CN101445573B

CN101445573B - Method for preparing single-dispersibility polystyrene-DVE

Info

Publication number: CN101445573B
Application number: CN2007101710845A
Authority: CN
Inventors: 顾顺超; 周锦鑫; 陈友
Original assignee: SHANGHAI RESIN FACTORY CO Ltd; Shanghai Jiaotong University
Current assignee: SHANGHAI RESIN FACTORY CO Ltd; Shanghai Jiaotong University
Priority date: 2007-11-27
Filing date: 2007-11-27
Publication date: 2012-05-02
Anticipated expiration: 2027-11-27
Also published as: CN101445573A

Abstract

The invention provides a method for preparing single-dispersibility polystyrene-DVE, comprising the steps as follows: mixed solution consisting of cinnamene (St), divinylbenzene (DVB) and benzoyl peroxide (BPO) is poured in polyvinyl alcohol solution, mixed for 0.2-1h at the temperature of 20-35 DEG C and heated to the temperature of 70-80 DEG C; subsequently, the temperature is kept for 0.75-1.0h; surfactant solution is added in the mixed solution with the temperature kept for 0.5-1.0h; subsequently, the mixed solution is heated to the temperature of 85-95 DEG C and the temperature is kept for 0.75-1.0h; subsequently, the mixed solution is aged and the single-dispersibility polystyrene-DVE is collected out of the reaction products. The cross-linked polystyrene-DVE provided by the method has the advantages of excellent performance, high mechanical strength, high attrition sphericity not less than 90%, and meeting the requirement of ion exchange resin framework with all indexes.

Description

The preparation method of single-dispersibility polystyrene-DVE

Technical field

The present invention relates to the preparation method of PS Archon.

Technical background

The styrene suspension crosslinking polymerization is the polymerization method a kind of commonly used that is used to prepare ion exchange resin skeleton multipolymer.Use suspension polymerization and prepare polymer microsphere, controllability and monodispersity that its main technic index is a microspherulite diameter.

In the suspension polymerization process, in the presence of stirring, monomeric drop is ceaselessly carrying out assembling and is disperseing.Along with the increase of extent of polymerization, the viscosity of liquid also can increase gradually, when transformation efficiency reaches certain degree; The drop of monomer and polymkeric substance is clamminess, and at this moment during two kinds of droplet collisions, just can stick together; Stir promotion caking on the contrary, get into suspension polymerization and lump critical days.For controlling the size-grade distribution of pearl body in the styrene suspension copolymerization effectively, prevent to expect that the bonding of grain is most important.

In the reaction of the suspension copolymerization of vinylbenzene and divinylbenzene, be water miscible organic polymer as the Z 150PH or the gelatin of dispersion agent, make monomer form resist with the aqueous phase interface interlayer mutually, can make the drop dispersion and prevent that they are adhered to one another.But along with the increase of polymerisation conversion in the reaction process, the viscosity of drop also increases thereupon, and list can not effectively prevent that with Z 150PH or gelatin drop from owing to collision merges, needing to add the dissemination that dispersion aids improves suspension system.

At present, the preparation method of traditional single-dispersibility polystyrene-DVE, effective yield of the single-dispersibility polystyrene-DVE that is obtained is lower, generally is merely about 75%, and high, the complex process of cost can not adapt to need of industrial production simultaneously.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of single-dispersibility polystyrene-DVE, to overcome the above-mentioned defective that prior art exists.

Method of the present invention comprises the steps:

Vinylbenzene (St), divinylbenzene (DVB) and Lucidol (BPO) mixed solution are poured in the polyvinyl alcohol water solution, under 20～35 ℃, stirred 0.2～1h then; Be warming up to 70～80 ℃, be incubated 0.75～1.0 hour, add water phase surfactant mixture; Behind insulation 0.5～1h, be warming up to 85～95 ℃, insulation 0.75～1.0h slaking; Make drop hardening balling-up, from reaction product, collect single-dispersibility polystyrene-DVE then.

Said tensio-active agent is selected from non-ionics, AS, cats product or amphoterics;

Said non-ionics such as fiber are verivate or dehydration sorb sugar ester etc.;

Said AS such as carboxylate salt, vitriol, sulphonate or phosphoric acid salt etc.;

Said cats product such as quaternary amine etc.;

Said amphoterics such as amino acid etc.

Can be a kind of of above-mentioned tensio-active agent or its mixture;

The weight concentration of water phase surfactant mixture is 0.005%～0.1%;

The weight concentration of polyvinyl alcohol water solution is 0.05～1.0%;

In the reaction system, the parts by weight of each component are:

40～100 parts of vinylbenzene (St)

0～20 part of divinylbenzene (DVB)

0.1～0.8 part of Lucidol (BPO)

0.05～1.0 part of polyvinyl alcohol water solution

0.005～0.1 part of water phase surfactant mixture.

The present invention prepares the polymerization reaction late stage of PS Archon process at suspension polymerization; Through adding the method for tensio-active agent, the viscosity of control reaction system, the heat transfer efficiency of improvement system; Strengthen the dissemination of suspension system; With the generation that prevents to lump with fine powder, improve the yield of the effective sphere diameter of PS Archon, the yield of 26 orders～effective sphere diameter of 60 orders is more than 95%.Crosslinked polystyrene Archon material property provided by the invention is good, has higher physical strength, mill rate of small round spheres >=90%, and each item index satisfies the requirement of ion exchange resin skeleton.

Embodiment

If no special instructions, be weight part among the embodiment.

Comparative Examples 1

The mixed solution of 75 parts of vinylbenzene (St), 11 parts of divinylbenzenes (DVB), 0.4 part of Lucidol (BPO) is poured in the aqueous solution of 100 parts of deionized waters and 0.2 part of Z 150PH composition, under the room temperature, mechanical stirring 0.5h; Be warming up to 75 ℃, behind insulation 0.75h under 75 ℃, be warming up to 92 ℃; And insulation 1h, get into maturation stage, make drop hardening balling-up; Ball is filtered, washs, dries, sieves, and obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes.

Size distribution is following:

The order number	＞26 orders	26～30 orders	30～40 orders	40～60 orders	＜60 orders
						Quality percentage yield	25.3	3.6	10.8	50.4	9.9

Have a large amount of macrobead dung and＜60 purpose fine powders, the 26 orders～effective sphere diameter copolymerization of 60 purposes Archon is merely 64.8%.

Embodiment 1

The mixed solution of 75 parts of vinylbenzene (St), 11 parts of divinylbenzenes (DVB), 0.4 part of Lucidol (BPO) is poured in the aqueous solution of 100 parts of deionized waters and 0.2 part of Z 150PH composition, under 35 ℃, stirred 1h then; Be warming up to 80 ℃, be incubated 1.0 hours, add 0.01 part of lauryl sodium sulfate aqueous solution; Behind the insulation 1h, be warming up to 95 ℃, insulation 1.0h slaking; Make drop hardening balling-up, filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes.

The weight concentration of lauryl sodium sulfate aqueous solution is 0.005%.

Size distribution is following:

The order number	＞26 orders	26～30 orders	30～40 orders	40～60 orders	＜60 orders
						Quality percentage yield	1.9	3.0	9.9	84.2	1.0

A spot of macrobead dung and＜60 purpose fine powders are only arranged, and 26 orders～the effective sphere diameter copolymerization of 60 purposes Archon is up to 97.1%, and major part concentrates between 40～60 orders.

Embodiment 2

The mixed solution of 75 parts of vinylbenzene (St), 5 parts of divinylbenzenes (DVB), 0.4 part of Lucidol (BPO) is poured in the aqueous solution of 100 parts of deionized waters and 0.2 part of Z 150PH composition, under 20 ℃, stirred 0.2h then; Be warming up to 70 ℃, be incubated 0.75 hour, add the aqueous solution of 0.03 part of polysorbate60; Behind the insulation 0.5h, be warming up to 85 ℃, insulation 0.75h slaking; Make drop hardening balling-up, filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes.

The weight concentration of the polysorbate60 aqueous solution is 0.1%.

Size distribution is following:

The order number	＞26 orders	26～30 orders	30～40 orders	40～60 orders	＜60 orders
						Quality percentage yield	1.5	2.5	11.3	83.5	1.2

A spot of macrobead dung and＜60 purpose fine powders are only arranged, and 26 orders～the effective sphere diameter copolymerization of 60 purposes Archon is up to 97.3%, and major part concentrates between 40～60 orders.

Embodiment 3

The mixed solution of 75 parts of vinylbenzene (St), 9 parts of divinylbenzenes (DVB), 0.5 part of Lucidol (BPO) is poured in the aqueous solution of 100 parts of deionized waters and 0.15 part of Z 150PH composition, under 20 ℃, stirred 0.2h then; Be warming up to 70 ℃, be incubated 0.75 hour, add the aqueous solution of 0.02 part of cetyl trimethylammonium bromide; Behind the insulation 0.5h; Be warming up to 85 ℃, insulation 0.75h slaking makes drop hardening balling-up; Filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes.

The weight concentration of the cetyl trimethylammonium bromide aqueous solution is 0.01%.

Size distribution is following:

The order number	＞26 orders	26～30 orders	30～40 orders	40～60 orders	＜60 orders
						Quality percentage yield	1.3	2.1	18.9	75.5	2.2

A spot of macrobead dung and＜60 purpose fine powders are only arranged, and 26 orders～the effective sphere diameter copolymerization of 60 purposes Archon is up to 96.5%, and major part concentrates between 40～60 orders.

Claims

1. the preparation method of single-dispersibility polystyrene-DVE is characterized in that, comprises the steps: the mixed solution of 75 parts of vinylbenzene, 11 parts of divinylbenzenes, 0.4 part of Lucidol is poured in the aqueous solution of 100 parts of deionized waters and 0.2 part of Z 150PH composition; Under 35 ℃, stir 1h then, be warming up to 80 ℃; Be incubated 1.0 hours, add 0.01 part of lauryl sodium sulfate aqueous solution, behind the insulation 1h; Be warming up to 95 ℃, insulation 1.0h slaking makes drop hardening balling-up; Filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes; The weight concentration of lauryl sodium sulfate aqueous solution is 0.005%.

2. the preparation method of single-dispersibility polystyrene-DVE is characterized in that, comprises the steps:

The mixed solution of 75 parts of vinylbenzene, 5 parts of divinylbenzenes, 0.4 part of Lucidol is poured in the aqueous solution of 100 parts of deionized waters and 0.2 part of Z 150PH composition, under 20 ℃, stirred 0.2h then; Be warming up to 70 ℃, be incubated 0.75 hour, add the aqueous solution of 0.03 part of polysorbate60; Behind the insulation 0.5h, be warming up to 85 ℃, insulation 0.75h slaking; Make drop hardening balling-up, filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes; The weight concentration of the polysorbate60 aqueous solution is 0.1%.

3. the preparation method of single-dispersibility polystyrene-DVE is characterized in that, comprises the steps:

The mixed solution of 75 parts of vinylbenzene, 9 parts of divinylbenzenes, 0.5 part of Lucidol is poured in the aqueous solution of 100 parts of deionized waters and 0.15 part of Z 150PH composition, under 20 ℃, stirred 0.2h then; Be warming up to 70 ℃, be incubated 0.75 hour, add the aqueous solution of 0.02 part of cetyl trimethylammonium bromide; Behind the insulation 0.5h, be warming up to 85 ℃, insulation 0.75h slaking; Make drop hardening balling-up, filter then, wash, dry, sieve, obtaining granularity is the qualified copolymerization Archons of 26 orders～60 purposes; The weight concentration of the cetyl trimethylammonium bromide aqueous solution is 0.01%.