A kind of aqua-solution method prepares the method for linear bisphenol A phenolic resin
(1) technical field:
The present invention relates to a kind of preparation method of linear bisphenol A phenolic resin.
(2) background technology:
The synthetic employing of linear bisphenol A phenolic resin (BPA-Novolac is abbreviated as BPN) is solvent method at present.This method adopts methyl iso-butyl ketone (MIBK) (MIBK) as solvent, solid polyformaldehyde, dihydroxyphenyl propane and strongly acidic catalyst (example hydrochloric acid, sulfuric acid etc.) is joined in the solvent together prepare the BPN resin by addition, condensation reaction.The advantage of this synthetic method is that reaction process is controlled easily, can synthesize the BPN resin of higher molecular weight.But this method also has following deficiency: (1) during as industrial production, owing to adopt MIBK as solvent, the cost height, energy consumption is big during recovery; (2) directly all join in the reaction system solid formaldehyde, because formaldehyde has the ability of very strong attack phenyl ring under the strongly acidic catalyst effect, cause probably that four adjacent hydrogen of phenolic hydroxyl group all are substituted in the structure of bisphenol A, form build but not the bisphenol A phenolic resin of line style.
(3) summary of the invention:
The cost height that exists at the synthetic linear bisphenol A phenolic resin of solution method, big, the prepared high deficiency of the linear bisphenol A phenolic resin degree of branching of energy consumption when reclaiming the present invention proposes a kind of method for preparing linear bisphenol A phenolic resin with aqua-solution method.
The present invention is raw materials used distilled water, liquid formaldehyde and middle strong acid or the mixing acid of comprising in preparation.Wherein:
Dihydroxyphenyl propane: liquid formaldehyde (37%)=1: 0.8~1.3 (mol ratios);
Middle strong acid: dihydroxyphenyl propane=10~40: 100 (weight ratios);
Mixing acid: dihydroxyphenyl propane=3~10: 100 (weight ratios);
Dihydroxyphenyl propane: distilled water=100: 100~200 (weight ratio).
During preparation:
(1) dihydroxyphenyl propane, middle strong acid or mixing acid, distilled water are joined in the reaction vessel together and stirs, make it to mix;
(2) water-bath is heated to 60 ℃~100 ℃, be incubated and begin and add liquid formaldehyde with the mode that drips;
(3) after the dropping liquid formaldehyde finishes, continue insulation reaction, until reaching required molecular weight;
(4) after reaction finishes, with the mixed solution sucking-off of middle strong acid or mixing acid and distilled water, so that recycle;
(5) reaction product distilled water wash, and add the sodium bicarbonate neutralization, last vacuum-drying obtains faint yellow transparent solid---linear bisphenol A phenolic resin.
By the BPN resin of method for preparing, its productive rate can reach 103%~110% of BPA consumption.Liquid-phase chromatographic analysis shows that residual BPA content is 10%~20%.Gel permeation chromatography (GPC) analysis revealed, the Mw of aqua-solution method synthetic linear bisphenol A phenolic resin reaches as high as 2800, and its molecular weight dispersion coefficient is between 1.2~2.4.
The present invention adopts (1) distilled water to replace the MIBK solvent, can reduce environmental pollution like this, reduces cost; (2) adopt liquid formaldehyde to replace solid polyformaldehyde, and reinforced with the mode that drips, can make in the reaction system, content of bisphenol A is excessive greatly, guarantees to form linear structure; (3) strong acid or mixing acid guarantee that as catalyzer the color and luster of product is more shallow in the employing; (4) mixed solvent can recycle after reaction finishes.
(4) description of drawings:
Accompanying drawing 1 is a line style BPA-Novolac molecular structure;
Accompanying drawing 2 is build BPA-Novolac molecular structures.
(5) embodiment:
Embodiment one:
With dihydroxyphenyl propane, distilled water, phosphoric acid, liquid formaldehyde, sodium bicarbonate preparation preparation linear bisphenol A phenolic resin, its batching is:
Dihydroxyphenyl propane 0.5mol (114.3 gram)
Distilled water 114.3 grams
Phosphoric acid (85%) 26.9 gram
Liquid formaldehyde (37%) 40.5 gram
Sodium bicarbonate 5 grams
The preparation method:
Raw material dihydroxyphenyl propane, phosphoric acid and distilled water are joined in the there-necked flask of the 500ML that thermometer, agitator and constant pressure funnel are housed by proportioning, formaldehyde is joined in the constant pressure funnel.Starting agitator mixes dihydroxyphenyl propane, phosphoric acid and distilled water.Temperature is risen to 85 ± 2 ℃ then, begin to drip formaldehyde, the dropping time is 5 hours.Continue reaction 6 hours, stopped reaction is poured out reaction solution, so that recycle.Add distilled water and sodium bicarbonate then, washed product, until neutrality, and under 100 ℃, vacuum-drying under the 500mmHg, products obtained therefrom is faint yellow transparent solid thing.
Product performance:
Mw=1754.3 Mn=971.06 Pd=1.806 (test of GPC method)
The residual BPA=14.80% of productive rate=105.6% (in BPA) (liquid phase chromatography test)
Softening temperature=113 ℃ (ring and ball method test) hydroxyl equivalent (g/eq)=126.2 (potentiometric titration)
Embodiment two:
With dihydroxyphenyl propane, distilled water, boric acid, sulfuric acid, liquid formaldehyde preparation preparation linear bisphenol A phenolic resin, its batching is:
Dihydroxyphenyl propane 0.5mol (114.3 gram)
Distilled water 114.3 grams
Boric acid 2 grams
Sulfuric acid (98%) 1.5 gram
Liquid formaldehyde (37%) 40.5 gram
Sodium bicarbonate 4 grams
The preparation method:
Raw material dihydroxyphenyl propane, the vitriol oil, boric acid and distilled water are joined in the there-necked flask of the 500ML that thermometer, agitator and constant pressure funnel are housed by proportioning, formaldehyde is joined in the constant pressure funnel.Starting agitator mixes dihydroxyphenyl propane, the vitriol oil, boric acid and distilled water.Temperature is risen to 75 ± 2 ℃ then, begin to drip formaldehyde, the dropping time is 3 hours.Continue reaction 5 hours, stopped reaction is poured out reaction solution, so that recycle.Add distilled water and sodium bicarbonate then, washed product, until neutrality, and under 100 ℃, vacuum-drying under the 500mmHg, products obtained therefrom is faint yellow transparent solid thing.Product performance: Mw=1404.6 Mn=893.22 Pd=1.5726 (test of GPC method) the residual BPA=11.40% of productive rate=103.4% (in BPA) (liquid phase chromatography test) softening temperature=98 ℃ (ring and ball method test) hydroxyl equivalent (g/eq)=129.41 (potentiometric titration).