WO2018120258A1 - 低碳环保型发泡剂组合物 - Google Patents

低碳环保型发泡剂组合物 Download PDF

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WO2018120258A1
WO2018120258A1 PCT/CN2017/000461 CN2017000461W WO2018120258A1 WO 2018120258 A1 WO2018120258 A1 WO 2018120258A1 CN 2017000461 W CN2017000461 W CN 2017000461W WO 2018120258 A1 WO2018120258 A1 WO 2018120258A1
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hfc
low
foaming agent
agent composition
mass percentage
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PCT/CN2017/000461
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English (en)
French (fr)
Inventor
洪江永
杨波
赵阳
张彦
周华东
欧阳豪
龚海涛
方敏
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浙江衢化氟化学有限公司
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Application filed by 浙江衢化氟化学有限公司 filed Critical 浙江衢化氟化学有限公司
Priority to KR1020187018040A priority Critical patent/KR102133321B1/ko
Priority to US16/076,324 priority patent/US10392328B2/en
Priority to JP2018533904A priority patent/JP6561211B2/ja
Priority to EP17886157.1A priority patent/EP3560990B1/en
Publication of WO2018120258A1 publication Critical patent/WO2018120258A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • C08J9/148—Halogen containing compounds containing carbon and halogen atoms only perfluorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the invention relates to the field of foaming agent application, in particular to a low carbon environment-friendly foaming agent composition.
  • the foaming agent systems currently used in the home appliance industry are mainly cyclopentane, HFC-245fa, HFC-245fa/cyclopentane, and a small amount of R-134a, 365mfc.
  • All-water foaming systems each with advantages and disadvantages, the physical properties of different blowing agents will directly affect the performance of the final foam products.
  • HFC-245fa has a GWP of 790 and is non-flammable. It does not require investment in explosion-proof equipment. Its foamed products have lower thermal conductivity, better fluidity, better strength and dimensional stability, but have higher GWP values. In the future, under the increasingly strict environmental requirements of the world, it will gradually be replaced.
  • HFO-1233zd generally considered ODP value is about 0, GWP value is 1, no flammability, low toxicity, no explosion-proof device for foaming process, boiling point 19 ° C, close to room temperature, easy to operate, can be used on HFC-245fa foaming equipment Direct use, good compatibility with polyols, low gas phase thermal conductivity, good foam insulation performance, currently international companies push HFO-1233zd for polyurethane foam industry.
  • HFO-1233zd is a new generation of foaming agent that can meet various process and environmental protection requirements. It is energy efficient, non-combustible, free of volatile organic compounds, low GWP, safe and environmentally friendly. However, the cells formed by the single component still have certain defects, so they are often used in combination with other components.
  • An azeotrope-like composition of pentafluoropropane, chlorotrifluoropropene and hydrogen fluoride as disclosed in Chinese Patent Publication No. CN102300975A, issued December 28, 2011, which discloses a ternary composition and its provision.
  • a method of preparing the azeotrope-like composition The ratios, temperatures, and pressures of the various group-classified azeotrope compositions are provided.
  • the invention is a composition comprising 1,1,1,3,3-pentafluorobutane (HFC- A composition of 365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) wherein the HFC-365mfc/HFC-245fa weight ratio is from 60:40 to 75:25.
  • HFC-A composition of 365mfc 1,1,1,3,3-pentafluoropropane
  • HFC-245fa 1,1,1,3,3-pentafluoropropane
  • FIG. 11 Another example is Chinese Patent Publication No. CN102574756A, published on Jul. 11, 2012, entitled: azeotrope of 1-chloro-3,3,3-trifluoropropene and HFC-245eb, and azeotrope-like composition
  • the invention relates to an azeotrope comprising a mixture of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 1,1,1,2,3-pentafluoropropane (HFC-245eb) and an azeotrope-like mixture Composition, and its use.
  • HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
  • HFC-245eb 1,1,1,2,3-pentafluoropropane
  • the blowing agent composition disclosed in the above patent has a high GWP value, or a large thermal conductivity, or a complete machine when used. There are disadvantages such as high energy consumption, and therefore, it is required to develop a foaming agent composition having better foaming properties and environmental performance.
  • An object of the present invention is to overcome the disadvantages of the prior art and to provide an environmentally friendly foaming agent composition having a low GWP value, a small thermal conductivity, and low energy consumption.
  • a low-carbon environment-friendly foaming agent composition which is composed by mass percentage:
  • the low carbon environment-friendly foaming agent composition of the present invention preferably has a mass percentage composition of:
  • the low carbon environment-friendly foaming agent composition of the present invention preferably has a mass percentage composition of:
  • the low carbon environment-friendly foaming agent composition of the present invention preferably has a mass percentage composition of:
  • the low carbon environment-friendly blowing agent composition of the present invention has a boiling point of 18 to 19 ° C at 101.3 KPa.
  • the present invention also provides a method of preparing the composition by physically mixing the components in a liquid phase at a mass percentage thereof to obtain the low carbon environment-friendly foaming agent composition.
  • HFO-1233zd 1-Chloro-3,3,3-trifluoropropene (HFO-1233zd), generally considered to have an ODP value of about 0, a GWP value of 1, no flammability, low toxicity, no explosion-proof device for the foaming process, and a boiling point of 19 ° C. Close to room temperature, easy to operate, can be directly used on HFC-245fa foaming equipment, good compatibility with polyol, low gas phase thermal conductivity, good foam insulation performance. However, the cells formed by the single component still have certain defects.
  • HFC-245eb 1,1,1,2,3-pentafluoropropane
  • boiling point 23 ° C non-flammable, no need to invest in explosion-proof equipment, its foam products have lower thermal conductivity, better fluidity, better Strength and dimensional stability, with a GWP of 290
  • HFC-245eb is the next generation of environmentally friendly fourth-generation refrigerant synthesis.
  • the blowing agent composition of the invention is used in the polyurethane foaming industry, compared with the existing foaming agent system (HFC-245fa and cyclopentane), respectively, than the same type of HFC-245fa and the cyclopentane system refrigerator
  • the thermal conductivity is reduced by 5 to 50% (compared to the HFC-245fa system) and 5 to 30% (compared to the cyclopentane system).
  • the blowing agent composition of the invention is used in the polyurethane foaming industry, compared with the existing foaming agent system (HFC-245fa and cyclopentane), respectively, than the same type of HFC-245fa and the cyclopentane system refrigerator
  • the overall energy consumption of the machine is reduced by 2 to 35% (compared to the HFC-245fa system) and 3 to 55% (compared to the cyclopentane system).
  • the GWP value is low, and the blowing agent composition of the invention is greatly reduced relative to the simplex HFC-245fa;
  • the thermal conductivity is small, and the foaming agent composition of the invention can significantly reduce the thermal conductivity.
  • the thermal conductivity is reduced by 12.5 to 42.8% (compared to the HFC-245fa system) and 9.4 to 25.9% ( Compared with the cyclopentane system) and 0.4 to 15.9% (compared with the same proportion of HFO-1233zd and HFC-245eb mixed without HFC-254ca system);
  • the foaming agent composition of the invention can significantly reduce energy consumption, when used in the refrigerator, the overall energy consumption of the machine is reduced by 13.8 ⁇ 32.3% (compared with HFC-245fa system) and 14 ⁇ 50.2% (compared to the cyclopentane system) and 8.9 to 24.8% (compared to the same proportion of HFO-1233zd and HFC-245eb mixed without HFC-254ca system).
  • HFO-1233zd 600 g of HFO-1233zd, 399 g of HFC-245eb and 1 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 60%, HFC The mass percentage of -245eb is 39.9%, and the mass percentage of HFC-254ca is 0.1%.
  • the properties were tested and the results are shown in Tables 1-3, wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.3 ° C at 101.3 KPa.
  • HFO-1233zd 989.9 g of HFO-1233zd, 10 g of HFC-245eb and 0.1 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 98.99%, HFC The mass percentage of -245eb is 1%, and the mass percentage of HFC-254ca is 0.01%.
  • Tables 1-3 wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.9 ° C at 101.3 KPa.
  • HFO-1233zd 699 g of HFO-1233zd, 300 g of HFC-245eb and 1 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 69.9%, HFC The -245eb has a mass percentage of 30% and HFC-254ca has a mass percentage of 0.1%.
  • the properties were tested and the results are shown in Tables 1-3, wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.5 ° C at 101.3 KPa.
  • HFO-1233zd 799 g of HFO-1233zd, 200 g of HFC-245eb and 1 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 79.9%, HFC The mass percentage of -245eb is 20%, and the mass percentage of HFC-254ca is 0.1%.
  • the properties were tested and the results are shown in Tables 1-3, wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.6 ° C at 101.3 KPa.
  • HFO-1233zd 849 g of HFO-1233zd, 150 g of HFC-245eb and 1 g of HFC-254ca were mixed in a liquid phase in a cylinder to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 84.9%, HFC The -245eb has a mass percentage of 15% and HFC-254ca has a mass percentage of 0.1%.
  • the properties were tested and the results are shown in Tables 1-3, wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.7 ° C at 101.3 KPa.
  • HFC-245eb and 10 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition, and the mass percentage of HFO-1233zd was 89%, HFC-245eb The mass percentage is 10%, and the mass percentage of HFC-254ca is 1%.
  • the properties were tested and the results are shown in Tables 1-3, wherein the low carbon environment-friendly blowing agent composition had a boiling point of 18.8 ° C at 101.3 KPa.
  • HFO-1233zd 750 g of HFO-1233zd, 249 g of HFC-245eb and 1 g of HFC-254ca were mixed in a cylinder in a liquid phase to obtain a low-carbon environment-friendly foaming agent composition
  • HFO-1233zd was 75% by mass
  • HFC The -245eb has a mass percentage of 24.9%
  • HFC-254ca has a mass percentage of 0.1%.
  • Test its performance see the results Table 1-3, wherein the low carbon environment-friendly blowing agent composition has a boiling point of 18.6 ° C at 101.3 KPa.
  • the thermal conductivity is measured according to GB10295-88;
  • Boiling point measurement determined by an automatic comparison boiling point meter.
  • Table 1 lists the environmental properties of the environmentally friendly foaming agent compositions prepared in Examples 1 to 7. As can be seen from Table 1, the environmentally friendly blowing agent compositions prepared in Examples 1 to 7 had an ODP of 0, and had no destructive effect on the atmospheric ozone layer, and the GWP was smaller than HFC-245fa (GWP was 790).
  • Table 2 lists the thermal conductivity properties of the environmentally friendly foaming agent compositions prepared in Examples 1 to 7. As can be seen from Table 2, the environmentally friendly foaming agent compositions prepared in Examples 1 to 7 were mixed with HFC-245fa system, cyclopentane system and the same proportion of HFO-1233zd and HFC-245eb without HFC-254ca. Compared with the system, the thermal conductivity is greatly reduced.
  • Table 3 compares the energy consumption of the refrigerator with the environmentally friendly foaming agent composition prepared in Examples 1 to 7 when used in a refrigerator.
  • the environmentally friendly foaming agent compositions prepared in Examples 1 to 7 were mixed with HFC-245fa system, cyclopentane system and the same proportion of HFO-1233zd and HFC-245eb without HFC-254ca. Compared with the system, the energy consumption of the whole refrigerator is greatly reduced, and the energy consumption level is excellent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种低碳环保型发泡剂组合物，按质量百分比，组成为：1-氯-3，3，3-三氟丙烯60～98.99％，1，1，1，2，3-五氟丙烷1～39.9％，1，2，2，3-四氟丙烷0.01～1％，所述低碳环保型发泡剂组合物GWP值比单工质的HFC-245fa低，具有环保、发泡性能优和发泡设备改造小等特点，可以降低导热系数和整机能耗水平。

Description

一种低碳环保型发泡剂组合物 技术领域
本发明涉及发泡剂应用领域，特别涉及一种低碳环保型发泡剂组合物。
背景技术
目前在家电行业(包括冰箱、冰柜和热水器)中使用的替代HCFC-141b的发泡剂体系主要有环戊烷、HFC-245fa、HFC-245fa/环戊烷，以及少量的R-134a、365mfc和全水发泡体系，各有优缺点，不同发泡剂的物理性能会直接影响到最终泡沫制品的性能。HFC-245fa GWP值为790，不可燃，无需投资防爆设备，其泡沫制品具有更低的导热系数、更好的流动性、更好的强度和尺寸稳定性，但是其GWP值较高，这在将来全球日趋严格的环保要求下，必将被逐渐取代。
HFO-1233zd，通常认为ODP值约为0，GWP值为1，没有可燃性，毒性低，发泡过程无需防爆装置，沸点19℃，接近室温，操作方便，可在HFC-245fa发泡设备上直接使用，与多元醇相容性良好，气相热导率低，所发泡沫绝热性能较好，目前国际大公司力推HFO-1233zd用于聚氨酯发泡行业。HFO-1233zd是可以同时满足各种工艺及环保要求的新一代发泡剂，具有高效节能、不燃、不含可挥发性有机物，低GWP，安全环保等特点。但其单组份所形成的泡孔仍有一定缺陷，因此常与其他组分混配使用。
如中国专利公开号CN102300975A，公开日期2011年12月28日，发明名称：五氟丙烷、氯三氟丙烯和氟化氢的类共沸组合物，该申请案公开了一种三元组合物及其提供制备所述类共沸组合物的方法。提供了各种组分类共沸组合物的比例、温度和压力。
又如中国专利公开号CN1756793A，公开日期2006年4月5日，发明名称：氢氟碳化合物组合物，该发明是一种包含1，1，1，3，3-五氟丁烷(HFC-365mfc)和1，1，1，3，3-五氟丙烷(HFC-245fa)的组合物，其中HFC-365mfc/HFC-245fa重量比为60∶40-75∶25。该组合物使用在聚氨酯发泡领域。
又如中国专利公开号CN102574756A，公开日期2012年07月11日，发明名称：1-氯-3，3，3-三氟丙烯和HFC-245eb的共沸混合物以及类共沸混合物的组合物，该发明涉及包含1-氯-3，3，3-三氟丙烯(HCFO-1233zd)以及1，1，1，2，3-五氟丙烷(HFC-245eb)的共沸混合物以及类共沸混合物的组合物、以及其用途。
上述专利中公开的发泡剂组合物存在或GWP值高、或导热系数大、或使用时整机 能耗高等缺点，因此，需要开发具有更好发泡性能和环保性能的发泡剂组合物。
发明内容
本发明的目的是克服现有技术的缺点，提供一种GWP值低，导热系数小，能耗低的环保型发泡剂组合物。
为了解决上述技术问题，本发明是通过以下技术方案实现的：一种低碳环保型发泡剂组合物，按质量百分比，组成为：
1-氯-3，3，3-三氟丙烯           60～98.99％
1，1，1，2，3-五氟丙烷          1～39.9％
1，2，2，3-四氟丙烷             0.01～1％
本发明的低碳环保型发泡剂组合物，按质量百分比组成优选为：
1-氯-3，3，3-三氟丙烯           69.99～94.99％
1，1，1，2，3-五氟丙烷          5～30％
1，2，2，3-四氟丙烷             0.01～1％
本发明的低碳环保型发泡剂组合物，按质量百分比组成优选为：
1-氯-3，3，3-三氟丙烯           80～89.99％
1，1，1，2，3-五氟丙烷          10～19.9％
1，2，2，3-四氟丙烷             0.01～1％
本发明的低碳环保型发泡剂组合物，按质量百分比组成优选为：
1-氯-3，3，3-三氟丙烯           85～89.99％
1，1，1，2，3-五氟丙烷          10～14.99％
1，2，2，3-四氟丙烷             0.01～1％
优选的，本发明的低碳环保型发泡剂组合物在101.3KPa下具有18～19℃的沸点。
本发明的还提供该组合物的制备方法：将各组分按其质量百分比在液相状态下进行物理混合，得到所述的低碳环保型发泡剂组合物。
1-氯-3，3，3-三氟丙烯(HFO-1233zd)，通常认为ODP值约为0，GWP值为1，没有可燃性，毒性低，发泡过程无需防爆装置，沸点19℃，接近室温，操作方便，可在HFC-245fa发泡设备上直接使用，与多元醇相容性良好，气相热导率低，所发泡沫绝热性能较好。但其单组份所形成的泡孔仍有一定缺陷。
1，1，1，2，3-五氟丙烷(HFC-245eb)，沸点23℃，不可燃，无需投资防爆设备，其泡沫制品具有更低的导热系数、更好的流动性、更好的强度和尺寸稳定性，其GWP值为290，HFC-245eb作为新一代环保的第四代制冷剂合成的中间体。
1，2，2，3-四氟丙烷(HFC-254ca)，沸点26℃，不可燃，无需投资防爆设备，其泡沫制品具有更低的导热系数、更好的流动性、更好的强度和尺寸稳定性。
本发明的发泡剂组合物，使用在聚氨酯发泡行业，与现有发泡剂体系(HFC-245fa和环戊烷)相比，分别比相同型号的HFC-245fa以及环戊烷体系冰箱在导热系数方面降低5～50％(与HFC-245fa体系相比)和5～30％(与环戊烷体系相比)。
本发明的发泡剂组合物，使用在聚氨酯发泡行业，与现有发泡剂体系(HFC-245fa和环戊烷)相比，分别比相同型号的HFC-245fa以及环戊烷体系冰箱在整机能耗方面降低了2～35％(与HFC-245fa体系相比)和3～55％(与环戊烷体系相比)。
与现有技术相比，本发明的优点为：
1、GWP值低，本发明的发泡剂组合物相对于单工质HFC-245fa大大降低；
2、导热系数小，本发明的发泡剂组合物可以显著降低导热系数，在冰箱中使用时，在导热系数方面降低12.5～42.8％(与HFC-245fa体系相比)和9.4～25.9％(与环戊烷体系相比)和0.4～15.9％(与同比例HFO-1233zd与HFC-245eb混合不加HFC-254ca体系相比)；
3、能耗低，本发明的发泡剂组合物可以显著降低能耗，在冰箱中使用时，在整机能耗方面降低了13.8～32.3％(与HFC-245fa体系相比)和14～50.2％(与环戊烷体系相比)和8.9～24.8％(与同比例HFO-1233zd与HFC-245eb混合不加HFC-254ca体系相比)。
具体实施方式
下面通过实施例对本发明的内容作进一步说明，但本发明并不限于这些实施例。
实施例1
将600克HFO-1233zd、399克HFC-245eb和1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量60％，HFC-245eb的质量百分含量39.9％，HFC-254ca的质量百分含量0.1％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.3℃。
实施例2
将989.9克HFO-1233zd、10克HFC-245eb和0.1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量98.99％，HFC-245eb的质量百分含量1％，HFC-254ca的质量百分含量0.01％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.9℃。
实施例3
将699克HFO-1233zd、300克HFC-245eb和1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量69.9％，HFC-245eb的质量百分含量30％，HFC-254ca的质量百分含量0.1％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.5℃。
实施例4
将799克HFO-1233zd、200克HFC-245eb和1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量79.9％，HFC-245eb的质量百分含量20％，HFC-254ca的质量百分含量0.1％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.6℃。
实施例5
将849克HFO-1233zd、150克HFC-245eb和1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量84.9％，HFC-245eb的质量百分含量15％，HFC-254ca的质量百分含量0.1％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.7℃。
实施例6
将890克、100克HFC-245eb和10克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量89％，HFC-245eb的质量百分含量10％，HFC-254ca的质量百分含量1％。对其性能进行测试，结果见表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.8℃。
实施例7
将750克HFO-1233zd、249克HFC-245eb和1克HFC-254ca于液相下在钢瓶中混合，得到低碳环保型发泡剂组合物，HFO-1233zd的质量百分含量75％，HFC-245eb的质量百分含量24.9％，HFC-254ca的质量百分含量0.1％。对其性能进行测试，结果见 表1-3，其中在101.3KPa下该低碳环保型发泡剂组合物沸点为18.6℃。
将实施例1～7中所制得的低碳环保型发泡剂组合物与HFC-245fa及环戊烷的性能进行比较，说明本发明的特点与效果，结果见表1～3。其中：
导热系数测定按GB10295-88执行；
能耗测定按GB/T8059.3-1995执行；
沸点测定：用自动比较沸点测定计测定。
表1 发泡剂环境性能比较
工质 ODP GWP
实施例1 0 117
实施例2 0 4
实施例3 0 88
实施例4 0 59
实施例5 0 45
实施例6 0 30
实施例7 0 74
HFC-245eb 0 290
HFO-1233zd 0 1
HFC-254ca 0 190
表1列出了实施例1～7中所制得的环保型发泡剂组合物的环境性能。从表1可以看出，实施例1～7中所制得的环保型发泡剂组合物的ODP为0，对大气臭氧层没有破坏作用，GWP都小于HFC-245fa(GWP为790)。
表2 发泡剂导热系数性能比较
Figure PCTCN2017000461-appb-000001
Figure PCTCN2017000461-appb-000002
表2列出了实施例1～7中所制得的环保型发泡剂组合物的导热系数性能。从表2可以看出，实施例1～7中所制得的环保型发泡剂组合物与HFC-245fa体系、环戊烷体系和同比例HFO-1233zd与HFC-245eb混合不加HFC-254ca体系相比，导热系数大幅下降。
表3 发泡剂能耗比较
Figure PCTCN2017000461-appb-000003
表3对实施例1～7中所制得的环保型发泡剂组合物在冰箱中使用时冰箱的整机能耗进行了对比。从表3可以看出，实施例1～7中所制得的环保型发泡剂组合物与HFC-245fa体系、环戊烷体系和同比例HFO-1233zd与HFC-245eb混合不加HFC-254ca体系相比，冰箱整机能耗大幅下降，具有优异的能耗水平。

Claims (6)

  1. 一种低碳环保型发泡剂组合物，其特征在于按质量百分比，组成为：
    1-氯-3，3，3-三氟丙烯        60～98.99％
    1，1，1，2，3-五氟丙烷        1～39.9％
    1，2，2，3-四氟丙烷          0.01～1％。
  2. 根据权利要求1所述的低碳环保型发泡剂组合物，其特征在于按质量百分比组成为：
    1-氯-3，3，3-三氟丙烯       69.99～94.99％
    1，1，1，2，3-五氟丙烷       5～30％
    1，2，2，3-四氟丙烷         0.01～1。
  3. 根据权利要求1所述的低碳环保型发泡剂组合物，其特征在于按质量百分比组成为：
    1-氯-3，3，3-三氟丙烯         80～89.99％
    1，1，1，2，3-五氟丙烷        10～19.9％
    1，2，2，3-四氟丙烷            0.01～1％。
  4. 根据权利要求1所述的低碳环保型发泡剂组合物，其特征在于按质量百分比组成为：
    1-氯-3，3，3-三氟丙烯         85～89.99％
    1，1，1，2，3-五氟丙烷        10～14.99％
    1，2，2，3-四氟丙烷           0.01～1％。
  5. 根据权利要求1所述的低碳环保型发泡剂组合物，其特征在于所述组合物在101.3KPa下具有18～19℃的沸点。
  6. 权利要求1～5任一所述的低碳环保型发泡剂组合物的制备方法，其特征在于将各组分按其质量百分比在液相状态下进行物理混合。
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