CN1418232A - 聚酯多元醇以及聚酯多元醇用于制造耐水解性能改进的聚氨酯铸造弹性体的用途 - Google Patents
聚酯多元醇以及聚酯多元醇用于制造耐水解性能改进的聚氨酯铸造弹性体的用途 Download PDFInfo
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Abstract
本发明涉及平均当量为200～4000的聚酯多元醇，它是通过α，ω－二羧酸与1，4－丁二醇、1，6－己二醇、1，3－丙二醇或1，5－戊二醇以及具有3～6个羟基的多元醇反应而制造的。本发明的聚酯多元醇可用于制造耐水解性能改进的聚氨酯浇注弹性体。
Description
本发明提供聚酯多元醇，它可用于制造耐水解性能改进的聚氨酯浇注弹性体。
已知聚氨酯可浇注弹性体是通过聚酯多元醇与多异氰酸酯的反应制造的。聚酯多元醇同公知的聚醚多元醇相比，具有许多优点，比如其能够以特别经济的方式提供总体机械性能良好的聚氨酯弹性体。实践中采用的聚酯多元醇多为聚己二酸亚乙基酯。可惜的是，与其它聚酯多元醇类似，聚己二酸亚乙基酯的缺点是由其制备的弹性体容易水解，这是许多应用所不允许的。为了补偿聚氨酯弹性体容易水解的缺点，可能的是向所用的聚酯多元醇中添加适宜的抗水解剂，但是这会提高相应的制造方法的成本。
而且，为了改进所采用的聚酯多元醇的耐水解性能，在技术上可能采用相对较长链的二醇和/或酸组分来制造聚酯多元醇，比如聚己二酸亚丁基酯。可惜的是，这样做的后果可能是会提高聚氨酯弹性体制备过程中结晶的风险。结果是，所获得的弹性体在室温下一般具有令人难以接受高水平的硬度。而且，这样合成的聚酯多元醇，其高的熔点对加工不利。
本发明的目的是提供聚酯多元醇，由所述聚酯多元醇可制备耐水解性能良好但机械性能如低温性能和抗冲击性能不受损害并且很容易加工的聚氨酯浇注弹性体(所采用的聚氨酯系统的铸塑时间长并且凝固时间短)。
因此，本发明提供平均当量为(从试验测定的OH数计算而来)200～4000的聚酯多元醇，其通过
a)α，ω-二羧酸或其衍生物
与
b)1，4-丁二醇
c)1，6-己二醇
d)1，3-丙二醇或1，5-戊二醇或其混合物以及
e)具有3～6个羟基的多元醇，
反应制备其中组分b)的用量为51摩尔％～85摩尔％，组分c)的用量为7摩尔％～25摩尔％，组分d)的用量为7摩尔％～25摩尔％而组分e)的用量为0.2摩尔％～2.5摩尔％，基于多元醇b)～e)的总量计。
根据本发明，优选的聚酯多元醇包含组分b)的量为60摩尔％～70摩尔％、组分c)的量为12摩尔％～22摩尔％、组分d)的量为12摩尔％～22摩尔％和组分e)的量为0.75摩尔％～1.75摩尔％，基于多元醇b)～e)的总量计。
适宜的α，ω-二羧酸或其衍生物(结构组分a))特别是具有2～12个碳原子、优选4～6个碳原子的二羧酸。更特别优选相应的脂肪族二羧酸。
适宜二羧酸的例子包括丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸和对苯二甲酸，优选己二酸。
优选的二羧酸衍生物包括，比如二羧酸酸酐或由1～4个碳原子的醇与前述二羧酸构成的二羧酸单或二酯。特别优选由己二酸与甲醇、乙醇、1，2-乙二醇或1，4-丁二醇构成的二羧酸酯。
根据本发明所述，以具有3～6个羟基的多元醇用作组分e)。优选采用具有3个羟基的多元醇。更特别地，在根据本发明制备聚酯多元醇时，用作组分e)的多元醇是分子中具有3～16个碳原子的，更特别优选3～6个碳原子。适宜的例子包括三羟甲基丙烷、甘油、山梨醇和季戊四醇。
多元醇组分e)可以单独或以混合物的形式使用，最适宜的混合比例取决于聚酯多元醇的目标用途，并且容易通过适当的初步试验来确定。
根据本发明的聚酯多元醇既可以在没有催化剂也可以在存在公知的酯化反应催化剂的情况下进行制备，适宜地在惰性气体比如氮、氦和/或氩的气氛下进行。温度为约150℃～300℃，优选180℃～230℃。对此既可在常压下也可以在减压(＜100mbar)下操作。
根据本发明，所述组分a)～e)的反应持续进行，直到聚酯多元醇达到低于10、优选低于1的所需酸值。
适宜的酯化反应催化剂的例子包括金属、金属氧化物或金属盐形式的铁、镉、钴、铅、锌、锑、镁、钛和/或锌催化剂。
当然，在适宜的稀释剂和/或夹带剂(Schleppmitteln)如苯、甲苯、二甲苯和/或氯苯的存在下，也可在液相中而不是熔体中进行本发明聚酯多元醇的制备反应。通过共沸蒸馏除去酯化反应过程中产生的水。
聚酯多元醇的制备本身是已知的并且可参见比如E.Müller，Houben-Weyl，Methoden der organischen Chemie，Thieme-Verlag，Stuttgart，第14卷。
如所述，本发明的聚酯多元醇可用于制备聚氨酯，特别是“CASE”(Coatings Adhesives Sealants/Elastomers)用途的聚氨酯以及聚氨酯纤维，并且特别是聚氨酯浇注弹性体。这些弹性体可以制备成蜂窝状的或实心的形式。
蜂窝状的至实心聚氨酯弹性体的制备可按已知的方式进行，具体是：任选在公知的增链剂、发泡剂以及聚氨酯化学中公知的其它添加剂的存在下，通过本发明聚酯多元醇与文献已知的多异氰酸酯的反应混合物进行反应，要求用于反应的起始物质保持异氰酸酯系数为70～130。
制造聚氨酯可浇注弹性体所需的多异氰酸酯、增链剂、活化剂、发泡剂、助剂和添加剂是公知的并且可参见比如R.Vieweg，A.Hchtlen(主编)：“Kunststoff Handbuch”，第VIII卷，Carl-Hanser-Verlag，München，1993，第3章。
制备蜂窝状的至实心聚氨酯弹性体的方法也是已知的。关于这方面可参照R.Vieweg，A.Hchtlen(主编)：“KunststoffHandbuch”，第VIII卷，Carl-Hanser-Verlag，München，1993，第8章。
采用本发明新型聚酯多元醇制备的弹性体可在各种纤维和模塑制品制造领域获得应用，优选机械工程领域和运输行业。蜂窝状弹性体特别适于制造阻尼和弹性元件，实心弹性体优选用于轮胎、辊子、涂层和滚筒，还有辊子涂层，以及制造各种各样的带。
实施例A.酯的制备对比实施例1
市售的干燥聚己二酸亚丁基酯二醇，其羟值为52mg KOH/g，用作对比。实施例1(本发明)
聚酯多元醇
A的制备
在配备有蒸馏塔(回流比可控)和锥形蒸馏接收容器的可加热反应容器(配有取样装置)中，将36.0kg(0.4mol)1，4-丁二醇、10.4kg(0.1mol)1，5-戊二醇、11.8kg(0.1mol)1，6-己二醇和1.22kg(0.009mol)三羟甲基丙烷添加到82.61kg(0.566mol)己二酸中，并且在N2气氛下蒸馏所形成的水(3h)直至温度升至180℃和酸值约40。在添加完22g的SnCl2水合物之后，将压力连续降低至10～15mbar继续缩聚反应，而温度在该过程(2h)中升高到230℃。向熔体中补充醇，以补偿由于副反应(形成THF等)或塔上损失而损失的醇。当OH值达到44并且酸值达到约0.4时，通过冷却到室温使反应终止，并且将装置充满N2。B.可浇注弹性体的制备对比实施例1 多元醇组合物
向对比实施例A.1的干燥的聚己二酸亚丁基酯二醇(98重量份)中添加抗水解剂Stabaxol1(2重量份)并且在80℃贮存16h，然后在低于100mbar的低压下脱气。
Stabaxol 1是来自Rheinchemie公司的抗水解剂(位阻碳二亚胺)。
搅拌加入来自Bayer AG Leverkusen的DesmodurPC(50.5重量份)(改性4，4′-MDI，NCO含量：26.4％)。然后在不产生气泡的情况下经30s搅拌加入干燥的1，4-丁二醇(9.38重量份)，随后将反应混合物倒入加热的模具(约110℃)中。
反应以溶解在1，4-丁二醇中的DABCODC2(0.001重量份)(制造商：Air Products)进行催化。
约20min之后，从模具中取出铸件。不再进行进一步的热处理。
铸件在7天后达到其最终硬度并且显示出表1所示的性能。
如果在脱模或在初始贮存过程中铸件周围有冷空气循环的话，会使模塑制品发生所不希望的硬化。
为了测定该硬化倾向，在脱模后将6mm厚的弹性体片材贮存在温度为6℃～10℃的室中，以在贮藏室中模拟典型的冬季条件。另一片6mm厚的弹性体片材贮存在加热至约25℃的大的无气流室中。24h之后，两个样品均在25℃贮存30min以均衡温度(调节)。25℃贮存的片材其Shore硬度为84，而冷条件下贮存的片材其Shore A硬度为89(参见表1)。
所制造的片材强的温度依赖性的Shore A硬度表明，在制造过程中由于温度波动无法保证稳定的片材质量。对比实施例2
按照对比实施例1所述用干燥的聚己二酸亚丁基酯二醇(98重量份)、单体4，4′-MDI(Desmodur44，来自Bayer AG Leverkusen；40.6重量份)以及9.69重量份1，4-丁二醇重复弹性体的制备。
为了测定硬化倾向，如对比实施例1所述进行操作。硬化倾向非常明显(参见表1)。实施例1(本发明)
OH值为44的干燥聚酯多元醇
A(制备方法见实施例A.1)(100重量份)在80℃和低于100mbar的低压下脱气，不加抗水解剂。
搅拌加入改性单体MDI，DesmodurPC(来自Bayer AG，Leverkusen的市售产品；50.5重量份)。然后在不形成气泡的情况下经30s搅拌加入干燥的1，4-丁二醇(9.81重量份)，随后将反应混合物倾倒入加热的模具(约110℃)中。
反应通过溶解在1，4-丁二醇中的DABCODC2(0.004重量份)(制造商：Air Products)进行催化。
约20min之后，从模具中取出铸件。不进行进一步的热处理。
铸件在7天之后达到其最终硬度并且显示表1所示的性能。
为了测定硬化倾向，在各种温度下贮存，如对比实施例1所述进行。
24h之后，两个样品均在25℃贮存30min以均衡温度(调节)。两个片材样品的Shore A硬度均为84。实施例2(本发明)
用单体MDI Desmodur44(来自Bayer AG，Leverkusen的市售产品)(39.8重量份)代替DesmodurPC，和9.91重量份1，4-丁二醇重复实施例1所述的弹性体制备过程。铸件在7天之后达到其最终硬度(Shore A为87)并且显示表1所示的性能。没有观察到铸件的硬化倾向。为了评价硬化倾向，在各种温度下贮存，如对比实施例1所述。贮存在各种温度下的片材样品其Shore A硬度在每种情况下均为88(参见表1)。
如本发明实施例所示，从温度非依赖的、恒定的Shore A硬度的角度而言，可保证所制造的片材各个部分质量稳定。对比实施例3
将对比实施例A.1的干燥的聚己二酸亚丁基酯(110重量份)在124℃和低于100mbar的低压下脱气30min。
搅拌加入来自Bayer AG，Leverkusen的Desmodur15(21重量份的萘-1，5-二异氰酸酯)。2min之后，逐步施加真空。15min之后，温度不再升高并且放热反应停止。
然后在不形成气泡的情况下经30s搅拌加入干燥的1，4-丁二醇(3.3重量份)，随后将反应混合物倾倒入热的模具(约110℃)中。
约20min之后，从模具中取出铸件，然后在110℃下回火24h。
铸件在约14天之后达到其最终硬度并且显示表1所示的性能。实施例3(本发明)
将实施例A.1的干燥的聚酯多元醇(125.8重量份)在127℃和低于100mbar的低压下脱气30min。
搅拌加入来自Bayer AG，Leverkusen的Desmodur15(21重量份)(萘-1，5-二异氰酸酯)。2min之后，逐步施加真空。15min之后，温度不再升高并且放热反应停止。
然后在不形成气泡的情况下经30s搅拌加入干燥的1，4-丁二醇(3.3重量份)，随后将反应混合物倾倒入热的模具(约110℃)中。
约20min之后，从模具中取出铸件，然后在110℃下回火24h。
铸件在约14天之后达到其最终硬度并且显示表1所示的性能。
从表1可以看出，由本发明聚酯多元醇
A制造的弹性体(参见实施例1-3)其耐水解性比由聚己二酸亚丁基酯二醇制造的弹性体(参见对比实施例1-3)的耐水解性更优异。
从本发明聚酯多元醇A制造的弹性体在所考虑的温度范围内显示出可比较的非温度依赖性的tanδ和储能模量变化，而且聚己二酸亚丁基酯制造的弹性体在20℃～50℃的范围内却显示出大的tanδ和储能模量的温度依赖性。来自扭摆试验的这些结果表明，在室温下，由聚己二酸亚丁基酯制造的弹性体相当硬，不具有弹性，因此价值低。表1
机械性能(制造之后4星期)
潮湿条件下的老化(80℃，水)
| 对比实施例1 | 实施例1 | 对比实施例2 | 实施例2 | 对比实施例3 | 实施例3 | |||
| 冷贮存 | 1天后Shore A硬度 | 在6℃ | 89 | 84 | 96 | 88 | - | - |
| 25℃贮存 | 1天后Shore A硬度 | 在25℃ | 84 | 84 | 93 | 88 | - | - |
| Shore A | 88 | 88 | 89 | 90 | 88 | 87 | ||
| Shore D | 32 | 31 | 35 | 33 | 34 | 27 | ||
| 屈服应力 | MPa | 46 | 33 | 30 | 33 | 35 | 33 | |
| 抗冲击性 | ％ | 50 | 51 | 60.5 | 64 | 67 | 72 | |
| 压缩变定22℃ | ％ | 11 | 9.3 | 14.8 | 10.5 | 22 | 10.5 | |
| 压缩变定70℃ | ％ | 37 | 35.7 | 28.5 | 20.8 | 19.3 | 16.9 | |
| 扭摆试验 | ||||||||
| 20℃下tanδ | 0.076 | 0.066 | 0.063 | 0.047 | 0.044 | 0.023 | ||
| 50℃下tanδ | 0.033 | 0.032 | 0.036 | 0.028 | 0.017 | 0.019 | ||
| 110℃下tanδ | 0.042 | 0.020 | 0.045 | 0.025 | 0.014 | 0.019 | ||
| 20℃下储能模量 | MPa | 13.6 | 9.9 | 54 | 21.5 | 42 | 19.4 | |
| 50℃下储能模量 | MPa | 10.6 | 8.6 | 21.9 | 19.3 | 23.9 | 20.4 | |
| 110℃下储能模量 | MPa | 5.2 | 5.0 | 9.4 | 14.5 | 24.2 | 21.3 |
9天后
| Shore A | 77 | 78 | n.d. | 90 | n.d. | n.d. | ||
| 屈服应力 | MPa | 16.6 | 22.0 | n.d. | 23.6 | n.d. | n.d. |
14天后
Unus.＝样品不可用(屈服应力＜10MPa)n.d.＝未测定
| Shore A | Unus. | Unus. | 92 | 86 | Unus. | 81 | ||
| 屈服应力 | MPa | Unus. | Unus. | 11.8 | 26.2 | Unus. | 30 |
Claims (3)
1.平均当量为200～4,000的聚酯多元醇，通过
a)α，ω-二羧酸或其衍生物
与
b)1，4-丁二醇
c)1，6-己二醇
d)1，3-丙二醇或1，5-戊二醇或其混合物
以及
e)具有3～6个羟基的多元醇，反应进行制备，其中组分b)的用量为51摩尔％～85摩尔％，组分c)用量为7摩尔％～25摩尔％，组分d)用量为7摩尔％～25摩尔％和组分e)用量为0.2摩尔％～2.5摩尔％，基于多元醇b)～e)的总量计。
2.按照权利要求1的聚酯多元醇，其特征在于组分b)的用量为60摩尔％～70摩尔％、组分c)的用量为12摩尔％～22摩尔％、组分d)的用量为12摩尔％～22摩尔％并且组分e)的用量为0.75摩尔％～1.75摩尔％，基于多元醇b)～e)的总量计。
3.按照权利要求1的聚酯多元醇的用途，用作制备聚氨酯弹性体用的结构组分。
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| HUP0204377A3 (en) | 2005-07-28 |
| BR0108861A (pt) | 2003-04-29 |
| CN1154676C (zh) | 2004-06-23 |
| EP1274758B1 (de) | 2005-12-21 |
| AR030192A1 (es) | 2003-08-13 |
| HUP0204377A2 (en) | 2003-05-28 |
| KR20020076345A (ko) | 2002-10-09 |
| AU2001233782A1 (en) | 2001-09-12 |
| US6809172B2 (en) | 2004-10-26 |
| DE50108463D1 (de) | 2006-01-26 |
| EP1274758A1 (de) | 2003-01-15 |
| DE10010047A1 (de) | 2001-09-06 |
| WO2001064768A1 (de) | 2001-09-07 |
| US20030040597A1 (en) | 2003-02-27 |
| ATE313577T1 (de) | 2006-01-15 |
| JP2003528172A (ja) | 2003-09-24 |
| ES2254369T3 (es) | 2006-06-16 |
| CA2401833A1 (en) | 2001-09-07 |
| MXPA02008527A (es) | 2003-01-28 |
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