-60 ℃ one-tenth press by muzzle.
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| CN 200910015329 CN101602275B (en) | 2009-05-18 | 2009-05-18 | Phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof |
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| CN 200910015329 CN101602275B (en) | 2009-05-18 | 2009-05-18 | Phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof |
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| CN102501469A (en) * | 2011-10-12 | 2012-06-20 | 山东圣泉化工股份有限公司 | Phenolic aldehyde color steel sandwich panel and preparation method thereof |
| CN103481591A (en) * | 2013-09-23 | 2014-01-01 | 山东圣泉化工股份有限公司 | Sandwich composite board with metal surfaces |
| CN104213688A (en) * | 2013-05-29 | 2014-12-17 | 钟祥鼎茂科技有限公司 | Production method for environment-friendly inflaming retarding and heat insulation light color steel composite plate |
| CN105971219A (en) * | 2016-06-24 | 2016-09-28 | 湖州千豪家私有限公司 | Leather decoration ceiling |
| CN107151542A (en) * | 2017-07-12 | 2017-09-12 | 康利源科技（天津）股份有限公司 | The formula of electrical laminated wood alcohol-soluble phenolic resin |
| CN107815064A (en) * | 2017-11-21 | 2018-03-20 | 广西吉宽太阳能设备有限公司 | A kind of flame-proof phenolic cellular insulant and preparation method thereof |
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| CN115302917A (en) * | 2022-08-29 | 2022-11-08 | 山东北理华海复合材料有限公司 | Metal surface phenolic foam sandwich board for building |
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| CN107815064A (en) * | 2017-11-21 | 2018-03-20 | 广西吉宽太阳能设备有限公司 | A kind of flame-proof phenolic cellular insulant and preparation method thereof |
| CN114316185A (en) * | 2022-01-11 | 2022-04-12 | 黎明化工研究设计院有限责任公司 | Toughened, mildewproof and antibacterial full-water-based foaming polyurethane foam and preparation method and application thereof |
| CN114316185B (en) * | 2022-01-11 | 2023-10-31 | 黎明化工研究设计院有限责任公司 | Toughened mildew-proof antibacterial all-water-based foaming polyurethane foam and preparation method and application thereof |
| CN115302917A (en) * | 2022-08-29 | 2022-11-08 | 山东北理华海复合材料有限公司 | Metal surface phenolic foam sandwich board for building |
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