CN86103442A - 低摄水量的热塑性聚酰胺膜塑材料 - Google Patents
低摄水量的热塑性聚酰胺膜塑材料 Download PDFInfo
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Abstract
低摄水量的热塑性聚酰胺模塑材料是在聚酰胺中加入0.3-15％(重量)的至少含有一个环氧乙基的环氧化合物，其分子式为(Ⅰ)其中R1和R2是氢、烷基、芳烷基或芳香基；或R2是式(Ⅱ)的基团，其中X可以是氧、硫或带取代基的氮；R3可以是取代或无取代的芳族、脂环族、芳脂族或脂肪族基团，这些基团也可以含有环氧乙基，但中间由其他基团隔开。缩水甘油醚是最适宜的环氧化合物。本发明的模塑材料尤其适用于制造摩托车、仪器、设备或机器的结构件。
Description
本发明涉及热塑性聚酰胺模塑材料，由于加入至少含有一个环氧乙基的环氧化合物，从而该材料的吸水性降低了。
聚酰胺的性质不仅与羧酸酰胺基团的极性有关，而且也与这些基团之间形成氢键有关。不过极性是聚酰胺具有吸水性的基本原因，因此，摄水量直接与聚合物分子中酰胺基的数目有关。不仅放置在水中的聚酰胺样品会吸水，而且暴露于潮湿空气中，例如周围环境（即有潮气），样品同样也会吸水。
聚酰胺（以下称为PA）的重要实施性质如冲击韧性、断裂仲长和柔韧性，特别是像PA6和PA6.6短链聚酰胺的性质，在很大程度上取决于摄水量。如果PA6注射模塑部件经调湿处理，那么它们的缺口冲击韧性性将增加，但同时，与新挤出的部件相比较，它们的硬度和尺寸稳定性将会降低。因此，某些PA的性质由于吸水可能有所改进，而其他性质又可能变得不利。
如果所要求的部件需承受（及/或）增强强力作用，那么保持或改进聚酰胺模塑部件的硬度及尺寸稳定性便成为基本条件。例如摩托车、仪器、设备或和机器的结构构件就要满足这种要求。
为了改进聚酰胺的某些性质，例如加入适当的添加剂以提高它们的硬度和尺寸稳定性，对这种加工工艺我们是熟悉的。这是能够通过加入如纤维或无机物之类的增强材料来实现，但是，一般来说，模塑制件的重量以及它们的脆性也随之增加了。
为了改进新挤出聚合物的韧性，象聚烯烃之类的国产或进口聚合物干料，例如聚乙烯、聚丙烯、或它们的共聚物;以及带有极性侧基的聚合物，如聚醋酸乙烯酯;还有橡胶类弹性体，如丁二烯-丙烯腈共聚物;或者是经改性后得到的聚合物，如封端聚合物都可以加入。通过测定，有关的冲击性质实际上得到了改善，可是酰胺基的吸水作用和使硬度降低的缺陷依然存在。
通过增加聚酰胺分子中酰胺基之间的原子数目，韧性同样有所提高，例如由长链二胺与类似的二元羧酸进行缩聚，或者由多重链的内酰胺缩聚。可是由此引起的热稳定性和硬度的降低则又必须重新加以考虑，因此，此类PA的使用受到了一定的限制。
DS-3248329（DS-丹麦标准协会）指出，减少聚酰胺吸水性，增加它的尺寸稳定性，可以通过引入特殊的长链苯酚来实现，而这种苯酚至多在邻位上有一个取代基。十二烷基苯酚，2-羟基-联苯，壬基酚和2-苯基-2-（4-羟苯基）-丙烷等尤其适用。用这种方法，据说这些添加剂在降低摄水量方面的作用由于某些缺点的存在使评价效果成了问题。首先在挤出期间可能会产生烟和气味;其次用酚基改性的PA部件染有浅红到橙的颜色，对于许多用途，这种颜色令人不快。此外，在聚酰胺中酚基添加剂经不起冲洗，即用某些溶剂如水和甲醇，尤其在高温下，比较容易从薄的模塑部件中除去。从而，减少摄水量作用也便失效了。
如果扩展聚酰胺的用途，模塑制品既韧又硬，而且尺寸稳定性和热稳定性都好，那将是非常需要的。现已发现，在聚酰胺中加入某些环氧化合物，产生很强的疏水作用，这样克服了上述的缺点。
在聚酰胺中引入环氧化物，人们早已知道，多官能团环氧化物会引起交联，而受到局限。用这些产物其目的是为了增加聚酰胺的强度，或者是得到具有良好热稳定性的粘合体系配方。
依据本发明，在按重量计100份可热塑成型的聚酰胺中，加入0.3至15份，最好是0.5至12份的环氧化合物，目的是为了降低吸水性。在聚酰胺中引入环氧化合物有可能产生憎水性（减少摄水量），对于这一点以前一直不知道，也没有用过。
用于上述目的的环氧化合物是那些至少具有一个环氧基，具有分子结构如（Ⅰ），
这里R1可以为氢、烷基、芳烷基或芳香基;R2可以为氢、烷基、芳烷基或芳香基，最好是分子通式为（Ⅱ）的基团
这里X是氧、硫或NR4，R3和R4分别为氢、取代的或无取代的芳族、脂环族、芳脂族基团，或者是还包含环氧基的脂肪族基团，中间由其他基团隔开，但R3和R4不同是氢。
缩水甘油醚是最好的环氧化物。环氧基团或缩水甘油醚基团，在本发明所使用的环氧化物中可以重复出现。
下列单、双或多元缩水甘油醚可以作为环氧化合物的实例：正-丁基缩水甘油醚，2-乙基己基缩水甘油醚，长链脂肪醇的缩水甘油醚，乙二醇二缩水甘油醚，丁氧基-二亚乙基缩水甘油醚，新戌二醇二缩水甘油醚，丁二醇二缩水甘油醚，己二醇二缩水甘油醚，苯基苯酚缩水甘油醚，甲苯基缩水甘油醚，对叔丁基苯基缩水甘油醚，苯基苯酚缩水甘油醚，二羟二苯基丙烷二缩水甘油醚，间苯二酚和邻苯二酚的二缩水甘油醚，异氰脲酸三缩水甘油酯与壬基苯基缩水甘油醚。当然也可以使用它们的混合物。
普遍认为适用的聚酰胺至少含有四种环状组成可以是结晶的，部分结晶或者是无定形的聚酰胺。这种聚酰胺可以由内酰胺或二元胺与二元羧酸反应制得，例如PA4到PA12;以及PA4.6，6.6，6.7，6.8，6.9，6.10，6.12，8.8，12.12或其他聚酰胺可以通过脂肪族，脂环族，芳代脂肪或芳香族二元羧酸与二元胺进行缩聚制得，例如间苯二酸，对苯二酸，叔丁基间苯二酸或癸二酸，与己二胺，异佛尔酮二胺（isophoronediamine），TCD，MNB或二环烷烃（dicycanes）反应。
聚酰胺合金及混合物也是适宜的聚酰胺。它们是以聚酰胺为主混有少量其他聚合物或填料，或者聚合物及填料兼而有之，增强剂，颜料或任何类型的添加剂，或者是颜料及添加剂一起加入。
因此，本专利发明的聚酰胺可以包含添加剂，如稳定剂，结晶促进剂以及脱模剂。
本发明聚酰胺也可以这样制得，将未经处理的聚酰胺在它的熔点以上与改性剂混合，然后用通常的方法在螺杆机或配料机中经挤出处理。
按照本发明经改性处理的模塑聚酰胺材料与未经改性处理的模塑材料相比较，它的优点为摄水量低，硬度较高，而且尺寸稳定性好。因此不管是否增强，它们特别适用于做车身构件。在挤出加工中，它的用途扩展到做电缆包皮，例如光导纤维的电缆包皮。
下列实施例1-4，8和9，解释了本发明，而实施例5，6，7，10，11和12为比较实施例。所有相对粘度值（ηrel）都是在25℃，以间甲苯为溶剂，溶液的重量百分浓度为0.5%的条件下测定的。
实施例1-7
聚酰胺6颗粒（ηrel＝2.8）先在混合转筒中与添加剂（见表1）充分混匀（除了实施例5不用添加剂），然后经双波纹挤出机（two-wave extruder）挤出。在实施例1-4中添加剂为烷基缩水甘油醚，而在实施例6和7中，添加剂为DE-A-3248329中所述的酚。
均相的熔融液体挤出物经-水浴牵引成细棒状，在造粒机中粉碎，然后将颗粒干燥脱去残存的水份，使含水量不超过0.05%（重量百分）。至少在实施例1中，用这样方法处理聚酰胺的粘度没有任何明显的变化。
为了证实吸水，将注射模塑的聚酰胺样品，在50℃的水中放置几周，并由称重测定它们的摄水量。本发明的聚酰胺与未改性的聚酰胺试样相比较，摄水量降低。摄水量检测用卡尔·费希尔分析法（Karl Fisher analysis）和许尔斯光度分析法（Chemische Werke Huels colorimetric analysis;）参看Kuststoffe，9（1970）668-674。
为了更好地表征硬度，在某些实施例中，按照DIN53，452（DIN-德国工业规格）测定经改性产品的弹性模量E。
实施例8-12
无定形的共聚酰胺是由月桂内酰胺间苯二酸及拉罗明（Laromin＊）制得（此后称为Co PA;ηrel＝1.5）。经与先前实施例同样方法改性，详见表2。实施例10所用的无定形Co PA没有添加剂，而在实施例11和12中，加入DE-A-3248329中所述的酚。至于无定形聚酰胺共聚物，其摄水量减少不明显，可是对于实施例8和9中，本专利发明样品却仍然十分明显。
实施例6，7，11和12的试样为橙色或浅红色，在50℃温水中经不起冲洗。在一次提取试验中，酚与抽提取的低聚物，均可在红外光谱和气相色谱中检出。实施例1-5，8，9和10试样为白色或灰白色，任何添加物几乎都不能冲洗掉。
＊Laromin
表1
实施例 PA6% 添加剂 添加剂 摄水量 弹性模量E
（重量） %（重量） 牛顿/毫米2
1 96 C13-C15烷基缩水甘油醚 4 7.18 830
2 95 对-叔丁基苯基缩水甘油醚5 6.38 835
3 96 苯基缩水甘油醚 4 7.42 -
4 96 邻甲苯基缩水甘油醚 4 7.45 -
5 100 - - 9.56 780
6 96 邻-对-壬基苯酚 4 7.78 612
7 94 邻-苯基苯酚 6 6.98 681
表2
实施例 Co PA 添 加 剂 添加剂 摄水量
%（重量） %（重量）
8 96 邻甲苯基缩水甘油醚 4 3.18
9 95 对-叔丁基苯基缩水甘油醚 5 3.14
10 100 - - 3.88
11 95 邻苯基苯酚 5 3.46
12 96 叔丁基苯酚 4 3.30
Claims (6)
1、一种摄水量低的热塑性聚酰胺模塑材料，其中包括：按重量计100份聚酰胺，加入至少含有一个环乙氧基的环氧化合物0.3至15份，环氧化合物的分子式为(Ⅰ)
式中R1可以为氢、烷基、芳烷基或芳香基；R2可以为氢、烷基、芳烷基、芳香基或取代基团，其分子式为(Ⅱ)
式中X是氧、硫或NR4，R3和R4分别为氢、取代的或无取代的芳族、脂环族、芳脂族或脂肪族基团，它们也还可以带有环乙氧基团，中间由其他基团隔开，但R3和R4两者不同是氢。
2、按照权利要求1所述的模塑材料，其中包括环氧化合物重量份数0.5至12份。
3、按照权利要求1或2所述的模塑材料，其中R2为分子式（Ⅱ）的取代基团。
4、按照权利要求3所述的模塑材料，其中环氧化合物为缩水甘油醚。
5、按照权利要求3所述的模塑材料，其中环氧化合物为芳香基-缩水甘油醚。
6、按照权利要求3所述的模塑材料，其中环氧化合物为取代的芳香基-缩水甘油醚。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2080/85-8 | 1985-05-15 | ||
| CH2080/85A CH665424A5 (de) | 1985-05-15 | 1985-05-15 | Thermoplastische polyamidformmassen mit verminderter wasseraufnahme. |
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| CN86103442A true CN86103442A (zh) | 1986-11-19 |
| CN1009202B CN1009202B (zh) | 1990-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN86103442A Expired CN1009202B (zh) | 1985-05-15 | 1986-05-15 | 低摄水量的热塑性聚酰胺膜塑材料 |
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| Country | Link |
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| US (1) | US4767811A (zh) |
| JP (1) | JPS61261353A (zh) |
| KR (1) | KR950001320B1 (zh) |
| CN (1) | CN1009202B (zh) |
| AU (1) | AU591670B2 (zh) |
| BE (1) | BE904763A (zh) |
| BR (1) | BR8602188A (zh) |
| CA (1) | CA1271591A (zh) |
| CH (1) | CH665424A5 (zh) |
| DE (1) | DE3616280C3 (zh) |
| ES (1) | ES8706752A1 (zh) |
| FR (1) | FR2582007B1 (zh) |
| GB (1) | GB2175305B (zh) |
| IT (1) | IT1191892B (zh) |
| NL (1) | NL8601214A (zh) |
| SE (1) | SE469077B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109777102A (zh) * | 2018-11-10 | 2019-05-21 | 湖南七纬科技有限公司 | 一种断桥铝合金门窗专用的有机氟改性尼龙隔热条 |
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| US5187228A (en) * | 1986-10-03 | 1993-02-16 | Dexter Corporation | Stabilizer for compatibilized polycarbonate and polyamide polymer blends |
| GB8714234D0 (en) * | 1987-06-17 | 1987-07-22 | Du Pont Canada | Extrusion of compositions of polyamides & epoxides |
| JPH0725928B2 (ja) * | 1987-11-21 | 1995-03-22 | 新日本理化株式会社 | 熱可塑性樹脂組成物 |
| JP2897222B2 (ja) * | 1988-10-14 | 1999-05-31 | 東レ株式会社 | 熱可塑性ポリアミド組成物 |
| JP5668876B2 (ja) * | 2014-02-07 | 2015-02-12 | 横浜ゴム株式会社 | 熱可塑性エラストマー組成物の製造方法 |
| CN116622227B (zh) * | 2023-07-24 | 2023-09-15 | 广东永鑫华新型材料有限公司 | 一种低吸水率玻纤增强尼龙材料的制备方法 |
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| GB803518A (en) * | 1956-01-19 | 1958-10-29 | Beck Koller & Co England | New synthetic resin compositions |
| US2994456A (en) * | 1959-10-05 | 1961-08-01 | Gen Mills Inc | Metallic containers |
| DE1495842A1 (de) * | 1964-10-31 | 1969-05-08 | Bayer Ag | Verfahren zur Herstellung von hochmolekularen vernetzten Polyamiden |
| US3498953A (en) * | 1966-09-26 | 1970-03-03 | Wyandotte Chemicals Corp | Treatment of polyamides,polyurethanes,polyureas and polyurethane-ureas with polyhalogenous alkylene oxides |
| DE1905102A1 (de) * | 1969-02-01 | 1970-08-06 | Bayer Ag | Modifizierte Polyamide mit erhoehter Affinitaet gegenueber sauren Farbstoffen |
| DE2011678A1 (de) * | 1969-03-19 | 1970-09-24 | Toray Industries, Inc., Chuo, Tokio | Hochviskoses Polyamid und Verfahren zu dessen Herstellung |
| DE2144687C3 (de) * | 1971-09-07 | 1976-01-02 | Gerhard Dipl.-Chem. Dr. 6114 Gross Umstadt Illing | Verwendung von härtbaren Epoxydharzen, als Zusatz zu thermoplastischen Kunstharzmassen |
| JPS5320119B2 (zh) * | 1972-03-16 | 1978-06-24 | ||
| JPS5060552A (zh) * | 1973-09-28 | 1975-05-24 | ||
| JPS50150796A (zh) * | 1974-05-27 | 1975-12-03 | ||
| JPS574669B2 (zh) * | 1974-05-31 | 1982-01-27 | ||
| US4071486A (en) * | 1976-12-20 | 1978-01-31 | Chevron Research Company | Epoxide thermal stabilization additive for polypyrrolidone |
| SU618383A1 (ru) * | 1976-12-22 | 1978-08-05 | Институт Естественных Наук Бурятского Филиала Со Ан Ссср | Способ получени модифицированных полиамидов |
| JPS543163A (en) * | 1977-06-08 | 1979-01-11 | Ube Ind Ltd | Polyamide composition for foam molding |
| JPS5910700B2 (ja) * | 1978-12-06 | 1984-03-10 | 東洋紡績株式会社 | ポリエステル樹脂組成物 |
| JPS574669A (en) * | 1980-06-11 | 1982-01-11 | Hitachi Ltd | Superimposing system between superimposed signal and picture control signal |
| US4383065A (en) * | 1980-12-29 | 1983-05-10 | Chevron Research Company | Stabilized polypyrrolidone composition |
| IL65726A (en) * | 1982-05-10 | 1985-08-30 | Makhteshim Chem Works Ltd | Method for preparing flame retardant thermoplastic nylon resin compositions and the compositions obtained |
| DE3248329A1 (de) * | 1982-12-28 | 1984-06-28 | Bayer Ag, 5090 Leverkusen | Polyamide mit verminderter wasseraufnahme |
| JPS6096631A (ja) * | 1983-10-31 | 1985-05-30 | Toyoda Gosei Co Ltd | ポリアミド−ゴムブレンド組成物 |
| JPS61126170A (ja) * | 1984-11-21 | 1986-06-13 | Toray Ind Inc | ポリアミド樹脂組成物 |
| DE3508531A1 (de) * | 1985-03-09 | 1986-09-18 | Bayer Ag, 5090 Leverkusen | Hydrophobierte, leichtfliessende thermoplastische polyamide |
-
1985
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- 1986-05-12 KR KR1019860003677A patent/KR950001320B1/ko not_active IP Right Cessation
- 1986-05-13 IT IT48008/86A patent/IT1191892B/it active
- 1986-05-14 ES ES554955A patent/ES8706752A1/es not_active Expired
- 1986-05-14 DE DE3616280A patent/DE3616280C3/de not_active Expired - Fee Related
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- 1986-05-14 BE BE0/216656A patent/BE904763A/fr not_active IP Right Cessation
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- 1986-05-14 FR FR8606950A patent/FR2582007B1/fr not_active Expired
- 1986-05-14 BR BR8602188A patent/BR8602188A/pt not_active IP Right Cessation
- 1986-05-15 CN CN86103442A patent/CN1009202B/zh not_active Expired
- 1986-05-15 CA CA000509285A patent/CA1271591A/en not_active Expired - Lifetime
- 1986-05-15 JP JP61109740A patent/JPS61261353A/ja active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777102A (zh) * | 2018-11-10 | 2019-05-21 | 湖南七纬科技有限公司 | 一种断桥铝合金门窗专用的有机氟改性尼龙隔热条 |
Also Published As
| Publication number | Publication date |
|---|---|
| SE8602191D0 (sv) | 1986-05-14 |
| US4767811A (en) | 1988-08-30 |
| FR2582007A1 (fr) | 1986-11-21 |
| AU5734986A (en) | 1986-11-20 |
| GB8611224D0 (en) | 1986-06-18 |
| SE469077B (sv) | 1993-05-10 |
| ES554955A0 (es) | 1987-07-01 |
| BE904763A (fr) | 1986-09-01 |
| SE8602191L (sv) | 1986-11-16 |
| FR2582007B1 (fr) | 1989-06-02 |
| GB2175305A (en) | 1986-11-26 |
| BR8602188A (pt) | 1987-01-13 |
| CH665424A5 (de) | 1988-05-13 |
| CN1009202B (zh) | 1990-08-15 |
| ES8706752A1 (es) | 1987-07-01 |
| CA1271591A (en) | 1990-07-10 |
| IT8648008A0 (it) | 1986-05-13 |
| IT1191892B (it) | 1988-03-23 |
| DE3616280A1 (de) | 1986-11-20 |
| NL8601214A (nl) | 1986-12-01 |
| DE3616280C3 (de) | 1994-10-20 |
| GB2175305B (en) | 1988-06-08 |
| JPS61261353A (ja) | 1986-11-19 |
| KR950001320B1 (ko) | 1995-02-17 |
| KR860009074A (ko) | 1986-12-20 |
| AU591670B2 (en) | 1989-12-14 |
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