CN105885329A - 用于泡沫注塑成型的分子筛 - Google Patents
用于泡沫注塑成型的分子筛 Download PDFInfo
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- CN105885329A CN105885329A CN201610084536.5A CN201610084536A CN105885329A CN 105885329 A CN105885329 A CN 105885329A CN 201610084536 A CN201610084536 A CN 201610084536A CN 105885329 A CN105885329 A CN 105885329A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000001746 injection moulding Methods 0.000 title claims description 22
- 239000006260 foam Substances 0.000 title claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 238000002347 injection Methods 0.000 claims abstract description 13
- 239000007924 injection Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 48
- 238000000465 moulding Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000011145 styrene acrylonitrile resin Substances 0.000 claims description 2
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 3
- 239000012778 molding material Substances 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 229960004424 carbon dioxide Drugs 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
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Abstract
本发明涉及一种包含至少一种热塑性合成材料和用于吸收氮和/或二氧化碳的分子筛的模塑材料，其中所述合成材料是一种适用于化学或物理发泡工艺的合成材料，而所述分子筛由沸石材料或碳分子筛(carbon molecular sieve,CMS)构成，并且涉及一种注塑模制品及其生产方法和应用。
Description
技术领域
本发明涉及一种包含至少一种热塑性合成材料和用于吸收氮和/或二氧化碳的分子筛的模塑材料，并且涉及一种由该模塑材料制成的注塑模制品及其生产方法和应用。
如今，合成材料在汽车制造中占15％与20％之间的重量百分比，并且呈上升趋势。合成材料通常作为外装部分和内饰部分，其中后者通过将注塑成型构件与不同的表面装饰物粘接而获得相应的视觉、触觉及功能特性。特别是，合成材料部件作为用于汽车内饰的注塑模制品而安装，例如仪表板、门饰板或中控台。上述部分可以设置有或者涂装有装饰部。
另外，汽车工业在轻量构造上的竞争使得合成材料的应用平台日益广阔，其中，物理发泡，即使用空气(氮、CO2)代替合成材料，或化学发泡的使用日益增加。在物理发泡时，按照或相似工艺，将例如氮、二氧化碳或一种化学起泡剂在超临界状态下在塑化加工过程中在压力下注入合成材料熔体中并均匀地分布。在注入无压模具之后，气体从熔体中分离，形成细孔泡沫结构。保压压力的取消、粘度的降低、缩痕和变形的最小化或消除都是加强上述趋势的重要方面。
背景技术
发泡聚合物产品在本专业领域中是公知的，并且具有多种应用可行方案。泡沫被例如用于缓冲、绝缘、减重、减震以及热力、化学和电子惰性。使用发泡颗粒或常规聚合物加工工艺，例如挤出、注塑、反应注塑和机械混合，能够生产热塑性聚合物泡沫。泡沫挤出工艺通常包括以下步骤：将聚合物在挤出机中熔化；添加气体或一种在挤出温度和标准压力下形成为气体状态的化合物(起泡剂)或气体源，例如一种通过分解而产生气体的化合物；然后由成型模具挤出熔化的热塑性聚合物，以形成泡沫结构。通常还会在熔化的聚合物中添加成核剂，以改善所得泡沫的孔径大小和均匀性。
例如US 5726214、US 4877815和US 3072583中公开了制造发泡聚合物产品的方法。JP 08-12796公开了在组合物中使用氮化硼和沸石的组合作为成核剂，以发泡氟聚合物树脂。
在DE 602 19 054中发现沸石在不添加气体或化学发泡工具的情况下能够单独地用来发泡可熔化加工的热塑性聚合物。。
现有技术的方法具有下列缺点，即在生成泡沫时或生成泡沫之后，出现不希望的模制品排气现象，这尤其减慢了涂覆构件的完成，从而使得更贵并且不便。如果过早施加涂覆材料，上述排气现象将导致不利的起泡，所以目前为止不得不长时间等待排气减弱，直到能够将涂覆材料施加到模制品上。
发明内容
本发明的任务在于，提供一种模塑材料，一种相应的注塑模制品或合成材料模制品及其方法，其中这样减少或抑制排气：使得模制品在其制造完成后尽可能直接设置涂覆面或涂层，期间并不因为排气而起泡。
根据本发明，上述任务通过根据权利要求1的特征的模塑材料、根据权利要求8的注塑模制品，及其根据权利要求10的制造方法和根据权利要求13的应用来解决。
根据本发明的模塑材料包括至少一种热塑性合成材料和用于吸收氮和/或二氧化碳的分子筛，其中所述合成材料是一种适用于化学或物理发泡工艺的合成材料，并且所述分子筛由沸石材料或碳分子筛(carbon molecular sieve,CMS)构成。
根据本发明，模塑材料或由其制成的模制品的排气在借助分子筛发泡之后明显减少或得到抑制。此时，例如沸石在挤出机中受热释放出结晶水。汽化的结晶水形成细微的气泡，混入的起泡剂能够积聚在这些气泡上。这一方面改善了气泡形成、即发泡模制品的质量，即均匀分配相同大小的气泡。另一方面意外的是，沸石也有助于合成材料泡沫在其形成后的稳定性。这可能是因为环境空气中的结晶水和部分起泡剂在熔体稍微冷却后又重新吸收在沸石上。从而迅速降低泡沫中的气压。
本发明框架中的另一种分子筛材料，例如在可购买得到的氮气生成器中使用的分子筛材料，是所谓的分子筛碳，一种颗粒状的碳材料。有多种方法来制造这种颗粒状的碳材料。其中一种方法是，将酚或呋喃系列的树脂原料吸附在多孔的碳吸附剂的表面上，然后聚合和/或缩合。接着进行碳化，使得在吸附剂中形成多细孔的结构(JP-OS49-37036)。另一种方法是，在通过热分解而产生碳的碳氢化合物中添加焦炭，然后对其进行热处理，以沉淀焦炭的细孔中的碳(JP-OS52-18675)。另一种方法则是，将一种在室温下呈粘性的有机材料与细微的炭颗粒混合，接着使其呈颗粒状并且碳化(JP-OS 57-175715)。
然而，分离氮和氧的分子筛的细孔的孔径大小必须控制在0.35nm至0.5nm的范围之内。实验证明，沸石Na-A(SYLOSIV孔径大小0.4nm)、沸石ZSM-5(硅质岩，孔径大小0.5nm)或沸石A4(K80，斜发沸石，孔径大小0.4nm)是特别有效的分子筛。
优选的，模塑材料中含有至少90％至99.999％重量百分比的合成材料，以及0.001％至10％重量百分比的分子筛。上述质量分配一方面保证了气体吸收的最大化，另一方面分子筛的量充分小，而不会损害由模塑材料制成的模制品的机械性能。此外，特别是沸石分子筛在上述质量中具有填充物的性能。
优选的，作为沸石材料的分子筛的孔开口直径在根据DIN66134和/或DIN 66135规定的0.3nm至0.5nm范围内，并且沸石材料的颗粒的尺寸在0.1μm至20μm范围内。例如实验中使用沸石NA-A(SYLOSIV孔径大小0.4nm)、沸石ZSM-5(硅质岩，孔径大小0.5nm)或沸石A4(K80，斜发沸石，孔径大小0.4nm)作为分子筛。
优选的，沸石材料的孔开口直径在0.37nm至0.43nm范围内。
试验中能够表明，沸石材料的颗粒的尺寸优选的在ISO13320规定的4μm至6μm范围内，以展现良好的排气吸收性。
优选的，模塑材料包含0.05％至5.00％重量比的沸石材料。进一步优选的是，模塑材料包含0.05％至1.00％重量比的沸石材料。
优选的是，热塑性合成材料选自由丙烯腈－丁二烯－苯乙烯共聚物(ABS)、苯乙烯-丙烯腈(SAN)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)或其混合物构成的族。这里，所述热塑性合成材料可以是纤维强化的或非强化的。
由前述模塑材料制成的注塑模制品具有用于吸收氮和/或二氧化碳的分子筛，其优选地将氮和/或二氧化碳积聚在其表面。然而，通过在注塑模制品的容积内均匀分布分子筛，使其能够在离开注塑模具后也同样能均匀吸收泡沫气体。
与不含分子筛的注塑模制品相比，根据本发明的注塑模制品减少了氮和/或二氧化碳排放。
优选的，注塑模制品还具有涂层，特别是装饰层。只有这样分子筛对于模制品的积极作用才对外部观察者可见，因为将皮革装饰物或薄膜直接施加到从注塑模具中取出的模制品上后，皮革装饰物或薄膜下方的气泡不可见。
根据本发明的制造注塑模制品的方法包括以下步骤：
a)将至少一种热塑性合成材料与分子筛混合，优选地与孔开口直径在DIN66134和/或DIN66135规定的0.3nm至0.5nm范围内的沸石材料混合；
b)熔化模塑材料，并且在压力下供应氮(N2)和/或二氧化碳(CO2)；
c)将均匀的熔体挤出或注入注塑模具中；
d)冷却；
e)施加装饰层，其中使用分子筛以减少氮(N2)和/或二氧化碳(CO2)排放，或者将注塑模制品(1)与另一构件粘接。
优选的，步骤d)与步骤e)之间的时间间隔少于5小时。在将皮革装饰物或薄膜施加到约5小时前从注塑模具中取出的模制品上之后，皮革装饰物或薄膜下方的气泡不可见，由此外部观察者能够察觉到分子筛对于模制品的积极作用。借助模制品中的分子筛及其相应方法，加快了涂覆构件的制造，并因此更加便利和节省成本。
优选的，模塑材料的挤出或注塑在80°至300℃的温度范围内完成。分子筛在该温度下不影响发泡过程，但能够在冷却时发挥作用。
根据本发明的注塑模制品用于生产构件，该构件是有涂层的车辆、飞机或轮船的配件，或者是车辆、飞机或轮船的配件的部分，优选的是有涂层或涂覆的内饰构件。
具体实施方式
接下来，结合几个实例进一步说明本发明，而不以此限制本发明。
图1和图2示出传统的，即不含额外的分子筛的注塑模制品的图片，注塑模制品具有装饰层，该装饰层在将模制品从注塑模具中取出(Abmusterung)之后3.5小时(图1)和至少44小时(图2)被施加。明显可以看出图1中的大量地起泡。
意外地发现，模塑材料或由其制成的模制品的排气在借助分子筛的发泡过程之后明显减少或得到抑制。在传统的注塑模制品的情况中，即不含额外的分子筛时，要根据使用的合成材料在将模制品从注塑模具中取出(Abmusterung)至少约44小时后才能够大范围无泡地施加装饰层(参见图2)。于是，目前为止不得不花很长的时间来等待排气减弱，直到能够在模制品上施加涂覆。图3示例性地示出了沸石A的空心结构，沸石A是一种合成的无色的结晶态的硅铝酸盐，其水合钠形式具有以下分子式：Na12((AlO2)12(SiO2)12)27H2O。集合名词沸石A隐含了上述化合物的多种变体(Varianten)。它们都具有相同的硅铝酸盐晶格，但包含了例如钾离子或钙离子等其他离子来取代钠离子。根据本发明的合适的分子筛可以是孔径在0.3nm至0.5nm范围内的沸石A。
Claims (13)
1.一种模塑材料，包含至少一种热塑性合成材料和用于吸收氮和/或二氧化碳的分子筛，其中所述合成材料是适用于化学或物理发泡工艺的合成材料，并且所述分子筛由沸石材料或碳分子筛(carbonmolecular sieve,CMS)构成。
2.根据权利要求1所述的模塑材料，其中所述模塑材料含有至少90％至99.999％重量百分比的合成材料，以及0.001％至10％重量百分比的分子筛。
3.根据权利要求1或2所述的模塑材料，其中，所述沸石材料的颗粒的尺寸在0.1μm至20μm范围内，并且所述沸石材料的孔开口直径在DIN66134和/或DIN 66135规定的0.3nm至0.5nm范围内。
4.根据权利要求3所述的模塑材料，其中，所述沸石材料的颗粒的尺寸在ISO13320规定的4μm至6μm范围内。
5.根据权利要求3所述的模塑材料，其中，所述沸石材料的孔开口直径在0.37nm至0.43nm范围内。
6.根据权利要求1至5之一所述的模塑材料，包含0.05％至5.00％重量百分比的所述沸石材料。
7.根据权利要求1至6之一所述的模塑材料，其中热塑性合成材料选自由丙烯腈－丁二烯－苯乙烯共聚物(ABS)、苯乙烯-丙烯腈(SAN)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)或其混合物构成的族。
8.一种由权利要求1至7中的任一项所述的模塑材料制成的注塑模制品，其中，用于吸收氮和/或二氧化碳的所述分子筛至少部分地积聚在所述注塑模制品的表面。
9.根据权利要求8所述的注塑模制品，其中，所述注塑模制品(1)额外具有涂层，特别是装饰层。
10.一种用于制造根据权利要求8或9所述的注塑模制品的方法，包括以下步骤：
a)将至少一种热塑性合成材料与分子筛混合，优选地与孔开口直径在DIN66134和/或DIN66135规定的0.3nm至0.5nm范围内的沸石材料混合；
b)熔化所述模塑材料，并且在压力下供应氮(N2)和/或二氧化碳(CO2)；
c)将均匀的熔体挤出或注入注塑模具中；
d)冷却；
e)施加装饰层或者将所述注塑模制品与另一构件粘接。
11.根据权利要求10所述的方法，其中步骤d)与步骤e)之间的时间间隔少于5小时。
12.根据权利要求10所述的方法，其中所述模塑材料的挤出或注塑在80°至300℃的温度范围内完成。
13.一种用于生产构件的根据权利要求8或9所述的注塑模制品或根据权利要求1至7所述的模塑材料的应用，其中，所述构件是有涂层的车辆、飞机或轮船的配件，或者是车辆、飞机或轮船的配件的部分，优选的是有涂层或涂覆的内饰构件。
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| CN112795091A (zh) * | 2020-12-30 | 2021-05-14 | 苏州申赛新材料有限公司 | 一种发泡材料及其制得的发泡产品 |
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Application publication date: 20160824 |