CN104387541B - A kind of toughening modifying phenol formaldehyde foam and preparation method thereof - Google Patents
A kind of toughening modifying phenol formaldehyde foam and preparation method thereof Download PDFInfo
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- CN104387541B CN104387541B CN201410618408.5A CN201410618408A CN104387541B CN 104387541 B CN104387541 B CN 104387541B CN 201410618408 A CN201410618408 A CN 201410618408A CN 104387541 B CN104387541 B CN 104387541B
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Abstract
The invention discloses a kind of toughening modifying phenol formaldehyde foam, be mainly prepared from by the raw material of following quality proportioning, 40 80 parts of toughening modifying phenolic resin；Complexed surfactant 24 parts；Composite foamable agent 36 parts；48 parts of mixed acid firming agent.It uses sulphuric acid, phosphoric acid, boric acid, pyrovinic acid, DBSA, camphorsulfonic acid etc. to be mixed to prepare inorganic organic mixed acid by a certain percentage is firming agent and complexed surfactant, solidification rate is suitable with expansion rate, the phenol formaldehyde foam uniform foam cell of preparation is fine and smooth, and phenolic resin foam is of light color；It uses triphenyl phosphate, triphenyl phosphite, triphenyl borate to be crosslinking enhancer, improves phenol formaldehyde foam mechanical property further.
Description
Technical field
The invention belongs to new material technology field, be specifically related to toughness reinforcing, enhancing modified and the phenolic aldehyde of a kind of phenolic resin
Foam and preparation method thereof.
Background technology
Phenolic resin has heat-resist, and mechanical strength is high, steady performance, be widely used in preparing fiberglass,
Moulding compound, coating, binding agent, binder for fire-resistant materials, insulation material etc..The characteristic such as the most fire-retardant, safe and environment-friendly makes it become
For novel building thermal insulation material, also it is described as " king of insulation " by insider.But, phenolic resin there is also shortcoming, as
Phenolic resin after solidification is because being only connected by methylene between aromatic core, and Chain Flexibility is poor, fragility is big, the phenol formaldehyde foam toughness of preparation
Little, dry linting rate is high, thus have impact on its popularization and application.Therefore, the toughening modifying to phenolic foam is studied and is had weight
The meaning wanted.To this end, carried out the developmental research of Novel fireproof building thermal insulation material-modified phenolic foam.
Phenol formaldehyde foam toughness reinforcing, can be realized by following several method: 1. add outer toughener, by the way of blended
Reach the purpose of toughening metlbond foam;2. by the chemical reaction of resol with toughener, toughness reinforcing purpose is reached;
3. phenol synthesis phenolic resin is replaced with the modified phenol of part band flexible chain.
The present invention and the Chinese invention patent of Application No. 201310050567.5 " a kind of toughening modifying phenolic resin and phenol
The preparation method of aldehyde foam ", " a kind of hydroxy-terminated polysiloxane increases for the Chinese invention patent of Application No. 201310088594.1
The preparation method of tough phenol-formaldehyde resin modified " and Chinese invention patent " a kind of polyetheramine increasing of Application No. 201210332508.2
Tough phenol formaldehyde foam and preparation method thereof " compare, mainly there is some difference following: the toughener that (1) is used is different: patent of invention
Toughener added by " a kind of toughening modifying phenolic resin and the preparation method of phenol formaldehyde foam " is propylene glycol, tetramethylolmethane, fatty alcohol
Polyoxyethylene ether, polyvinylpyrrolidone and isocyanates, patent of invention " a kind of hydroxy-terminated polysiloxane toughening modifying phenolic aldehyde
The preparation method of resin " added by toughener be hydroxy-terminated polysiloxane, patent of invention " a kind of polyetheramine toughening metlbond foam and
Its preparation method " added by toughener be polyetheramine, and the present invention use in the synthesis of phenolic resin add aromatic hydrocarbons polyester polyols
Alcohol carries out modification by copolymerization as toughness reinforcing segment；(2) present invention uses triphenyl phosphate or triphenyl phosphite or boric acid the most simultaneously
It is combined as crosslinking enhancer between triphenylmethyl methacrylate or three, improves the intensity of phenol formaldehyde foam further.
Summary of the invention
It is an object of the invention to provide a kind of toughness reinforcing, enhancing modified phenolic resin and the preparation method of phenol formaldehyde foam.Pass through
A kind of Aromatic Polyester Polyols of design, as plasticized modifier, uses triphenyl phosphate or triphenyl phosphite or triphenyl borate
For crosslinking enhancer, it is grafted upper flexible chain by the chemical reaction of phenolic hydroxyl group and methylol, thus obtains the modified first of intrinsic toughening
Rank phenolic resin, introduces flexible ester bond and ehter bond in phenolic resin structure, and toughness is strong, intensity is high in preparation, little, the mechanics that falls slag rate
The phenol formaldehyde foam that performance is good.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of toughening modifying phenol formaldehyde foam, is mainly prepared from by the raw material of following quality proportioning, toughening modifying phenolic aldehyde tree
Fat 40-80 part；Complexed surfactant 2-4 part；Composite foamable agent 3-6 part；Mixed acid firming agent 4-8 part.
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, toughening modifying phenolic resin 50-70 part；Compound
Surfactant 2.5-3.5 part；Composite foamable agent 4-5 part；Mixed acid firming agent 6-7 part.
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, 60 parts of toughening modifying phenolic resin；Composite surface
Activating agent 3 parts；Composite foamable agent 4.5 parts；6.5 parts of mixed acid firming agent.
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described composite foamable agent is with petroleum ether (60-90
DEG C), petroleum ether (30-60 DEG C), dichloromethane, dimethoxym ethane and a fluorine dichloroethanes be mixed to prepare.
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described composite foamable agent example oil in mass ratio
Ether (60-90 DEG C): petroleum ether (30-60 DEG C): dichloromethane: dimethoxym ethane: a fluorine dichloroethanes=1:0.5-0.8:0.5-0.9:
0.2-0.6:0.3-0.9 is mixed to prepare (preferably, described composite foamable agent example petroleum ether (60-90 DEG C) in mass ratio: petroleum ether
(30-60 DEG C): dichloromethane: dimethoxym ethane: a fluorine dichloroethanes=1:0.6:0.7:0.5:0.6 is mixed to prepare).
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described complexed surfactant with tween 80 and
NPE is mixed to prepare.Mass ratio tween 80: NPE=1:0.5-0.5:1 is mixed to prepare
(preferably, complexed surfactant example tween 80 in mass ratio: NPE 1:0.5 is mixed to prepare).
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described mixed acid firming agent be sulphuric acid, phosphoric acid,
Boric acid, pyrovinic acid, DBSA and camphorsulfonic acid are mixed to prepare.
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described mixed acid firming agent example sulfur in mass ratio
Acid: phosphoric acid: boric acid: pyrovinic acid: DBSA: camphorsulfonic acid=1:0.3-0.8:0.1-0.6:0.2-1:0.5-
1.5:0.1-0.6 be mixed to prepare (preferably, described mixed acid firming agent example sulphuric acid in mass ratio: phosphoric acid: boric acid: pyrovinic acid:
DBSA: camphorsulfonic acid=1:0.4:0.5:0.6:0.9:0.5 is mixed to prepare).
Foregoing toughening modifying phenol formaldehyde foam, preferred scheme is, described toughening modifying phenolic resin is by following side
Prepared by method:
(1) Aromatic Polyester Polyols is prepared: by ethylene glycol, diglycol, triethylene-glycol, a contracting dipropyl two
Alcohol, glycerol add reactor, warming while stirring, the most under agitation add p-phthalic acid, M-phthalic acid, phthalic anhydride, so
Rear addition catalyst (preferably titanate esters), first controls at low temperatures, reacts certain time, then rises high-temperature, and is incubated certain
Time, evacuation of lowering the temperature, maintain certain time, cooling discharge obtains product Aromatic Polyester Polyols；
(2) toughening modifying phenolic resin is prepared: add reactor after first being dissolved by phenol, then it is molten to add formaldehyde stage by stage
Liquid, base catalyst, regulate pH=9, adds triphenyl phosphate or triphenyl phosphite or triphenyl borate is made at a certain temperature
Become phenolic resin prepolymer, add Aromatic Polyester Polyols, regulate mixture pH=5 with formic acid, continue at 85 DEG C-90 DEG C
Reaction 1h, adds alkaline solution regulation pH=7.5, makes mixture be cooled to rapidly 75 DEG C with psychrolusia；Decompression dehydration 1-at 75 DEG C
1.5h, viscosity controls at 20-30mPas, obtains toughening modifying phenolic resin.
Step (2) described base catalyst is NaOH 10-30% aqueous solution.
The technical advantage of the present invention is embodied in:
1. using Aromatic Polyester Polyols as intrinsic toughening agent phenol-formaldehyde resin modified, phenol formaldehyde foam toughness is obviously improved, and falls
Slag is little, and compressive strength is high, and comprehensive mechanical property is good；
2. using triphenyl phosphate, triphenyl phosphite, triphenyl borate is crosslinking enhancer, improves phenolic aldehyde further
Foam mechanical property；
3. use sulphuric acid, phosphoric acid, boric acid, pyrovinic acid, DBSA, camphorsulfonic acid etc. to mix by a certain percentage
Closing and preparing inorganic-organic mixed acid is firming agent, and solidification rate is suitable with expansion rate, the phenol formaldehyde foam of preparation, uniform foam cell
Exquisiteness, phenolic resin foam is of light color, gradually heats up, it is ensured that the homogeneity of reaction.
4. use petroleum ether (60-90 DEG C), petroleum ether (30-60 DEG C), dichloromethane, dimethoxym ethane, a fluorine dichloroethanes
(HCFC-14lb) composite foamable agent, expansion rate is suitable, the phenol formaldehyde foam of preparation, uniform foam cell are fine and smooth.
Accompanying drawing explanation
Fig. 1-5 is respectively embodiment 1-5 gained phenol formaldehyde foam sectional view.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described, not limiting of its scope.Simultaneously
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as without special
Illustrate, the most commercially obtain.
The conventional treatment of the present invention: toughness reinforcing, the enhancing modified of a kind of phenolic resin and the preparation method of phenol formaldehyde foam are first
Add reactor after being dissolved by phenol, then add formalin, Caustic soda aqueous solution stage by stage, regulate pH=9, add phosphoric acid triphen
Ester or triphenyl phosphite or triphenyl borate make phenolic resin prepolymer at a certain temperature, add aromatic hydrocarbons polyester polyols
Alcohol (I), with formic acid regulate reactant liquor pH=5, continue at 85 DEG C-90 DEG C react 1h, add a certain amount of alkaline solution regulation pH
=7.5, make mixture be cooled to rapidly 75 DEG C with psychrolusia；Decompression dehydration 1-1.5h at 75 DEG C, viscosity controls at 20-30mPas.
Continue reaction certain time and make a kind of toughening modifying phenolic resin (II).It is sequentially added into toughening modifying phenolic resin in a mold
(II), surface active agent tween-80, composite foamable agent is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding mixed acid firming agent, soon
Speed stirring so that it is be scattered in rapidly in mixing liquid, mixed liquor be placed in ready mould, constant temperature in 70 DEG C of baking ovens
Ripening 3h, the demoulding, obtain toughness reinforcing, enhancing modified phenol formaldehyde foam (III).
Toughening modifying phenolic resin (II) recited above, adds reactor, then adds in batches after first being dissolved by 72 parts of phenol
Enter 117 parts of formalins, 2 parts of base catalysts (described base catalyst is NaOH 10-30% aqueous solution), regulate pH=9,
Add 6 portions of triphenyl phosphates or triphenyl phosphite or triphenyl borate is warming up to 85 DEG C-90 DEG C, keep 1 hour, make phenolic aldehyde
Resin prepolymer, adds 3-30%(and accounts for phenol quality) Aromatic Polyester Polyols (I), insulation 85 DEG C-90 DEG C, continue reaction 1
Hour, make toughening modifying phenolic resin (II), its performance indications are: outward appearance, brownish red transparency liquid；Solid content, ＞ 75%；
Viscosity (25 DEG C, mPas) 2000-20000；Free phenol, ＜ 8%.
Aromatic Polyester Polyols recited above (I), preparation method specifically: by 12 parts of ethylene glycol, 20 part of one contracting diethyl
Glycol, 5 parts of triethylene-glycols, 3 parts of dipropylene glycols, 1 part of glycerol add reactor, warming while stirring, are then stirring
Mix 22 parts of p-phthalic acids of lower addition, 15 parts of M-phthalic acids, 16 parts of phthalic anhydrides, be subsequently adding 0.3 part of catalyst Ti acid esters, control
Still temperature processed is at 180～220 DEG C, and gas phase temperature controls 98-100 DEG C, maintains 5-6 hour.It is warming up to 220～250 DEG C, is incubated 4-
6 hours.Being cooled to 1 80～200 DEG C, evacuation reaches 0.08～0.09MPa maintenance about 2 hours, is cooled to 60 DEG C of dischargings
Obtaining product (I), its performance indications are: outward appearance, yellow is to brown viscous liquid；Hydroxyl value (mg KOH/g), 150-450；Acid number
(mg KOH/g), 3.0；Moisture (wt%) 0.2；Viscosity (25 DEG C, mpa .s) 2000-20000.
Toughness reinforcing, the preparation method of enhancing modified phenol formaldehyde foam (III) recited above, preparation method specifically: in a mold
It is sequentially added into 60 parts of toughening modifying phenolic resin (I), 3 parts of complexed surfactants, 1.5 parts of foaming agent petroleum ether (60-90 DEG C),
2 parts of petroleum ether (30-60 DEG C), 1 part of dichloromethane is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding 5 parts of mixed acid firming agent, soon
Speed stirring so that it is be scattered in rapidly in mixing liquid, mixed liquor be placed in ready mould, constant temperature in 70 DEG C of baking ovens
Ripening 3h, the demoulding, obtain toughening modifying phenol formaldehyde foam (III).
Mixed acid firming agent recited above, is sulphuric acid, phosphoric acid, boric acid, pyrovinic acid, DBSA, Camphora
Sulfonic acid is mixed to prepare by a certain percentage.More preferably, mixed acid mass ratio specifically sulphuric acid: phosphoric acid: boric acid: methyl sulphur
Acid: DBSA: camphorsulfonic acid=1:0.3-0.8:0.1-0.6:0.2-1:0.5-1.5:0.1-0.6(mass ratio).
Complexed surfactant described above is mixed to prepare by a certain percentage with tween 80 and NPE.
More preferably, complexed surfactant ratio is tween 80: NPE=1:0.5-0.5:1 is mixed to prepare
(mass ratio).
Composite foamable agent recited above, is to have petroleum ether (60-90 DEG C), petroleum ether (30-60 DEG C), dichloromethane, first
Acetal, a fluorine dichloroethanes (HCFC-14lb) are mixed to prepare by a certain percentage.More preferably, composite foamable agent mass ratio
Specifically petroleum ether (60-90 DEG C): petroleum ether (30-60 DEG C): dichloromethane: dimethoxym ethane: a fluorine dichloroethanes (HCFC-14lb)
=1:0.5-0.8:0.5-0.9:0.2-0.6:0.3-0.9(mass ratio).
1 one kinds of toughening modifying phenol formaldehyde foams of embodiment, are mainly prepared from by the raw material of following quality proportioning, toughness reinforcing change
40 parts of phenolic resin of property；Complexed surfactant 4 parts；Composite foamable agent 6 parts；4 parts of mixed acid firming agent.
Phenol/formaldehyde is added by certain mol proportion the three-neck flask being equipped with condenser, motor stirrer and thermometer
In, start agitator and use heating in water bath；In treating bottle, mixture preheating is stirring evenly and then adding into a certain amount of 20% sodium hydroxide
Solution as catalyst, regulates pH=9, adds triphenyl phosphate, slowly heats up, and treats that the temperature of mixture reaches 85 DEG C-90 in bottle
DEG C keep after 1 hour, add 3%(and account for phenol quality) benzoic anhydride polyester polyol, with the pH=5 of formic acid regulation reactant liquor, continues to exist
React 1h at 85 DEG C-90 DEG C, add a certain amount of 20% sodium hydroxide solution regulation pH=7.5, make mixture rapid with psychrolusia
It is cooled to 75 DEG C；At 75 DEG C, decompression dehydration 1-1.5h i.e. obtains expandable phenolic resin.
It is sequentially added into benzoic anhydride polyester polyol plasticizing phenol formaldehyde in a mold, surface active agent tween-80, composite foamed
Agent, is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding firming agent mixed acid, quickly stirs so that it is be scattered in rapidly mixing liquid
In, mixed liquor is placed in ready mould, cooked at constant 3h, the demoulding in 70 DEG C of baking ovens.
Embodiment 2 toughening modifying phenol formaldehyde foam, is mainly prepared from by the raw material of following quality proportioning, toughening modifying phenol
Urea formaldehyde 50 parts；Surface active agent tween-80 2.5 parts；Composite foamable agent 4 parts；6 parts of mixed acid firming agent.
Phenol/formaldehyde is added by certain mol proportion the three-neck flask being equipped with condenser, motor stirrer and thermometer
In, start agitator and use heating in water bath；In treating bottle, mixture preheating is stirring evenly and then adding into a certain amount of 20% sodium hydroxide
Solution as catalyst, regulates pH=9, adds triphenyl phosphite and slowly heats up, treat in bottle the temperature of mixture reach 85 DEG C-
90 DEG C kept after 1 hour, added 5%(and accounted for phenol quality) benzoic anhydride polyester polyol, with dilute formic acid by the pH=5 of mixture, continue
Continue reaction 1h at 85 DEG C-90 DEG C, add a certain amount of 20% sodium hydroxide solution regulation PH=7.5, make mixture with psychrolusia
It is cooled to rapidly 75 DEG C；At 75 DEG C, decompression dehydration 1-1.5h i.e. obtains expandable phenolic resin.
It is sequentially added into benzoic anhydride polyester polyol plasticizing phenol formaldehyde in a mold, surface active agent tween-80, composite foamed
Agent, is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding firming agent mixed acid, quickly stirs so that it is be scattered in rapidly mixing liquid
In, mixed liquor is placed in ready mould, cooked at constant 3h, the demoulding in 70 DEG C of baking ovens.
Embodiment 3 toughening modifying phenol formaldehyde foam, is mainly prepared from by the raw material of following quality proportioning, toughening modifying phenol
Urea formaldehyde 70 parts；Complexed surfactant 3.5 parts；Composite foamable agent 5 parts；7 parts of mixed acid firming agent.
Phenol/formaldehyde is added by certain mol proportion the three-neck flask being equipped with condenser, motor stirrer and thermometer
In, start agitator and use heating in water bath；In treating bottle, mixture preheating is stirring evenly and then adding into a certain amount of 20% sodium hydroxide
Solution as catalyst, regulates PH=9, adds triphenyl borate and slowly heats up, and treats that the temperature of mixture reaches 85 DEG C-90 in bottle
DEG C keep after 1 hour, add 10%(and account for phenol quality) benzoic anhydride polyester polyol, with dilute formic acid by the pH=5 of mixture, continue
Continue reaction 1h at 85 DEG C-90 DEG C, add a certain amount of 20% sodium hydroxide solution regulation PH=7.5, make mixture with psychrolusia
It is cooled to rapidly 75 DEG C；At 75 DEG C, decompression dehydration 1-1.5h i.e. obtains expandable phenolic resin.
It is sequentially added into benzoic anhydride polyester polyol plasticizing phenol formaldehyde in a mold, surface active agent tween-80, composite foamed
Agent, is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding mixed acid firming agent, quickly stirs so that it is be scattered in rapidly mixing liquid
In, mixed liquor is placed in ready mould, cooked at constant 3h, the demoulding in 70 DEG C of baking ovens.
Embodiment 4 toughening modifying phenol formaldehyde foam, is mainly prepared from by the raw material of following quality proportioning, toughening modifying phenol
Urea formaldehyde 60 parts；Complexed surfactant 3 parts；Composite foamable agent 4.5 parts；6.5 parts of mixed acid firming agent.
Phenol/formaldehyde is added by certain mol proportion the three-neck flask being equipped with condenser, motor stirrer and thermometer
In, start agitator and use heating in water bath；In treating bottle, mixture preheating is stirring evenly and then adding into a certain amount of 20% sodium hydroxide
Solution, as catalyst, regulates PH=9, slowly heats up, after the temperature of mixture in bottle reaches 85 DEG C-90 DEG C holdings 1 hour,
Add 15%(and account for phenol quality) benzoic anhydride polyester polyol, adjust the pH=5 of reactant liquor with formic acid, continue to react at 85 DEG C-90 DEG C
1h, adds a certain amount of 20% sodium hydroxide solution regulation PH=7.5, makes mixture be cooled to rapidly 75 DEG C with psychrolusia； 75
At DEG C, decompression dehydration 1-1.5h i.e. obtains benzoic anhydride polyester polyol plasticizing phenol formaldehyde.
It is sequentially added into benzoic anhydride polyester polyol plasticizing phenol formaldehyde in a mold, surface active agent tween-80, composite foamed
Agent, is sufficiently stirred for being allowed to mix homogeneously, is subsequently adding mixed acid firming agent, quickly stirs so that it is be scattered in rapidly mixing liquid
In, mixed liquor is placed in ready mould, cooked at constant 3h, the demoulding in 70 DEG C of baking ovens.
Embodiment 5 toughening modifying phenol formaldehyde foam, is mainly prepared from by the raw material of following quality proportioning, toughening modifying phenol
Urea formaldehyde 60 parts；Composite foamable agent 4.5 parts；6.5 parts of mixed acid firming agent.
Phenol/formaldehyde is added by certain mol proportion the three-neck flask being equipped with condenser, motor stirrer and thermometer
In, start agitator and use heating in water bath；In treating bottle, mixture preheating is stirring evenly and then adding into a certain amount of 20% sodium hydroxide
Solution, as catalyst, regulates PH=9, slowly heats up, after the temperature of mixture in bottle reaches 85 DEG C-90 DEG C holdings 1 hour,
Add 15%(and account for phenol quality) benzoic anhydride polyester polyol, adjust the pH=5 of reactant liquor with formic acid, continue to react at 85 DEG C-90 DEG C
1h, adds a certain amount of 20% sodium hydroxide solution regulation PH=7.5, makes mixture be cooled to rapidly 75 DEG C with psychrolusia； 75
At DEG C, decompression dehydration 1-1.5h i.e. obtains benzoic anhydride polyester polyol plasticizing phenol formaldehyde.
It is sequentially added into benzoic anhydride polyester polyol plasticizing phenol formaldehyde, composite foamable agent in a mold, is sufficiently stirred for being allowed to mixed
Close uniformly, be subsequently adding mixed acid firming agent, quickly stir so that it is be scattered in rapidly in mixing liquid, mixed liquor is placed in standard
In the mould got ready, cooked at constant 3h, the demoulding in 70 DEG C of baking ovens.
Each embodiment gained phenolic resin main performance is shown in Table 1；Each embodiment gained phenol formaldehyde foam main performance is shown in Table 2.
Table 1. phenolic resin main performance
Table 2. phenol formaldehyde foam main performance
Fig. 1-5 is respectively embodiment 1-5 gained phenol formaldehyde foam sectional view.Test result indicate that, add composite surface activity
Agent (embodiment 1-4) ratio does not adds complexed surfactant (embodiment 5) and compares, and the phenolic foams of preparation is uniform, abscess is thin
Greasy, structural integrity, heat conductivity are little, compressive strength is high.
Claims (11)
1. a toughening modifying phenol formaldehyde foam, is characterized in that, is mainly prepared from by the raw material of following quality proportioning, toughening modifying
Phenolic resin 40-80 part；Complexed surfactant 2-4 part；Composite foamable agent 3-6 part；Mixed acid firming agent 4-8 part；Described multiple
Close foaming agent to be mixed to prepare with 60-90 DEG C of petroleum ether, 30-60 DEG C of petroleum ether, dichloromethane, dimethoxym ethane and a fluorine dichloroethanes；
Described mixed acid firming agent is that sulphuric acid, phosphoric acid, boric acid, pyrovinic acid, DBSA and camphorsulfonic acid are mixed to prepare；By
Prepared by following method:
(1) Aromatic Polyester Polyols is prepared: by ethylene glycol, diglycol, triethylene-glycol, dipropylene glycol, sweet
Oil adds reactor, warming while stirring, the most under agitation adds p-phthalic acid, M-phthalic acid, phthalic anhydride, is subsequently adding
Catalyst Ti acid esters, first controls at low temperatures, reacts certain time, then rises high-temperature, and held for some time, and cooling is taken out true
Sky, maintains certain time, and cooling discharge obtains product Aromatic Polyester Polyols；
(2) toughening modifying phenolic resin is prepared: add reactor after first being dissolved by phenol, then add formalin, alkali stage by stage
Property catalyst, regulate pH=9, add triphenyl phosphate or triphenyl phosphite or triphenyl borate makes phenol at a certain temperature
Urea formaldehyde prepolymer, adds Aromatic Polyester Polyols, regulates mixture pH=5 with formic acid, continues to react at 85 DEG C-90 DEG C
1h, adds alkaline solution regulation pH=7.5, makes mixture be cooled to rapidly 75 DEG C with psychrolusia；Decompression dehydration 1-at 75 DEG C
1.5h, viscosity controls, at 20-30mPa s, to obtain toughening modifying phenolic resin.
Toughening modifying phenol formaldehyde foam the most according to claim 1, is characterized in that, toughening modifying phenolic resin 50-70 part；Multiple
Close surfactant 2.5-3.5 part；Composite foamable agent 4-5 part；Mixed acid firming agent 6-7 part.
Toughening modifying phenol formaldehyde foam the most according to claim 1, is characterized in that, 60 parts of toughening modifying phenolic resin；Compound
3 parts of surfactant；Composite foamable agent 4.5 parts；6.5 parts of mixed acid firming agent.
Toughening modifying phenol formaldehyde foam the most according to claim 1, is characterized in that, described complexed surfactant with tween-
80 and NPE be mixed to prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 4, is characterized in that, described complexed surfactant is according to quality
Ratio tween 80: NPE=1:0.5-0.5:1 is mixed to prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 4, is characterized in that, described complexed surfactant is in mass ratio
Example tween 80: NPE 1:0.5 is mixed to prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 1, is characterized in that, described composite foamable agent example in mass ratio
60-90 DEG C of petroleum ether: 30-60 DEG C of petroleum ether: dichloromethane: dimethoxym ethane: a fluorine dichloroethanes=1:0.5-0.8:0.5-0.9:
0.2-0.6:0.3-0.9 is mixed to prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 7, is characterized in that, described composite foamable agent example in mass ratio
60-90 DEG C of petroleum ether: 30-60 DEG C of petroleum ether: dichloromethane: dimethoxym ethane: a fluorine dichloroethanes=1:0.6:0.7:0.5:0.6 mixes
Close and prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 1, is characterized in that, described mixed acid firming agent example in mass ratio
Sulphuric acid: phosphoric acid: boric acid: pyrovinic acid: DBSA: camphorsulfonic acid=1:0.3-0.8:0.1-0.6:0.2-1:0.5-
1.5:0.1-0.6 be mixed to prepare.
Toughening modifying phenol formaldehyde foam the most according to claim 9, is characterized in that, described mixed acid firming agent is in mass ratio
Example sulphuric acid: phosphoric acid: boric acid: pyrovinic acid: DBSA: camphorsulfonic acid=1:0.4:0.5:0.6:0.9:0.5 mixes system
?.
11. toughening modifying phenol formaldehyde foam according to claim 1, it is characterized in that, step (2) described base catalyst is
NaOH 10-30% aqueous solution.
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| 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 |
| CN113943445B (en) * | 2021-09-01 | 2023-02-28 | 四川东树新材料有限公司 | Organic ester curing agent and application thereof |
| CN114933777B (en) * | 2022-06-21 | 2023-10-31 | 安徽长鹿特种电缆有限公司 | Preparation method of special double-conductor coaxial cable for rectifier |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648163A (en) * | 2004-12-31 | 2005-08-03 | 中国兵器工业集团第五三研究所 | Fiber filled phenolic foam plastics |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
| CN102964772A (en) * | 2012-12-05 | 2013-03-13 | 福建天利高新材料有限公司 | Chopped fiber reinforced phenolic resin foam material and preparation method thereof |
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2014
- 2014-11-06 CN CN201410618408.5A patent/CN104387541B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648163A (en) * | 2004-12-31 | 2005-08-03 | 中国兵器工业集团第五三研究所 | Fiber filled phenolic foam plastics |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
| CN102964772A (en) * | 2012-12-05 | 2013-03-13 | 福建天利高新材料有限公司 | Chopped fiber reinforced phenolic resin foam material and preparation method thereof |
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| CN104387541A (en) | 2015-03-04 |
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