阅读说明：本技术 一种发泡母料、其制备方法及应用 (Foaming master batch, preparation method and application thereof ) 是由 许卫民 雷周桥 刘鹏 肖懿 黎泽顺 容敏智 阮文红 卢俊文 于 2020-11-09 设计创作，主要内容包括：本发明公开了一种发泡母料、其制备方法及应用。发泡母料包括液体载体、发泡剂及助剂；所述的发泡母料的制备方法为：将原料加入容器中,以500r/min-3000r/min的转速研磨分散均匀；所述发泡母料应用于注塑、挤出发泡塑料。本发明所述发泡母料,发泡剂溶于液体载体中或以微米级的尺度均匀分散于液体载体中,生产效率高且工艺安全简单,不会造成污染；避免了挤出工艺,防止发泡剂分解,生产安全；发泡液体母料使用时均匀附着在塑料颗粒表面,在树脂中具有极佳的分散性,有力保证了发泡剂与颜料的均匀分散。(The invention discloses a foaming master batch, a preparation method and application thereof. The foaming master batch comprises a liquid carrier, a foaming agent and an auxiliary agent; the preparation method of the foaming master batch comprises the following steps: adding the raw materials into a container, and grinding and dispersing uniformly at a rotating speed of 500r/min-3000 r/min; the foaming master batch is applied to injection molding and extrusion foaming plastics. According to the foaming master batch, the foaming agent is dissolved in the liquid carrier or is uniformly dispersed in the liquid carrier in a micron-sized scale, so that the production efficiency is high, the process is safe and simple, and pollution is avoided; the extrusion process is avoided, the decomposition of the foaming agent is prevented, and the production is safe; when in use, the foaming liquid master batch is uniformly attached to the surface of plastic particles, has excellent dispersibility in resin, and powerfully ensures the uniform dispersion of the foaming agent and the pigment.)

1. A foaming mother material is composed of liquid carrier, foaming agent and assistant.

2. The foaming masterbatch according to claim 1, wherein the foaming masterbatch comprises the following components in parts by weight: 20-60 parts of liquid carrier, 10-80 parts of foaming agent and a proper amount of auxiliary agent.

3. The foaming concentrate of claim 1, wherein: the liquid carrier is a liquid oligomer, a plasticizer, a vegetable oil and/or a mineral oil.

4. The foaming concentrate of claim 3, wherein: the liquid oligomer comprises an acrylate liquid polymer and an acrylamide liquid polymer.

5. The foaming concentrate of claim 1, wherein: the auxiliary agent comprises a foaming auxiliary agent and a dispersing auxiliary agent.

6. The foaming concentrate of claim 5, wherein: the auxiliary agent also comprises an antioxidant and a stabilizer.

7. The foaming concentrate of any of claims 1-6, wherein: the foaming agent is one or a mixture of more of sodium bicarbonate, zinc carbonate, azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate, azoaminobenzene, diisopropyl azodicarboxylate, diethyl azodicarboxylate, dinitrosopentamethylenetetramine, benzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, 1, 3-benzenesulfonyl hydrazide, 4 ' -oxybis-benzenesulfonyl hydrazide, 3 ' -disulfonyl hydrazide diphenyl sulfone, 4 ' -oxybis (benzenesulfonylamino urea), trihydrazino triazine, 5-phenyltetrazole, nitroguanidine, dihydrazide and hydrazinodicarbonamide.

8. A process for the preparation of a foaming concentrate according to any of claims 1 to 7, characterized in that it comprises the following steps: adding the raw materials into a container, and grinding and uniformly dispersing at a rotating speed of 500r/min-3000 r/min.

9. Use of a foaming masterbatch according to any one of claims 1 to 7 in injection moulded, extruded foamed plastics.

10. Use of a foaming concentrate according to claim 9, characterized in that: the mass ratio of the foaming master batch to the foaming material is 0.5-6: 100.

Technical Field

The invention belongs to the technical field of foaming, and particularly relates to a foaming master batch, and a preparation method and application thereof.

Background

In the field of plastic processing, in order to reduce the weight of plastic, enhance the heat insulation, sound insulation and shock resistance of materials, or realize certain appearance design of materials, foaming agents are usually added into the plastic, and a plurality of fine cells are formed in the materials through a foaming process, so that the application is very wide.

Currently, there are two main forms of foamed plastics produced using chemical blowing agents: the foaming agent is directly used, so that dust is easy to fly, potential safety hazards exist, and the environment is damaged. One is to use a foaming master batch. The foaming master batch is prepared by mixing an excessive foaming agent, a dispersing agent, a foaming auxiliary agent, a resin carrier and the like, and then carrying out plastication, sheet-pulling, granulation or extrusion granulation, and the foaming master batch enables the production of the foaming plastic to be more environment-friendly and simpler. However, the processing and use of the foamed masterbatch is still problematic. Firstly, the foaming master batch needs to mix resin carrier, foaming agent, dispersant, foaming auxiliary agent etc. together, kneads at a high speed, plastify the pulling-on piece and cut grain or extruder plastify and cut grain and form, and the process is loaded down with trivial details, the energy consumption is high, and the compounding process can cause dust pollution. Secondly, the plastication or extrusion process of the foaming master batch is limited by the characteristic that the foaming agent is easily decomposed at high temperature, and the product waste and even production safety problems are easily caused if the foaming agent is decomposed due to improper control of the processing process. Thirdly, when the foamed plastic is produced, the foaming master batch is added into the matrix resin granules or powder according to a certain proportion, and the uneven mixing of the materials can cause uneven dispersion of the foaming agent, easily cause uneven foam holes of the foamed plastic and the like.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a foaming master batch.

The invention also provides a preparation method of the foaming master batch.

The invention also provides application of the foaming master batch.

The invention achieves the aim through the following technical scheme, and the foaming master batch comprises a liquid carrier, a foaming agent and an auxiliary agent.

The foaming master batch takes the liquid carrier and the foaming agent as raw materials, and the foaming agent is dissolved in the liquid carrier or uniformly dispersed in the liquid carrier in a micron-sized scale, so that the production efficiency is high, the process is safe and simple, and pollution is avoided; the extrusion process is avoided, the decomposition of the foaming agent is prevented, and the production is safe; when in use, the foaming liquid master batch is uniformly attached to the surface of plastic particles, has excellent dispersibility in resin, and powerfully ensures the uniform dispersion of the foaming agent and the pigment.

In one embodiment, the foaming master batch comprises the following components in parts by weight: 20-60 parts of liquid carrier, 10-80 parts of foaming agent and a proper amount of auxiliary agent.

In one embodiment, the liquid carrier is a liquid oligomer, a plasticizer, a vegetable oil, and/or a mineral oil.

In one embodiment, the liquid oligomer includes an acrylate liquid polymer and an acrylamide liquid polymer.

In one embodiment, the auxiliary agent includes a foaming auxiliary agent and a dispersing auxiliary agent.

In one embodiment, the additive further comprises an antioxidant and a stabilizer.

In one embodiment, the foaming agent is one or a mixture of sodium bicarbonate, zinc carbonate, azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, azoaminobenzene, diisopropyl azodicarboxylate, diethyl azodicarboxylate, dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, 1, 3-benzenedisulfonylhydrazide, 4 ' -oxybis-benzenesulfonylhydrazide, 3 ' -disulfonylhydrazide diphenylsulfone, 4 ' -oxybis (benzenesulfonylaminourea), trihydrazinotriazine, 5-phenyltetrazole, nitroguanidine, dihydrazide, or hydrazinodiamide.

The invention also provides a preparation method of the foaming master batch, which comprises the following steps: adding the raw materials into a container, and grinding and uniformly dispersing at a rotating speed of 500r/min-3000 r/min.

The invention also provides application of the foaming master batch in injection molding and extrusion of foamed plastics.

In one embodiment, the mass ratio of the foaming master batch to the foaming material is 0.5-6: 100.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof will be described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The foaming master batch comprises a liquid carrier, a foaming agent and an auxiliary agent. The foaming master batch takes a liquid carrier and a foaming agent as raw materials, the foaming agent is dissolved in the liquid carrier or uniformly dispersed in the liquid carrier in a micron-scale, the production efficiency is high, the process is safe and simple, and no pollution is caused; the extrusion process is avoided, the decomposition of the foaming agent is prevented, and the production is safe; when in use, the foaming liquid master batch is uniformly attached to the surface of plastic particles, has excellent dispersibility in resin, and powerfully ensures the uniform dispersion of the foaming agent and the pigment.

In one embodiment, the foaming master batch comprises the following components in parts by weight: 20-60 parts of liquid carrier, 10-80 parts of foaming agent and a proper amount of auxiliary agent.

For example, liquid carriers 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, and 60 parts; 10 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 55 parts, 65 parts and 80 parts of foaming agent. The parts by mass may be combined arbitrarily within the range.

Wherein the liquid carrier is a liquid oligomer, a plasticizer, a vegetable oil and/or a mineral oil. The blowing agent can be dispersed in these liquid carriers to form a good foaming masterbatch.

Preferably, the liquid oligomer includes an acrylate-based liquid polymer and an acrylamide-based liquid polymer.

For example, the liquid carrier is one or a combination of trioctyl trimellitate (TOTM), dibutyl phthalate (DBP), dioctyl phthalate (DOP), dioctyl terephthalate (DOTP), dibutyl sebacate (DBS), di (2-ethylhexyl) sebacate (DOS), di (2-ethylhexyl) adipate (DOA), cyclohexane 1, 2-dicarboxylic acid diisononyl ester, tricresyl phosphate (TCP), trioctyl phosphate (TOP), technical or food grade white oils, epoxidized fatty acid esters, and epoxy tetrahydrophthalic acid di (2-ethylhexyl) ester, tetrapolyricinoleate, and hexapolyricinoleate. The blowing agent can be dispersed in the liquid carrier to prepare a liquid foaming master batch.

The foaming agent can be selected from one or a mixture of more of sodium bicarbonate, zinc carbonate, azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate, azoaminobenzene, diisopropyl azodicarboxylate, diethyl azodicarboxylate, dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, 1, 3-benzenesulfonylhydrazide, 4 ' -oxybis-benzenesulfonylhydrazide, 3 ' -disulfonylhydrazide diphenylsulfone, 4 ' -oxybis (benzenesulfonylaminourea), trihydrazinotriazine, 5-phenyltetrazole, nitroguanidine, dihydrazide and hydrazinodiamide.

The auxiliary agent comprises a foaming auxiliary agent and a dispersing auxiliary agent. The foaming aid may assist in the foaming, while the dispersing aid and the assisting blowing agent are dispersed in the liquid carrier. Wherein, the foaming auxiliary agent is 0.5 to 30 parts, and the dispersing auxiliary agent is 0.1 to 10 parts.

Wherein the foaming auxiliary agent comprises a foaming promoter, a nucleating agent, a filling agent, a cross-linking agent and the like.

Specifically, the foaming aid is, for example: one or more of calcium carbonate, calcium stearate, calcium oxide, silicon dioxide, titanium dioxide, talcum powder, carbon black, zinc acetate, zinc stearate, zinc oxide, mica and dicumyl peroxide.

Wherein the dispersing auxiliary agent is a wetting dispersant or a viscosity regulator.

Specifically, the dispersing auxiliary agent comprises one or a mixture of more of Bike BYK-108, BYK-111, BYK-160, BYK-185, BYK-9076, BYK-9077, BYK-2100, BYK-2105, ANTI-TERRA-U100, Luoborun 8000, 20000, 27000, 24000, 32500, 36000 and 47000 hyper-dispersants, Yingchuandigao 685, 740W, gas-phase silicon dioxide, bentonite, polyethylene glycol and polyisobutylene.

In one embodiment, the additives further include other additives, such as an antioxidant, a stabilizer, and the like. 0.1 to 10 portions of other auxiliary agents.

Specifically, the antioxidant comprises one or a mixture of more of an antioxidant 168, an antioxidant 1010, an antioxidant 1076 and an antioxidant 245, and the stabilizer comprises one or a mixture of more of tribasic lead sulfate, dibasic lead phosphite and dibasic lead stearate.

The invention also provides a preparation method of the foaming master batch, which comprises the following steps: adding the raw materials into a container, and grinding and uniformly dispersing at a rotating speed of 500r/min-3000 r/min.

During the grinding process, heat is generated, and cooling water can be used for cooling outside the grinding container so as to control the temperature of the raw material not to be too high, for example, to control the temperature not to be higher than 60 ℃. Of course, other methods may be used to cool the feedstock to ensure that the temperature of the feedstock is not too high.

The grinding dispersion time can be 20min-60 min.

The invention also provides application of the foaming master batch in injection molding and extrusion of foamed plastics.

Specifically, the foaming master batch can be used for preparing the following foaming materials: foaming processing of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (EVA), thermoplastic rubber (TPR), Polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), and Polycarbonate (PC).

In one embodiment, the mass ratio of the foaming master batch to the foaming material is 0.5-6: 100. by adopting the mass ratio, the foaming effect can be better realized, and the waste caused by excessive use amount can be avoided.

Embodiments of the present invention will be further illustrated by the following examples.

Example one

The foaming masterbatch described in this example includes: 40 parts of dioctyl terephthalate, 50 parts of azodicarbonamide, BYK-1111 parts, 10 parts of zinc oxide, 3 parts of zinc stearate, 1680.5 part of antioxidant and 0.5 part of fumed silica, and the raw materials are added into a high-speed grinding machine, cooling water is adopted for circular cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 1200r/min, and the grinding time is 20 min. The foamed master batch obtained after grinding can be used for extruding low-foaming PP, and the adding proportion is 3%.

Example two

The foaming masterbatch described in this example includes: 40 parts of dioctyl terephthalate, 50 parts of azodicarbonamide, 200000.5 parts of luobou, 4 parts of dicumyl peroxide, 10 parts of talcum powder and 1680.5 part of antioxidant, wherein the raw materials are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 1500r/min, and the grinding time is 20 min. The foaming master batch obtained after grinding can be used for extruding low-foaming PE, and the adding proportion is 2%.

EXAMPLE III

The foaming masterbatch described in this example includes: the grinding process comprises the following steps of adding 35 parts of tricresyl phosphate, 65 parts of sodium bicarbonate, 200000.5 parts of Luborun, 20002 parts of polyisobutylene PB and 10100.5 parts of antioxidant into a high-speed grinding machine, and circularly cooling by adopting cooling water in the grinding process to ensure that the liquid temperature is not higher than 60 ℃, the grinding speed is 1500r/min, and the grinding time is 20 min. The foaming liquid master batch obtained after grinding can be used for extruding foaming PE, and the adding proportion is 4%.

Example four

The foaming masterbatch described in this example includes: 68#45 parts of white oil, 55 parts of azodicarbonic acid barium salt, BYK-1111 parts, 5 parts of zinc oxide, 1 part of zinc stearate, 5 parts of calcium carbonate and 10100.5 parts of antioxidant, wherein the raw materials are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 1500r/min, and the grinding time is 20 min. The foaming master batch obtained after grinding can be used for injection molding foaming ABS, and the addition proportion is 2%.

EXAMPLE five

The foaming masterbatch described in this example includes: 40 parts of cyclohexane 1, 2-dicarboxylic acid diisononyl ester, 40 parts of azodicarbonamide, 200000.5 parts of Luborun, 2 parts of dicumyl peroxide, 15 parts of zinc oxide and 1 part of titanium dioxide, and the raw materials are added into a high-speed grinding machine, and cooling water is adopted for circulating cooling in the grinding process to ensure that the liquid temperature is not higher than 60 ℃, the grinding speed is 1500r/min, and the grinding time is 20 min. The foaming master batch obtained after grinding can be used for extruding foaming PE, and the adding proportion is 4%.

EXAMPLE six

The foaming masterbatch described in this example includes: 40 parts of acrylate liquid polymer, 40 parts of azodicarbonamide, BYK-90761 parts, 5 parts of zinc oxide, 1 part of zinc stearate, 5 parts of calcium carbonate and 1680.5 part of antioxidant are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 1500r/min, and the grinding time is 20 min. The foaming master batch obtained after grinding can be used for injection molding ABS foaming, and the addition proportion is 3%.

EXAMPLE seven

The foaming masterbatch described in this example includes: 60 parts of acrylate liquid polymer, 35 parts of azodicarbonic acid barium salt, 6851 parts of Desgastin, 5 parts of zinc oxide, 1 part of zinc stearate and 10100.5 parts of antioxidant are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 1500r/min, and the grinding time is 20 min. The foaming master batch obtained after grinding can be used for injection molding PC foaming, and the addition proportion is 2%.

Example eight

The foaming masterbatch described in this example includes: 30 parts of acrylate liquid polymer, 10 parts of dioctyl phthalate, 20 parts of azodicarbonamide, 25 parts of tribasic lead sulfate, 1 part of dibasic lead phosphite, 2 parts of dibasic lead stearate and 10 parts of calcium carbonate, wherein the raw materials are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding rotating speed is 2000r/min, and the grinding time is 30 min. The foaming master batch obtained after grinding can be used for extruding PVC foaming, and the adding proportion is 3%.

Example nine

The foaming masterbatch described in this example includes: 40 parts of dioctyl terephthalate, 20 parts of trioctyl phosphate, 50 parts of azodicarbonamide, 30 parts of azodiisobutyronitrile, BYK-1111 parts, 10 parts of zinc oxide, 3 parts of zinc stearate, 1680.5 part of antioxidant and 0.5 part of fumed silica, and the raw materials are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is enabled to be not higher than 60 ℃, the grinding rotating speed is 1200r/min, and the grinding time is 60 min. The foamed master batch obtained after grinding can be used for extruding low-foaming PP, and the adding proportion is 6%.

Example ten

The foaming masterbatch described in this example includes: 20 parts of trioctyl phosphate, 10 parts of azodicarbonamide, 10 parts of zinc oxide, 1680.5 parts of antioxidant and 0.5 part of fumed silica, and the raw materials are added into a high-speed grinding machine, cooling water is adopted for circulating cooling in the grinding process, the liquid temperature is not higher than 60 ℃, the grinding speed is 1200r/min, and the grinding time is 15 min. The foamed master batch obtained after grinding can be used for extruding low-foaming PP, and the adding proportion is 0.5%.

Comparative example 1

Weighing 100 parts of PP, 35 parts of azodicarbonamide, 10 parts of zinc oxide, 3 parts of zinc stearate and 0.5 part of antioxidant 168, mixing uniformly, using a Z-type kneader at 120 ℃ for 60min, plastifying and thining for 3 times at 120 ℃ and 0.5mm in roll gap, plasticizing fully, pulling a piece on a two-roll vehicle, cooling and punching, and cutting the piece into particles to obtain the foaming master batch. And adding the mixture into PP for extrusion foaming to obtain the low-foaming PP.

Comparative example No. two

Weighing 100 parts of LDPE, 40 parts of azodicarbonamide, 4 parts of dicumyl peroxide, 10 parts of talcum powder and 0.5 part of antioxidant 168 in parts by weight, mixing uniformly, and using a Z-type kneader at the temperature of 120 ℃ for 60 min; and then plasticating and thining by two rollers at the temperature of 120 ℃, the roller gap being 0.5mm, thining for 3 times, fully plasticizing, then pulling the piece on a two-roller vehicle, cooling and punching, and cutting the pulling piece into particles to obtain the foaming master batch. Then adding LDPE for extrusion foaming to obtain the low-foaming PE.

The foamed plastic sample plates prepared in the first to tenth examples and the first to second comparative examples are subjected to appearance comparative analysis, and it is found that the foamed plastic sample plates prepared in the first to eighth examples have good cell dispersion and uniform size, while the foamed plastic sample plates prepared in the first to second comparative examples have similar foaming conditions, low cell uniformity and complicated process.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.