CN102504153A - Method for preparing foaming phenolic formaldehyde resin - Google Patents
Method for preparing foaming phenolic formaldehyde resin Download PDFInfo
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- CN102504153A CN102504153A CN2011103512489A CN201110351248A CN102504153A CN 102504153 A CN102504153 A CN 102504153A CN 2011103512489 A CN2011103512489 A CN 2011103512489A CN 201110351248 A CN201110351248 A CN 201110351248A CN 102504153 A CN102504153 A CN 102504153A
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Abstract
The invention discloses a method for preparing a foaming phenolic formaldehyde (PF) resin. The foaming phenolic formaldehyde resin is synthesized by using paraformaldehyde and a phenol as raw materials, a mixture of a polyether polyol or a polyester polyol and nano particles as a modifier, and a mixture of hydrotalcite and barium hydroxide as a catalyst and by two-stage temperature control. The viscosity of the foaming phenolic formaldehyde resin is 1,000 to 3,000cps, and the solid content in the foaming phenolic formaldehyde resin is 75 to 85 percent. The compression strength (10 percent) of a phenolic thermal-insulation material prepared from the foaming phenolic formaldehyde resin reaches 0.29Mpa, the coefficient of heat conductivity is less than 0.03W/M, the density is 34.7 to 57.6kg/m<3>, the rate of closed cells is 94.8 to 99.2 percent, the oxygen index reaches 46.5 to 52.4, the water absorption rate is 1.10 to 1.92 percent, and the dimensional stability (v/v) is 0.27 to 0.49 percent. Compared with the conventional PF production process, the method does not comprise a dehydrating step and is environment-friendly without discharging waste water containing phenol and aldehyde.
Description
Technical field
The present invention relates to the preparation method of foamable resol.
Background technology
The heat-insulation and heat-preservation material is one of widely used material of building trade, at present abroad widespread use be foaming PF and foaming flame-retardant polyurethane, other occasions are mainly used inorganic heat insulation material.In China; Owing to price and other reasons, architecture exterior wall insulating materials is mainly the polystyrene foamed material at present, but because this material is not fire-retardant; In application, produced serious problem, therefore forbidden using as external-wall heat-insulation material from country in 2009.Domesticly need new novel material badly with fire-retardant, heat insulating functions and moderate substituting PS class.Wherein comparatively ideal substitute products are phenolic foam material.
Phenolic foamed plastics is at first invented at the World War II initial stage by Germany scientist Bayer, realizes suitability for industrialized production after 1940.The initial stage phenolic foamed plastics can substitute cork, at first is used in the aircraft industry.Under the condition that the resol suitability for industrialized production reaches its maturity, American-European, Japan begins one's study and develops low density phenol formaldehyde foam (PF) technology, and is applied to construction work as material of construction.The phenolic foamed plastics of Britain scientist development subsequently can be incubated lagging material and use, and it is grown up.To the fifties, U.S. UCC company the low density phenolic foamed plastics with resin on and aspect such as foam process carried out a large amount of research, make phenolic foamed plastics developed once more.60～seventies, the progress of phenolic foamed plastics ME, particularly Germany and France are developed into phenolic foamed plastics sandwich panel continuous production processes, have promoted the application of phenolic foamed plastics greatly.Along with the manufacturing technology of phenolic foamed plastics and the improvement and the development of equipment, the technology of large size foam board is day by day ripe, makes the performance of phenolic foamed plastics have more usability, and has unique flame retardant resistance and dimensional stability.
The phenolic composite that has comprised the PF foam since the nineties is developed on a large scale very much; At first receiving the militaries such as English, U.S.A payes attention to; Use it for space flight and aviation, defence and military field; After be applied to civilian aircraft, boats and ships, station again, the place that fire protection requirements such as oil well are strict, and progressively push fields such as Highrise buildings, hospital, Sports facilities to.To 21 century; Every field is higher to the requirement of material; The foamed phenolic resin material of exploitation can not satisfy the needs of development in science and technology in the past; The research to novel foamed phenolic resin material has been set about by a lot of countries in the world; Use different processes to make the phenolic aldehyde composite plastic, aspect the product development of novel phenolic resins and matrix material thereof and development, obtained certain achievement, but the novel phenolic resins surface is prone to efflorescence, internal structure is loose and size distortion greatly, defectives such as poor mechanical property are also solved at present at all; Therefore greatly limited it and applied aspect construction wall heat-insulation and heat-preservation, so development of new modified foaming phenolic resin material has great importance.
The main method of novolak resin is phenol, formaldehyde solution are reacted for some time under catalyst action after at present, makes through decompression dehydration again.Reaction process has produced considerable aldehyde-containing sewage, and the quality of product is unstable, the poor mechanical property of the foamed products of producing thus.
Roughly mainly contain and improve resol flexible approach: toughner outside 1. in resol, adding, like tree elastomer, paracril, nitrile rubber under the carboxyl, carboxylated nbr, styrene-butadiene rubber(SBR), terminal hydroxy group polyhutadiene, terminal hydroxy group polyhutadiene.Organosilicon and thermoplastic resin etc.; 2. in resol, add the intrinsic toughening agent, as make the phenolic hydroxyl group etherificate, at the long hydrocarbon chain (like cashew nut oil (CNSL), organosilicon, tung oil etc.) of the internuclear introducing of phenol and other flexible groups etc.; 3. use spun glass, strongtheners such as woven fiber glass improve fragility.Though during the outer toughner of these that use the intensity of resin is improved, contain alkene owing in the side chain, thermotolerance is affected, and the properties-correcting agent cost is also higher relatively.Though and intrinsic toughening agent such as cashew nut oil are improved the intensity of phenolic aldehyde, because the impurity (non-polymeric component) among the CNSL is more, and composition and contain the most differently because of the place of production, often cause product properties unstable [1-3].The comprehensive production status of resol at present; Though phenolic resin modified method is a lot; But be applicable to that foaming is not very desirable with the preparation of resol and the foam performance that makes thereof, and needs a kind of new simple method of demand to come resin is carried out modification for this reason.
Summary of the invention
But to the preparation process of present foamed phenolic resin and technology and be the deficiency of aspect of performance existence of the foam of feedstock production thus, but the present invention aims to provide a kind of preparation method of foamed phenolic resin.But foamed phenolic resin is as producing the fire-retardant heat insulation material.
But a kind of preparation method of foamed phenolic resin may further comprise the steps:
(1) be 94 by phenol and Paraformaldehyde 96 mass ratio: 45-60, in reactor drum, add phenol and the Paraformaldehyde 96 that accounts for proportional quantity 60-80%, make reactor drum be warmed up to 40-50 ℃, constant temperature 20-30min simultaneously; Described phenol is that mol ratio is 1: the phenol of 0.05-0.15 and Resorcinol mixture;
(2) adding mass concentration is the base catalysis agent solution of 10-30%, hydrotalcite in the alkaline catalysts and Ba (OH)
2Mass ratio be 1: 1, add-on is the 5-20% of phenol quality, under 40-50 ℃ of condition, heats 10-20min, is warming up to 70-80 ℃ of down reaction 30-60min then;
(3) adding mass ratio is 1: the properties-correcting agent that the mixture of the polyether glycol of 1-3: 0.2-0.5, the pure and mild nano particle of polyester polyols is formed, and the add-on of properties-correcting agent is the 3-10% of phenol quality; The number-average molecular weight of polyester polyol is 400-600; The number-average molecular weight of polyether glycol is 100-200; Nano particle is the nano particle of wilkinite, zeyssatite or silicon-dioxide, and the granularity 80-100 order of nano particle reacts 10-30min again; Described polyether glycol is the addition polymer of glycerine, terepthaloyl moietie, Ucar 35, TriMethylolPropane(TMP), tetramethylolmethane, triethylene diamine, trolamine, quadrol and propylene oxide; Polyester polyol is organic di-carboxylic acid, acid anhydrides and polyolcondensation product;
(4) add remaining Paraformaldehyde 96 in (1) step, make temperature of reaction be upgraded to 90-100 ℃, under this temperature, react 60-90min;
(5) reaction system is cooled to 60-70 ℃, add acid acceptor, the pH value of regulation system is 7, and neutralizing agent is that mass concentration is hydrochloric acid or the sulfuric acid of 10-30%; Reduce to the room temperature discharging, but obtain foamed phenolic resin.
Through detecting, but the viscosity that obtains foamed phenolic resin is 1000-3000cps, solid content 75-85%.
But foamed phenolic resin of the present invention, by 100 parts in proportioning resol, 2 parts of emulsifying agents, 6 parts of whipping agents, solidifying agent foams as producing the fire-retardant heat insulation material for 12 parts.The preparation process is following: it is even with resol and emulsifier mix to press proportional quantity, adds whipping agent then and stirs, and fully adds solidifying agent behind the mixing again and stirs; Mix; Pour into rapidly in the mould at 60-75 ℃ of foaming 10min, after the 30min slaking, take out again, promptly obtain phenolic foam material.The performance of the phenolic foam material of producing is seen table 1.Can know that from analytical results the performance of the pnenolic aldehyde foam material of gained meets the index request of ISO4896-84 phenolic foams international standard fully.
Beneficial effect: characteristics of the present invention are: (1) adds the curing speed that Resorcinol can be accelerated resin, also can improve intensity.(2) add the properties-correcting agent that the pure and mild bentonitic mixture of polyether glycol, polyester polyols is formed simultaneously, polyether glycol can not only be well and resin compatible, and hydroxyl wherein can generate ehter bond with the phenolic hydroxyl group condensation in the resin; Also can carry out aldol reaction with formaldehyde; So just be equivalent between a plurality of molecular resins, insert a flexible blocks, small molecules in the resin is connected together, so the interlaminar resin chain be elongated; Space structure obtains changing, and snappiness is improved.Nano particle is because the singularity of surface and structure has the property that some other materials are difficult to obtain, because the dimensional effect and the surface effects of nanoparticle; Can well be dissolved in all be dispersed in the resin matrix, the mixture of compatible and bonding of generation nanoscale is after resin is processed foam material; Receive when impacting at matrix, crack between particle and matrix, along with the granular of particle; Surface-area increases; Material receives and produces more crackle when impacting, and absorbs more energy, thereby reaches toughness reinforcing purpose.Simultaneously, inorganic nano-particle has stress concentration and stress radiating balancing effect, through absorbing impact energy and quantity of radiant energy, makes matrix thing obvious stress concentration phenomenon, reaches the mechanical balance state of matrix material.Inorganic nano-particle has the transmission ofenergy effect, and the matrix resin crack propagation is obstructed and passivation, finally possibly stop crackle, and the unlikely destructiveness that develops into ftractures, thereby reaches toughness reinforcing purpose.The nano particle that adds has simultaneously also increased the flame retardant resistance of resin.(3) in the reaction process, adding the 60-80% of Paraformaldehyde 96 total amount earlier, 70-80 ℃ of reaction down, at this moment mainly is that addition reaction takes place, and polycondensation is not also carried out, and thermal discharge reduces, and reaction is control easily; Add remaining Paraformaldehyde 96 again, under 90-100 ℃ of condition, react, at this moment system is mainly carried out polycondensation, and the Paraformaldehyde 96 that adds simultaneously also can carry out the part addition reaction with the activatory phenyl ring, but amount is few, and thermal discharge is limited.Divide two stages to carry out reaction process like this, not only simple to operate, and also exothermic heat of reaction controls easily, guaranteed the safety in the production process.
Compare with present traditional P F production technique, method of the present invention does not need dehydrating step, and reaction process is not discharged the waste water that contains phenol, aldehyde, but is the friendly process that foamed phenolic resin is produced.Production process is simple to operate, and the intensity of the foams of processing with the expandable phenolic resin of the present invention preparation is high, and over-all properties is excellent, is suitable for the manufacturing of various fire-retardant heat insulation materials.
Process detects, but obtains the viscosity 1000-3000cps of foamed phenolic resin, solid content 75-85%.
But the compressive strength with the phenol formaldehyde foam heat-insulating fireproof material of the foamed phenolic resin preparation of the present invention preparation reaches 0.29Mpa; Thermal conductivity is lower than 0.03W/M.K; Density is 34.7-57.6kg/m
3Rate of closed hole reaches 94.8-99.2%; Oxygen index reaches 46.5-52.4; Water-intake rate reaches 1.10-1.92%; Dimensional stability (v/v) reaches 0.27-0.49%.
Embodiment
Embodiment 1:
(1) is 94: 45 by phenol and Paraformaldehyde 96 mass ratio, in reactor drum, adds phenol and the Paraformaldehyde 96 that accounts for proportional quantity 80%, make reactor drum be warmed up to 40 ℃ simultaneously, insulation 20min; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) add mass concentration is the hydrotalcite of 10-30% and the base catalysis agent solution of hydrated barta composition, add-on be phenol quality 5%, under 40 ℃ of conditions, heat 10min, be heated to 70 ℃ and keep reacting 60min under this temperature then.
(3) adding mass ratio is the properties-correcting agent that the pure and mild wilkinite of polyether glycol, hexanodioic acid and Ucar 35 institute synthetic polyester polyols that 1: 1: 0.2 propylene oxide and glycerine condensation forms is formed, and the add-on of properties-correcting agent is 5% of a phenol quality, reacts 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose wilkinites.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, reaction 60min.
(5) cool to 60 ℃, the adding mass concentration is 10% hydrochloric acid neutralization, and regulating the pH value is 7, reduces to the room temperature discharging, obtains the transparent expandable phenolic resin liquid of light brown.
Institute's synthetic resin is detected; The free phenol (HG5-1342-1980) 4.30% of the expandable phenolic resin of the present invention's preparation; Free aldehyde (HG/T2622-1994) 1.20, the viscosity of resin (HG/T2712-95) 2650cps, solid content (GJB1059.1-90) 83.6%.Below the performance of products index of each embodiment all carry out check and analysis according to the method in the standard of using among the embodiment 1.
Embodiment 2:
(1) be to reactor drum in to add phenol at 94: 51 with Resorcinol with account for proportional quantity 75% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.08, makes reactor drum be warmed up to 45 ℃, soaking time 25min simultaneously.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) adding concentration is 25% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 7% of a phenol quality, under 45 ℃ of conditions, heats 10min, is heated to 70 ℃ and keep 60min then.
(3) add mass ratio be 1: 2: 0.2 by propylene oxide and terepthaloyl moietie synthetic polyether glycol, the properties-correcting agent of the pure and mild zeyssatite composition of suberic acid and terepthaloyl moietie synthetic polyester polyols, the add-on of properties-correcting agent is 6% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose zeyssatite.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 80min.
(5) cool to 60 ℃, the adding mass concentration is 15% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging, obtains the transparent expandable phenolic resin liquid of light brown.The free phenol 4.10% of this resol, free aldehyde 1.25%, the viscosity 2710cps of resin, solid content 82.7%.
Embodiment 3:
(1) be to reactor drum in to add phenol at 94: 54 with Resorcinol with account for proportional quantity 70% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.12, makes reactor drum be warmed up to 40 ℃ simultaneously.Soaking time 30min.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) adding concentration is 20% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 8% of a phenol quality, under 45 ℃ of conditions, heats 15min, is heated to 75 ℃ and keep 50min then.
(3) the adding mass ratio is 1: 2: 0.4 propylene oxide and a Ucar 35 synthetic polyether glycol, the properties-correcting agent that the pure and mild silicon-dioxide of Kui diacid and glycerine synthetic polyester polyols is formed, and the add-on of properties-correcting agent is 4% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 500; The number-average molecular weight of polyether glycol is 150; Nano particle is that granularity is 90 purpose silicon-dioxide.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 75min.
(5) cooling is at 60 ℃, and the adding mass concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown.The free phenol 3.30% of this resol, free aldehyde 1.42%, the viscosity 2470cps of resin, solid content 81.5%.
Embodiment 4:
(1) be to reactor drum in to add phenol at 94: 60 with Resorcinol with account for proportional quantity 60% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.15, makes reactor drum be warmed up to 50 ℃ simultaneously.Soaking time 20min.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) adding concentration is 10% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 20% of a phenol quality, under 50 ℃ of conditions, heats 20min, is heated to 80 ℃ and keep 30min then.
(3) add mass ratio be 1: 3: 0.4 by propylene oxide and TriMethylolPropane(TMP) synthetic polyether glycol; The properties-correcting agent of forming by phthalic acid and the pure and mild zeyssatite of tetramethylolmethane synthetic polyester polyols; The add-on of properties-correcting agent is 8% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose zeyssatite.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 98 ℃, and the reaction times is 90min.
(5) cooling is at 70 ℃, and the adding mass concentration is 25% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown.The free phenol 2.30% of this resol, free aldehyde 1.68%, the viscosity 2830cps of resin, solid content 83.5%.
Embodiment 5:
(1) be to reactor drum in to add phenol at 94: 57 with Resorcinol with account for proportional quantity 65% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.10, makes reactor drum be warmed up to 45 ℃ simultaneously, and the reaction times is 30min.Soaking time 25min, described phenol are that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 10%, add-on is 20% of a phenol quality, under 50 ℃ of conditions, heats 18min, is heated to 76 ℃ and keep 45min then.
(3) add mass ratio be 1: 2.5: 0.5 by propylene oxide and quadrol synthetic polyether glycol; The properties-correcting agent of forming by Tetra hydro Phthalic anhydride and the pure and mild wilkinite of glycerine synthetic polyester polyols; The add-on of properties-correcting agent is 5% of a phenol quality, reaction times 20min; The number-average molecular weight of used polyester polyol is 500; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose wilkinites.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 80min.
(5) cooling is at 70 ℃, and the adding mass concentration is 20% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown.The free phenol 2.68% of this resol, free aldehyde 1.52%, the viscosity 1870cps of resin, solid content 78.7%.
Embodiment 6:
(1) be to reactor drum in to add phenol at 94: 54 with Resorcinol with account for proportional quantity 70% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.10, makes reactor drum be warmed up to 45 ℃, soaking time 30min simultaneously.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 20%, add-on is 10% of a phenol quality, under 50 ℃ of conditions, heats 15min, is heated to 75 ℃ and keep 40min then.
(3) add mass ratio be 1: 2.0: 0.4 by propylene oxide and triethylene diamine synthetic polyether glycol; The properties-correcting agent of forming by toluene dicarboxylic acid anhydride and the pure and mild silicon-dioxide of butyleneglycol synthetic polyester polyols; The add-on of properties-correcting agent is 10% of a phenol quality, reaction times 15min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 150; Nano particle is that granularity is 80 purpose silicon-dioxide.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 80min.
(5) cooling is at 70 ℃, and the adding mass concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown.The free phenol 2.43% of this resol, free aldehyde 1.49%, the viscosity 2470cps of resin, solid content 82.1%.
Embodiment 7:
(1) be to reactor drum in to add phenol and Resorcinol at 94: 54 and account for proportional quantity 75% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.06, makes reactor drum be warmed up to 45 ℃ simultaneously, is incubated 30min.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 15%, add-on is 12% of a phenol quality, under 50 ℃ of conditions, heats 15min, is heated to 80 ℃ and keep 35min then.
(3) add mass ratio be 1: 2.5: 0.2 by propylene oxide and tetramethylolmethane synthetic polyether glycol; The properties-correcting agent of forming by isophthalic anhydride and the pure and mild wilkinite of terepthaloyl moietie synthetic polyester polyols; The add-on of properties-correcting agent is 8% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose wilkinites.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 75min.
(5) cooling is at 60 ℃, and the adding mass concentration is 15% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown. the free phenol 2.49% of this resol, free aldehyde 1.47%, the viscosity 1030cps of resin, solid content 79.3%.
Embodiment 8:
(1) be to reactor drum in to add phenol at 94: 51 with Resorcinol with account for proportional quantity 65% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio; The ratio of phenol and Resorcinol is 1: 0.08; Make reactor drum be warmed up to 45 ℃ simultaneously, the reaction times is 30min, soaking time 25min.Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol.
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 20%, add-on is 8% of a phenol quality, under 50 ℃ of conditions, heats 20min, is heated to 75 ℃ and keep 50min then.
(3) add mass ratio be 1: 3: 0.2 by propylene oxide and trolamine synthetic polyether glycol; The properties-correcting agent of forming by hexanodioic acid and the pure and mild zeyssatite of tetramethylolmethane synthetic polyester polyols; The add-on of properties-correcting agent is 7% of a phenol quality, reaction times 15min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose zeyssatite.
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 70min.
(5) cooling is at 70 ℃, and adding concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging.Obtain the transparent expandable phenolic resin liquid of light brown.The free phenol 2.53% of this resol, free aldehyde 1.61%, the viscosity 2275cps of resin, solid content 81.7%.
Embodiment 9:
But the foamed phenolic resin that utilizes embodiment 1-8 to make prepares the phenol formaldehyde foam heat-insulating fireproof material according to following quality proportioning.
But 100 parts of foamed phenolic resins, 2 parts of silicone oil, 6 parts of sherwood oils, 12 parts in solidifying agent; Solidifying agent is that mass ratio is the mixture of 1: 1 hydrochloric acid and phosphoric acid.Preparation technology is following: press proportional quantity, but with foamed phenolic resin and emulsifier mix, stir; Adding whipping agent then stirs; Add solidifying agent again and stir, pour into as early as possible in the mould,, after the 30min slaking, take out again, obtain the phenol formaldehyde foam heat-insulating fireproof material at 60-75 ℃ of foaming 10min.With the technical indicator of the phenol formaldehyde foam heat-insulating fireproof material of expandable phenolic resin of the present invention preparation, see table 1.
The technical indicator of the phenol formaldehyde foam heat-insulating fireproof material of table 1 preparation
Can know that from the result of table 1 technical indicator of the phenol formaldehyde foam heat-insulating fireproof material of preparation also meets the index request of ISO4896-84 phenolic foams international standard fully.
Reference:
[1] Ge Dongbiao, Wang Shuzhong, Hu Fu increases. the progress of resol toughening modifying [J]. glass reinforced plastic/matrix material, 2003,5.
[2] Tang Lulin, Li Naining, Wu Peixi. high-performance pnenolic aldehyde resin and utilisation technology thereof [M]. Beijing: Chemical Industry Press, 2007,10.
[3] Liu Faxi, Xu Qingyu, Dai Sanwei, king white horse with a black mane Lee. phenolic resin modified research new development. summary, 2008,7.
Claims (9)
1. the preparation method of an expandable phenolic resin; It is characterized in that its step and condition are following: (1) is 94 by phenol and Paraformaldehyde 96 mass ratio: 45-60 adds phenol and the Paraformaldehyde 96 that accounts for proportional quantity 60-80% in reactor drum; Make reactor drum be warmed up to 40-50 ℃, constant temperature 20-30min simultaneously; Described phenol is that mol ratio is 1: the phenol of 0.05-0.15 and Resorcinol mixture;
(2) adding mass concentration is the base catalysis agent solution of 10-30%, hydrotalcite in the alkaline catalysts and Ba (OH)
2Mass ratio be 1: 1, add-on is the 5-20% of phenol quality, under 40-50 ℃ of condition, heats 10-20min, is warming up to 70-80 ℃ of down reaction 30-60min then;
(3) adding mass ratio is 1: the properties-correcting agent that the mixture of the polyether glycol of 1-3: 0.2-0.5, the pure and mild nano powder of polyester polyols is formed, and the add-on of properties-correcting agent is the 3-10% of phenol quality; The number-average molecular weight of polyester polyol is 400-600; The number-average molecular weight of polyether glycol is 100-200; Nano particle is the nano particle of wilkinite, zeyssatite or silicon-dioxide, and the granularity 80-100 order of nano particle reacts 10-30min again; Described polyether glycol is the addition polymer of glycerine, terepthaloyl moietie, Ucar 35, TriMethylolPropane(TMP), tetramethylolmethane, triethylene diamine, trolamine, quadrol and propylene oxide; Polyester polyol is organic di-carboxylic acid, acid anhydrides and polyolcondensation product;
(4) add remaining Paraformaldehyde 96 in (1) step, make temperature of reaction be upgraded to 90-100 ℃, under this temperature, react 60-90min;
(5) reaction system is cooled to 60-70 ℃, add acid acceptor, the pH value of regulation system is 7, and neutralizing agent is that mass concentration is hydrochloric acid or the sulfuric acid of 10-30%; Reduce to the room temperature discharging, but obtain foamed phenolic resin.
2. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) is 94: 45 by phenol and Paraformaldehyde 96 mass ratio, in reactor drum, adds phenol and the Paraformaldehyde 96 that accounts for proportional quantity 80%, make reactor drum be warmed up to 40 ℃ simultaneously, insulation 20min; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) add mass concentration is the hydrotalcite of 10-30% and the base catalysis agent solution of hydrated barta composition, add-on be phenol quality 5%, under 40 ℃ of conditions, heat 10min, be heated to 70 ℃ and keep reacting 60min under this temperature then;
(3) adding mass ratio is the properties-correcting agent that the pure and mild wilkinite of polyether glycol, hexanodioic acid and Ucar 35 institute synthetic polyester polyols that 1: 1: 0.2 propylene oxide and glycerine condensation forms is formed, and the add-on of properties-correcting agent is 5% of a phenol quality, reacts 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose wilkinites;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, reaction 60min;
(5) cool to 60 ℃, the adding mass concentration is 10% hydrochloric acid neutralization, and regulating the pH value is 7, reduces to the room temperature discharging, but obtains foamed phenolic resin light brown transparent liquid.
3. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 51 with Resorcinol with account for proportional quantity 75% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.08, makes reactor drum be warmed up to 45 ℃, soaking time 25min simultaneously; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) adding concentration is 25% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 7% of a phenol quality, under 45 ℃ of conditions, heats 10min, is heated to 70 ℃ and keep 60min then;
(3) add mass ratio be 1: 2: 0.2 by propylene oxide and Ucar 35 synthetic polyether glycol, the properties-correcting agent of the pure and mild zeyssatite composition of suberic acid and terepthaloyl moietie synthetic polyester polyols, the add-on of properties-correcting agent is 6% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose zeyssatite;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 80min.
(5) cool to 60 ℃, the adding mass concentration is 15% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging, but obtains foamed phenolic resin light brown transparent liquid.
4. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 54 with Resorcinol with account for proportional quantity 70% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.12, makes reactor drum be warmed up to 40 ℃, soaking time 30min simultaneously; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) adding concentration is 20% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 8% of a phenol quality, under 45 ℃ of conditions, heats 15min, is heated to 75 ℃ and keep 50min then;
(3) the adding mass ratio is 1: 2: 0.4 propylene oxide and a Ucar 35 synthetic polyether glycol, the properties-correcting agent that the pure and mild silicon-dioxide of Kui diacid and glycerine synthetic polyester polyols is formed, and the add-on of properties-correcting agent is 4% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 500; The number-average molecular weight of polyether glycol is 150; Nano particle is that granularity is 90 purpose silicon-dioxide;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 75min;
(5) cooling is at 60 ℃, and the adding mass concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging, but obtains foamed phenolic resin light brown transparent liquid.
5. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 60 with Resorcinol with account for proportional quantity 60% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.15, makes reactor drum be warmed up to 50 ℃, soaking time 20min simultaneously; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) adding concentration is 10% hydrotalcite and hydrated barta base catalysis agent solution, and add-on is 20% of a phenol quality, under 50 ℃ of conditions, heats 20min, is heated to 80 ℃ and keep 30min then;
(3) add mass ratio be 1: 3: 0.4 by propylene oxide and TriMethylolPropane(TMP) synthetic polyether glycol; The properties-correcting agent of forming by phthalic acid and the pure and mild zeyssatite of tetramethylolmethane synthetic polyester polyols; The add-on of properties-correcting agent is 8% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose zeyssatite;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 98 ℃, and the reaction times is 90min;
(5) cooling is at 70 ℃, and the adding mass concentration is 25% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging, but obtains foamed phenolic resin light brown transparent liquid.
6. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 57 with Resorcinol with account for proportional quantity 65% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio; The ratio of phenol and Resorcinol is 1: 0.10; Make reactor drum be warmed up to 45 ℃ simultaneously, the reaction times is 30min, soaking time 25min; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 10%, add-on is 20% of a phenol quality, under 50 ℃ of conditions, heats 18min, is heated to 76 ℃ and keep 45min then;
(3) add mass ratio be 1: 2.5: 0.5 by propylene oxide and quadrol synthetic polyether glycol; The properties-correcting agent of forming by Tetra hydro Phthalic anhydride and the pure and mild wilkinite of glycerine synthetic polyester polyols; The add-on of properties-correcting agent is 5% of a phenol quality, reaction times 20min; The number-average molecular weight of used polyester polyol is 500; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose wilkinites;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 80min;
(5) cooling is at 70 ℃, and the adding mass concentration is 20% sulfuric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging, but obtains foamed phenolic resin light brown transparent liquid.
7. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 54 with Resorcinol with account for proportional quantity 70% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.10, makes reactor drum be warmed up to 45 ℃, soaking time 30min simultaneously; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 20%, add-on is 10% of a phenol quality, under 50 ℃ of conditions, heats 15min, is heated to 75 ℃ and keep 40min then;
(3) add mass ratio be 1: 2.0: 0.4 by propylene oxide and triethylene diamine synthetic polyether glycol; The properties-correcting agent of forming by toluene dicarboxylic acid anhydride and the pure and mild silicon-dioxide of butyleneglycol synthetic polyester polyols; The add-on of properties-correcting agent is 10% of a phenol quality, reaction times 15min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 150; Nano particle is that granularity is 80 purpose silicon-dioxide;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 80min;
(5) cooling is at 70 ℃, and the adding mass concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging; But obtain foamed phenolic resin light brown transparent liquid.
8. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol and Resorcinol at 94: 54 and account for proportional quantity 75% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio, the ratio of phenol and Resorcinol is 1: 0.06, makes reactor drum be warmed up to 45 ℃ simultaneously, is incubated 30min; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 15%, add-on is 12% of a phenol quality, under 50 ℃ of conditions, heats 15min, is heated to 80 ℃ and keep 35min then;
(3) add mass ratio be 1: 2.5: 0.2 by propylene oxide and tetramethylolmethane synthetic polyether glycol; The properties-correcting agent of forming by isophthalic anhydride and the pure and mild wilkinite of terepthaloyl moietie synthetic polyester polyols; The add-on of properties-correcting agent is 8% of a phenol quality, reaction times 20min; The number-average molecular weight of polyester polyol is 400; The number-average molecular weight of polyether glycol is 100; Nano particle is that granularity is 80 purpose wilkinites;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 95 ℃, and the reaction times is 75min;
(5) cooling is at 60 ℃, and the adding mass concentration is 15% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging; But obtain foamed phenolic resin light brown transparent liquid.
9. the preparation method of a kind of expandable phenolic resin as claimed in claim 1 is characterized in that, its step and condition are following:
(1) be to reactor drum in to add phenol at 94: 51 with Resorcinol with account for proportional quantity 65% Paraformaldehyde 96 by phenol and Paraformaldehyde 96 mass ratio; The ratio of phenol and Resorcinol is 1: 0.08; Make reactor drum be warmed up to 45 ℃ simultaneously, the reaction times is 30min, soaking time 25min; Described phenol is that mol ratio is the mixture of 1: 0.05 phenol and Resorcinol;
(2) add the hydrotalcite and the hydrated barta base catalysis agent solution of concentration 20%, add-on is 8% of a phenol quality, under 50 ℃ of conditions, heats 20min, is heated to 75 ℃ and keep 50min then;
(3) add mass ratio be 1: 3: 0.2 by propylene oxide and trolamine synthetic polyether glycol; The properties-correcting agent of forming by hexanodioic acid and the pure and mild zeyssatite of tetramethylolmethane synthetic polyester polyols; The add-on of properties-correcting agent is 7% of a phenol quality, reaction times 15min; The number-average molecular weight of polyester polyol is 600; The number-average molecular weight of polyether glycol is 200; Nano particle is that granularity is 100 purpose zeyssatite;
(4) add remaining Paraformaldehyde 96 in (1) step, temperature of reaction is 90 ℃, and the reaction times is 70min;
(5) cooling is at 70 ℃, and adding concentration is 20% hydrochloric acid neutralization, and regulating pH value is 7, reduces to the room temperature discharging; But obtain foamed phenolic resin is the light brown transparent liquid.
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| CN104327229A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Toughening modified phenolic resin and preparation method thereof |
| CN104909756A (en) * | 2015-06-04 | 2015-09-16 | 合肥和安机械制造有限公司 | Composite modified diatomite-carbonized foamed phenolic resin-base heat insulating material for fork truck engine exhaust pipes and preparation method thereof |
| CN105001386A (en) * | 2015-06-09 | 2015-10-28 | 中国林业科学研究院林产化学工业研究所 | High-activity phenolic compound modified expandable phenolic resin and preparation method thereof |
| CN105111393A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Preparation method of foamable phenolic resin |
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| CN101768326A (en) * | 2010-01-15 | 2010-07-07 | 上海虞城新型建材有限公司 | Preparation method of modified phenolic resin and application thereof |
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| CN104327229A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Toughening modified phenolic resin and preparation method thereof |
| CN105732923A (en) * | 2014-12-11 | 2016-07-06 | 苏州美克思科技发展有限公司 | Preparation method of low acidic phenolic foam insulation material |
| CN105732923B (en) * | 2014-12-11 | 2018-05-25 | 苏州美克思科技发展有限公司 | A kind of preparation method of low in acidity phenolic aldehyde foam thermal insulation material |
| CN104909756A (en) * | 2015-06-04 | 2015-09-16 | 合肥和安机械制造有限公司 | Composite modified diatomite-carbonized foamed phenolic resin-base heat insulating material for fork truck engine exhaust pipes and preparation method thereof |
| CN105001386A (en) * | 2015-06-09 | 2015-10-28 | 中国林业科学研究院林产化学工业研究所 | High-activity phenolic compound modified expandable phenolic resin and preparation method thereof |
| CN105111393A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Preparation method of foamable phenolic resin |
| CN106243613A (en) * | 2016-08-01 | 2016-12-21 | 合肥广能新材料科技有限公司 | Phenol formaldehyde foam thermal insulating composite panel and preparation method thereof |
| CN109486103A (en) * | 2018-11-15 | 2019-03-19 | 苏州宏久航空防热材料科技有限公司 | A kind of hybrid foam insulation |
| CN112142368A (en) * | 2020-10-22 | 2020-12-29 | 中国海洋石油集团有限公司 | Low-temperature consolidation type material for offshore oilfield water injection well |
| CN112724447A (en) * | 2020-12-14 | 2021-04-30 | 苏州圣杰特种树脂有限公司 | Wall surface heat-preservation phenolic resin foam material and preparation method thereof |
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