WO2017206821A1 - 一种制冷设备环保节能结构层及其应用 - Google Patents

一种制冷设备环保节能结构层及其应用 Download PDF

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WO2017206821A1
WO2017206821A1 PCT/CN2017/086254 CN2017086254W WO2017206821A1 WO 2017206821 A1 WO2017206821 A1 WO 2017206821A1 CN 2017086254 W CN2017086254 W CN 2017086254W WO 2017206821 A1 WO2017206821 A1 WO 2017206821A1
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hfo
refrigeration equipment
parts
energy
silicone
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PCT/CN2017/086254
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English (en)
French (fr)
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官焕祥
何超雄
陈平绪
魏金刚
黄宝奎
李玉虎
林士文
戴建建
陈庆
王亮
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金发科技股份有限公司
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Publication of WO2017206821A1 publication Critical patent/WO2017206821A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D11/00—Self-contained movable devices, e.g. domestic refrigerators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • 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.
  • 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.
  • CP cyclopentane
  • HCFC hydrofluoroalkane
  • HFO hydrofluoroolefin
  • GWP greenhouse effect potential
  • ODP zero ozone depletion potential
  • 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).
  • 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. .
  • the polymer 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.
  • 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.
  • 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.
  • the present invention is directed to overcoming the above-mentioned deficiencies of the prior art, and provides an end cap made of a modified aromatic vinyl resin, which overcomes the difficulty of compatibility between the ABS end cap and the HFO foamed heat insulating layer. Effectively resistant to HFO foaming agent corrosion, cracking does not occur under high and low temperature cycle changes, while retaining the advantages of good formability and high gloss of ABS end caps.
  • 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 aromatic vinyl resin.
  • Another object of the present invention is to provide an environmentally-friendly and energy-saving structural layer of the refrigeration equipment in preparing a refrigerator, a freezer and a wine cabinet. application.
  • a silicone-based polymer in the preparation of an end cap of a refrigeration device, the silicone-based polymer is blended with ABS to prepare a modified aromatic vinyl resin, and then prepared into a refrigeration device end cap; the modified aromatic In the vinyl resin, the weight content of the silicone-based polymer is 20 to 95% based on the total amount of the silicone-based polymer and ABS; the silicone-based polymer is a silicone-toughened vinyl cyanide-aromatic Group of ethylene polymers.
  • the inventors have found that the use of a silicone-toughened vinyl cyanide-aromatic vinyl polymer to replace a portion of the ABS resin greatly improves the material's resistance to high and low temperatures, aging and chemical resistance.
  • the weight content of the silicone-based polymer is from 20 to 95% in the modified aromatic vinyl resin, the end cap does not cause cracking.
  • the silicone toughened vinyl cyanide-aromatic ethylene polymer has a weight content of from 30 to 95%.
  • the inventors have found that when the amount of silicone-toughened vinyl cyanide-aromatic vinyl polymer is within this range, the end cap can be further smoothed.
  • the silicone-based polymer content of the present invention may further preferably be from 30 to 60% in view of molding processability. When the content of the silicone-based polymer is too high, the cost also rises remarkably.
  • the silicone-based polymer of the present invention is further preferably used in an amount of from 30 to 40% in terms of overall performance and cost.
  • 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.
  • the silicone toughened vinyl cyanide-aromatic ethylene polymer is a core-shell structured polymer, the core is composed of silicone and acrylate, and the shell is composed of vinyl cyanide-aromatic ethylene.
  • 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.
  • HFO foamed rigid polyurethane foam layers are made by reacting a polyol, a HFO-containing blowing agent, a catalyst, and an isocyanate.
  • the HFO-containing foaming agent is a single foaming agent composed of a HFO-based foaming agent or a HFO-based foaming agent and A mixed blowing agent composed of other non-HFO type blowing agents.
  • the HFO-based blowing agent is at least one of trans 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) and hexafluorobutene (HFO-1336mmz).
  • the mixed blowing agent is a mixture of a HFO-based blowing agent and an alkane and/or HFC-based blowing agent.
  • the alkane is pentane
  • the pentane is at least one selected from the group consisting of cyclopentane, isopentane and n-pentane.
  • 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.
  • 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.
  • the invention is further illustrated by the following specific examples, but the examples are not intended to limit the invention in any way.
  • the raw material reagents employed in the examples of the present invention are conventional commercially available raw material reagents.
  • the preparation method of the rigid polyurethane foam refers to the prior art.
  • the following examples and comparative examples refer to a silicone-toughened vinyl cyanide-aromatic ethylene polymer as a silicone-based polymer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the end cap detection results of the examples and the comparative examples when the weight content of the silicone-toughened vinyl cyanide-aromatic ethylene polymer in the modified aromatic vinyl resin is 20 to 95%, The prepared end cap is resistant to high and low temperature and is not prone to cracking; when the weight content of the silicone-toughened vinyl cyanide-aromatic vinyl polymer is 30 to 95%, the surface of the end cap is smooth and flat; When the amount of the silicon toughened vinyl cyanide-aromatic ethylene polymer or the silicone toughened vinyl cyanide-aromatic ethylene polymer used is insufficient, the requirements for the end cap of the refrigeration equipment are not obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种制冷设备环保节能结构层及其应用。所述结构层由HFO发泡硬质聚氨酯泡沫层与改性芳香族乙烯基树脂端盖组成，所述改性芳香族乙烯基树脂为有机硅类聚合物与丙烯腈-丁二烯-苯乙烯聚合物的熔融共混物，在所述改性芳香族乙烯基树脂中，有机硅类聚合物的重量含量为20～95％。本发明所制备的制冷设备环保节能结构层克服了现今制冷设备中HFO发泡剂与ABS端盖配合使用会出现材料开裂的问题，提高了制冷设备环保节能性能，同时由于其含有ABS材料，保留了良好的成型性和光泽性，使得制冷设备的结构设计能实现多样化和品味高端化。

Description

一种制冷设备环保节能结构层及其应用 技术领域
本发明属于制冷设备制造技术领域，具体地，本发明涉及一种制冷设备环保节能结构层。
背景技术
制冷设备一般使用硬质聚氨酯泡沫作为隔热层，而硬质聚氨酯泡沫目前一般采用环戊烷(CP)、氢氟烷烃(HCFC、HFC)和氢氟烯烃(HFO)作为发泡剂。由于第四代发泡剂氢氟烯烃HFO具有较低的温室效应潜值(GWP)以及零消耗臭氧潜值(ODP)，同时使用HFO发泡剂的隔热层能提高制冷设备保温性能，有效降低制冷设备能耗等级，因此节能环保的HFO将逐步会取代之前的氢氟氯烃等发泡剂(CP、HCFC、HFC)。
但是，HFO作为发泡剂时，HFO对制冷设备中塑料制件有严重腐蚀性，特别是HFO对常用的丙烯腈-丁二烯-苯乙烯(ABS)端盖产生严重的环境应力，其中HFO腐蚀性比CP、HCFC和HFC更为严重。目前行业内普遍认为HFO发泡剂难以应用在ABS端盖的制冷设备，原因在于，HFO发泡剂属于含氟化合物，容易侵蚀树脂，其沸点较低，常温下容易气化，活动性能更大。当HFO发泡剂进入ABS树脂内，由于HFO发泡剂具有较强的溶剂化作用，高分子在HFO发泡剂影响下会发生增塑。其中ABS中丁二烯橡胶更容易吸收发泡剂，丁二烯橡胶与丙烯腈-苯乙烯界面相互作用变弱，在应力集中区特别是制冷设备ABS制件边角部位以及低温接触区域更容易遭受破坏，常常表现为多重银纹和开裂。另外，ABS端盖具有较好的成型性能和较高的光泽度，这使得制冷设备的结构设计更为多样化和品味更加高端化。因此，必须寻找解决ABS门体端盖与HFO发泡隔热层相互兼容的应用方法。
专利CN 103319834公开了以HIPS、PE和SBS共混改性HIPS材料作为制冷设备口框，虽然具有较好耐化学腐蚀性，但该改性HIPS材料制备过程较为复杂，而且其光泽较差，难以满足制冷设备制件外观所要求的高端品味。
发明内容
本发明旨在克服上述现有技术的缺陷，提供一种由改性芳香族乙烯基树脂制成的端盖，所述端盖克服了ABS端盖与HFO发泡隔热层难以兼容的难题，有效耐HFO发泡剂腐蚀，在高低温循环变化下，不会发生开裂，同时保留了ABS端盖成型性好以及光泽度较高的优点。
本发明的另一目的在于提供一种包含由所述改性芳香族乙烯基树脂制成的端盖的制冷设备环保节能结构层。
本发明的另一目的在于提供所述制冷设备环保节能结构层在制备冰箱、冰柜和酒柜中的 应用。
本发明的上述发明目的通过以下方案予以实现。
有机硅类聚合物在制备制冷设备端盖中的应用，所述有机硅类聚合物与ABS共混制备成改性芳香族乙烯基树脂，再制备成制冷设备端盖；所述改性芳香族乙烯基树脂中，相对于有机硅类聚合物与ABS的总量，有机硅类聚合物的重量含量为20～95％；所述有机硅类聚合物为有机硅增韧的乙烯基氰-芳香族乙烯聚合物。
发明人发现，采用有机硅增韧的乙烯基氰-芳香族乙烯聚合物替代部分ABS树脂，可极大的提升材料的耐高低温、抗老化与耐化学腐蚀性能。当所述改性芳香族乙烯基树脂中，有机硅类聚合物的重量含量为20～95％时，端盖不会产生开裂现象。
优选地，所述有机硅增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％。发明人发现，当有机硅增韧的乙烯基氰-芳香族乙烯聚合物的用量在此范围内时，可进一步使端盖平整光滑。
有机硅类聚合物的含量过高时，会给改性芳香族乙烯基树脂的成型性能带来负面影响，使得难以通过加工注塑成端盖。考虑成型加工性能，本发明有机硅类聚合物含量可进一步优选为30～60％。有机硅类聚合物的含量过高时，成本也会显著上升。综合性能和成本的优势，本发明有机硅类聚合物的用量进一步优选为30～40％。
优选地，所述改性芳香族乙烯基树脂中，ABS的重量含量至少为5％。
所述改性芳香族乙烯基树脂中，还可以含有适量的助剂，所述助剂可以是润滑剂、抗氧剂等本领域常用的助剂。
所述有机硅增韧的乙烯基氰-芳香族乙烯聚合物为核壳型结构聚合物，核由有机硅和丙烯酸酯组成，壳由乙烯基氰-芳香族乙烯组成，所述乙烯基氰为丙烯腈或甲基丙烯腈，所述芳香族乙烯为苯乙烯、α-甲基苯乙烯或乙烯基甲苯。
一种制冷设备环保节能结构层，包括由HFO发泡硬质聚氨酯泡沫层与由所述改性芳香族乙烯基树脂制成的端盖。
所述HFO发泡硬质聚氨酯泡沫层可以沿用已知技术的HFO发泡硬质聚氨酯泡沫层。通常地，这种HFO发泡硬质聚氨酯泡沫层由多元醇、含HFO的发泡剂、催化剂和异氰酸酯反应制成。
优选地，所述含HFO的发泡剂为HFO类发泡剂构成的单一发泡剂或由HFO类发泡剂与 其他非HFO类发泡剂组成的混合发泡剂。
作为一种可选方案，所述HFO类发泡剂为反式1-氯-3,3,3-三氟丙烯(HFO-1233zd)、六氟丁烯(HFO-1336mmz)的至少一种。
作为一种可选方案，所述混合发泡剂为HFO类发泡剂与烷烃和/或HFC类发泡剂组成的混合物。
更优选地，所述烷烃为戊烷，所述戊烷为选自环戊烷、异戊烷和正戊烷的至少一种。
更优选地，所述HFC类发泡剂为HFC-245、HFC-365mfc、HFC-134a的至少一种。
所述制冷设备环保节能结构层在制备冰箱、冰柜和酒柜中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明采用改性芳香族乙烯基树脂替代ABS树脂，既保留了ABS端盖自身光泽度较高，成型性好的优点，又显著提高了端盖的耐化学腐蚀性，解决了现今制冷设备ABS端盖不能使用HFO发泡剂的问题；使用改性芳香族乙烯基树脂提高了制冷设备环保节能性能；本发明端盖的成型工艺与目前常用ABS端盖一致，保留了良好的成型性，可使制冷设备的结构设计更为多样化和品味更加高端化。
具体实施方式
下面结合具体实施例对本发明进行进一步说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规市购的原料试剂。
以下实施例的份数均按重量份计。
硬质聚氨酯泡沫的制备方法参考现有技术。
为简化表述，以下实施例和对比例将有机硅增韧的乙烯基氰-芳香族乙烯聚合物简称为有机硅类聚合物。
实施例1
S1.将90份聚醚多元醇H815、3份催化剂PC-5、18份HFO-1233zd、14份环戊烷、0.7份甲季铵盐、2.5份硅类泡沫稳定剂B8445、1.5份水和108份异氰酸酯M20S进行反应，制备硬质聚氨酯泡沫。
S2.将70份ABS、30份有机硅类聚合物METABLEN SRK-200A、1份抗氧剂1010和0.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结 构层。
实施例2
S1.将80份聚醚多元醇GR-635C、2.5份催化剂PC-5、18份HFO-1233zd、6份HFC-134a、8份HFC-365mfc、0.5份甲季铵盐、2.0份硅类泡沫稳定剂AK8809、1份水和138份异氰酸酯PAPI27进行反应，制备硬质聚氨酯泡沫。
S2.将60份ABS、40份有机硅类聚合物SX-006、1份抗氧剂1076和0.5份润滑剂硬脂酸钙共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
实施例3
S1.将88份聚醚多元醇H815、3份催化剂PC-5、13份HFO-1336mmz、8份环戊烷、3份HFC-134a、10份HFC-365mfc、0.7份甲季铵盐、2.0份泡沫稳定剂L-6952、1.5份水和108份异氰酸酯PM-200进行反应，制备硬质聚氨酯泡沫。
S2.将40份ABS、60份有机硅类聚合物METABLEN SRK-200A、1.0份抗氧剂1010和1.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
实施例4
S1.将70份聚醚多元醇GR-635C、1.5份催化剂PC-5、26份HFO-1233zd、0.7份甲季铵盐、2.0份硅类泡沫稳定剂B8445、1份水和148份异氰酸酯M20S进行反应，制备硬质聚氨酯泡沫。
S2.将50份ABS、50份有机硅类聚合物SX-006、1.5份抗氧剂1076和1份润滑剂硬脂酸钙共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
实施例5
S1.将80份聚醚多元醇H815、1.3份催化剂PC-5、30份HFO-1233zd、0.7份甲季铵盐、1.8份硅类泡沫稳定剂AK8809、1份水和148份异氰酸酯PAPI27进行反应，制备硬质聚氨酯泡 沫。
S2.将15份ABS、85份有机硅类聚合物METABLEN SRK-200A、1.0份抗氧剂1010和0.5份润滑剂硬脂酸钙共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
实施例6
S1.将80份聚醚多元醇GR-635C、1.3份催化剂PC-5、30份HFO-1233zd、0.7份甲季铵盐、1.8份硅类泡沫稳定剂L-6952、1份水和148份异氰酸酯PM-200进行反应，制备硬质聚氨酯泡沫。
S2.将5份ABS、95份有机硅类聚合物SX-006、1.0份抗氧剂1076和0.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
实施例7
S1.将90份聚醚多元醇H815、3份催化剂PC-5、18份HFO-1233zd、14份环戊烷、0.7份甲季铵盐、2.5份硅类泡沫稳定剂B8445、1.5份水和108份异氰酸酯M20S进行反应，制备硬质聚氨酯泡沫。
S2.将80份ABS、20份有机硅类聚合物METABLEN SRK-200A、1份抗氧剂1010和0.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
对比例1
S1.将90份聚醚多元醇H815、3份催化剂PC-5、18份HFO-1233zd、14份环戊烷、0.7份甲季铵盐、2.5份硅类泡沫稳定剂B8445、1.5份水和108份异氰酸酯M20S进行反应，制备硬质聚氨酯泡沫。
S2.将100份ABS、1份抗氧剂1010和0.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
对比例2
S1.将90份聚醚多元醇H815、3份催化剂PC-5、18份HFO-1233zd、14份环戊烷、0.7份甲季铵盐、2.5份硅类泡沫稳定剂B8445、1.5份水和108份异氰酸酯M20S进行反应，制备硬质聚氨酯泡沫。
S2.将85份ABS、15份有机硅类聚合物METABLEN SRK-200A、1份抗氧剂1010和0.5份润滑剂EBS共混，注塑机注塑成型，加工制备改性芳香族乙烯基树脂端盖。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂端盖复合成制冷设备环保节能结构层。
对上述实施例1～7和对比例1、2的组装制冷设备环保节能结构层进行高低温交替5个循环测试(-40℃～70℃，12h)，观察结构层端盖表面是否出现裂纹(目测)及是否光滑平整(指触及目测)，其检测结果见表1。
表1实施例和对比例端盖检测结果
  检测结果
实施例1 无明显开裂，光滑平整
实施例2 无明显开裂，光滑平整
实施例3 无明显开裂，光滑平整
实施例4 无明显开裂，光滑平整
实施例5 无明显开裂，光滑平整
实施例6 无明显开裂，光滑平整
实施例7 无明显开裂，表面略微粗糙
对比例1 开裂
对比例2 开裂
根据实施例和对比例的端盖检测结果可知，当所述改性芳香族乙烯基树脂中，有机硅增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％时，所制备的端盖耐高低温性好，不容易出现裂纹；当有机硅增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％时，端盖的表面光滑平整；不使用有机硅增韧的乙烯基氰-芳香族乙烯聚合物或使用的有机硅增韧的乙烯基氰-芳香族乙烯聚合物的量不够时，均达不到对制冷设备端盖的要求。

Claims (9)

  1. 有机硅类聚合物在制备制冷设备端盖中的应用，其特征在于，所述有机硅类聚合物与ABS共混制备成改性芳香族乙烯基树脂再制备成制冷设备端盖；所述改性芳香族乙烯基树脂中，相对于有机硅类聚合物与ABS的总量，有机硅类聚合物的重量含量为20～95％；所述有机硅类聚合物为有机硅增韧的乙烯基氰-芳香族乙烯聚合物。
  2. 根据权利要求1所述应用，其特征在于，所述有机硅类聚合物为有机硅增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％。
  3. 根据权利要求1所述应用，其特征在于，所述改性芳香族乙烯基树脂中，ABS的重量含量至少为5％。
  4. 一种制冷设备环保节能结构层，其特征在于，包括HFO发泡硬质聚氨酯泡沫层与权利要求1或2或3所述改性芳香族乙烯基树脂制成的端盖。
  5. 根据权利要求4所述制冷设备环保节能结构层，其特征在于，所述HFO发泡硬质聚氨酯泡沫层由多元醇、含HFO的发泡剂、催化剂和异氰酸酯反应制成。
  6. 根据权利要求5所述制冷设备环保节能结构层，其特征在于，所述含HFO的发泡剂为HFO类发泡剂构成的单一发泡剂或由HFO类发泡剂与其他非HFO类发泡剂组成的混合发泡剂。
  7. 根据权利要求6所述制冷设备环保节能结构层，其特征在于，所述HFO类发泡剂为反式1-氯-3,3,3-三氟丙烯、六氟丁烯的至少一种。
  8. 根据权利要求6所述制冷设备环保节能结构层，其特征在于，所述混合发泡剂为HFO类发泡剂与烷烃和/或HFC类发泡剂组成的混合物。
  9. 权利要求4至8任意一项权利要求所述制冷设备环保节能结构层在制备冰箱、冰柜和酒柜中的应用。
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