CN103044842A - Method for preparing doublet acrylonitrile butadiene styrene (ABS) resin - Google Patents

Abstract

The invention relates to a method for preparing doublet acrylonitrile butadiene styrene (ABS) resin. Styrene-butadiene latex with small diameter and butadiene latex with large diameter are fully stirred and mixed together and are added with part emulsifier, styrene, acrylonitrile, dodecyl mercaptan and desalted water at the temperature of 40-80 DEG C, when the temperature is heated to 42-50 DEG C, part activator and cumyl hydroperoxide are added to react for 0.5-2 hours, a continuous feeding mode is adopted to add the residual emulsifier, styrene, acrylonitrile, dodecyl mercaptan and desalted water in 1-3 hours, the activator and the cumyl hydroperoxide are added to cure for 0.3-1 hour, the obtained ABS latex is added into concentrated sulphuric acid at the temperature of 80-98 DEG C for 5-20 minutes, coagulating, filtering and drying are carried out so as to obtain dry powder, the dry powder is mixed with styrene-acrylonitrile copolymer (SAN), and an extruding machine is used to extrude and pelletize so as to obtain an ABS finished product. The impact strength, tensile strength and gloss of the resin are all improved.

Description

A kind of preparation method of bimodal ABS resin

Technical field

The invention belongs to the engineering plastics ABS production technical field, particularly bimodal ABS resin of a kind of efficient easily control and preparation method thereof.

Background technology:

ABS resin is the thermoplastic polymer that is formed by divinyl, vinylbenzene, three kinds of monomer copolymerizations of vinyl cyanide, is one of resin important in the engineering macromolecular material.Bimodal ABS resin is an ABS resin new technology that grows up on general ABS resin basis, refer in the grafting process to add the rubber particles of two kinds of (or more than) different-grain diameters, the cooperation of large small particle size is toughened resin effectively, obtain high impact, high tensile, the goods of high comprehensive performance.

Preparing the present topmost method of bimodal ABS resin is to adopt emulsion grafting polymerization technology respectively graft copolymerization vinylbenzene and vinyl cyanide on large particle diameter polyhutadiene emulsion particle and small particle size butadiene-styrene latex grain, obtain ABS latex, again two kinds of latex are mixed rear cohesion in certain proportion, obtain powder, with granulation after powder and the SAN blend obtain having bimodal distribution, the ABS product of good mechanical property, namely adopt the method for mixing after the first grafting.

Patent US691908 with the latex of small particle size (60-150nm) and large particle diameter (260-500nm) latex with the certain proportion blending after grafting prepare the higher bimodal ABS resin of shock strength, but this technology mainly is to adjust refractive index by the control gel content, for the preparation of Transparent ABS Resin, the performance requriementss such as impact intensity and tensile strength are not high.

The polymkeric substance that patent US5434218 forms take vinylbenzene and Acrylamide polymerization is as matrix, take median size as 100-500nm and Polybutadiene-styrene-acrylonitrile graft copolymer of 600-10000nm as during dispersion adds matrix, obtain the moulding mixture of high-impact performance.

Patent EP0507117 and patent EP0505799 are that the butadiene-styrene that adopts two kinds of different-grain diameters-acrylonitrile graft copolymer adds among the SAN in order to improve the performance of moulding mixture.

Patent EP2157129 has prepared a kind of bimodal ABS resin, adopting median size is two kinds of conjugated diene polymers of 80-150nm and 250-350nm, thereon grafting aromatic hydrocarbon ethylene based compound and vinyl cyanide, the multipolymer and the polysiloxane Masterbatch that add again methacrylic resin or acrylate mixture, aromatic hydrocarbon ethylene based compound and vinyl cyanide, thereby when keeping the ABS resin physicals, improve its colourability.

Patent 200810105657.9 is mixed small part particle diameter 100nm styrene-butadiene latex grafting gained ABS latex take particle diameter 300nm polybutadiene latex grafting gained ABS latex as main, and the epoxy glue curdling is obtained the ABS powder, and again blending granulation obtains ABS resin.

The bimodal ABS Technology Need of this kind carries out the preparation of two kinds of different ABS latex, and the time spent is longer, needs when condensing simultaneously two kinds of ABS latex are mixed, and has increased the workload of cohesion unit.In order to enhance productivity, the production control process that is more prone to, in the emulsion graft polymerization process, with particle diameter 300nm polybutadiene latex as basic latex, mix small part particle diameter 100nm styrene-butadiene latex, jointly carry out graft polymerization, directly can obtain bimodal ABS latex, the cohesion granulation obtains the ABS finished product.

Summary of the invention:

The purpose of this invention is to provide a kind of bimodal ABS resin and preparation method thereof, for improving the production efficiency of bimodal ABS resin, improve the controllability of production process, adopt the method for grafting after mixing first, take the size two kinds of particle diameters latex as basic latex carries out grafting, once obtain bimodal ABS latex.

The preparation method of bimodal ABS resin of the present invention:

1) at first small particle size styrene-butadiene latex and large particle diameter polybutadiene latex are fully mixed the adding reactor, again with partial emulsifier, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water adds in the reactor, temperature is controlled at 40～80 ℃, when temperature rises to 42～50 ℃, add the part activator, hydrogen phosphide cumene, react after 0.5～2 hour, adopt the mode of continuous charging in 1～3 hour, to add remaining emulsifying agent, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water, add the remaining activator of rear adding, hydrogen phosphide cumene, after the slaking 0.3～1 hour, reaction finishes, and obtains ABS latex;

2) with 1) the ABS latex that obtains adds and has been added with in the water of 0.1～5 part of vitriol oil, stirs, heating, and temperature is controlled at 80～98 ℃, and the time is 5～20 minutes, after the cohesion, filtration drying obtains dry mash, dry mash is mixed with SAN, use the forcing machine extruding pelletization, obtain the ABS final finished;

3) above-mentioned 1) used component is by weight:

4) component of activator is by weight above-mentioned 3):

5) above-mentioned 3) component of emulsifying agent is by weight:

0.2～10 part of nilox resin acid potash soap

90～99.8 parts of de-salted waters;

Described small particle size styrene-butadiene latex: solid content: 25～55%, particle diameter: 80～120nm, pH value are 8～12;

Described large particle diameter polybutadiene latex: solid content: 45～65%, particle diameter: 260～340nm, pH value are 8～12.

The ABS resin that the present invention obtains is compared with general ABS resin, and under the prerequisite of not losing flowing property, the resistance to impact shock of product, tensile strength and glossiness all improve a lot.

Embodiment:

Embodiment 1:

1, ABS graft polymerization:

At first small particle size styrene-butadiene latex and large particle diameter polybutadiene latex are fully mixed the adding reactor, again with partial emulsifier, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water adds in the reactor, temperature is controlled at 65 ℃, when temperature rises to 48 ℃, add the part activator, hydrogen phosphide cumene, react after 1 hour, adopt the mode of continuous charging in 2 hours, to add remaining emulsifying agent, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water, add the remaining activator of rear adding, hydrogen phosphide cumene, after the slaking 0.8 hour, reaction finishes, and obtains ABS latex;

2, with above-mentioned 1 resulting ABS latex with the white steel strainer filtering of 100 purposes, add oxidation inhibitor, adding has been added with in the water of 2 parts of vitriol oils, stirs, heats, temperature is controlled at 93 ℃, time is 15 minutes, and with the slurries filter-cloth filtering of slaking, whizzer dries, obtain wet mash, put into electric heating constant-temperature blowing drying box, 80 ℃ of dryings 8 hours, obtain dry mash.Dry mash is mixed with SAN, use the forcing machine extruding pelletization, obtain the ABS final finished.

3, component and umber:

1) component and the umber that comprise of activator:

2) component and the umber that comprise of emulsifying agent:

1 part of nilox resin acid potash soap

99 parts of de-salted waters

3) above-mentioned 1ABS graft polymerization component and umber:

Embodiment 2:

1, ABS graft polymerization:

At first small particle size styrene-butadiene latex and large particle diameter polybutadiene latex are fully mixed the adding reactor, again with partial emulsifier, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water adds in the reactor, temperature is controlled at 40 ℃, when temperature rises to 50 ℃, add the part activator, hydrogen phosphide cumene, react after 2 hours, adopt the mode of continuous charging in 3 hours, to add remaining emulsifying agent, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water, add the remaining activator of rear adding, hydrogen phosphide cumene, after the slaking 1 hour, reaction finishes, and obtains ABS latex;

2, with above-mentioned 1 resulting ABS latex with the white steel strainer filtering of 100 purposes, add oxidation inhibitor, adding has been added with in the water of 2.5 parts of vitriol oils, stirs, heats, temperature is controlled at 95 ℃, time is 15 minutes, and with the slurries filter-cloth filtering of slaking, whizzer dries, obtain wet mash, put into electric heating constant-temperature blowing drying box, 80 ℃ of dryings 10 hours, obtain dry mash.Dry mash is mixed with SAN, use the forcing machine extruding pelletization, obtain the ABS final finished.

3, component and umber:

1) component and the umber that comprise of activator:

2) component and the umber that comprise of emulsifying agent:

1.2 parts of nilox resin acid potash soaps

98.8 parts of de-salted waters

3) above-mentioned 1ABS graft polymerization component and umber:

Embodiment 3:

1, ABS graft polymerization:

At first small particle size styrene-butadiene latex and large particle diameter polybutadiene latex are fully mixed the adding reactor, again with partial emulsifier, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water adds in the reactor, temperature is controlled at 80 ℃, when temperature rises to 42 ℃, add the part activator, hydrogen phosphide cumene, react after 0.5 hour, adopt the mode of continuous charging in 1 hour, to add remaining emulsifying agent, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water, add the remaining activator of rear adding, hydrogen phosphide cumene, after the slaking 0.3 hour, reaction finishes, and obtains ABS latex;

2, with above-mentioned 1 resulting ABS latex with the white steel strainer filtering of 100 purposes, add oxidation inhibitor, adding has been added with in the water of 2.0 parts of vitriol oils, stirs, heats, temperature is controlled at 94 ℃, time is 15 minutes, and with the slurries filter-cloth filtering of slaking, whizzer dries, obtain wet mash, put into electric heating constant-temperature blowing drying box, 80 ℃ of dryings 10 hours, obtain dry mash.Dry mash is mixed with SAN, use the forcing machine extruding pelletization, obtain the ABS final finished.

3, component and umber

1) component of activator and emulsifying agent and umber are identical with embodiment 2.

2) above-mentioned 1ABS graft polymerization component and umber:

The results are shown in Table 1

Table 1 embodiment 1-3ABS end properties test result

Claims (1)

1. the preparation method of a bimodal ABS resin is characterized in that:

1) at first small particle size styrene-butadiene latex and large particle diameter polybutadiene latex are fully mixed the adding reactor, again with partial emulsifier, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water adds in the reactor, temperature is controlled at 40～80 ℃, when temperature rises to 42～50 ℃, add the part activator, hydrogen phosphide cumene, react after 0.5～2 hour, adopt the mode of continuous charging in 1～3 hour, to add remaining emulsifying agent, vinylbenzene, vinyl cyanide, lauryl mercaptan, de-salted water, add the remaining activator of rear adding, hydrogen phosphide cumene, after the slaking 0.3～1 hour, reaction finishes, and obtains ABS latex;

2) with 1) the ABS latex that obtains adds and has been added with in the water of 0.1～5 part of vitriol oil, stirs, heating, and temperature is controlled at 80～98 ℃, and the time is 5～20 minutes, after the cohesion, filtration drying obtains dry mash, dry mash is mixed with SAN, use the forcing machine extruding pelletization, obtain the ABS final finished;

3) above-mentioned 1) used component is by weight:

4) component of activator is by weight above-mentioned 3):

5) above-mentioned 3) component of emulsifying agent is by weight:

0.2～10 part of nilox resin acid potash soap

90～99.8 parts of de-salted waters;

Described small particle size styrene-butadiene latex: solid content: 25～55%, particle diameter: 80～120nm, pH value are 8～12;

Described large particle diameter polybutadiene latex: solid content: 45～65%, particle diameter: 260～340nm, pH value are 8～12.