CN103709348A - Production method for anti-ablation temperature-resistant phenolic resin - Google Patents

Abstract

The invention discloses a production method for anti-ablation temperature-resistant phenolic resin. The method comprises the following steps by adopting the following raw materials: (1) preparing raw materials including phenol, industrial solid formaldehyde, sodium hydroxide, distilled water, boric acid, and dimethyl polysiloxane; (2) feeding the phenol, the sodium hydroxide and the distilled water into a reaction kettle for agitating; (3) adding the industrial solid formaldehyde by four times; (4) feeding boric acid, performing reflux mixing, and dehydrating; (5) adding the dimethyl polysiloxane; and (6) cooling to 60 DEG C and then discharging. According to the phenolic resin prepared by adopting the method, the temperature resistance property is enhanced compared with that of non-modified phenolic resin; due to introduction of inorganic element silicon boron with higher bond energy, the thermal stability, namely the anti-ablation property is better; in addition, the dimethyl polysiloxane and the phenolic resin are a copolymer with a block structure, so that the thermal stability is favorably improved.

Description

A kind of production method of anti-ablation heatproof resol

Technical field

The invention belongs to macromolecular organic compound technical field, relate to a kind of production method of anti-ablation heatproof resol.

Background technology

Resol is with phenols and aldehyde compound polycondensation and the general designation of the resin making, its raw material is easy to get, with low cost, production technique and equipment are simple, moulding product has good thermotolerance, winter hardiness, dimensional stability, forming process, low smoke and flame retardant resistance, is widely used in the resin matrix of the anti-ablative composite material of heatproof.

But the progress along with industrial technology, traditional resol is because the phenolic hydroxyl group on molecular structure and methylene radical are easily oxidized, its resistance toheat is affected, and the extensibility of resol is low, fragility is large, has greatly limited its application in high performance material.For improving the performance of resol, expand its use range, domestic resol industry has been carried out a large amount of research work to the modification of resol, and therefore, the thermotolerance and the toughness that how to improve resol are phenolic resin modified research problem demanding prompt solutions.

Summary of the invention

The technical problem to be solved in the present invention is that the defect that easily causes resol to degrade to hot oxygen sensitivity for phenol core and methylene radical in resol structure, sets about from molecular structure, synthesizes a kind of improved anti-ablation heatproof resol.

Technical scheme of the present invention is, a kind of production method of anti-ablation heatproof resol is provided, and the method comprises and adopts following raw material and processing step:

(1), by following weight ratio, be equipped with raw material:

(2), by step (1) phenol, the sodium hydroxide of standby weight part, distilled water drops into mix and blend in reactor;

(3), the temperature in the kettle of controlling aforesaid reaction vessel is 75～85 ℃ of scopes, adds the standby industrial solid formaldehyde of step (1) institute of 1/4th weight parts every 10 minutes, add for four times;

(4) temperature in the kettle of, controlling aforesaid reaction vessel is 95～105 ℃ of scopes and keep this temperature 60～70 minutes, by step (1) the boric acid of standby weight part drop in reactor, recirculate mixing 20 minutes, opens the vacuum pump of this reactor, underpressure distillation, dehydration.

(5), be cooled to 80 ℃, stop dehydration, add the dimethyl polysiloxane of the standby weight part of step (1) institute, continuation mix and blend.Be warming up to 110 ℃, measure gelation point.When gel time reaches 80～110s, during 180 ℃ of temperature, finish mix and blend.

(6), be cooled to 60 ℃, discharging, obtains anti-ablation heatproof resol finished product of the present invention.

The invention has the beneficial effects as follows:

1, the resol that present method is produced is to have introduced B and Si in common resol structure, make on the phenolic hydroxyl group of strong polarity-H(hydrogen bond) by Si-O key (siloxane bond) part in the B-O key in step (4) (boron oxygen key) and step (5), replaced, to a certain extent passivation the activity of phenyl ring, therefore, than unmodified resol, need higher solidification value, come therefrom, the temperature tolerance of gained resol strengthens.

2, the resol that present method is produced has been introduced the higher inorganic elements silicon boron of bond energy, and the thermostability that makes resol is that Burning corrosion resistance can be better; Meanwhile, dimethyl polysiloxane and resol are a kind of multipolymers of inlaying segment structure, are conducive to improve the thermostability of resol.

Embodiment:

Embodiment 1:

(1), get phenol 350 ㎏, industrial solid formaldehyde 175 ㎏, sodium hydroxide 1.5 ㎏, distilled water 80 ㎏, boric acid 14 ㎏, dimethyl polysiloxane 21 ㎏.

(2), by step (1) phenol, the sodium hydroxide of standby weight part, distilled water drops into mix and blend in reactor;

(3), the temperature in the kettle of controlling aforesaid reaction vessel is 75～85 ℃ of scopes, adds the standby industrial solid formaldehyde of step (1) institute of 1/4th weight parts every 10 minutes, add for four times;

(4) temperature in the kettle of, controlling aforesaid reaction vessel is 95～105 ℃ of scopes and keep this temperature 60 minutes, by step (1) the boric acid of standby weight part drop in reactor, recirculate mixing 20 minutes, opens the vacuum pump of this reactor, underpressure distillation, dehydration;

(5), be cooled to 80 ℃, stop dehydration, add the dimethyl polysiloxane of the standby weight part of step (1) institute, continuation mix and blend.Be warming up to 110 ℃, measure gelation point.When gel time reaches 80～110s, during 180 ℃ of temperature, finish mix and blend.

(6), be cooled to 60 ℃, discharging, obtains anti-ablation heatproof resol finished product.

Embodiment 2:

(1), get phenol 400 ㎏, industrial solid formaldehyde 225 ㎏, sodium hydroxide 2 ㎏, distilled water 150 ㎏, boric acid 16 ㎏, dimethyl polysiloxane 24 ㎏;

Step (2)～(3) are with embodiment 1;

(4) temperature in the kettle of, controlling aforesaid reaction vessel is 95～105 ℃ of scopes and keep this temperature 70 minutes, by step (1) the boric acid of standby weight part drop in reactor, recirculate mixing 20 minutes, opens the vacuum pump of this reactor, underpressure distillation, dehydration;

Step (5)～(6) are with embodiment 1.

Claims (1)

1. a production method for anti-ablation heatproof resol, the method comprises and adopts following raw material and step:

(1), by following weight ratio, be equipped with raw material:

(2), by step (1) phenol, the sodium hydroxide of standby weight part, distilled water drops into mix and blend in reactor;

(3), the temperature in the kettle of controlling aforesaid reaction vessel is 75～85 ℃ of scopes, adds the standby industrial solid formaldehyde of step (1) institute of 1/4th weight parts every 10 minutes, add for four times;

(4) temperature in the kettle of, controlling aforesaid reaction vessel is 95～105 ℃ of scopes and keep this temperature 60～70 minutes, by step (1) the boric acid of standby weight part drop in reactor, recirculate mixing 20 minutes, opens the vacuum pump of this reactor, underpressure distillation, dehydration;

(5), be cooled to 80 ℃, stop dehydration, add the dimethyl polysiloxane of the standby weight part of step (1) institute, continuation mix and blend; Be warming up to 110 ℃, measure gelation point, when gel time reaches 80～110s, during 180 ℃ of temperature, finish mix and blend;

(6), be cooled to 60 ℃, discharging, obtains anti-ablation heatproof resol finished product.