CN102408531A - Thermosetting phenolic resin and preparation method thereof - Google Patents
Thermosetting phenolic resin and preparation method thereof Download PDFInfo
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- CN102408531A CN102408531A CN201110257187XA CN201110257187A CN102408531A CN 102408531 A CN102408531 A CN 102408531A CN 201110257187X A CN201110257187X A CN 201110257187XA CN 201110257187 A CN201110257187 A CN 201110257187A CN 102408531 A CN102408531 A CN 102408531A
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Abstract
The invention provides a thermosetting phenolic resin and a preparation method thereof. The preparation method for the thermosetting phenolic resin comprises the following steps: in the presence of a basic catalyst, allowing phenolic compounds and aldehyde compounds to undergo a condensation reaction so as to obtain a primary material of the phenolic resin; adding a cross-linking agent into the primary material of the phenolic resin and carrying out insulation to obtain the thermosetting phenolic resin. According to the invention, after the primary material of the phenolic resin is prepared from phenolic compounds and aldehyde compounds, the cross-linking agent is added into the primary material of the phenolic resin, which enables cross-linkage of the phenolic resin to be increased, low molecular weight linear long-chain structures of the phenolic resin to be reduced and three-dimensional network structures to be increased, and since it is not easy for the three-dimensional network structures to be decomposed into micro-molecules and get volatilized at a high temperature, structural and dimensional stability and carbon yield of the phenolic resin are enhanced; operation is simple, the cross-linking agent is cheap and easily available, and cost for raw materials for the phenolic resin is low.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of heat-reactive phenolic resin and preparation method thereof.
Background technology
Resol is claimed bakelite again, is the superpolymer that phenols and aldehydes make through condensation reaction.Heat-reactive phenolic resin is a synthetic resins of realizing suitability for industrialized production the earliest; It is one of three big thermosetting resins; Resol has that raw material is easy to get, characteristics such as with low cost, heat-resisting, is widely used about machinery, traffic, electronic apparatus and aerospace field.
Good temperature resistance can be one of outstanding characteristic of resol.With respect to other resins, in hot environment, the carbon yield of resol is higher, and this helps keeping the resol stability of structure.This characteristic of resol makes it in high temperature resistant burn-out proof field of materials important use arranged.
In recent years, along with being gradually improved of smelting technology, furnace temperature constantly raises, and this resistance toheat to resol is also had higher requirement.The preparation method of traditional heat-reactive phenolic resin is: under the catalysis of alkaline matters such as sodium hydroxide, excessive aldehyde compound and phenolic cpd reaction generate resol.Traditional heat-reactive phenolic resin has a large amount of low molecular weight volatile things to generate in solidification process; Under hot conditions; These small molecules volatile matter volatilizations cause resol carbon yield problem of lower, and resol is prone to take place volumetric shrinkage during high temperature; In refractory materials, produce hole and cracking, compressive strength and high-temperature oxidation resistant intensity are difficult to satisfy the demand of manufacturer production gradually.
In order to address the above problem, prior art adopts two kinds of methods usually: a kind of is the consumption that improves resol; Second kind is that resol is carried out modification, like organic montmorillonite modified phenolic resin, organic boron modified phenolic resin, boric acid-tung oil modified phenolic resin etc.Method can make cost increase on the one hand in above-mentioned first, and the volatilization gas that another invention produces when also making high temperature is more, and environmental-protecting performance is not good.The most cost of properties-correcting agent that above-mentioned second method adopts is higher, and production technique is also comparatively numerous and diverse.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of a kind of cost thermoset phenolic resin lower, easy and simple to handle.
In view of this, the present invention provides a kind of preparation method of heat-reactive phenolic resin, comprising:
Under the condition that basic catalyst exists, phenolic cpd compounds and aldehyde compound class chemical combination generation condensation reaction obtain resol and just expect;
Just add linking agent in the material to said resol, said linking agent and the resol just weight ratio of material are (2～20): 100, after 70 ℃～90 ℃ insulations, obtain heat-reactive phenolic resin.
Preferably, said linking agent is hexamethylenetetramine, hexamethylene diamine adipate, trimeric cyanamide or quadrol.
Preferably, the weight ratio of the first material of said linking agent and resol is (8～12): 100.
Preferably, the time of said insulation is 5min～30min.
Preferably, the mol ratio of said phenolic cpd and aldehyde compound is 1: (1.5～3.5).
Preferably, the temperature of said condensation reaction is 70 ℃～85 ℃.
Preferably, said phenolic cpd is a phenolic cpd, and aldehyde compound is an aldehyde compound.
The present invention also provides a kind of heat-reactive phenolic resin, its at 800 ℃ carbon yield greater than 46%.
The present invention provides a kind of preparation method of heat-reactive phenolic resin, comprising: under the condition that basic catalyst exists, phenolic cpd and aldehyde compound generation condensation reaction obtain resol and just expect; Just add linking agent in the material to said resol, obtain heat-reactive phenolic resin after the insulation.With respect to existing resol preparation method, the present invention just adds linking agent in the material to resol after preparing the first material of resol with phenolic cpd and aldehyde compound; Improve the degree of crosslinking of resol; Resol lower molecular weight linear long chain structure is reduced, and tridimensional network increases, and network structure is difficult for resolving into the small molecules volatilization during high temperature; Strengthen resol structure and size stability thus, improve the carbon yield of resol.Above-mentioned preparation method only need prepare resol earlier and just add linking agent again behind the material and promptly get, and easy and simple to handle, linking agent is cheap and easy to get, and the resol raw materials cost is lower.
The experiment proof: with respect to traditional heat-reactive phenolic resin, the carbon yield of the thermosetting resin that provides of the present invention improves 6%～9%, and rate of polymerization is faster.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of heat-reactive phenolic resin, comprise the steps:
Under the condition that basic catalyst exists, phenolic cpd and aldehyde compound generation condensation reaction obtain resol and just expect;
Just add linking agent in the material to said resol, said linking agent and the resol just weight ratio of material are (2～20): 100, after 70 ℃～90 ℃ insulations, obtain heat-reactive phenolic resin.
Among the above-mentioned preparation method, the first step is that phenolic cpd and aldehyde compound condensation generate the resol process of material just.In the reaction, the mol ratio of phenolic cpd and aldehyde compound preferably is controlled to be 1: (1.5～3.5), more preferably 1: (2～3).Phenolic cpd preferably adopts phenol, Resorcinol, meta-cresol or p-tert-butylphenol, more preferably adopts phenol.Aldehyde compound preferably adopts formaldehyde.Basic catalyst preferably adopts yellow soda ash cheap and easy to get or sodium hydroxide, and the add-on of catalyzer and the mol ratio of phenolic cpd are preferably (100: 1～3).The too high meeting of catalyzer add-on makes speed of response too fast, and wayward, by product also increases; The catalyzer add-on is crossed to hang down and then can be made the reaction times long, reduces production efficiency.
The temperature of condensation reaction preferably is set to 70 ℃～85 ℃.Reaction times those skilled in the art can select according to speed of reaction, preferably when 80%～98% aldehyde compound participated in the reaction after stopped reaction, the reaction times can be 1h～4h.
After the condensation reaction, contain a large amount of unreacted aldehyde compounds and phenolic cpd in the mixture that reaction obtains, the too high meeting of above-mentioned level of residual monomers impacts the resistance toheat of resol.For this reason, the mixture heating up to 90 that need under vacuum condition, reaction be obtained ℃～100 ℃ preferably heats until aldehyde compound content less than 1%, obtains resol and just expects.
The resol that obtains according to the method described above is prone to produce more small molecules volatile matter when high temperature, this also is one of existing resol carbon yield reason of lower, in order to reduce the influence of above-mentioned small molecules volatile matter to the resol carbon yield; In second step of the present invention; Just add linking agent in the material to resol, the purpose that adds linking agent is to improve the degree of crosslinking of resol, and resol lower molecular weight linear long chain structure is reduced; Tridimensional network increases; Network structure is difficult for resolving into the small molecules volatilization during high temperature, strengthens resol structure and size stability thus, improves carbon yield.
Linking agent preferably adopts hexamethylenetetramine, hexamethylene diamine adipate, trimeric cyanamide or quadrol, more preferably adopts hexamethylenetetramine.Linking agent that adds and the resol just weight ratio of material are (2～20): 100, be preferably (8～12): 100.The too high product crosslinking degree that makes easily of linking agent add-on is excessive, and the phenolic resin bonded performance that makes reduces greatly, can cause solid still when serious.The linking agent add-on is crossed to hang down and then can be made the degree of crosslinking of resol low excessively, is difficult to play the effect of rock steady structure.
After in resol, adding linking agent, resol and linking agent generation crosslinking reaction, the temperature of crosslinking reaction are made as 70 ℃～90 ℃; Be preferably 75 ℃～85 ℃; The too high crosslinking reaction that then can make of temperature is too violent, is difficult to control level of response, causes solid still when serious; Temperature is crossed the low reaction time course, reduces production efficiency, increases cost.
The time of crosslinking reaction, promptly soaking time preferably is made as 5min～30min, and the reaction times is long more, and the degree of crosslinking of resol is high more, and the too high resol that then can make of degree of crosslinking loses adhesiveproperties.
Obtain according to the method described above also can in resol, add the viscosity that solvent is regulated resol according to request for utilization behind the resol, solvent preferably adopts furfuryl alcohol.
Can know that by such scheme the present invention just adds linking agent in the material to resol after preparing the first material of resol with phenolic cpd and aldehyde compound; Improve the degree of crosslinking of resol; Resol lower molecular weight linear long chain structure is reduced, and tridimensional network increases, and network structure is difficult for resolving into the small molecules volatilization during high temperature; Strengthen resol structure and size stability thus, improve the carbon yield of resol.Above-mentioned preparation method only need prepare resol earlier and just add linking agent again behind the material and promptly get, and easy and simple to handle, linking agent is cheap and easy to get, and the resol raw materials cost is lower.
Accordingly, the present invention also provides a kind of heat-reactive phenolic resin, and it greater than 46%, is about 46%～52% at 800 ℃ carbon yield.Has the better heat-resisting performance.
In order further to understand the present invention, below in conjunction with embodiment heat-reactive phenolic resin its preparation method provided by the invention to be described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
1, be to add in reaction kettle at 1: 0.02 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 75 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 2.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, to the first adding 10g hexamethylenetetramine in the material of resol, slowly be heated to 80 ℃, constant temperature 15min is cooled to room temperature, obtains heat-reactive phenolic resin.
Embodiment 2
1, be to add in reaction kettle at 1: 0.01 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 70 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 1.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, to the first adding 5g hexamethylenetetramine in the material of resol, slowly be heated to 75 ℃, constant temperature 15min is cooled to room temperature, obtains heat-reactive phenolic resin.
Embodiment 3
1, be to add in reaction kettle at 1: 0.03 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 85 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 3.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, to the first adding 20g hexamethylenetetramine in the material of resol, slowly be heated to 90 ℃, constant temperature 15min is cooled to room temperature, obtains heat-reactive phenolic resin.
Embodiment 4
1, be to add in reaction kettle at 1: 0.02 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 80 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 2.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, to the first adding 8g hexamethylene diamine adipate in the material of resol, slowly be heated to 80 ℃, constant temperature 15min is cooled to room temperature, obtains heat-reactive phenolic resin.
Embodiment 5
1, be to add in reaction kettle at 1: 0.02 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 75 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 2.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, just add the 12g trimeric cyanamide in the material to resol, slowly be heated to 80 ℃, constant temperature 15min is cooled to room temperature, and the furfuryl alcohol of adding 5% stirs, and obtains heat-reactive phenolic resin.
Embodiment 6
1, be to add in reaction kettle at 1: 0.02 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 80 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 2.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol and just expect.
2, get the resol that 100g step 1 obtains and just expect, just add the 10g quadrol in the material to resol, slowly be heated to 80 ℃, constant temperature 15min is cooled to room temperature, and the furfuryl alcohol of adding 5% stirs, and obtains heat-reactive phenolic resin.
Comparative example 1
1, be to add in reaction kettle at 1: 0.02 phenol and sodium hydrogencarbonate according to the amount ratio, heated and stirred to 75 ℃ adds formaldehyde solution then in reaction kettle; The formaldehyde that adds and the mol ratio of phenol are 1: 2.5; Isothermal reaction 3～4 hours is heated to 95 ℃ under 0.05MPa, be lower than at 1% o'clock until formaldehyde content and stop heating; Be cooled to room temperature, obtain resol.
The resol of embodiment 1～6 and comparative example 1 preparation is carried out viscosity, free phenol, polymerization velocity and carbon yield test, test result is listed in table 1.
Table 1 resol test result
Can be known by The above results: with respect to traditional heat-reactive phenolic resin, the carbon yield of the thermosetting resin that provides of the present invention improves 6%～9%, and rate of polymerization is faster; Above-mentioned preparation method only needs to expect that just the back adds the comparatively cheap linking agent of price and promptly gets preparing resol that easy and simple to handle, cost is lower.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (8)
1. the preparation method of a heat-reactive phenolic resin is characterized in that, comprising:
Under the condition that basic catalyst exists, phenolic cpd compounds and aldehyde compound class chemical combination generation condensation reaction obtain resol and just expect;
Just add linking agent in the material to said resol, said linking agent and the resol just weight ratio of material are (2～20): 100, after 70 ℃～90 ℃ insulations, obtain heat-reactive phenolic resin.
2. preparation method according to claim 1 is characterized in that, said linking agent is hexamethylenetetramine, hexamethylene diamine adipate, trimeric cyanamide or quadrol.
3. according to the preparation method of claim 1, it is characterized in that said linking agent and the resol just weight ratio of material are (8～12): 100.
4. preparation method according to claim 1 is characterized in that, the time of said insulation is 5min～30min.
5. preparation method according to claim 1 is characterized in that, the mol ratio of said phenolic cpd and aldehyde compound is 1: (1.5～3.5).
6. preparation method according to claim 1 is characterized in that, the temperature of said condensation reaction is 70 ℃～85 ℃.
7. according to the preparation method of claim 1, it is characterized in that said phenolic cpd is a phenolic cpd, aldehyde compound is an aldehyde compound.
8. a heat-reactive phenolic resin is characterized in that, its at 800 ℃ carbon yield greater than 46%.
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| CN105462162A (en) * | 2016-02-02 | 2016-04-06 | 安徽建筑大学 | A-grade fireproof toughening thermosetting resole and preparation method thereof |
| CN109467662A (en) * | 2018-10-12 | 2019-03-15 | 北京玻钢院复合材料有限公司 | A kind of RTM type boron bakelite resin and preparation method thereof |
| CN109735110A (en) * | 2019-01-15 | 2019-05-10 | 哈尔滨工业大学 | A kind of modified phenolic-organic siliconresin composite material and preparation method |
| CN109810278A (en) * | 2019-01-14 | 2019-05-28 | 陕西康源化工有限责任公司 | One kind having spherical phenolic resin compound of microvoid and its preparation method and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462162A (en) * | 2016-02-02 | 2016-04-06 | 安徽建筑大学 | A-grade fireproof toughening thermosetting resole and preparation method thereof |
| CN105462162B (en) * | 2016-02-02 | 2018-01-02 | 安徽建筑大学 | A kind of A levels fire prevention toughened thermosetting resol and preparation method thereof |
| CN109467662A (en) * | 2018-10-12 | 2019-03-15 | 北京玻钢院复合材料有限公司 | A kind of RTM type boron bakelite resin and preparation method thereof |
| CN109467662B (en) * | 2018-10-12 | 2021-06-04 | 北京玻钢院复合材料有限公司 | RTM type boron phenolic resin and preparation method thereof |
| CN109810278A (en) * | 2019-01-14 | 2019-05-28 | 陕西康源化工有限责任公司 | One kind having spherical phenolic resin compound of microvoid and its preparation method and application |
| CN109735110A (en) * | 2019-01-15 | 2019-05-10 | 哈尔滨工业大学 | A kind of modified phenolic-organic siliconresin composite material and preparation method |
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