阅读说明：本技术 一种聚烯烃发泡产品专用均泡剂的制备与应用 (Preparation and application of foam homogenizing agent special for polyolefin foaming product ) 是由 邹威 郭俊毅 马育红 张晨 于 2019-10-21 设计创作，主要内容包括：本发明提供了一种可用于聚烯烃发泡产品均泡剂的合成。本发明的聚烯烃发泡产品均泡剂的结构为一侧是长碳链,另外一侧是有机硅侧链。所述均泡剂的制备方法,包括如下步骤：将长碳链脂肪酸或者是酸酐改性的聚烯烃和氨基硅油反应,以N,N-二环己基碳酰亚胺和4-二甲氨基吡啶为催化剂,以二氯甲烷作为溶剂,制得有机硅缩合长碳链脂肪酸或酸酐改性的聚烯烃的均泡剂。此类均泡剂在发泡过程中能使泡沫混合均匀,降低泡孔内壁的应力,防治泡沫塌陷,具有良好的成核和稳泡作用,提高闭孔率,提升回弹性能,制备高性能的聚烯烃发泡产品。(The invention provides a synthesis method of a foam stabilizer for polyolefin foaming products. The structure of the foam stabilizer for polyolefin foaming products is that one side is a long carbon chain and the other side is an organic silicon side chain. The preparation method of the foam homogenizing agent comprises the following steps: reacting long-carbon-chain fatty acid or anhydride modified polyolefin with amino silicone oil, taking N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and taking dichloromethane as a solvent to prepare the organosilicon condensation long-carbon-chain fatty acid or anhydride modified polyolefin foam stabilizer. The foam homogenizing agent can uniformly mix foams in the foaming process, reduces the stress of the inner wall of a foam hole, prevents foam collapse, has good nucleation and foam stabilization effects, improves the closed cell rate, improves the resilience performance, and prepares a high-performance polyolefin foaming product.)

1. The synthesis and application of the foam homogenizing agent special for polyolefin foaming products are characterized in that the foam homogenizing agent is synthesized by condensation reaction of long-carbon-chain fatty acid or anhydride modified polyolefin and organosilicon, and the structure of the synthesized foam homogenizing agent is that one side of the synthesized foam homogenizing agent is a long carbon chain, so that good compatibility with polyolefin melt is provided; and the other end is organic silicon, so that the surface tension of the system can be reduced, nucleation can be promoted, and the function of supporting the foam body can be realized.

2. The foam stabilizer special for polyolefin foam products as claimed in claim 1, wherein the foam stabilizer is obtained by reacting polyolefin modified by long-chain fatty acid or anhydride with amino silicone oil, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and dichloromethane as a solvent, and is applied to polyolefin foam products.

3. The foam stabilizer special for polyolefin foaming products according to claim 2, wherein the synthesis of the foam stabilizer comprises the following raw materials: the fatty acid comprises one or a compound of lauric acid, myristic acid, stearic acid and oleic acid, and the anhydride modified polyolefin comprises anhydride grafted polyethylene, polypropylene, polyvinyl acetate, ethylene caprylic acid copolymer, amino silicone oil, N, N-dicyclohexyl carbodiimide, 4-dimethylamino pyridine and dichloromethane.

4. The foam stabilizer for polyolefin foaming products according to claim 3, wherein the viscosity of the amino silicone oil is 500 ~ 100000 mPa.s.

5. The foam stabilizer special for polyolefin foaming products as claimed in claim 3, wherein the foam stabilizer comprises the following raw materials, by weight, the molar ratio of carboxyl in the fatty acid to amino in the aminosilicone oil is 2: 1 ~ 1: 1, the molar ratio of acid anhydride in the anhydride-modified polyolefin to amino in the aminosilicone oil is 2: 1 ~ 1: 1, the addition amount of N, N-dicyclohexylcarbodiimide is 1-2 wt% of the fatty acid, and the amount of 4-dimethylaminopyridine is 1-2 wt% of the fatty acid.

6. The special foam homogenizing agent for the polyolefin foaming products according to claims 1-4, which is characterized by comprising the following steps of dissolving long-carbon-chain acid or anhydride modified polyolefin in dichloromethane, adding amino silicone oil under stirring, adding N, N-dicyclohexyl carbodiimide and 4-dimethylamino pyridine as catalysts, and after the reaction is finished, separating and purifying to obtain the polypropylene foam homogenizing agent, wherein the concentration of a reaction solution is 20 ~ 40wt%, the reaction temperature is 30 ~ 60 ℃, and the reaction time is 6 ~ 10 hours.

7. The foam stabilizer according to claims 1-4, wherein the foam stabilizer is suitable for foaming polyethylene, polypropylene, polyvinyl chloride, and polystyrene products.

8. The foam equalization agent material for polyolefin foam according to claims 1-5, wherein the foam equalization agent is added into a polyolefin foaming system, so that the effects of reducing the density of a foamed product, reducing the diameter of cells and improving the closed cell rate can be achieved, and the foam equalization agent can be widely applied to the field of polyolefin foaming materials.

Technical Field

The invention relates to a foam stabilizer for preparing high performance, in particular to a foam stabilizer required for preparing polyolefin foam, and application effect and performance of the foam stabilizer.

Background

The foam is a polymer material containing a large number of cells and having a plastic as a basic component, and therefore can be said to be a composite plastic having a gas as a filler. Compared with pure plastic, the composite material has many excellent properties, such as light weight, high specific strength, impact load absorption, good heat insulation and sound insulation properties, and the like. Therefore, the method is widely applied to the fields of industry, agriculture, building, transportation and the like. Since the advent of foamed plastics, the foamed plastics have been widely used and are of a variety, and among them, the more common conventional foamed plastics mainly include polypropylene (PP) Polyurethane (PUR), Polystyrene (PS), polyvinyl chloride (PVC), Polyethylene (PE), phenol resin (PF), and the like.

The foam homogenizing agent is one of essential components in the foaming process of the foam plastic, is a high-efficiency surfactant, and has the functions of nucleating, emulsifying each component in the formula, stabilizing foam, opening the pores of the foam, punching holes and the like. Silicone surfactants are the most important stabilizers in foams and have found wide application in the manufacture of rigid and flexible foams. In the early 20 th 50 s, a siloxane surfactant is researched and applied as a foam stabilizer, and polyether modified polysiloxane is rapidly developed and applied with excellent foam stabilizing performance along with the requirement of a one-step production process, wherein a Si-C type hydrolysis-resistant foam stabilizer is a main variety in the polyether modified polysiloxane.

Collapse, coarse holes and cracking of air holes in the foaming process of polyolefin materials are key factors influencing the performance of products. In view of this, a special foam equalizer for polyolefin foam products is to be synthesized at present, which can achieve a uniform cell structure, improve the closed cell rate, improve the resilience, and prepare high-performance polyolefin foam products. According to the invention, the organic silicon is condensed with the polyolefin modified by the fatty acid or the anhydride with the long carbon chain, so that the foam homogenizing agent suitable for the polyolefin foaming product is obtained, and the foam homogenizing agent has a good use effect.

Disclosure of Invention

The invention aims to synthesize the foam homogenizing agent special for the polyolefin foaming product, so as to solve the problems of collapse, coarse pores and cracking of air pores in the foaming process of the polyolefin material, effectively reduce the surface tension of solid-gas phases in the foaming process and achieve the aim of homogenizing and refining the pores.

In order to solve the problems, the invention provides the foam stabilizer special for the polyolefin foaming product, wherein one end of the foam stabilizer special for the polyolefin foaming product is a long carbon chain so as to provide good compatibility with polyolefin melt; and the other end is organic silicon, so that the interfacial tension of solid-gas two phases in the foaming process is effectively reduced, and the aims of homogenizing and refining the foam pores are fulfilled. Reacting octadecanoic acid with amino silicone oil under the conditions that N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine are used as catalysts and dichloromethane is used as a solvent to obtain the foam homogenizing agent.

Preferably, the special foam stabilizer for polyolefin foaming products comprises the following raw materials: octadecanoic acid, anhydride modified polyolefin, amino silicone oil, N, N-dicyclohexyl carbodiimide, 4-dimethylamino pyridine and dichloromethane.

Preferably, the special foam stabilizer for polyolefin foaming products comprises the following raw materials in parts by weight: the molar ratio of carboxyl in the fatty acid to amino in the amino silicone oil is 2: 1-1: 1, the ratio of acid anhydride in the acid anhydride modified olefin to amino in amino silicone oil is 2: 1-1: the addition amount of 1, N, N-dicyclohexylcarbodiimide is 1-2 wt% of the fatty acid, and the mass of 4-dimethylaminopyridine is 1-2 wt% of the fatty acid.

Preferably, the long carbon chain acid is octadecanoic acid.

Preferably, the viscosity of the amino silicone oil is 500-100000 mPa.s.

Preferably, the foaming agent of the polyolefin foamed product is supercritical CO_2。

Preferably, the synthetic foam stabilizer is applied to the polyolefin foam, and the effect of the foam stabilizer is shown by comparing the cell diameter, the product density, the closed cell ratio, the elongation at break, and the like, compared with the polyolefin foam without the foam stabilizer.

The preparation method of the polyolefin foam stabilizer comprises the following steps:

dissolving long-carbon-chain acid or anhydride modified polyolefin in dichloromethane, adding amino silicone oil under the condition of stirring, adding N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and separating and purifying after the reaction is finished to obtain the polyolefin foam stabilizer.

Compared with the prior art, the invention has the following beneficial effects:

the invention synthesizes the foam homogenizing agent special for the polyolefin foam material, wherein one end of the foam homogenizing agent is a long carbon chain so as to provide good compatibility with a precursor of a reaction of polyolefin foam; and the other end is organic silicon, so that the surface tension of a solid-gas phase in the foaming process is effectively reduced, and the aims of homogenizing and refining the foam pores are fulfilled. The special foam homogenizing agent has a simple preparation process, plays a role in homogenizing foam holes, refining foam holes, reducing product density and improving closed-cell rate in the production of polyolefin foam products, and has a good using effect.

Detailed Description

The examples of the present invention, in which the specific conditions are not specified, were conducted under the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The raw materials used in the examples are all commercially available.

TABLE 1 manufacturer information of raw materials used in the examples

It should be noted that the above are only sources of the raw materials used in this embodiment, other commercially available conventional products may also be used as the raw materials of the present invention, and the implementation of the technical solution and the implementation of the technical effect of the present invention are not affected by the raw materials of different manufacturers and models.