CN117120526A - 包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的发泡剂 - Google Patents
包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的发泡剂 Download PDFInfo
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- CN117120526A CN117120526A CN202280026937.9A CN202280026937A CN117120526A CN 117120526 A CN117120526 A CN 117120526A CN 202280026937 A CN202280026937 A CN 202280026937A CN 117120526 A CN117120526 A CN 117120526A
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- China
- Prior art keywords
- foam
- chloro
- hcfo
- cyclopentane
- tetrafluoropentene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004604 Blowing Agent Substances 0.000 title claims abstract description 77
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000006260 foam Substances 0.000 claims abstract description 114
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920000582 polyisocyanurate Polymers 0.000 claims abstract description 25
- 239000011495 polyisocyanurate Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims description 102
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 239000011496 polyurethane foam Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 5
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 239000008137 solubility enhancer Substances 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 17
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- -1 for example Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 22
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- 150000003077 polyols Chemical class 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
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- 150000001412 amines Chemical class 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
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- 125000003118 aryl group Chemical group 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005903 polyol mixture Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- LNVRXFUZNCFBBU-IJRZPAASSA-L (z)-2,3-bis(6-methylheptyl)but-2-enedioate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCC\C(C([O-])=O)=C(C([O-])=O)/CCCCCC(C)C LNVRXFUZNCFBBU-IJRZPAASSA-L 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- ZMBQZWCDYKGVLW-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1(N)C=CC=CC1N ZMBQZWCDYKGVLW-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QLSQYTKEUVPIJA-UHFFFAOYSA-N 2-(1-aminopropan-2-ylamino)ethanol Chemical compound NCC(C)NCCO QLSQYTKEUVPIJA-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 description 1
- NCUPDIHWMQEDPR-UHFFFAOYSA-N 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol Chemical compound CN(C)CCOCCN(C)CCO NCUPDIHWMQEDPR-UHFFFAOYSA-N 0.000 description 1
- LXNMUWFCIDYUCM-UHFFFAOYSA-N 2-[3-(dimethylamino)propyl]-1-N',1-N',5-N,5-N,2-pentamethylpentane-1,1,5-triamine Chemical compound CN(CCCC(C(N(C)C)N)(C)CCCN(C)C)C LXNMUWFCIDYUCM-UHFFFAOYSA-N 0.000 description 1
- ZWXQPERWRDHCMZ-UHFFFAOYSA-N 2-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)NC(C)(C)C ZWXQPERWRDHCMZ-UHFFFAOYSA-N 0.000 description 1
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- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本公开提供了用于聚氨酯和聚异氰脲酸酯泡沫的发泡剂,该发泡剂包含Z‑1‑氯‑2,3,3,3‑四氟戊烯(HCFO‑1224yd(Z))和环戊烷,该‑1‑氯‑2,3,3,3‑四氟戊烯(HCFO‑1224yd(Z))和环戊烷的量分别为65重量%至99重量%和1重量%至35重量%。本公开还提供了泡沫,这些泡沫由聚氨酯泡沫或聚异氰脲酸酯泡沫以及包含Z‑1‑氯‑2,3,3,3‑四氟戊烯(HCFO‑1224yd(Z))和环戊烷的发泡剂形成,具有低初始λ值。
Description
相关申请的交叉引用
本申请要求2021年3月30日提交的美国临时申请63/167,950号的优先权,该美国临时申请全文以引用方式并入本文。
技术领域
本公开涉及包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物。本公开还提供了包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的发泡剂混合物,使用这些组合物起泡的方法,以及包含这些组合物的泡沫。
背景技术
基于氟碳化合物的流体已广泛用于工业中的许多应用中,包括用作制冷剂、气溶胶推进剂、发泡剂、传热介质、气态电介质和灭火。
工业界一直在寻求新的基于氟碳化合物的混合物,其提供另选方案并且被认为是当今使用的CFC、HCFC和HFC的环境更安全的替代品。特别要关注的是具有低臭氧损耗潜势和低全球变暖潜势的含有氢氟烃、氟代烯烃、含碘化合物和其他氟化化合物的混合物。此类混合物是本公开的主题。
发明内容
本公开提供了可发泡组合物,该可发泡组合物包含泡沫形成剂和发泡剂组合物,该发泡剂组合物包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物。基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,该发泡剂组合物可包含约1重量%至约35重量%的量的环戊烷和约65重量%至约99重量%的量的Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))。该可发泡组合物可包括聚氨酯泡沫和异氰脲酸酯泡沫中的至少一者。
本公开还提供了使用发泡剂组合物形成的泡沫,该发泡剂组合物包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷的量为1重量%至35重量%并且Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为65重量%至99重量%。这些泡沫的初始λ值可以为20.5mW/mK或更小。
附图说明
图1是如实施例1所述的聚氨酯泡沫中初始λ对环戊烷的摩尔百分比的图。
图2是如实施例2所述的聚异氰脲酸酯泡沫中初始λ对环戊烷的摩尔百分比的图。
具体实施方式
本公开提供了包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,其在下文进一步详细描述。本公开还提供了组合物,并且特别是发泡剂、可发泡组合物、起泡制品和用于形成泡沫的方法和系统,其利用Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物。
已经令人惊讶地发现,当基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量以约1重量%至约35重量%的量添加环戊烷时,使用包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的组合的发泡剂形成的泡沫显示低初始λ值。
环戊烷的量也可描述为摩尔百分比。具体地,当基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总摩尔数以约1mol%至约50mol%的量添加环戊烷时,使用包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的组合的发泡剂形成的泡沫显示低初始λ值。
由于在发泡剂组合物中使用烃通常对所得泡沫中的初始λ值有害,因此本领域技术人员将预期向包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的发泡剂组合物中添加环戊烷将导致所得泡沫的初始λ值与添加到发泡剂组合物中的环戊烷的量成比例地立即升高。然而,已经令人惊讶地发现,基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,当将环戊烷以高达约35重量%的量添加到Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))中时,使用Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))作为发泡剂形成的泡沫的初始λ值保持基本上不变。
这表现出显著的商业优点,因为与环戊烷相比,Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))相对昂贵,因此,使用Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物作为发泡剂的泡沫可具有期望的初始λ值,但与使用单独的Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))作为发泡剂制备的泡沫相比,可相对更便宜地生产。
I.包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物的发泡剂
氟碳流体具有可期望用于多种应用(包括用作发泡剂)和其他应用的特性。遗憾的是,现在据信在工业应用中使用某些氢氟烃“HFC”加剧全球变暖,并且因此已限制了它们的现代用途。然而,包含HFC的新环境安全组合物的鉴定是复杂的,这是由于使得它们可用于这些应用中的许多特性是不易于预测的。例如,希望发泡剂组合物不但具有可接受的环境特性,而且具有化学稳定性、低毒性或无毒性、低易燃性或无易燃性等等。还希望发泡剂在使用时具有极佳的性能,例如极佳的绝热特性和其他希望的泡沫特点。
用于制作常规发泡材料(诸如,例如热塑性材料和热固性材料)的方法和组合物早已为人们所知。这些方法和组合物通常利用化学和/或物理发泡剂来在聚合物基体中形成发泡结构。此类发泡剂包括,例如偶氮化合物、各种挥发性有机化合物(VOC)和氯氟烃(CFC)。化学发泡剂通常发生某种形式的化学变化,包括与形成聚合物基体(通常在预定温度/压力下)的材料的化学反应,该化学反应导致气体诸如氮气、二氧化碳或一氧化碳的释放。最常用的化学发泡剂之一是水。物理发泡剂通常溶解于聚合物或聚合物前体材料中,然后体积膨胀(再次在预定温度/压力下)促进发泡结构的形成。物理发泡剂经常与热塑性泡沫结合使用,但化学发泡剂也可代替或补充物理发泡剂与热塑性泡沫结合使用。通常化学发泡剂和/或物理发泡剂与热固性泡沫结合使用。当然,某些化合物和包含它们的组合物可能同时构成化学发泡剂和物理发泡剂。
本公开的发泡剂可包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物。基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷可以约1重量%或更大、约5重量%或更大、约10重量%或更大、约15重量%或更大、约20重量%或更小、约25重量%或更小、约30重量%或更小、约35重量%或更小、或由这些端点所涵盖的任何值的量存在于混合物中。基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))可以约65重量%或更大、约70重量%或更大、约75重量%或更大、约80重量%或更大、约85重量%或更小、约90重量%或更小、约95重量%或更小、约99重量%或更小、或这些端点所涵盖的任何值的量存在于混合物中。
当该发泡剂仅包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷时,以上百分比是基于该发泡剂组合物的总重量。
另选地,该发泡剂可基本上由Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物组成。另选地,该发泡剂可由Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物组成。
当用作发泡剂时,Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物可以与一种或多种另外的发泡剂组合使用,诸如以下中的一者或多者:1,1-二氟乙烷(HFC-152a)、1,1,1,3,3-五氟丙烷(HFC-245fa)、1,1,1,2-四氟乙烷(HFC-134a)、1,1,2,2,-四氟乙烷(HFC-134)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、丙烷、丁烷、戊烷、己烷、E-1,3,3,3-四氟丙烯(HFO-1234ze(E))、2,3,3,3-四氟丙烯(HFO-1234yf)、E-1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz(E))、Z-1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz(Z))、E-1-氯-3,3,3-三氟丙烯(HFO-1233zd(E))、Z-1-氯-3,3,3-三氟丙烯(HFO-1233zd(Z))、E-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(E))、1,1-二氯-2,3,3,3-四氟丙烯(HFO-1214ya)、反式-二氯乙烯(反式-DCE)、甲酸甲酯、甲缩醛、甲酸、乙酸、C1-C4醛、C3-C4酮、C2-C4醚、二醚、水以及它们的组合。
当添加水时,其通常以小于5重量%的量存在,诸如5重量%或更小、4重量%或更小、3重量%或更小、2重量%或更小、或1重量%或更小。
II.包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物的可发
泡组合物
本公开提供了可发泡组合物,该可发泡组合物包含诸如上述的那些的发泡剂组合物和一种或多种能够形成泡沫的组分。具体地讲,该混合物非常适合于聚氨酯和聚异氰脲酸酯泡沫组合物。原则上,将该混合物添加到可发泡组合物中,该可发泡组合物可含有在特定反应条件下反应以制备泡沫所需的其它组分。
如本文所用,术语“泡沫形成剂”用于指能够形成泡沫结构(优选通常多孔状泡沫结构)的组分或组分的组合,不包括例如添加剂,诸如阻燃剂、表面活性剂、交联剂、消泡剂、增溶剂、填料、分散剂、抗菌剂、粘度降低改性剂、蒸气压改性剂、着色剂和染料。
能够形成泡沫的一种或多种组分可为能够形成热固性泡沫的组合物。热固性泡沫的示例可包括聚氨酯和聚异氰脲酸酯泡沫。
本公开还涉及包含本公开的发泡剂组合物的闭孔泡沫。泡沫可为硬质泡沫、软质泡沫或自结皮泡沫。优选地,本公开涉及包含发泡剂组合物的闭孔硬质泡沫,该发泡剂组合物包含上述Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物。
本公开提供的泡沫可为块、厚板、层合物、面板(诸如原位浇注面板)、喷涂泡沫、泡沫等等。本公开中所述的泡沫(尤其是本文所公开的热固性泡沫)可用于多种应用中,在某些优选的实施方案中,本公开包括根据本公开的器具泡沫,包括器具泡沫,诸如冷藏机泡沫、冷冻机泡沫、冷藏机/冷冻机泡沫;面板泡沫;以及其他冷动或低温制造应用。
本公开的泡沫尤其提供用于器具、制冷、运输和建筑行业(例如作为建筑围护结构)。本文所述的泡沫提供一种或多种优异的特征、特点和/或特性,除了与本公开的发泡剂相关联的低全球变暖潜能值之外,还包括:绝热效率(尤其对于热固性泡沫)、尺寸稳定性、压缩强度、绝热特性的老化以及阻燃性等等。
泡沫可为热固性泡沫或热塑性泡沫。热塑性泡沫可以为聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)或聚对苯二甲酸乙二醇酯(PET)。热固性泡沫可以为聚异氰脲酸酯(PIR)或聚氨酯(PU)泡沫。
本公开的发泡剂可以按占可发泡组合物的总重量的百分比,以约2重量%或更大、约3重量%或更大、约4重量%或更大、约5重量%或更大、约6重量%或更大、约7重量%或更大、约8重量%或更小、约9重量%或更小、约10重量%或更小、约11重量%或更小、约12重量%或更小、约13重量%或更小、约14重量%或更小、约15重量%或更小、或在涵盖这些端点的任何范围内的量存在于可发泡组合物中。可发泡组合物的总重量包括热塑性和热固性泡沫的所有组分。
III.形成泡沫的方法
预期所有目前已知的和可获得的用于形成泡沫的方法和系统均容易地适于结合本公开的组合物使用。例如,本公开的方法通常将发泡剂掺入可发泡组合物,然后优选地通过包括导致本文所述的发泡剂体积膨胀的一个步骤或一系列步骤使组合物发泡。一般来讲,预期用于掺入发泡剂和用于发泡的目前使用的系统和装置可根据本公开的组合物容易地使用。事实上,据信本公开的一个优点是提供通常与现有发泡方法和系统相容的改善的发泡剂。
因此,本领域的技术人员应当理解,本公开包括用于使所有类型的泡沫(包括热固性泡沫和热塑性泡沫)发泡的方法和系统。因此,本公开涉及在常规加工条件下结合常规发泡设备使用本发明的发泡剂。因此,本发明的方法包括母料型操作、共混型操作、第三料流发泡剂的添加和在混合头处发泡剂的添加。
相对于热塑性泡沫,优选的方法通常包括将发泡剂引入到热塑性材料(优选地为热塑性聚合物)中,然后使热塑性材料经受能有效导致发泡的条件。
例如,将发泡剂引入热塑性材料的步骤可包括将发泡剂引入到包含热塑性材料的挤出机(例如螺杆挤出机)中,并且导致发泡的步骤可包括降低热塑性材料上的压力,从而导致发泡剂膨胀并且促进材料发泡。
本领域的技术人员应当理解,特别是鉴于本文包含的公开内容,形成和/或添加到可发泡组合物中的本公开的发泡剂的顺序和方式通常不影响本公开的可操作性。例如,在可挤出泡沫的情况下,发泡剂的各种组分以及甚至可发泡组合物的组分在被引入到挤出设备中之前不可混合,或者甚至组分不可被添加到挤出设备中的相同的位置。此外,发泡剂可直接引入或作为预混物的一部分引入,然后该预混物将进一步被添加到可发泡组合物的其他部分中。
因此,可能期望在挤出机中的第一位置处引入发泡剂的一种或多种组分,该第一位置在发泡剂的一种或多种其它组分的添加位置的上游,预期这些组分将在挤出机中结合在一起和/或以这种方式更有效地操作。然而,可优选提前将发泡剂的两种或更多种组分组合,并且将其一起引入到可发泡组合物中,可直接引入,也可作为随后被进一步添加到该可发泡组合物的其他部分中的预混物的一部分。
本公开还涉及形成热固性泡沫,诸如聚氨酯(PU)或聚异氰脲酸酯(PIR)的方法。该方法通常包括提供本公开的发泡剂组合物,将发泡剂组合物(直接或间接)添加到可发泡组合物中,并且使可发泡组合物在可有效形成泡沫或多孔状的结构的条件下反应,如本领域所熟知的。可根据本公开使用本领域熟知的任何方法,诸如“聚氨酯化学与技术”,第I卷和第II卷,Saunders和Frisch,1962年,纽约州纽约市约翰威立出版有限公司(“Polyurethanes Chemistry and Technology,”Volumes I and II,Saunders andFrisch,1962,John Wiley and Sons,New York,NY)中所述的那些方法,该文献以引用方式并入本文。一般来讲,此类优选的方法包括通过组合异氰酸酯、多元醇或多元醇混合物、本公开的发泡剂组合物以及任选的其他材料(诸如催化剂、表面活性剂、阻燃剂、着色剂或其它添加剂)来制备热固性泡沫(例如,聚氨酯或聚异氰脲酸酯泡沫)。
在预混配方中提供用于聚氨酯或聚异氰脲酸酯泡沫的组分是方便的。最典型地,将预混配方预混成两种组分。异氰酸酯和任选的某些表面活性剂构成第一组分,通常称为“A”组分。多元醇或多元醇混合物、表面活性剂、催化剂、阻燃剂构成第二组分,通常称为“B”组分。发泡剂组合物可存在于A组分和/或B组分中。例如,如果发泡剂组合物包含两种发泡剂,则第一发泡剂可存在于A组分中,并且第二发泡剂可存在于B组分中。
Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物可以按占总多元醇预混物树脂(B组分)的百分比,以约10重量%或更大、约15重量%或更大、约20重量%或更小、约25重量%或更小、约30重量%或更小、或这些端点所涵盖的任何值的量存在于多元醇预混物混合物(B组分)中。
本公开的多元醇预混物混合物可包含另外的组分。此类任选的另外的化合物包括但不限于任选的其它发泡剂,诸如E-1-氯-2,3,3,3-四氟丙烯(HCFO-1224yd(E))、Z-1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz(Z))、E-1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz(E))、E-1-氯-3,3,3-三氟丙烯(HFO-1233zd(E))、1,1-二氯-2,3,3,3-四氟丙烯(HFO-1214ya)、E-1,3,3,3-四氟丙烯(1234ze(E))、2,3,3,3-四氟丙烯(HFO-1234yf)和1,1-二氯-2,2-二氟乙烯(HFO-1112);烃,诸如异戊烷和正戊烷;氢氟烃,诸如1,1,1,3,3-五氟丙烷(HFC-245fa)和1,1,1,3,3-五氟丁烷(HFC-365mfc);有机酸,诸如甲酸、乙酸;各种多元醇;水;催化剂,诸如胺催化剂或金属催化剂;阻燃剂,诸如有机阻燃剂和/或无机阻燃剂;表面活性剂(硅或非硅氧烷);交联剂;消泡剂;增溶剂;填料;分散剂;抗菌剂;粘度降低改性剂;蒸气压调节剂;着色剂;和染料。
合适的多元醇可包括例如含蔗糖的多元醇;含苯酚、苯酚甲醛的多元醇;含葡萄糖的多元醇;含山梨醇的多元醇;含甲基葡糖苷的多元醇;含芳香族胺的多元醇,诸如含邻甲苯二胺(o-TDA)的多元醇;芳族聚酯多元醇;甘油;乙二醇;二乙二醇;丙二醇;与(b)中的一者或多者缩合的(a)中的一者或多者,其中(a)选自甘油、乙二醇、二甘醇、三羟甲基丙烷、乙二胺、季戊四醇、大豆油、卵磷脂、妥尔油、棕榈油和蓖麻油;并且(b)选自环氧乙烷、环氧丙烷、环氧乙烷和环氧丙烷的混合物;以及它们的组合。
合适的催化剂可包括胺催化剂和/或金属催化剂。胺催化剂可包括但不限于伯胺、仲胺或叔胺。可用的叔胺催化剂非排他性地包括例如N,N-二甲基环己胺、N,N-二甲基乙醇胺、二甲基氨基乙氧基乙醇、N,N,N'-三甲基氨基乙基乙醇胺、N,N,N'-三甲基-N'-羟乙基双氨基乙醚、四甲基亚氨基双丙胺、2-[[2-[2-(二甲基氨基)乙氧基]乙基]甲基氨基]乙醇、五甲基二亚乙基三胺、五甲基二亚丙基三胺、N,N,N',N”,N”-五甲基二亚丙基三胺、1,1,4,7,10,10-六甲基三亚乙基四胺、N,N-双(3-二甲基氨基丙基)-N-异丙醇胺、N'-(3-(二甲基氨基)丙基)-N,N-二甲基-1,3-丙二胺、双(3-二甲基氨基丙基)-N,N-二甲基丙二胺、双-(2-二甲基氨基乙基)醚、N,N',N”-二甲基氨基丙基六氢三嗪、四甲基亚氨基双丙胺、三甲基-N',2-羟乙基丙二胺、双-(3-氨基丙基)-甲胺、N,N-二甲基-1,3-丙二胺、1-(二甲基氨基)十六烷、苄基二甲胺、3-二甲基氨基丙基脲、二环己基甲胺;乙基二异丙胺;二甲基异丙胺;甲基异丙基苄胺;甲基环戊基苄胺;异丙基-仲丁基-三氟乙胺;二乙基-(α-苯乙基)胺、三正丙胺,或它们的组合。可用的仲胺催化剂非排他性地包括二环己胺;叔丁基异丙基胺;二叔丁胺;环己基叔丁胺;二仲丁胺、二环戊胺;二-(α-三氟甲基乙基)胺;二-(α-苯基乙基)胺;或它们的组合。
金属催化剂可包括钾催化剂,诸如例如辛酸钾(Dabco K15)和乙酸钾(Polycat46);锡催化剂,诸如例如二(十二烷硫基)二丁基锡(Dabco T120,Fomrez UL-1)、二异辛基马来酸二丁基锡(Dabco T125)、二(十二烷硫基)二甲基锡(Fomrez UL-22)、二(十二烷硫基)二辛基锡(Fomrez UL-32)和二-(2-巯基乙酸异辛酯)二丁基锡(Fomrez UL-6);和铋羧酸盐,诸如例如Bicat 8108、Bicat 8210等。
合适的异氰酸酯可包括任何有机聚异氰脲酸酯,其均可用于聚氨酯或聚异氰脲酸酯泡沫合成中,包括脂族和芳族聚异氰脲酸酯。合适的有机聚异氰脲酸酯包括在聚氨酯化学领域中熟知的脂族、脂环族、芳脂族、芳族和杂环的异氰酸酯。这些描述于例如美国专利4,868,224;3,401,190;3,454,606;3,277,138;3,492,330;3,001,973;3,394,164;3,124.605;和3,201,372中。
添加某些表面活性剂以作为泡孔稳定剂。一些代表性材料以DC-193、B-8404和L-5340的名称出售,它们通常为聚硅氧烷聚氧化烯嵌段共聚物,诸如美国专利2,834,748、2,917,480和2,846,458号中所公开的那些,这些专利中的每一篇均以引用方式并入。多元醇预混物的其它任选的添加剂可包括阻燃剂,诸如三(2-氯乙基)-磷酸酯、三(2-氯丙基)磷酸酯、三(2,3-二溴丙基)-磷酸酯、三(1,3-二氯丙基)-磷酸酯、其他无卤素磷酸酯诸如磷酸三乙酯、3-(6-氧代二苯并[c,e][1,2]氧磷-6-基)丙酸丁酯;(聚磷酸铵、各种卤化芳香族化合物、氧化锑、三水合铝、聚氯乙烯等。
聚氨酯或聚异氰脲酸酯泡沫可容易地通过将A侧组分和B侧组分混合在一起以形成泡沫来制备,泡沫例如块、厚板、层合物、原位浇注面板和其他物品、喷涂泡沫、泡沫等等。混合可通过手动混合(例如,用于小型制备)或机器混合技术。
本发明的方法和系统还包括形成包含根据本公开的发泡剂的单组分热固性泡沫,优选地为聚氨酯泡沫。发泡剂的一部分可包含在单组分泡沫的泡沫形成剂中,优选地溶解在容器内的压力下为液体的泡沫形成剂中,并且发泡剂的第二部分可以单独的气相存在。在此类系统中,包含/溶解的发泡剂在很大程度上用于导致泡沫膨胀,并且单独的气相用于赋予泡沫形成剂推动力。此类单组分系统通常并且优选地包装在容器中,诸如气溶胶型罐中,因此本公开的发泡剂优选地用于使泡沫膨胀和/或提供从包装中运输泡沫/可发泡材料的能量,并且优选地两者兼而有之。此类系统和方法可包括向包装中装入完全配制体系(优选地异氰酸酯/多元醇体系),并且将根据本公开的气体发泡剂掺入包装,该包装优选地为气溶胶型罐。
IV.泡沫
如上所述,已经令人惊讶地发现,使用包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的发泡剂形成的泡沫显示低λ值。具体地,如图1所示,当环戊烷相对于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为最多35重量%时,初始λ没有明显增加。考虑到通常烃和特别是环戊烷的高初始λ值,预期Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的初始λ值将在添加环戊烷时立即增加。然而,如本文所公开的,当添加最多约33重量%的环戊烷时,初始λ值保持基本上不变。
当本文所公开的Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物用作聚氨酯或聚异氰脲酸酯泡沫中的发泡剂时,初始λ(在10℃的平均温度下)可以为19mW/mK或更大、19.2mW/mK或更大、19.4mW/mK或更大、19.6mW/mK或更大、19.8mW/mK或更小、20.0mW/mK或更小、20.2mW/mK或更小、20.4mW/mK或更小、20.5mW/mK或更小、或这些值所涵盖的任何值。
本公开的泡沫可以为例如块、厚板或层合物的形式。本公开的泡沫可用作器具泡沫,诸如例如在冷藏机、冷冻机、冷却器、冷藏车、有轨车和热水器中。本公开的泡沫可用于泡沫芯金属面板中。这些泡沫芯金属面板可通过连续或不连续的生产方法来制造,并且这两种方法都适于在本公开的范围内使用。在建筑工业中,此类刚性面板形式的制品可用作商业结构的建筑围护结构中的绝缘材料。
可根据本公开的泡沫形成实施方案使用或适用本领域熟知的任何方法,诸如“聚氨酯化学与技术”,第I卷和第II卷,Saunders和Frisch,1962年,纽约州纽约市约翰威立出版有限公司(“Polyurethanes Chemistry and Technology,”Volumes I and II,Saundersand Frisch,1962,John Wiley and Sons,New York,NY)中所述的那些方法,该文献以引用方式并入本文。
以下非限制性实施例用于说明本公开。
实施例
使用以下起始材料配制所有泡沫(聚异氰脲酸酯(PIR)和聚氨酯(PU)):得自斯泰潘公司(Stepan)的Stepanpol PS2352(聚酯多元醇,羟值:240mg KOH/g,官能度:2);得自陶氏公司(Dow)的Voranol 490(蔗糖/甘油引发的聚醚多元醇,羟值:490mg KOH/g,官能度:4.3);得自陶氏公司(Dow)的Voranol 391(胺(邻二氨基甲苯)引发的多元醇,羟值:395mgKOH/g,官能度:4);得自陶氏公司(Dow)的Voranol 270(甘油引发的聚醚多元醇,羟值:238mg KOH/g,官能度:3);得自英威达公司(Invista)的Terate HT5510(“HT5510”)(芳族聚酯多元醇,羟值:260mg KOH/g,官能度:2);Tegostab B84210(“B84210”)(得自赢创公司Evonik)的硅表面活性剂);Tegostab B8465(“B8465”)(得自赢创公司Evonik)的硅表面活性剂);Dabco K15(“K15”)(得自赢创公司(Evonik)的在二甘醇中的辛酸钾);Polycat 8(得自赢创公司(Evonik)的N,N-二甲基环己胺);Polycat 5(得自赢创公司(Evonik)的五甲基二亚乙基三胺);Polycat 41(得自赢创公司(Evonik)的1,3,5-三[3-(二甲基氨基)丙基]六氢-1,3,5-三嗪);得自巴斯夫公司(BASF)的Lupranate M20(聚合物异氰酸酯,31.5% NCO,官能度:2.7);TCPP(磷酸三(1-氯-2-丙基)酯)磷含量:9.4重量%;氯含量:33重量%。
基于以下实施例中所述的配方,通过手工混合配制泡沫。使用LaserComp FOX50记录λ值,样品尺寸为12"x12"x1"。
实施例1:聚氨酯泡沫中的Z-1-氯-2,3,3,3-四氟丙烯(HCFO-1224yd(Z))和环戊烷
将Z-1-氯-2,3,3,3-四氟丙烯(HCFO-1224yd(Z))和环戊烷的各种混合物用作聚氨酯泡沫中的发泡剂,测试它们的初始λ值。不同泡沫的组成示于下表1中,其中每种组分以每百份(php)多元醇的份数表示。
表1
然后使用ASTM C518中所述的方法测试所形成的每种泡沫的初始λ。当使用1重量%至35重量%的环戊烷和65重量%至99重量%的Z-1-氯-2,3,3,3-tetrafluoropene(HCFO-1224yd(Z))的混合物作为发泡剂时,初始λ值为约19.5mW/mK或更小,并且在添加更大量的环戊烷时开始上升。这些结果以图形形式示于图1中。
实施例2:聚异氰脲酸酯泡沫中的Z-1-氯-2,3,3,3-tetrafluoropene(HCFO-
1224yd(Z))和环戊烷
将Z-1-氯-2,3,3,3-四氟丙烯(HCFO-1224yd(Z))和环戊烷的各种混合物用作聚异氰脲酸酯泡沫中的发泡剂,测试它们的初始λ值。不同泡沫的组成示于下表2中。所有值以每百份(php)多元醇的份数表示。
表2
然后测试所形成的每种泡沫的初始λ。当使用1重量%至24重量%的环戊烷和76重量%至99重量%的Z-1-氯-2,3,3,3-tetrafluoropene(HCFO-1224yd(Z))的混合物作为发泡剂时,初始λ值为约20.5mW/mK或更小,并且在添加更大量的环戊烷时开始上升。这些结果以图形形式示于图2中。
方面
方面1为一种可发泡组合物,所述可发泡组合物包含:泡沫形成剂;和发泡剂组合物,所述发泡剂组合物包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,基于所述Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷的量为1重量%至35重量%并且Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为65重量%至99重量%。
方面2为根据方面1所述的可发泡组合物,其中所述泡沫形成剂包括聚氨酯泡沫和聚异氰脲酸酯泡沫中的至少一者。
方面3为根据方面1或方面2所述的可发泡组合物,所述可发泡组合物还包含至少一种表面活性剂。
方面4为根据方面1至3中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种催化剂。
方面5为根据方面1至4中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种易燃性抑制剂。
方面6为根据方面1至5中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种辅助剂,所述辅助剂选自:聚合物改性剂、增韧剂、着色剂、染料、溶解度增强剂、流变改性剂、增塑剂、抗菌剂、粘度降低改性剂、填料、蒸气压改性剂、以及这些中的任何两种或更多种的组合。
方面7为一种泡沫,所述泡沫由以下项形成:泡沫形成剂;和发泡剂组合物,所述发泡剂组合物包含Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷的量为1重量%至35重量%并且Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为65重量%至99重量%。
方面8为根据方面7所述的泡沫,其中所述泡沫形成剂包括聚氨酯泡沫或聚异氰脲酸酯泡沫。
方面9为根据方面7或方面8所述的泡沫,其中所述泡沫的初始λ值为20.5mW/mK或更小。
方面10为一种块,所述块包含根据方面7至9中任一项所述的泡沫。
方面11为一种厚板,所述厚板包含根据方面7至9中任一项所述的泡沫。
方面12为一种层合物,所述层合物包含根据方面7至9中任一项所述的泡沫。
方面13为根据方面7至9中任一项所述的泡沫,所述泡沫呈器具泡沫形式。
如本文所用,短语“在任意两个前述值之间限定的任意范围内”字面上是指任意范围可选自在此类短语之前列出的任意两个值,而无论这些值是在列表的较低部分中还是在列表的较高部分中。例如,一对值可选自两个较低值、两个较高值、或者较低值和较高值。
如本文所用,单数形式“一个”、“一种”和“该”包括复数,除非上下文中另外明确地指出其他情况。此外,当量、浓度或其他值或参数作为范围、优选范围或者上限优选值和下限优选值的列表给出时,应当理解为具体地公开由任何一对任何上限范围或优选值以及任何下限范围或优选值形成的所有范围,而不论这些范围是否单独地公开。当数值的范围在本文中列举时,除非另外指明,否则该范围旨在包括其端值以及该范围内的所有整数和分数。当限定范围时,不旨在将本公开的范围限制于所列举的具体值。
如本文所用,短语“在任意两个前述值之间限定的任意范围内”字面上是指任意范围可选自在此类短语之前列出的任意两个值,而无论这些值是在列表的较低部分中还是在列表的较高部分中。例如,一对值可选自两个较低值、两个较高值、或者较低值和较高值。
应当理解,上述说明仅仅是对本公开的例示。在不脱离本公开的情况下,本领域中的技术人员可设计出各种另选方案和修改形式。因此,本公开旨在涵盖落入所附权利要求书的范围内的所有此类另选方案、修改形式和变型。
Claims (13)
1.一种可发泡组合物,所述可发泡组合物包含:
泡沫形成剂;和
发泡剂组合物,所述发泡剂组合物包含:
Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,基于所述Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷的量为1重量%至35重量%并且Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为65重量%至99重量%。
2.根据权利要求1所述的可发泡组合物,其中所述泡沫形成剂包括聚氨酯泡沫和聚异氰脲酸酯泡沫中的至少一者。
3.根据权利要求1或权利要求2所述的可发泡组合物,所述可发泡组合物还包含至少一种表面活性剂。
4.根据权利要求1至3中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种催化剂。
5.根据权利要求1至4中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种易燃性抑制剂。
6.根据权利要求1至5中任一项所述的可发泡组合物,所述可发泡组合物还包含至少一种辅助剂,所述辅助剂选自:聚合物改性剂、增韧剂、着色剂、染料、溶解度增强剂、流变改性剂、增塑剂、抗菌剂、粘度降低改性剂、填料、蒸气压改性剂、以及这些中的任何两种或更多种的组合。
7.一种泡沫,所述泡沫由以下项形成:
泡沫形成剂;和
发泡剂组合物,所述发泡剂组合物包含:
Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的混合物,基于Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))和环戊烷的总重量,环戊烷的量为1重量%至35重量%并且Z-1-氯-2,3,3,3-四氟戊烯(HCFO-1224yd(Z))的量为65重量%至99重量%。
8.根据权利要求7所述的泡沫,其中所述泡沫形成剂包括聚氨酯泡沫或聚异氰脲酸酯泡沫。
9.根据权利要求7或权利要求8所述的泡沫,其中所述泡沫的初始λ值为20.5mW/mK或更小。
10.一种块,所述块包含根据权利要求7至9中任一项所述的泡沫。
11.一种厚板,所述厚板包含根据权利要求7至9中任一项所述的泡沫。
12.一种层合物,所述层合物包含根据权利要求7至9中任一项所述的泡沫。
13.根据权利要求7至9中任一项所述的泡沫,所述泡沫呈器具泡沫形式。
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