CN103059338B

CN103059338B - Polymerizable organic strong acid / sulfuric acid composite curing agent and foamable phenolic resin combination thereof

Info

Publication number: CN103059338B
Application number: CN201210559477.4A
Authority: CN
Inventors: 胡和丰; 黄洪亮; 方琳; 邱郑富; 刘瑞瑞
Original assignee: University of Shanghai for Science and Technology
Current assignee: BEIJING POLYTECH INC.
Priority date: 2012-12-21
Filing date: 2012-12-21
Publication date: 2014-10-01
Anticipated expiration: 2032-12-21
Also published as: CN103059338A

Abstract

The invention discloses a polymerizable organic strong acid / sulfuric acid composite curing agent and a foamable phenolic resin combination thereof. The combination comprises 100 parts of liquid A-stage phenolic resin, 7-9 parts of foaming agents, 2-6 parts of foam stabilizer, and 6-10 parts of polymerizable organic strong acid / sulfuric acid composite curing agents. The polymerizable organic strong acid / sulfuric acid composite curing agents are obtained through phenol or metacresol sulfonated in slightly excessive concentrated sulfuric acid, postprocessing processes of separation and the like are not needed, preparation processes are simple, and cost in low. The polymerizable organic strong acid / sulfuric acid composite curing agent can be chemically bonded with phenolic resin and directly brought in structure of foams, the polymerizable organic strong acid / sulfuric acid composite curing agent is not easy to permeate, small in corrosivity of base materials due to the fact that the potential of hydrogen (PH) value of the obtained foams reaches up to 5.8, rapid in foaming speed, and free from foam collapse and foam contraction.

Description

Polymerizable organic acid/sulfuric acid composite curing agent and can foamed phenolic resin composition

Technical field

The present invention relates to a kind of polymerizable organic acid/sulfuric acid composite curing agent and can foamed phenolic resin composition.

Background technology

Foam of polymers is because of its porous, light weight, the low heat preserving and insulating material that is used as of heat transfer coefficient.Conventional several polymer foams have polyurethane foam, polystyrene foam, polyethylene, phenolic resin foam etc. at present.Although wherein urethane, polystyrene, polyethylene high insulating effect, intensity are high, but all exist that heat resisting temperature is low, the shortcoming such as easy firing, burning easily drip, the amount of being fuming is large, make it in actual applications, particularly the application at aspects such as high-temperature pipe insulation, buildings is restricted.And phenolic foam material is when having high insulating effect, also there is good thermotolerance, use temperature can reach 250 ℃.More valuable is that it has good resistance to flame, and in the time of certainly putting out, burn, the amount of being fuming is little, chance fire penetrates without dropping, low-smoke low-toxicity, flame resistant etc.Thereby make it in heat-insulation and heat-preservation field, there is unique status, quite active in the research and development of developed country, America and Europe and various countries, the Middle East specify in architectural design and preferentially select phenol formaldehyde foam as heat-insulating heat-preserving material.

Phenolic foam material is to take liquid A step phenolic resin to coordinate with whipping agent, suds-stabilizing agent, solidifying agent and other auxiliary agents the thermoset closed-cell foam material processing as main raw material.Expandable phenolic resin is under certain temperature and the initiation at solidifying agent, there is crosslinking reaction, emit large calorimetric simultaneously, impel low-boiling foaming agent gasification, and under the effect of suds-stabilizing agent, form microvesicle pore structure and fixed by resin, obtain the uniform phenolic foams of foam structure.

Can cause the solidifying agent that liquid A step phenolic resin is cured reaction and be generally mineral acid as sulfuric acid, phosphoric acid, Hydrogen bromide, boric acid etc., can be also that organic acid is as Phenylsulfonic acid, tosic acid, acetic acid, naphthene sulfonic acid etc.Mineral acid has fast, the completion of cure of short, expansion rate inductive phase, is difficult for producing the features such as bubble phenomenon and good stability of the dimension of collapsing; Organic acid has longer inductive phase, foaming slowly, easily produces the phenomenons such as bubble phenomenon and contraction of collapsing.Also have mineral acid and organic acid compound use to improve its effect.But no matter be that organic acid, mineral acid or its mixture are as solidifying agent, in the agent of phenol resin composition foaming after fixing, still with free state, be present in foams, foams pH value is low, acid large, and free acidic substance easily infiltrate into surface and some base materials is produced to stronger corrodibility, thereby limited the application of phenol formaldehyde foam at numerous areas such as military affairs, space flight, buildings.For a long time, phenolic foam material is the focus that people pay close attention to the etching problem of base material always.For addressing this problem, Chinese scholars has been carried out a series of research.

US7605189 provides a kind of preparation technology of phenol formaldehyde foam, the solid-state whipping agent of resol and thermolysis is prepared to gel sheet material after evenly through hot-rolling is mixing on rolling press, reheat and make whipping agent resolve into gas formation phenolic foams, and further after the high-temperature heat treatment of 170 ℃, form the phenol formaldehyde foam of high strength, light weight and low acidity.The method utilizes under methylol high temperature self condensation to form crosslinking structure, without using acid curing agent, thus the corrosion problems of having avoided acid curing agent to bring, but the method requires highly to equipment, and complex process, controls difficulty large, solidification value is high, and energy consumption is large, and cost is higher; WO9404604 provides a kind of and has prepared phenol formaldehyde foam by resol, alkyl-alkoxyl group phenols tensio-active agent and silanol copolymer analog tensio-active agent, Skellysolve A, mineral acid and aromatic sulphonic acid, again curing foam is placed at 63～71 ℃ to NH3 36h, the method of the residual acid in neutralization reaction, the acidity of reduction phenol formaldehyde foam.But the method need to by preparation phenol formaldehyde foam again under NH3 environment in and 36 hours, the production cycle is long, operation is more complicated, production efficiency is low; JP2010285496 provides a kind of method of preparing phenol formaldehyde foam by resol, Skellysolve A, xylene monosulfonic acid, organosilicon and calcium carbonate, and the prepared phenol formaldehyde foam acidity of the method is low, and pH reaches 6.0; CN101305034A and CN101305035A disclose a kind of phenolic foams, and its proportioning raw materials is: 100 parts, resol; 1 ~ 20 part of whipping agent; 5 ~ 25 parts of catalyzer; 1 ~ 20 part of mineral filler; 1 ~ 6 part, tensio-active agent.Catalyzer is at least one in Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, naphthene sulfonic acid, EBSA and sulfocarbolic acid; Mineral filler is at least one in following material: metal oxide is as aluminum oxide or zinc oxide; Metal-powder is as zinc; Metal hydroxides is as aluminium hydroxide, magnesium hydroxide; Or metal carbonate is as magnesiumcarbonate, barium carbonate, calcium carbonate, zinc carbonate, phenol formaldehyde foam pH value prepared by the method is more than or equal to 5.Above method is by adding one or more in alkaline inorganics metal-powder, metal oxide, metal hydroxides or metal carbonate etc., make after phenolic foam slowly in and residual acid, to reduce the acidity of phenol formaldehyde foam, reduce its corrodibility.But in aforesaid method, only use organic acid as solidifying agent, and be neutralized agent consumption in the partly solidified dose of batch mixing process before phenolic resin curing, reach same expansion rate, need greatly increase the consumption of solidifying agent even up to 25%; CN102675821A provides a kind of preparation method of low acid phenol formaldehyde foam, and its proportioning raw materials is: 100 parts of expandable phenolic resins; 2 ~ 8 parts, tensio-active agent; 5 ~ 10 parts of whipping agents; 10 ~ 50 parts of neutralizing agents; 1 ~ 5 part of acid-acceptor; 10 ~ 20 parts, solidifying agent.Neutralizing agent is at least one in hydrated barta, magnesium hydroxide, magnesium oxide, calcium oxide, calcium carbonate etc.; Acid-acceptor is the amino-contained polymer beads of glutaraldehyde cross-linking, and the phenol formaldehyde foam acidity of preparation is low, and pH is 5 ~ 6.The method is at CN101305034A, on the basis of CN101305035A and JP2010285496, with organic bases acid-acceptor, replace the inorganic neutralizing agent of part, consumption to solidifying agent in the time of can reducing batch mixing, reduce the consumption of solidifying agent, can be down to 20%, but so-called acid-acceptor is in fact also a kind of neutralizing agent, it is just a kind of organic weak base, slower with reacting of solidifying agent, can reduce the consumption to solidifying agent in batch mixing process, but do not solve the problem that acid curing agent consumption is large, and in aforesaid method, add the apparent density of prepared phenol formaldehyde foam after inorganic neutralizing agent or acid-acceptor to increase, security and heat-insulating property reduce.

Summary of the invention

One of object of the present invention is to provide a kind of polymerizable organic acid/sulfuric acid composite curing agent.

What two of object of the present invention was to provide a kind of low acid low-corrosiveness can foamed phenolic resin composition.

The present invention using polymerisable organic acid with a small amount of sulfuric acid mixture as solidifying agent, polymerisable organic acid is sulfocarbolic acid or m-cresolulfonic acid, by phenol or meta-cresol Direct Sulfonation and obtaining in the slightly excessive vitriol oil, and after sulfonation finishes, add the polymerisable thinner dissolution of part, take and guarantee that composite curing agent is as homogeneous phase is with easy to use.Sulfocarbolic acid and m-cresolulfonic acid have following structure:

Sulfocarbolic acid m-cresolulfonic acid

When it is during as first rank liquid phenolic resin solidifying agent, can occur react as follows with resol:

Acid curing agent is connected on the integral part that becomes foams in resol structure with chemical bond-linking, can infiltration migration to foam surface, thereby the pH value of prepared phenol formaldehyde foam can reach 5.8, has greatly alleviated the acid attack to base material.The employing product that Direct Sulfonation technique obtains in the excessive vitriol oil is the mixture of sulfocarbolic acid or m-cresolulfonic acid and a small amount of sulfuric acid, excessive a small amount of sulfuric acid is without separation, be present in while just in time having made up the foaming of organic acid solidifying agent in solidifying agent inductive phase longer, curing speed is slower, the shortcoming of easily collapsing bubble or shrinking.

According to above-mentioned mechanism, the present invention adopts following technical scheme:

Polymerizable organic acid/sulfuric acid composite curing agent, is characterized in that this solidifying agent is comprised of sulfocarbolic acid or m-cresolulfonic acid, sulfuric acid and thinner, and wherein the mol ratio of sulfocarbolic acid or m-cresolulfonic acid and sulfuric acid is 1:0.1～0.3; Described thinner is at least one in ethylene glycol, glycol ether, Triethylene glycol, and its consumption accounts for 20%～35% of solidifying agent total mass.

A kind of method of preparing above-mentioned polymerizable organic acid/sulfuric acid composite curing agent, the concrete steps that it is characterized in that the method are: phenol or meta-cresol are preheated to 75～85 ℃, stir in lower 1 hour and slowly add the vitriol oil, add rear continuation reaction 2.5～3.5 hours; Add thinner, cooling discharging after stirring, obtains polymerizable organic acid/sulfuric acid composite curing agent again; The mol ratio of described phenol or meta-cresol and sulfuric acid is 1:1.1～1:1.3.

Can a foamed phenolic resin composition, by above-mentioned polymerizable organic acid/sulfuric acid composite curing agent, be solidifying agent, it is characterized in that the composition of said composition and mass fraction thereof are:

100 parts of liquid A step phenolic resins;

7 ~ 9 parts of whipping agents;

2 ~ 6 parts of suds-stabilizing agents;

6 ~ 10 parts of polymerizable organic acid/sulfuric acid composite curing agents.

Above-mentioned liquid A step phenolic resin solid content is that the viscosity of 80 ~ 85%, 25 ℃ is 2000 ~ 5000mpa.s.

Above-mentioned whipping agent is a kind of in low boiling point solvent Skellysolve A, methylene dichloride, sherwood oil.

Above-mentioned suds-stabilizing agent is at least one in Tweens tensio-active agent, silicone tensio-active agent or class of department class tensio-active agent.

Above-mentioned Tweens tensio-active agent is: at least one in tween-80, Tween-60, tween 20.

Above-mentioned silicone tensio-active agent is: at least one in DC-193, DC-198, DC-2525.

Above-mentioned class of department class tensio-active agent is: at least one in span-80, Si Ban-60, Si Ban-20.

Organic acid in polymerizable organic acid/sulfuric acid composite curing agent described in composition of the present invention can be sulfocarbolic acid or m-cresolulfonic acid.Active site in Foaming of phenolic resin process on sulfocarbolic acid or m-cresolulfonic acid can with resole on methylol condensation, be introduced directly in foamy structure, become a part for foams.Rather than the form of free acid is present in foams, the corrodibility of infiltration migration to foam surface and to base material.Its reaction signal formula is as follows:

In above-mentioned preparation process, the ratio of phenol or meta-cresol and sulfuric acid is 1:1.1 ~ 1:1.3.Sulfuric acid is slightly excessive, and after sulfonation reaction, excessive sulfuric acid forms polymerizable organic acid/sulfuric acid composite curing agent with sulfocarbolic acid or m-cresolulfonic acid in system.When excess sulfuric acid is too much, the free acid after foaming in foams is many, and pH value is low; Sulfuric acid is very little time, and in composite curing agent, inorganic acid is few, and the curing speed that can slow down when curing, even causes the bubble phenomenon of collapsing.Optimized phenol or meta-cresol and sulfuric acid ratio are 1:1.15 ~ 1:1.25.

Above-mentioned steps described thinner is a kind of or its mixture in ethylene glycol, glycol ether, Triethylene glycol, and its consumption accounts for 20% ~ 35% of solidifying agent total amount.Thinner plays dissolution effect in system, guarantees that composite curing agent keeps homogeneous phase, with easy to use.The thinner adopting can participate in reaction simultaneously, becomes a part for foamy structure, and foams are played to toughening effect.Its reaction formula is as follows:

Compare with conventional art, the present invention has following outstanding substantial advantage and marked improvement:

1. adopt polymerizable organic acid/sulfuric acid composite curing agent, during foaming, solidifying agent is directly connected and is incorporated in foam structure with foams with chemical bond, without infiltration migration, prepared foams pH value Gao Keda 5.8, corrodibility to base material is little, and expansion rate is fast, without collapsing bubble phenomenon.

2. phenol or meta-cresol sulfonation in the slightly excessive vitriol oil, product is without waiting post-processing step through separation, excessive sulfuric acid and the sulfocarbolic acid of generation or m-cresolulfonic acid are directly made polymerizable organic acid/sulfuric acid composite curing agent through thinner hydrotropy, technique is simple, cost is low, workable.

3. the present invention does not add any inorganic neutralizing agent or acid-acceptor, and solidifying agent usage quantity is few, is only 6 ~ 10%, system phenol formaldehyde foam apparent density low, heat insulation effect and security are good.

Embodiment

Following instance is in order to further illustrate the present invention, rather than limitation of the scope of the invention.

Embodiment 1:

1. 141g phenol is added in reactor and is preheated to 80 ℃; stir in lower 1 hour 165g (98%) vitriol oil is slowly added to reaction vessel, add rear continuation reaction 3 hours; add ethylene glycol 116g, cooling discharging after stirring, obtains solidifying agent C-1.

2. in plastic beaker, take successively 90g liquid A step phenolic resin, 2.7g DC-193,8.1g methylene dichloride, 7.2g solidifying agent C-1, after high-speed stirring emulsification, insert in the 200*200*40 steel die that is preheated to 40 ℃, mould is put into the 60-75 ℃ of baking oven 20min that foams, cooling and demolding, obtain foam structure evenly, apparent density is 0.043g/cm ³phenol formaldehyde foam, it is 5.8 that its rate of closed hole is greater than 92%, pH value.

Embodiment 2:

1. 141g phenol is added in reactor and is preheated to 80 ℃; stir in lower 1 hour 180g (98%) vitriol oil is slowly added to reaction vessel, add rear continuation reaction 3 hours; add glycol ether 80g, cooling discharging after stirring, obtains solidifying agent C-2.

2. in plastic beaker, take successively 90g liquid A step phenolic resin, 2.7g DC-193,8.1g methylene dichloride, 6.3g solidifying agent C-2, after high-speed stirring emulsification, insert in the 200*200*40 steel die that is preheated to 40 ℃, mould is put into the 60-75 ℃ of baking oven 20min that foams, cooling and demolding, obtain foam structure evenly, apparent density is 0.041g/cm ³phenol formaldehyde foam, its rate of closed hole is more than 92%, pH value is 5.6.

Embodiment 3:

1. 162g meta-cresol is added in reactor and is preheated to 80 ℃; stir in lower 1 hour 172.5g (98%) vitriol oil is slowly added to reaction vessel, add rear continuation reaction 3 hours; add Triethylene glycol mixture 175g, cooling discharging after stirring, obtains solidifying agent C-3.

2. in plastic beaker, take successively 90g liquid A step phenolic resin, 3.6g tween-80,6.3g Skellysolve A, 7.8g solidifying agent C-3, after high-speed stirring emulsification, insert in the 200*200*40 steel die that is preheated to 40 ℃, mould is put into the 60-75 ℃ of baking oven 20min that foams, cooling and demolding, obtain foam structure evenly, apparent density is 0.045g/cm ³phenol formaldehyde foam, its rate of closed hole is that 93%, pH value is 5.8.

Embodiment 4:

1. 162g meta-cresol is added in reactor and is preheated to 80 ℃; stir in lower 1 hour 195g (98%) vitriol oil is slowly added to reaction vessel, add rear continuation reaction 3 hours; add ethylene glycol and Triethylene glycol compound 11 8g, cooling discharging after stirring, obtains solidifying agent C-4.

2. in plastic beaker, take successively 90g liquid A step phenolic resin, 3.6g tween-80,6.3g Skellysolve A, 6.7g solidifying agent C-4, after high-speed stirring emulsification, insert in the 200*200*40 steel die that is preheated to 40 ℃, mould is put into the 60-75 ℃ of baking oven 20min that foams, cooling and demolding, obtain foam structure evenly, apparent density is 0.042g/cm ³phenol formaldehyde foam, it is 5.5 that its rate of closed hole is greater than 92%, pH value.

Claims

1. polymerizable organic acid/sulfuric acid composite curing agent, is characterized in that this solidifying agent is comprised of sulfocarbolic acid or m-cresolulfonic acid, sulfuric acid and thinner, and wherein the mol ratio of sulfocarbolic acid or m-cresolulfonic acid and sulfuric acid is 1:0.1～0.3; Described thinner is at least one in ethylene glycol, glycol ether, Triethylene glycol, and its consumption accounts for 20%～35% of solidifying agent total mass; Described sulfocarbolic acid or m-cresolulfonic acid are prepared by following method: phenol or meta-cresol are preheated to 75～85 ℃, stir in lower 1 hour and slowly add the vitriol oil, add rear continuation reaction 2.5～3.5 hours; The mol ratio of described phenol or meta-cresol and sulfuric acid is 1:1.1～1:1.3.

2. can a foamed phenolic resin composition, by polymerizable organic acid/sulfuric acid composite curing agent according to claim 1, be solidifying agent, it is characterized in that the composition of said composition and mass fraction thereof are:

100 parts of liquid A step phenolic resins;

7 ~ 9 parts of whipping agents;

2 ~ 6 parts of suds-stabilizing agents;

3. composition according to claim 2, is characterized in that described liquid A step phenolic resin solid content is that the viscosity of 80 ~ 85%, 25 ℃ is 2000 ~ 5000mPa.s.

4. composition according to claim 2, is characterized in that described whipping agent is a kind of in low boiling point solvent Skellysolve A, methylene dichloride, sherwood oil.

5. composition according to claim 2, is characterized in that described suds-stabilizing agent is at least one in Tweens tensio-active agent, silicone tensio-active agent or class of department class tensio-active agent.

6. composition according to claim 5, is characterized in that described Tweens tensio-active agent is: at least one in tween-80, Tween-60, tween 20.

7. composition according to claim 5, is characterized in that described silicone tensio-active agent is: at least one in DC-193, DC-198, DC-2525.

8. composition according to claim 5, is characterized in that described class of department class tensio-active agent is: at least one in span-80, Si Ban-60, Si Ban-20.