CN103237839B - 一种填充泡沫 - Google Patents
一种填充泡沫 Download PDFInfo
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- CN103237839B CN103237839B CN201180058317.5A CN201180058317A CN103237839B CN 103237839 B CN103237839 B CN 103237839B CN 201180058317 A CN201180058317 A CN 201180058317A CN 103237839 B CN103237839 B CN 103237839B
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- foam
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- potassium
- hexanolactam
- monomer
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- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title description 5
- 239000006260 foam Substances 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical group [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 2
- YRSNSRSCRMBJPY-UHFFFAOYSA-N azepan-2-one;potassium Chemical compound [K].O=C1CCCCCN1 YRSNSRSCRMBJPY-UHFFFAOYSA-N 0.000 claims description 2
- YIFCDKDXYUCWAZ-UHFFFAOYSA-L magnesium;azepan-2-one;dibromide Chemical compound [Mg+2].[Br-].[Br-].O=C1CCCCCN1 YIFCDKDXYUCWAZ-UHFFFAOYSA-L 0.000 claims description 2
- HZPUIBHNYFZDLB-UHFFFAOYSA-L magnesium;azepan-2-one;dichloride Chemical compound [Mg+2].[Cl-].[Cl-].O=C1CCCCCN1 HZPUIBHNYFZDLB-UHFFFAOYSA-L 0.000 claims description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 abstract description 7
- 206010000269 abscess Diseases 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical class O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical class O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920006864 PPE/PS Polymers 0.000 description 1
- 101150004822 PSAN gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
Abstract
本发明涉及用聚酰胺填充的开泡孔沫，还涉及其生产方法。
Description
本发明涉及用聚酰胺填充的开孔泡沫，及其生产方法。
许多已知的现有方法都由例如聚合材料组成。关于各种类型泡沫的综述例如有“Polymeric Foams and Foam Technology”，edited byD.Klempner and V.Sendijarevic,Carl Hanser Verlag,Munich,2ndedition,2004。此处“泡沫”可定义为通过将气泡引入液体或固体中所制成的一种材料。
开孔泡沫原则上也是已知的。术语“开孔”定义的是一种泡沫结构，其中每个泡孔(cell)单元包括至少两个微孔(pore)或被破坏的面。此外，大多数的泡孔边缘必须形成至少三个孔的部分。相反，在闭泡孔沫中，泡孔不具有任何微孔或被破坏的面。开孔塑料泡沫通常以聚乙烯(PE)、聚氨酯(PU)和聚氯乙烯(PVC)为基础制备(参见Arnim Kraatz’s thesis,2007,Halle University)。通常，开孔泡沫常为柔软的。
开孔泡沫可由例如金属或塑料材料组成。
现有技术描述了通过加入其它物质来改进热塑性材料或热固性材料的性能的方法。这一类型方法的实例有与另一种聚合物混合以形成一种均相体系(例如PMMA和PSAN,或PPO和聚苯乙烯—参见ModernStyrenic Polymers，John Wiley and Sons,Ltd，2003，page699，part6，Styrenic Blends)，添加润滑剂以提高其流动性(Plastics AdditivesHandbook，5th Edition，Hanser Publishers，Chapter5，Lubricants)，添加玻璃纤维以提高其刚度(Handbuch der TechnischenPolymerchemie，VCH Verlag，1993,page651，part12.4.5.1，reinforcedplastics)，以及将橡胶加至刚性热塑性塑料中以改进其抗压强度和韧性(Mechanical Properties of Polymers Based on Nanostructure andMorphology，Taylor and Francis Publishers，2005，Chapter11，Structure-Property Relationships in Rubber Modified AmorphousThermoplastic Polymers)。
在聚合泡沫中包含其他物质—如聚合物—通常可使其中各种组分(即，泡沫和包含于泡沫中的聚合物)的机械性能相互促进(强化效应)。在一些情况下，例如，泡沫低温熔化得到控制或耐燃性得到提高。
在现有方法(大部分为注模法)中，因通常聚合物的粘度太高，故不能提供填充聚合物的泡沫的互穿网(interpenetrating network)。泡沫的微孔通过现有方法即便可以，也仅可为聚合物不完全填充。此外，试图填充泡沫微孔经常会损坏或破坏该泡沫。
本发明的目的是提供一种用聚合物尽可能完全填充开孔泡沫的微孔而不破坏泡沫的方法。这一方法会提供一种具改良性能的复合材料，所述改良性能例如改良的机械性能(例如韧性、延展性和压缩后的可恢复性)。
令人吃惊的是，我们已经发现前述目的可通过在开孔泡沫存在的情况下由内酰胺单体的催化阴离子聚合来实现。
本发明因此提供了一种生产复合材料的方法，其包括将开孔泡沫(S)用至少一种内酰胺类单体(M)至少部分地浸透，其后通过使用催化剂使单体(M)至少部分地阴离子聚合。
本申请的其它主题为通过本发明方法制得的一种复合材料，以及通过本发明方法获得的复合材料在运动器材中作为耐火部件或增强部件的用途。
在本发明的优选实施方案中，一相对另一相进行有利的改进(相互强化效应)。所述效应可被用于例如复合材料的增强、冲击改性或提高其断裂伸长。进一步的优势是与用常规方法生产的复合材料相比，本发明的复合材料的吸水性有所减少。
本文中的术语“复合材料”是指一种结合了两种或多种不同组分材料的工程材料。
术语“三聚氰胺-甲醛泡沫”包含三聚氰胺-甲醛缩合物，其中除三聚氰胺之外，可包含最高达50重量％，优选最高达20重量％的能够形成热固性树脂的其他化合物，且除甲醛之外，可包含最高达50重量％，优选最高达20重量％的其他醛类作为共缩合单元(co-condensed units)。
然而，本发明优选未改性的三聚氰胺-甲醛缩合物。
其他能够形成热固性树脂的化合物的实例为被烷基、氨基甲酸酯、脂族胺、苯酚和苯酚衍生物取代的三聚氰胺。有用醛类的实例为乙醛、丙烯醛和苯甲醛。
关于三聚氰胺-甲醛缩合物进一步的详述参见Houben-Weyl,Methoden der organischen Chemie,volume14/2,1963,page319to402。
能够形成热固性树脂的化合物与醛的摩尔比可在1:1.5至1:4.5之间的较宽范围内变化；在三聚氰胺-甲醛缩合物的情况下，优选为1:2.5至1:3.5。
所述三聚氰胺树脂有利地包含共缩合的亚硫酸酯基团。关于三聚氰胺-甲醛缩合物进一步的详述见US4,540,717。
在本发明方法后，泡沫和聚酰胺各自形成连续相。由此，在所述方法结束时，体系中包括至少两种共连续相或至少两种主相。本发明复合材料的形态被认为主要决定于其孔径。
具体地，本发明的方法如下进行。其中所述泡沫优选为干燥的泡沫。
将泡沫(S)与一种混合物接触，所述混合物例如包含单体(M)、催化剂和任选活化剂的溶液。这可例如通过下述过程完成，将所述泡沫浸入含有单体(M)、催化剂和任选活化剂的溶液中，或通过用该溶液喷洒泡沫(S)，或将该溶液刷到所述泡沫上。这一步骤优选在减压条件下进行。
后续聚合过程的温度通常在85℃至200℃范围内，优选为95℃至180℃，更优选为105℃至160℃。
所述单体(M)可仅位于泡沫(S)的微孔内。然而，在泡沫(S)、因而在复合物(W)的表面具有一层薄聚合物膜也是有利的。
泡沫(S)与单体(M)的比值可变。其通常在90:10至10:90范围内，优选80:20至20:80，更优选为60:40至40:60。
根据本发明，所述泡沫可由例如金属、塑料或如木材(如软木)的天然产物组成。所述泡沫还可由这些材料的混合物组成。
在优选的实施方案中，所述泡沫由金属或由塑料与金属的混合物组成。所述金属优选选自铝和镁。
在更优选的实施方案中，所述泡沫由塑料组成。
能够形成合适泡沫的塑料的实例为PSU(聚砜)、PEI(聚醚酰亚胺)、PI(聚酰亚胺)、聚氨基甲酸酯、PA(聚酰胺)、PLA(聚交酯)、PPE/PS(聚苯醚/聚苯乙烯)、amsan(丙烯腈/α-甲基苯乙烯)、PC(聚碳酸酯)、聚丙烯、三聚氰胺-甲醛。
特别优选的是三聚氰胺-甲醛泡沫，例如BASF SE的
根据本发明，所述泡沫在最高达90℃、优选最高达105℃、更优选最高达130℃时需是热稳定的。
所述泡沫可具有规则或不规则微孔结构。不规则微孔结构的一个实例是如出现在蜂房中的蜂窝结构。其通常具有六边形微孔结构。
单体(M)是内酰胺类化合物。其实例有己内酰胺、哌啶酮、吡咯烷酮、十二内酰胺或其混合物，优选己内酰胺、十二内酰胺或其混合物，更优选己内酰胺或十二内酰胺。
有用的催化剂尤其包括己内酰胺钠、己内酰胺钾、己内酰胺溴化镁、己内酰胺氯化镁、二己内酰胺镁、氢化钠、金属钠、氢氧化钠、甲醇钠、乙醇钠、丙醇钠、丁醇钠、氢化钾、金属钾、氢氧化钾、甲醇钾、乙醇钾、丙醇钾和丁醇钾，优选氢化钠、金属钠、己内酰胺钠，更优选己内酰胺钠(如10，一种在己内酰胺中含有18重量％己内酰胺钠的溶液)。
本发明的一种优选实施方案使用至少一种活化剂(也称引发剂)。但是，活化剂的使用并非完全必要的。
有用的活化剂尤其包括脂族二异氰酸酯(如亚丁基二异氰酸酯、六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、十亚甲基二异氰酸酯、十一亚甲基二异氰酸酯和十二亚甲基二异氰酸酯)、或其他芳香二异氰酸酯(如甲苯甲酰二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-亚甲基二(苯基异氰酸酯)、4,4’-亚甲基二(环己基异氰酸酯))或多异氰酸酯(如六亚甲基二异氰酸酯、BASF SE的HI100)、脲基甲酸酯(如乙基脲基甲酸酯)或其混合物，优选六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯，更优选六亚甲基二异氰酸酯。有用的活化剂还包括酰卤，或者酰卤或异氰酸酯与内酰胺的任何反应产物。
内酰胺与催化剂的摩尔比可于较大范围内变动，通常在1:1至10000:1范围内，优选10:1至1000:1，更优选50:1至300:1。活化剂与催化剂的摩尔比可于较大范围内变动，通常在100:1至1:10000范围内，优选10:1至1:100，更优选1:1至1:10。
完成本发明的方法后，即单体(M)聚合反应结束后，形成的复合材料可任意地进行后成型(例如通过加热和弯曲)。
由本发明方法所获得的复合材料作为耐火部件或强化部件尤其有用，例如在汽车构造或运动器材中。
实施例
下列实施例用来说明本发明的一些方面。所述实施例不应以任何方式被视为限定本发明的范围。
所有组分与装置都是干燥的。
实施例1
将由(由三聚氰胺树脂制成的柔性开孔泡沫)组成的、尺寸为55×20×95mm3的泡沫放置于铝箔制成的尺寸为65×30×105mm3的盘子中。将所述盘子置于干燥箱中在氮气条件下于150℃干燥数小时。
在氮气条件下于两个玻璃烧瓶中分别制备下述溶液：
1:38.45g己内酰胺+11.55gC10(一种由Brüggemann制备聚酰胺的催化剂；在己内酰胺中有17％己内酰胺钠)
2：44.89g己内酰胺+5.11gC20(一种由Brüggemann制备聚酰胺的活化剂；在己内酰胺中有80％封端二异氰酸酯)，
并且通过磁力搅拌使其熔融。110℃下将溶液1和2混合15秒，然后将其加入到在N2条件下的干燥箱中的铝盘中，直至盘子加满为止。通过简单晃动移走多余的液体。10分钟之后聚合反应完成。将铝盘从干燥箱中取出冷却。将模制品从铝盘中移走。所述模制品由填充聚己内酰胺的泡沫(BASF的)的互穿网组成。VN(粘数)＝180，残余己内酰胺＝1.9重量％
该模制品的密度为1.1g/ml。
实施例2
将尺寸为55×20×95mm3的聚酰胺(PA)开孔泡沫放入玻璃烧瓶中。所述烧瓶于150℃下排空数小时。
在氮气条件下于两个玻璃烧瓶中分别制备下述溶液：
1：38.45g己内酰胺+11.55gC10
2：44.89g己内酰胺+5.11gC20，
并且通过磁力搅拌使其熔融。110℃下将溶液1和2混合15秒，然后将其通过阀门加入到PA泡沫中。10分钟之后聚合反应完成。
泡沫的微观横截面表明存在互穿网。
在用己内酰胺单体处理前和处理后，分别将泡沫浸入水中30分钟。发现处理前的吸水性明显高于处理后的吸水性。
同样，己内酰胺聚合后泡沫的刚度明显高于聚合前的刚度。
Claims (5)
1.一种改善开孔泡沫的机械性能的方法，其包括将开孔泡沫(S)用至少一种内酰胺类单体(M)至少部分地浸透，其后通过使用催化剂使单体(M)至少部分地阴离子聚合，其中所述泡沫(S)是三聚氰胺-甲醛泡沫并且所述泡沫(S)由塑料组成。
2.根据权利要求1所述的方法，其中所述单体(M)选自己内酰胺、哌啶酮、吡咯烷酮、十二内酰胺及其混合物。
3.根据权利要求1或2所述的方法，其中所述催化剂选自己内酰胺钠、己内酰胺钾、己内酰胺溴化镁、己内酰胺氯化镁、二己内酰胺镁、氢化钠、金属钠、氢氧化钠、甲醇钠、乙醇钠、丙醇钠、丁醇钠、氢化钾、金属钾、氢氧化钾、甲醇钾、乙醇钾、丙醇钾和丁醇钾。
4.根据权利要求1或2所述的方法，其中所述阴离子聚合使用活化剂。
5.根据权利要求1或2所述的方法，其中所述泡沫具有蜂窝结构。
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| PCT/EP2011/071119 WO2012072543A1 (de) | 2010-12-02 | 2011-11-28 | Schaum mit füllung |
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| DE1953347C3 (de) * | 1969-10-23 | 1975-02-06 | Bayer Ag, 5090 Leverkusen | Verfahren zur Modifizierung von offenzelligen Polyurethans-Schaumstoffen |
| DE2022208A1 (de) * | 1970-05-06 | 1971-12-02 | Rudolph Koepp & Co Chem Fab Ag | Verbesserte Hochfrequenz-schweissbare Schaumstoffe und Verfahren zu ihrer Herstellung |
| US4511678A (en) | 1979-04-17 | 1985-04-16 | Basf Aktiengesellschaft | Resilient foam based on a melamine-formaldehyde condensate |
| JPS5991134A (ja) * | 1982-11-18 | 1984-05-25 | Asahi Chem Ind Co Ltd | 高周波接着性の多孔体 |
| US5147345A (en) * | 1991-08-12 | 1992-09-15 | The Procter & Gamble Company | High efficiency absorbent articles for incontinence management |
| JP3354220B2 (ja) * | 1993-07-09 | 2002-12-09 | 日清紡績株式会社 | メラミン系樹脂発泡体 |
| JP3450768B2 (ja) * | 1999-11-25 | 2003-09-29 | 住友ゴム工業株式会社 | 繊維強化樹脂製品、テニスラケット及び繊維強化樹脂製品の製造方法 |
| JP4647069B2 (ja) * | 2000-09-11 | 2011-03-09 | 株式会社サクラクレパス | 汚れ落とし具 |
| DE10321789A1 (de) * | 2003-05-14 | 2004-12-09 | Basf Ag | Polyamide |
| ES2358473T3 (es) * | 2007-05-11 | 2011-05-11 | Decathlon | Artículo de confección con efecto de contención heterogéneo para la práctica de un deporte. |
| EP2039489A1 (en) * | 2007-09-21 | 2009-03-25 | Recticel | Process for the production of a foamed article. |
| US9347004B2 (en) * | 2009-06-16 | 2016-05-24 | The Boeing Company | Flame propagation resistant foam and method |
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| CN103237839A (zh) | 2013-08-07 |
| WO2012072543A1 (de) | 2012-06-07 |
| MY163312A (en) | 2017-09-15 |
| EP2646503B1 (de) | 2016-03-30 |
| JP2013544312A (ja) | 2013-12-12 |
| KR20130118915A (ko) | 2013-10-30 |
| EP2460847A1 (de) | 2012-06-06 |
| EP2646503A1 (de) | 2013-10-09 |
| JP6002143B2 (ja) | 2016-10-05 |
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Effective date of registration: 20191209 Address after: 300 jiangxinsha Road, Pudong New Area, Shanghai Patentee after: BASF AUX Y CHEMICALS CO., LTD. Address before: Ludwigshafen, Germany Patentee before: BASF European Company |