CN103450264A - Preparation method of phosphorus-modified phenolic resin - Google Patents

Abstract

The invention discloses a preparation method of a phosphorus-modified phenolic resin, which comprises the following steps: performing polycondensation on p-tert-octylphenol, bisphenol A, paratert-butyl phenol and formaldehyde under the action of a catalyst to obtain a phenolic condensation intermediate; and reacting the intermediate with monohydroxy alcohols and organic phosphorus heterocyclic compounds at a preset temperature for preset time under catalytic conditions to prepare the phosphorus-modified phenolic resin. The method solves the problem of complete dependency on the phosphorus-modified phenolic resin imported from abroad in the past, and enhances the heat resistance, binding strength, peel strength, favorable space size, excellent electric properties, mechanical strength and other physicochemical performance indexes of the original phosphorus-modified phenolic resin, so that the phosphorus-modified phenolic resin has relatively good application properties when being applied to the field of electronic chemicals.

Description

The preparation method of phosphorus modified phenolic resins

Technical field

The invention belongs to phosphorus modified epoxy field, be specifically related to a kind of preparation method of phosphorus modified phenolic resins.

Background technology

At present, domestic phosphorus modified resin system also only is confined at the phosphorus modified epoxy resin system, is mainly used in and take the electronic seal plastic coating as main field of coating.In recent years along with the service requirements of field of coating, the continuous lifting of application performance, physics to the phosphorus modified epoxy resin curing agent, chemistry application performance parameter request is also had higher requirement thereupon, general phosphorus modified epoxy can not meet the application requiring of this electronics application high-end field, answer the special requirement in market, the U.S. in 20 record at the beginning of, some international large chemical company starts to need to explore by organic phosphates heterogeneous ring compound class as luxuriant and rich with fragrance as phosphorus for satisfying the market, annular phosphate class raw material is applied in dihydroxyphenyl propane and modified formaldehyde resin, through several years, with the combination of application, explore, produce phosphorus modified bisphenol A urea formaldehyde in research and development in recent years, and it is successfully applied to the halogen-free flame-resistant electronic field.So far, along with the raising day by day of China's field of coating application demand, in the high-end field of this application, just rely on the import of this type of phosphorus modified phenolic resins fully, seriously limited the development of China's field of coating, and expensive, and each performance also has much room for improvement.

Summary of the invention

The invention provides a kind of preparation method of phosphorus modified phenolic resins, solved the problem that in the past relies on external import phosphorus modified phenolic resins fully.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

The molecular structural formula of phosphorus modified phenolic resins of the present invention is:

，

In formula ,-R1 representative-C ₃h ₇,-C ₄h ₉,-C ₅h ₁₁; N value 0-3 ,-R2-representative ,

,

;

The preparation method of above-mentioned phosphorus modified phenolic resins comprises the following steps:

A, phenol, formaldehyde and water are added in reaction vessel, with the catalyst reaction, obtain the phenol formaldehyde condensation body, temperature of reaction is 50 ℃～100 ℃, and the reaction times is 1～5 hour; The mol ratio of described phenol and described formaldehyde is 1:2～3, and the mass percent that described catalyzer accounts for the total mass of described formaldehyde and described phenol is 1%～5%, and the mass percent that described water accounts for the total mass of described formaldehyde and described phenol is 10%～15%;

B, introducing monohydroxy-alcohol, 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, make catalyzer with aluminium sesquioxide and sulfuric acid, first be warmed up to 80 ℃～120 ℃ insulation reflux dewaterings phenol formaldehyde condensation bodies that steps A is obtained and carry out monolateral end-blocking etherificate, the reaction times is 4～6 hours; Be warmed up to 100 ℃～160 ℃ remaining methylol end-blocking grafting of the other side that are incubated dehydration phenol formaldehyde condensation body that steps A is obtained, the reaction times is 9～11 hours, obtains this phosphorus modified phenolic resins again; Described monohydroxy-alcohol and described phenol mol ratio are 2～5:1, and described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and described phenol mol ratio are 0.8～1.5:1; The mass percent that described aluminium sesquioxide accounts for described phenol total mass is 0.5%～1.5%, and the mass percent that described sulfuric acid accounts for described phenol total mass is 0.1%～0.8%;

Wherein, described phenol is the mixed phenol to tert-octylphenol, dihydroxyphenyl propane and p-tert-butylphenol three;

Described catalyzer is a kind of in an acidic catalyst, basic catalyst;

Described an acidic catalyst is a kind of of tosic acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid;

Described basic catalyst is a kind of of sodium hydroxide, potassium hydroxide, calcium hydroxide, triethylamine, ammoniacal liquor;

Described monohydroxy-alcohol is a kind of of butanols, propyl alcohol, amylalcohol.

Owing to adopting technique scheme, the present invention has following beneficial effect:

1, the invention solves the problem that in the past relies on external import phosphorus modified phenolic resins fully, promoted the physical and chemical performance indexs such as heat-resisting, the bonding and stripping strength of original phosphorus modified epoxy thing, good bulk and excellent electrical property and physical strength, the coating performance that makes this phosphorus modified phenolic resins be applied to the electronic chemical product field is better.

2, optimize the working condition of traditional pure phenolic resin, adopted solvent-free reaction pattern, environmental contamination reduction.

3, take tert-octylphenol, dihydroxyphenyl propane, p-tert-butylphenol are first prepared to resol as matrix, and then by the organic phosphates heterogeneous ring compound as 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy and monohydroxy-alcohol carry out the even end-blocking of methylol under the catalytic condition of setting, form the phosphorus modified phenolic resins of serial different physical and chemical performances, its adhesiveproperties, thermally-stabilised, ageing-resistant, machinability, electric property, film forming stability can etc. better in the single phosphorus modified bisphenol A urea formaldehyde product of import.

4, can, according to the electronics coating process requirement of different manufacturers, by the proportioning of adjusting raw material phenol, the kind of alcohol etc., make the epoxy hardener phosphorus modified phenolic resin fat prod that more adapts to different service requirementss.

Embodiment

Table 1, table 2, table 3, table 4 are reaction raw materials component and the reaction conditions in embodiment 1～embodiment 20, and wherein the phenol described in embodiment 1～embodiment 20 is the mixed phenol to tert-octylphenol, dihydroxyphenyl propane, p-tert-butylphenol three.

According to following preparation steps, prepared by reaction raw materials component and reaction conditions that associative list 1, table 2, table 3, table 4 provide:

A, get phenol, formaldehyde and water respectively and join in four-hole boiling flask and mix, then add catalyst mix even, four-hole boiling flask is put into to the electric mantle heating and carry out condensation reaction and obtain the phenol formaldehyde condensation body, after cooling, it is emitted, minute remove residual moisture;

In B, phenol formaldehyde condensation body add-back four-hole bottle that steps A is obtained, add monohydroxy-alcohol and 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy mixes, add aluminium sesquioxide and sulfuric acid to make catalyzer, first heating up is incubated afterwards reflux dewatering reaction the phenol formaldehyde condensation body is carried out take monolateral end-blocking as main etherification reaction again; Remaining methylol carries out the end-blocking grafting to phenol formaldehyde condensation body the other side to adjust temperature again, obtains this phosphorus modified phenolic resins.

According to table 1, table 2, table 3, table 4 and above-mentioned preparation process, the chemical structural formula that embodiment 1～embodiment 20 obtains this phosphorus modified phenolic resins is evenly:

，

In formula ,-R1 representative-C ₃h ₇,-C ₄h ₉,-C ₅h ₁₁; N value 0-3 ,-R2-representative

,

, .

  

Phosphorus modified phenolic resins of the present invention can add ether solvent, adjusts flowing property, viscosity, solid content and the film forming speed of material, so that pack, use and construct.

Table 1:

。

Table 2:

。

Table 3:

。

Table 4:

?。

Table 5, table 6 are Performance Detection that the solidifying agent that obtains after phosphorus modified phenolic resins of the present invention adds redix carries out, and with the Performance Ratio of external two company's products, result is as follows:

Table 5:

。

Table 6:

。

Claims (1)

1. the preparation method of a phosphorus modified phenolic resins is characterized in that:

The chemical structural formula of described phosphorus modified phenolic resins is:

，

In formula ,-R1 representative-C ₃h ₇,-C ₄h ₉,-C ₅h ₁₁; N value 0-3 ,-R2-representative ,

,

;

The preparation of described phosphorus modified phenolic resins comprises the steps:

A, phenol, formaldehyde and water are added in reaction vessel, with the catalyst reaction, obtain the phenol formaldehyde condensation body, temperature of reaction is 50 ℃～100 ℃, and the reaction times is 1～5 hour; The mol ratio of described phenol and described formaldehyde is 1:2～3, and the mass percent that described catalyzer accounts for the total mass of described formaldehyde and described phenol is 1%～5%, and the mass percent that described water accounts for the total mass of described formaldehyde and described phenol is 10%～15%;

B, introducing monohydroxy-alcohol, 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, make catalyzer with aluminium sesquioxide and sulfuric acid, first be warmed up to 80 ℃～120 ℃ insulation reflux dewaterings phenol formaldehyde condensation bodies that steps A is obtained and carry out monolateral end-blocking etherificate, the reaction times is 4～6 hours; Be warmed up to 100 ℃～160 ℃ remaining methylol end-blocking grafting of the other side that are incubated dehydration phenol formaldehyde condensation body that steps A is obtained, the reaction times is 9～11 hours, obtains this phosphorus modified phenolic resins again; Described monohydroxy-alcohol and described phenol mol ratio are 2～5:1, and described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and described phenol mol ratio are 0.8～1.5:1; The mass percent that described aluminium sesquioxide accounts for described phenol total mass is 0.5%～1.5%, and the mass percent that described sulfuric acid accounts for described phenol total mass is 0.1%～0.8%;

Wherein, described phenol is the mixed phenol to tert-octylphenol, dihydroxyphenyl propane and p-tert-butylphenol three;

Described catalyzer is a kind of in an acidic catalyst, basic catalyst;

Described an acidic catalyst is a kind of of tosic acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid;

Described basic catalyst is a kind of of sodium hydroxide, potassium hydroxide, calcium hydroxide, triethylamine, ammoniacal liquor;

Described monohydroxy-alcohol is a kind of of butanols, propyl alcohol, amylalcohol.