CN116867362A - 由纤维素酯组合物形成的泡沫 - Google Patents
由纤维素酯组合物形成的泡沫 Download PDFInfo
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- CN116867362A CN116867362A CN202180093543.0A CN202180093543A CN116867362A CN 116867362 A CN116867362 A CN 116867362A CN 202180093543 A CN202180093543 A CN 202180093543A CN 116867362 A CN116867362 A CN 116867362A
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- foam
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000006260 foam Substances 0.000 title claims abstract description 97
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- 229920000642 polymer Polymers 0.000 claims abstract description 92
- 239000004014 plasticizer Substances 0.000 claims abstract description 39
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 25
- -1 glycerin ester Chemical class 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 239000002667 nucleating agent Substances 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
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- 239000002253 acid Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- HIZCTWCPHWUPFU-UHFFFAOYSA-N Glycerol tribenzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(OC(=O)C=1C=CC=CC=1)COC(=O)C1=CC=CC=C1 HIZCTWCPHWUPFU-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000005456 glyceride group Chemical group 0.000 claims description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 6
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 235000021388 linseed oil Nutrition 0.000 claims description 6
- 239000000944 linseed oil Substances 0.000 claims description 6
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- AHSGHEXYEABOKT-UHFFFAOYSA-N 2-[2-(2-benzoyloxyethoxy)ethoxy]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOCCOC(=O)C1=CC=CC=C1 AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- GFPSCFPBWQWHFU-UHFFFAOYSA-N C(C)(=O)OCC(O)CO.C1(=CC=CC=C1)C(=O)O Chemical compound C(C)(=O)OCC(O)CO.C1(=CC=CC=C1)C(=O)O GFPSCFPBWQWHFU-UHFFFAOYSA-N 0.000 claims description 4
- PJLLCGNQPWXWGL-UHFFFAOYSA-N [3-benzoyloxy-2-(benzoyloxymethyl)-2-methylpropyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(COC(=O)C=1C=CC=CC=1)(C)COC(=O)C1=CC=CC=C1 PJLLCGNQPWXWGL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 claims description 3
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 claims description 3
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 claims description 3
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- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 229960004365 benzoic acid Drugs 0.000 claims description 3
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 3
- 229960002903 benzyl benzoate Drugs 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
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- PCYQQSKDZQTOQG-NXEZZACHSA-N dibutyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCC PCYQQSKDZQTOQG-NXEZZACHSA-N 0.000 claims description 3
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 3
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
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- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 claims description 3
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- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- 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
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
公开了一种可生物降解的泡沫材料。可生物降解的泡沫材料由纤维素酯聚合物和至少一种增塑剂制成。纤维素酯聚合物组合物与一种或多种发泡剂组合,并形成闭孔泡沫。该泡沫材料非常适合用于包装。
Description
相关申请
本申请基于并要求2020年12月11日提交的序列号为63/124,540的美国临时专利申请的优先权,其通过引用并入本文。
背景技术
每年,全球塑料产量都在不断增加。每年生产的塑料中有一半以上的量用于生产塑料瓶、容器、吸管和其它一次性物品。例如,每年生产和投入使用的一次性塑料吸管超过1亿根。
废弃的一次性塑料制品,包括各种不同类型的包装,通常不会被回收并最终进入垃圾填埋场。此外,其中许多物品没有得到妥善处理,最终进入世界各地的溪流、湖泊和海洋中。事实上,由于洋流和产品的浮力,塑料垃圾往往会聚集并集中在世界某些地区的海洋中。
鉴于上述情况,本领域技术人员已尝试生产由可生物降解的聚合物制成的塑料制品。然而,许多可生物降解的聚合物缺乏常规聚合物如聚丙烯和/或聚乙烯的物理性质和特性。
在替代石油基聚合物时面临重大问题的一个特殊领域是泡沫制品的生产。聚烯烃聚合物(如聚乙烯和聚丙烯聚合物,以及聚苯乙烯)广泛应用于各种泡沫应用以生产坐垫、保护性包装、绝缘材料、体育用品、医疗产品等。例如,可通过使用几种不同的工艺将线性低密度聚乙烯制成泡沫密度范围宽的泡沫。线性低密度聚乙烯具有理想的流变特性,如熔体强度和应变硬化,这使得该聚合物特别适合生产泡沫制品。
然而,在可生物降解的泡沫制品的生产中,目前需要一种聚烯烃聚合物的替代品。更具体地,需要一种能够形成闭孔泡沫的可生物降解的聚合物组合物。
发明内容
总之,本公开涉及一种可生物降解的聚合物组合物,该组合物非常适合生产具有良好机械性能和加工性能的泡沫制品和产品。根据本公开,可生物降解的聚合物组合物含有纤维素酯聚合物,该纤维素酯聚合物不仅可生物降解,而且可由可再生资源形成。本公开的纤维素酯聚合物组合物可被配制成具有优异的透明特性和熔体强度,同时保持可生物降解性。
例如,在一个实施方式中,本公开涉及一种可生物降解的泡沫组合物。该泡沫组合物包含由聚合物组合物形成的闭孔泡沫,聚合物组合物包含纤维素酯聚合物,纤维素酯聚合物包含二乙酸纤维素。二乙酸纤维素的乙酰基取代度为约1.5至约3,例如约2至约3。纤维素酯聚合物与增塑剂共混。增塑剂可以是多甘油酯。增塑剂以约8wt%至约45wt%的量存在于聚合物组合物中。聚合物组合物还包含成核剂。根据本公开制成的闭孔泡沫的密度可小于约1g/cm3,例如小于约0.9g/cm3,例如小于约0.8g/cm3。
在一个实施方式中,增塑剂可包含三甘油酯。在一个方面,还可使用各种其它增塑剂。这些增塑剂包括三(氯异丙基)磷酸酯、三(2-氯-1-甲基乙基)磷酸酯、甘油、单乙酸甘油酯、柠檬酸三乙酯、乙酰基三乙基柠檬酸酯、邻苯二甲酸酯、己二酸酯、聚乙二醇、三乙酸甘油酯、二乙酸甘油酯、磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、三丁基邻乙酰基柠檬酸酯、酒石酸二丁酯、乙基邻苯甲酰苯甲酸酯、N-乙基甲苯磺酰胺、邻甲苯基对甲苯磺酸酯、芳族二醇、取代的芳族二醇、芳族醚、三丙酸甘油酯、三苯精、甘油酯、甘油三苯甲酸酯、甘油乙酸苯甲酸酯、聚乙二醇、聚乙二醇酯、聚乙二醇二酯、二-2-乙基己基聚乙二醇酯、甘油酯、二乙二醇、聚丙二醇、聚乙二醇二缩水甘油醚、二甲亚砜、N-甲基吡咯烷酮、碳酸丙烯酯、C1-C20二羧酸酯、马来酸二丁酯、马来酸二辛酯、间苯二酚单乙酸酯、邻苯二酚、邻苯二酚酯、苯酚类、环氧化大豆油、蓖麻油、亚麻籽油、环氧化亚麻籽油、基于聚乙二醇的双官能缩水甘油醚、烷基内酯、磷脂、2-苯氧基乙醇、乙酰水杨酸、对乙酰氨基酚、萘普生、咪唑、三乙醇胺、苯甲酸、苯甲酸苄酯、水杨酸、4-羟基苯甲酸、丙基-4-羟基苯甲酸酯、甲基-4-羟基苯甲酸酯、乙基-4-羟基苯甲酸酯、苄基-4-羟基苯甲酸酯、甘油基三苯甲酸酯、二苯甲酸新戊酯、三乙二醇二苯甲酸酯、三羟甲基乙烷三苯甲酸酯、丁基羟基甲苯、丁基羟基茴香醚、山梨醇、木糖醇、乙二胺、哌啶、哌嗪、己二胺、三嗪、三唑、吡咯和它们的混合物。在一个特定的实施方式中,增塑剂包括1,2,3-三乙酰二醇(1,2,3-triacetylglycol)。
纤维素酯聚合物通常可以约15wt%至约85wt%的量存在于聚合物组合物中,例如约55wt%至约80wt%的量。在一个方面,纤维素酯聚合物主要由二乙酸纤维素组成。
用于生产闭孔泡沫的聚合物组合物中可含有各种不同的成核剂。例如,成核剂可包括无机颗粒,如任何合适的无机矿物。成核剂的具体示例包括二氧化钛、二氧化镁、聚碳酸酯酸的钠盐、聚烯烃基质中的碳酸盐化合物、滑石或其混合物。成核剂可以至多约2wt%的量存在于聚合物组合物中。
闭孔泡沫可制成各种不同的制品和产品。在一个方面,可生物降解的泡沫是泡沫板的形式。例如,闭孔泡沫可用于生产包装材料。
本公开还涉及一种生产可生物降解的泡沫的方法。该方法包括将上述聚合物组合物与发泡剂组合。可使用任何合适的发泡剂,包括物理发泡剂、化学发泡剂等。在一个方面,超临界流体在超临界流体注入系统中用作发泡剂。例如,发泡剂可包括烃气、二氧化碳、氮气或其混合物。可选择地,发泡剂可包括羧酸和烷醇胺。由该方法形成的闭孔泡沫的密度可比用于形成泡沫的聚合物组合物的密度小至少8%,例如小至少10%,例如小至少15%。
该方法可利用任何合适的泡沫形成设备和系统。例如,可使用挤出机,如串联挤出系统或单螺杆挤出机形成泡沫。也可以使用超临界流体注入系统。
所产生的泡沫材料可用于多种多样的应用。此外,还可根据需要对泡沫材料进行进一步加工。例如,泡沫材料可以被模塑成任何合适的形状。在一个实施方式中,泡沫材料可用于热成型工艺,以生产各种制品和层压材料。
下面更详细地讨论本公开的其它特征和方面。
附图说明
在说明书的其余部分中,包括参考附图,更具体地阐述了本公开的完整且可行的内容,其中:
图1是示出根据本公开制成的泡沫制品的透视图。
在本说明书和附图中,重复使用的附图标记旨在表示本发明的相同或相似的特征或元件。
具体实施方式
本领域普通技术人员将理解,本讨论仅是示例性实施方式的描述,并不旨在限制本公开的更宽的方面。
一般来说,本公开涉及一种非常适合生产泡沫制品的增塑纤维素酯聚合物组合物。根据本公开,将纤维素酯聚合物组合物与发泡剂(如起泡剂)组合并挤出,以形成具有各种有益特性的闭孔泡沫。例如,聚合物组合物具有优异的熔体强度,有利于加工。根据本公开制成的泡沫制品还具有优异的机械性能。此外,该聚合物组合物可生物降解,与使用石油基聚合物相比具有许多优点。
本公开的纤维素酯聚合物组合物特别适合用于生产闭孔泡沫。闭孔泡沫可用于多种不同应用。通常,本公开的泡沫材料可用于替代过去制造的聚乙烯和/或聚丙烯泡沫。例如,本公开的泡沫材料特别适合用于包装材料。在一个方面,泡沫材料可用于生产食品包装。泡沫材料可制成独立产品,或者可与其它材料组合使用。例如,在一个方面,泡沫可与涂层板组合来生产包装材料。
根据本公开,聚合物组合物包含纤维素酯聚合物和至少一种增塑剂。此外,聚合物组合物包含成核剂和可选地其它各种添加剂和成分。在形成泡沫材料时,聚合物组合物与发泡剂(如气体)组合并挤压成泡沫。挤出的泡沫材料可以具有任何合适的形状。例如,在一个方面,泡沫材料被挤压成片材、板材、型材、管材、板等。
在一个实施方式中,形成泡沫基底,然后用于热成型工艺。在热成型过程中,泡沫基底被加热,然后被加工成所需的三维形状。基底可在阳模或阴模上成型。热成型有两种主要类型,通常称为真空成型或压力成型。这两种热成型均使用热量和压力将泡沫基底成型为最终形状。真空成型期间,将泡沫基底置于模具上,并使用真空,以将其制成三维产品。压力成型期间,压力可选地与真空力组合使用,以将泡沫基底模塑成型。
使用热成型生产三维制品具有许多优点。例如,热成型允许以快速的周转时间生产所有不同类型的形状。对设计的修改也可以快速有效地进行。热成型还具有成本效益,并可生产出具有美观外观的制品。
在热成型过程中,泡沫基底所承受的温度和压力可根据各种不同因素而变化,包括泡沫基底的厚度和要成型的产品的类型。一般来说,热成型可在约75℃至约120℃的温度下进行,例如约75℃至约100℃。然而,也可以使用更高的温度。如上所述,泡沫基底还承受压力和/或吸力,这些压力和/或吸力将泡沫基底压向模具,使泡沫基底符合模具的形状。模塑后,可根据需要对三维制品进行修整和/或抛光。
通常,可以将任何合适的纤维素酯聚合物掺入本公开的聚合物组合物中。在一个方面,纤维素酯聚合物是乙酸纤维素。
乙酸纤维素可以通过用乙酸活化纤维素之后酯化纤维素来形成。纤维素可以从多种类型的纤维素材料获得,包括但不限于:植物来源的生物质,玉米秸秆,甘蔗秆、甘蔗渣和甘蔗残余物,稻麦秸秆,农用草,硬木,硬木浆,软木,软木浆,棉短绒,柳枝稷,甘蔗渣,草本植物,再生纸,废纸,木屑,纸浆和废纸,废木材,间伐材,柳木,杨木,多年生草(例如,芒草(Miscanthus)科的草),细菌纤维素,种子壳(例如,大豆),玉米秆,糠,和其它形式的木头,竹子,豆皮,韧皮纤维(例如洋麻、大麻、黄麻和亚麻),农业残余产品,农业废物,牲畜排泄物,微生物,藻纤维素,海藻和所有其它近似或根本上源自植物的材料。此类纤维素原料优选以丸粒、碎片、剪切物(clip)、片材、磨损纤维、粉末形式或使其适合进一步纯化的其它形式加工。
在一些实施方式中,适用于生产本公开组合物的纤维素酯可以具有酯取代基,酯取代基包括但不限于C1-C20脂族酯(例如乙酸酯、丙酸酯或丁酸酯)、官能化C1-C20脂族酯(例如,琥珀酸酯、戊二酸酯、马来酸酯)、芳族酯(例如,苯甲酸酯或邻苯二甲酸酯)、取代的芳族酯等、其任何衍生物、以及其任何组合。
组合物中使用的乙酸纤维素可以是二乙酸纤维素或三乙酸纤维素。在一个实施方式中,乙酸纤维素主要包含二乙酸纤维素。例如,乙酸纤维素可包含小于1wt%的三乙酸纤维素,例如小于约0.5wt%的三乙酸纤维素。二乙酸纤维素可以构成大于90wt%的乙酸纤维素,例如大于约95wt%,例如大于约98wt%,例如大于约99wt%的乙酸纤维素。
通常,乙酸纤维素的分子量可以大于约10000,例如大于约20000,例如大于约30000,例如大于约40000,例如大于约50000。乙酸纤维素的分子量通常小于约300000,例如小于约250000,例如小于约200000,例如小于约150000,例如小于约100000,例如小于约90000,例如小于约70000,例如小于约50000。上面指出的分子量是指数均分子量。可以使用凝胶渗透色谱法使用聚苯乙烯等效物或标准物来确定分子量。
纤维素酯聚合物的生物降解取决于各种因素,包括取代度。例如,可使用ASTMTest 871-96(2010)测量纤维素酯的取代度。掺入聚合物组合物中的乙酸纤维素聚合物的取代度通常可大于约1.5,例如大于约2.0,例如大于约2.1,例如大于约2.2,例如大于约2.3。取代度通常小于约3,例如小于约3.0,例如小于约2.7,例如小于约2.6,例如小于约2.4。
纤维素酯聚合物或乙酸纤维素通常可具有大于约0.5dL/g的特性粘度,例如大于约0.8dL/g,例如大于约1dL/g,例如大于约1.2dL/g,例如大于约1.4dL/g,例如大于约1.6dL/g。特性粘度通常小于约2dL/g,例如小于约1.8dL/g,例如小于约1.7dL/g,例如小于约1.65dL/g。特性粘度可以通过形成0.20g/dL纤维素酯在98/2wt/wt丙酮/水中的溶液并在#25Cannon-Ubbelohde粘度计中于30℃下测量溶液和溶剂的流动时间来测量。然后,可以使用修正的Baker-Philippoff方程来确定特性粘度(“IV”),对于该溶剂体系,该方程为方程1。
其中
t1=以秒为单位的溶液(具有纤维素酯)平均流动时间,t2=以秒为单位的溶剂平均流动时间,k=溶剂常数(对于98/2wt/wt丙酮/水为10),以及c=浓度(0.200g/dL)。
乙酸纤维素通常以大于约15wt%的量、例如以大于约25wt%的量、例如以大于约35wt%的量、例如以大于约45wt%的量、例如以大于约55wt%的量存在于聚合物组合物中。乙酸纤维素通常以小于约85wt%的量、例如以小于约80wt%的量、例如以小于约75wt%的量、例如以小于约70wt%的量、例如以小于约65wt%的量存在于聚合物组合物中。
根据本公开,纤维素酯聚合物与一种或多种增塑剂组合。
特别适用于聚合物组合物中的增塑剂包括多甘油酯。例如,增塑剂可以包含单甘油酯、双甘油酯或三甘油酯。在一个特定的方面,增塑剂包含1,2,3-三乙酰二醇。但在其它方面,增塑剂可以是单独的二乙酰二醇或单乙酰二醇,或二乙酰二醇或单乙酰二醇与三乙酰二醇的组合。其它合适的增塑剂包括三(氯异丙基)磷酸酯、三(2-氯-1-甲基乙基)磷酸酯、柠檬酸三乙酯、乙酰三乙基柠檬酸酯、甘油或其混合物。
增塑剂的其它实例包括但不限于磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、乙酰基三丁基柠檬酸酯、三丁基邻乙酰基柠檬酸酯、酒石酸二丁酯、乙基邻苯甲酰基苯甲酸酯、N-乙基甲苯磺酰胺、邻甲苯基对甲苯磺酸酯、芳族二醇、取代的芳族二醇、芳族醚、三丙酸甘油酯、三苯精、甘油、甘油酯、甘油三苯甲酸酯、甘油乙酸苯甲酸酯、聚乙二醇、聚乙二醇酯、聚乙二醇二酯、二-2-乙基己基聚乙二醇酯、甘油酯、二乙二醇、聚丙二醇、聚乙二醇二缩水甘油醚、二甲亚砜、N-甲基吡咯烷酮、碳酸丙烯酯、C1-C20二羧酸酯、己二酸二甲酯(和其它二烷基酯)、马来酸二丁酯、马来酸二辛酯、间苯二酚单乙酸酯、邻苯二酚、邻苯二酚酯、苯酚类、环氧化大豆油、蓖麻油、亚麻籽油、环氧化亚麻籽油、其它植物油、其它种子油、基于聚乙二醇的双官能缩水甘油醚、烷基内酯(例如,γ-戊内酯)、烷基磷酸酯、芳基磷酸酯、磷脂、香料(包括本文所述的一些,例如丁香酚、肉桂醇、樟脑、甲氧基羟基苯乙酮(香草乙酮)、香兰素和乙基香兰素)、2-苯氧基乙醇、二醇醚、二醇酯、二醇酯醚、聚二醇醚、聚二醇酯、乙二醇醚、丙二醇醚、乙二醇酯(例如,乙二醇二乙酸酯)、丙二醇酯、聚丙二醇酯、乙酰水杨酸、对乙酰氨基酚、萘普生、咪唑、三乙醇胺、苯甲酸、苯甲酸苄酯、水杨酸、4-羟基苯甲酸、丙基-4-羟基苯甲酸酯、甲基-4-羟基苯甲酸酯、乙基-4-羟基苯甲酸酯、苄基-4-羟基苯甲酸酯、甘油基三苯甲酸酯、二苯甲酸新戊酯、三乙二醇二苯甲酸酯、三羟甲基乙烷三苯甲酸酯、丁基羟基甲苯、丁基羟基茴香醚、山梨醇、木糖醇、乙二胺、哌啶、哌嗪、己二胺、三嗪、三唑、吡咯等、其任何衍生物及其任何组合。
在一个方面,碳酸酯可以用作增塑剂。示例性碳酸酯可以包括但不限于丙烯碳酸酯、丁烯碳酸酯、二苯基碳酸酯、苯基甲基碳酸酯、二甲苯基碳酸酯、甘油碳酸酯、二甲基碳酸酯、二乙基碳酸酯、乙烯碳酸酯、丙烯碳酸酯、异丙基苯基2-乙基己基碳酸酯、苯基2-乙基己基碳酸酯、异丙基苯基异癸基碳酸酯、异丙基苯基十三烷基碳酸酯、苯基十三烷基碳酸酯等及其任意组合。
在又一方面,增塑剂可以是多元醇苯甲酸酯。示例性多元醇苯甲酸酯可以包括但不限于甘油三苯甲酸酯、丙二醇二苯甲酸酯、二乙二醇二苯甲酸酯、二丙二醇二苯甲酸酯、三乙二醇二苯甲酸酯、蔗糖苯甲酸酯、聚乙二醇二苯甲酸酯、新戊二醇二苯甲酸酯、三羟甲基丙烷三苯甲酸酯、三羟甲基乙烷三苯甲酸酯、季戊四醇四苯甲酸酯、蔗糖苯甲酸酯(取代度为1-8)及其组合。在一些情况下,三苯甲酸酯如甘油三苯甲酸酯可以是优选的。在一些情况下,多元醇苯甲酸酯在25℃下可以是固体并且在25℃的水溶性小于0.05g/100mL。
在一个方面,增塑剂不含邻苯二甲酸酯。事实上,聚合物组合物可以被配制成不含邻苯二甲酸酯。例如,邻苯二甲酸酯可以约0.1%或更少的量、例如约0.001%或更少的量存在于聚合物组合物中。
通常,一种或多种增塑剂可以约8wt%至约45wt%的量、例如以约20wt%至约40wt%的量存在于聚合物组合物中。在一个方面,一种或多种增塑剂可以大于约21wt%的量、例如以大于约23wt%的量、例如以大于约25wt%的量、例如以大于约27wt%的量、例如以大于约30%的量、例如以大于约32%的量并且通常以小于约38wt%的量、例如以小于约35wt%的量存在于聚合物组合物中。
乙酸纤维素可以相对于增塑剂存在,使得乙酸纤维素与一种或多种增塑剂的重量比为约60:40至约85:15,例如约70:30至约80:20。在一个实施方式中,乙酸纤维素与增塑剂的重量比为约75:25。
本公开的聚合物组合物还可以包含成核剂。在一个方面,成核剂可以包括无机颗粒,例如任何合适的矿物颗粒。成核剂的例子包括二氧化钛、聚碳酸酯酸的盐(如聚碳酸酯酸的钠盐)、碳酸盐化合物(如碳酸钙)、滑石、其它无机矿物颗粒、氧化硅、氧化镁、氧化铝、硅酸钙、纤维素粉末、甲壳素、壳聚糖和其混合物。在一个方面,成核剂可以是聚合物基质中的碳酸盐化合物。
成核剂可通常以大于约0.1wt%的量存在于聚合物组合物中,例如以大于约0.5wt%的量,例如以大于约0.7wt%的量,例如以大于约1wt%的量,例如以大于约1.1wt%的量。一种或多种成核剂通常以小于约2wt%的量、例如以小于约1.8wt%的量、例如以小于约1.5wt%的量、例如以小于约1.3wt%的量存在于聚合物组合物中。
除了纤维素酯聚合物、一种或多种成核剂和一种或多种增塑剂外,聚合物组合物可以包含其它各种添加剂和成分。例如,聚合物组合物可以包含一种或多种酸清除剂,其可用于减少酸排放,如乙酸排放。合适的酸清除剂包括碱金属盐、碱土金属盐、碳酸盐、氧化物、氢氧化物、胺或其混合物。具体的酸清除剂包括氧化锌、氧化镁、碳酸钙、碳酸钠铝、硅酸铝、水滑石和其混合物。一种或多种酸清除剂可以约0.1wt%至约5wt%的量、例如以约0.3wt%至约2wt%的量存在于聚合物组合物中。
除了如上所述的酸清除剂之外,聚合物组合物还可以包含气味掩蔽剂。例如,气味掩蔽剂可以吸收气味和/或产生其自身的气味。可以掺入组合物中的掩蔽剂包括沸石,特别是合成沸石、香精等。
可以包括在聚合物组合物中的其它添加剂和成分包括抗氧化剂、颜料、润滑剂、软化剂、抗细菌剂、抗真菌剂、防腐剂、阻燃剂及其组合。各上述添加剂通常可以以约5%或更少的量、例如以约2%或更少的量并且通常以约0.1%或更大的量、例如以约0.3%或更大的量存在于聚合物组合物中。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的阻燃剂可以包括但不限于二氧化硅、金属氧化物、磷酸盐、邻苯二酚磷酸盐、间苯二酚磷酸盐、硼酸盐、无机水合物、芳族多卤化物等,以及其任何组合。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的抗真菌剂和/或抗细菌剂可以包括但不限于:多烯类抗真菌剂(例如游霉素、龟裂霉素、菲律宾菌素、制霉菌素、两性霉素B、坎底辛和哈霉素);咪唑类抗真菌剂,如咪康唑(可从WellSpringPharmaceutical Corporation以获得)、酮康唑(可从麦克尼尔消费者保健公司(McNeil consumer Healthcare以/>商购)、克霉唑(可从默克公司(Merck)以和LOTRAMIN/>以及从拜耳公司(Bayer)以/>商购)、益康唑、奥莫康唑、联苯苄唑、布康唑、芬替康唑、异康唑、奥昔康唑、舍他康唑(可从OrthoDematologics以/>商购)、硫康唑和噻康唑;三唑类抗真菌剂,例如氟康唑、伊曲康唑、艾沙康唑、雷夫康唑、泊沙康唑、伏立康唑、特康唑和阿巴康唑);噻唑类抗真菌剂(例如,阿巴芬净);烯丙胺类抗真菌剂(例如,特比萘芬(可从诺华消费者保健公司(Novartis Consumer Health,Inc.)以/>商购)、萘替芬(可从麦氏制药(MerzPharmaceuticals)以/>商购)和布替萘芬(可从默克公司以LOTRAMIN/>商购));棘白菌素类抗真菌剂(例如,阿尼芬净、卡泊芬净和米卡芬净);蓼二醛;苯甲酸;环吡酮;托萘酯(例如,可从MDS Consumer Care,Inc.以/>商购);十一碳烯酸;氟胞嘧啶;5-氟胞嘧啶;灰黄霉素;氯丙炔碘;辛酸;及其任何组合。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的防腐剂可以包括但不限于苯甲酸酯、对羟基苯甲酸酯(例如,丙基-4-羟基苯甲酸酯系列)等,以及其任何组合。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的颜料和染料可以包括但不限于植物染料、蔬菜染料、二氧化钛、二氧化硅、酒石黄、E102、酞菁蓝、酞菁绿、喹吖啶酮、苝四羧酸二酰亚胺、二恶嗪、芘酮双偶氮(perinones disazo)颜料、蒽醌颜料、炭黑、金属粉末、氧化铁、群青、碳酸钙、高岭土、氢氧化铝、硫酸钡、氧化锌、氧化铝、液体和/或颗粒形式的染料(阳离子染料,可从Clariant Services获得)(例如,Brilliant Yellow K-6G液体、/>Yellow K-4GL液体、Yellow K-GL液体、/>Orange K-3GL液体、/>Scarlet K-2GL液体、/>Red K-3BN液体、/>Blue K-5R液体、Blue K-RL液体、/>Turquoise K-RL液体/颗粒、Brown K-BL液体),/>染料(助色团,可从BASF获得)(例如,Yellow 3GL、Fastusol C Blue 74L)等等,其任何衍生物,以及其任何组合。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的颜料和染料可以是食品级颜料和染料。在一些实施方式中,食品级颜料和染料的示例包括但不限于植物染料、蔬菜染料、二氧化钛等,以及其任何组合。
在一些实施方式中,抗氧化剂可以减轻本文所述的纤维素酯塑料在储存、运输和/或应用期间的氧化和/或化学降解。在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的抗氧化剂可以包括但不限于花青素、抗坏血酸、谷胱甘肽、硫辛酸、尿酸、白藜芦醇、类黄酮、胡萝卜素(例如,β-胡萝卜素)、类胡萝卜素、生育酚(例如,α-生育酚、β-生育酚、γ-生育酚和δ-生育酚)、生育三烯酚、生育酚酯(例如,生育酚乙酸酯)、泛醇、没食子酸、褪黑激素、仲芳胺、苯并呋喃酮、受阻酚、多酚、受阻胺、有机磷化合物、硫酯、苯甲酸酯、内酯、羟胺、丁基羟基甲苯(“BHT”)、丁基羟基茴香醚(“BHA”)、对苯二酚等,以及其任何组合。
在一些实施方式中,适合与本文所述的纤维素酯塑料结合使用的抗氧化剂可以是食品级抗氧化剂。在一些实施方式中,食品级抗氧化剂的示例可以包括但不限于抗坏血酸、维生素A、生育酚、生育酚酯、β-胡萝卜素、类黄酮、BHT、BHA、对苯二酚等,以及其任何组合。
为了从聚合物组合物形成泡沫材料,将发泡剂与聚合物组合物组合,并经受导致形成泡沫的加工条件。在一个方面,例如,聚合物组合物和发泡剂进料通过挤出机以形成泡沫材料。在一个方面,泡沫材料可制成片材。可选择地,可将泡沫材料进料到模具中,以生产模塑制品。
通常,可以使用任何合适的发泡剂。合适的发泡剂包括物理发泡剂和化学发泡剂。在一个方面,超临界流体(如二氧化碳或碳氢化合物)在超临界流体注入系统中用作发泡剂。
化学发泡剂包括偶氮二甲酰胺、偶氮二异丁腈、苯磺酰肼、4,4-氧代苯磺酰氨基脲、对甲苯磺酰氨基脲、偶氮二甲酸钡、N,N'-二甲基-N,N'-二亚硝基对苯二甲酰胺和三肼三嗪。有些产品以其商品名命名,例如Boehringer Ingelheim Chemical Inc.生产的HydrocerolTM,它是聚碳酸酯酸的钠盐和聚烯烃基质中的碳酸盐化合物。众所周知,它的起泡温度相对较低,发泡剂可根据特定应用的需要选择较高或较低的起泡温度。
发泡剂可以是有机试剂或无机试剂。合适的有机发泡剂包括具有1-9个碳原子的脂肪烃、具有1-4个碳原子的卤化脂肪烃和具有1-3个碳原子的脂肪醇。脂肪烃包括甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、新戊烷等。氟化烃的例子包括氟甲烷、全氟甲烷、氟乙烷、1,1-二氟乙烷(HFC-152a)、1,1,1-三氟乙烷(HFC-143a)、1,1,1,2-四氟乙烷(HFC-134a)、五氟乙烷、全氟乙烷、2,2-二氟丙烷、1,1,1-三氟丙烷、全氟丙烷、全氟丁烷和全氟环丁烷。用于本发明的部分卤化的氯烃和氯氟烃包括氯甲烷、二氯甲烷、氯乙烷、1,1,1-三氯乙烷、1,1-二氯-1-氟乙烷(HCFC-141b)、1-氯-1,1-二氟乙烷(HCFC-142b)、1,1-二氯-2,2,2-三氟乙烷(HCFC-123)和1-氯-1,2,2,2-四氟乙烷(HCFC-124)。全卤化氯氟烃包括三氯一氟甲烷(CFC-11)、二氯二氟甲烷(CFC-12)、三氯三氟乙烷(CFC-113)、二氯四氟乙烷(CFC-114)、一氯七氟丙烷和二氯六氟丙烷。用作发泡剂的脂肪醇包括甲醇、乙醇、正丙醇和异丙醇。
合适的无机发泡剂包括二氧化碳、氮气、氩气、水、空气、氮气和氦气。无机发泡剂还包括:碳酸氢钠;碳酸钠;碳酸氢铵;碳酸铵;亚硝酸铵;亚硝基化合物,如N,N'-二甲基-N,N'-二亚硝基对苯二甲酰胺和N,N'-二亚硝基五亚甲基四胺;偶氮化合物,如偶氮二甲酰胺、偶氮二异丁腈、偶氮环己腈、偶氮二氨基苯和偶氮二甲酸钡;磺酰肼化合物,如苯磺酰肼、甲苯磺酰肼、对,对'-氧双(苯磺酰肼)和二苯砜-3,3'-二磺酰肼;以及叠氮化合物,如叠氮化钙、4,4'-二苯基二磺酰叠氮和对甲苯磺酰叠氮。
在优选的实施方式中,发泡剂选自丁烷、异丁烯、二氧化碳、戊烷、己烷、庚烷、苯、甲苯、氯甲烷、三氯乙烯、二氯乙烷、三氯氟甲烷。
在一个实施方式中,发泡剂可以是脂肪酸和烷醇酰胺的组合,例如油酸和二乙醇酰胺的混合物。
向纤维素酯聚合物组合物中添加发泡剂的方式取决于各种因素,包括所使用的发泡剂类型。例如,在聚合物组合物处于熔融状态时,气体发泡剂可在挤出机中与聚合物组合物组合。然而,其它发泡剂可与聚合物组合物混配,在聚合物组合物被进料到挤出机时与聚合物组合物共混,或在聚合物组合物在挤出机中时添加到聚合物组合物中。
通常,发泡过程中纤维素酯聚合物组合物的熔融挤出温度可为约140℃至约245℃。挤出机可包括具有任何适当形状的喷嘴,用于生产具有所需相应形状的泡沫材料。如上所述,在一个实施方式中,挤出机可具有出料模头,其产生如图1所示的泡沫板。
参照图1,泡沫板10由本公开的聚合物组合物形成,在一个方面,其可以具有闭孔泡沫结构。
根据本公开制成的泡沫材料通常具有小于约1g/cm3的密度。例如,泡沫材料的密度可小于约0.9g/cm3,例如小于约0.8g/cm3,例如小于约0.7g/cm3。根据本公开制成的闭孔泡沫的密度通常可比用于形成泡沫的聚合物组合物的初始密度小至少5%,例如小至少8%,例如小至少10%,例如小至少15%,例如小至少20%。
根据本公开制成的泡沫材料可以用于多种多样的应用。例如,泡沫材料可包含在消费品、工业品、建筑材料、包装材料和汽车零件中。根据本公开制成的泡沫制品可包括食品包装、硬包装、管材、结构泡沫、浮具、隔绝、缓冲应用等。
在不脱离在所附权利要求中更具体阐述的本发明的精神和范围的情况下,本领域普通技术人员可以对本发明进行这些和其它修改和变型。另外,应当理解的是,各个实施方式的各方面可以全部互换或部分互换。此外,本领域普通技术人员将理解,前述描述仅是示例性的,并且不旨在限制如所附权利要求中进一步描述的本发明。
Claims (27)
1.一种可生物降解的泡沫组合物,包含:
由聚合物组合物形成的闭孔泡沫,所述聚合物组合物包含纤维素酯聚合物,所述纤维素酯聚合物包括二乙酸纤维素,所述二乙酸纤维素的乙酰基取代度为约1.5至约3,所述纤维素酯聚合物与增塑剂共混,所述增塑剂包括多甘油酯,所述增塑剂在所述聚合物组合物中的量为约8wt%至约45wt%,所述聚合物组合物还包含成核剂,并且其中所述闭孔泡沫的密度小于1.0g/cm3。
2.根据权利要求1所述的可生物降解的泡沫组合物,其中,所述闭孔泡沫的密度小于0.9g/cm3,例如小于0.8g/cm3。
3.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述增塑剂包括三甘油酯。
4.根据权利要求1或2所述的可生物降解的泡沫组合物,其中,所述增塑剂还包括三(氯异丙基)磷酸酯、三(2-氯-1-甲基乙基)磷酸酯、甘油、柠檬酸三乙酯、乙酰基三乙基柠檬酸酯、己二酸酯、聚乙二醇、磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、三丁基邻乙酰柠檬酸酯、酒石酸二丁酯、乙基邻苯甲酰苯甲酸酯、N-乙基甲苯磺酰胺、邻甲苯基对甲苯磺酸酯、芳族二醇、取代的芳族二醇、芳族醚、三丙酸甘油酯、三苯精、甘油酯、甘油三苯甲酸酯、甘油乙酸苯甲酸酯、聚乙二醇酯、聚乙二醇二酯、二-2-乙基己基聚乙二醇酯、甘油酯、二乙二醇、聚丙二醇、聚乙二醇二缩水甘油醚、二甲亚砜、N-甲基吡咯烷酮、丙烯碳酸酯、C1-C20二羧酸酯、马来酸二丁酯、马来酸二辛酯、间苯二酚单乙酸酯、邻苯二酚、邻苯二酚酯、苯酚类、环氧化大豆油、蓖麻油、亚麻籽油、环氧化亚麻籽油、基于聚乙二醇的双官能缩水甘油醚、烷基内酯、磷脂、2-苯氧基乙醇、乙酰水杨酸、对乙酰氨基酚、萘普生、咪唑、三乙醇胺、苯甲酸、苯甲酸苄酯、水杨酸、4-羟基苯甲酸、丙基-4-羟基苯甲酸酯、甲基-4-羟基苯甲酸酯、乙基-4-羟基苯甲酸酯、苄基-4-羟基苯甲酸酯、甘油基三苯甲酸酯、二苯甲酸新戊酯、三乙二醇二苯甲酸酯、三羟甲基乙烷三苯甲酸酯、丁基羟基甲苯、丁基羟基茴香醚、山梨醇、木糖醇、乙二胺、哌啶、哌嗪、己二胺、三嗪、三唑、吡咯及其混合物。
5.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述增塑剂包括1,2,3-三乙酰二醇。
6.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述二乙酸纤维素以约15wt%至约85wt%的量、例如约55wt%至约80wt%的量存在于所述聚合物组合物中,并且所述增塑剂以约20wt%至约40wt%的量存在于所述组合物中。
7.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述纤维素酯聚合物基本上由二乙酸纤维素组成。
8.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述成核剂包括无机颗粒。
9.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述成核剂包括二氧化钛、聚碳酸酯酸的钠盐、聚烯烃基质中的碳酸盐化合物、滑石或无机矿物。
10.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述成核剂以约0wt%至约2wt%的量存在于所述可生物降解的泡沫组合物中。
11.根据前述权利要求中任一项所述的可生物降解的泡沫组合物,其中,所述泡沫组合物为泡沫板的形式。
12.一种由根据前述权利要求中任一项所述的可生物降解的泡沫组合物制成的制品。
13.根据权利要求12所述的制品,其中,所述制品包括泡沫包装材料。
14.一种生产可生物降解的泡沫的方法,包括:
将聚合物组合物与发泡剂组合,所述聚合物组合物包含纤维素酯聚合物,所述纤维素酯聚合物包括二乙酸纤维素,所述二乙酸纤维素的乙酰基取代度为约1.5至约3,所述聚合物组合物还包含已经与所述纤维素酯聚合物共混的增塑剂,所述增塑剂包括多甘油酯,所述增塑剂在所述聚合物组合物中的量为约8wt%至约40wt%,所述聚合物组合物还包含成核剂,以及其中所述聚合物组合物和所述发泡剂被挤出并形成闭孔泡沫,所述闭孔泡沫的密度比所述聚合物组合物的密度小至少8%。
15.根据权利要求14所述的方法,其中,所述闭孔泡沫的密度比所述聚合物组合物的密度小至少10%,例如小至少15%,例如小至少20%。
16.根据权利要求14所述的方法,其中,所述增塑剂包括三甘油酯。
17.根据权利要求14所述的方法,其中,所述增塑剂包括1,2,3-三乙酰二醇。
18.根据权利要求14-17中任一项所述的方法,其中,所述二乙酸纤维素以约15wt%至约85wt%的量、例如约55wt%至约80wt%的量存在于所述聚合物组合物中,并且所述增塑剂以约12wt%至约35wt%的量存在于所述组合物中。
19.根据权利要求14-18中任一项所述的方法,其中,所述闭孔泡沫的密度小于0.9g/cm3,例如小于0.8g/cm3。
20.根据权利要求14-19中任一项所述的方法,其中,所述成核剂包括二氧化钛或滑石。
21.根据权利要求14-20中任一项所述的方法,其中,所述发泡剂包括烃气、二氧化碳、氮气或其混合物。
22.根据权利要求14-21中任一项所述的方法,其中,所述发泡剂包括羧酸和烷醇酰胺。
23.一种泡沫制品,包括:
热成型泡沫基底,所述热成型泡沫基底包括由聚合物组合物形成的闭孔泡沫,所述聚合物组合物包含纤维素酯聚合物,所述纤维素酯聚合物的乙酰基取代度为约1.5至约3,所述纤维素酯聚合物与增塑剂共混,所述增塑剂在所述聚合物组合物中的量为约8wt%至约45wt%,并且其中所述闭孔泡沫基底的密度小于1.0g/cm3。
24.根据权利要求23所述的泡沫制品,其中,所述闭孔泡沫基底的密度小于0.9g/cm3,例如小于0.8g/cm3。
25.根据权利要求23或24所述的泡沫制品,其中,所述增塑剂包括三甘油酯、聚乙二醇或其混合物。
26.根据权利要求23-25中任一项所述的泡沫制品,其中,所述泡沫制品包括型材、管材或板材。
27.根据权利要求23-25中任一项所述的泡沫制品,其中,所述泡沫制品包括包装。
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