阅读说明：本技术 混合型苯丙共聚树脂及其制备方法与应用 (Mixed styrene-acrylic copolymer resin and preparation method and application thereof ) 是由 向海波 郭勇 陈君山 戴耀民 于 2020-06-10 设计创作，主要内容包括：本发明公开了混合型苯丙共聚树脂及其制备方法与应用,将苯丙共聚树脂树脂粉、炭黑、聚乙烯蜡、3,5-二叔丁基水杨酸的锌化合物、硅微粉在常规混料机中预混常规混练,待排料冷却后粉碎,过筛得到混合型苯丙共聚树脂；在三元共聚物存在下,由树脂A、树脂B、树脂C共挤出制备苯丙共聚树脂。本发明得到无规混合型苯丙共聚树脂粉末的粒径为5～12微米,作为碳粉打印,具有良好的长期稳定性。(The invention discloses a mixed styrene-acrylic copolymer resin and a preparation method and application thereof, wherein styrene-acrylic copolymer resin powder, carbon black, polyethylene wax, a zinc compound of 3, 5-di-tert-butyl salicylic acid and silicon micropowder are premixed and mixed conventionally in a conventional mixer, and are crushed and sieved after discharging and cooling to obtain the mixed styrene-acrylic copolymer resin; in the presence of the terpolymer, the styrene-acrylic copolymer resin is prepared by co-extruding the resin A, the resin B and the resin C. The particle size of the obtained random mixed styrene-acrylic copolymer resin powder is 5-12 microns, and the random mixed styrene-acrylic copolymer resin powder is printed as carbon powder and has good long-term stability.)

1. A mixed styrene-acrylic copolymer resin is prepared by premixing styrene-acrylic copolymer resin, carbon black, polyethylene wax, zinc compound of 3, 5-di-tert-butyl salicylic acid and silicon micropowder in a conventional mixer, conventionally mixing, discharging, cooling, pulverizing, and sieving to obtain mixed styrene-acrylic copolymer resin; in the presence of the terpolymer, co-extruding the resin A, the resin B and the resin C to prepare styrene-acrylic copolymer resin; the preparation of the resin A comprises the steps of adding styrene, hydroxyethyl acrylate, monobutyl maleate, an initiator and a crosslinking agent into boiling toluene, and removing a solvent after heat preservation reaction to obtain the resin A; the preparation of the resin B comprises the steps of adding styrene, butyl acrylate, an initiator and a cross-linking agent into boiling dimethylbenzene, and removing a solvent after heat preservation reaction to obtain the resin B; the preparation of the resin C is that styrene, butyl methacrylate, an initiator and a cross-linking agent are added into boiling toluene, and the solvent is removed after the heat preservation reaction to obtain the resin C.

2. The mixed type styrene-acrylic copolymer resin as claimed in claim 1, wherein the weight ratio of the resin A to the resin B to the resin C is 45: 40-45: 10-15.

3. The hybrid styrene-acrylic copolymer resin as set forth in claim 2, wherein the weight ratio of the resin A, the resin B and the resin C is 45: 41.5: 13.5.

4. The mixed styrene-acrylic copolymer resin as claimed in claim 1, wherein the amount of the terpolymer is 0.3-0.4% of the sum of the weight of the resin A, the weight of the resin B and the weight of the resin C.

5. The hybrid styrene-acrylic copolymer resin as set forth in claim 1, wherein the crosslinking agent is divinylbenzene or butanediol diacrylate; the initiator is cumene hydroperoxide or di-tert-butyl peroxide.

6. The mixed styrene-acrylic copolymer resin as set forth in claim 1, wherein the resin A is prepared by mixing styrene, hydroxyethyl acrylate and monobutyl maleate at a molar ratio of 6: 2.5: 1.5, the dosage of the initiator is 1.3 percent of the weight sum of the styrene, the hydroxyethyl acrylate and the monobutyl maleate, and the dosage of the cross-linking agent is 4 percent of the weight sum of the styrene, the hydroxyethyl acrylate and the monobutyl maleate.

7. The mixed styrene-acrylic copolymer resin as claimed in claim 1, wherein in the preparation of the resin B, the molar ratio of the styrene to the butyl acrylate is 8: 2, the amount of the initiator is 2% of the sum of the weight of the styrene and the butyl acrylate, and the amount of the cross-linking agent is 8% of the sum of the weight of the styrene and the butyl acrylate; in the preparation of the resin C, the molar ratio of the styrene to the butyl methacrylate is 3: 1, the dosage of the initiator is 4 percent of the sum of the weight of the styrene and the butyl methacrylate, and the dosage of the cross-linking agent is 3 percent of the sum of the weight of the styrene and the butyl methacrylate.

8. The mixed type styrene-acrylic copolymer resin as claimed in claim 1, wherein in the preparation of the resin A, the reaction is carried out for 2.5 hours at 110 ℃; in the preparation of the resin B, the reaction is carried out for 3 hours at the temperature of 140 ℃; in the preparation of the resin C, the reaction was carried out at 110 ℃ for 2 hours.

9. The mixed styrene-acrylic copolymer resin as claimed in claim 1, wherein the weight ratio of the styrene-acrylic copolymer resin, the carbon black, the polyethylene wax, the zinc compound of 3, 5-di-tert-butyl salicylic acid and the silicon micropowder is 100: 8.3: 1.5: 3: 1.2.

10. The use of the mixed styrene-acrylic copolymer resin as defined in claim 1 for the preparation of carbon powder.

Technical Field

The invention belongs to a high polymer synthesis technology, and particularly relates to a mixed styrene-acrylic copolymer resin, and a preparation method and application thereof.

Background

Disclosure of Invention

The invention discloses a mixed styrene-acrylic copolymer resin based on a block polymer, and a preparation method and application thereof, wherein styrene-acrylic resins with different molecular weights are obtained through selection of monomers and limitation of polymer parameters, and then are co-extruded to obtain resin powder with the particle size of 0.4-1.3 mm, and the resin powder is used for carbon powder printing and has good long-term stability.

The invention adopts the following technical scheme:

a mixed styrene-acrylic copolymer resin is prepared by premixing styrene-acrylic copolymer resin, carbon black, polyethylene wax, zinc compound of 3, 5-di-tert-butyl salicylic acid and silicon micropowder in a conventional mixer, conventionally mixing, discharging, cooling, pulverizing, and sieving to obtain mixed styrene-acrylic copolymer resin; in the presence of the terpolymer, co-extruding the resin A, the resin B and the resin C to prepare styrene-acrylic copolymer resin; the preparation of the resin A comprises the steps of adding styrene, hydroxyethyl acrylate, monobutyl maleate, an initiator and a crosslinking agent into boiling toluene, and removing a solvent after heat preservation reaction to obtain the resin A; the preparation of the resin B comprises the steps of adding styrene, butyl acrylate, an initiator and a cross-linking agent into boiling dimethylbenzene, and removing a solvent after heat preservation reaction to obtain the resin B; the preparation of the resin C is that styrene, butyl methacrylate, an initiator and a cross-linking agent are added into boiling toluene, and the solvent is removed after the heat preservation reaction to obtain the resin C.

In the invention, the weight ratio of the resin A to the resin B to the resin C is 45: 40-45: 10-15, preferably 45: 41.5: 13.5; the prepared styrene-acrylic copolymer resin has good thermal property and electrical property according to a proper proportion, can be suitable for high-performance printing, and particularly has good long-term stability.

In the invention, the use amount of the block polymer is 0.3-0.4% of the sum of the weight of the resin A, the weight of the resin B and the weight of the resin C. The styrene-acrylic resin with good electrical property can be obtained by direct coextrusion without adding the block polymer, but the long-term stability is slightly inferior, the block polymer originally used among different resins is creatively added into the same resin A, resin B and resin C in a small amount, the printing performance of a product obtained by coextrusion is improved, and the improvement of the uniformity of the three resin interfaces is probably facilitated by adding the block polymer. In the prior art, resins with different glass transition temperatures and softening points are mixed by blending, and resin powder with wide Tg is expected to be obtained so as to improve the printing performance, but the interface problem exists, so that the printing effect is poor.

In the invention, the cross-linking agent is divinyl benzene or butanediol diacrylate; the initiator is cumene hydroperoxide or di-tert-butyl peroxide.

In the invention, in the preparation of the resin A, the mol ratio of styrene to hydroxyethyl acrylate to monobutyl maleate is 6: 2.5: 1.5, the dosage of the initiator is 1.3 percent of the sum of the weight of the styrene, the hydroxyethyl acrylate and the monobutyl maleate, and the dosage of the cross-linking agent is 4 percent of the sum of the weight of the styrene, the hydroxyethyl acrylate and the monobutyl maleate; in the preparation of the resin B, the molar ratio of the styrene to the butyl acrylate is 8: 2, the dosage of the initiator is 2 percent of the sum of the weight of the styrene and the butyl acrylate, and the dosage of the cross-linking agent is 8 percent of the sum of the weight of the styrene and the butyl acrylate; in the preparation of the resin C, the molar ratio of the styrene to the butyl methacrylate is 3: 1, the dosage of the initiator is 4 percent of the sum of the weight of the styrene and the butyl methacrylate, and the dosage of the cross-linking agent is 3 percent of the sum of the weight of the styrene and the butyl methacrylate.

In the invention, in the preparation of the resin A, the reaction is carried out for 2.5 hours at the temperature of 110 ℃; in the preparation of the resin B, the reaction is carried out for 3 hours at the temperature of 140 ℃; in the preparation of the resin C, the reaction was carried out at 110 ℃ for 2 hours.

In the invention, the solvent is removed by vacuum reduced pressure distillation, and the operation of the vacuum reduced pressure distillation is a conventional technology, so that the solvent can be removed.

In the invention, the resin A, the resin B, the resin C and the terpolymer are added into a screw extruder, and styrene-acrylic copolymer resin is prepared by coextrusion; screw extrusion is a conventional technology, and the specific selection does not influence the realization of the technical effect of the invention.

In the invention, the weight ratio of the styrene-acrylic copolymer resin, the carbon black, the polyethylene wax, the zinc compound of the 3, 5-di-tert-butyl salicylic acid and the silicon micro powder is 100: 8.3: 1.5: 3: 1.2.

Detailed Description