CN104592717A - M-acetenyl benzene azo biphenyl type phenolic foam and preparation method thereof - Google Patents
M-acetenyl benzene azo biphenyl type phenolic foam and preparation method thereof Download PDFInfo
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- CN104592717A CN104592717A CN201510056133.5A CN201510056133A CN104592717A CN 104592717 A CN104592717 A CN 104592717A CN 201510056133 A CN201510056133 A CN 201510056133A CN 104592717 A CN104592717 A CN 104592717A
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Abstract
The invention discloses an m-acetenyl benzene azo biphenyl type phenolic foam and preparation method thereof. The phenolic foam is prepared from m-acetenyl benzene azo biphenyl type phenolic resin, a solvent, a foaming agent and a fluorine-containing surfactant by means of foaming and curing; the preparation method is simple to operate, mild in reaction condition, easy to control, and capable of satisfying the industrial production requirement; the obtained m-acetenyl benzene azo biphenyl type phenolic foam is uniform in pores, high in heat resistance, fire resistance and carbon residue rate, low in thermal conductivity and high in compression strength; the M-acetenyl benzene azo biphenyl type phenolic foam can be widely applied to the fields such as aviation, spaceflight and the like.
Description
Technical field
The present invention relates to a kind of novel acetylenylbenzene azo biphenyl type phenol formaldehyde foam and preparation method thereof, belong to polymeric foamed material field.
Background technology
Porous plastics since appearance, due to its have that density is little, specific tenacity is high, the excellent properties such as heat insulation and sound insulation, and be widely used in the fields such as industry, agricultural, building, communications and transportation, aerospace.Numerous porous plastics can only use within the scope of 0 ~ 150 DEG C, the performance requriements used in the military fields such as Aeronautics and Astronautics can not be met, and high temperature resistant porous plastics can long continuous operation under the hot conditions more than 200 DEG C, have instantaneous heat-resisting can up to 540 DEG C.Due to thermotolerance, low thermal conductivity that it is outstanding, high temperature resistant porous plastics is one of research direction becoming Developing High Performance Foam Plastics.
Phenol formaldehyde foam is that matrix obtains through foamed solidification with resol, have the title of " king of insulation ".In numerous porous plastics, phenol formaldehyde foam is heat-resisting with it, lower thermal conductivity coefficient, difficult combustion from putting out, low smog, flame resistant penetrate, it is in widespread attention without unrestrained thing, the advantage such as cheap to meet fire.In the last few years, along with the fields such as Highrise buildings, communications and transportation, naval vessel, aerospace improve constantly the thermal stability of syntactic foam plastics and flammability, made the development of phenol formaldehyde foam more rapid.
But, traditional phenol formaldehyde foam because of itself intrinsic defect, as: fragility, poor heat stability, life-time service temperature are low, foamed solidification time need catalyzer, be difficult to meet higher performance requriements.Therefore, the special type phenolic foam of novel high-performance particularly high temperature resistant, resistance to ablation, lower thermal conductivity, high flame retardant the Design & preparation with the phenol formaldehyde foam of certain physical strength becomes one of high performance important research direction of phenol formaldehyde foam.
Summary of the invention
The present invention is directed to the defect that phenol formaldehyde foam traditional in prior art exists, object is that to be to provide a kind of foam cell even, and there is superior heat resistance and acetylenylbenzene azo biphenyl type phenol formaldehyde foam between flame retardant resistance, high Residual carbon, lower thermal conductivity and stronger compressive strength, this phenol formaldehyde foam can be widely used in the numerous areas such as Aeronautics and Astronautics.
Another object of the present invention is to provide a kind of technique simple, the gentle and method that is acetylenylbenzene azo biphenyl type phenol formaldehyde foam between holding described in manageable preparation of reaction conditions.
The invention provides acetylenylbenzene azo biphenyl type phenol formaldehyde foam between one, this acetylenylbenzene azo biphenyl type phenol formaldehyde foam is obtained by foamed solidification by following content of component: 100 parts, an acetylenylbenzene azo biphenyl type resol, solvent 10 ~ 59 parts, whipping agent 1 ~ 28 part, 2 ~ 18 parts, tensio-active agent, between described, acetylenylbenzene azo biphenyl type resol has formula 1 structure:
Wherein, molecular weight is between 495 ~ 10000.
Of the present invention acetylenylbenzene azo biphenyl type phenol formaldehyde foam also comprises following preferred version:
Between preferred, acetylenylbenzene azo biphenyl type phenol formaldehyde foam is obtained by foamed solidification by 100 parts, an acetylenylbenzene azo biphenyl type resol, solvent 18 ~ 52 parts, whipping agent 5 ~ 24 parts, 4 ~ 16 parts, tensio-active agent.
In preferred scheme, whipping agent is 4, at least one in 4 '-OBSH, Cellmic C 121, N, N-dinitrosopentamethylene tetramine.
In preferred scheme, solvent is at least one in acetone, butanone, DMF, tetrahydrofuran (THF).
Fluorochemical surfactant of the present invention is branched chain type perfluoroalkyl polyoxy Vinyl Ether nonionogenic tenside FY-F501 or is H30.Can buy in producers such as Guangzhou Fu Yuangui Science and Technology Ltd. or Zichuan, Zibo City Huahai chemical plant.
Present invention also offers a kind of described between the preparation method of acetylenylbenzene azo biphenyl type phenol formaldehyde foam, this preparation method is after acetylenylbenzene azo biphenyl type resol, tensio-active agent, solvent and a whipping agent being mixed, load in mould, foam curing molding at 100 ~ 250 DEG C of temperature.
The preparation method of of the present invention acetylenylbenzene azo biphenyl type phenol formaldehyde foam also comprises following preferred version:
In preferred scheme, initial blowing temperature is 100 ~ 160 DEG C; Most preferably be 120 ~ 150 DEG C.
In preferred scheme, the initial blowing temperature hold-time is 10 ~ 60min; Most preferably be 15 ~ 50min.
In preferred scheme, mould is opening or seals type.
Of the present invention acetylenylbenzene azo biphenyl type resol prepares by the following method:
Step 1: 3-aminophenylacetylene is slowly added drop-wise to after in the hydrochloric acid soln of 12 ~ 18wt%, be cooled to-5 ~ 0 DEG C, the sodium nitrite solution of 30 ~ 40wt% is slowly dripped again in described hydrochloric acid soln, after dropwising, 0 ~ 2 DEG C of reaction 1.0 ~ 2.5 hours, obtain an ethynyl phenyl diazonium salt solution;
Step 2: under Friedel-Crafts catalyst, phenol and 4,4 '-dichloromethyl biphenyl carries out Fu-Ke and reacts at 80 ~ 110 DEG C, obtains biphenyl type resol; Gained biphenyl type resol and an alkynyl phenyl diazonium salt, in basic solution, carry out linked reaction under being not more than the temperature of 0 DEG C, obtain an acetylenylbenzene azo biphenyl type resol.
Wherein, in step 1, the mol ratio of 3-aminophenylacetylene and Sodium Nitrite is 1:0.9 ~ 1.3.The mol ratio of 3-aminophenylacetylene and hydrochloric acid is 1:2 ~ 5.In step 2, Fu-Ke reacts the time of carrying out is 2 ~ 7h.The time that linked reaction is carried out is 4 ~ 7h.Phenol and 4, the mol ratio of 4 '-dichloromethyl biphenyl is 2 ~ 11:1.The mass ratio of 3-aminophenylacetylene and biphenyl type resol is 0.9 ~ 1.7:1.
Beneficial effect of the present invention: the present invention has acetylenylbenzene azo biphenyl type resol between novel texture be used for foaming formulation by a kind of first, this acetylenylbenzene azo biphenyl type resol at a lower temperature can self cure, and has good thermotolerance and higher Residual carbon.This acetylenylbenzene azo biphenyl type resol prepares density at 100 ~ 450Kg/m under proper condition in conjunction with the fluorochemical surfactant of suitable proportion, solvent and whipping agent
3between foam, and this foam cell is comparatively even, particle diameter is between 100 ~ 900 μm, and this foam has the feature of high heat resistance, high flame retardant, high Residual carbon, lower thermal conductivity and higher compressive strength simultaneously, can be widely used in the numerous areas such as Aeronautics and Astronautics, launch vehicle.Of the present invention acetylenylbenzene azo biphenyl type phenolic resin foam preparation method technique is simple, reaction conditions is easily controlled, and is applicable to applying on a large scale.
Accompanying drawing explanation
The FT-IR spectrogram of the biphenyl type bakelite B N that [Fig. 1] is prepared for embodiment 1 and an acetylenylbenzene azo biphenyl type resol EPABN.
[Fig. 2] is the GPC figure of acetylenylbenzene azo biphenyl type resol EPABN between embodiment 1 preparation.
[Fig. 3] for embodiment 1 obtained between the SEM figure of acetylenylbenzene azo biphenyl type phenolic resin foam.
[Fig. 4] for embodiment 1 obtained between the TGA figure of acetylenylbenzene azo biphenyl type phenolic resin foam.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
For measuring a measuring method for acetylenylbenzene azo biphenyl type phenolic foams physical and chemical performance in embodiment.
Apparent density measures: measure according to standard A STMD1662.
Compressive strength: test by GJB1585A-2004, specimen shape is right cylinder, is of a size of Φ 25mm × 30mm.
Thermal conductivity is tested: test by GB 3399-82, specimen shape is right cylinder, is of a size of Φ 28mm × 9mm.
Critical oxygen index is tested: test by GB/T2406.2-2009.
Embodiment 1
Step (one): take 4,4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.24g, phenol 38.77g, concentrated hydrochloric acid 2.25g, put into the 250mL four-hole boiling flask taking into account reflux condensing tube with mechanical stirring device, temperature, stir and be warming up to 90 DEG C, back flow reaction 5h at this temperature.After reaction terminates, rapid temperature increases to 180 DEG C underpressure distillation, arrives out while hot, cools and obtain light yellow biphenyl type resol, and biphenyl type phenolic resin structure FT-IR schemes as shown in Figure 1.
Step (two): the hydrochloric acid soln measuring 99.30g 15%, put into the 250mL four-hole boiling flask with mechanical stirring device, prolong and thermometer, take 18.75g 3-amino-benzene acetylene, dropwise instill in acid solution, form milk-like slurry, wait to dropwise, system is cooled to-5 DEG C.Take Sodium Nitrite 11.39g, be dissolved in 21.15g distilled water, be mixed with 35%NaNO
2the aqueous solution, then dropwise instills above-mentioned milk-like slurry, fully stirs, and waits to drip and react 1.5h at 0 DEG C, reacts complete and adds appropriate urea, then filter and obtain the diazonium salt solution that red-brown is transparent.Product cryopreservation, with do with.
Step (three): measure 135mL dehydrated alcohol, put into the 250mL four-hole boiling flask with mechanical stirring device, prolong and thermometer, add the biphenyl type phenolic aldehyde 15g of synthesis, sodium hydroxide 14.03g, mechanical stirring, treats that biphenyl type phenol formaldehyde resin dissolves is complete, is cooled to 0 DEG C, dropwise instill the diazonium salt solution synthesized, and react 5h at 0 DEG C.React complete, add acid solution, regulate PH to 7, product precipitate, suction filtration, wash, put into dry 10h at vacuum drying oven 60 DEG C, obtain brown-red powder.Between prepared, the number-average molecular weight of acetylenylbenzene azo biphenyl type resol (EPABN) is 1656.
Step (four): take acetylenylbenzene azo biphenyl type resol, 0.64g FY-F501,3mLN between 8g, dinethylformamide and 1.44g Cellmic C 121, mix, load opening sealed mold, the curing molding that foams at 125 DEG C/0.7h+150 DEG C/1h+170 DEG C/1h+190 DEG C/4h+210 DEG C/1h+225 DEG C/4h DEG C obtains an acetylenylbenzene azo biphenyl phenolic resin foam.
Between gained, acetylenylbenzene azo biphenyl type phenolic resin foam density is 115Kg/m
3, can reach 62% at the carbon yield of 1000 DEG C of nitrogen atmospheres, 5% thermal weight loss decomposition temperature is 457 DEG C, and compressive strength is 0.553Mpa, and oxygen index is 42, and thermal conductivity is 0.059Wm
-1k
-1.
Embodiment 2
Between obtained with embodiment 1, foam prepared by acetylenylbenzene azo biphenyl type resol:
Take acetylenylbenzene azo biphenyl type resol, 0.24g H30,1.1mL N between 3g, dinethylformamide and 0.54g Cellmic C 121, mix, load and to remain silent sealed mold, the curing molding that foams under 130 DEG C/0.5h+150 DEG C/1h+170 DEG C/1h+190 DEG C/4h+210 DEG C/1h+225 DEG C/4h obtains an acetylenylbenzene azo biphenyl type phenolic resin foam.
Between gained, acetylenylbenzene azo biphenyl type phenolic resin foam density is 190Kg/m
3, can reach 62% at the carbon yield of 1000 DEG C of nitrogen atmospheres, 5% thermal weight loss decomposition temperature is 457 DEG C, and compressive strength is 1.537Mpa, and oxygen index is 45, and thermal conductivity is 0.065Wm
-1k
-1.
Embodiment 3
Step (one): take 4; 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.18g, phenol 15.14g, concentrated hydrochloric acid 2.52g; put into the 250mL four-hole boiling flask taking into account reflux condensing tube with mechanical stirring device, temperature; nitrogen protection; stir and be warming up to 100 DEG C, back flow reaction 6h at this temperature.After reaction terminates, rapid temperature increases to 180 DEG C underpressure distillation, arrives out while hot, cools and obtain light yellow biphenyl type resol.
Step (two): the hydrochloric acid soln measuring 119.16g 15%, put into the 250mL four-hole boiling flask with mechanical stirring device, prolong and thermometer, take 22.5g 3-amino-benzene acetylene, dropwise instill in acid solution, form milk-like slurry, wait to dropwise, system is cooled to-5 DEG C.Take Sodium Nitrite 13.52g, be dissolved in 31.55g distilled water, then dropwise instill above-mentioned milk-like slurry, fully stir, wait to drip and react 2.0h at 0 DEG C, react complete and add appropriate urea, then filter and obtain the diazonium salt solution that red-brown is transparent.Product cryopreservation, with do with.
Step (three): measure 135mL dehydrated alcohol, put into the 250mL four-hole boiling flask with mechanical stirring device, prolong and thermometer, add the biphenyl type phenolic aldehyde 15g of synthesis, sodium hydroxide 16.02g, mechanical stirring, treats that biphenyl type phenol formaldehyde resin dissolves is complete, is cooled to 0 DEG C, dropwise instill the diazonium salt solution synthesized, and react 6h at 0 DEG C.React complete, add acid solution, regulate PH to 7, product precipitate, suction filtration, wash, put into dry 10h at vacuum drying oven 60 DEG C, obtain brown-red powder.Between prepared, the number-average molecular weight of acetylenylbenzene azo biphenyl type resol (EPABN) is 7035.
Step (four): take acetylenylbenzene azo biphenyl type resol, 0.40g H30,1.5mLN between 4g, dinethylformamide and 0.64g Cellmic C 121, mix, load and to remain silent sealed mold, the curing molding that foams under 125 DEG C/0.5h+150 DEG C/1h+170 DEG C/1h+190 DEG C/4h+210 DEG C/1h+225 DEG C/4h obtains an acetylenylbenzene azo biphenyl type phenolic resin foam.
Between gained, acetylenylbenzene azo biphenyl type phenolic resin foam density is 280Kg/m
3, can reach 63% at the carbon yield of 1000 DEG C of nitrogen atmospheres, 5% thermal weight loss decomposition temperature is 457 DEG C, and compressive strength is 5.152Mpa, and oxygen index is 49, and thermal conductivity is 0.073Wm
-1k
-1.
Embodiment 4
Between obtained with embodiment 3, foam prepared by acetylenylbenzene azo biphenyl type resol:
Take acetylenylbenzene azo biphenyl type resol, 0.66g FY-F501,2mL N between 5.5g, dinethylformamide and 0.77g Cellmic C 121, mix, load and to remain silent mould, the curing molding that foams under 120 DEG C/0.6h+150 DEG C/1h+170 DEG C/1h+190 DEG C/4h+210 DEG C/1h+225 DEG C/4h obtains an acetylenylbenzene azo biphenyl type phenolic resin foam.
Between gained, acetylenylbenzene azo biphenyl type phenolic resin foam density is 353Kg/m
3, can reach 63% at the carbon yield of 1000 DEG C of nitrogen atmospheres, 5% thermal weight loss decomposition temperature is 457 DEG C, and compressive strength is 8.099Mpa, and oxygen index is 51, and thermal conductivity is 0.084Wm
-1k
-1.
Claims (7)
1. an acetylenylbenzene azo biphenyl type phenol formaldehyde foam between, be is characterized in that, obtained by following content of component by foamed solidification:
Between 100 parts, acetylenylbenzene azo biphenyl type resol,
Solvent 10 ~ 59 parts,
Whipping agent 1 ~ 28 part,
Fluorochemical surfactant 2 ~ 18 parts,
Between described, acetylenylbenzene azo biphenyl type resol has formula 1 structure:
Wherein, molecular weight is between 495 ~ 10000.
2. acetylenylbenzene azo biphenyl type phenol formaldehyde foam between as claimed in claim 1, it is characterized in that, obtained by foamed solidification by 100 parts, an acetylenylbenzene azo biphenyl type resol, solvent 18 ~ 52 parts, whipping agent 5 ~ 24 parts, 4 ~ 16 parts, tensio-active agent.
3. acetylenylbenzene azo biphenyl type phenol formaldehyde foam between as claimed in claim 2, it is characterized in that, described whipping agent is 4, at least one in 4 '-OBSH, Cellmic C 121, N, N-dinitrosopentamethylene tetramine.
4. acetylenylbenzene azo biphenyl type phenol formaldehyde foam between as claimed in claim 2, it is characterized in that, described solvent is at least one in acetone, butanone, DMF, tetrahydrofuran (THF).
5. the method for acetylenylbenzene azo biphenyl type phenol formaldehyde foam between preparing described in any one of Claims 1 to 4, it is characterized in that, after between inciting somebody to action, acetylenylbenzene azo biphenyl type resol, tensio-active agent, solvent and whipping agent mix, load in mould, foam curing molding at 100 ~ 250 DEG C of temperature.
6. method as claimed in claim 5, it is characterized in that, initial blowing temperature is 100 ~ 160 DEG C.
7. method as claimed in claim 6, it is characterized in that, the initial blowing temperature hold-time is 10 ~ 60min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599804A (en) * | 2020-12-16 | 2021-04-02 | 邓乃英 | Fe-N co-doped porous carbon-oxygen reduction catalyst with controllable pore diameter structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944486A (en) * | 2006-09-28 | 2007-04-11 | 四川大学 | O-phthalo nitrile modified high ortho phenolic resin and its preparing method |
| CN103709381A (en) * | 2014-01-08 | 2014-04-09 | 中南大学 | Preparation method of phenol-biphenyl type phenolic resin hollow microspheres |
| CN103724652A (en) * | 2014-01-08 | 2014-04-16 | 中南大学 | Method for preparing dicyanophenyl etherified phenol-diphenyl phenolic resin hollow microsphere |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944486A (en) * | 2006-09-28 | 2007-04-11 | 四川大学 | O-phthalo nitrile modified high ortho phenolic resin and its preparing method |
| CN103709381A (en) * | 2014-01-08 | 2014-04-09 | 中南大学 | Preparation method of phenol-biphenyl type phenolic resin hollow microspheres |
| CN103724652A (en) * | 2014-01-08 | 2014-04-16 | 中南大学 | Method for preparing dicyanophenyl etherified phenol-diphenyl phenolic resin hollow microsphere |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599804A (en) * | 2020-12-16 | 2021-04-02 | 邓乃英 | Fe-N co-doped porous carbon-oxygen reduction catalyst with controllable pore diameter structure and preparation method thereof |
| CN112599804B (en) * | 2020-12-16 | 2023-12-26 | 嘉兴倍创网络科技有限公司 | Fe-N co-doped porous carbon oxygen reduction catalyst with controllable pore diameter structure and preparation method thereof |
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