CN103483489B

CN103483489B - A kind of preparation method of catalytic resin for nonyl phenol

Info

Publication number: CN103483489B
Application number: CN201310451714.XA
Authority: CN
Inventors: 王金明; 张勇
Original assignee: Kai Rui Environmental Protection Science And Technology Co Ltd
Current assignee: Kai Rui Environmental Protection Science And Technology Co Ltd
Priority date: 2013-09-27
Filing date: 2013-09-27
Publication date: 2015-12-09
Anticipated expiration: 2033-09-27
Also published as: CN103483489A

Abstract

The invention provides a kind of preparation method of the catalytic resin for the preparation of nonyl phenol, comprise the following steps: in a kettle., by weight, add the vinylbenzene of 100 parts, the divinylbenzene of 5-20 part, the N-isopropylmaleimide of 0.5 ~ 5 part as comonomer, the chain-transfer agent of 0.01 ~ 0.05 part, the pore-creating agent of 20-60 part, 85 DEG C of reaction 2h are warming up to after 80 DEG C of reaction 6h, be warming up to 95 DEG C of reaction 6h again, terminate reaction, reaction generates polymerization Archon, after oven dry, pore-creating agent extracting is clean, dry stand-by; Join in sulfuric acid by the polymerization Archon obtained, the mass ratio of polymerization Archon and sulfuric acid is 1:1-1:3, carries out sulfonation reaction 10-30h, obtain the catalytic resin for the preparation of nonyl phenol at 80-110 DEG C.The catalytic resin thermotolerance that method of the present invention obtains is high, and side reaction is few, long reaction time.

Description

A kind of preparation method of catalytic resin for nonyl phenol

Technical field

The present invention relates to a kind of production Zeo-karb method, particularly a kind of preparation method of catalytic resin for nonyl phenol.

Background technology

Nonyl phenol is a kind of important fine chemical material and intermediate, and outward appearance is colourless or weak yellow liquid at normal temperatures, and slightly phenol smell, water insoluble, is dissolved in acetone.Mainly for the production of tensio-active agent, also for fields such as oxidation inhibitor, textile auxiliary, lubricating oil additive, farm chemical emulgent, modifier, resin and rubber stabilizers.Nonyl phenol can cause the phenomenon of feminizing of the male fish in sewage work downstream, is endocrine disrupter or the environmental hormone type organic with estrogen effect.

The preparation method of the nonyl phenol of prior art is based on Zeo-karb continuous processing and Zeo-karb interrupter method.

Zeo-karb continuous processing adopts polystyrene resin to be catalyzer.Anhydrous phenol and nonene enter preheater preheats to 70 DEG C using the proportioning of 1.73:1 and the recirculated air (as addition material) containing phenol and nonene, then the first paragraph fixed-bed reactor in two sections of fixed bed reaction systems are entered, being heated to 120 DEG C (temperature outs), is 96.3% by the nonyl phenol yield of two reactor.The nonyl phenol generated and a small amount of binonylphenol enter product tower at the bottom of recovery tower, and by distillation, product content reaches more than 99% (weight).

Zeo-karb interrupter method with gel-type or macroporous type storng-acid cation exchange resin for catalyzer.Phenol and nonene first alkylation under resin catalysis, portion of product sends into the reactor that first is equipped with resin, unreacted raw material is separated and is recycled, the reaction mixture obtained is through distillation removing inert compound and water, the reactant of distillation resultant product and the first reactor merges, purify through vacuum distilling, product content reaches more than 98% (weight).This is the technique adopted before u. s. mesh, and the former Soviet Union and Poland also adopt this technique; China's Changzhou chemical industry two factory and Daqing Petrochemical factory all adopt the graduate technology of the sub-organic synthesis of Polish Bradley Hough Buddhist nun.

Poland Patent CN1082530 " preparation method of n nonylphenol ", reacts by phenol and nonene the method preparing nonyl phenol under acidic ion exchange resin exists.The method is carried out in two steps: phenol contacts with gel-type and/or macroporous type cationite under alkylate exists with the mixture of tripropylene by the first step; Mixture containing phenol, nonene etc. contacts with macroporous cation exchangers by second step.

The resin catalyst used by above patent and known technology, has the shortcoming that thermostability is poor, production cost is higher.In order to promote domestic production, reducing production cost, being necessary further to study, finding suitable dealdehyding resin.

Summary of the invention

The object of the invention is to: for the deficiencies in the prior art, provide a kind of preparation method of the catalytic resin for the preparation of nonyl phenol, it is high that the catalytic resin obtained has thermotolerance, the advantages such as side reaction is few, long reaction time.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

A kind of preparation method of the catalytic resin for the preparation of nonyl phenol is provided, comprises the following steps:

1). the preparation of polyreaction Archon

In a kettle., by weight, the vinylbenzene of 100 parts, the divinylbenzene (be preferably 10 parts) of 5-20 part, the N-isopropylmaleimide of 0.5 ~ 5 part is added as comonomer, the chain-transfer agent of 0.01 ~ 0.05 part, the pore-creating agent (being preferably 40 parts) of 20-60 part, after 80 DEG C of reaction 6h, be warming up to 85 DEG C of reaction 2h, then be warming up to 95 DEG C of reaction 6h, terminate reaction, reaction generates polymerization Archon, after oven dry, pore-creating agent extracting is clean, dry stand-by;

2). sulfonation reaction

By step 1) the polymerization Archon that obtains joins in sulfuric acid, and the mass ratio of polymerization Archon and sulfuric acid is 1:1-1:3, carries out sulfonation reaction 10-30h, obtain the catalytic resin for the preparation of nonyl phenol at 80-110 DEG C.

Step 1) described in chain-transfer agent preferred dithiobenzoic acid styroyl ester.

Step 1) described in pore-creating agent be selected from liquid wax, white oil, containing organic alcohols more than 3 carbon atoms or any one or two or more mixtures in gasoline, be preferably liquid wax.

The rosin products that the inventive method obtains has following beneficial effect:

Relative to ordinary resin catalyzer, resin catalyst prepared by the inventive method, thermotolerance is high, side reaction is few, long reaction time, therefore under close proportioning raw materials, application the inventive method gained resin-made is for the technique of nonyl phenol, nonyl phenol yield is higher than the technique of the existing resin catalyst of application, and can reduce production cost, the resin that therefore the inventive method obtains can substitute same kind of products at abroad well simultaneously.

Embodiment

Following instance is only further illustrate the present invention, is not restriction the scope of protection of the invention.

Embodiment 1:

1). the preparation of polyreaction Archon

By weight, add the vinylbenzene of 100 parts, the divinylbenzene of 10 parts, the N-isopropylmaleimide of 3 parts as comonomer, the dithiobenzoic acid styroyl ester of 0.02 part, the liquid wax of 40 parts, 85 DEG C of reaction 2h are warming up to after 80 DEG C of reaction 6h, after oven dry, pore-creating agent extracting is clean, dry stand-by.

2). sulfonation reaction

By step 1) the polymerization Archon that obtains joins in sulfuric acid, and polymerization Archon is 1:2 with the mass ratio of sulfuric acid, and react 18h at 80-110 DEG C, sulfonation obtains a kind of catalytic resin for the preparation of nonyl phenol.Products obtained therefrom is numbered KRB-1.

Embodiment 2

Step 1) in the N-isopropylmaleimide that adds change 0.5 part into, the other the same as in Example 1.Products obtained therefrom is numbered KRB-2.

Embodiment 3

Step 1) in the N-isopropylmaleimide that adds change 5 parts into, the other the same as in Example 1.Products obtained therefrom is numbered KRB-3.

Embodiment 4

Step 1) in the dithiobenzoic acid styroyl ester that adds change 0.01 part into, the other the same as in Example 1.Products obtained therefrom is numbered KRB-4.

Embodiment 5

Step 1) in the dithiobenzoic acid styroyl ester that adds change 0.01 part into, the other the same as in Example 2.Products obtained therefrom is numbered KRB-5.

Embodiment 6

Step 1) in the dithiobenzoic acid styroyl ester that adds change 0.01 part into, the other the same as in Example 3.Products obtained therefrom is numbered KRB-6.

Embodiment 7

Step 1) the dithiobenzoic acid styroyl ester that adds changes 0.05 part into, the other the same as in Example 1.Products obtained therefrom is numbered KRB-7.

Embodiment 8

Step 1) in the dithiobenzoic acid styroyl ester that adds change 0.05 part into, the other the same as in Example 2.Products obtained therefrom is numbered KRB-8.

Embodiment 9

Step 1) in the dithiobenzoic acid styroyl ester that adds change 0.05 part into, the other the same as in Example 3.Products obtained therefrom is numbered KRB-9.

The test in the work-ing life of embodiment 10. resin catalyst:

The resin catalyst product obtained in embodiment 1-9 is loaded in fixed-bed reactor respectively, anhydrous phenol and nonene are with 1.5:1(mol) proportioning then enter two sections of fixed-bed reactor, temperature out 120 DEG C, exit sampling analysis in reactor, be less than 70% be inefficacy by the nonyl phenol yield of two reactor, statistics dealdehyding resin work-ing life, the results are shown in Table 1.Use D001 ion exchange resin to do catalysis to carry out as a comparison simultaneously.

Table 1: the comparison in test sample work-ing life that different process is made

Numbering	Work-ing life sky
		KRB－1	205
KRB－2	172
		KRB－3	212
KRB－4	158
		KRB－5	142
KRB－6	149
		KRB－7	179
KRB－8	200
		KRB－9	230
KRB－10	194
		D001 ion exchange resin	97

Claims

1. for the preparation of a preparation method for the catalytic resin of nonyl phenol, it is characterized in that, step is as follows:

1). the preparation of polyreaction Archon

In a kettle., by weight, the vinylbenzene of 100 parts, the divinylbenzene of 10 parts, the N-isopropylmaleimide of 0.5 ~ 5 part is added as comonomer, the chain-transfer agent of 0.01 ~ 0.05 part, the pore-creating agent of 40 parts, after 80 DEG C of reaction 6h, be warming up to 85 DEG C of reaction 2h, then be warming up to 95 DEG C of reaction 6h, terminate reaction, reaction generates polymerization Archon, after oven dry, pore-creating agent extracting is clean, dry stand-by;

2). sulfonation reaction

2. method according to claim 1, is characterized in that: step 1) described in chain-transfer agent be dithiobenzoic acid styroyl ester.

3. method according to claim 1, is characterized in that: step 1) described in pore-creating agent be selected from liquid wax, white oil, containing organic alcohols more than 3 carbon atoms or any one or two or more mixtures in gasoline.

4. method according to claim 1, is characterized in that: described pore-creating agent is liquid wax.