CN104356326A - Organic-ester-cured phenolic aldehyde resin and preparation method thereof - Google Patents
Organic-ester-cured phenolic aldehyde resin and preparation method thereof Download PDFInfo
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- CN104356326A CN104356326A CN201410736090.0A CN201410736090A CN104356326A CN 104356326 A CN104356326 A CN 104356326A CN 201410736090 A CN201410736090 A CN 201410736090A CN 104356326 A CN104356326 A CN 104356326A
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Abstract
The invention provides organic-ester-cured phenolic aldehyde resin and a preparation method thereof. The organic-ester-cured phenolic aldehyde resin is prepared from the following components in parts by weight: 55-90 parts of phenol, 120-210 parts of formaldehyde, 10-50 parts of lignin and 80-150 parts of caustic soda liquid. According to the organic-ester-cured phenolic aldehyde resin, the production cost is decreased, the usage amount of toxic substances such as formaldehyde and phenol is reduced and meanwhile, such problems of existing products as difficulty in cleaning sand and disadvantage of recycling of used sand due to poor collapsibility are solved.
Description
Technical field
The present invention relates to a kind of organic ester hardening resol, relate to its preparation method simultaneously.
Background technology
China is the first big country of world production foundry goods.Cast steel more than 80% adopts water virus in process of production, substantially cannot regeneration, has the alkaline old sand of up to ten million ton to abandon every year, causes serious environmental pollution, does not meet the environmental protection policy of country.Power consumption is large, toxic gas burst size is large, worker laboring environment is severe to adopt hot core box resin technique then to exist; Triethylamine cold-box, sulfurous gas cold-box are a large amount of with an organic solvent, furan resin hardener contains a large amount of element sulphur, can discharge benzene class sulfur dioxide gas during application, and serious harm operator healthy also damages environment.And organic ester hardening resol adopts nontoxic cheap water as solvent, therefore to environment without any pollution, to being engaged in the workman of casting without any harm, it is a kind of environmental type foundry binders, without furfuryl alcohol in this resin glue, also not containing elements such as N, S, P, not containing sulfonic acid in solidifying agent.Therefore, can effectively prevent from producing the casting flaw such as carburizing, sulfurizing in steel casting surface layer; Because this resin exists " secondary hardening " phenomenon, namely the alkalescent phenol resin sand after its sclerosis still maintains certain thermoplasticity, during cast, phenolic resin film is through of short duration thermoplasticity stage, form firm resin molding again, therefore the core sand of this resin has deformability more good than furan resin-sand, thus, the generation of Hot Tearing in Steel Castings class defect can be reduced; Can greatly improve casting quality, improve Working environment, increase work efficiency, start in recent years extensively to be adopted by domestic steel foundry.
Xylogen is the organism of a kind of extensive existence of nature, is not widely used so far, not only causes the waste of resource, also causes the pollution of environment.Due to the structure of xylogen having phenyl ring, aldehyde radical and hydroxyl above, may be used for the synthesis of resol, be used for replacing phenol to reduce costs and toxic substance consumption, but due to the structure of xylogen also containing ketone group, carboxyl, methoxyl group and ethylene linkage etc., cause side reaction more when synthesizing for resol, quality product is difficult to control, and limits it and uses.
Use lignin synthesis resol, do a lot of research both at home and abroad, such as, in patent CN 101358120A, lignin synthesis resol is utilized to be used as wood adhesive, but need to process xylogen with sulfuric acid, hydrochloric acid, trifluoroacetic acid, beta naphthal and oxygenant, technique is more complicated and add toxic substance consumption.In patent CN 101607297A, utilize novolak resin to be used as casting binder, but organobentonite raising strength and stability will be added, and must use be dried.
Current along with the continuous increase of global demand of petroleum and the decline of storage capacity, oil constantly appreciates, and as the phenol of raw material production along with when the river rises the boat goes up, cause derived product resol cost increase, profit constantly reduces.Xylogen, as the reproducible natural biomass organic materials of one, is used for replacing phenol and reducing formaldehyde consumption, can reduces costs and toxic substance consumption.Utilize phenol and formaldehyde to prepare resole under strong alkali catalyst exists, then react with it with xylogen, also can obtain the tackiness agent of better performances.The chemical affinity of resole and xylogen is better, has the reactive behavior with xylogen copolymerzation with cross-linking.
Although organic ester hardening resol plurality of advantages, because this resin exists " secondary hardening " phenomenon, hot strength is higher, causes collapsibility poor, have impact on the regeneration of resin sand, affects and limits this technique further genralrlization and use.Because xylogen adds use, improve molding sand high temperature collapsibility simultaneously, be conducive to the recycling of old sand, the recovery utilization rate of resin sand can be improved.
Summary of the invention
In order to solve Problems existing in currently available technology, the invention provides the casting organic ester hardening alkaline phenolic resin of a kind of low cost, low phenol and formaldehyde toxic substance consumption.
Another object of the present invention is improved the casting organic ester hardening alkaline phenolic resin of molding sand high temperature collapsibility, solve currently available products because of collapsibility poor, cause sand removal difficulty, be unfavorable for the problem of the recycling of old sand.Because xylogen adds use, phenolic resin structure is changed, and under high temperature, intensity decreases, thus improves molding sand high temperature collapsibility, is conducive to the recycling of old sand.
Therefore the present invention proposes a kind of organic ester hardening alkaline phenolic resin adhesive composition, comprises the aqueous solution of alkalescent phenol resin, alkali, and described alkalescent phenol resin replaces part phenol and formaldehyde to obtain with xylogen.
Organic ester hardening resol provided by the invention, the composition primarily of following weight part is prepared from:
Phenol 55 ~ 90
Formaldehyde 120 ~ 210
Xylogen 10 ~ 50
Liquid caustic soda 80 ~ 150;
Described alkali lye is the potassium hydroxide of 48% or the sodium hydroxide of 35%.
The present invention also provides a kind of preparation method of organic ester hardening alkaline phenolic resin, and it comprises the steps:
1, phenol and xylogen are after thawing, add the half of liquid caustic soda total amount, are warming up to 90 DEG C of reactions 30 minutes;
2, in one hour, formaldehyde was added dropwise at 30 minutes, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour;
3, be cooled to 70 ~ 80 DEG C and add remainder liquid caustic soda, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), cooling;
The water of 3-17 weight part is added when 4, being cooled to below 30 DEG C.
Further, described phenol is the polyatomic phenols such as alkylbenzene phenols or pyrocatechol, Resorcinol, Resorcinol such as cresols, xylenol, butylphenol, one or more in the bisphenols such as dihydroxyphenyl propane, Bisphenol F.
Further, described xylogen is high reactivity xylogen, and high reactivity xylogen is the xylogen that a kind of conventional reactive behavior is higher, because of methylol in its xylogen with phenolic hydroxyl group quantity is many and aromatic ring replaces less and active high.In addition, the preferred conifer xylogen of high reactivity xylogen of the present invention, broad-leaved wood element or one or more of vegetation class xylogen.
Above resin can add the silane coupling agent accounting for weight resin 1.0%, is used for improving binding agent to the adhesion strength of sand grains, and the attachment reducing resin sand is broken.Silane conventional in prior art comprises triamino propyl trimethoxy silicane, N-(2-ethylamine)-3-TSL 8330, phenyl-trimethylsilicane or three-glycidyl ether propyl trimethoxy silicane.
The present invention utilizes xylogen under strongly alkaline conditions, with formaldehyde generation hydroxymethylation, decreases because of the structural ketone group of xylogen, carboxyl, methoxyl group and ethylene linkage etc., affects side reaction during resol synthesis.Utilize phenol and formaldehyde to prepare resole under strong alkali catalyst exists, then react with it with xylogen, also can obtain the tackiness agent of better performances.The chemical affinity of resole and xylogen is better, has the reactive behavior with xylogen copolymerzation with cross-linking, participates in addition, polycondensation together, obtain resol alkaline aqueous solution.
The present invention does not need to carry out complicated pre-treatment to xylogen.Be utilize xylogen under strongly alkaline conditions, with formaldehyde generation hydroxymethylation, decrease because of the structural ketone group of xylogen, carboxyl, methoxyl group and ethylene linkage etc., affect side reaction during resol synthesis.Participate in addition, polycondensation together with phenol, obtain resol alkaline aqueous solution.
On the structural unit of xylogen, existing phenolic hydroxyl group has aldehyde radical again, therefore at synthesis xylogen---during resol, namely xylogen can be used as phenol and formaldehyde reaction, can be used as again aldehyde and phenol reactant, both can save formaldehyde, can save again and replace phenol to reduce production cost, current phenol price is high more than 10,000 yuan/ton, xylogen only has 1,000 to several thousand yuan/ton, reduces formaldehyde toxic substance consumption simultaneously.Part 10 ~ 50% phenol can be replaced after xylogen adds and reduce by 2 ~ 10% formaldehyde consumptions.
Because xylogen adds use, phenolic resin structure is changed, and under high temperature, intensity decreases, thus improves molding sand high temperature collapsibility, is conducive to the recycling of old sand.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In reaction flask, add phenol 90g, startup stirring adds xylogen 10g and melts; Add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 170g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 48% potassium hydroxide solution 120g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 3g, cooling.
Embodiment 2
In reaction flask, add phenol 70g, startup stirring adds xylogen 30g and melts; Add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 162g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 48% potassium hydroxide solution 143g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 6g, cooling.
Embodiment 3
In reaction flask, add phenol 60g, startup stirring adds xylogen 40g and melts; Add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 165g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 150g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 6g, cooling.
Embodiment 4
In reaction flask, add phenol 55g, startup stirring adds xylogen 50g and melts; Add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 145g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 48% potassium hydroxide solution 80g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 17g, cooling.
Embodiment 5
In reaction flask, add phenol 90g, startup stirring adds xylogen 10g and melts; Add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 169g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 143g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 3g, cooling.
Embodiment 6
In reaction flask, add phenol 70g, startup stirring adds xylogen 30g and melts; Add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 210g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 120g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 6g, cooling.
Embodiment 7
In reaction flask, add phenol 70g, startup stirring adds xylogen 30g and melts; Add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 162g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 48% sodium hydroxide solution 120g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 6g, cooling.
Embodiment 8
In reaction flask, add phenol 55g, startup stirring adds xylogen 50g and melts; Add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 30 minutes;
37% formaldehyde 155g is added dropwise to, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour in 30 minutes to one hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 130g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), add water 17g, cooling.
Above resin can add the silane coupling agent accounting for weight resin 1.0%, is used for improving binding agent to the adhesion strength of sand grains, and the attachment reducing resin sand is broken.Silane conventional in prior art comprises triamino propyl trimethoxy silicane, N-(2-ethylamine)-3-TSL 8330, phenyl-trimethylsilicane or three-glycidyl ether propyl trimethoxy silicane.
Comparative example 1
In reaction flask, add phenol 100g, start stirring and add 37% formaldehyde 173g, be warming up to 80 ~ 90 DEG C, in 30 minutes to one hour, be added dropwise to content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 1 ~ 2 hour;
Be cooled to 70 ~ 80 DEG C and add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), cooling.
Comparative example 2
In reaction flask, add phenol 100g, start stirring and add 37% formaldehyde 173g, be warming up to 80 ~ 90 DEG C, in 30 minutes to one hour, be added dropwise to content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions 1 ~ 2 hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), cooling.
Comparative example 3
In reaction flask, add phenol 100g, start stirring and add 37% formaldehyde 173g, be warming up to 80 ~ 90 DEG C, in 30 minutes to one hour, be added dropwise to content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 1 ~ 2 hour;
Be cooled to 70 ~ 80 DEG C and add content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), cooling.
Comparative example 4
In reaction flask, add phenol 100g, start stirring and add 37% formaldehyde 173g, be warming up to 80 ~ 90 DEG C, in 30 minutes to one hour, be added dropwise to content 35% sodium hydroxide solution 43g, be warming up to 90 DEG C of reactions 1 ~ 2 hour;
Be cooled to 70 ~ 80 DEG C and add content 48% potassium hydroxide solution 43g, be warming up to 90 DEG C of reactions, reach 80 ~ 200mPa.s(25 DEG C to make resin viscosity), cooling.
Above resin can add the silane coupling agent accounting for weight resin 1.0%, is used for improving binding agent to the adhesion strength of sand grains, and the attachment reducing resin sand is broken.Silane conventional in prior art comprises triamino propyl trimethoxy silicane, N-(2-ethylamine)-3-TSL 8330, phenyl-trimethylsilicane or three-glycidyl ether propyl trimethoxy silicane.
Ultimate compression strength and collapsibility test result
Take 1000g standard sand, pour in the mulling alms bowl of resin sand mixer.Start resin sand mixer, the 4.5g vanay weighed up evenly is poured in agitator kettle, stir 60s; Again the 18g resin weighed up is poured in agitator kettle, shake out after continuing to stir 120s.Make the cylindrical standard sample meeting the regulation of GB/T 2684, ultimate compression strength tested by the gentle 24H of the putting sand strength testing machine of sample chamber.
Room temperature is deposited 24H sample and distinguish roasting 30 minutes at 300 DEG C, 400 DEG C temperature, and the high-temperature residual recorded after cooling examination ultimate compression strength, this resin collapsibility of the low proof of intensity results is good.
From embodiment and comparative example, the present invention replaces part 10 ~ 50% phenol by utilizing xylogen and reduces by 2 ~ 10% formaldehyde toxic substance consumptions, improve molding sand high temperature collapsibility simultaneously, be conducive to the recycling of old sand, although normal temperature ultimate compression strength slightly reduces, but still the service requirements of Foundry Production can be met.
Claims (2)
1. an organic ester hardening resol, is characterized in that, is prepared from by the composition of following weight part:
Phenol 55 ~ 90
Formaldehyde 120 ~ 210
Xylogen 10 ~ 50
Liquid caustic soda 80 ~ 150;
Described alkali lye is the potassium hydroxide of 48% or the sodium hydroxide of 35%.
2. a preparation method for organic ester hardening resol according to claim 1, is characterized in that, comprise the steps:
1) phenol and xylogen are after thawing, add the half of liquid caustic soda total amount, are warming up to 90 DEG C of reactions 30 minutes;
2) in one hour, formaldehyde was added dropwise at 30 minutes, 90 ~ 95 DEG C of isothermal reactions 1 ~ 2 hour;
3) be cooled to 70 ~ 80 DEG C and add remainder liquid caustic soda, be warming up to 90 DEG C of reactions, to make resin viscosity reach 80 ~ 200mPa.s, cooling;
4) water of 3-17 weight part is added when being cooled to below 30 DEG C.
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| CN103497295A (en) * | 2013-10-14 | 2014-01-08 | 南京林业大学 | In-situ ultrasonic polymerization preparation method for industrial alkali lignin modified phenolic resin |
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| CN103497295A (en) * | 2013-10-14 | 2014-01-08 | 南京林业大学 | In-situ ultrasonic polymerization preparation method for industrial alkali lignin modified phenolic resin |
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