阅读说明：本技术 一种酚醛树脂的合成方法 (A kind of synthetic method of phenolic resin ) 是由 宋彦哲 王克军 杜孟成 宋来崇 韩涛 杜丽丽 于 2019-10-12 设计创作，主要内容包括：本发明提供了一种酚醛树脂的合成方法,先将苯酚加热获得熔融苯酚,再将催化剂溶于甲醛水溶液中,混合均匀,使混合液与苯酚在微通道反应管中流动、混合,然后连续进入带搅拌的四口烧瓶,经反应、保温、脱水、终止、减压蒸馏即得到酚醛树脂；还可以在脱水后加入改性剂,之后经过终止、减压蒸馏即得到改性酚醛树脂。在本发明的合成方法中,首先苯酚常温下结晶态,加热熔融成液态,便于进料；再有,催化剂与甲醛水溶液配置成混合物料,该工艺是两股进料,通过利用微通道反应管预先混合原料和连续进料,提高反应过程的传质和传热效率,进而提高整个工艺过程的反应效率。将反应过程从原有技术的3-5小时缩短至1-2小时。(The present invention provides a kind of synthetic methods of phenolic resin, first phenol is heated and obtains melting phenol, catalyst is dissolved in formalin again, it is uniformly mixed, mixed liquor is set to flow, mix in the reaction tube of microchannel with phenol, then the four-hole boiling flask with stirring is continuously entered, reacted, heat preservation, dehydration, termination, vacuum distillation obtain phenolic resin；Modifying agent can also be added after dewatering, obtain phenol-formaldehyde resin modified by terminating, being evaporated under reduced pressure later.In synthetic method of the invention, crystalline state under phenol room temperature, heating melting are convenient for charging at liquid first；Further more, catalyst and formalin are configured to mixed material, which is two bursts of chargings, by being pre-mixed raw material and continuous feed using microchannel reaction tube, improves the mass transfer and heat transfer efficiency of reaction process, and then improve the reaction efficiency of entire technical process.Reaction process is foreshortened to 1-2 hours from the 3-5 hour of original technology.)

1. a kind of synthetic method of phenolic resin, which comprises the following steps:

Step 1: phenol being heated, the phenol melted at 50-60 DEG C, kept the temperature spare；The first for being 37% by mass fraction Aldehyde aqueous solution is uniformly mixed with catalyst, is mixed raw material, stand for standby use；The molar ratio of the phenol and formaldehyde is 1:0.6 ~0.8, the catalyst accounts for the 0.1%~1.0% of phenol quality；

Step 2: step 1 gained mixed raw material is flowed and is mixed in the reaction tube of microchannel with phenol, water-bath temperature control 70~ 100℃；The reacted pipe end of material continuously enters in four-hole boiling flask, and the feed time that the material enters four-hole boiling flask is 10 ~60min, residence time of the material in reaction tube are 5-30s；Charging simultaneously be stirred simultaneously oil bath temperature control 80~110 DEG C, continue to stir after charging and keeps the temperature 10-40min；

Step 3: after heat preservation, reaction unit being changed to distillation state and carries out thermal dehydration, terminator, vacuum distillation is added Obtain phenolic resin.

2. the synthetic method of phenolic resin according to claim 1, which is characterized in that mole of the phenol and formaldehyde Than for 1:0.7；The catalyst accounts for the 0.3% of phenol quality.

3. the synthetic method of phenolic resin according to claim 1, which is characterized in that the catalyst is urged for highly acid Agent is one of sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid.

4. the synthetic method of phenolic resin according to claim 1, which is characterized in that the melting benzene in the step 1 M-cresol solution is added in phenol to be mixed, keeps the temperature later spare, the mass ratio of the additional amount of m-cresol solution and phenol is 5- 9:100。

5. the synthetic method of phenolic resin according to claim 1, which is characterized in that microchannel plate in the step 2 Should pipe internal diameter be 0.8mm, be stainless steel material；The water-bath control temperature of microchannel reaction tube is 80 DEG C；Material enters four mouthfuls The feed time of flask is 30min；Residence time of the material in reaction tube is 15s；The temperature of four-hole boiling flask passes through oil bath control Temperature is 95 DEG C；Soaking time is 30min.

6. the synthetic method of phenolic resin according to claim 1, which is characterized in that in the step 3, thermal dehydration Temperature is 120 DEG C.

7. the synthetic method of phenolic resin according to claim 1, which is characterized in that in the step 3, thermal dehydration Temperature is 160 DEG C, changes back stream and modifying agent is added and reacted, after terminator is added, vacuum distillation obtains modified phenol Urea formaldehyde.

8. the synthetic method of phenolic resin according to claim 7, which is characterized in that the modifying agent additional amount and benzene The mass ratio of phenol is 0.2~0.6:1；Modifying agent is one of cashew nut oil, tall oil, rosin, fatty acid；After modifying agent is added Reaction time be 1~2h.

9. the synthetic method of phenolic resin according to claim 8, which is characterized in that the matter of the modifying agent and phenol Amount is than being 0.4:1.

10. the synthetic method of phenolic resin according to claim 1, which is characterized in that terminator is in the step 3 The molar ratio of the liquid alkaline that mass fraction is 32%, catalyst and liquid alkaline is 1:0.5.

Technical field

The present invention relates to a kind of synthetic methods of phenol-formaldehyde resin modified, in particular belong to a kind of synthesis side of phenolic resin Method.

Background technique

Natural rubber, the hardness of synthetic rubber (such as butadiene-styrene rubber, nitrile rubber), elasticity modulus are all lower, Wu Faman The actual application demand of foot, it is therefore desirable to add reinforcing agent in sizing material to improve its hardness and elastic modulus.Reinforcing agent refers to The auxiliary agent of sizing material hardness, dynamic modulus can be improved, traditionally improving sizing material hardness is to improve the ratio of supporting material (such as carbon black), But this method can bring a series of technological problems, and reinforced resin is used then to can avoid these problems.

Phenol Resin as Rubber Reinforcing Filler generally comprises unmodified phenolic resin, cashew nut oil modified alkyd resin, tall oil and changes Property phenolic resin.Wherein, unmodified phenolic resin polarity is big, water absorption rate is high, and good benefit is not achieved in the poor compatibility with rubber Potent fruit, and the phenolic resin that oil is modified reduces the polarity of phenolic resin, increases interpenetrating networks density, it is easier to be scattered in Rubber, reinforcing effect are more preferable.It can be used for tire bead position, tyre surface, it can also be used to the products such as conveyer belt, V-belt, sealing strip, Especially it is widely applied in radial triangle rubber.The production technology of existing phenol-formaldehyde resin modified, there are the reaction time it is long, The problems such as low efficiency, improves the competitiveness of domestic relevant enterprise and product, is conducive to China so improving to prior art The development of functional rubber auxiliary agent industry.

Summary of the invention

The present invention provides a kind of synthetic methods of phenolic resin, to reach the mass transfer and heat transfer effect that improve in reaction process Rate shortens the purpose in reaction time.

A kind of synthetic method of phenolic resin, which comprises the following steps:

Step 1: phenol being heated, the phenol melted at 50-60 DEG C, kept the temperature spare；It is 37% by mass fraction Formalin uniformly mixed with catalyst, be mixed raw material, stand for standby use；The molar ratio of the phenol and formaldehyde is 1: 0.6~0.8, the catalyst accounts for the 0.1%~1.0% of phenol quality；

Step 2: step 1 gained mixed raw material being flowed and mixed in the reaction tube of microchannel with phenol, water-bath temperature control exists 70~100 DEG C；The reacted pipe end of material continuously enters in four-hole boiling flask, and the material enters the feed time of four-hole boiling flask For 10~60min, residence time of the material in reaction tube is 5-30s；Charging be stirred simultaneously simultaneously oil bath temperature control 80~ 110 DEG C, continues to stir after charging and keep the temperature 10-40min；

Step 3: after heat preservation, reaction unit being changed to distillation state and carries out thermal dehydration, through terminator, vacuum is added Distillation obtains phenolic resin.

Preferably, the molar ratio of the phenol and formaldehyde is 1:0.7；The catalyst accounts for the 0.3% of phenol quality.

Preferably, the catalyst is strongly acidic catalyst, is one of sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid.

Preferably, in the melting phenol in the step 1 be added m-cresol solution mixed, keep the temperature later it is spare, The additional amount of m-cresol solution and the mass ratio of phenol are 5-9:100.

Preferably, the internal diameter of microchannel reaction tube is 0.8mm in the step 2, is stainless steel material；Microchannel plate is answered The water-bath control temperature of pipe is 80 DEG C；The feed time that material enters four-hole boiling flask is 30min；Stop of the material in reaction tube Time is 15s；The temperature of four-hole boiling flask is 95 DEG C by oil bath control temperature；Soaking time is 30min.

Preferably, in the step 3, thermal dehydration temperature is 120 DEG C.

Preferably, in the step 3, thermal dehydration temperature is 160 DEG C, changes back stream and modifying agent is added and reacted, After terminator, vacuum distillation be added obtain phenol-formaldehyde resin modified.

Preferably, the mass ratio of the modifying agent additional amount and phenol is 0.2~0.6:1；Modifying agent is cashew nut oil, appropriate One of your oil, rosin, fatty acid；Reaction time after modifying agent is added is 1~2h.

Preferably, the mass ratio of the modifying agent and phenol is 0.4:1.

Preferably, terminator is liquid alkaline that mass fraction is 32%, the molar ratio of catalyst and liquid alkaline in the step 3 For 1:0.5.

Compared with prior art, the present invention advantage is:

Specific embodiment

The invention will be described in further detail With reference to embodiment, unless otherwise instructed, following embodiments Each raw material used is commercial product.