WO2017206820A1 - 制冷设备环保节能结构层及其应用 - Google Patents

制冷设备环保节能结构层及其应用 Download PDF

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WO2017206820A1
WO2017206820A1 PCT/CN2017/086253 CN2017086253W WO2017206820A1 WO 2017206820 A1 WO2017206820 A1 WO 2017206820A1 CN 2017086253 W CN2017086253 W CN 2017086253W WO 2017206820 A1 WO2017206820 A1 WO 2017206820A1
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hfo
parts
environmentally
energy
vinyl resin
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French (fr)
Inventor
魏金刚
何超雄
陈平绪
官焕祥
李玉虎
程庆
林士文
戴建建
王亮
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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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
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • F25D23/06—Walls
    • 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
    • F25D23/06—Walls
    • F25D23/065—Details
    • F25D23/066—Liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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.
  • Rigid polyurethane foam is generally used as a heat insulation layer between the outer casing and the inner lining of the refrigeration equipment, and rigid polyurethane foam is generally used as cyclopentane (CP), hydrofluoroalkane (HCFC, HFC) and hydrofluoroolefin (HFO).
  • CP cyclopentane
  • HCFC hydrofluoroalkane
  • HFO hydrofluoroolefin
  • a blowing agent in which the fourth-generation blowing agent hydrofluoroolefin HFO has a lower greenhouse effect potential (GWP) and zero ozone depletion potential (ODP), while the insulation layer using HFO foaming agent can improve refrigeration.
  • GWP greenhouse effect potential
  • ODP zero ozone depletion potential
  • the insulation performance of the equipment effectively reduces the energy consumption level of the refrigeration equipment, so the energy-saving and environmentally-friendly HFO will gradually replace the previous foaming agents such as hydrochlorofluorocarbons (CFC, HCFC,
  • HFO acrylonitrile-butadiene-styrene
  • CFC, HCFC and HFC are more serious.
  • ABS-lined refrigeration equipment the ABS lining has better forming properties 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 a preparation application method for solving the compatibility between the ABS liner and the HFO foam insulation layer.
  • the HFO foaming agent is a fluorine-containing compound, it easily erodes the resin, has a low boiling point, is easily vaporized at normal temperature, and has a higher activity property.
  • 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.
  • the butadiene rubber in ABS absorbs the foaming agent more easily, and the interface interaction between butadiene rubber and acrylonitrile-styrene becomes weaker, and it is more susceptible to stress in the stress concentration zone, especially the lining corner of the refrigeration equipment and the low temperature contact zone. Destruction, often manifested as multiple silver streaks and cracks.
  • Patent CN102173159 discloses ABS layered composite sheet as the inner tank of the refrigeration equipment, but the preparation process of the layered composite structure is complicated, and the ABS layered composite sheet is still difficult to resist the corrosion of the HFO foaming agent.
  • the layered composite sheet needs to be prepared by a multi-layer coextrusion method, and the molding equipment has a large investment and a complicated molding process.
  • the present invention is directed to overcoming the above-mentioned deficiencies of the prior art, and provides a lining sheet made of a modified aromatic vinyl resin, which overcomes the difficulty in compatibility of the ABS lining sheet with the HFO foam insulation layer.
  • the problem is that it is effective against HFO foaming agent corrosion, and cracking does not occur under high and low temperature cycle changes.
  • Another object of the present invention is to provide an environmentally-friendly and energy-saving structural layer of a refrigeration equipment comprising a lining plate made of the modified aromatic vinyl 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.
  • EPDM rubber toughened vinyl cyanide-aromatic ethylene polymer for use in the preparation of lining sheets for refrigeration equipment, said EPDM toughened vinyl cyanide-aromatic ethylene polymer and ABS
  • the mixture is prepared into a modified aromatic vinyl resin, and then prepared into a lining plate of a refrigeration device; among the modified aromatic vinyl resins, a vinyl cyanide-aromatic ethylene polymer toughened with respect to ethylene propylene diene rubber
  • the ethylene cyanide-aromatic ethylene polymer toughened with EPDM is 20 to 95% by weight based on the total amount of ABS.
  • 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.
  • the weight content of the ethylene propylene-aromatic ethylene polymer toughened by the ethylene propylene diene monomer is 20 to 95% in the modified aromatic vinyl resin, the lining sheet does not cause cracking.
  • 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 lining sheet can be further smoothed.
  • the content of the vinyl cyanide-aromatic ethylene polymer toughened by the EPDM rubber may further preferably be from 30 to 60% in view of molding processability.
  • 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.
  • the ethylene propylene diene rubber toughened vinyl cyanide-aromatic ethylene polymer has a weight content of from 30 to 95%.
  • 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 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, ⁇ -methylstyrene or vinyltoluene.
  • An environmentally-friendly and energy-saving structural layer of a refrigeration device comprising a HFO foamed rigid polyurethane foam layer and a lining plate 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 mixed foaming agent composed of a HFO-based foaming agent and other non-HFO-based foaming 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 forming process of the lining sheet according to the present invention can be carried out according to the molding process of the existing ABS lining sheet.
  • 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 to replace part of the ABS resin, which significantly improves the chemical corrosion resistance of the lining sheet, and solves the problem that the ABS lining sheet can not use the HFO foaming agent in the current refrigeration equipment;
  • the vinyl resin improves the environmental protection and energy-saving performance of the refrigeration equipment;
  • the molding process of the inner liner sheet of the invention is consistent with the commonly used ABS liner sheet, and the good formability is retained, so that the structural design of the refrigeration equipment is more diversified and the taste is more high-end. Chemical.
  • 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 refer to the EPDM-toughened vinyl cyanide-aromatic ethylene polymer as an EPDM-based polymer.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the rigid urethane foam layer and the modified aromatic vinyl resin lining sheet are combined into an environmentally-friendly and energy-saving structural layer of the refrigeration equipment.
  • the ethylene propylene-aromatic ethylene polymer toughened by the ethylene propylene diene monomer has a weight content of 20 to 95.
  • the prepared lining sheet 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 lining The surface of the sheet is smooth and flat; when the amount of the vinyl cyanide-aromatic vinyl polymer toughened without the EPDM rubber or the ethylene propylene-aromatic ethylene polymer toughened with the EPDM rubber is insufficient, None of the requirements for the lining sheet of the refrigeration equipment can be achieved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Polyurethanes Or Polyureas (AREA)
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Abstract

涉及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内衬板材组成，所述改性芳香族乙烯基树脂为三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物，在所述改性芳香族乙烯基树脂中，三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％。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内衬板材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，同时由于其仍含有ABS材料，保留了良好的成型性，使得制冷设备的结构设计能实现多样化和品味高端化。

Description

[根据细则37.2由ISA制定的发明名称]　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
制冷设备外壳和内衬之间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，其中第四代发泡剂氢氟烯烃HFO由于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(CFC、HCFC、HFC)。
但是HFO作为发泡剂时，HFO对制冷设备内衬有严重腐蚀性，特别是HFO对丙烯腈-丁二烯-苯乙烯(ABS)内衬产生严重的环境应力，其中HFO腐蚀性比之前的CFC、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内衬的制冷设备。另外，ABS内衬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内衬与HFO发泡隔热层相互兼容的制备应用方法。
由于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内衬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。
专利CN102173159公开了ABS层状复合板材作为制冷设备内胆，但层状复合结构制备过程较为复杂，而且ABS层状复合板材仍难以抵抗HFO发泡剂腐蚀。层状复合板材需要采用多层共挤方法制备，成型设备投入较大，成型工艺复杂。
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内衬板材，所述内衬板材克服了ABS内衬板材与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。
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内衬板材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。
三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物在制备制冷设备内衬板材中的应用，所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物与ABS共混制备成改性芳香族乙烯基树脂，再制备成制冷设备内衬板材；所述改性芳香族乙烯基树脂中，相对于三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物与ABS的总量，三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％。
发明人发现，采用三元乙丙橡胶增韧的乙烯基氰-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，三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％时，内衬板材不会产生开裂现象。
优选地，所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％。发明人发现，当三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的用量在此范围内时，可进一步使内衬板材平整光滑。
三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯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，板材难以加工吸塑成型。考虑成型加工性能，本发明三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的含量可进一步优选为30～60％。三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯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，本发明三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的用量进一步优选为30～40％。
优选地，所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％。
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。
所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物中，所述三元乙丙橡胶为接枝的 EPDM橡胶，接枝物为丙烯腈-苯乙烯，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内衬板材。
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。
本发明所述的内衬板材的成型工艺可以依照现有的ABS内衬板材的成型工艺进行。
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部分ABS树脂，显著提高了内衬板材的耐化学腐蚀性，解决了现今制冷设备ABS内衬板材不能使用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；本发明内衬板材的成型工艺与目前常用ABS内衬板材一致，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，以下实施例将所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物简称为EPDM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EPDM类聚合物UMG
Figure PCTCN2017086253-appb-000001
ESA30、1份抗氧剂1010和0.5份润滑剂1076共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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EPDM类聚合物
Figure PCTCN2017086253-appb-000002
ESA20、1份抗氧剂1076和0.5份润滑剂硬脂酸钙共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材复合成制冷设备环保节能结构层。
实施例3
S1.将88份多元醇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EPDM类聚合物UMG E700N、1.0份抗氧剂1010和1.5份润滑剂1076共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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EPDM类聚合物Kumho EP AES HW 600G、1.5份抗氧剂1076和1份润滑剂硬脂酸钙共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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份异氰酸酯进行反应，制备硬质聚氨酯泡沫。
S2.将15份ABS、85份EPDM类聚合物UMG
Figure PCTCN2017086253-appb-000003
ESA30、1.0份抗氧剂1010和0.5份润滑剂硬脂酸钙共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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、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EPDM类聚合物
Figure PCTCN2017086253-appb-000004
ESA20、1.0份抗氧剂1076和0.5份润滑剂EBS共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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EPDM类聚合物UMG
Figure PCTCN2017086253-appb-000005
ESA30、1份抗氧剂1010和0.5份润滑剂1076共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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1076共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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EPDM类聚合物UMG
Figure PCTCN2017086253-appb-000006
ESA30、1份抗氧剂1010和0.5份润滑剂1076共混，吸塑成型机吸塑成型，加工制备改性芳香族乙烯基树脂内衬板材。
将上述硬质聚氨酯泡沫层与上述改性芳香族乙烯基树脂内衬板材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℃12h～70℃，12h)，观察结构层内衬板材表面是否出现裂纹(目测)及是否光滑平整(指触及目测)，其检测结果见表1。
表1实施例和对比例内衬板材检测结果
  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内衬板材检测结果可知，当所述改性芳香族乙烯基树脂中，三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％时，所制备的内衬板材耐高低温性好，不容易出现裂纹；当三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为30～95％时，内衬板材的表面光滑平整；不使用三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物或使用的三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的量不够时，均达不到对制冷设备内衬板材的要求。

Claims (9)

  1. 三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物在制备制冷设备内衬板材中的应用，其特征在于，所述三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物与ABS共混制备成改性芳香族乙烯基树脂再制备成制冷设备内衬板材；所述改性芳香族乙烯基树脂中，相对于三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物与ABS的总量，三元乙丙橡胶增韧的乙烯基氰-芳香族乙烯聚合物的重量含量为20～95％。
  2. 根据权利要求1所述应用，其特征在于，所述三元乙丙橡胶增韧的乙烯基氰-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内衬板材。
  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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