CN104945842A - Vinasse-reinforced modified phenolic resin foam material and preparation methods thereof - Google Patents
Vinasse-reinforced modified phenolic resin foam material and preparation methods thereof Download PDFInfo
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- CN104945842A CN104945842A CN201410114909.XA CN201410114909A CN104945842A CN 104945842 A CN104945842 A CN 104945842A CN 201410114909 A CN201410114909 A CN 201410114909A CN 104945842 A CN104945842 A CN 104945842A
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Abstract
The invention provides two preparation methods of a vinasse-reinforced modified phenolic resin foam material. According to the first preparation method, vinasse used as a reinforcing filler is added into a resin for curing and foaming, and the vinasse-reinforced modified phenolic resin foam material is prepared by foaming and curing the following components: 100 parts of phenolic resin, 2-8 parts of surfactant, 4-12 parts of foaming agent, 8-15 parts of curing agent and 4-15 parts of vinasse. The wine making waste vinasse is subjected to surface treatment to enhance the compatibility with the resin, and the physical blending foaming is utilized to prepare the biomass foam material. According to the second preparation method, a vinasse liquefaction liquid is utilized for chemical modification to reinforce the phenolic resin, and a physical foaming process is utilized to prepare the foam material. The vinasse-reinforced modified phenolic resin foam material is prepared from 100 parts of vinasse liquefaction modified phenolic resin, 2-8 parts of surfactant, 4-12 parts of foaming agent and 8-15 parts of curing agent. Compared with the traditional petroleum-base foam, the vinasse biomass-base foam material prepared by the two methods has obvious economic and environment-friendly advantages, and has the advantages of excellent mechanical strength, excellent toughness and favorable thermal-insulation and sound-insulation properties.
Description
Technical field
The invention belongs to phenolic resin foam and preparing technical field thereof, particularly relate to vinasse Physical and chemical method enhancing modified prepares high strength toughness resol insulating foam.
Background technology
Nearly 20 years, the liquor of China was produced in explosive growth, and liquor-making enterprises all will discharge a large amount of distiller biomass every year, and total amount reaches more than 2,000 ten thousand tons.They all concentrate on a few place on a ground, city one, and a large amount of vinasse residuum creates catastrophic destruction to ecology, has had a strong impact on local natural ecological environment.
Phenolic aldehyde vinasse insulating foam, as a kind of novel biomass composite foam material, is compared to traditional petroleum based foams material, has degradable, low cost, environmental protection and energy saving, low stain, the multiple advantage such as high strength.And the abundance of vinasse, vinasse are used for resol as reinforcing filler, achieve the Green Chemistry production model of industrial waste recycle.And phenolic resin foam itself is also a kind of thermal insulation, fire retardant material of excellent performance, it is lightweight, good stability of the dimension, chemical resistance are good, good heat resistance, difficult fire, certainly puts out, low smog, flame resistant penetrate, it is fiery without dropping, cheap to meet, and are the desirable sound insulation of the industries such as building, petrochemical complex, lagging material.
Current biomass-based foam materials research both domestic and external mainly concentrates on rosin, vegetables oil, lignocellulose and starch-based foam material, and the intensity of phenol formaldehyde foam and toughness not high.Why adopt vinasse modified phenolic resins foam, because vinasse can very well and phenolic compatible and can as the low novel enhanced filler of cost to improve the mechanical strength of foam first, another is then because vinasse can be used for modified phenolic resins by the reactive behavior small molecules liquefier of liquefaction degraded, improves the toughness of phenol formaldehyde foam from structure.There is bibliographical information phenol resin timber matrix material before, but very few to the research report of vinasse enhancing modified and tough-increased phenolic insulating foam and preparation thereof.
Summary of the invention
The present invention innovatively provides two kinds of method-physical modifications and chemical modification, prepares the resol insulating foam of the vinasse modification of high strength toughness.
One, the phenolic aldehyde vinasse foam of physical modification
1, by weight, the phenolic aldehyde vinasse foam of this physical modification be by following component through foamed solidification gained:
2, described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, is preferably Skellysolve A, pentamethylene, the at least one of sherwood oil etc., described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid.
3, according to the phenolic aldehyde vinasse composite foam material that claim 1 is stated, it is characterized in that, described vinasse will pulverize 40-80 mesh sieve 100-120 DEG C of oven dry, and by it at 100-120 DEG C of dry 3h.
4, vinasse phenolic resin foam according to claim 1, is characterized in that, described filler vinasse, and its treatment process is 1: 1 ~ 3.5 prepare filler by the method for heating in water bath by mass ratio. treatment process:
By mass ratio be 1: 1 ~ 3.5 the low melting point organic compound such as solid paraffin, stearic acid, stearyl alcohol and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 40 ~ 60 object fillers.
5, according to vinasse phenolic aldehyde composite foam material according to claim 1, it is characterized in that, described solidification value is 60-80 DEG C, and set time is 10-30min.
6, the preparation method of phenolic aldehyde vinasse foam according to any one of claim 1-5, it is characterized in that, the synthesis of described resol adopts following processing step:
The sodium hydroxide solution of 94 parts of phenol and 20-25 part 20%wt is joined in there-necked flask, heats and stir; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
Two, vinasse chemical modification resol
One), the first vinasse chemical modification resol
By weight, the resol of this thing modification synthesizes gained by following component:
1, the preparation of the sylvan urea formaldehyde of vinasse liquefier and modification:
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 100-120 DEG C, cross drying for standby after 40-80 mesh sieve.
(2), the phenol of 94 parts of meltings and a certain amount of vitriol oil are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 150-185 DEG C, and the vinasse processed are added in there-necked flask by certain solid-to-liquid ratio (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
(3), the sodium hydroxide solution of the liquefier of the process in (2) and 20-25 part 20%wt is joined in there-necked flask, heat and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
2, the phenolic aldehyde vinasse resin foam according to claim two (1), is characterized in that, described modified phenolic resins foamed solidification, by weight, be by following component through synthesis modification gained:
Described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, be preferably Skellysolve A, pentamethylene, the one in sherwood oil etc., described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid, in described, low solidification value is 60-80 DEG C.
The present invention innovatively adopts vinasse modified phenolic resins foam, and one is because vinasse cost is low, aboundresources, biodegradable.Second be vinasse as novel reinforcing filler, can in resin matrix can good compatible dispersion not affect solidification, its mechanical strength and heat-insulating property can be strengthened significantly.
The present invention's vinasse chemical modification resol, utilize the active small molecular of vinasse liquefier as properties-correcting agent and resole generation graft reaction, make it measure the large branched group of grafting, the toughness of phenol formaldehyde foam and intensity and its heat resistance can be improved.
1, preferably, described its resol of vinasse physical modification by weight, is by following component synthesis modification gained:
2, described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, is preferably Skellysolve A, pentamethylene, at least one in sherwood oil, described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid.
3, phenolic aldehyde vinasse composite foam material according to claim 1, is characterized in that, described vinasse will pulverize 40-80 mesh sieve 100-120 DEG C of oven dry, and by it at 100-120 DEG C of dry 3h.
4, vinasse phenolic resin foam according to claim 1, is characterized in that, described filler vinasse, and its treatment process is 1: 1 ~ 3.5 prepare filler by the method for heating in water bath by mass ratio. treatment process:
By mass ratio be 1: 1 ~ 3.5 the low melting point organic compound such as solid paraffin, stearic acid, stearyl alcohol and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 40 ~ 60 object fillers.
5, vinasse phenolic aldehyde composite foam material according to claim 1, is characterized in that, described solidification value is 60-80 DEG C, and set time is 10-30min.
6, the preparation method of phenolic aldehyde vinasse foam according to any one of claim 1-4 is prepared, it is characterized in that, the synthesis of described resol adopts following processing step: join in there-necked flask by the sodium hydroxide solution of 94 parts of phenol and 20-25 part 20%wt, heat and stir; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
7, preparation method according to claim 1, is characterized in that, the foaming of described phenolic resin foam obtains by the following method:
1). the 40-80 object vinasse 100 parts of resol, 2-8 part emulsifying agent (tween-80, OP-10, dimethyl silicone oil and DC-193), 4-15 part processed/stearic acid filler mixing, adds homogenizer high speed at normal temperatures and stirs 3-5 minute;
2). 4 parts of pentamethylene are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8-12 part concentrated hydrochloric acid is added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 70 DEG C solidifies 10-30min.
Two), preferred vinasse chemical modification phenolic resin foam
Phenolic aldehyde vinasse resin foam according to claim 1, is characterized in that, described chemical method modified phenolic resins, by weight, be by following component through synthesis modification gained:
1, the preparation of the sylvan urea formaldehyde of vinasse liquefier and modification:
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 100-120 DEG C, cross drying for standby after 40-80 mesh sieve.
(2), the phenol of 94 parts of meltings and a certain amount of vitriol oil are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 150-185 DEG C, and the vinasse processed are added in there-necked flask by certain solid-to-liquid ratio for (3.5-30: 94) (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
(3), the sodium hydroxide solution of the liquefier of the process in (2) and 20-25 part 20%wt is joined in there-necked flask, heat and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
2, phenolic aldehyde vinasse resin foam according to claim 1, is characterized in that, described modified phenolic resins foamed solidification, by weight, be by following component through synthesis modification gained:
Described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, be preferably Skellysolve A, pentamethylene, at least one in sherwood oil etc., described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid, in described, low solidification value is 60-80 DEG C.
Utilize above-mentioned two kinds of methods, industrialization is produced vinasse and is strengthened improvement phenolic resin foam multifunctional material, and the general technical path of industrialization as shown in Figure 1.Concrete production unit mainly comprises: drying machine, pulverizer, reactor, blending device, forming machine.
The present invention compared with prior art, has following positively effect:
1, the Novel phenolic vinasse composite foam toughness that obtains of the present invention and the general lagging material of intensity phenol formaldehyde ratio high.This biolobic material foam materials energy biodegradable, environmental protection.
2, solve a difficult problem for large-scale brewery vinasse process, realize the recycle of waste material vinasse, low cost of manufacture, and higher economic benefit can be realized.
3, vinasse enhancing modified phenol formaldehyde foam of the present invention is a kind of thermal insulation, lagging material of excellent performance.Intensity is high, good toughness, good stability of the dimension, chemical resistance are good, good heat resistance, difficult fire, certainly puts out, low smog, flame resistant penetrate, it is fiery good without dropping, soundproof effect to meet.
4, the feature in the performance of phenolic aldehyde vinasse foam and price, it is had many uses, as at building thermal insulation material, chemical industry corrosion resistant material, insulating material, phenolic aldehyde vinasse sheet material, insulating material, Biodegradable materials etc. have larger purposes, and therefore the application prospect of phenolic aldehyde vinasse composite foam material is very considerable.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are just for being further detailed the present invention; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to foregoing invention content, still belong to protection scope of the present invention.
In addition, what deserves to be explained is that the number in following examples added by each material is weight part.
Embodiment one
1, the process of vinasse filler
By mass ratio be 1: 1 solid stearic acid thing and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 40 object fillers.
2, the synthesis of resol
Just the sodium hydroxide solution of 94 parts of phenol and 20 parts of 20%wt joins in there-necked flask, heats and stirs; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foaming of phenolic resin foam:
1). by 100 parts of resol, 2 parts of emulsifier tweens-80, the 4 parts of 40 object vinasse processed/stearic acid filler mixing, add homogenizer high speed at normal temperatures and stir 3 minutes;
2). 4 parts of pentamethylene are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 50 DEG C solidifies 10-min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 3000mPa.s, and solid content is 75%.
Embodiment two
1, the process of vinasse filler
By mass ratio be 1: 3.5 solid stearic acid thing and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 60 object fillers.
2, the synthesis of resol
Just the sodium hydroxide solution of 94 parts of phenol and 25 parts of 20%wt joins in there-necked flask, heats and stirs; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foaming of phenolic resin foam:
1). by 100 parts of resol, 8 parts of emulsifier tweens-80, the 15 parts of 80 object vinasse processed/stearic acid filler mixing, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 12 parts of Skellysolve As are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 12 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 80 DEG C solidifies 30min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 3500mPa.s, and solid content is 76%.
Embodiment three
1, the process of vinasse filler
By mass ratio be 1: 1.5 solid stearic acid thing and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 50 object fillers.
2, the synthesis of resol
Just the sodium hydroxide solution of 94 parts of phenol and 23 parts of 20%wt joins in there-necked flask, heats and stirs; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foaming of phenolic resin foam:
1). by 100 parts of resol, 4 parts of emulsifier op-10s, the 10 parts of 80 object vinasse processed/stearic acid filler mixing, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 10 parts of sherwood oils are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8 parts are added in the resin compound described in (2) to methylsulphonic acid, rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 70 DEG C solidifies 25min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 3100mPa.s, and solid content is 75.60%.
Embodiment four
1, the process of vinasse filler
By mass ratio be 1: 2.5 solid stearic acid thing and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 80 object fillers.
2, the synthesis of resol
Just the sodium hydroxide solution of 94 parts of phenol and 22 parts of 20%wt joins in there-necked flask, heats and stirs; When temperature is elevated to 80 DEG C, add 57 parts of paraformaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foaming of phenolic resin foam:
1). by 100 parts of resol, 2 parts of emulsifying agent DC-193, the 8 parts of 60 object vinasse processed/paraffin sizing mixing, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 4 parts of pentamethylene are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 12 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 60 DEG C solidifies 15min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 4000mPa.s, and solid content is 77.60%.
Embodiment five
1, the pre-treatment of vinasse and liquefaction
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 100 DEG C, cross drying for standby after 40 mesh sieves.
(2), the phenol of 94 parts of meltings and 0.09 part of vitriol oil are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 135 DEG C, and the vinasse processed are added in there-necked flask by solid-to-liquid ratio 3.5: 94 (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
2, the synthesis of modified phenolic resins
The sodium hydroxide solution of the liquefier of the process in (2) and 20 parts of 20%wt is joined in there-necked flask, heats and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foamed solidification of modified resin
1). by 100 parts of modified phenolic resinss, 2 parts of emulsifier tweens-80, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 12 parts of Skellysolve As are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 12 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 80 DEG C solidifies 30min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 4000mPa.s, and solid content is 75.40%.
Embodiment six
1, the pre-treatment of vinasse and liquefaction
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 120 DEG C, cross drying for standby after 80 mesh sieves.
(2), the phenol of 94 parts of meltings and 10 parts of vitriol oils are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 185 DEG C, and the vinasse processed are added in there-necked flask by solid-to-liquid ratio 35: 94 (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
2, the synthesis of modified phenolic resins
The sodium hydroxide solution of the liquefier of the process in (2) and 25 parts of 20%wt is joined in there-necked flask, heats and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foamed solidification of modified resin
1). by 100 parts of modified phenolic resinss, 8 parts of emulsifying agent DC-193, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 4 parts of Skellysolve As are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 60 DEG C solidifies 10min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 4500mPa.s, and solid content is 77.50%.
Embodiment seven
1, the pre-treatment of vinasse and liquefaction
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 120 DEG C, cross drying for standby after 50 mesh sieves.
(2), the phenol of 94 parts of meltings and 10 parts of vitriol oils are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 155 DEG C, and the vinasse processed are added in there-necked flask by solid-to-liquid ratio 10: 94 (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
2, the synthesis of modified phenolic resins
The sodium hydroxide solution of the liquefier of the process in (2) and 22 parts of 20%wt is joined in there-necked flask, heats and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foamed solidification of modified resin
1). by 100 parts of modified phenolic resinss, 6 parts of emulsifier tweens 80, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 10 parts of Skellysolve As are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 10 parts of concentrated hydrochloric acids are added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 70 DEG C solidifies 30min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 4200mPa.s, and solid content is 77.30%.
Embodiment eight
1, the pre-treatment of vinasse and liquefaction
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 120 DEG C, cross drying for standby after 70 mesh sieves.
(2), the phenol of 94 parts of meltings and 10 parts of vitriol oils are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 165 DEG C, and the vinasse processed are added in there-necked flask by solid-to-liquid ratio 28: 94 (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above.
2, the synthesis of modified phenolic resins
The sodium hydroxide solution of the liquefier of the process in (2) and 24 parts of 20%wt is joined in there-necked flask, heats and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
3, the foamed solidification of modified resin
1). by 100 parts of modified phenolic resinss, 4 parts of emulsifier op-10s, add homogenizer high speed at normal temperatures and stir 5 minutes;
2). 8 parts of Skellysolve As are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8 parts are added in the resin compound described in (2) to methylsulphonic acid, rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 75 DEG C solidifies 20min.
4, performance test
With NDJ-8S viscometer at 25 DEG C, 6.0RPM measurement of rotating speed resol glue paste viscosity is 4200mPa.s, and solid content is 75.70%.
Claims (9)
1. the vinasse modified phenolic resins insulating foam of high strength, is characterized in that, by weight, this high-strength insulation phenolic aldehyde vinasse foam be by following component through foamed solidification gained:
Described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, is preferably Skellysolve A, pentamethylene, at least one in sherwood oil etc., described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid.
2. phenolic aldehyde vinasse composite foam material according to claim 1, is characterized in that, described vinasse will pulverize 40-80 mesh sieve 100-120 DEG C of oven dry, and by it at 100-120 DEG C of dry 3h.
3. vinasse phenolic resin foam according to claim 1, is characterized in that, described filler vinasse, and its treatment process is 1: 1 ~ 3.5 prepare filler treatment process by the method for heating in water bath by mass ratio:
By mass ratio be 1: 1 ~ 3.5 the low melting point organic compound such as solid paraffin, stearic acid, stearyl alcohol and vinasse powder add in container, in the water-bath of 90 DEG C, add the coupling agent KH550 of 4% of filler total amount; Continuous stirring, until mix completely; By the sample drying grinding and sieving obtained, obtain 40 ~ 60 object fillers.
4. vinasse phenolic aldehyde composite foam material according to claim 1, is characterized in that, described solidification value is 60-80 DEG C, and set time is 10-30min.
5. the preparation method of preparation phenolic aldehyde vinasse foam according to any one of claim 1-4, it is characterized in that, the synthesis of described resol adopts following processing step: join in there-necked flask by the sodium hydroxide solution of 94 parts of phenol and 20-25 part 20%wt, heat and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes in batches.One is divided into 4 batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
6. preparation method according to claim 1, is characterized in that, the foaming of described phenolic resin foam obtains by the following method:
1). the 40-80 object vinasse 100 parts of resol, 2-8 part emulsifying agent (tween-80, OP-10, dimethyl silicone oil and DC-193), 4-15 part processed/stearic acid filler mixing, adds homogenizer high speed at normal temperatures and stirs 3-5 minute;
2). 4 parts of whipping agents are added in the mixture described in (1), high-speed stirring 3 minutes;
3). 8-12 part solidifying agent is added in the resin compound described in (2), rapid stirring 1 minute;
4). poured in preheated mould by the mixture in (3), the baking oven being placed in 60-80 DEG C solidifies 10-30min.
7. the phenolic aldehyde vinasse resin foam of high tenacity intensity, is characterized in that, described modified phenolic resins, by weight, be by following component through synthesis modification gained:
8. the preparation of the sylvan urea formaldehyde of vinasse liquefier and modification:
(1), the vinasse of beverage distlilery pulverize after being dried to over dry at 100-120 DEG C, cross drying for standby after 40-80 mesh sieve;
(2), the phenol of 94 parts of meltings and a certain amount of vitriol oil are placed in agitator is housed, in the there-necked flask of condensing works, at the preheating 5min of 150-185 DEG C, and the vinasse processed are added in there-necked flask by certain solid-to-liquid ratio (vinasse powder/phenol), after liquefaction 3h, by liquefier high speed centrifugation, be separated the liquid obtained above;
(3), the sodium hydroxide solution of the liquefier of the process in (2) and 20-25 part 20%wt is joined in there-necked flask, heat and stir; When temperature is elevated to 80 DEG C, add 57 parts of solid formaldehydes, one is divided into 4 batches in batches, within every 10 minutes, adds a collection of; Reaction 3.0h terminates reaction, resol is cooled to room temperature and is neutralized to neutrality with acetic acid again.
9. phenolic aldehyde vinasse resin foam according to claim 7, is characterized in that, described modified phenolic resins foamed solidification, by weight, be by following component through synthesis modification gained:
Described tensio-active agent is nonionogenic tenside, be preferably at least one in tween-80, OP-10, dimethyl silicone oil and DC-193, described whipping agent is low-boiling-point organic compound, and its boiling point is 30-80 DEG C, be preferably Skellysolve A, pentamethylene, at least one in sherwood oil etc., described solidifying agent is hydrochloric acid, the vitriol oil, p-methyl benzenesulfonic acid, at least one in phosphoric acid, in described, low solidification value is 60-80 DEG C.
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| CN113149515A (en) * | 2021-04-21 | 2021-07-23 | 贵州国锐鑫节能科技有限公司 | Red mud insulation board and preparation method thereof |
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