CN114269856B - 高结晶度聚酰胺泡沫颗粒和泡沫模制品 - Google Patents
高结晶度聚酰胺泡沫颗粒和泡沫模制品 Download PDFInfo
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- CN114269856B CN114269856B CN202080059471.3A CN202080059471A CN114269856B CN 114269856 B CN114269856 B CN 114269856B CN 202080059471 A CN202080059471 A CN 202080059471A CN 114269856 B CN114269856 B CN 114269856B
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- polyamide
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- copolyamide
- foam particles
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- 239000002245 particle Substances 0.000 title claims abstract description 65
- 229920002647 polyamide Polymers 0.000 title claims abstract description 58
- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 239000006260 foam Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229920002959 polymer blend Polymers 0.000 claims abstract description 24
- 150000004985 diamines Chemical class 0.000 claims abstract description 20
- 239000000539 dimer Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
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- 238000002844 melting Methods 0.000 claims description 13
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- 238000000034 method Methods 0.000 claims description 13
- -1 8-aminooctalactam Chemical compound 0.000 claims description 12
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 12
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002667 nucleating agent Substances 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 4
- KVCSMSMGPOBJDI-UHFFFAOYSA-N 12-amino-azacyclododecan-2-one Chemical compound NC1CCCCCCCCCC(=O)N1 KVCSMSMGPOBJDI-UHFFFAOYSA-N 0.000 claims description 2
- WCVPFJVXEXJFLB-UHFFFAOYSA-N 4-aminobutanamide Chemical compound NCCCC(N)=O WCVPFJVXEXJFLB-UHFFFAOYSA-N 0.000 claims description 2
- WYPXLRODNLXDQJ-UHFFFAOYSA-N 6-aminopiperidin-2-one Chemical compound NC1CCCC(=O)N1 WYPXLRODNLXDQJ-UHFFFAOYSA-N 0.000 claims description 2
- JVGZXCCKUMXEOU-UHFFFAOYSA-N 7-aminoazepan-2-one Chemical compound NC1CCCCC(=O)N1 JVGZXCCKUMXEOU-UHFFFAOYSA-N 0.000 claims description 2
- YIHGPNRYQNMZQC-UHFFFAOYSA-N 8-aminoazocan-2-one Chemical compound NC1CCCCCC(=O)N1 YIHGPNRYQNMZQC-UHFFFAOYSA-N 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- LERJDXBQVKEGIG-UHFFFAOYSA-N NC1CCCCCCCC(=O)N1 Chemical compound NC1CCCCCCCC(=O)N1 LERJDXBQVKEGIG-UHFFFAOYSA-N 0.000 claims 1
- DBRFKZWKLNAYES-UHFFFAOYSA-N NC1CCCCCCCCC(=O)N1 Chemical compound NC1CCCCCCCCC(=O)N1 DBRFKZWKLNAYES-UHFFFAOYSA-N 0.000 claims 1
- RSDOASZYYCOXIB-UHFFFAOYSA-N beta-alaninamide Chemical compound NCCC(N)=O RSDOASZYYCOXIB-UHFFFAOYSA-N 0.000 claims 1
- 150000003949 imides Chemical class 0.000 abstract 1
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
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- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 5
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- 238000000113 differential scanning calorimetry Methods 0.000 description 4
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical compound O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
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- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
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- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
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- YZAZXIUFBCPZGB-FJEDDJBMSA-N (e)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O.CCCCCCCC\C=C\CCCCCCCC(O)=O YZAZXIUFBCPZGB-FJEDDJBMSA-N 0.000 description 1
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- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- PQKZFHHQCJHGQF-UHFFFAOYSA-N 4-aminoazetidin-2-one Chemical compound NC1CC(=O)N1 PQKZFHHQCJHGQF-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- AMOKUAKXKXBFIW-WJDWOHSUSA-N 9-[(z)-non-3-enyl]-10-octylnonadecanedioic acid Chemical compound OC(=O)CCCCCCCCC(CCCCCCCC)C(CCCCCCCC(O)=O)CC\C=C/CCCCC AMOKUAKXKXBFIW-WJDWOHSUSA-N 0.000 description 1
- RDSLSIIVSGZAGJ-ONYUMSKCSA-N CCCCCC\C=C\CCCCCCCCCC(O)=O.CCCCCC\C=C\CCCCCCCCCC(O)=O Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O.CCCCCC\C=C\CCCCCCCCCC(O)=O RDSLSIIVSGZAGJ-ONYUMSKCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
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- WPBWJEYRHXACLR-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O.OC(=O)CCCCCCCC(O)=O WPBWJEYRHXACLR-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 238000007056 transamidation reaction Methods 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
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- OJZPLABBUZLWRL-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound C(CCCCCCCCCCN)N.C(CCCCCCCCCCN)N OJZPLABBUZLWRL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J9/16—Making expandable particles
-
- 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
- C08J9/16—Making expandable particles
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Abstract
聚酰胺泡沫颗粒,其包含聚合物混合物,所述聚合物混合物包含(A)25至95重量%的至少一种聚酰胺和(B)5至75重量%的至少一种共聚酰胺,所述酰亚胺(A)不同于共聚酰胺(B),所述至少一种共聚酰胺(B)是通过聚合下列组分制备的:(B1)15至84重量%的至少一种内酰胺,(B2)16至85重量%的单体混合物(M);所述单体混合物(M)包含:(M1)至少一种C32‑C40二聚体酸和(M2)至少一种C4‑C12二胺;其中组分(B1)和(B2)的和为100重量%;一种制备这种聚酰胺泡沫颗粒的方法和通过蒸汽箱成型可获得的聚酰胺颗粒泡沫模制品。
Description
本发明涉及一种包含聚合物混合物的聚酰胺泡沫颗粒,所述聚合物混合物包含
(A)25-95重量%的至少一种聚酰胺,该聚酰胺不同于共聚酰胺(B),和
(B)5-75重量%的至少一种经下列组分聚合制备的共聚酰胺
(B1)15-84重量%的至少一种内酰胺,
(B2)16-85重量%的单体混合物(M),包含
(M1)至少一种C32-C40二聚体酸,和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)总和为100重量%,
以及一种制备所述聚酰胺泡沫颗粒的方法,以及通过蒸汽箱成型可获得的聚酰胺颗粒泡沫模制品。
WO 2014/198779涉及一种从断裂伸长率超过100%的热塑性弹性体生产膨胀颗粒的方法,该方法通过用CO2和/或N2浸渍聚合物熔体并在水下造粒机中将经浸渍的熔体通过模板挤出,来获得封闭表皮的膨胀颗粒。
WO 2017/013510公开了一种发泡材料,其含有50-90重量百分比的半结晶树脂,和10至50重量百分比的聚(苯醚)。半结晶树脂可以是一种或多种聚酰胺、聚酯和聚烯烃。发泡材料的密度为40-700kg/m3。其可通过一下方式来制备:向熔融的含半结晶树脂和聚(苯醚)的热塑性材料中加入发泡剂,从而生成预发泡熔融热塑性材料,然后挤出预发泡熔融热塑性材料来生成发泡材料。发泡材料可用来形成需要耐溶剂性的制品。
WO 2011/134996和US 2011/294910涉及可膨胀颗粒,其包含A)聚合物基体、B)物理发泡剂组分和任选地其他添加剂,所述A)聚合物基体由下列组成:A1)至少55重量%的聚酰胺(基于组分A1)和A2)总量计),具有最高达30%的结晶度,任选地熔化温度在100至340℃范围,以及玻璃化转变温度在0至150℃范围,和A2)0-45重量%一种或多种不同于组分A1)的热塑性聚合物;其中所述可膨胀颗粒适合生产颗粒泡沫,用于在汽车业、航空业、建筑业、包装业、体育和娱乐业,以及用于交通运输和/或建筑物中。为了获得低密度泡沫颗粒,可膨胀颗粒必须在预发泡步骤中膨胀。
EP 3 272 798 A1公开了一种聚酰胺树脂泡沫模塑制品和一种制备所述制品的方法,所述聚酰胺数字泡沫模塑制品特征在于包含聚酰胺树脂并具有10-50%的结晶度X和基于X射线衍射图中具有最小峰宽的峰计算时10nm或更大的晶体尺寸D。加热含有二氧化碳气体的树脂基材致使发泡,从而获得密度为300kg/m3的预膨胀颗粒。
PCT/EP2019/068716涉及一种基于聚酰胺的泡沫颗粒及其制备方法,所述聚酰胺包括85-100重量%的长链聚酰胺。
WO 2018/050487涉及一种聚合物膜,和一种生产该聚合物薄膜的方法,以及该聚合物薄膜作为包装薄膜的用途,所述聚合物膜包括至少一种共聚酰胺,所述共聚酰胺通过聚合至少一种内酰胺和包括至少一种C32-C40二聚体酸和C4-C12二胺的单体混合物来制备。
US 4 212 777涉及一种直链柔性高拉伸强度的共聚酰胺,其通过一种二聚体脂肪酸、六亚甲基二胺和己内酰胺获得,用于制模,挤出或纺丝。
在汽车行业中,需要具有高温度稳定性和足够的力学稳定性的结构和半结构泡沫,其可用于轻量结构组分并进行电沉积涂层工艺。
本发明的目的是提供一种泡沫颗粒用于生产高温稳定性的颗粒泡沫模制品,以及一种生产该泡沫颗粒和颗粒泡沫模制品的方法,其特别适合通过高温条件如电沉积涂层工艺。特别是泡沫颗粒应该具有高结晶度,应该可通过连续的一步法获得低体积密度,以及应该可转化为高温下具有高存储模量E'和高热反射温度的颗粒泡沫模制品。
包括聚合物混合物的聚酰胺泡沫颗粒解决了这个问题,所述聚合物混合物包含
(A)25-95重量%的至少一种聚酰胺,该聚酰胺不同于共聚酰胺(B),和
(B)5-75重量%的至少一种共聚酰胺,所述共聚酰胺通过聚合下列组分制备
(B1)15至84重量%的至少一种内酰胺,
(B2)16至85重量%的单体混合物(M),其包含
(M1)至少一种C32-C40二聚体酸和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)的加和为100重量%。
聚酰胺泡沫颗粒优选具有100至500kg/m3,最优选在150至280kg/m3的体积密度。
聚合物混合物形成泡沫颗粒基体。聚酰胺泡沫颗粒优选包含80至100重量%的聚合物混合物以及0至20重量%的添加剂(C),更优选从85至99.9重量%的聚合物混合物和0.1至15重量%的添加剂(C)。聚合物混合物优选由组分(A)和(B)组成。聚酰胺泡沫颗粒更优选包含聚合物混合物,所述聚合物混合物由40至90重量%的聚酰胺(A)、10至60重量%的共聚酰胺(B)组成。
聚酰胺泡沫颗粒可包含其他添加剂(C),例如成核剂、发泡剂、染料、颜料、阻燃剂、IR-吸收剂和/或无机填料。在100%聚合物混合物之外,所有添加剂(C)的总量优选为0至20重量%。添加剂(C)的总量更优选为0.1-15重量%,基于100%的聚合物混合物计,最优选基于100%的组分(A)和(B)的总量计。优选聚酰胺颗粒包含:(C)在组分(A)和(B)之外,0-50重量%的,更优选0.1-1重量%的成核剂。优选的成核剂是滑石粉。组分(A)和(B)加和优选为100%,基于聚酰胺泡沫颗粒的所有聚合物组分计。
聚酰胺泡沫颗粒优选包含
(A)25-95重量%的至少一种聚酰胺,该聚酰胺不同于共聚酰胺(B),和
(B)5-75重量%的至少一种共聚酰胺,其通过聚合下列组分制备
(B1)15-84重量%的至少一种内酰胺,
(B2)16-85重量%的单体混合物(M),其包含
(M1)至少一种C32-C40二聚体酸和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)的总和为100重量%,
(C)0.1-1重量%的成核剂,基于(A)和(B)的总和计。
组分(A)
组分(A)包含至少一种聚酰胺,该聚酰胺不同于共聚酰胺(B)。组分(A)优选不包含由单体混合物(M)制备的共聚酰胺,所述单体混合物(M)包括
(M1)至少一种C32-C40二聚体酸和
(M2)至少一种C4-C12二胺。
组分(A)优选包含至少一种聚酰胺,其选自:聚己内酰胺(PA6)、聚丁烯二酰胺(PA4.6)、聚己二酰二胺(PA6.6)、聚六亚甲基癸二酰胺(PA 6.12)、聚六亚甲基十二烷二酰胺(PA 6.12)、聚-11-氨基十一烷二酰胺(PA 11)、聚月桂内酰胺(PA 12)、聚间苯二甲基二胺(PAMXD 6)、聚五亚甲基癸二酰胺(PA 510)、6T/Z(Z=内酰胺)、6T/6I、6T/6I/XY、6T/XT(X=直链或支链C4-C18-二胺)、XT(X=C4-C18-二胺)、6.12.PA PACM 12(PACM=对二氨基二环己基甲烷)、PA MACM 12(MACM=3,3-二甲基-对氨基二环己基甲烷)、PA MPMD 6(MPMD 2-甲基五亚甲基二胺)、PA MPMD T、PA MPMD 12、聚六亚甲基异酞酰胺(PA 6I)、聚六亚甲基异酞酰胺共六亚甲基对苯二酰胺(PA 6I/6T)、PA 6-3-T(对苯二甲酸聚酰胺,和2,2,4-三甲基六亚甲基二胺与2,4,4-三甲基六亚甲基二胺的混合物)、聚亚丁基癸二酰胺(PA 4.10)、聚十亚甲基癸二酰胺(PA 10.10)、聚五亚甲基己二酰胺(PA5.6)、PA 6/66和PA 66/6、PA 6Y(Y=C4-C18-二酸)及其转酰胺产物。
组分(A)最优选选自:聚己内酰胺(PA6)、聚六亚甲基己二酰胺(PA 6.6)和聚六亚甲基癸二酰胺(PA 6.10)、聚六亚甲基异酞酰胺共六亚甲基对苯二酰胺(PA 6I/6T)或其混合物,特别是聚己内酰胺(PA6)和(PA 6I/6T)的混合物。
聚酰胺(A)特别优选具有多于20%的结晶度、任选地100-340℃(DIN EN ISO11357-3:2014)的熔化温度Tm,以及40至135℃(DIN EN ISO 11357-2:2014)的玻璃化转变温度。根据本发明,结晶度采用差示扫描量热法(DSC)DIN EN ISO 11357_3_2018测定,通过熔化信号的积分得到,即,100%结晶度对应于230J/g(Journal of Polymer Science PartB Polymer Physics 35(1997)2219-2231)。
组分(B)
根据本发明,至少一种共聚酰胺由聚合15重量%至84重量%的组分(B1)和16重量%至85重量%的组分(B2)制备得到;优选共聚酰胺已由聚合40重量%至83%的组分(B1)和17重量%至60重量%的组分(B2)制备得到;特别优选该至少一种共聚酰胺已由聚合60重量%至80重量%的组分(B1)和20重量%至40重量%的组分(B2)制备得到,其中组分(B1)和(B2)的总和为100%。
组分(B1)和(B2)的聚合可在催化剂的存在下发生。合适的催化剂为本领域技术人员已知且可以催化组分(B1)和(B2)聚合的全部催化剂。这类催化剂为本领域技术人员已知。优选的催化剂是磷化合物,例如次磷酸钠、亚磷酸、三苯基膦或亚磷酸三苯酯。
组分(B1)和(B2)的聚合生成共聚酰胺,所述共聚酰胺因此得到衍生自组分(B1)的结构单元和衍生自组分(B2)的结构单元。衍生自组分(B2)的结构单元包含衍生自组分组分(M1)和(M2)的结构单元。
至少一种共聚酰胺优选是一种无规共聚物。
至少一种共聚酰胺通常具有20-50℃,优选23至47℃,特别优选25-45℃的玻璃化转变温度(Tg),根据DIN EN ISO 11357-2:2014测定。
至少一种共聚酰胺通常具有150-210℃,优选在160至205℃,特别优选160-200℃的熔化温度(Tm),根据DIN EN ISO 11357-3:2014测定。
至少一种共聚酰胺通常具有150至300mL/g之间的粘数(viscosity number,VN),按至少一种共聚酰胺在重量比1:1的苯酚/邻二氯苯混合物的0.5重量%溶液中测定。至少一种共聚酰胺的粘数(VN)为160至290mL/g,更优选170至280mL/g,按至少一种共聚酰胺在重量比1:1的苯酚/邻二氯苯混合物的0.5重量%溶液中测定。
组分(B1)
组分(B1)为至少一种内酰胺。在本发明语境中,内酰胺应理解为意为在环部分优选具有4至12,更优选5至8个碳原子的环酰胺。
合适的内酰胺选自,例如,3-氨基丙内酰胺(丙-3-内酰胺;β-内酰胺;β-丙内酰胺),4-氨基丁内酰胺(丁-4-内酰胺;γ-内酰胺;γ-丁内酰胺),5-氨基戊内酰胺(2-哌啶酮;δ-内酰胺;δ-戊内酰胺),6-氨基己内酰胺(己-6-内酰胺:ε-内酰胺;ε-己内酰胺),7-氨基庚内酰胺(庚-7-内酰胺;ζ-内酰胺;ζ-庚内酰胺),8-氨基辛内酰胺(辛-8-内酰胺;η-内酰胺;η-辛内酰胺),9-氨基壬内酰胺(壬-9-内酰胺;θ-内酰胺;θ-壬内酰胺),10-氨基癸内酰胺(癸-10-内酰胺;ω-癸内酰胺),11-氨基十一内酰胺(十一-11-内酰胺;ω-十一内酰胺)和12-氨基十二内酰胺(十二-12-内酰胺;ω-十二内酰胺)。
内酰胺可以是未取代或至少单取代的。如果使用至少单取代的内酰胺,它们可在环氮原子和/或环碳原子上具有一个、二个或更多个取代基,所述取代基独立选自:C1-至C10-烷基、C5-至C6-环烷基和C5-至C10-芳基。
合适的C1-至C10-烷基取代基为,例如,甲基、乙基、丙基、异丙基、正丁基、仲丁基和叔丁基。合适的C5-至C6-环烷取代基的实例为环己基。优选的C5-至C10-芳基取代基为苯基和蒽基。
优选使用未取代的内酰胺,优选γ-内酰胺(γ-丁内酰胺)、δ-内酰胺(δ-戊内酰胺)和ε-内酰胺(ε-己内酰胺)。特别优选δ-内酰胺(δ-戊内酰胺)和ε-内酰胺(ε-己内酰胺),特别优选ε-己内酰胺。
单体混合物(M)
根据本发明,组分(B2)是一种单体混合物(M)。单体混合物(M)包含组分(M1)至少一种C32-C40二聚体酸,和组分(M2)至少一种C4-C12二胺。
单体混合物(M)包含,例如,45至55mol%的组分(M1)和45至55mol%的组分(M2),优选47至53mol%的组分(M1)和47至53mol%的组分(M2),更优选49至51mol%的组分(M1)和49至51mol%的组分(M2),每种情况下基于单体混合物(M)的总摩尔量。
另外,组分(B2)也可包含:组分(M3)至少一种C4-C20二酸。优选组分(B2)由组分(M1)和(M2)组成。
组分(M1)
根据本发明,组分(M1)为至少一种C32-C40二聚体酸。在本发明的语境中,“至少一种C32-C40二聚体酸”意为具体一种C32-C40二聚体酸或两种或更多种C32-C40二聚体酸的混合物。适合用于制备至少一种C32-C40二聚体酸的不饱和脂肪酸为本领域技术人员已知,并且是例如不饱和C16脂肪酸、不饱和C18脂肪酸和不饱和C20脂肪酸。
特别优选组分(M1)是至少一种C36二聚体酸。该至少一种C36二聚体酸优选从不饱和C18脂肪酸制备。C36二聚体酸更优选从选自以下的C18脂肪酸制备:岩芹酸(petroselicacid)((6Z)-十八-6-烯酸),油酸((9Z)-十八-9-烯酸)、反油酸((9E)-十八-9-烯酸)、异油酸(vaccenic acid)((11E)-十八-11-烯酸)和亚油酸((9Z,12Z)-十八-9,12-二烯酸)。从不饱和脂肪酸制备组分(M1)时,可能额外生成三聚体酸;也可能剩余未反应的不饱和脂肪酸残余物。
根据本发明,组分(M1)优选包含不多于0.5重量%的未反应的不饱和脂肪酸和不多于0.5重量%的三聚体酸,更优选不多于0.2重量%的未反应的不饱和脂肪酸和不多于0.2重量%的三聚体酸,每种情况下基于组分(M1)的总重量。
可使用的二聚体酸可商购获得。它们的实例包括Oleon的Radiacid0970、Radiacid0971、Radiacid0972、Radiacid0975、Radiacid0976和Radiacid0977,Croda的Pripol 1006、Pripol 1009、Pripol 1012、和Pripol 1013,BASF SE的Empol 1008、Empol1012、Empol 1061和Empol 1062,以及Arizona Chemical的Unidyme 10和Unidyme Tl。
组分(M1)具有例如190至200mg KOH/g的酸值。
组分(M2)
根据本发明,组分(M2)为至少一种C4-C12二胺。在本发明语境中,“至少一种C4-C12二胺”指一种C4-C12二胺,或者两种或更多C4-C12二胺的混合物。
合适的组分(M2)选自,例如,1,4-二氨基丁烷(丁烷-1,4-二胺;四亚甲基二胺;腐胺)、1,5-二氨基戊烷(五亚甲基二胺;戊烷-1,5-二胺;尸胺)、1,6-二氨基己烷(六亚甲基二胺;己烷-1,6-二胺)、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷(十亚甲基二胺)、1,11-二氨基十一烷(十一亚甲基二胺)和1,12-二氨基十二烷(十二亚甲基二胺)。
组分(M2)优选选自:四亚甲基二胺、五亚甲基二胺、六亚甲基二胺、十亚甲基二胺和十二亚甲基二胺。
组分(M3)
根据本发明,组分(B2)中任一组分(M3)是至少一种C4-C20二酸。在本发明语境中,“至少一种C4-C20二酸”指一种C4-C20二酸,或者两种或更多种C4-C20二酸的混合物。
合适的组分(M3)例如选自:丁二酸(琥珀酸(succinic acid))、戊二酸(戊二酸(glutaric acid))、己二酸(肥酸(adipic acid))、庚二酸(庚二酸(pimelic acid))、辛二酸(软木酸(suberic acid))、壬二酸(杜鹃酸(azelaic acid))、癸二酸(皮脂酸(sebacicacid))、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸和十六烷二酸。
组分(M3)优选选自:戊二酸(戊二酸(glutaric acid))、己二酸(肥酸(adipicacid))、癸二酸(皮脂酸(sebacic acid))和十二烷二酸。
组分(C)
除了聚合物混合物之外,聚酰胺泡沫颗粒可包含其他添加剂例如成核剂、残留发泡剂、染料、颜料、阻燃剂、IR-吸收剂和/或无机填料。最优选将滑石粉用作组分(C)。
本发明主题也是一种制备上述聚酰胺泡沫颗粒的方法,其包含下列步骤
a)提供聚合物混合物,其包含
(A)25至95重量%的至少一种聚酰胺,
(B)5至75重量%的至少一种通过聚合下列组分制备的共聚酰胺
(B1)15至84重量%的至少一种内酰胺,
(B2)16至85重量%的单体混合物(M),包含,
(M1)至少一种C32-C40二聚体酸和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)的加和为100重量%,
b)将聚合物混合物熔化,并且在熔化之前或之后加入0至5重量%,优选0.1至1wt.%的成核剂,基于100%的聚合物混合物计,
c)用基于100%的聚合物混合物计,0.1至4.0重量%,优选0.2至2.5重量%的二氧化碳、氮或其混合物浸渍熔化的聚合物混合物,形成经浸渍的聚合物熔体,
d)在水下造粒机中,将经浸渍的聚合物熔体挤出并造粒,形成聚酰胺泡沫颗粒。
优选将滑石粉用作成核剂(步骤b的组分(C))。
优选方法在步骤a)中提供包含上述的组分(A)和(B)的聚合物混合物,用于聚酰胺泡沫颗粒。
包括二氧化碳、氮或其混合物作为发泡剂和任选地成核剂和其他辅助添加剂的聚合物熔体,优选通过温度控制在150℃和350℃之间的多孔盘挤出进入造粒室,使用切割装置将通过被控温的多孔盘压制的聚合物熔体分割成单个膨胀颗粒,并使用液体流从造粒室中排出颗粒。
通常使用挤出机和/或熔体泵来制备聚酰胺颗粒泡沫,所述聚酰胺颗粒泡沫包含聚合物熔体、发泡剂和任选地其他助剂,例如IR-吸收剂(即石墨,炭黑)或共发泡剂(例如乙醇、水或丙酮)。这些设备也用来生成将聚合物熔体压入通过穿孔板所需的压力。在方法中,使熔体具有后续造粒所需温度。造粒所需的压力和熔体所需温度取决于聚合物、助剂、发泡剂和组分间的混合比例。聚合物熔体通过被控温的穿孔板进入造粒室。造粒室由被控温的液体流穿过,其压力为0.1bar至20bar,优选高于环境压力0.5至15bar。
在造粒室中,聚合物强制通过被控温的穿孔板,成型为股条(strand),切割装置将其分割成单个膨胀颗粒。切割装置可为例如快速旋转刀片。所得颗粒的形状取决于穿孔板开孔的形状和尺寸以及熔体强制通过穿孔板的孔的压力,以及取决于熔体强制通过穿孔板的孔所处的压力,并且取决于切割设备的速度。优选可选择强制压力、切割设备速度和穿孔板中孔的尺寸,使颗粒基本为球形或椭圆的。
颗粒通过流经造粒室的被控温的液体从造粒室排出。选择被控温的液体的温度和压力,试聚合物股条/颗粒通过其所含有的发泡剂可控地膨胀,且颗粒表面产生未破损的表皮。造粒室中液体的温度优选为5℃至90℃,以便颗粒可进行受控膨胀,其中形成未破损的泡沫表皮。液体的温度优选为10℃至90℃,并且更优选为50℃至80℃。根据本发明,被控温的穿孔板的温度优选为150℃至350℃,更优选250℃至320℃。
颗粒与被控温的液体一起流入干燥器,在其中颗粒与液体分离。最终的膨胀颗粒收集于容器中,而液体被过滤并通过泵送回造粒室。
泡沫颗粒更低的体积密度可通过进一步使用压缩气体或蒸汽、IR或微波辐射实现。
本发明的又一主题是一种通过在100至150℃的温度下将本发明的聚酰胺泡沫颗粒蒸汽箱成型来制备聚酰胺颗粒泡沫模制品的方法,以及根据该方法可获得的聚酰胺颗粒泡模制品。其它熔接技术,比如射频和变温(Fox Velution),Artecama也适用。
聚酰胺颗粒泡沫模制品可用于车身(carrosserie)零件的结构强化。
根据本发明的颗粒泡沫模制品,展现高热挠曲温度,具有良好机械性能,如120-200℃温度范围内具有良好的碰撞吸收能力。颗粒泡沫模制品的另外的优点是它的各向同性、对称的泡沫结构,可实现复杂的3D几何图形,以及可调节的密度特征。颗粒泡沫模制品优选用于下列行业加强结构部件:汽车、航空航天和消费品行业,如车身零件、风能结构的刀片镶嵌、运动或休闲设备、交通运输或包装。
实施例
原材料:
B 40 聚酰胺6,BASF SE,密度为1120-1150kg/m3,粘数(VN)为240-260ml/g,熔点220℃
Flex F 38共聚酰胺6/6.36,BASF SE,密度为1060-1090kg/m3,相对粘度(RV)3.7-3.9,熔点199℃,
PA3426聚酰胺6I/6T,DuPont,密度1.19g/cm3,无定型尼龙(聚酰胺)树脂,玻璃转变温度125℃
滑石Talc microtalk IT extra,mondo mineral,平均颗粒尺寸d50%<2μm)
发泡剂二氧化碳4.6 (CO2),Praxair,纯度99.999%氮气5.0(N2)Praxair,纯度99.999%
方法:
可膨胀或膨胀颗粒的颗粒体积密度根据DIN ISO 697:1982测定。
部件密度根据DIN EN ISO 845--10:2009测定。
玻璃化转变温度Tg通过DSC根据DIN EN ISO 11357-2:2014,在加热速率20K/min下测定。
熔化温度Tm采用DSC根据DIN EN ISO 11357-3:2014测定。
相对结晶度由差示扫描量热法(DSC),通过积分熔化信号测定,即,100%结晶度对应230J/g(Journal of Polymer Science Part B Polymer Physics 35(1997)2219-2231)。根据本发明的测定根据DIN EN ISO 11357_3:2018进行。
热挠曲温度根据DIN 53424:1978测定,温度范围为20-230℃,使用Gabo Eplexor500以及频率为1Hz。使用干样品进行测试(7d/80℃/真空)。
存储模量E’采用DMTA根据ISO 6721-1:2019)测定,温度范围为-50至230℃,使用Gabo Eplexor 500以及频率为1Hz。使用干样品(7d/80℃/真空)。
实施例1–11和对比实施例C1–C4:
熔体浸渍在由下列组成的设备中进行:Leistritz公司的双螺杆挤出机,分为8个等长的区域(Z1...Z8),螺杆直径为18mm,长径比为40;熔体泵(MP);启动阀(start-upvalve,SV);熔体过滤器;穿孔模板(DP)和水下造粒机(UWP)。
将聚乙烯袋中的聚酰胺和滑石混合均匀,然后送入通过剂量单元送入双螺杆挤出机。在挤出机1/3处熔化聚酰胺。在挤出机长度的大约1/3后,借助isco泵(Axel Semrau公司的活塞泵)泵送推进剂并将其注入挤出机。在挤出机其余部分中,通过双螺杆挤出机的温度控制冷却聚合物熔体。当通过穿孔板时,聚合物熔体的温度对应于区域8的设定温度。通过熔体泵(MP),设定挤出机的压力特征(压力-速度控制),使发泡剂与混合物熔体完全混合。除了设定双螺杆挤出机的压力特征之外,熔体泵也用于传送发泡剂并将聚合物熔体压入通过下列装置(启动阀、熔体滤网和穿孔板)。将穿过穿孔板(每孔直径1mm)后出现的熔体股条加压引入水下造粒机(UWP),来得到膨胀聚酰胺颗粒,每个颗粒的重量约为3.5mg。挤出机的总产量保持恒定为4kg/h。水箱中的股条,被刀片环上的6个刀片切割。刀片环以约3500rpm旋转,因此产生颗粒重量为3.5mg的膨胀颗粒,该膨胀颗粒通过水环路从穿孔板运送入干燥器,然后被分离进入收集容器。
使用的原料重量比和可膨胀或膨胀泡沫颗粒的性质汇总于表1。发泡剂添加的比例基于100重量%聚合物计。每个实施例的工艺参数汇总于表2中。温度基于温度值设定,并在各个仪器部分测量。
颗粒泡沫模制品
通过注射压缩空气,将预膨胀颗粒装入模具空腔中,(空腔尺寸:长300mm,宽200以及高25mm)。12mm裂缝填充物施加于高度压缩的颗粒。模具被安装在成型机中,然后向空腔提供128℃饱和蒸汽8秒钟(交叉蒸汽加热),然后向空腔提供128℃饱和蒸汽10秒钟(高压釜蒸汽加热),经预膨胀颗粒的热熔合来模制预膨胀颗粒。向模具空腔供冷却水20秒钟来冷却得到的经成型并经熔接的产品。工艺条件和颗粒泡沫模制品的性能汇总于表3和4中。
对比实施例C3和实施例2展示了将无定型聚酰胺6I/6T(PA3426)替换为聚酰胺6/6.36(/>Flex 38)得到更高结晶度和在温度高于160℃时更高的存储模量E’(表4)。
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表4:颗粒泡沫模制品的性质
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Claims (12)
1.聚酰胺泡沫颗粒,其包含聚合物混合物,所述聚合物混合物包含:
(A)25至95重量%的至少一种聚酰胺,其不同于共聚酰胺(B),和
(B)5至75重量%的至少一种共聚酰胺,所述共聚酰胺通过聚合下列组分制备:
(B1)15至84重量%的至少一种内酰胺,
(B2)16至85重量%的单体混合物(M),其包含,
(M1)至少一种C32-C40二聚体酸,和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)的和为100重量%。
2.根据权利要求1的聚酰胺泡沫颗粒,其中单体混合物(M)包含45至55mol%的组分(M1),和45至55mol%的组分(M2),每种情况下基于组分(M)的总摩尔量计。
3.根据权利要求1或2的聚酰胺泡沫颗粒,其中组分(B1)选自:3-氨基丙内酰胺、4-氨基丁内酰胺、5-氨基戊内酰胺、6-氨基己内酰胺、7-氨基庚内酰胺、8-氨基辛内酰胺、9-氨基壬内酰胺、10-氨基癸内酰胺、11-氨基十一内酰胺和12-氨基十二内酰胺。
4.根据权利要求1或2的聚酰胺泡沫颗粒,其中组分(M2)选自:四亚甲基二胺、五亚甲基二胺、六亚甲基二胺、十亚甲基二胺和十二亚甲基二胺。
5.根据权利要求1或2的聚酰胺泡沫颗粒,其中至少一种共聚酰胺(B)的熔化温度Tm是150至210℃,根据ISO 11357-2:2014测定。
6.根据权利要求1或2的聚酰胺泡沫颗粒,包含聚合物混合物,所述聚合物混合物由下列组成:40至90重量%的聚酰胺(A),10至60重量%的共聚酰胺(B)。
7.根据权利要求1或2的聚酰胺泡沫颗粒,其体积密度是100至500kg/m3。
8.一种制备聚酰胺泡沫颗粒的方法,包括下列步骤:
a)提供一种聚合物混合物,包含
(A)25至95重量%的至少一种聚酰胺,其不同于共聚酰胺(B),
(B)5至75重量%的至少一种共聚酰胺,其通过聚合下列组分制备:
(B1)15至84重量%的至少一种内酰胺,
(B2)16至85重量%的单体混合物(M),其包含,
(M1)至少一种C32-C40二聚体酸,和
(M2)至少一种C4-C12二胺,
其中组分(B1)和(B2)的总和为100重量%,
b)将聚合物混合物熔化,并且在熔化之前或之后加入0至5重量%的成核剂,基于100%的聚合物混合物计,
c)用基于100%的聚合物混合物计,0.1至4.0重量%的二氧化碳、氮气或其混合物浸渍熔化的聚合物混合物,形成经浸渍聚合物熔体,
d)在水下造粒机中,将经浸渍的聚合物熔体挤出并造粒,形成聚酰胺泡沫颗粒。
9.根据权利要求8的方法,其中加入0.1至1重量%的滑石粉作为成核剂。
10.一种通过将根据权利要求1至7中任一项的聚酰胺泡沫颗粒在100至150℃的温度范围内蒸汽箱成型来制备聚酰胺颗粒泡沫模制品的方法。
11.聚酰胺颗粒泡沫模制品,其可根据权利要求10的方法获得。
12.根据权利要求11的聚酰胺颗粒泡沫模制品用于汽车、航空航天和消费品行业中结构部件强化的用途。
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US4212777A (en) * | 1977-10-28 | 1980-07-15 | Rhone-Poulenc Industries | Linear, flexible, high tensile strength copolyamides |
JP2012111940A (ja) * | 2010-11-01 | 2012-06-14 | Toyobo Co Ltd | ポリアミド樹脂組成物およびポリアミド樹脂発泡成形体 |
EP3272798A4 (en) * | 2015-03-18 | 2018-01-24 | Asahi Kasei Kabushiki Kaisha | Polyamide resin foam-molded article and method for producing polyamide resin foam-molded article |
WO2018050487A1 (de) * | 2016-09-14 | 2018-03-22 | Basf Se | Polymerfilm enthaltend ein copolyamid eines diamins, einer dimersäure und eines lactams |
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HUE028448T2 (en) | 2010-04-27 | 2016-12-28 | Basf Se | Expandable polyamide granulate |
US20110294910A1 (en) | 2010-04-27 | 2011-12-01 | Basf Se | Expandable pelletized polyamide material |
US20160032068A1 (en) * | 2013-05-15 | 2016-02-04 | Toyobo Co., Ltd. | Polyamide resin composition for foam molded body, and foam molded body of polyamide resin comprising same |
ES2646539T3 (es) | 2013-06-13 | 2017-12-14 | Basf Se | Procedimiento para la fabricación de granulado expandido |
KR20180031029A (ko) | 2015-07-22 | 2018-03-27 | 사빅 글로벌 테크놀러지스 비.브이. | 발포 물질 및 이 물질과 연관된 물품 및 방법 |
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US4212777A (en) * | 1977-10-28 | 1980-07-15 | Rhone-Poulenc Industries | Linear, flexible, high tensile strength copolyamides |
JP2012111940A (ja) * | 2010-11-01 | 2012-06-14 | Toyobo Co Ltd | ポリアミド樹脂組成物およびポリアミド樹脂発泡成形体 |
EP3272798A4 (en) * | 2015-03-18 | 2018-01-24 | Asahi Kasei Kabushiki Kaisha | Polyamide resin foam-molded article and method for producing polyamide resin foam-molded article |
WO2018050487A1 (de) * | 2016-09-14 | 2018-03-22 | Basf Se | Polymerfilm enthaltend ein copolyamid eines diamins, einer dimersäure und eines lactams |
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CN114269856A (zh) | 2022-04-01 |
US20220340727A1 (en) | 2022-10-27 |
EP4031606B1 (en) | 2023-07-26 |
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