CN101613446A - The production method of bisphenol A modified phenolic resin - Google Patents

Abstract

A kind of production method with bisphenol A modified phenolic resin is a raw material with phenol, formaldehyde, hydrated barta, dihydroxyphenyl propane and water, makes the resol of light color under 45-90 ℃ of medium temperature condition.This resin can be widely used in makes tackiness agent, especially the tackiness agent of bamboo and wood products, because make properties-correcting agent with dihydroxyphenyl propane, can reduce the oxidized probability of free phenol, can generate methylol with excessive formaldehyde reaction, then through being condensed into the condenses that methene key connects, alternative part phenol is again because of adopting Ba (OH) ₂Substitute Na (OH) ₂Weakened alkalescence, katalysis relaxes reaction and is easy to control, and in the same time, free phenol oxidation probability is little, and color of resin is more shallow.Therefore, the present invention has with bisphenol A modified phenolic resin that free phenol content reduces, raw materials cost descends, technology is simple, the advantage that the resol color is shoaled.

Description

The production method of bisphenol A modified phenolic resin

Technical field

The present invention relates to the preparation of a kind of organic macromolecule, is to be properties-correcting agent with dihydroxyphenyl propane, prepares the method for modified phenolic resins.

Background technology

Resol is the most frequently used resin of bamboo wood processing, spoken approvingly of by the people with the bonding strength height.But the resol that ordinary method is produced is brown even dark-brown, and the natural figure production of bamboo timber is hidden, reduce or drowning these decorative patterns, influence appearing of natural beauty, consumption to the user has negative effect, and therefore, light resol receives the concern of industry with the people.CN931055156 discloses " manufacture method of light colour modified rosin phenolic aldehyde resin ", make properties-correcting agent with rosin, Quilonum Retard or lithium hydroxide are made catalyzer, through the condensation reaction of phenol and formaldehyde, and the rosiny addition reaction, at last with glycerine carry out esterification vacuumize product.This method technology is complicated, and raw materials cost is higher.CN881019949 has announced the manufacture method of terpene phenolic resin, and phenol and formaldehyde do to add thermal condensation under the catalyzer with sulfuric acid, are carried out alkylation reaction with terpenes, makes alkylating agent with terebinthine monoterpene, and cost height, yield are low.CN931049555 discloses " manufacture method of sesquiterpene phenolic aldehyde resin ", be under the composite catalyst effect that constitutes by sulfuric acid and boron trifluoride ethyl ether complex, the thermal condensation of phenol and formaldehyde, sesquiterpene hydrocarbonylation with the heavy turpentine class forms again, with manufacturing terpene phenolic resin ratio, cost hangs down 15-20%, and yield is high to＞90%, and look shallow.The foregoing invention patent all is the useful trial to light resol preparation, sees that raw materials cost height and technology are than complicated problems but all exist.

Summary of the invention

The objective of the invention is above-mentioned deficiency, provide that a kind of raw materials cost is lower, the simple light resol production method of technology at prior art.

Above-mentioned purpose can realize by following measure: production method process the following step of this bisphenol A modified phenolic resin:

(1) get the raw materials ready: wanting to buy purity to Chemical Manufacture or supply enterprise is that 99% commercial-grade phenol, purity are that 37% technical grade formaldehyde and purity are 98% technical grade hydrated barta; To Russian or Japanese inward BPA by name, chemical name is 2, and 2-diphenylol propane, effective content are 95% dihydroxyphenyl propane tankage, prepare enough process water;

(2) proportion design: each raw material and weight part proportioning value thereof are phenol 290-310 parts, formaldehyde 380-420 part, add-on 290-310 part first wherein, add-on 90-110 part for the second time, hydrated barta 28-32 part, dihydroxyphenyl propane 60-80 part, water 160-200 part, wherein add-on 90-110 part first, add-on 70-90 part for the second time;

(3) production operation: according to the proportioning value of step (2), in reactor, add all phenol of fusing earlier, begin to heat and stir, add Ba (OH) again ₂Add water first, be warming up to 45-50 ℃, insulation reaction 20 minutes, add formaldehyde first, be warming up to 85-90 ℃, insulation reaction 30 minutes, cool to 80 ℃ again, add dihydroxyphenyl propane and add formaldehyde for the second time, be warming up to 85-90 ℃, after the insulation reaction 50 minutes, begin viscosimetric first, after this surveyed once every 10 minutes, when the method for falling the bubble in 25 ℃ records viscosity is that 4.5-5.0 is during second, for the second time add water, continue to stir, be cooled to 50 ℃ after blowing.

The invention has the beneficial effects as follows with the dihydroxyphenyl propane tankage to substitute part phenol, both reduced raw materials cost, also reduced the content of free phenol, realize the hope that the resol color shoals simultaneously again.

Embodiment

The present invention is described in further detail below in conjunction with embodiment: earlier each raw material and weight part thereof are listed in the table below with seven embodiment:

Embodiment 1 (consulting raw material and the weight part proportioning numerical value of corresponding embodiment 1 in the table):

Get the phenol of 290 parts of fusings, add in the reactor, begin heating and stir, to add purity again be 98% 28 parts of hydrated bartas and add 90 parts in water first, is warming up to 45-50 ℃, insulation reaction 20min, add 290 parts in formaldehyde first, be warming up to 85-90 ℃, insulation reaction 20min, be cooled to 80 ℃, add 60 parts of dihydroxyphenyl propanes and 90 parts in formaldehyde for the second time, be warming up to 85-90 ℃, begin viscosimetric first behind the insulation reaction 50min, after this survey once every 10min, when viscosity reaches 4.5-5.0S (25 ℃, the method for falling the bubble), add for the second time 70 parts in water, continue to stir, be cooled to 50 ℃ after blowing.

All the other embodiment 2-7 all by raw material and the weight part proportioning numerical value of each corresponding embodiment in the table, make with embodiment 1 same procedure, just the intensification value 45-50 ℃ with 85-90 ℃ of two intervals in the visual response progress control voluntarily and just can.Preferred among seven embodiment with embodiment 1-3, especially embodiment 2.

Chemism of the present invention and design considerations are:

The color of resol is because free phenol is oxidized to due to the quinonyl, and therefore how reducing the oxidized probability of phenolic group is to make the key of light resol.The content of dihydroxyphenyl propane is about 95% in the dihydroxyphenyl propane tankage, in the structure of dihydroxyphenyl propane, contain two phenolic hydroxyl groups, 2 active sites are arranged on the ortho position of each hydroxyl, form a methylol, dihydroxymethyl, trishydroxymethyl with the excess formaldehyde reaction, at a certain temperature, form the condenses that methene key connects by condensation reaction between methylol, therefore utilize the dihydroxyphenyl propane tankage can substitute part phenol, both reduced production cost, and reduced the content of free phenol again, the color of resin shoals again simultaneously; The alkalescence of hydrated barta than sodium hydroxide a little less than, katalysis relaxes, reaction is easy to control, in the same time, the probability that free phenol is oxidized to quinonyl is little, the color of resin is more shallow.

Claims (1)

1, a kind of production method of bisphenol A modified phenolic resin is characterized in that through the following step:

(1) get the raw materials ready: wanting to buy purity to Chemical Manufacture or supply enterprise is that 99% commercial-grade phenol, purity are that 37% technical grade formaldehyde and purity are 98% technical grade hydrated barta; To Russian or Japanese inward BPA by name, chemical name is 2, and 2-diphenylol propane, effective content are 95% dihydroxyphenyl propane tankage, prepare enough process water;

(2) proportion design: each raw material and weight part proportioning value thereof are phenol 290-310 parts, formaldehyde 380-420 part, add-on 290-310 part first wherein, add-on 90-110 part for the second time, hydrated barta 28-32 part, dihydroxyphenyl propane 60-80 part, water 160-200 part, wherein add-on 90-110 part first, add-on 70-90 part for the second time;

(3) production operation: according to the proportioning value of step (2), in reactor, add all phenol of fusing earlier, begin to heat and stir, add Ba (OH) again ₂Add water first, be warming up to 45-50 ℃, insulation reaction 20 minutes, add formaldehyde first, be warming up to 85-90 ℃, insulation reaction 30 minutes, cool to 80 ℃ again, add dihydroxyphenyl propane and add formaldehyde for the second time, be warming up to 85-90 ℃, after the insulation reaction 50 minutes, begin viscosimetric first, after this surveyed once every 10 minutes, when the method for falling the bubble in 25 ℃ records viscosity is that 4.5-5.0 is during second, for the second time add water, continue to stir, be cooled to 50 ℃ after blowing.