WO2017206823A1

WO2017206823A1 - Environment-friendly, energy-saving structural layer for refrigeration equipment and application thereof

Info

Publication number: WO2017206823A1
Application number: PCT/CN2017/086256
Authority: WO
Inventors: 黄宝奎; 何超雄; 陈平绪; 魏金刚; 程庆; 王亮; 李玉虎; 林士文; 戴建建
Original assignee: 金发科技股份有限公司
Priority date: 2016-05-31
Filing date: 2017-05-27
Publication date: 2017-12-07
Also published as: CN107446299A; CN107446299B

Abstract

Disclosed are an environment-friendly, energy-saving structural layer for refrigeration equipment and an application thereof. The structural layer consists of an HFO-foamed, rigid polyurethane foam layer and a modified aromatic vinyl-based resin end cap. The modified aromatic vinyl-based resin is a melt blend of an acrylonitrile-butadiene-styrene (ABS) and an ethylene propylene diene monomer rubber-toughened vinyl cyanide-aromatic vinyl polymer. The ethylene propylene diene monomer rubber-toughened vinyl cyanide-aromatic vinyl polymer has a content by weight of 20-95% of the modified aromatic vinyl-based resin. The environment-friendly, energy-saving structural layer for refrigeration equipment prepared by the present invention overcomes the problem of material cracking in current refrigeration equipment when an HFO foaming agent is used in combination with an ABS end cap, thereby improving environment-friendly and energy-saving properties of refrigeration equipment. Since the structural layer comprises an ABS-containing material, the structural layer also provides good forming properties and gloss, allowing diversified and high-end structural design for refrigeration equipment.

Description

Environmental protection and energy-saving structural layer of refrigeration equipment and its application

Technical field

The invention belongs to the technical field of refrigeration equipment manufacturing, and in particular, the invention relates to an environmental protection and energy-saving structural layer of a refrigeration equipment.

Background technique

Refrigeration equipment generally uses rigid polyurethane foam as a heat insulation layer, while rigid polyurethane foams currently generally use cyclopentane (CP), hydrofluoroalkane (HCFC, HFC) and hydrofluoroolefin (HFO) as blowing agents. Because the fourth-generation blowing agent hydrofluoroolefin HFO has a low greenhouse effect potential (GWP) and zero ozone depletion potential (ODP), the use of HFO foaming agent insulation layer can improve the insulation performance of refrigeration equipment, effective Reduce the energy consumption level of refrigeration equipment, so the energy-saving and environmentally friendly HFO will gradually replace the previous foaming agents such as hydrochlorofluorocarbons (CP, HCFC, HFC).

However, when HFO is used as a foaming agent, HFO is highly corrosive to plastic parts in refrigeration equipment. In particular, HFO generates severe environmental stress on commonly used acrylonitrile-butadiene-styrene (ABS) end caps, among which HFO Corrosion is more serious than CP, HCFC and HFC. At present, HFO foaming agent is widely considered to be difficult to apply to refrigeration equipment of ABS end caps. The reason is that HFO foaming agent is a fluorine-containing compound, which easily erodes the resin, has a low boiling point, is easily vaporized at normal temperature, and has higher activity. . When the HFO foaming agent enters the ABS resin, the polymer will undergo plasticization under the influence of the HFO foaming agent due to the strong solvation effect of the HFO foaming agent. Among them, butadiene rubber in ABS absorbs foaming agent more easily, and the interface interaction between butadiene rubber and acrylonitrile-styrene becomes weaker, which is easier in stress concentration areas, especially in the corners of ABS parts and low temperature contact areas. Destroyed, often manifested as multiple silver streaks and cracks. In addition, the ABS end cap has better forming performance and higher gloss, which makes the structural design of the refrigeration equipment more diversified and the taste is more high-end. Therefore, it is necessary to find an application method for solving the compatibility between the ABS door end cover and the HFO foam insulation layer.

Patent CN 103319834 discloses that HIPS, PE and SBS blended modified HIPS materials are used as the refrigeration equipment mouth frame. Although the chemical corrosion resistance is good, the preparation process of the modified HIPS material is complicated, and the gloss is poor, and it is difficult. Meet the high-end taste required for the appearance of refrigeration equipment parts.

Summary of the invention

The present invention is directed to overcoming the above-mentioned drawbacks of the prior art, and provides an end cap made of a modified ABS resin, which overcomes the difficulty that the ABS end cap is difficult to be compatible with the HFO foamed heat insulating layer, and is effectively resistant. HFO foaming agent corrosion, under the high and low temperature cycle change, cracking will not occur, while retaining the ABS end cap good formability and high gloss.

Another object of the present invention is to provide an environmentally-friendly and energy-saving structural layer of a refrigeration apparatus comprising an end cap made of the modified ABS resin.

Another object of the present invention is to provide an application of the environmental protection and energy-saving structural layer of the refrigeration equipment in preparing a refrigerator, a freezer and a wine cabinet.

The above object of the invention is achieved by the following means.

EPDM rubber toughened vinyl cyanide-aromatic ethylene polymer for use in preparing end caps for refrigeration equipment, said EPDM toughened vinyl cyanide-aromatic ethylene polymer blended with ABS Prepared as a modified aromatic vinyl resin, and then prepared into a refrigeration equipment end cap; among the modified aromatic vinyl resins, a vinyl cyanide-aromatic vinyl polymer toughened with respect to ethylene propylene diene rubber and ABS The total amount of ethylene propylene-aromatic ethylene polymer toughened by EPDM rubber is 20 to 95% by weight.

The inventors have found that replacing the ABS resin with a vinyl cyanide-aromatic ethylene polymer toughened with ethylene propylene diene rubber can greatly improve the high and low temperature resistance, aging resistance and chemical resistance of the material. When the weight content of the ethylene propylene-aromatic ethylene polymer toughened by the EPDM rubber is 20 to 95% in the modified aromatic vinyl resin, the end cap does not cause cracking.

Preferably, the ethylene propylene diene rubber toughened vinyl cyanide-aromatic ethylene polymer has a weight content of from 30 to 95%. The inventors have found that when the amount of the vinyl cyanide-aromatic vinyl polymer toughened by the EPDM rubber is within this range, the end cap can be further smoothed.

When the content of the ethylene-propylene-aromatic vinyl polymer toughened by the EPDM rubber is too high, the molding property of the modified aromatic vinyl resin is adversely affected, making it difficult to form an end cap by injection molding. The content of the vinyl cyanide-aromatic vinyl polymer toughened by the ethylene propylene diene rubber of the present invention may further preferably be from 30 to 60% in view of molding processability. When the content of the vinyl cyanide-aromatic vinyl polymer toughened by the EPDM rubber is too high, the cost is also remarkably increased. The ethylene terephthalate-toughened vinyl cyanide-aromatic ethylene polymer toughened by the present invention is further preferably used in an amount of from 30 to 40% in terms of overall performance and cost.

Preferably, in the modified aromatic vinyl resin, the ABS has a weight content of at least 5%.

The modified aromatic vinyl resin may further contain an appropriate amount of an auxiliary agent, and the auxiliary agent may be a lubricant, an antioxidant, or the like which is commonly used in the art.

In the ethylene-propylene-aromatic ethylene polymer toughened by the EPDM rubber, the ethylene propylene diene monomer is grafted EPDM rubber, the graft is acrylonitrile-styrene, the vinyl cyanide is acrylonitrile or methacrylonitrile, and the aromatic ethylene is styrene, α-methylstyrene or vinyltoluene.

An environmentally-friendly and energy-saving structural layer of a refrigeration device, comprising an HFO foamed rigid polyurethane foam layer and an end cap made of the modified aromatic vinyl resin.

The HFO foamed rigid polyurethane foam layer may be coated with a HFO foamed rigid polyurethane foam layer of the known art. Typically, such HFO foamed rigid polyurethane foam layers are made by reacting a polyol, a HFO-containing blowing agent, a catalyst, and an isocyanate.

Preferably, the HFO-containing foaming agent is a single foaming agent composed of a HFO-based foaming agent or a mixed foaming agent composed of a HFO-based foaming agent and other non-HFO-based foaming agents.

As an alternative, the HFO-based blowing agent is at least one of trans 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) and hexafluorobutene (HFO-1336mmz).

As an alternative, the mixed blowing agent is a mixture of a HFO-based blowing agent and an alkane and/or HFC-based blowing agent.

More preferably, the alkane is pentane, and the pentane is at least one selected from the group consisting of cyclopentane, isopentane and n-pentane.

More preferably, the HFC-based blowing agent is at least one of HFC-245, HFC-365mfc, and HFC-134a.

The environmental protection and energy-saving structural layer of the refrigeration device is used in preparing a refrigerator, a freezer and a wine cabinet.

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

The invention adopts the modified aromatic vinyl resin instead of the ABS resin, which not only retains the advantages of high glossiness and good formability of the ABS end cap, but also significantly improves the chemical corrosion resistance of the end cap, and solves the current refrigeration equipment ABS. The end cap can not use the problem of HFO foaming agent; the use of modified aromatic vinyl resin improves the environmental protection and energy saving performance of the refrigeration equipment; the forming process of the end cap of the invention is consistent with the commonly used ABS end cap, and retains good formability, The structural design of the refrigeration equipment is more diversified and the taste is more high-end.

detailed description

The invention is further illustrated by the following specific examples, but the examples are not intended to limit the invention in any way. Unless otherwise indicated, the raw material reagents employed in the examples of the present invention are conventional commercially available raw material reagents.

The parts of the following examples are all by weight.

The preparation method of the rigid polyurethane foam refers to the prior art.

To simplify the description, the following examples refer to the EPDM-toughened vinyl cyanide-aromatic ethylene polymer as an EPDM-based polymer.

Example 1

S1. 90 parts of polyether polyol H815, 3 parts of catalyst PC-5, 18 parts of HFO-1233zd, 14 parts of cyclopentane, 0.7 parts of quaternary ammonium salt, 2.5 parts of silicon-based foam stabilizer B8445, 1.5 parts of water and 108 parts of isocyanate M20S were reacted to prepare a rigid polyurethane foam.

S2. 70 parts of ABS, 30 parts of EPDM type polymer UMG

ESA30, 1 part of antioxidant 1010 and 0.5 part of lubricant EBS are blended, injection molding machine is injection molded, and modified aromatic vinyl resin end cap is processed.

The rigid polyurethane foam layer and the modified aromatic vinyl resin end cap are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.

Example 2

S1. 80 parts of polyether polyol GR-635C, 2.5 parts of catalyst PC-5, 18 parts of HFO-1233zd, 6 parts of HFC-134a, 8 parts of HFC-365mfc, 0.5 parts of quaternary ammonium salt, 2.0 parts of silicon foam The stabilizer AK8809, 1 part of water and 138 parts of isocyanate PAPI27 were reacted to prepare a rigid polyurethane foam.

S2. 60 parts of ABS, 40 parts of EPDM polymer

ESA20, 1 part of antioxidant 1076 and 0.5 part of lubricant calcium stearate are blended, injection molding machine is injection molded, and modified aromatic vinyl resin end cap is processed.

Example 3

S1. 88 parts of polyether polyol H815, 3 parts of catalyst PC-5, 13 parts of HFO-1336mmz, 8 parts of cyclopentane, 3 parts of HFC-134a, 10 parts of HFC-365mfc, 0.7 parts of quaternary ammonium salt, 2.0 A portion of the foam stabilizer L-6952, 1.5 parts of water and 108 parts of isocyanate PM-200 were reacted to prepare a rigid polyurethane foam.

S2. 40 parts of ABS, 60 parts of EPDM type polymer UMG E700N, 1.0 part of antioxidant 1010 and 1.5 parts of lubricant EBS were blended, injection molding machine was injection molded, and modified aromatic vinyl resin end cap was processed.

Example 4

S1. 70 parts of polyether polyol GR-635C, 1.5 parts of catalyst PC-5, 26 parts of HFO-1233zd, 0.7 parts of quaternary ammonium salt, 2.0 parts of silicone-based foam stabilizer B8445, 1 part of water and 148 parts of isocyanate M20S The reaction was carried out to prepare a rigid polyurethane foam.

S2. 50 parts of ABS, 50 parts of EPDM polymer Kumho EP AES HW 600G, 1.5 parts of antioxidant 1076 and 1 part of lubricant calcium stearate are blended, injection molding machine is injection molded, and modified aromatic vinyl is processed. Resin end cap.

Example 5

S1. Reacting 80 parts of polyether polyol H815, 1.3 parts of catalyst PC-5, 30 parts of HFO-1233zd, 0.7 parts of quaternary ammonium salt, 1.8 parts of silicon-based foam stabilizer AK8809, 1 part of water and 148 parts of isocyanate PAPI27 To prepare a rigid polyurethane foam.

S2. 15 parts of ABS, 85 parts of EPDM type polymer UMG

ESA30, 1.0 part of antioxidant 1010 and 0.5 part of lubricant calcium stearate were blended, injection molding machine was injection molded, and modified aromatic vinyl resin end cap was processed.

Example 6

S1. 80 parts of polyether polyol GR-635C, 1.3 parts of catalyst PC-5, 30 parts of HFO-1233zd, 0.7 parts of quaternary ammonium salt, 1.8 parts of silicon-based foam stabilizer L-6952, 1 part of water and 148 parts The isocyanate PM-200 was reacted to prepare a rigid polyurethane foam.

S2. 5 parts of ABS, 95 parts of EPDM polymer

ESA20, 1.0 part of antioxidant 1076 and 0.5 part of lubricant EBS were blended, injection molding machine was injection molded, and modified aromatic vinyl resin end cap was processed.

Example 7

S2. 80 parts of ABS, 20 parts of EPDM type polymer UMG

Comparative example 1

S2. 100 parts of ABS, 1 part of antioxidant 1010 and 0.5 part of lubricant EBS were blended, injection molding machine was injection molded, and modified aromatic vinyl resin end cap was processed.

Comparative example 2

S2. 85 parts of ABS, 15 parts of EPDM-based polymer UMG

The environmentally-friendly and energy-saving structural layers of the assembled refrigeration equipment of the above Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to high and low temperature alternating 5 cycles test (-40 ° C to 70 ° C, 12 h), and the cracks on the surface of the end layer of the structural layer were observed. Visually) and whether it is smooth and flat (touch and visual), the test results are shown in Table 1.

Table 1 Example and Comparative End Cap Detection Results

	检测结果Test results
实施例1Example 1	无明显开裂，光滑平整No obvious cracking, smooth and flat
实施例2Example 2	无明显开裂，光滑平整No obvious cracking, smooth and flat
实施例3Example 3	无明显开裂，光滑平整No obvious cracking, smooth and flat
实施例4Example 4	无明显开裂，光滑平整No obvious cracking, smooth and flat

实施例5Example 5	无明显开裂，光滑平整No obvious cracking, smooth and flat
实施例6Example 6	无明显开裂，光滑平整No obvious cracking, smooth and flat
实施例7Example 7	无明显开裂，表面略微粗糙No obvious cracking, slightly rough surface
对比例1Comparative example 1	开裂Cracking
对比例2Comparative example 2	开裂Cracking

According to the end cap detection results of the examples and the comparative examples, it is known that, in the modified aromatic vinyl resin, the ethylene propylene-aromatic ethylene polymer toughened by the ethylene propylene diene monomer has a weight content of 20 to 95%. When the end cap is prepared, it is resistant to high and low temperature and is not prone to cracking; when the weight content of the vinyl cyanide-aromatic ethylene polymer toughened by the EPDM rubber is 30 to 95%, the surface of the end cap Smooth and flat; when the amount of vinyl cyanide-aromatic vinyl polymer toughened without EPDM rubber or the ethylene propylene-aromatic vinyl polymer toughened with EPDM rubber is insufficient, To the requirements for the end caps of refrigeration equipment.

Claims

Use of an ethylene propylene diene rubber toughened vinyl cyanide-aromatic ethylene polymer for preparing an end cap of a refrigeration apparatus, characterized in that the ethylene propylene diene monomer toughened vinyl cyanide-aromatic ethylene polymer It is prepared by blending with ABS to prepare a modified aromatic vinyl resin and then preparing into a refrigeration equipment end cap; in the modified aromatic vinyl resin, the vinyl cyanide-aromatic ethylene polymerized with respect to the ethylene propylene diene rubber is toughened. The total content of the ABS and the ethylene propylene-aromatic ethylene polymer toughened by the EPDM rubber is 20 to 95% by weight.
The use according to claim 1, wherein the ethylene propylene diene rubber toughened vinyl cyanide-aromatic ethylene polymer has a weight content of from 30 to 95%.
The use according to claim 1, wherein the modified aromatic vinyl resin has an ABS content of at least 5% by weight.
An environmentally-friendly and energy-saving structural layer of a refrigeration device, comprising: an end cap made of a HFO foamed rigid polyurethane foam layer and the modified aromatic vinyl resin according to claim 1 or 2 or 3.
The environmentally-friendly and energy-saving structural layer of the refrigeration equipment according to claim 4, wherein the HFO foamed rigid polyurethane foam layer is produced by reacting a polyol, a HFO-containing blowing agent, a catalyst, and an isocyanate.
The environmental protection and energy-saving structural layer of the refrigeration equipment according to claim 5, wherein the HFO-containing foaming agent is a single foaming agent composed of a HFO-based foaming agent or a non-HFO-based foaming agent and other non-HFO-based foaming agents. A mixed blowing agent composed of a foaming agent.
The environmentally-friendly and energy-saving structural layer of the refrigeration equipment according to claim 6, wherein the HFO-based foaming agent is at least one of trans 1-chloro-3,3,3-trifluoropropene and hexafluorobutene.
The environmentally-friendly and energy-saving structural layer of the refrigeration equipment according to claim 6, wherein the mixed foaming agent is a mixture of a HFO-based blowing agent and an alkane and/or HFC-based blowing agent.
The application of the environmental protection and energy-saving structural layer of the refrigeration equipment according to any one of claims 4 to 8 in preparing a refrigerator, a freezer and a wine cabinet.